Fluorine-containing oil- and water-repellant copolymers
BACKGROUND OF THE INVENTION 
     This invention relates to fluorine-containing oil- and water-repellent copolymers. 
     Fluorine-containing polymers are known which impart oil and water repellency to substrates such as fabric and paper. There is nothing in the art, however, that teaches the copolymers of this invention. The instant copolymers have oil and water repellency properties as well as unique aqueous and organic solubility properties. The copolymers are useful for treating substrates where mild drying conditions are desirable, such as woolen apparel, upholstery fabrics and leather. The copolymers are also useful for treating textiles and particularly paper in applications where oil, water or organic solvent repellency is desired. 
     SUMMARY OF THE INVENTION 
     This invention concerns copolymers comprising 
     (I) FROM 50 TO 85 PERCENT BY WEIGHT OF UNITS DERIVED FROM A MONOMER OF THE FORMULA 
     
         R.sub.f QO.sub.2 CC(R)═CH.sub.2 
    
     wherein 
     R f  is a straight- or branched-chain perfluoroalkyl group containing from 2 to 20 carbon atoms, 
     R is H or CH 3 , 
     Q is alkylene of 1 to 15 carbon atoms, hydroxyalkylene of 3 to 15 carbon atoms, 
     
         --C.sub.n H.sub.2n (OC.sub.q H.sub.2q).sub.m --, 
    
     
         --SO.sub.2 NR.sup.1 (C.sub.n H.sub.2n)--, 
    
     or 
     
         --CONR.sup.1 (C.sub.n H.sub.2n)--, 
    
     wherein 
     R 1  is H or C 1-4  alkyl, 
     N IS 1 TO 15, 
     Q IS 2 TO 4, AND 
     M IS 1 TO 15; AND 
     (II) FROM 50 TO 15 PERCENT BY WEIGHT OF UNITS DERIVED FROM A MONOMER OR A MIXTURE OF MONOMERS SELECTED FROM THE GROUP 
     
         (CH.sub.2 ═C(R)COZ(CH.sub.2).sub.r.sup.+ NR.sup.2 R.sup.3 R.sup.4)X.sup.- 
    
     and 
     
         CH.sub.2 ═C(R)COZ(CH.sub.2).sub.r NR.sup.2 R.sup.3 (O) 
    
