CA2047698A1 - Free-radical curable compositions - Google Patents

Abstract

Free-radical curable compositions contain a (meth)acrylate oligomer and at least one of a single functional diluent, a mixture of single functionality diluents and a dual functional monomer wherein the ratio of electron-rich double bonds to electron deficient double bonds in the compositions is in the range of about 5:1 to about 1:5. The compositions can further comprise at least one of a reactant having a saturated backbone and an average of at least one electron deficient ethylenically unsaturated end group per molecule of saturated reactant and an oligomer having an average of at least one electron-rich ethylenically unsaturated group per molecule of oligomer. These compositions are useful as coatings for various substrates.

Description

WO90/10661 PCT/US90/012~3 2 ~ ~7 ~ '3 FREE-RADICAL CURABLE COMPOSITIONS

Cross-Reference to Related A~rlications ' ' This application is a Coh~inuation-in-Part of U.S. Application Serial No. 404,578, filed September 8, 1989 which is a Continuation~in-Part of U.S. Appli~ation Serial No. 319,566 filed March 7,`'1989 , . ... .. . . ~ . ~ . ..
: . . . . : .
Technical_ Field This invention is directed to free-radical .. ... . . . ...... . .
curable compositions that are useful as coati~gs for -various substrates.' -B~ckqround of'the_Irventi-3n 15- ` `; Therè arè`many applications that require a , , rapidly curable coating composition'``tha~ adheres to a substrate, ls~flexiblé', does not di'scoior and has low - . .
toxicity. ~For example, optical glass fibers are frequently coated with two suFerposed coatings. The , "
coating that contacts the glass'ï's a relatively soft, primary coatingitha~!must'satis~actorily àdhere'to the 'jl'fiber and betsoft'enough3'to''résist''"mi'cr`ob`èndi'ng 'ëspecially"at low servlce temperature's.~ The'outer, ~SexposedCcoating-is a mùch~h~arder~3s~ec'ondary c'o'a`ting that 33'3providés`'the dëslrë~'rre ~ nce''to~handling forces yet ? ~1 -t ~b`"~'f'1 x`'i-bl' "en'oru'g'h3'~tlo~e'nable~ith'è' c~'o''à't'è'd'~'f`i'ber to "",~ 3Y ~ f~ d ~ '~d3~q-t~'w~i~t~h '!' ;~IJ r~ c~i'n'g'C~h3è~ coatl'g ~t~r3~ -3~l~c~ 3 Ot'h'eri~a~pp'licait~on3s~ e~ o`Fticai~'~abrication~
-~'coatings' ~ su~53~ aftes~including gIass,'me~ai, wood, : ~3b `' '''J ~` ~plltarst'~c, r~e'rq~p'a~pêr~3c'o~crete~and3fa7bric~s,~Sand ~adhesives also re~uire'compositicns'~hat are`fast r ~ ~ r~ t ~ 1 lr ~ ~ r ~ r~ r~ ! L~ 'i' r~ r ~ ~ J ~ ~ Ir , curing,'have low'`~to~icity and provide good physlcal p~`rt ~ e~ fi~ '3 ~ L~ .s~ t~ "~
~3~ Jsa~ ~LLa~comp~ositio~s~h~t~ n~ ~ '~ owt~m'~ u'~ar weight -,, ;~
!35~m'et~ àcr~late`ailuè'n~s~ha'v"er''~ e~ 'u't'ilize'd`-'f'or`~many Of ~ ' .iT i r ~t'L ~ <~ tz ~ t ~'3dii'uen~s'~are'~azardous'' ~ human~'hè`alth~~~Thérè~ore, 'it :: , .: . .

:

WO90/1066t PCT/US90/012~
2 ~ s ~.-- 2 - ..

is desirable to eliminate or reduce the amount of low molecular weight (meth)acrylate diluents present in a ' composition.
Vinyl ether composltions have been utilized as replacements or (meth)acrylates. Alt~ough ~inyl ethers :.
rapidly cure when exposed to ultraviolet light in the presence of a cationic curing catalyst, their cure under : ' cationic oonditions leaves catalyst residues that discolor ~he cured compositions and cause them t~ be sensitive to water. Furthermore, vinyl ether containing ollgomers having relatively high equivalent weights, e.g., an equivalent weight in excess of.about 500, do not cationically cure upon,exposure to dosages of energy less than 3 Joules per square centimeter. Vinyl ethers ~., do not homopolymerize in the presence of free-radical initiators. Therefore, vinyl ethers are not suitable ., replacements for,(methjacrylates .. , , , . . . ~ .. . . .. .. .. .. .. .. .. . .
, , . Unsa,turated polyesters, e.g.!.,maleates and fumarates, are known to,,be.substantially non-toxic, but aref.unsa,tis~actory as re~ acements for ,(meth?acrylates because the,lr!,,ratje,o~f~cure:,when,exposed to,,ultraviolet light is.not satisfactory for certain..applications.
European Patent Application,,No.,Ø322,808 ..
published on 05.07.89 discloses,a radiation.curable 2~ comoosition that comprises an..ethylenic,ally.~unsaturated nc,~c~,c~p~o,31ye,sx,;t,er~,c,omponejntza~d,Ja,,vin~ etherj component havl~g ?r~ an~average3of t.least.~two~inyl~ether groups per 5,~ mol~e~cul~ej~of~the~ yltc~e~theL~r~c~o~mponen~t~. The;.,u,nsaturated ~ lyesjterclcompone,nt,can,~be~a,pol~ er!, ol,igomer.or ' ., 3~ r,j~m~lX~tlur,e,~t.he,r,e.3..~ Co~at~ gs~r,oduceLd~fro~m th~ls~
composition are bri~tle and hard because.of~the large amount of eles-tron deficient.e~hylenically unsaturated . i p .o?~ L~ l s;J ~1~?10 n~ L '-3 -? Ll ~ ~ r t .'. ,~ h L ~ J s J . .; _ ~, rs. ~ _l ;groups in the bacXbo~ne,,iof~th~,,e~sjp,o~lyest~.r,~co"p,",./
~ leads to short cha~n~,se~ment~ be~ween cross,llnks. The : .35 :; vinyl~ethesr component reacts with,.theiurssa~urated group :; ` -. . ., : . , , . .: ..
.. ., . ,. : .. :. :

WO90/10661 ~CT/USgO/01244 2 !~

and results in a high degree of cross-linking that causes the cured composition to be brittle, inflexible and hard. Thus, coatings produced from the compo~ition of this European Patent Application do not possess the needed flexibility,and so~tness for applications, such as ~ptical glass fiber coatings, that require a,flexible and soft coating.
SummarV of the_Invention The invention is directed to free-radical curable compositions that comprise a (meth)acrylate oligomer; and a~ least one of a single functionality diluent, a mixture of single functionality diluents, and a dual functional..monomer, wherein the ratio of electron-rich double bonds to electron deficient double lS bonds'in the compositions is in th~ range of about 5:l to about 1:5. ,, Optionally, the compositions of the present invention can,further comprise at least one of~a ..
reactant"having,,a,satura~ed..backbone.,and an;average of ,~
at.;least~one,electron,de~clent ethylenically ,~unsaturated end;group per~rolecule ~f reactant,andjan :,,,oligomer.,,having an-averagerof~at.least one electron-rich ., ethylenically unsaturated ,group,per,molecule of.
..,,,ol~gomer,,.~,The-electron deficient group of the reactant .,;
25 ~ prefe,ra~ly,-an,e,thylenlcally!unsaturated dlcarboxylate ~, .~~,?.,group,. ,~he"electron-,rich group.LoX~this,~oligo~er is ~,;preferably,;,a vi,n,yl,~ethe,,,r",~gr,ou,pO.~ ?~ c. ;.~
~ `J 1' ..'.. ,~h,e,,,(me,th)acrylate,~oligomer has a..num~er i average"molecular~weigh,t~.o~r~at least about~l000.daltons ~,.^and preferably , onstitutei~`a mlnor~am~ount;of~.the~
composition.. : ~f~ L5 ~ p~.L~S~ tl O ~ ~.F~ C~ L~ ;
.CV 3."~ c The;~slngle~r~functiQnal~i~t~d~iluent has only one ; type,of reacti,v,e~,,group~e.,g.~ an.jelectron-rich ",~
;ethylenically! unsaturated qroup such as~a.pre~erred vinyl ether group or an~electron deficient et~ylenically :
~' .. .

