the instant invention provides a macromer containing perfluoropolyalkylether and polyalkylether segments and ethylenically unsaturated moieties , having the formula i , more specifically as seen in formulas ia to id , z is --( c a f 2a o ) b -- cf 2 --, where x is a direct bond , -- ch 2 --, -- ch 2 och 2 chohch 2 --, -- ch 2 ( och 2 ch 2 ) y -- or carbonyl where y is 1 to 10 and where in each case the carbon atom is attached to z or g ; q is a direct bond or -- aconh -- r -- nhco -- where a is oxa or imino and r is a divalent aliphatic group having from 2 to 14 carbon atoms , a divalent 5 - or 6 - membered cycloaliphatic group having 5 to 14 carbon atoms or an arylene group having 6 to 14 carbon atoms ; l is -- a ( c m h 2m o ) n c m h 2m ay -- or l 1 where y is a direct bond or h and m is 2 to 4 or mixtures thereof and n is 5 to 100 , where a is attached to q ; t is -- conh -- r 5 a -- or -- conh -- r -- nhcoor 5 a -- or -- conh -- r -- nhco -- a -- or -- r 5 a -- or direct bond where the carbonyl group is attached to l , where r 5 is alkylene or hydroxy - substituted alkylene of 2 to 15 carbon atoms and r is as above ; ## str1 ## where r 1 is hydrogen or methyl , and r 2 is hydrogen , methyl or -- coor 3 where r 3 is hydrogen or alkyl of 1 to 4 carbon atoms with the proviso that , when r 1 is methyl , r 2 is hydrogen , r 4 is hydrogen or methyl and g is --( c a f 2a o ) b -- cf 2 [ ch 2 -- oconh -- r -- nhcooch 2 cf 2 ( oc a f 2a ) b ] x or --( c a f 2a o ) b -- cf 2 [ ch 2 -- nhconh -- r -- nhconhch 2 cf 2 ( oc a f 2a ) b ] x where x is 1 to 3 ; ## str2 ## where n 1 is 5 to 100 , z is 1 to 10 and y is a direct bond or h . in the foregoing perfluoropolyether portion , z , of the macromonomer , a is preferably 1 or 2 , and b is preferably 3 to 50 . x is preferably -- ch 2 -- or -- ch 2 ( och 2 ch 2 ) y -- where y is 1 or 2 . q is preferably -- oconh -- r -- nhco -- where r is a radical derived from diisocyanates including hexane - 1 , 6 - diisocyanate , trimethyl - hexane - 1 , 6 - diisocyanate , tetramethylene - diisocyanate , phenylene - 1 , 4 - diisocyanate , toluene - 2 , 4 - diisocyanate , toluene - 2 , 6 - diisocyanate , m - and p - tetramethylxylene - diisocyanate , isophorone - diisocyanate and cyclohexane - 1 , 4 - diisocyanate , and most preferably isophorone - diisocyanate . l is preferably a polyalkylether , -- o ( c m h 2m o ) n c m h 2m o -- where m is 2 or a mixture of 2 and 3 , more preferably m = 2 and n is 10 - 50 . where m is a mixture of 2 and 3 , the mixture contains a major proportion of m = 2 . t is preferably -- conh -- r 5 a -- is preferably preferably ethylene . where t is -- conh -- r -- nhcoor 5 a --, r is preferably a radical derived from isophorone diisocyanate and r 5 is preferably ethylene . e is preferably ## str3 ## where r 1 is preferably methyl and r 2 is preferably hydrogen . where e is ## str4 ## r 1 and r 2 are preferably hydrogen . where e is ## str5 ## where g is present , x is preferably 1 , and r is preferably a radical derived from isophorone diisocyanate . where l 1 is present , a is preferably oxa , r is preferably a radical derived from isophorone diisocyanate , z is preferably 1 to 5 and preferably n = n 1 . the vinylic macromonomers of formula i can be prepared by methods known , per se . for example , the perfluoropolyalkylether / polyalkylether containing divinylic macromonomers of formula ia can be prepared in a three - step sequential synthesis . in the first step , a perfluoropolyalkylether dialkanol of the formula hoch 2 --( c a f a o ) b ( cf 2 )-- ch 2 oh is reacted with two moles of a difunctional reactive diisocyanate of the formula ocn -- r -- nco in the presence of a urethane catalyst to form the corresponding reactive group containing endcapped derivative , z 1 ( nco ) 2 , where z 1 is a moiety containing a perfluoropolyalkylether segment . in the second step , the resulting endcapped perfluoropolyalkylether derivative z 1 ( nco ) 2 can then be reacted with two moles of a polyoxyalkylene diol of the formula ho --( c m h 2m o ) n h preferably in the presence of a conventional aprotic solvent at a temperature between about - 10 ° c . to about 100 ° c ., to form the corresponding polyalkylether - perfluoropolyalkylether - polyalkylether derivative of the formula ## str6 ## in the third step , this triblock diol can be then reacted with two moles of reactive group containing vinylic monomer , wherein the reactive group is an isocyanate , say , of the formula ## str7 ## wherein r , a , r 1 , and r 2 are as above defined and t = 0 or 1 , at a temperature between about - 10 ° c . to about 100 ° c . in the presence of a conventional aprotic solvent , in the further presence or absence of a catalytic amount of urethane catalyst . materials comprising polymers of the formulas ib and id are formed by partial ( or incomplete ) capping in a reaction step . these materials are useful where post - polymerization modifications are performed such as tinting with reactive dyes . suitable aprotic solvents for conducting the reactions include formamide , n , n - dimethylformamide , phosphoric acid tri - dimethylamide , n - methyl - 2 - pyrrolidone , n , n - dimethylacetamide , acetamide , acetonitrile , acetone , tert - butyl acetate and preferably isopropyl acetate . suitable urethane catalysts include tertiary amines such as trimethylamine , triethylamine , n , n - dimethylbenzylamine , or an organo - metallic urethane catalyst , such as stannous octoate or dibutyltin dilaurate , or sodium acetate . alternatively the difunctional reactive agent can be an activated carboxy , such as anhydride , an acid halide , a carboxy ester or oxirane , or is a leaving group , such as halide , sulfato or the like . it is clear that reactants in the various steps of the synthesis be coreactive , e . g . if the perfluoropolyalkylether is terminated with an amine group , the reactive agent can contain an isocyanate , ester , acid halide , halide and the like . these coupling reactions are well known in the art . the perfluoropolyalkylether starting materials are known and some are commercially available . they are described in u . s . pat . nos . 3 , 810 , 874 , 3 , 810 , 875 , 3 , 847 , 978 , 4 , 085 , 137 , 4 , 094 , 911 , 4 , 089 , 319 and and 4 , 440 , 918 and european patent applications ep 0084406 and ep 0211237 and japanese patent applications cited in the background of the invention . perfluoropolyalkylether dimethanols can be prepared by photooxidation of tetrafluoroethylene followed by cleavage and reduction reactions . some of these are available from ausimont , usa and are known as fomblin zdol derivatives such as fomblin zdol 2000 , fomblin zdeal 2000 and fomblin z - disoc with the respectives formulas being z ( ch 2 oh ) 2 , z ( cooch 3 ) 2 , z ( conh - c 6 h 3 ( ch 3 ) nco )] 2 where z = cf 2 o ( c 2 f 4 o ) r --( cf 2 o ) s -- cf 2 ( r / s ˜ 0 . 7 ). one can also chain extend these materials , for example the diols with diisocyanates , before use . difunctional ( or multifunctional ) reactive materials such as diisocyanate , diester , diepoxides and so on are known and many are commercially available . the polyalkylether starting materials are also well known and many are commercially available ( e . g . from aldrich , olin and , polysciences ). hydroxy terminated polyethylene glycols , average molecular weights 200 - 10 , 000 are available from aldrich chemical company , inc . usa . amine - terminated polyethylene glycols are known and some are commercially available , for example , jeffamine d - 400 ( jefferson chemical and texaco ). it is also possible to use polyalkylether copolymers such as ethylene / propylene oxide polymeric diols where the more hydrophilic ethylene oxide is in major proportion . many polymeric copolymeric diols are known and are described in u . s . pat . no . 4 , 780 , 488 . these copolymers include poloxamers which are sold under the trade name pluronic ( basf wyandotte ). one can also chain - extend the diols with , for example , diisocyanates before use . in the third step of the reaction , the reactive vinylic group is introduced . isocyanate terminated vinylic monomers are known and some are described in u . s . pat . no . 