     wherein 
     R is H or CH 3 , 
     R 2  and R 3  are each C 1-4  alkyl, hydroxyethyl, benzyl or R 2  and R 3  together with the nitrogen atom form a morpholine, pyrrolidine or piperidine ring, 
     R 4  is H or C 1-4  alkyl or R 2 , R 3  and R 4  together with the nitrogen atom form a pyridine ring, 
     Z is --O-- or --NR 4  --, 
     r is 2 to 4, and 
     X -  is an anion. 
     Preferred weight ratios of the components of the copolymers of this invention, based on total weight percent, are from 65 to 85 weight percent of monomer (i) and from 15 to 35 weight percent of monomer (ii). A particularly preferred copolymer of this invention comprises 75 weight percent of R f  CH 2  CH 2  O 2  CC(CH 3 )═CH 2  wherein R f  is perfluoroalkyl of 4 to 14 carbon atoms and 25 weight percent of CH 2  ═C(R)CO 2  CH 2  CH 2  N(C 2  H 5 ) 2  (O). 
     DETAILS OF THE INVENTION 
     The fluorinated monomers are R f  -alkylene-O 2  CC(R)═CH 2 , as disclosed in U.S. Pat. Nos. 2,642,416, 3,384,627, 3,392,046, 3,282,905, 3,532,659 and 3,102,103; R f  (hydroxyalkylene)O 2  CC(R)═CH 2  as disclosed in U.S. Pat. No. 3,514,420; R f  C n  H 2n  (OC q  H 2q ) m  O 2  CC(R)═CH 2  as disclosed in British Pat. No. 1,243,106; R f  SO 2  NR 1  (C n  H 2n )O 2  CC(R)═CH 2  as disclosed in U.S. Pat. No. 2,803,615; and R f  CONR 1  (C n  H 2n )O 2  CC(R)═CH 2  as disclosed in U.S. Pat. Nos. 3,304,278 and 3,578,487. 
     A particularly preferred fluorinated monomer is R f  CH 2  CH 2  O 2  CC(R)═CH 2 , wherein R f  and R are as defined. Such monomers are known and can be prepared by either esterification of the appropriate alcohol, R f  CH 2  CH 2  OH, with acrylic acid or methacrylic acid or by transesterification with methyl acrylate or methyl methacrylate, for example, as described in U.S. Pat. No. 3,282,905. The methacrylate esters are preferred over the acrylate esters. The perfluoroalkyl group, R f , can be either straight- or branched-chain, with the former being preferred. The monomers, R f  CH 2  CH 2  OCOC(R)═CH 2 , can contain a single perfluoroalkyl group, for example, perfluorooctyl, or a mixture of perfluoroalkyl groups. The alcohols, R f  CH 2  CH 2  OH, are commercially available as mixtures wherein R f  contains about 4 to 14 carbon atoms, predominantly six and eight carbon atoms. Monomers prepared from such alcohol mixtures are preferred. 
     The most preferred perfluoroaliphatic monomer is that wherein R is CH 3  and R f  is a mixture of perfluoroalkyl groups, CF 3  CF 2  (CF 2 ) s  --, wherein s is 2, 4, 6, 8, 10 and 12 in the approximate weight ratio of 2/35/30/18/8/3; such a monomer has a weight average molecular weight of 522. The corresponding acrylate monomer has a weight average molecular weight of 508. 
     The second essential monomer (ii) used in the copolymer of this invention is a dialkylaminoalkyl acrylate or a dialkylaminoalkyl methacrylate or corresponding acrylamide or methacrylamide as either the amine salt, quaternary ammonium or amine oxide form. Mixtures of the various salt forms are also operable herein. A preferred amine salt monomer is: ##STR1## Preferred quaternary ammonium monomers are: ##STR2## and 
     
         CH.sub.2 ═C(R)CONHCH.sub.2 CH.sub.2 CH.sub.2.sup.+ N(CH.sub.3).sub.3 X.sup.-. 
    