unsaturated group such as a preferred dicarboxylate group on the same molecule of diluent. `- :
The dual functional monomer has at lea~t one electron-rich ethylenically unsaturated group such as a Yinyl ether qroup and at least one electron deficient ethylenically unsaturated group such as an unsaturated dicarboxylate group~ ` ' The saturated reactant is the reaction pro~uct of a polyester backbone containing component and/or a non-polyester backbone containing component and an electron deficient ethylenically unsaturated end group ~ontaining~oomponent. - ~
The vinyl ether containi~g oligomer is the reaction product'of a saturated bac~bone~containing ' component and a vinyl! ether having a hydroxyl group or an amine group. ' ' ~
The oomp~sitions of the present invention are surable upon exposuré'to ionizing radiation, actinic energy'and heat. The;cured''composïtions''exhi~it'good 3 fl'ex'ib'ility',~:tens'ilé"'strëngth',~'p'ercent-'elongation, toughness,':abra'sion re'si'stànce';~'tear resistance~and ~ -~adhèsion'to'~''sub'strates;''The''(me'th)acrylate~'oligomers ~'-'~'are''relatively'''inexpens'ive';/a'nd''th'éir-'use`can'!lower'the cos~';of'the'composit''io'ns'.'~
25- ~ 9i'~ Suit'a'b'le''u's~e''s'~f'o'ri'th~s`e oompositions~include t'~'`c'p't'ic'al' g'Ia's's~'f~ ie'r!coa't'ïngs',~.p`aper:~'coa'tirigs'~'c`oa~'ings '`'-:
?f or'~XëLmë~à'll;izat`'io'n'~'o'~'; non-'me'tal'l`ic~sub'strat'es";r'~e.g., plastics, coatings for'`r'ub~èr,`-'met'a'l';w'ood,~'c'o'n'c'rete, ièatXër,: fa~ric'~;'a'n`d'g`las's,''-op~`càl~!fabr`ication, 30 ~ ;iamination`of glàss a~nd'otXër'm'aterials,`~.e~',;~''\''`' compos'i~es'r~déntistry',!iprosthè~ics',' adhesives~ inks, '~
~lexigraphic printing~plates,~and the likê:~r~f~
`~' J ~ Z~ Even`~w~`en~th'e''o'ligomer'"~'containing the vinyl ether~'m'o~'e'ty`'his '! a'n`~equivàle'h't~'w'èight"in~ex`cess'of about ' 500','c'ompositions':of-'thé present invention that~oontain .

. . ~, , ~ -~: , ' ',;' ' ' ~` i ' ' WOso/10661 PCT/~S90/012~
- 2 ~
.

the vinyl ether containing oligomers are cura~le by a ' ~ , free-radical mechanism. Cationic curing of these' ' , oligomers is not practical. '' 'Thus, the present invention provides compositions having many properties desired by`industry while overcoming'the shortcomings of the prior art.' Detailed Descr'ption of Preferred_Embodiments -' ' The present invention is directed to free-radical curable compositions that comprise a ~meth)acrylate oligomer and at-least one of a sinyle ,' functionality diluent, a mix~ure of single functionality diluents and~a dual functional monomer, wherein the ratio of electron-rich double bond to electron-deficient ... . ~ . ..... . . . . .............. . . . . ..
double bonds in the'co~positions is in'the range-of-'about ~:l to about 1:5. ' ';
' ' The free-radical curable compositions of ~he present"invention can further comprise at least one of a saturated reactant having a saturated backbone and an ` , , , , . ~ . .. ~ . .. . .. .. . . . .
average of at l'east~one electron deficiènt ethylenically unsàturatéd~ènd3~g~roup;per mol'ècu'l`e'/o~C'satù`r'a''~ë'~re'actant '~
and''a'n oligomer having an average of at least one -'ëlectron`rich~ethyleni-cal~ly"unsa~urat'ed-group per-~moI'écule1'of'~oligomer.~- Thè`'eiëctron~dëflcient ' q~
''~ et-hyI'enically unsa~uràted'~end;group';of,the~saturâted reàctantrs prefèra~i'y~a~dicar~oxylàte~group.--~T~ë~
'' elëc~ronJr~ch ethyIen~càily unsa'~urà'tëd-~'group~o~3~hë
oligomer having at least one'~èlec'tro'~n~ric~-~'group~q's~
preféra~i'y`'a2`vinyi eth`è'r~group~
` I The ~er,m`l"tméthlt?acryl!~e~ and vàrious -; ?
~ grammatic~'~forms~the'reof,~ SéfntifIes~e`sters;tha~!a'rè
the r~aC`~l~ produc~ ' f;;~cr'y'l (or~mèt~acrylic acid with "~
' 9e a5'~Rdr~o~xy lrgi~ofuop~-coin~-ain~ ~p~o~ua~~ rt~ 3r.~ ~r~
,J~f~ 13 ~ C~ 'Th~e t`erm I ~ l`e-~fun ~ iona'l~ity~diiue ~"~`-as ' '' used in its var~o!us~ 5ram~matti~ca'~tforms-~'idèfines'~à diluent ~, ha~ing only one ~ype of reactive group, e.g., an .:

: ~ . : ~: .
. .

. . . . . ..

, .

WO90/10661 Pff~T/U~t90/01~44 ' electron-rich ethylenically unsaturated group ~uch as a vinyl ether group,or an electron deficient ethylenically unsaturated group such as a maleate on the sa~e ~olecule of diluent. However, this diluent can be, polyfunctional, i.e~ ! a molecule can have more than one reactive group provided all reactive.groups are of the same type. An admixture of single.functionality diluents can have eiectron-rich groups and electron deficient groups. . , . ..~ , lO~ The single functionality diluent, including ad~ixtures thereof,.is preferably selected, i.e., both the type of reactive group(s).of the single, .~functlonality-diluent~s),and the amount utilized are . ~.
chosen, to provide in ~he composition a ratio of - ,, electron-rich dou~le bonds to electron deficient double bonds of about 5-1 to;about 1:5, preferably about 2:1 to about 1:2. Most preferably,this ratio is about l.l ,.. The term ''dual functional,monomer", as used hereln,.defines a ~monomer,~havi~g at,least one ?
,~...,e}ectron-richj..ethylenically unsaturated group that~
preferablyj is a vlny!L~e,ther.group,and,at,least,one , electron.def.icient,e,thylenicaliy unsaturated group that preferably.is~a~dicarboxylate,group.,,, ~he~ratio,of~
eljectron-r3ch groups~to~electr~,on,,de;ficient groups .ln the ' 25 mo~,o,mer,c,,a~nj.~b,e3,selP,c,,t,,,ed~to,ja,cahice~yeithje,;,d,esired~5ratlofof electron-rich~,~oublejbondsrto~electr,on def,icient dou~le bonds~in~t~hff~com~pf?sltllo~n~ c~ ;^t~ L ~ ?~
The tff~rm ~vlnyl.t~ether~ itSi;V,aLrl,oUS,~
gramm~ati~C~a} ;f~.o~rm~s~3"reEerciLto~a"vinyl~gro~up bound to an ~.oxyge,n~.a,to,m.,.whicc,h ls.~bound.~ ta3,,carb~o,n;,at,o~m,,,.;,;,~",~ æ
.~he ,(meth)aon~at~e "oligomers~ sui ~ ~ use i in the present inyle~ ~;on p~r~eferab1y contain an avlrage ~f~at~leaSt~`ab u~t~l~2~ Lor~eL~p~r~e~fer,~a, I~,Y ~da~About 2 to about uf4i (meth)acrylate~grou~s~perrr-oli9o ~ i, .,.,-~ r~

:` : : : ,, ., ~ i .

