CA2184376A1 - Fluorinated acrylic monomers containing urethane groups and their polymers - Google Patents

Abstract

A composition of formula (I) is disclosed wherein R is H or -CH3; R' is alkyl of 2-8 carbon atoms; R" is fluorinated alkyl of 8-20 carbon atoms. Polymers of the composition are useful to coat onto substrates to impart oil and water repellency.

Description

W096/05172 21 84376 Pcr/usg4/llss9 TITLE OF THE INVENTION
FLUORINATED ACRYLIC MONOMERS CONTAINING URETHANE
GROUPS AND THEIR POLYMERS

This application is ~ continuation-in-part of Application Serial No. 08/289,159 filed August 11, 1994.
FIEIn OF THE INVENTION
This invention relates to acrylic monomers which conta~n urethane un~ts and perfluorinated alkyl groups; and to their polymers, including copolymers; and to Lr tes coated with the polymer .
~Ç~R0UND OF THE INVENTION
Compounds and polymers having perfluorinated s~de chains are known to have oil and water repellant properties. One such class of compounds that are ~ c al~ for such polymers are fluorinated acryl~c res~ns.
Fluorinated acrylic resins are known and are available commercially. For example, perfluoroalkyl acrylates, CH2 - CH - COO - CH2CH2(CF2)nF, are available as Zonyl\ TA-N from the DuPont Company.
Fluorinated acrylic resins whlch contain urethane units are also known, as seen by L~na. et al. USP 5,744,056. These resins can be applied to a number of substrates to provide coatings or to be ~mbibed into the substrate in order make use of the resins as protectiYe coatings.
However, the water and oil repellancy of such perfluorinated alkyl acrylic resins can be improved. The pendant perfluoro alk~l side chains on the acrylic polymers have proven to be difficult to WO 96105172 2 1 ~ 4 3 7 6 PCTIUS941115S9 orient in ~ confi~uration best suited to provide water and oil repel l an~y .
SUHliARY OF THE INl~ElllION
It has been dliscovered that to provide optimum water and o~l 5 repellancy the pendant perfluor1nated alxyl groups should be long chained and should be permanently aligned parallel to ad~acent pendant groups at~ached to adjacent acrylic backbone units. Thus a coated substrate ~ill present a surface protected by an array of pendant perfluoroalkyl groups so as to maximtze water and o~l 10 repel l ancy .
In this invellt10n. the pend~nt perfluoroalkyl groups are mod~fied by the prese~ce of ureth~ne groups intermediate the acrylic backbone and the perfluorinated groups. The affinity of the urethane groups for one another keeps the entire pendant chain l5 substant~ally in fixed al~gnment even wben sub~ected to adverse conditions such ~s heat.
The monomers of tbe ~nvention are represented by the formula:
¢~ :~
~--Rl~ Nk~--OR1~ I
where~n R is H or - CH3; Rl is alkyl of 2-8 carbons; and Rll is fluorinated alkYl of 8-20 carbons.
Preferably ~11 is alkyl perfluoroalkyl (CH2)n Rf where n is 1 or 2 and Rf 1s perfluorinated alkyl of 6-14 carbons).
In a more limit~d b~ t inventive monomers can be r. ~_ .t~ by the formula:
C~
~14i C~--N~ E~N~--opv ::