4 , 665 , 123 . some are commercially available such as isocyanatoethyl methacrylate ( dow corning , usa ) and m - isopropenyl - 2 , 2 - dimethylbenzyl - isocyanate ( m - tmi , cyanamid ). epoxy terminated vinylic monomers , e . g . glycidyl methacrylate , are known and are commercially available . the derivatives of formula i are advantageously polymerized in the presence of an inert diluent or solvent , such as a suitable organic solvent , including a lower alkanol , e . g . ethanol , methanol or the like , or an aprotic solvent such as n , n - dimethylformamide , acetamide , acetonitrile , n , n - dimethylacetamide , dimethyl sulfoxide , acetone , tert - butyl acetate , isopropyl acetate or mixture thereof . also , aqueous / organic solvent systems may be employed . the derivatives of formula i are polymerized in the presence of actinic radiation or in the presence of a conventional free radical initiator , such as a peroxide , e . g . di - tert - butyl peroxide , benzoyl peroxide , lauryl peroxide , decanoyl peroxide , acetyl peroxide , succinic acid peroxide , methyl ethyl ketone peroxide , 2 , 4 - dichlorobenzoyl peroxide , isopropyl peroctoate , tert - butyl hydroperoxide , tert - butyl perpivalate , tert - butyl peroctoate , diisopropyl peroxydicarbonate , cumene hydroperoxide , tert - butyl perbenzoate , tert - butyl peroxymaleic acid , tert - butyl peroxyacetate , and potassium persulfate , an azo compound , e . g . 2 , 2 - azo - bis - isobutyronitrile , 2 , 2 &# 39 ;- azo - bis -( 2 , 4 - dimethylvaleronitrile ), 1 , 1 &# 39 ;- azo - bis -( cyclohexane carbonitrile ), 2 , 2 &# 39 ;- azo - bis -( 2 , 4 - dimethyl - 4 - methoxyvaleronitrile ) and phenyl - azo - isobutyronitrile , a photoinitiator , e . g . benzoin methyl ether and 1 - hydroxycyclohexyl phenyl ketone or actinic radiation such as uv light or ionizing rays e . g . gamma rays or x - rays . the derivatives of formula i are advantageously polymerized upon placement into a mold . the mold may be a conventional spin - casting mold for preparing contact lenses such as described in u . s . pat . no . 3 , 408 , 429 , or in a static mold , e . g . as described in u . s . pat . no . 4 , 347 , 198 . alternately , one may prepare a swollen lens blank , dry the lens blank to form the corresponding xerogel , shape the xerogel into a contact lens precurser by lathing methods known to the art , and swell the shaped xerogel in aqueous medium to form the corresponding contact lens , as described in reissue u . s . pat . no . 27 , 401 . the solution of derivatives of formula i are advantageously placed into a mold in the shape of a contact lens and polymerized . after polymerization , the crosslinked polymer is equilibrated in aqueous or aqueous saline solution . optimally this post treatment further includes a heat treatment of the molded lens shaped polymer . such heat treatment is characteristically conducted at a temperature between about 60 ° to 100 ° c ., e . g . in the presence of an aqueous medium . the treatment can vary greatly , but usually is accomplished in about 5 to 90 minutes . the purpose of this post treatment is to dimensionally stabilize the crosslinked contact lens material . also , the treatment may further serve to sterilize such lens material . the resultant contact lenses are optically clear , strong , flexible , highly oxygen permeable and wettable . further , the instant lenses are characterized by their ease of manufacture . in the following examples , all parts are by weight unless otherwise described . a description of testing methods used on the polymer films is as follows : ( a ) oxygen permeability ( dk ) is determined from measurements on a schema versatae or createch polarographic cell ( b ) wettability or lubricity is evaluated by a feel comparison to crosslinked polyhema ( i . e . polymerized 2 - hydroxyethyl methacrylate + 1 % ethylene glycol dimethacrylate ). the surface lubricity of polyhema is designated ( b ); more wettable than polyhema is designated ( a ) and a less wettable surface than polyhema is designated ( c ). ( c ) tensile strength is qualitatively evaluated by pulling on a sheet of the material by hand and then comparing the result to a material previously evaluated by a micromechanical tester to be 14 kg / cm 2 . a measurement found to be similar to this &# 34 ; standard &# 34 ; is designated ( 2 ); a higher value is designated ( 1 ); a lower value is designated ( 3 ); while a much lower value is designated ( 4 ). this example illustrates the sequential synthesis of the perfluoropolyether / polyether urethane - linked adduct , z 1 ( ipdi - peg - iem ) 2 , where z 1 is a perfluoropolyether , ipdi is isophorone diisocyanate , peg is a polyethylene glycol and iem is isocyanatoethyl methacrylate ; and , the solution polymerization of this adduct . 30 . 06 g ( 0 . 0136 mole ) fomblin zdol 2000 ( mw 2200 ; montedison , ausimont ) is combined with 6 . 07 g ( 0 . 