WO90/10661 PCT/US90/012~
i --` 2`~ J3 These (meth)acrylate oligomers are illustrated by Cargill 1570, a diacrylate ester of Bisphenol A
epichlorohydrin epoxide resin having a number average ~olecular w~ight of about 700 daltons that is commercially available from Cargill, Carpentersville IL.
- The term "dalton", as used herein~in its various grammatical forms~ defines a unit of mass that is 1~12th the mass of carbon-12. ~ :
. The:(meth)acrylate oligomer can be a poly(meth)acrylate of an epoxy functional resin. These poly(meth)acrylates preferably contain an averaye of more than about two (meth)aerylate groups per;ollgomer :-and are exemplified by the?commercial product Novacure 3700 avaiiable from Interez, Inc., Louisville, XY, which is.the diester of Epon 828 and acrylic acid. Epon 828 ..is.an epoxy functional resin that is a diglycldyl ether of.Bisphenol A that is commercially avai;lable.from Shell Chemicals, New York, NY. ..~The number average..molecular ~:weight of.lNovacure 3700 is about.50~.daltons and of Epon . :~
828.-is about 390~.daltons.~ . ::,'`3"rl :.?'-'."' .i~
Dia~rylate-modified polyurethanes ? are also - ~ euseful.as~the-(meth)acryla~e oligomers, especially.those ;.~that^.employ a?polyester base., Particularly.pref~rred 'ar.eracrylate-~capped polyurethanes~.that,jare~the~urethane c~
re,action~,products~of;,a,,lhydroxy-functional polyester especially30ne hav.ing an average of about~2 to,.a~out 5 hydroxy;:.groups~per!molecu~le,;~wikh~a;monoacrylate~
~e~monoisocyanate.;~These a~rylate-capped pol~ur~thanes are 30 5: Jillustrated~by~a. pol~yes~er~imade-by rea~cting~trlmethylol ~.
.a~:.pr,opane~with,aaicap,,~olactoneJCto a~"~,umber, aver~ge~ r, : ~ molecular weight of~abgut~600~ daltons~ollowed~by i~
~;reaction~wi~h~lthreermolar~propor~aons~cf~the.;reaction - produ~t-..of.;1 mol of~2-hydroxyethyl;acrylate~with;l mol of isophorone diisocyanate. ~The end product.is a : :
~ , ` , ' WOgO/10661 PCT/U~90/012~

2 ~

polyurethane triacrylate. ~he urethane-forming reaction '.
is conventionally'performed at about 60C in the presence of about 1 percent by wei~ht of dibutyltin dilaurate. A commercial, polyester-based polyacrylate-modified polyuret~ane that is useful herein is Uvithane ' :' 893 a~ailable from Thiokol Chemical Corp~, Trenton, NJ.
The-polyester in thè'~vithane 893 product is a polyester ' of adipic acid'with a~out 1.2 molar proportions of ethylene glyr_ol polyesterified to an acid number. of less than about 5.: Thi's polyester is converted.as described above to a'polyacrylate-modified polyurethane.that is a .
semi-solid at room temperature and that has an average unsaturation'equivalent.of-about 0.15 to aboutØ175 éthylenically unsaturated groups per 100 grams of resin.
- In polyéster processing, the acid.number, defined as the number of~milligrams of base required to neutraliæe-'one gram of polyester, is used to monitor the progrèss of;'the reaction.'""The lower the acid number, ~!thë-'fur'the'r the`'r'eaction has progressed.~. ..'-;.i:.~...~
i~ ' '`'A'pol`yacrylate'-modifié'd polyurethane..that~is .
suitable as the (meth)acrylate~'oligomer is:.the reaction ~.
product'of'l mol'of dïisocyanate, l~mol.:of . :
;~ 2-hydro'xyet~yl'acryIate ~EA)"-andlabout~l:;weight~percent ~di~'uty~"~in 'dii'a'ùra~è-reactë~ 'at.a.~temperature.~of.about ~S ~ ocJfor a'itimë;~peri'od~of~4~hôurs'~tha~ois~`subsequently rëactëd~'at a~"temp'e'r'ature~'o~:rabout~6~C.~or.~,a;.time.~period ~o~;~boùt-2:hour's with~ Smoll~of~-.a~ommercial.r.hydroxy.
end~ nc'tio~n`a'l~'rcapro'lacto'ne'-polyester.~.;Amsuitable.~' ~ capro~'àc't'on`ë'p^o'I'ye's~ter''iis~athe rea'ction product..of~2:mols '~'~-'caprolictone~a'n~d ~ mo'l~ f~e~hy~éne glycol~.rea ted~at a tempera~ur'ë o'~à~'ou* 6'0~C '~orua~ime~period o~ hours.
A s'ui~ablecommerciai~ ~aprolactone polyesteriis~fo: i %~ava'ilable~from~Unioni~Car~iaë Corp~ Dan~ury;~eCT~;-.under 'the~trade''~es''i'gna~io*~Tonë3~%-lOO'which ~as~a~umber average~molecular~weight of a~out 345 àaltons~

.
. . . ~ I .

WO90/10661 PCT/US90/012~
7 ~

_ 9 _ The number average molecular weight of the (meth)aorylate oligomers is preferably.a~out 1,000 to :.
about 15,000, more preferably about 1,200 to about 6,000, daltons.- - .
The eguivalent weight of the-(meth)acrylate oligomers is pre~erably about 500 to about 5,000, more '~
preferably about 600 to about 3, ooa.
The single functionality diluents suitable:for use herein include vinyl ether diluents, vinyl amides, divinyl.ethers,.et~ylenically;unsaturated monocar~oxylates and dicarboxylates that are not acrylates, the.like and mixtures thereof.
, :- --Further:representative.of the single , ~ -functionality diluents are N-vinyl pyrr~lidinone~ --N-vinylri~idazole,,2-vinylpyridine, N-vinyl.carbazole, ' N-vinyl caprolactam, the like, and.mixtures thereof.
. ., Representative of.other.single.~unctionality :, diluents are the;.divin~l ethers-of triethylene,~lycol or , ,.
of any other diol, such as l,6 hexane diol or dibutylene ~.
glycol.'~one may aiso use;polyvlnylates'of other ?~^.
polyhydric alcohols, such as glycerin or trimethylol propane`.~' Polyhydric:poly'ethers can be used, such as ethylene oxide, propyl~ne oxide sr butylene oxide ~ adducts.~o~::polyhydric.alc~ols,:.illustrated~y.ethylene '.
:~ ' 25 glycol /~ u~ylenetglycol~,;g'lycerin,.'trimethy~lol~propane or pentaerythritol~ ),t~ r~ "~ sc-~..t~ L.s ~ qu~!~r~
~s~ ~s~,o~ Pxeferr'ed.sing}e.~funetionality,.diluents are triethylene':glycol 'divinyl~ether.:commerc~ally~av`a`ilable '' ~xom,~.GAF..under.,the::trade~designation.-Rapi'cure DVE-3, ~`30 .~ rdiethyl~maleate;~butane!d'iol div~inyl éther,~ l,4-cycio~
.hexane dimethanol divinylC~etherJLJoctyl~vinyl ether,i~
diethyl furmarate dimethyl male~ate,'~he:like,:and;~L
L.miXtures .ithereof~ a~ r~ r~e~ ;c~?s~ ;
.;r~.i ;Jr~ 5r~ ,?, ~ r~ r~ .
' ' ~"

: .