wo 961~5172 2 1 8 4 3 7 6PCT~usg4tlls~9 where R is H or CH3; Rv jS - CH2CH2 (CF2Jn F or -CH2(CF2)n F and n is a cardinal number of 6-14.
the polymers of the invention include homopolymers and copolymers of the monomers of the invention. The effect of these S monomers in forming polymers with fixed side chains, i.e., side chains fixed into ~ set pattern can be seen in Figure 1 where the affinity of the -NHCOO- urethane groups is self evident.
Also included in the invent10n are - I.1..te~ coated with the polymers of the invention.
BRIEF DESCRIPTION OF THE DRAilIN6 Figure 1 is a molecular model of a polymer of the invention.
DETAILED aESCRlPTlON OF THE INVENTION
Referring to Figure 1, the symbol ~~ represents the -CH2-CR- backbone of the polymer formed from the mono~er of the invention; the symbol--_ represents the urethane linkage;
and the --- lines between these linkages represents molecular attraction between the urethane linkages. It is this attraction that greatly enhances the bonding, or 'fixing," potential of applicants polymers over the polymers of USP 5,144,056.
The monomers of the invention can be prepared by first reacting ~ perfluoroalkyl alcohol, e.g., HO-CH2CH2~CF2thf' ;II
where n is a cardinal number of 6-14, which are available commercially, with 4,4' diphenyl methane diisocyonate (MDI). An WO 96/05172 2 1 ~ 4 3 7 6 PCTIUS94/11559 excess of MDI is employed in order to enh~nce formation of the u ~; - adduct product OCN~ ~N~--QR~
Then the ad,iuct IV is reacted with w-hydroxyalkyl acrylate, prefer~bly 2 hjd.u,~ h,l acrylate. A slight excess is used to facil1tate reaction of all the -~C0 groups of adduct IV. Thus the monomer of formula I of the invention is formed.
The first step cf synthesizing monomer 1, prep~ration of intermediate IV, is carried out at elevated, ~L~ s under an inerl: di ;~ , e.g., anhydrous nitrogen, as isocyanate groups are moisture se~sitive, and ln an organic ~ u.l..; solvent, such as toluene. The intermediate IV is purified by recrystallization.
The second step, which is the reaction of IV wlth 2-hydroxyalkyl 15 acrylate, is also carried out under an inert ~ ~r' e and an organic solvent,, usually anhydrous t~ hJdlùr~ v,. (THF) at reflux.
In order to ensllre a IO^X yield, ~ small excess of 2-hydroxyalkyl acrylate may be used. The unreacted 2-hydroxyalkyl acrylate can be removed by water extraction or reprecipitation of monomer I in 20 water.
Monomer I can be homopolymerized or copolymerized with other copolymerlzable . , in proport~ons of about l to 9û percent by we1ght, pref~rably 50-90 percent, of monomer 1.
Examples ol: , include lower olefinlc hJd~u....vu,,s, 25 halogenated or ~oth~rwise, such as ethylene, propylene, lsobutene, 3-chloro-1-isobutene, butadiene, isoprene, chloro- and di-chlorobut~dienes, fluoro- and dlfluorobutadienes, 2,5-dimethyl-1,5-hexadiene, diisobutylene; vinyl, allyl or vinylidene halides, such as vinyl chloride or vinylidene chloride, vinyl fluoride or 30 vinyl jdene fluoride, allyl bromide, ~ethallyl chloride;
styrene an~i its derivatives, such a vinyltoluene, x-methylstyrene, x-~y ~hJlstyrene, divinylbenzene, N-vinylcarbazole; vinyl esters such as vinyl acetate, vinyl propionate, the vinyl esters of the acids known commercially by the name "Versatic acids,~ vinyl isobutyrate, vinyl succinate, vinyl is~ ate, vinyl stearate, divinyl carbonate; allyl esters such a ally~ acetate and allyl ~e --te; alkyl vinyl or alkyl allyl ethers, halogenated or otherw~se, such a cetyl vinyl ether, dodecyl 5 vinyl ether, isobutyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, tetra allyl~A~ I , vinyl alkyl ketones such a vinyl methyl ketone, ' ~tc~ acids, for example acrylic, methacrylic, a-chloroacryl ~c, crotonic, maleic, fumarlc, itacon1c, citracon~c and senecioic acids, their anhydrides and their esters such as lO vinyl, allyl, methyl, butyl, isobutyl, hexyl, heptyl ethyl-2-hexyl, cyclohexyl, lauryl, stearyl and l-alkoxyethyl acrylates and methacrylates, dimethyl male-te, ethyl crotonate, acid methyl maleate, acid butyl itaconate, glycol or polyalkylene glycol diacrylates and d' lha.,~lates, such as ethylene glycol or tri-15 ethylene glycol ~ late, dichlL ~ht ,~ 7toalkyl acrylatesand methacrylates such as di-chl~ t ~th~l methacrylate, and also actd bis(methacryloyloxyethyl) phosphate and methacryloyloxpropyl~ lane; acrylonltrile, methacrylonitrile, 2-chloroacrylonitrile, 2-cyano-ethyl acrylate, 20 methyleneglutaronitrile, vinylidene cyanide, alkyl cyanoacrylates such a isopropyl cyanoacrylate, trisacryloyl~ h~' ~ s-triazine, vinyltri-chlorosilane, v1nyll,; l' ~,ilane, vinyltriethoxyilane, N-vinyl-2-pyrrolidone; allyl alcohol, allyl glycolate, isobutenediol, allyloxyethanol, o-allylphenyl, divinylcarbtnol, 25 glycerol allyl ether, arylamide, methacrylamide, malea~ide and maletm1de, N-(cyanoethyl)acryl~rnide, N-tsopropylacrylamide, d1acetoneacrylamide, N-(h,d~uA~ ~hJl-)acrylamide and methacrylamide, N-(alkoxymethly-)acrylamides and methacrylamides, glyoxal bisacryl-amide, sodium acrylate or methacrylate, 2-sulpho-30 ethyl acrylate, vinylsulphonic and ~, p sulphonic acids andtheir alkali metal salts, 3-amino-crotono- nitrile, monoallyl amine, vinylpyridines, glycidyl acrylate or methacrylate, allyl glycidyl ether, acrolein, N,N-dimethylaminoeth~l or N-tert-WO96/05172 2 1 8 4 3 7 6 PCT/US9~/11559 butylamino ethyl methacrylate; the unsaturated fluorine esters of the general formula:
R
Rf - W - 0 - C - C - CH - R
ol in which Rf is perfluoralkyl of 2-20 carbons, R is H or methyl and W is a divalent linking moiety.
Among the ~ ioned ~ ~, more special ".6r.~ ?
is gjven to simple alkyl acrylates and methacrylates or those containing a hydroxyl, amino or sulphonic acid functional group, methacrylates of polyethylene glycol ethers, vinyl ethers, vinyl or vinylidene chlor~de and fluor~de, vinyl pyrrolldone, acrylamide and 1ts derivatives, and acrylic or methacrylic acid.
The fluorinated polymers of the invention can be prepared by polymerization in an organic solvent or in an aqueous emulsion, at a temperature which can range from room i e to the boiling point of the reaction medium, but preferably at between 70 and 100C.
The polymerization in a solvent medium can be carried out in ketonic solvents (for example acetone, methyl ethyl ketone, methyl isobutyl ketone)~ alcohols (for example isopropanol), esters (for example ethyl acetate or butyl acetate), êthers (for example diisopropyl ether, ethylene glycol êthyl or methyl ether, te~r ~d~ur- , dioxane), aliphatic or aromatic ll~v'.u.~,'vu.,s, halogenated l~Jv'lv.a~ - (for example perchloroethylene, l,l,l-trichloroethane, trichlorotrifluoroethane), dimethylformamdie or N-methyl-2 pyrrolidone.
The polymerization is performed in the presence of one or more initiators, which can be used in the proportion of about O.l to 1.5X relative to the total weight of the monomers involved. As initiators, peroxides can be used, such as, for example, benzoyl peroxide, lauryl peroxide, succinyl peroxide and tert-butyl perpivalate, or azo compounds such as, for example, 2,2,-azo-bisisobutyronitrile, 4,4,-azobis(4-cyanopentanoic acid) and azodicarbonamide. lt is also possible to polymerize in the WO96/05172 2 1 8 4 3 ~ 6 PCT/US94/11559 presence of UV rad~ation and photoinitiators such as L - ~, 2-methylanthraquinone or 2 chlorothioxanthone. The length of the polymeric chains can, if so desired, be adjusted by means of chain transfer agents such as alkyl merc-ptans, carbon tetrachloride Ot S triphenylmethane, used in the proportion of 0.05 to 0.5% relative to the total weight of monomers.
The polymeri2ation in aqueous emulsion can be carried out according to well-known techniques, in discontinuous or continuous fashion. The surfactants used for the emulsification can be cationic, anionic or nonionic, according to the ionic nature desired for the final dispersion, and are preferably chosen from the best oil-in-water emulsifiers which are as little wettlng as possible. Cationic/nonionic or anionic/nonionic surfactant systems are preferably used. As examples of ~. r~ - is which can be used, the following may be mentioned more especially: in the catlonic series, long-chain tertlary amlne salts such as N,N-dimethyloctadecylamine acetate, and the quaternary ammonium salts of fatty amines such as trimethylcetylammonium bromlde or trimethyldodecylammonium chloride; in the anionic series, alkali metal salts of long-chatn alkylsulphonic atds and alkali metal arylalkyl sulphonates; in the nonionic series, condensatlon products of ethylene oxide with fatty alcohols or with alicyl phenol s .
It can also be ad- ~n to use surfactants having a perfluorinated h, . ~c chain, such as, for example, ammonium perfl. ~ e or potassium N-perfluorooctylsulphonyl-N-ethyl ~ i . - !tat~ .
To facilitate the emulsificat~on of the monomers, it is generally necessary to use organic solvents such as, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), glycols or ethylene glycol ethers, alcohols (methanol, ethanol, isopropanol), or mixtures of these solvents. The amount of solven~
should not generally exceed the total weight of the monomers.
As ~nitiators of polymerization in aqueous emulsion, it is - 35 possible to use water-soluble products, such as inorganic peroxides (for example hydrogen perox~de) and persalts (for example potassiw-persulphate), or initiators which are insoluble in water such as organic peroxides and the azo compounds mentioned above.