02734 mole ) ipdi and 10 μl dibutyltin dilaurate , mixed well and stirred overnight at room temperature forming z 1 ( ipdi ) 2 . the percentage of isocyanate reacted ( generally 48 - 54 %) is determined by dibutylamine titration and varies with the precise value of the z 1 molecular weight actually used . then , the calculated molar amount of peg is added to a solution ( solvent , 30 - 70 %) of z 1 ( ipdi ) 2 to form z 1 ( ipdi - peg ) 2 . then a urethane catalyst , i . e . dibutyltin dilaurate ( 0 . 66 ml per gram of solute ) is added and the solution allowed to react at 50 ° c . with stirring overnight ( complete disappearance of isocyanate ir absorption at 2270 cm - 1 ). the calculated molar amount of iem is added , with rapid stirring , to a solution of z 1 ( ipdi - peg ) 2 and reacted at 40 °- 50 ° c . ( see example 2 samples 1 - 3 ) or at room temperature ( see example 2 sample 5 and 6 ). the z 1 ( ipdi - peg - iem ) 2 adduct in solvent is mixed with initiator ( benzoin methyl ether , bme ), poured into flat &# 34 ; sandwich &# 34 ; molds and polymerized with uv light ( sylvania , blacklight blue , 15 w ) at room temperature for 3 hours . the polymerized films are removed from the molds , extracted in water several times , heated in boiling water for 10 minutes and then allowed to equilibrate in room temperature water ( generally overnight ). this example shows the resultant water content and oxygen permeability values of perfluoropolyalkylether / peg hydrogels , i . e . crosslinked z 1 ( ipdi - peg - iem ) 2 , solution polymerized using different molecular weights of peg ( 400 , 600 ) in various amounts of solvent ( acetone ). __________________________________________________________________________wt . % in the polymerization mixture wt . % % h . sub . 2 o dksample z . sub . 1 ipdi peg ( mw ) iem acetone bme content ( barrer ) __________________________________________________________________________1 39 . 2 7 . 9 14 . 3 ( 400 ) 5 . 5 33 . 0 0 . 1 14 . 5 67 . 02 20 . 3 4 . 1 7 . 4 ( 400 ) 2 . 9 65 . 3 0 . 2 28 . 9 68 . 43 34 . 7 7 . 1 19 . 0 ( 600 ) 4 . 9 34 . 3 0 . 04 29 . 2 46 . 24 31 . 6 6 . 4 17 . 4 ↓ 4 . 5 40 . 1 0 . 3 37 . 3 51 . 65 26 . 0 5 . 3 14 . 3 ↓ 3 . 7 50 . 8 0 . 3 36 . 9 53 . 06 16 . 1 3 . 3 8 . 9 ↓ 2 . 3 69 . 5 0 . 4 49 . 2 51 . 5__________________________________________________________________________ as shown above , water content increases with higher molecular weight peg and reaction solvent content . the oxygen permeability , however , decreases with the higher molecular weight peg . this example illustrates a range of z 1 / peg hydrogel water contents obtained by varying the molecular weight of the peg and the proportion of solvent ipac ( isopropyl acetate ). films are made as in example 1 except that the molecular weight of the peg is 600 , 900 , 1000 or 1500 and the solvent used is isopropyl acetate . iem is reacted at 40 °- 50 ° c . for all samples . ______________________________________ % h . sub . 2 osam - wt . % in the polymerization mixture wt . % con - ple z . sub . 1 ipdi peg ( mw ) iem ipac bme tent______________________________________ 1 35 . 3 7 . 2 19 . 3 ( 600 ) 5 . 0 33 . 2 0 . 06 21 . 9 2 27 . 1 5 . 5 14 . 8 ↓ 3 . 8 48 . 8 0 . 06 31 . 2 3 20 . 8 4 . 2 11 . 3 ↓ 2 . 9 60 . 8 0 . 04 45 . 8 4 29 . 4 5 . 9 24 . 0 ( 900 ) 4 . 1 36 . 6 0 . 05 39 . 5 5 25 . 2 5 . 1 20 . 6 ↓ 3 . 6 45 . 7 0 . 04 40 . 7 6 20 . 9 4 . 2 17 . 1 ↓ 3 . 0 54 . 8 0 . 05 42 . 8 7 27 . 3 5 . 5 24 . 9 ( 1000 ) 3 . 9 38 . 4 0 . 05 42 . 9 8 23 . 8 4 . 8 21 . 7 ↓ 3 . 4 46 . 3 0 . 05 45 . 1 9 22 . 0 4 . 4 20 . 0 ↓ 3 . 3 47 . 7 0 . 05 45 . 010 20 . 2 4 . 1 18 . 3 ↓ 2 . 8 54 . 6 0 . 03 48 . 111 15 . 9 3 . 2 14 . 5 ↓ 2 . 2 64 . 2 0 . 05 54 . 212 13 . 9 2 . 8 12 . 6 ↓ 2 . 0 68 . 7 0 . 04 52 . 913 18 . 9 3 . 9 25 . 9 ( 1500 ) 2 . 7 48 . 6 0 . 05 57 . 914 16 . 5 3 . 4 22 . 6 ↓ 2 . 3 55 . 2 0 . 06 61 . 115 14 . 7 3 . 1 20 . 1 ↓ 2 . 1 60 . 1 0 . 07 61 . 5______________________________________ as shown above water content increases with increasing molecular weight peg and solvent content . this example shows the effect of hydrophilic comonomer addition on the physical properties of z 1 / peg hydrogel films . films are made as in example 3 except that comonomer n , n - dimethylacrylamide , dma ; n - vinylpyrrolidone , nvp ; or 2 - hydroxyethyl methacrylate , hema ) is added just prior to the addition of initiator . __________________________________________________________________________ physical properties of hydrogelwt . % in the polymerization mixture % % h . sub . 