.. .. . . . - .

W0~0/10661 PcT/~sso/ol2~
2 ~ .`3~S ~ ~.

The single functionality diluents can ha~e an average of a~out l to a~out 4, prefera~ly about l to about 3, reactive groups per molecule.
The dual functional monomer can be represented by the following.Formula I:
- O O ' ' '' Il ~1 ` `
(I) R'-~-C-(y)-c-Rb-~c~ H=~H2 . ~
wherein R~ is selected fro~ the group consisting of H, C~ to C~0 alkyl-or.allyl.groups,.Cs to C10 aryl-groups, metal ions, heteroatoms and combinations of carbon a3,d heteroatoms; Rb is a~3sent,or-selected from the group consistiny.of. O, C(Ra)2, heteroatoms or.:substituted ..
,heteroatoms: RC is an aliphatic, branched.or cyclic alXyl-group:or..an arylalkyl group that contains l.to about::lO carbon ato~s, and can contain..heteroatoms; and .:: Y:;is selected,from the.group consisting of:

20C=C ~ CH?,rL,~,C,1;~3~C; -, C~2;tW,a.~nd~"~c,~
d ~ Rd i ~ , 'CH''~H .',"'''~ '' '' CRdRd ~ - `

, ~?r~herein,each~Rd is~ independently selected~from~the group : ~ 25 ~;c~nsistingro~3~H;~:c1~o~rc~ ~alky~ groups-~ccs- tolc~o~ ary~
groups and electron withdrawing groups'.~5~ .v :.o .a~i a.~ ref.er.ably.,r:-R~ is.~aDC1-.*o.C~a~alkyl group, R~ is .,.i.0~ -.a'..C2.,to.;!C8~.alkyl..group.and each.,~d~ is ~ ..Therh~teroatoms..that:can~be present.^in~the:
'-::dua,~ unctional monomer.include:~non-carbon atoms'.,such as oxygen;~ nitr~gen,~sul~ur,~sili:con,~ phosphorus and~the :like.3 ~?~,.L g~ Ly~inL~ ~
Repres~ntative of electron:~wit~drawing~groups are CN, S02, S0~ CONH2, Cl, C02 and the like.
.
:, ~

The saturated reactant is the reactic,n product of a polyester backbone containing component and/or a non-polyester backbone containing component and an '' electron deficient ethylenically unsaturated end group containing component~ ' ' The saturated polyester bacXbone containing component can be represt~nted by hydroxy functional saturated dicarbctxylates, polycarbonates, polycapr,-,lactones and the'like.
Representative of the dicarbctxylates are the reaction products of saturated po1ycarboxylic'acids, or their anhydrides, and diols. 'Suitable saturated polycarboxylic acids and anhydrides include phthalic acid, isophthalic acid,'terephthalic acid, trimetillitic lS acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrachiorophthalic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, malonic acid, pimelic acid, sùberic acid, 2,2-dimethyisuccinic :' acid, 3,3-dimethylglutaric''acid, 2,2-dimethylglutaric acid;,^thé liké; anhydrldés'theréct~, and mixtures ' ..
~: r; ~ 3 i ~ Z ~ t ! ~ -,~ , r` J ~
ther,eof. Suitable diols i'nclude l,4-butane dlol, l~,8-0ctane d; .r i O~lrT ` '' ~t'ive aO~ t'hè'saturated P~lY es .. . .

are polyhexamethyiëne carbonate commèrciai'Iy available ~rom^PPG Indùitr~es under the trade d ' n rb 120 and polycyclohexane dimethylene carbonate .
r~ `r ~ ' ' 'd~--t~ ' ''~'u '` ~ '''2~' L ~ '~ ;f .L ~ J tll ~ J ~ t~ _~ " ,, ~ ft~;~3:r ~
trad~e~-deSi~-`n~a~td ~ t i"!'t ~If~t~h~eifiolycla~prlol~ctoT~és àrë
9 ~ 9 ~ ~ r ~ 3 ~ r." ~! L C~ S ~ ~2vO
the Tone Polyol series of products, e.g., Tone v ; , r3i~.~L f3~ CI~ t~rL~ r~ 3~ 'r~ r'~
- Oi21, 030l, 0310, 2201~and 2221, commerclally avallable ' from Unlon CarbIde~ New York, NY. Tone Polyol-0200, 0221, 2201 and 2221'are dlfunctionàLl. Tone Polyol ~0301 ' ~ L.~ s1~c~ yx~ ?-~ 0-.,~ 5~J ~ ~L~" 3 and 0310 are trifun~tio~al. . ~ , 7 1, .

WO90/10661 PCT/US90/012~
~.

The saturated, non-polyester backbone containing component can be represented by hydroxy functional polyethers, Bisphenol-A alkoxylates, and siloxanes and organic polyisocyanates, the like and mixtures thereof. The group linking the ethylenically unsaturàted group to the saturated non-polye`ster backbone (linking group) can be a urethane, urea, ether, or thio group and the like. The linking group can be an ester when the ethylenically unsaturated end group containing c~mponent is a preferred dicarboxylate, dicarboxylic acid or dicarboxylic anhydride.
Representative of the saturated polyethers are polyàlky}ene oxides, alkyl subst1tuted ~ ;
poly~te~rahydrofurans), and copolymers of the alkyl substitu~ed tetrahydrofurans and a cyclic ether.
Representative of the polyalkylene oxides are poly(propylenë oxide), commercially ava1lable from Union Carbide under the trade designation Niax PPG 1025 and poly(tetramethylene glycol), c mmerclallyiavallable from DuPont under the tràde designation Terathane lO00.
The alkyi substituted p~ly(tetrahydrofurans;
have ring structures that open during p~lymerization.
The alkvl ~roun o~ the alkyl su~stituted poly~tetrahydrofurans) has about I to about 4 carb~n ~ 1 3 .~ :~ t (,, 21 . I .) ~ .3 ~ ff~ s .~ U . t 1.1 ; 9 .: ~ S 2 i~ i~ . t .~ -atoms. Representative of th5 alkyl ~sJu~bs,t,~i~tlu~t!d ~rfi '~
poly(tetrahydrofurans) ~are poly(2-methyltetrahydrofuran) and poly(3-methylketrahyd;ro~usra-~in)~ Re~ ehsl~l the cyclic et~ers with which the alkyl substituted t~trahydrofurans can be copolymerized are~e~thylen!e , oxide, propylQ~e oxide, te~rahydrofuran and thf~ l~ke;
3r~ X~ S.~ ~nr~ L~J~.S ~,~;rl~ jr~
Representative of the Blsphenol-A alkoxylates ~ t~ f~ ~Y ~;~M ~L~ r,~ r~ . .
are those wherein the alkoxy yroup contiains about 2 to yr,~ !.-'r' ~ r~ rC~ S~ a~ rjc~ ~ ?
about 4 carbon atoms, e . g ., ethoxy. A commerclal ~isphe~o}-A alkoxylate is the Bisp~enol-A die~hyoxlate ,:

W090/1066] PCT/US90/012~

~ :~ t~J~r~

- 13 - ~

availa~le under the trade designation Dianol 22 from .
Akzo ~esearch, The Netherlands. - --Represéntative of the siloxanes is poly(dimethylsiloxane) ~ommercially available ~rom Dow Corning under the trad~ designation DC 193~ ' Any of a wide variety of crganic polyisocyanates, alone or in admixtùre, c,n be utilized, diisocyanates alone ~r in admixture with one another preferably c~nstituting all or almost all of this lo component. Representative diisocyànates include isophorone diisocyanate (IPDI), toluene diisocyanàte - (TDI), diphenylmethylene diisocyanate, hexamethylene .' diisocyanate, cyclohexylene diisocyanate, methylene ' ~' dicyclohexàne diisocyanate,-2,2,4-trimethyl lS hexamethylëne diisocyan'ate, m-phenylene diisocyanate, 4-chloro-i,3-phenylene diisocyanate,'~,4'-biphenylt~ne' diisocyanate, 1,5-naphthalene diisocyanate, 1,4-tëtramethylene~diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylenë diisocyanatë, 1,4-cyclohexylene diisocyanate',~and p~ly'alkyloxide''and ~
polyester-glycol diisocyanates such:às ' ^ - - - -'poiytëtramethylené ether5 gïy-cO-ii Sermlnated w-ith' TDI'and ' .
polyethylenic adipate terminated with TDI,lrèspectively.
~'' ' '~ ~The'poiyèster backbone-containing component '25 and/or~the'non-polyester''backbone co~aIning component ~`
~r "~?~ ~r^r ~ :'t~ t~r~ r ~ ti~ r q aré reacted with'an~èthy'len`ically unsaturated'group~'-conta*ning ~component~hati~can~;be~the~trëaction product o~
e~ t ~ c "r :~ .t .an ethylenica'lly'un''sa~urated'd-'ciarboxylid acid and a monohydricSalcoliioiio'r'~an~aforeinentioned~tcycï~c~ethër.~ '., 30 ~ Reprësentà~ive'~unsaturated~dlcarboxyi'ic ac~ds 3 r areTmalei`c~acid,''maië- ànfiydride,~'fuma~r~ àci'd,'l~and~ ' ' ~ta oni~ac~ rl;~r~s !t ~7 ;r r ~ r3d~ d ~ ~
3~.i 3~ ~ft~f `!Rèpresèntative'~of'thefmon~y'dri'c~ailco~ois~are~ . ' the Cjito C~0'7alcohols,."ë.g'; èthanol~,id~canoi, thé like 'aind'~xturés thèreof. '~'~' ~' ''; "'' '' ' '`"' '~
....

WO90/10661 PCr/VS90/01 If the ester produced by the reactio~ of the dicarboxylic acid, or anhydride, and the alcohol, or cyclic ether, has unreacted carboxyl groups, the ester can be conventionally reacted with a material having a group that is reactive with the carboxyl groups of the ester, e.g., ihydroxy groups and epoxy groups.
Preferably, this material is resinous and has a number average molecular weight of about 300,to about 5000, more preferably about 500.to about 3,500 daltons.
The saturated reactant preferably has an average of about ~ to about lO, more preferably about 2 to about 5, elec~ron deficient ethylenically unsaturated end groups per mo}ecule o~ reactant. . .
The e~uivalent weight of the saturated-reactant having electron.,defi,cient ethylenically ~ ' unsaturated end groups.is,preferably about lO0 to about lO,000, more preferably about~200 to"about l!000.
,; Oligomers having an.,average of at least one.
electron-r-chjethylenically.,unsa,turated end,group,per~
~olecule,.of,ol,lgomer.!,jpreferabl~a ,vinyl,ether.~,,,~, ,. `,;
containing oligomer!.can.be~utillzed in .addl~ion to,.;or ,~...... .in place.of,~"the.saturated,r.eactant in.the;corpositlons ,jof.the,,p,resent-inV~en5ti~on~ r ~ The.vlnyl.,etherlcontalning,oligomer can be pr*duced~ by con,ventionally~sr~a~cting~ai~m~o~nopydir~ic~or~6 ''S ,,,:
monoamine ~vinyl.,.eitherj.. and,La;"~aturated~b~ackboneJ~mo.,iet~3 . , ~ co~nt,alning~com~ojnent.~ The~ba~kpioin2l~co~n~tainlng ,comp,o,n,e,nt , r~,e~p,re,se,n~ted~byih~ydrioxy~ un~c~tlo~al poly,esters,~ 3 polyca,rbonates,jisiloxaneis,~.~polycaprol~acton~eis~
30 ~ Blsphenol-A~alkoxylates~.~p.~oilJyether~s~ an~d~or~ig ~- .
0.l.XiS.Q,CYanateOs,!,~,th~:3,l~lk,e~a,n~d, mi~xtur~es~theireof. ~The backbone of the ~inyl ether containing oli,gom~r~,can.3, ntain~repe~tlng~bacxbone.~units.~ he~grolup linking the ~ inyl~ether!~group t,o the~saturated.~back~ne .~linking.
:35 group) can be a urethane, urea, ester,,:;et~er,,or thlo ., ,~
~: . ' -:

WO90~10661 PCT/US90/012 ':''''' f-d -J -/~ 7 ~ ;~ ?

group and the like. Preferred linking groups ~re urethane, urea and ester groups. Mixtures of linking .
groups can be used.
~epresentative of the vinyl ethers suitable as S reactants in the production of the vinyl ether containing oligomer are conventional vinyl ethers including triethylene glycol monovinyl ether and l,i-cyclohexane dimethylol monovinyl ether.
Representative of the saturated polyesters, polyethers, polycaprolactones, Bisphenol-A alkoxylates, and siloxanes are those utilized in producing the saturated reactant.
i The oligomers containing vinyl ethr~r groups -can be t~e reaction ~roduct of àn organic polyisocyanate, preferably a diisocyanate (especially a diphenylalkane diisocyanate in which the alkané group contains l to 8 carbon atoms), and a transvinylated polyhydric alcohol mixture containing hydroxy groups that is the transvinyîation reaction product of (l) at least~one-vinyl ether-and~2j at least onè polyhydrlc -al'cohol;havIng!`an average of more than 2 hydroxy groups :
per molecule. The polyisocyàna~e is prese~t in an ' amount1ëffectiveito-consume~substantiàllyiall of t11e availablë~ hydroxy3groups in~the transvinyla~ion-mixture.
~; rtJ~ The'ite~trans~inyiationi~-as--ùsêd~in~its~ ~.. r~ .
various grammatical '~orm~ me'ans thàt thé'vinyi'ethër groùp;~of the~inyl'ethér andithe hydroxy!group of the alcohoilarè~iexchalngëd.~ }~ 3 ~ ..; ?~ L~ s~
~?~3~ 3 ~ 3 "~The'tèrms "~ansvinylition mixture`'; and 30 Si't~rr~nsvinylatlon'~pol~y~yd'r~c alcohol-`mixture",~as~iusë~ in -~
their-various-grammatical~-i'orms,-meah~unreacted ~ ~
polyhy~dr~J~aic'o~oir3 p'a~rtlal`ly'transviny`làt'e~'po/r~ ~ ric ~ `~alco ~ l~and~f~i~ly`~ans~, ~ f'~ed--polyh~yd~c`i,~lcghol~are ~pre,~sent~i'n~t'~ r'ansv'ln'yi!a'tion'reaction~pro'duc~So~ the vinyl~ëth`er-and`thë polyhydric alcohol. Thë

', ~:

- - ~ .