Regardless o~ the method by which they are obtained. the fluorinated polymers accord~ng to the invention can optionally be isolated accordin~ to known methods, such as, for example, precipitation or Ievaporation of the solvent.
S The fluorinaf ed polymers according to the invention are excellent l.~ ' lc and oleophobic agents on very diYerse ,-substrate materials such as paper, nonwoven art~cles, textiles based on natural, artificial or synthetic fibers, plastics, wood, met~ls, gl~ss, stone and cement. They are especially useful for I0 the protection of fabrics or paper or cast liners for m~nding bones. For examF,le, in a cast liner rnade of padding provided with a protective layer of liquid water-impermQable, water vapor-permeable mater1~1, such as stretched porous polytetrafluoroelhylene, the padding can be treated w1th the fluorinated polymers 3f the invention. The material can be on one or on both sides of the padding, but preferably is only on one slde. Fi i ~ ~, the material, when ~ade of a membrane of stretched porous polytetrafluoroethylene can itself be coated with a hydrophilic la~er that transports water by an absorption -evaporation mechanism, but which does not ~llow passage of air.
e~ ive cast liners of this type are descr~bed in U.S.P.
5,0I6,622 to horvell, 11 "~...t~i herein by reference.
The fluorln,lted polymers are also useful where enhanced h~,di"' ' ic or oleophobic properties are desired, such as on paper 25 products, such as photocopy paper, cardboard boxQs, wall paper, wall bo~rd, paper bags, paper filters, billboard paper. In general, where ~;ny paper needs to be protected, the polymers are useful. A~dltional paper products for coating include baseball cards, blueprin1 paper, cook book paper, wrapping paper for fast 30 foods, fjle carcls for recipe f11es, score cards (golf, baseball ~
other sporting ovents), instructions for items for things normally assembled outside, lab notebook paper, legal documents, licenses (fishing, huntillg, etc.), maps, menus, notebook paper for outdoor use, outdoor poster paper, Fl~ ~a.k~, sold at the shore, parking 35 tickets, practi~cal joke ite~s, table cloths, tags for outdoor use, text books for children, water/board safety books, wrapping paper, and the like.
For applicItion to substrates, the solutions of polymers are WO 96/05172 - PCT/lJS94111559 g generally diluted with a solvent identlcal to or compatible with that used for the polymerization; while the emulsions of polymers are diluted with water. The application of the solutions or emulsions can be carried out according to a number of techniques, 5 such as spraying, brush-coating, padding, or the like. Depending on their nature, the substrates treated can be dried at room t~ ~t-.,c or at t~ ,es which can range up to 200`C.
The amount Df polymer to be employed can vary within wlde limits, depending on the nature of the substrate and the fluorine 10 content of the polymer. On leather, this amount is generally within the range of about 1 to 10 g/m2.
The examples whlch follow, in which the parts and percentages are . ' ,t~2i to be by weight, except where otherwise stated, illustrate the invention wlthout limiting ~t.
EXAMP~ES
In addition to the moncmers and polymers described above, the following compounds and polymers were also synthesized for comparison studies; 2-acryloxylethyl lH,lH-perfluorooctyl methylened~-p phenyl dicarbamate (V); lH,lH-perfluorooctyl 20 methylenedi-p-phenyl dicarbamate (VI); and poly(2-perfluoroalkylethyl acrylate) (VII). These compositions have the ~olln~n~ ~o ul~:

W096/05172 2 1 8 4 3 7 6 ~CI`/US94/11559 C~2 CH
.

~2 -C,H~
C~O ' ocH~P,~(r~
Perfluoroalkyl acrylate (20nyl TA-N) and perfluoroalkyl ~lcohol (Zonyl 13A-N) wer~ obtained from the E. I. DuPont de Nemours and Company, Inc. and used wtthout further purificat~on. Azobis(2-methylpropionltlrile) (AlaN) (99%) was purchased from Alfa Products.
Diphenyl meth~nla dl~socyanate (MOI) was obt~ined from Mobay Chemical and st7red in an oven at 40`C to precip~tate any dlmer before using. 2-Hydroxylethyl acrylate (g7X) from Polysciences, Inc. were used as obtained. IH, IH-perfluorooctanol and fluorinated solvents were obtained from PCR Co. Anhydrous toluene was obtained from Aldrich Chemicals.
Proton I~MR analysis was done on a 360 MHz NMR ~ Lr~ ler by Spectra Data SErvice, Champaign, IL. HPLC, DSC and DCA analyses were carried out on HP-1090, TA-DSC-2910 and Cahn COA322, respectively .

-Il-balllpl9 1: Synthests of Bis(2-acryloxyl-2'-perfluoroalkyl)othyl m thyl~ned~-p-ph~nyl d~c~tbamat~ (Formula Il) MDI (82.8 9, 0.331 mol) was charged into a 500 ml, 3 necked dry round bottom flask equipped with a condenser, a magnetic S stirrer, nitrogen flow system and a heating mantle. Anhydrous toluene (lS0 ml) was added and the solution was heated to reflux under anhydrous nitrogen. Perfluoroalkyl alcohol (Zonyl BA-N) (34.0 9, 0.066 mol) was added dropwise over 30 minutes. The solution was then refluxed under nitrogen overnight.
Heat was removed. White crystalline solid was observed when the solution was cooled down to room t '~ ~. In S hours time at room t- ., the solid was filtered and recrystallized twice in anhydrous toluene under nitrogen and then vacuu~ dried overn1ght ~t room t~ , ~. About 35.0 grams of white lS crystalline sol1d was obtatned (some product was lost during recrystallizat10n). The solid showed one ma~or spot on thin layer chromatography (TLC) with another trace above the major spot. This solid product is intermediate IV.
The intermediate IV (23.0 9, 0.03009 mol) was charged into a 20 250 ml, 3 necked round bottom flask equipped as above. Anhydrous tt~ Jd~ur~ (THF) (100 ml) was added with 2 drops of Metacure T-12 catalyst (Air Products and Chemical, Inc.). 2-Hydroxylethyl acrylate (S.00 9, 0.04306 mol) was added slowly with a syringe.
The solution was refluxed under nitrogen with magnetical stirring 25 for 3 hours.
The solution was poured into 800 ml of distilled water with stirring in a beaker. The white precipitate was filtered, vacuum dried overnight at room t t ~ and weighted 25.9 9.
Exa~pl~ 2:
Equal molar of MDI was reacted with lH, lH-perfluorooctanol in anhydrous THF through controlled reaction, i.e. adding lH, IH-perfluorooctanol/THF solution to MDl/THF solution very slowly using a syringe pump. Kinetic control ûf the reaction maximized the yield of intermediate IV.

WO96/05172 2 1 ~ 4 3 7 6 PCIIUS94111559 After the reaction, 2-hydroxylethyl acryl~te (1 eq. of total hydroxyl to isocJ~anat~) was added into the flask to for~ a product mi xtur'e:
After removail of solvent, the mixture showed three spots on 5 TLC, indicating l~hat there were three ~a~or components in the mixture. The filrst two components were isolated and purified by column .I", '~ '~ and recrystall~zation. Proton NMR analysis and melting po1n~ m -~ ~ Ls evidenced that the first component was compound Yl md the second one was compound V. The third 10 component which l!las not purified was believed to be bis(2,2'-acryloxy)ethyl methylenedi-p-phenyl dlcarbamate whtch structure is shown as Vlll. The mixture was also quantitatively analy~ed by HPLC. As expected, the HPLC trace had three peaks. Their weight percentages are 30% (Vl), ~0% (V) and 30X (believed'to be (Vlll).
CH2-CH C~H~CH2 C-O ~ O O~C
Y~O ~ ~cH2~-H-c-ocH2cH2o H H
Exa~pl~ 3:
Excess MDI was reacted wlth IH, lH, 2H, 2H-perfluoroalkyl alcollol (Zonyl) BA-N) tmolar ratio of MDI to the alcohol was S to 1) in anhydrous toluen~ by slow add~tion to Zonyl BA-N to MDI. The intermediate IV was ~solated by recrystallization in anhydrous toluene under n~trog~n once and then reacted witb 2-hydroxylethyl acrylate to for~ a product mixture.
After remo~al of solvent, the mixture showed one maior spot on TLC and two tr~e ones, indicating that there were three components in the mixture ~DUt their relative amounts are different than those in Example 3. HPLC analysis also proved that there were three components in the mixture and their weight percentages were 8X (Vl analog), 90% tII) and 2% (believed to be VIII).