     a preferred amine oxide monomer is: ##STR3## The amine salt monomers are prepared by reacting the corresponding tertiary dialkylaminoalkyl acrylate or dialkylaminoalkyl methacrylate ester or corresponding acrylamide or methacrylamide with an organic or inorganic acid, such as hydrochloric, hydrobromic, sulfuric or acetic acid. The tertiary dialkylaminoalkyl acrylate or dialkylaminoalkyl methacrylate esters are known in the art and can be prepared by either reacting a tertiary amine alcohol of the formula, HO(CH 2 ) r  NR 2  R 3  with acryloyl or methacryloyl halide or, preferably, by transesterification with methyl acrylate or methyl methacrylate. 
     The tertiary dialkylaminoalkyl acrylamides or methacrylamides are prepared by acylating the corresponding dialkylaminoalkyl amine with acryloyl or methacryloyl halide in the presence of an acid acceptor such as triethylamine or pyridine. 
     The quaternary ammonium monomers are prepared by reacting the aforesaid acrylate or methacrylate esters or corresponding acrylamide or methacrylamide with a di-(lower alkyl) sulfate, a lower alkyl halide, trimethylphosphate or triethylphosphate. Dimethyl sulfate and diethyl sulfate are preferred quaternizing agents. 
     The amide oxide monomers have the formula CH 2  ═C(R)COZ(CH 2 ) r  NR 2  R 3  (O) as described hereinabove wherein NR 2  R 3  (O) represents ##STR4## They are prepared by reacting the aforesaid acrylate or methacrylate ester or corresponding acrylamide or methyacrylamide with conventional oxidizing agents such as hydrogen peroxide or peracetic acid and the like. 
     The nature of the anion, X - , in the quaternary ammonium and amine salt monomer is, in general, determined by the method of synthesis. Usually, X -  is a halide ion, such as chloride, bromide, or iodide, or an acetate ion, or a sulfate ion, or a phosphate ion or an alkylsulfate ion. It is known, however, that quaternary ammonium salts can also be prepared by reacting a tertiary amine with an alkyl ester of benzene or toluenesulfonic acid; in such event, X -  is a benzenesulfonate or toluenesulfonate anion. 
     The copolymers of the invention are obtained by polymerizing monomers (i) and (ii) by conventional solvent polymerization techniques. Any of the conventional neutral solvents such as ethyl acetate, acetone, 1,2-dichlorotetrafluoroethane, 1,1,2-trichloro-1,2,2-trifluoroethane, ethanol, isopropanol, and mixtures thereof can be used. Isopropanol is a particularly preferred polymerization solvent. The copolymer solutions can be diluted, if desired, with polymerization solvent and/or water. Alternatively, the copolymers can be isolated by removal of solvent. 
     Alternatively, and preferably, the aforesaid tertiary dialkylaminoalkyl acrylate or dialkylaminoalkyl methacrylate ester or corresponding acrylamide or methacrylamide is first polymerized with fluoromonomer (i) and the tertiary amine groups in the resultant copolymer are converted into the amine salt, quaternary ammonium or amine oxide form by acidification, quaternization or oxidation as already described. 
     The copolymers of the invention may be prepared by polymerizing fluoromonomer (i) with a mixture of two or more monomers of type (ii) using the same techniques previously described. Thus, for example, a copolymer may be functionalized with half the theoretically required amount of peracetic acid and sufficient acetic acid to give the mixed acetate/amine oxide functionality. Alternatively, fluoromonomer (i) may be copolymerized with a mixture of quaternary monomer and the free base monomer which may be functionalized after polymerization to give the amine oxide. 
     Conventional free-radical catalysts which are soluble in the solvent system can be used. Particularly preferred are azo compounds such as azobisisobutyronitrile. Catalyst concentration can be about 0.1 to 2 percent based on the weight of total monomers. 
     Conventional chain transfer agents, such as dodecyl mercaptan and isooctyl thioglycolate, and crosslinking agents, such as ethylene dimethacrylate, can be used in amounts of 0.1 to 2 percent by weight of the monomers to control the molecular weight of the polymer. 
     The copolymers of this invention are useful to impart oil, water, and organic solvent repellency to a wide range of substrates. Due to their unique combination of aqueous and organic solubility and repellency properties, the copolymers are easy to apply and require little if any curing; thus, they are particularly suitable for treating substrates such as woolen apparel, upholstered furniture, delicate fabrics and leather, where mild drying conditions are desirable. The copolymers are also useful for treating textiles and paper in applications where oil, water or organic solvent repellency is desired. 
     The copolymers of this invention are adapted to be marketed commercially in the form of stable, aqueous concentrates that can be diluted readily into aqueous treatment baths without floculation or other practical difficulties. They can be readily diluted with water or aqueous alcohol solution and applied to a wide variety of commercial substrates, including textile fibers, yarns, fabrics or paper by conventional means, such as by spraying, dipping, padding, roller-coating or exhaust techniques. 
    
    
     EXAMPLES 
     The following Examples illustrate the invention. Unless otherwise indicated, all parts and percentages are by weight. The percent by weight of monomer units in the copolymers is based on the weights of monomers charged. 
     EXAMPLE 1 
     A vessel was charged with 850 parts of a fluoromonomer (i) having the formula 
     