WO90/10661 PCT/usso/012~
~ ~ l3, ~

transvinylation mixture is preferably, but not necessarily, an equiilibrium mixture.
The term "substantially all", in its various grammatical forms, wh~Pn used in referPnce to the isocyanate consuming the hydroxy groups (hydroxy.
functionality), means that i~ the vinyl ether containing oligomer has hydroxy groups, they are not present in an amount that adversely affects the properties of the compositions.
; The transvinylated... aliphatic polyhydric alcohol mixture can contain partially vinylated polyhydric alcohols and at least about 3 percent tD
about 90 percent by weight of.unreacted polyhydric .. . . . . . . --alcohols. The polyiso~yanate consumes substantially all of the available hydroxy functionality. .Simple .
.. ..
monohydric alcohols (which are formed when a C1 to CL
alkyl vinyl ether is used~ are preferably removed ~to provide a transvinylation.mixture t~at is substantially .. ... . . .... . ...... . ... .. . . .
~freejof simple m~nohydr.ic alcohol., Such an alcohol i 20 functions to.terminate .the~vinyl~ether containing oligomer which is formed,..~.an..action thatlis undesirable, but,tolerable!in some lnstances.~
. The term "simpl~.monohydric alcohol"~, as~used ~.,in;its.various grammatlcal forms,.,refers;to alshort ;
chain.alcohol,containing 1 to~4~carb~nj.atoms and having .S
ojnly,~onerhydroxy group~per molecule ~ ~ "f ~
,3f~,J ~ ",~.The .transvinylat,ed mixture is.produ~-edlby .~, transvinylatin~ a vinyl ether with"at~least,one;lf~
poly~h,ydric!alo~,hol~;h,lchrpr2ferablyicontains an average ,. ,of~more than.2.~ydroxy groups~,per.molecule,..~wher.eafter ,~;
any si~mLonohydric alcohol.iby,.-,product;,lof~the~
tra~n~ ,inyl,a~io~n~rea,c~t;~on,~and. `,~!h~ transvinylatipn~r~l~
catalyst are.normally.removed. ~More,particularly.,..the ..~vinyl~etheir~contai~ing.oligomers,are prepared.from~the transvinylation reaction.produc~ of..an.arylalkyl~..,, , -.:
.

W090/10661 2 ?~ ,,, a ~ PCr/US90/Ot2M?
' .

- ~7 -polyhydric alcohol, which most preferably contains or consists of po}yhydric alcohols having an average of 3 or more hydroxy groups per molecule, and a vinyl ether which can cont.in one or more vinyl ~ther groups per molecule. The transvinylated reaction product contains partially transvinylated polyhydric alcohols as well as unreac~ed polyhydric alcohols, and it can also contain ' fully transvinylated polyhydric alcohols.
The transvinylation reaction is conveniently carried out in the presen~-e of a catalyst that is known for use in ~his reaction. While it ls not essential, the catalyst and the simple monohydric alcohol by-products of the reaction ~~an both be optionally removed, and this usually also removes any unreacted monovinyl ether which may,be present.
~ ; It is ,desired to,point out that the catalyst is conventlonally,removed by filtration, which is a particularly simple operatlon. Any simple monohydric alcohols and,any unreacted ,monovinyl~ether which can be present when a monovinyl ether is used in the r. , ~ ' transvlnylation,rea~tion are,~hlghly volatile~and easily removed by evaporatlon fr,om ~the,reactlon product, leavlng the b~lance of~,the,~transvinylation reaction product ~intact.~",This,meth^od of operation ;eliminates the ,~ .,J,J~ ,,; of,f ~,trh~e,L,,,,,~;m,,o?n~o,Jhy,dri,?c ~V, ,inyl ether,utillzed in conven,tional~cc?mp,oj~itio~sl~and o?ther components that ,~ , "",~"" "ll,e~d,,~??jff,~W;~l,t;,h~tt,hi,s?,,imoin,?hydr~ vlnyl eth~r, fro~
~Jthe~ otass~i,um~!hydr~?xide,catalys,t~used in ,thie reactlon rr ,with~la?-etylens.~The~distillation step u,tilized,1nt,th,,e prio~r,~,art,is~a,~iffi~-ult~operation,involvi,ns~ elev,ated 0~ j "émperja~t~u,reJ,wh~i~,c~,c,au, 5~e~5~ 3u~n~d,eslrLe~ ~s~id~eI,r2eactions; , F~iltratlon~byl~a~chr~omato~raphy procedure is~a repre~sentative~me~hod of~emolving ~h,eLrc,!a~talyst. In.,~t,hls p,roced~ure a L5 inch ~y.1.S, ~ .sillca ~ O~,olulmn~
,~ 230~5U.S.ASieve-series mes~ and~ha~ing a p~ neu~ra~l .
.

- ; : ~ , :

:: ., . ~ - . ~ -WO90/106~1 PCT/US90/012~

~ 18 --surface) has a 0.5 inch layer of activated carbon placed thereon The carbon''is commercially available from Darco under the trade désignation G-60 and ~passes through a lOO ~.S. Sieve Series mesh. The column is wettëd with triethylene glycol divinyl ether then the catalyst containing transvinylation mixture is poured through the column. The first ioo mil1iliters (ml) of eluent are discarded a~d the remaining eluent is collected as ~he transvinylation mixture.
. . .
lOThe catalyst utilized he~ein is a conventional ~ ' transv'inylatibn catalys~ and is lllustrated by the elements of Groups IB, IIB, IVB, VB, VIB, VIIB, and VIII '.
of the Periodic Table of Elements. Representative catalysts~include~paliadium, mercury,'copper, zinc, 15magnesium, cobalt,'mercuric acetate, mercury~-(II) salts, - :
lithium chloropalladite (I) dialkylpyridines, phosphates of thallium,'vanadium, chromium, manganese, iron' ., . .. ", . . .. ... ..... ... .. . .. ... .. . . ..... ..
cobalt, nickel, Group VI oxyacid''salts and mixtures thereof. ''A pres'ently prefërred catalyst is ;palladiu~

~ ' ''The' cat'alyst'used'herein'can~be a~finely divided po'w'der àn'd~'c'an'be'''removed by filtration. The?-addi~'i'o'n''of'ch'a'rcoal''to'the'transvinylation mixture can ass'lst the''`f-ltrat'iion~'pro'cess',' e.g.,`when a fineiy dlvidéd'powder-form~of~thé~3ata~st is utiliize'd.;- The'~
r~ ''3t`'~ h~ r~d~~y~vOi~at~ e'r~aikyi'-'''~
~ r '~ ''''h"'i'g's~'præsen?t-'when~an aIkyl m ethër'~s use'~ for''transvlny;a~ion ls'prefërabiy removed ' :
by vaporiza~on~!àn'd thlsiis~conveniently~performed~when me~ yi or.éthyl vinyl ether~ areJusëd~by"apply1ng a ^;
:~reduc'ed'~préss~re'~o ~hë~''r'eactio'~p'roduct'at~room`~
6 c~ r~'S~'rà ~m~p'er'à ~ r''~ of';a'bi'b~ut~:2'0 to about 30C. I~'is"''(de'sirè'd ~o~restrict t~é'purificat~o~
~~opè~at~ion~ s''impl'e~fi'ltra't'ion,'~ th~'i's'~is do~në`~e~re~in : 35 by usi~g'a` p'olyvinyl'ëthèr, 'such 'as al"divinyl éther of a ~'-:
.