WO 96/05172 PCT/I~S94/11559 Example 4: Preparation of Homopolymer of 11onom~r 11 The monomer made in Example I (10.17 9, 0.01160 mol) was charged into a 100 ml, 3 necked round bottom flask equipped with a condenser, magnetlc stirrer, nltrogen flow system and a t~ - ~tl.~e S controlled oil bath heating system. Anhydrous 1, 4-dioxane (IS ml) was added with a syringe. The mixture was stirred at 90`C with nitrogen bubbled through the solution for 10 minutes. Into the solution, AIBN (0.003800 9) ~n anhydrous 1, 4-dioxane (2 ml) was added wlth a syrlnge. The solution was then stirred at 90`C under nltrogen for overnight.
The polymer formed was precipitated ~nto 600 ml of methanol, filtered and v~cuum dried overnlght.
E~cample 5: Preparat~on of Copolpor ~ Mono~r 11 The monomer made in Example I (4.670 9, 0.005300 mol) and n-lauryl acrylate (4.670 9, 0.01943 ~ol) were charged into a 100 ml, 3 necked round bottom flask equlpped same as that ln Example 4.
Anhydrous 1, 4-Dioxane (15 ml) was syringed lnto the flask and , of the oll bath was ralsed to IOO`C. The ' , -solutlon was bubbled wlth nitrogen for 10 minutes and then under nitrogen. A13N (0.008110 9) in 1.5 ml of the 1, 4-d~oxane was syringed lnto the flask. Vlscosity lncrease was observed in 30 mlnutes. The solutlon was then stirred at lOO`C under nltrogen for overntght .
The polymer was preclpitated lnto 800 ml of methanol, filtered ~nd vacuum drled overn~ght.
Thls polymerization was also carried out in 1, 3-bi stri fl uoromethyl benzene (HFX) .
Example 6: Preparat~on of Copolymer Contalnlng llonomer 11 The monomer made in Example I (5.5Z 9, 0.006270 mol) and n-lauryl acrylate (1.950 9, 0.008100 mol) were charged into a 50 ml I necked round bottom flask equipped same as that in Example 4.

21 84~76 WO 96/0~i172 PCTIUS9~/11559 HFX (20 ml) was added with a syringe. T~ of the oil bath w~s raised to llO`C. The solution was bubbled with nitrogen for I0 minutes and then ~nder it. AIBN in 2 ml of HFX was syringed into the flask. The s,Dlution was stirred at IIO`C under nitrogen for 5 overnight.
The polymer was precipitated ~nto 800 ml of methanol, filtered and vacuum dried Dvernight.
Th1s polymerization was also carried in DMF.
..1.1~_ Examplo I: Pr-parat10n of Zonyl TA-N Ho~opolyn0r lH, lH, 2H,2H-Perfluoroalkyl acrylate (Zonyl TA-tl) (82.4 9, 0.I45 mol) was charged into a 250 ml, 3 necked round bottom flask equipped the same as ihat in Example 5. I00 ml of PF-5070 was added. T. ~ G oi the oil bath was ra1sed to reflux and meanwhile the solution was bubbled with nitrogen for I0 minutes.
I5 Into the flask, AIBN 0.0475 9, 0.000290 mol) in I0 ml of HFX was syringed. An inc:rease in viscos~ty was observed in 20 minutes.
The solution was then stirred for overnight at reflux under nl trogen .
The polymer was precipitated into a large quantlty of 20 meth~nol, f~lter~d and vacuum dried overnight.
This polymerizat~on was also carr1ed out in HFX and the same results were obta~ned.
e 2: Pr~para~ion of Copolymer Containing Zonyl TA-N
lH, lH, 2H, 2H-Perfluoroalkyl acrylate (Zonyl TA-N) (20.3 9, 0.0358 mol) and n-lauryl acrylate (6.85 9, 0.0285 mol) were charged into a I00 ml, 3 necked flask equipped same as that in example 5.
30 ml of HFX was added with a syringe. The solution was bubbled with nltrogen for I0 minutes. The flask was heated to IOO`C after AIBN in 2 ml of ilFX was added with a syringe. An increase in viscosity was observed in I0 minutes. The solution was then stirred at IOO`C under nitrogen overnight.