         CF.sub.3 CF.sub.2 (CF.sub.2).sub.s C.sub.2 H.sub.4 O.sub.2 CC(CH.sub.3)═CH.sub.2 
    
     wherein s is 2, 4, 6, 8, 10 and 12 in the respective relative amounts of 2:35:30:18:8:3 as determined by gas phase chromatographic analysis, said monomer having a weight average molecular weight of 522, 150 parts of monomer (ii), N,N-diethylaminoethyl methacrylate, and 429 parts of isopropyl alcohol. The charge was purged with nitrogen at reflux for 30 minutes and then cooled to 70° C. Azobisisobutyronitrile (4 parts) was then added to initiate polymerization and the charge was stirred for 17 hours at 67° to 73° C. under nitrogen. A yield of 1422 parts of copolymer dispersion was obtained (70.4% solids). 
     A mixture of 852.3 parts of the above copolymer dispersion (600 parts on a 100% basis), 1651.7 parts of anhydrous isopropyl alcohol, 57.2 parts of glacial acetic acid and 980 parts of water was stirred at 50° C. A solution of 60 parts of 30% hydrogen peroxide in 200 parts of water was added over 30 minutes at 48° to 50° C. The mixture was stirred at 47° to 53° C. for 2 hours and then at 68° C. to 70° C. for 4 additional hours. The mixture was cooled to room temperature and diluted with 120 parts of isopropyl alcohol and 80 parts of water. A total of 3834 parts of copolymer solution was obtained. The copolymer solids (15.1%) contained 85 percent of perfluoroalkylethyl methacrylate units and 15 percent of N,N-diethylaminoethyl methacrylate amine oxide units. 
     A 4 × 6 inch piece of 100% woven polyester fabric was immersed in a solution of 0.17 part of the copolymer solids of Example 1 dissolved in 15 ml of absolute ethanol. The ethanol was allowed to evaporate while the fabric was repeatedly dipped until all the copolymer solids were on the fabric. The treated fabric was air-dried and then oven-dried for 3 minutes at 80° C. and then tested for oil and water repellency. Oil repellency was determined using AATCC Standard Test Method 118-1972 of the American Association of Textile Chemists and Colorists. This test comprised placing a drop of one of eight test solutions carefully on the fabric on a flat horizontal surface. The nature of the test solutions was as follows: 
     
         ______________________________________                                    
Oil Repellency             Surface Tension                                
Rating     Test Solution   dynes/cm at 25° C.                      
______________________________________                                    
8          n-Heptane       20.0                                           
7          n-Octane        21.8                                           
6          n-Decane        23.5                                           
5          n-Dodecane      25.0                                           
4          n-Tetradecane   26.7                                           
3          n-Hexadecane    27.3                                           
2          65/35 Hexadecane-                                              
           &#34;Nujol&#34;         29.6                                           
1          &#34;Nujol&#34; (purified                                              
                           31.2                                           
           petroleum oil)                                                 
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     After two minutes, any penetration or wicking into the fabric was noted visually. The oil repellency rating corresponded to the highest numbered test solution for which a drop remained spherical or hemispherical and did not wick into the fabric for at least two minutes. 
     Water repellency of the treated fabric was determined by carefully placing a drop of seven test solutions on each of three locations at least two inches apart. The nature of the test solutions was as follows: 
     
         ______________________________________                                    
Water Repellency                                                          
Rating           Test Solution                                            
______________________________________                                    
7                100% isopropanol                                         
6                50/50 isopropanol-water                                  
5                30/70 isopropanol-water                                  
4                20/80 isopropanol-water                                  
3                10/90 isopropanol-water                                  
2                5/95 isopropanol-water                                   
1                2/98 isopropanol-water                                   
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     The water repellency rating correspond to the highest numbered test solution for which two of the three drops remained spherical or hemispherical and did not wick into the fabric for at least two minutes. The higher the water repellency rating, the better the resistance to staining by water-based substances. 
     Using this test method, treated fabrics with a rating of five or greater are excellent; three or four are good; and anything with a rating of one or greater can be used for certain purposes. The polyester fabric treated with the copolymer of Example 1 exhibited a 3 oil repellency rating and a 5 water repellency rating. 
     EXAMPLE 2 
     A vessel was charged with 70 parts of a fluoromonomer (i) having the formula 
     