: ' ~ ' "' :~ !

WO9o/10661 PCT/US90/01244 ~- 2 ~ f ;~

diol illustrated by triethylene glycol divinyl ether, as a transvinylation reactant.
The catalyst can be bound to a solid matrix such as charcoal, nickel, alumina, ion exchange resins, molecular,sieves, zeolites, or similar.,materials. The ,.
solid matrix having catalyst bound thereto can be in the , .
shape of beads, filings, part of the walls of a column, and the like. Alternatively, the solid matrix.having ,.
catalyst bound thereto can :~e,packed in a column.
lO , The product.... of the transvinylation reaction is a mixture containing partially transvinylated polyhydric al~f-ohols. Accordingly, there is present on these partially,transvinylated,polyhydric molecules at least one yiny} ether group and at"~least one,hydroxy group, so the transvinylation mixture.tends t~ deteriorate with time and~exposure to elevated temperature, at least partially by the formation of acetal groups. Reaction with a polyisociyanate in accordance with this.invention .. .. ... .. ... .. . . _ ... .. . .
significantly re,duce,s;.~the,~hydroxy./;content- to.minimize,.cr largely,avoid .this det,eriora,t,ion. Prior.,to ,reacti3n ^~
'~ith polyisocyanate, the present~,transvinylation.mixture ,doe~-not reguire~a,n elev,ated,temperature distillation ::
op,er~ation,.~The~-elimination,~of.~his-:distillation~
: , operation further.jminimizes~,this~deterioration,~of.-ithe-.
:25 transvinyl,ation ;mixture.~V~ T ~ J~ r~ ,r!,.:' ,,~
~`f'.~ f -r~,~ The;.transvinylation..-,mixture will normally..;~
cignt,ainrsome~unreacted,~polyhydric,,alcohols and.. so~e.. i." . ' fully,.,fvinylated,polyvinyl,?,alcohols-,,~as previously,;. s: . ' .
indicated, and,these are,~o,t~removed.,,~This;~introduce~s an ,impo,rt,ant~,conomy~a~J,th.e~.same~ e~that~,it enables f,:-one~t~;~ncre~ase~he~:~mol~e~cular~wei9ht~tand~the~vinyl;;ether ,~ ~un"c,t~onaiity,~,~y~reaC,tion~.,o~,lfthe-;"transvinylation!.miXture.. ...
with ~o.rgan,ic~polyisocyanates; ~.^.Increased.molecular ~c,r :weight, ; ~the ^presence( ~of . ~internal;.urethane -or urea -~ '' '-f 5 . ~ rt J i. _ C~ J, ._ .

., groups, and the increased vinyl ether fun~tionality all : :
introduce physical toughness into the cur~d products. ~ -In preferred practice, the partially ~.
transvinylated polyhydric alcohols in this invention co~tain from 3 percent to 25 percent unreacted ~ :
polyhydric alcohols, about 30 to about 94 percent - '~
partially transvinylated polyhydric alcohols, and from 3 percent to.25 percent fully transvinylated polyhydric :.
alcohols.--This is particularIy preferred when the .polyhydric alcohol that is transvinylated contains 3 or 4 hydroxy groups. .. :. . ' ' The transvinylation reaction to produce vinyl ethers is itself known, and illustrative articles ''`' ;describing.this reaction using alkyl vinyl ethers are, :
McKeon et.al:, "The Palladium (II) Catalyzed Vinyl .
Interchange Reaction - I", Tetrahedron 28:227-232 (1972) and McXeon et al., "The Palladium'~II) Catalyzed Vinyl' Interchange Reaction - II"-,'Tetrahedron'28:233-238 ~-~(l97Z)..~However,-~these articles'teach:'pùrifying~ the j!
reactioniproduct and do'not;suggest the-ùsie'of a' ?'~
transvinyl-ati~on~mixture. ~
~ A:method-of:synt~es'izing pure-vinyl: eth'ers ls .':
disclosed:in:.smith.et al ;~ FaciIe~:Synthe`sis:of Low:
and~High~Molecular.Weight:;iDivinyl:Ethers':'of Poly(oxyethyrene)~l, Polvmer Pre~rints;~28(2)":"264'-265~
~August~ 987).J Smith~.~eaches~the'~'synthesis of pure ~inyleethers~iusing trans'etherification~chemistry~bàsed on the'palladium .(II)Lcatalysts~of~poIy'toxyethylene)'~
glycolsJ and~ èthyl ~vinyl ~ ether ,~ . ' '3'~ '. .'l L.
~ 5;~e ~.Whilé:~the~-transvinyla~ionTmixture~ca'n`use a~i .`
~diolt~as'.the!.:po'l~hydric~al~ohol.~Lcit prefera~ly~èmploys' s~riols:~a`nd~tetrols;~(most:pre~erably~triols)~ In~eèd~
when:d'iolsbare~used~some higher~functional~po'ly'ollis''~
preferably:added..to~.the mixture that~is transvinylated or to the ~ransvinylation ~ixtur~e ~hat is reacted with : :.
' , . I

WO90~10661 PCT/US90/012~
2 ~ X, .
- 21 - . .

the diisocyanate. Suitable higher functional polyols .
include the triols and higher hydroxy functional p~lyols referred to herein.' Thus, the polyhydric alcohol can be a mixture o'f' alcohols and has an average hydroxy functionality per molecule of more than'2.
Moreover, the transvinylation reaction~forms unrefined transvinylation mixtures which are further ' ;' reacted to enhance stability of the transvinylation mixturè'ky the formation'of vinyl ether containing :.
oligomers in which'the'molécular weight and vinyl ether' '.
fùnctiona'ilty are both incrèased. ' - '''''"' ' :' Suitable polyhydric alcohols for use in this '' transvinylation reaction can be arylalkyl or'al'iphatic' : , polyhydric alcohols havlng an average:of more than 2, prefèrably at least 3," hydroxy groups per molecule'on -~
the aliphatic or alkyl portion thereof.' ~t is presently preferred'that the''polyhydric alcohols can have:up to'''~ ,.
about an average of about''lO hydroxy groups per "
The' poly ~dric"alc'ohoI''utilizedli's preferably ;'-;
: solùblei in the~ vinyi` ether~ and''has-a~number'average~
molecula'r-'w'êigX't'of''u,'p`' ~ about5~2,0`00'd'al't~0r,s'.~"'We ~
preferabiy èmpi4y'polyhydric ~a~oohol's t~tfâre':li'qui'd""at ro^om te'~pèratur'e~ '.Je .-;~- 'a'';~émpfer'atùrè";'of~about`20't'o':~'~
about 3~ ~C;;'or` ~ lch~V('l~f~so'~'id) hav'&'ra numb'er~ave`rage`
molecular weight below'~a~out~400'~daltonciJ rJ'-~ 3^~ ~7~
The a~Xyl`'a7roup~o~Lthèsie~ar~laikyirpolyhydric aloohols preferably c-3n ~in~ss~aboù~ ~ to'a~ou~ -io ;rm'o're'?
'i'r" ~ r'!7''~b'''~ ''3~ ~o'?à~b''~o'ut'6l,~ca'rbo~ àtomsi. The y 3~ group:o'f ~ ~ së` po'lyh'y~d5l'c'àlco~ols~prèfëràbly~c~onta'in~s; ~;~, , .
: ~up to abo ~ 2 ~ more~p~ree}er~blyi ùp-t~a~out-iO,-car~`o~
atoms ' ~ s~t3r3a3~i~V~rlarry~a ~ l~o ~hy~r'ical~ol ~nclude et~oxy~ ed`~poly ~ ~rio'phenols,~t~ydro~y~
substltu~e3 rlng s~ructurès~é~.g.~p~eno~ri-naphtfioi~ and :35 the like, t~a~ ~rë~alkoxyl~'ted,`~r~met~yio'i~benzenè'j~:~and :.
the like, and mixtures *hereof.