2 osample z . sub . 1 ipdi peg ( mw ) iem comonomer ipac bme content clarity wettability strength__________________________________________________________________________ 1 24 . 4 4 . 9 19 . 9 ( 900 ) 3 . 4 17 . 1 dma 30 . 3 0 . 05 54 . 4 clear a 3 2 24 . 5 4 . 9 20 . 0 ↓ 3 . 5 16 . 7 nvp 30 . 4 0 . 05 48 . 8 ↓ ↓ 3 3 24 . 5 4 . 9 20 . 0 ↓ 3 . 5 16 . 6 hema 30 . 5 0 . 05 37 . 1 ↓ ↓ 2 4 29 . 4 5 . 9 24 . 0 ↓ 4 . 1 -- 36 . 6 0 . 05 39 . 5 ↓ ↓ 2 5 24 . 8 5 . 0 22 . 6 ( 1000 ) 3 . 5 9 . 1 dma 35 . 0 0 . 05 52 . 6 ↓ ↓ 3 6 22 . 8 4 . 6 20 . 7 ↓ 3 . 2 16 . 6 32 . 1 0 . 05 57 . 1 ↓ ↓ ↓ 7 21 . 0 4 . 3 19 . 1 ↓ 3 . 0 9 . 5 43 . 1 0 . 06 54 . 4 ↓ ↓ ↓ 8 19 . 2 3 . 9 17 . 5 ↓ 2 . 7 17 . 4 39 . 4 0 . 05 60 . 1 ↓ ↓ 3 - 4 9 24 . 8 5 . 0 22 . 6 ↓ 3 . 5 9 . 2 nvp 34 . 9 0 . 05 48 . 6 ↓ ↓ 310 22 . 7 4 . 6 20 . 7 ↓ 3 . 2 16 . 8 32 . 0 0 . 05 54 . 7 hazy ↓ 411 21 . 1 4 . 3 19 . 2 ↓ 3 . 0 9 . 0 43 . 4 0 . 04 49 . 7 clear ↓ 312 19 . 2 3 . 9 17 . 4 ↓ 2 . 7 17 . 5 39 . 3 0 . 05 52 . 3 ↓ ↓ 413 24 . 8 5 . 0 22 . 6 ↓ 3 . 5 9 . 1 hema 35 . 0 0 . 05 42 . 7 ↓ ↓ 314 22 . 8 4 . 6 20 . 7 ↓ 3 . 2 16 . 6 32 . 1 0 . 05 40 . 0 ↓ ↓ ↓ 15 21 . 0 4 . 2 19 . 0 ↓ 3 . 0 9 . 8 43 . 0 0 . 05 44 . 9 sl . hazy ↓ ↓ 16 19 . 2 3 . 9 17 . 5 ↓ 2 . 7 17 . 4 39 . 4 0 . 05 44 . 8 sl . hazy ↓ ↓ 17 27 . 3 5 . 5 24 . 9 ↓ 3 . 9 -- 38 . 4 0 . 05 42 . 9 clear ↓ ↓ 18 15 . 7 3 . 3 21 . 5 ( 1500 ) 2 . 2 16 . 8 dma 40 . 5 0 . 05 69 . 6 ↓ ↓ 219 15 . 7 3 . 3 21 . 5 ↓ 2 . 2 16 . 8 nvp 40 . 5 0 . 05 63 . 2 ↓ ↓ 3 - 420 15 . 4 3 . 2 21 . 5 ↓ 2 . 2 18 . 9 hema 39 . 8 0 . 06 55 . 8 hazy ↓ 221 18 . 9 3 . 9 25 . 9 ↓ 2 . 7 -- 48 . 6 0 . 05 57 . 9 clear ↓ 3__________________________________________________________________________ dma = dimethylacrylamide ; nvp = nvinylpyrrolidone ; hema = 2hydroxyethyl methacrylate as shown above , addition of hydrophilic comonomers has little effect on wettability or tensile strength . this example compares the effect of initiator level on the physical properties of similar composition z 1 / peg hydrogel films . the films are prepared in a similar manner to that in example 1 . in general , 3 . 00 g ( 0 . 0016 mole ) fomblin zdol 2000 , mw 1851 ( previously bubbled with nitrogen for 2 hours while stored over molecular sieves ) is combined with 0 . 72 g ( 0 . 0032 mole ) ipdi and 2 . 5 μl dibutyltin dilaurate ( dbtl ) catalyst under nitrogen , mixed well and stirred overnight at room temperature . the percentage of isocyanate reacted is determined by titration to be 48 - 53 %. peg 1000 is reacted with z 1 ( ipdi ) 2 in the presence of solvent ( approximately 38 % by weight isopropyl acetate , ipac ). then 0 . 66 μl dbtl is added per gram solute and the solution reacted at 50 ° c . with stirring overnight under nitrogen . the solution is cooled to room temperature and initiator ( bme ) added . the solution is centrifuged five minutes ( eppendorf 5412 ) poured into &# 34 ; sandwich &# 34 ; molds and uv irradiated at room temperature for three hours . after water extraction , strength and wettability testing is performed . __________________________________________________________________________ physical properties of hydrogelwt . % in the polymerization mixture % h . sub . 2 osample z . sub . 1 ipdi peg iem ipac % bme content clarity wettability strength__________________________________________________________________________1 24 . 8 5 . 9 26 . 8 4 . 2 38 . 4 0 . 05 36 . 7 clear b 22 24 . 6 5 . 9 26 . 7 4 . 2 38 . 7 0 . 05 47 . 9 ↓ a 43 25 . 9 5 . 8 25 . 9 4 . 0 38 . 4 0 . 1 46 . 3 ↓ b 24 24 . 8 6 . 0 26 . 8 4 . 1 38 . 3 0 . 1 47 . 5 ↓ a 35 24 . 7 6 . 0 26 . 8 4 . 2 38 . 4 0 . 1 50 . 4 ↓ a 36 25 . 9 5 . 8 25 . 9 4 . 0 38 . 4 0 . 2 48 . 4 ↓ b 27 24 . 8 6 . 0 26 . 8 4 . 1 38 . 3 0 . 2 51 . 3 ↓ a 38 25 . 9 5 . 8 25 . 9 4 . 0 38 . 4 0 . 5 48 . 8 ↓ a 2__________________________________________________________________________ as shown above , increasing initiator level from 0 . 05 to 0 . 1 % and higher appears to improve property reproducibility especially water content and strength ; but no added strength is found by further increasing initiator level to 0 . 5 %. this example illustrates the effect of various crosslinking agents on the physical properties of perfluoropolyether / peg hydrogel films . the crosslinkers used are : a dimethacrylate of peg 600 , a dimethacrylate of zdol 1000 and ethylene glycol dimethacrylate . the dimethyacrylate of peg 600 is synthesized by combining 2 . 