         CF.sub.3 CF.sub.2 (CF.sub.2).sub.s C.sub.2 H.sub.4 O.sub.2 CC(CH.sub.3)═CH.sub.2 
    
     wherein s is 2, 4, 6, 8, 10 and 12 in the respective relative amounts of 2:35:30:18:8:3 as determined by gas phase chromatographic analysis, said monomer having a weight average molecular weight of 522, 30 parts of monomer (ii), N,N-diethylaminoethyl methacrylate, and 35 parts of isopropyl alcohol. The charge was purged with nitrogen at reflux for 30 minutes and then cooled to 70° C. Azobisisobutyronitrile (1.0 part) was then added to initiate polymerization and the charge was stirred for 17 hours at 80° to 83° C. under nitrogen. The charge was cooled to 50° C. and a mixture of 9.5 parts glacial acetic acid, 23 parts isopropanol and 23 parts water was added. Twenty parts of 30% hydrogen peroxide was added slowly to convert the polymer to the amine oxide. The charge was held at 50° C. for 1 hour after the peroxide addition. A mixture of 247 parts isopropanol and 205 parts water was then added and the charge m agitated for thirty minutes. A total of 646 parts of mcopolymer solution was obtained. The copolymer solids (14.7%) contained 70 percent of perfluoroalkylethyl methacrylate units and 30 percent of N,N-diethylaminoethyl methacrylate amine oxide units. 
     EXAMPLES 3 to 13 
     Examples 3 to 13 were prepared using the general procedure of Example 2. Data for Examples 3 to 13 are shown in Table I. A mixture of fluoromonomer (i), CF 3  CF 2  (CF 2 ) s  C 2  H 4  O 2  CC(CH 3 )═CH 2 , wherein s is 2, 4, 6, 8, 10 and 12, and N,N-diethylaminoethyl methacrylate (DEAM) monomer or diemthyl sulfate (DMS) quaternary DEAM monomer was polymerized at 80° to 83° C. ethacrylate (DEAM) monomer or diemthyl sulfate (DMS) quaternary DEAM monomer was polymerized at 80° to 83° C. in isopropanol as solvent, using azobisisobutyronitrile as initiator. 
     In Example 6, the DEAM quaternary units were present in the polymer as prepared, therefore, no further functionalization was required. The DEAM units in the remaining copolymers were functionalized after polymerization by conversion to either the amine acetate, amine sulfate, amine oxide salt or a mixture thereof. DEAM functionalization was effected by heating (50° to 60° C.) the copolymer dispersion with at least equivalent amounts of acetic acid, sulfuric acid, 30% hydrogen peroxide, 40% peracetic acid or mixtures thereof in aqueous-isopropanol solvent. The non-volatile solids content of the resulting copolymer solution was determined by drying a 0.4 to 0.6 part sample for 2 hours at 110° C. in a vacuum oven at 20-22 in of Hg. 
     
                       TABLE I                                                     
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PREPARATION OF COPOLYMERS*                                                
       Fluoro-  DEAM       Polymerization                                 
       monomer  Monomer    Solvent                                        
Example                                                                   
       (i)      (ii)       (isopropanol)                                  
                                      Initiator                           
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3      70       30         43         0.5                                 
4      70       30         43         0.5                                 
5      70       30         43         0.5                                 
6      70       30 (DMS    43         0.5                                 
                quaternary)                                               
7      85       15         35         1.0                                 
8      80       20         35         1.0                                 
9      75       25         35         1.0                                 
10     65       35         35         1.0                                 
11     60       40         35         1.0                                 
12     55       45         35         1.0                                 
13     50       50         35         1.0                                 
DEAM Functionalization                                                    
Example                                                                   
        Reagents     Solvents  Net Wt.                                    
                                      % Solids                            
______________________________________                                    
3      19.5 acetic acid                                                   
                     IPA 43    395    23.6                                
                     Water 237                                            
4      7.2 sulfuric acid                                                  
                     IPA 43    393    23.7                                
                     Water 250                                            
5      31 of 40%     IPA 43    386    23.7                                
       peracetic acid                                                     
                     Water 226                                            
6      --            IPA 43    398    23.7                                
                     Water 257                                            
7      9.5 acetic acid                                                    
                     IPA 282   618    15.9                                
       10.0 of 30% H.sub.2 O.sub.2                                        
                     Water 215                                            
8      9.5 acetic acid                                                    
                     IPA 282   615    15.2                                
       13.3 of 30% H.sub.2 O.sub.2                                        
                     Water 212                                            
9      9.5 acetic acid                                                    
                     IPA 282   619    15.2                                
       16.7 of 30% H.sub.2 O.sub.2                                        
                     Water 209                                            
10     9.5 acetic acid                                                    
                     IPA 282   605    15.7                                
       23.3 of H.sub.2 O.sub.2                                            
                     Water 202                                            
11     9.5 acetic acid                                                    
                     IPA 282   653    14.5                                
       26.7 of H.sub.2 O.sub.2                                            
                     Water 199                                            
12     9.5 acetic acid                                                    
                     IPA 282   629    15.6                                
       30.0 of H.sub.2 O.sub.2                                            
                     Water 195                                            
13     9.5 acetic acid                                                    
                     IPA 282   652    15.6                                
       33.3 of H.sub.2 O.sub.2                                            
                     Water 192                                            
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 *All numbers in the table are parts by weight except those in the last   
 column.                                                                  
 