Polymer was precipitated ~nto a large quantlty of methanol, ftltered and vacuum dried overntght.
Example 7: Coattng Compartson Study All samples were prepared under the same conditions except S coating solvent because there ts no common solvent for all studied polymers. Nylon-66 woven fabric was used as coating substrate.
The fabric samples were soaked tn methanol for 30 mtnutes, rinsed with methanol and air dried for one hour prtor to coating. After dtp-in coating, samples were ftrst atr dried for 20 minutes and then oven drted at 170`C for 10 minutes. Each sample ts described as follows:
Compartson Sample 1: 10" x 10~ sample w~s tre~ted wlth 3 wetght X of the polymer from Comparative Example 2 tn HFX.
Compartson Sample 2: 10~ x 10~ sample was treated with 3 weight % of the polymer from Comparative Example 2 tn PF-5070 which is a fluorinated solvent obtained from 3M Corp.
Inventton Sample 3: 10" X 10' sample was treated wtth 3 weight % of the polymer from Example S in THF.
Invention Sample 4: 10~ x ~0~ sample was treated wtth 3 20 weight % of the polymer from Example 6 tn THF.
Simulated laundering washings were done using a Parr shaker (h~d~ ). The shaktng bottle contatns water (300 ml) and Tide ~ L.~.t~d liquld soap (18 ml). Each sample was i~mersed in the soap solut10n in the bottle and the bottle shook for 24 hours 25 at 40C. Each sample was washed under the same conditions, and then r~nsed wtth warm water under the sa~e condtt10n.
The specimens for DCA, -- ~ ts were cut into 1.5 cm x 1.5 cm sizes. Two such spec1mens were taken from each f~bric sample ~t different locations. The DCA results for each sample were the 30 average values from the two specimens.
Four DCA data were obtained for each sample at room tr .-L ~: (1) before washing; (2) after washing, rinse and alr dried for overntght; (3) after washtng, rinse, air drted for overntght and then oven dried at 60C for 30 minutes; (4) after 35 washing, rinse, air dried for overnight; oven dried at 60C for 30 minutes and then oven dried at 170C for 20 minutes. The water receding contact angles are summarized in Table 1.

Tabl- 1: llat~r Rl~c~d~ng Contact ~ngles Under Di~fQr-nt Cond~tions SAMPLE i 2 3 4 Inltial (Before ~lashlna) 65.7 115 113 173 SAfter Air DriEd 19.4 52.5 79.0 81.7 24 hr. 60~C dried 32.1 56.0 90.6 91.7 Wash 170C drted 84.0 91.5 130 118 Table 1 shows that the polymers of the lnvent10n, ln whlch the quite unique polymerlc side ch~lns are highly stabllized . Thls 10 system offers very low and st-ble surface free energy which can be used as water/oil repellent coatlng materl~ls. Compared with polymers based o~ lH, lH, 2H, 2H-perfluoroalxyl acrylate which (Comparisons 1 and 2) are syste~s for water repellent co~tlngs, the lnventlve system ls superior ln terms of water repellency. The 15 hlgher the water recedlng contact angle, the better the water repellency. InYcntlon samples (Sa~ple 3 and 4) have much hlgher water repellency and launder~ng durabillty than copolymer and homopolymer of 11~, lH, 2H, 2H-perfluoroalkyl ~crylate treated samples .
20 ~pl- 8: Tr~llt~na P~D~rs Copolymer o~ E%ample 6 (0.4 9) was dlssolYed ln THF (200 ml) by warmtng to make a solutlon. Xerox copy papers (25 - 8~ x 11~) were treated with the solution by dipplng for a few seconds. The treated papers were l:hen alr drled for 15 mlnutes and then dried in qS an oven for 20 nllnutes at 100`C.
The treated papers showed enhanced h~J~ clty and oleophobltity, while other properties remain unchanged. Table 2 summarlzes hydrophoblclty and oleophoblctty of treated and untreated papers and Table 3 summarlzes other properties.