425 g ( 0 . 004 mole ) peg 600 with 1 . 2578 g ( 0 . 008 mol ) iem , mixing well and adding 2 μl dbtl and stirring overnight at room temperature . reaction completion is indicated by disappearance of isocyanate ir absorption at 2270 cm - 1 . the dimethacrylate of zdol 1000 , z 1 ( iem ) 2 , is synthesized by combining 1 . 1115 g ( 0 . 00085 mole ) fomblin zdol 1000 ( mw 1301 ) with 0 . 2652 g ( 0 . 0017 mole ) iem , mixing well and then adding 2 μl dbtl and stirring for three hours at room temperature . disappearance of the isocyanate ir absorption is used to monitor reaction completion . ethylene glycol dimethacrylate ( egdma ) is distilled from a commerical source ( sartomer ) before use . __________________________________________________________________________wt . % in the polymerization mixture physical properties of hydrogel peg % h . sub . 2 o wetta - sample z . sub . 1 ipdi 1000 iem ipac comonomer % bme content clarity bility strength__________________________________________________________________________1 22 . 4 5 . 4 24 . 3 3 . 8 34 . 8 9 . 3 peg 600 -( iem ). sub . 2 0 . 1 49 . 8 clear a 32 19 . 9 4 . 8 22 . 4 3 . 5 36 . 2 13 . 1 ↓ 0 . 1 48 . 3 ↓ a 43 20 . 7 4 . 9 22 . 3 3 . 5 35 . 4 13 . 2 ↓ 0 . 09 48 . 6 ↓ a 44 24 . 4 5 . 9 26 . 4 4 . 1 38 . 1 1 . 1 egdma 0 . 1 45 . 3 ↓ b 35 24 . 5 5 . 9 26 . 4 4 . 1 38 . 1 1 . 0 zdol 1000 ( iem ). sub . 2 0 . 1 53 . 6 ↓ a 2 - 36 24 . 7 5 . 9 26 . 7 4 . 2 38 . 5 ↓ 0 . 1 46 . 7 ↓ a 3__________________________________________________________________________ peg 600 ( iem ). sub . 2 = peg 600 dimethacrylate ; egdma = ethylene glycol dimethacrylate ; zdol 1000 ( iem ). sub . 2 = zdol 1000 dimethacrylate this example shows the physical properties of perfluoropolyether / peg hydrogel films made by combining the diadducts of z 1 ( ipdi - peg - iem ) 2 which have different pegs , but the same z 1 ( i . e . zdol 2000 ). the pegs used are 400 , 600 and 1000 . the reaction solutions are prepared in isopropyl acetate as in example 5 except that nitrogen degassing is not used . the solutions are mixed in various ratios just prior to initiator ( bme ) addition . __________________________________________________________________________ physical properties of hydrogelmole ratio wt . % in the polymerization mixtures % h . sub . 2 o wetta - samplez . sub . 1 -( ipdi - peg - iem ). sub . 2 z . sub . 1 ipdi peg ( mw ) iem ipac % bme content clarity bility strength__________________________________________________________________________1 1 peg 1000 / 1 peg 600 27 . 1 6 . 5 14 . 8 ( 1000 ) 4 . 6 38 . 3 0 . 05 39 . 0 clear a 3 8 . 7 ( 600 ) ↓ ↓ ↓ 2 3 peg 1000 / 1 peg 600 25 . 9 6 . 2 21 . 1 ( 1000 ) 4 . 3 38 . 4 0 . 06 42 . 4 ↓ ↓ ↓ 4 . 1 ( 600 ) ↓ ↓ ↓ 3 1 peg 1000 / 1 peg 400 28 . 6 6 . 5 15 . 6 ( 1000 ) 4 . 8 38 . 3 0 . 05 35 . 0 ↓ ↓ ↓ 6 . 1 ( 400 ) ↓ ↓ ↓ 4 3 peg 1000 / 1 peg 400 26 . 5 6 . 4 21 . 2 ( 1000 ) 4 . 5 38 . 3 0 . 05 40 . 9 ↓ ↓ ↓ 2 . 9 ( 400 ) ↓ ↓ ↓ 5 peg 1000 24 . 7 5 . 9 26 . 7 ( 1000 ) 4 . 2 38 . 5 0 . 1 46 . 7 ↓ ↓ ↓ __________________________________________________________________________ the results show that though the water content of a z 1 ( ipdi - peg 1000 - iem ) 2 film is lowered slightly by the copolymerization with z 1 ( ipdi - peg 400 - iem ) 2 or z 1 ( ipdi - peg 600 - iem ) 2 , the clarity , wettability and strength appear the same . this example shows the effect of a lower molecular weight ( i . e . approximately 1000 as opposed to approximately 2000 ) perfluoropolyether on the properties of a z 1 / peg hydrogel . the synthesis of these z 1 ( ipdi - peg - iem ) 2 diadducts is similar to that described in example 3 . more specifically , 5 . 0082 g ( 0 . 0038 mole ) fomblin zdol 1000 ( mw 1301 ) is reacted with 1 . 7121 g ( 0 . 0077 mole ) ipdi in solvent ( 20 % isopropyl acetate ) while stirring at room temperature overnight in the presence of 2 μl dbtl ; some samples ( i . e . sample numbers 3 , 5 and 6 ) are reacted without solvent . the z 1 ( ipdi ) 2 diadduct is then reacted with 2 moles of peg ( i . e . 200 , 400 , 600 , 900 or 1000 ). the peg is first dissolved in a certain quantity of isopropyl acetate ( the weight of solvent calculated to be 40 % of the final reaction mixture ) at 50 ° c . ( peg 600 , 900 , 1000 ) or at room temperature ( peg 200 , 400 ). in sample 1 for example , 0 . 2211 g ( 0 . 0011 mole ) peg 200 is dissolved in 0 . 5692 g ipac then 1 . 