    
     The polymers prepared in Examples 2 to 13 were diluted with water to form aqueous solutions. These polymers are sufficiently soluble in water to give uniform coverage or substrates. The applications were made on unbleached, unsized Kraft paper by immersing the paper into the treating solution, passing the treated paper between squeeze rollers and drying at room temperature, 80° C., 100° C. and 160° C. as shown in Table II. The concentration of the treating solution was adjusted to deposit 0.1 and 0.2 weight % of fluoromonomer units (in the polymer) on the paper. 
     The oil and water repellency results are summarized in Tables II and III. In Table II the weight ratio of fluoromonomer to DEAM monomer was held at a constant 70/30. Various functionalities of N,N-diethylaminoethyl methacrylate (DEAM) (acetate, sulfate, amine oxide and dimethyl sulfate quaternary) showed excellent water repellency and fair to good oil repellency at fluoromonomer concentrations of 0.1% or greater. 
     Table II also shows that the repellency obtained with these copolymers was almost independent of cure temperature. Even samples of treated paper dried at room temperature gave repellency. 
     
                                           TABLE II                                
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Oil and Water Repellency of                                               
Functionalized Fluoromonomer/DEAM Copolymers                              
On Unbleached Kraft Paper (70/30 weight ratio)                            
Copoly-                                                                   
     Repel-                                                               
         0.2% Fluoromonomer                                               
                        0.1% Fluoromonomer                                
mer  lency                                                                
         (owp)          (owp)                                             
from Ex.                                                                  
     of  160° C.                                                   
             100° C.                                               
                 80° C.                                            
                     RT 160° C.                                    
                            100° C.                                
                                80° C.                             
                                    RT                                    
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2    Oil 4   5   5   4  4   4   2   --                                    
     Water                                                                
         6   6   6   6  6   5   6   6                                     
3    Oil 4   5   4   3  3   --  3   2                                     
     Water                                                                
         6   5   6   6  6   5   6   5                                     
4    Oil 5   5   4   4  4   --  4   2                                     
     Water                                                                
         6   6   6   6  6   6   6   6                                     
5    Oil 4   3   3   3  3   --  1   1                                     
     Water                                                                
         6   5   6   5  6   5   6   5                                     
6    Oil 4   5   4   4  2   --  1   1                                     
     Water                                                                
         6   6   6   6  6   6   6   5                                     
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     Table III summarizes the repellency performance of copolymers of fluoromonomers with DEAM amine-oxide in which the concentration of fluoromonomer is varied between 15 to 50 percent. Water repellency was excellent over the whole range of concentrations but optimum oil repellency was obtained in the 70 to 85% fluoromonomer range. 
     
                       TABLE III                                                   
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Oil and Water Repellency of Fluoromonomer/DEAM                            
Amine Oxide Copolymers Containing Varying Amounts                         
of Fluoromonomer on Unbleached Kraft Paper                                
         Fluoro-                                                          
Copolymer                                                                 
         monomer    Repel-  Wt % Fluoromononer                            
From     DEAM       lency   on paper                                      
Example No.                                                               
         Amine Oxide                                                      
                    of      0.2      0.1                                  
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7        85/15      Oil     4        3                                    
                    Water   6        6                                    
8        80/20      Oil     5        4                                    
                    Water   6        6                                    
9        75/25      Oil     6        4                                    
                    Water   6        6                                    
2        70/30      Oil     4        4                                    
                    Water   6        6                                    
10       65/35      Oil     3        3                                    
                    Water   6        5                                    
11       60/40      Oil     2        1                                    
                    Water   5        5                                    
12       55/45      Oil     2        1                                    
                    Water   5        5                                    
13       50/50      Oil     0        0                                    
                    Water   5        4                                    
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