21 ~4376 TablQ 2: 14~ clty and Ol~ophobic1ty of Treat~d and UntrQat~d Pap~rs Test Treated Untreated Oi l Repel l ency 8 0 5 (QCTM602) Water Drop Repellency 5 4 (QCTM604) Impact Penetration 0.03 0.06 (MTCC42) (9) 10 Water AbsorptiYeness 19.9 29.5 (TAPP1441) (g/m2) Hydrost~tic Pressure 70.5 cm 47.2 cm (AATCC127) Spray Test 80 50 15 (QCTM601) Table 3: Some Properties of Treated and Untreated Papers .
T~T gTAT Control Tr~
1~ lght (5 ~ ) ll~n 77.815 78.0~,7 n--10 St~ D v 0.613 1.232 (inch ~ n 0.00388 0.00402 n-10 gtd D V 0.00012 0.00010 ~url y K~ l IS n 14.. 7 15.
TAPP~ 460 n~10 8t~ D V 2 .1 2 . 2 ~uDe ~ n 3J.3 31.6 q!APP3r ~03 n-20 gtd D-v 2.1 2.4 (g/1-~/2~ br a55 8~0 AgTII ~9~ 91-~- D v 11.6 10.5 n-10 ~ . 2. 3 r~
TAPP~ 2~ 2~ .~
n-10~, _Ot ~ D v -- D v ._ `-92.1 95.Q
~l-~cing 2~ D V 0. o.
r ~1~ ~ 10 . 7 . 20 .
(~ g/--~) D v Oj l~
'1 t ~ ~r D--V ~. 0.
~3tt ~ 2~ 26 . 2 ( 10--3 ) Tra~ D V 0 . 0 . _ -lg-Table 3: Some Properties of Treated and Untreated Papers (Cont'd) ~8T STAT eontrol Tr-~t d T~ ,~n 6~ 67 (~/ply) ~ 8~ D v o 6 TAPPI ~1~ ~ f l 59 n-3~, 3t Tr~n~ 8td D~ 5 2 T~ll- Pro~rtl TA~P~ ~,9J, _~, n 2~ . ~ 2 . -Load ~ ~ t D v Br ak (lb-) 1 t D-V
- n 2 . ~ 2 .
B.. ~ D v Forc- ~lb-/ln) _ n TrA1 D-V . .
Di~pl ~ V
Br~k (inch -) _~_n T~ D v _ n % ~long ~ D v 8r ak - " D V
T n~il- ~ 9 En rgy ~ ~ D v ~ _ lon - ~ 2 (ln-lb~in~) Trane ~ D v 3 ty TA~PI ~ n-10 lI an ~nltla_ Contact 1 ~ 8~ D v at~ o' 11 tt-ability ( /--c) Std D v ~LDll~ 9: Treatlnq OrthoDedtc Cast Patdtnc Copolymer of Example 6 (5.0 9) was dtssolved in THF (500 ml) by warmtng to mak~e a solutlon. Several rolls of polyester cast padding were dtpped tnto the solution for 20 seconds and then taken 5 out and the excess solutton was allowed to drip until dry. The paddings were the~ heated in an oven at IOO`C for 15 minutes. The treated paddtngs Ihad an o11 rat~ng of 6. Their fibers were highly water repellent. Because of the open structure of padding, water may be forced int~ the treated padding and p~ ' w-et. tt. However, 10 the water ts not retained and drlps out quickly. In another test, a treated paddtng was placed on the surf~ce of dtstilled water and no wetting was observed. The same p~ddtng was then placed on the surface of soap water (5 wt. X of ltquid Tide) and tt was wetted.
The wetted padding was then rinsed with disttlled water several I5 ttmes and shaken five tlmes. This paddtng w~s agatn put on tlhe surface of disttlled water and no wetttng was observed.

Claims (13)

WE CLAIM:

1. A composition of the formula:

wherein:
R is H or -CH3;
R' is alkyl of 2-8 carbon atoms;
R" is fluorinated alkyl of 8-20 carbon atoms.

2. The composition of Claim 1 wherein R" is alkylperfluoroalkyl of the formula -Rf-R- wherein R is alkyl of 1-2 carbon atoms and Rf is perfluoroalkyl of 6-14 carbon atoms.

3. The composition of Claim 2 wheretn R is -CH2CH2-.

4. A polymer comprising recurring units of a monomer of Claim 1.

5. A polymer comprising recurring units of a monomer of Claim 2.

6. A polymer comprising recurring units of a mononer of Claim 3.

7. A polymer of Claim 4 wherein comonomer units are present which are units of an alkyl acrylate or methacrylate.

8. A polymer of Claim 5 wherein comonomer units are present which are units of an alkyl acrylate or methacrylate.

9. A polymer of Claim 6 wherein comonomer untts are present which are units of an alkyl acrylate or methacrylate.

10. A coated composition comprising a substrate coated with the polymer of Claims 4, 5, 6, 7, 8 or 9.

11. The composotion of Claim 10 in which the substrate is a fabric.

12. The composition of Claim 10 in which the substrate is a paper.

13. The composition of Claim 10 in which the substrate is a padding.