2098 g of the z 1 ( ipdi ) 2 adduct is added , the mixture mixed well followed by the addition of 0 . 78 μl dbtl and stirring overnight at 50 ° c . the solution is then cooled to room temperature , 0 . 1714 g ( 0 . 0011 mole ) iem added and the mixture reacted with stirring at room temperature overnight . addition of initiator ( bme ), polymerization and water equilibration are similar to that described in example 1 . __________________________________________________________________________ physical properties of hydrogel % ipac in the oxygen permeabilitysamplemw peg polymerization mixture % bme % h . sub . 2 o content ( barrer ) observation__________________________________________________________________________1 200 40 0 . 48 5 . 92 25 . 3 very slightly hazy on edges ; wettability = b2 400 0 . 49 19 . 48 24 . 0 clear ; wettability = b3 600 0 . 06 34 . 29 20 . 8 clear ; yellow edges ; - wettability = a4 900 0 . 51 47 . 66 25 . 9 clear ; wettability = a5 1000 0 . 07 50 . 28 22 . 9 clear ; wettability = a6 1000 0 . 48 51 . 50 -- clear ; wettability = __________________________________________________________________________ a as shown above , water content and wettability increase with increasing molecular weight of peg . this example shows the effect of peg molecular weight and solvent content ( isopropyl acetate ) on various physical properties if perfluoropolyether / polyether hydrogels obtained using fomblin zdol tx 2000 ( z 1 tx , mw 2288 ) a perfluoropolyether with an additional 1 or 2 ethylene oxide units adducted to the terminal hydroxyl groups of zdol 2000 . films are made in a similar manner to those described in example 3 . the reaction of z 1 tx and two moles of ipdi is monitored by isocyanate titration and the percent isocyanate reacted is found to be approximately 50 % ( 47 - 52 %). the product , z 1 tx ( ipdi - peg - iem ) 2 is formed through the reaction of two moles of iem with z 1 tx ( ipdi - peg ) 2 adduct in ipac at room temperature overnight . as shown in the table below , in general , use of the perfluoropolyether z 1 tx yielded strong clear films whose percent water content increases with peg molecular weight and solvent content . __________________________________________________________________________ % ipac in the physical properties of hydrogelsample mw peg polymerization mixture % h . sub . 2 o content clarity / wettability / strength__________________________________________________________________________ 1 400 28 16 clear a 2 2 ↓ 39 17 clear b 1 3 ↓ 48 21 hazy b 2 4 ↓ 66 28 cloudy b 2 5 600 38 29 clear a 1 6 ↓ 50 30 sl . hazy a 2 7 ↓ 59 39 hazy b 3 8 900 29 39 clear a 4 9 ↓ 40 40 clear ↓ 110 ↓ 50 43 clear ↓ 111 ↓ 58 47 clear ↓ 112 1000 28 47 clear ↓ 113 ↓ 38 42 clear ↓ 114 ↓ 38 40 clear ↓ 215 ↓ 49 43 clear ↓ 116 ↓ 59 47 sl . hazy ↓ 417 1500 39 55 clear ↓ 218 ↓ 39 56 clear ↓ 219 ↓ 49 57 clear ↓ 220 ↓ 59 60 clear ↓ 1__________________________________________________________________________ this example shows the synthesis of a perfluoropolyether / polyether hydrogel in which the urethane group linking the perfluoropolyether chain and polyether chain ( reaction with ipdi ) is replaced by an ether linkage ; this is accomplished by using an epoxy - terminated peg . more specifically , 2 . 1091 g ( 0 . 00096 mole ) fomblin zdol 2000 ( mw 2200 ) is reacted at 60 ° c . overnight with 0 . 7749 g ( 0 . 00194 mole ) polyethylene glycol 400 diglycidyl ether ( pege 400 , polysciences ), using 0 . 0167 g triethylamine catalyst . after 16 hours , the temperature of the mixture ( opaque ) is raised to 70 ° c ., 0 . 0220 g triethylamine added and the mixture stirred overnight leading to a clear , yellow , viscous product , z 1 ( o - peg 400 ) 2 . then 0 . 5213 g ( 0 . 00017 mole ) of z 1 ( o - peg 400 ) 2 is combined with 1 . 8890 g dimethyl sulfoxide , dmso , ( aldrich gold label , 99 . 9 %) and 0 . 0539 g ( 0 . 00035 mole ) iem which is added dropwise to the rapidly stirring mixture . the solution is reacted at room temperature approximately 72 hours . then 0 . 0040 g bme is added and the solution poured into a &# 34 ; sandwich &# 34 ; mold and uv irradiated at room temperature for 13 hours resulting in a soft gel . this material after equilibration in water becomes a clear hydrogel film . this example shows the fabrication of prototype perfluoropolyether / polyether lenses from polypropylene contact lens molds . the reaction solution is made as in example 5 ( samples 3 - 5 ) using 0 . 1 % bme as initiator . the solution is pipetted into the lens molds and uv cured for 3 hours . after water extraction and boiling , one obtains optically clear , strong lenses . micromechanical tensile tests performed on the lenses yield the following properties ; stress of 3 . 6 kg / cm 2 , young &# 39 ; s modulus of 26 kg / cm 2 and a 13 % elongation . this example illustrates the preparation of hydrogels obtained via polymerization of partially iem capped z 1 ( ipdi - peg 1000 ) 2 adduct ( z 1 adduct ). the incompletely capped adduct , i . e . mixtures of peg - ipdi - z 1 - ipdi - peg - iem and iem - peg - ipdi - z 1 - ipdi - peg - iem , is prepared as in example 1 except that 50 %- 90 % of the amount of iem is added to partially react the peg 1000 hydroxyl groups . the adducts are then polymerized with or without comonomer ( dma , hema , nvp ) into sheets ( samples 1 - 5 ) or lenses ( samples 6 - 8 ) using uv irradiation ( 3 hours , 0 . 05 % bme initiator ) and water equilibration . __________________________________________________________________________polymerization mixturez . sub . 1 : ipdi : peg : iem % z . sub . 1 physical properties of hydrogelsamplemolar ratio adduct % ipac % comonomers % h . sub . 2 o content clarity wettability__________________________________________________________________________1 1 : 2 : 2 : 1 61 . 9 38 . 1 -- 54 . 7 clear a2 ↓ 54 . 6 45 . 4 -- 64 . 1 clear a3 ↓ 49 . 6 41 . 2 9 . 2 dma 68 . 7 clear a4 ↓ 49 . 6 41 . 2 9 . 2 hema 55 . 7 hazy a5 ↓ 49 . 7 41 . 2 9 . 1 nvp 58 . 3 clear a6 1 : 2 : 2 : 1 . 5 66 . 3 33 . 7 -- 52 . 9 clear a7 1 : 2 : 2 : 1 . 8 61 . 1 38 . 9 -- 52 . 7 clear a8 1 : 2 : 2 : 2 61 . 6 38 . 4 -- 48 . 7 clear a ( control ) __________________________________________________________________________ this example illustrates the preparation and physical properties of the hydrogels obtained when various amounts of the z 1 ( ipdi - peg - iem ) 2 diadduct ( z 1 diadduct ) are copolymerized with the reaction product ( rp adduct ) of z 1 ( ipdi - peg ) 2 and an equal molar amount of iem . the z 1 ( ipdi - peg - iem ) 2 diadduct is prepared as in example 1 using 37 . 4 % ipac as solvent . the rp adduct is also prepared as in example 1 with 38 . 1 % ipac except that 50 % of the amount of iem is added . these materials , i . e . z 1 diadduct and rp adduct in ipac are combined in various ratios and uv polymerized ( 3 hours , 0 . 05 % bme initiator ) into sheets . __________________________________________________________________________polymerization mixture % rp % z . sub . 1 physical properties of hydrogelsampleadduct diadduct % h . sub . 2 o content clarity wettability strength__________________________________________________________________________1 85 . 4 14 . 6 53 . 01 clear a 3 - 42 84 . 6 15 . 4 52 . 08 ↓ a 43 50 . 0 50 . 0 44 . 39 ↓ a 34 50 . 0 50 . 0 48 . 01 ↓ a 35 14 . 8 85 . 2 44 . 16 ↓ a 36 100 . 0 -- 54 . 71 ↓ a 47 -- 100 . 0 44 . 45 ↓ a 3__________________________________________________________________________ as shown above , water content tends to increase with increasing rp adduct content . this example illustrates the tensile strength of lenses polymerized from the z 1 ( ipdi - peg 1000 - iem ) 2 diadduct ( z 1 diadduct ) with or without additional comonomer adducts . the z 1 ( ipdi - peg 1000 - iem ) 2 diadduct is prepared as in example 1 . the comonomers used are prepared by reaction of 1 mole z 1 with one mole iem ( z 1 / iem ) or two moles iem ( z 1 ( iem ) 2 ) using dibutyltin dilaurates as catalyst . the diadduct in ipac is combined with the additional comonomer adduct ( s ) and polymerized using uv irradiation ( 3 hours , 0 . 1 % bme initiator ). __________________________________________________________________________polymerization mixture physical properties of hydrogel % z . sub . 1 % comonomer young &# 39 ; s modulus stresssamplediadduct adduct % ipac % h . sub . 2 o content ( kg / cm . sup . 2 ) ( kg / cm . sup . 2 ) % elongation__________________________________________________________________________1 61 . 0 1 . 0 z . sub . 1 -( iem ). sub . 2 38 . 0 47 . 6 21 ± 4 3 . 0 ± 0 . 9 14 ± 32 57 . 6 1 . 1 z . sub . 1 -( iem ). sub . 2 35 . 8 44 . 3 22 ± 5 2 . 9 ± 0 . 4 13 ± 3 5 . 5 z . sub . 1 / iem3 61 . 6 -- 38 . 4 48 . 7 25 ± 5 4 . 0 ± 0 . 7 15 ± 2control__________________________________________________________________________