- . . :

. : . ' .. , ' ;

WO90/10661 PCT/US90/~12 ,~

Preferred polyhydric alcohols are aliphatic polyhydric alcohals that contai~ 2 to I0 carbon atoms,, more preferably 3 to ~bout 6 carbon atoms, and are illustrated by ethylene glycol, butylene glycol, ester diol, 1,6-hexane diol, glycerol, trimethylol propane, pentaerythritc3l, and sorbitol. Trimethylol propane is particularly preferred. . .. .
, The polyhydric alcDhol can be a polyether, such as the ethylene oxide or propylene oxide adducts of ' lQ the polyhydric alcohols noted previously. ~hese are illustrated by the propylene oxide adduct o trimethylol propane th.~t has a number average molecular weight of abut.l500 daltons. . ., . ~ , , , ~ The polyhydric alcohol,can also be a saturated ..
polyester~,of the polyhydric,alcohols noted prevlously, ..
such as the reaction product of,trimethylol propane with epsilon caprolactone having a,number average molecular weight of about 600 and the reaction product of two mols, of ethylene glycol with one mol of adipic acid.
20 ~, ;; ;; ..~J ~ still ~other." polyhydr,ic,alcohols are;
illustratçd by,j~resinous;materials that contaln hydroxy groups,.;such..as,,sty;rene-allyl alcohol copoly~ers,, acryl,icicopolymers ,containing,2,percent to 20 percent of cop,o,lymerized32-,hydr.oxyçthy?,acrylate, and even starch or""c,e,,l,l.~ulose.~ How.~e,v,er,.the~se.havei,a~higher hydroxy ~'unctionality than,.is,~now,p~efe,jrred.;j,l ~,;, ,,,j, , , ~ "
~ ,,L~,~Thefpoly,hxd,rlc,,alcohol ,ca,n a,lso be.,,amine substitutedl.,e.g.J .,triæt~h,,an,~c,3,,lam~i,n,~je; ~ 3~c; ~
~ ,r3 ~ r It,,!;~s~,desired,to,stress that the reac~ian with acetylene.utilizedi,~n,lt~he~pr~,lo,,,r~a~r,r,t~,,,i,!s~no,,,t"",~a,ppl,,,,i,",ca.,.,,~l,r~
many,rOf the~polyhyJd~rlc~al~o~lh~ ts~wqhi~chJ~l~ar~ p~ J ~i~; , , attra,~ti,v~e~~Lorj~tuse~in~p,rod~ci ~ tpe~presentf~;E
trans~inyla,tji~o,n,m,i"xture.,~?~o9l~y~st,e~rs and ~olycarbona~e5, Lris~ch~a5~l,6-hexane~dlci ~o?~carbonate having a molecular ~:35 ~,jweight,;,o,,f~ab;out,.,l,,,OOO,daltons,,,are degraded!by the ' " ' potassium hydroxide catalyst used in reaction withacetyle~e, but can be transvinylated in accordance with the present transvinylation.process.
Suitable vinyl ethers can be repres2nted by . '~
the following general Formula II:

~ / C = C - C ~ c1 - Ri . ~ .
wherein R', R~, R9, Rh, and Ri are each independently selected from the group of hydrogen and lower alkyl groups contàining l to 4 carbon atoms; R', or.Rf,.and.R9 joined~together,can.be part.of a ring.structure; R', or Rt, and Rh, or Ri, joined together can be part of a ring structure, and R9 and Rh, or R', joined together ~an be Z0 part of a ring structure, RJ.is an aromatic or aliphatlc group that~ls. reactive only at.,the site~s) where. a.,vlnyl ether",,containin~ radi.,cal.. is bound,~x;is,.O or .l,;,.a~d,n ls ,.~,t ', equal to l to ld, preferably l to 4, with .the.proviso.
that,nL~is,less,than~or equal to the~number .of reactive slte,~,,of Rj. ;~ ? " .-,~ ., I!;~..-;~:~ .~^t.~., r;t~.,. ~ ,/"'~'"'~,' ' "' `'.- ''11., .''"'.~'~._~.~
,R3rcan contain~heteroatoms,~.i.e., atoms other t;h~an~:gcja~bqon~,a~oms,,x,,su,ch-~as ~ygJen,..nitroge,n,.lsulfur, ,t sili~c~n,3,phosphorus~"~and ~ixtures of.heteroatomsialone or in combination with carbon atoms.~ R3,.~can contain~
q,~,pOaboSut,,~20,,,pr~efe~rably~ l;to,.1a~.out.alO,,atoms. R~ is ,~,,pre~er,ably a,straight or.,branched,,.,carbon.~containi~g~
group containing~ t,o~aJb~Ut8,~m~,rJedl.Pr~e~fe~abldy~tl~to~ ,a ~abo~ 4,,~ arbon.~atoms,a~nd~an;pre~erably,.~contai~-~oxygen ~ ~ ~ 'J ~ c~ ; r~-r ~ ~t ~ v ~ r y;~t c ~
epresenta~ive3~of3yin~?~ ethe~rs~of:Formula~
arè dihydropyran~and~dimethylol_~enzene..;dlvinyl.~ether.

. :

, ,, : ~ :

~ . .: - . .

:

WO 90/10661 PCI'/lJS90/0~244 S2 i~ r~

Preferred vinyl ethers'for use in the transvinylation reaction can be represented by the f'ollowing general Formula III:
.
( I I I ) ( CH2 = CH ~ ~ C~2 tn R
.

wherein Rk is an aliphatic group that is reactive only at the site(s) where a vinyl ether containing radical is bound and n is equal to 1 to 4.
R~ contains at least one carbon atom and can contain heteroatoms and mixtures of heteroatoms. "
Preferably, Rk contains 1 to~about 4-carbon atoms and can'contai'n oxygen atoms. - ' '' ''' : Vinyl ethers having the structure of'For~ula III are illustrated by divinyl ethers, such as 1,4-butane dioi divinyl ether, 1,6-hexane diol divinyl ether, and triethylene glycol dlvinyl ether. Polyvinyl ' '`
ethers of'higher functionaiity are''illustràted ~y ''''''' ~trime~hylol~propane~trlvinyl ethër'~and pëntaerythrl~tol'~
,,, ,.. , .. ,, j, ~, ,, . ~. . . . . ......................... .
tetravinyl~ether;' ~ ~ ~ ~^~~'~'^' ' ` '~'' ~ '' ''`~'''~ '~
~ Illustrative monovinyl éthérs having thé ' ' structure of Formula III are ethyl vinyl ether, methyl ^ ' ~'iny~ èther, n-butylivinyl-~'ether,~and~the-'like/
incluti~ing phe'nyl ~lnyl;ethér.^;The`'présêntly'pre~erréd mon`o~iinyl;~ethe'r`is~ ~thyï~ vinyî éther which releasés ~ ' ethanrol~ron `ré~àction~2~ s it(,-`.. ~.~.. ~ .i ' .' ~,.. ""~ t ~ Y; "
The~equivalent~-ratio of~the vinyl ethe'r't'o'the `' ~hydrôxy~groups~n^ti~`e poiyhy~dric alcohoï 3is inithe range ~30 ~ ~of fi~outYo.5 i^toC~ab'o~ 5'~1"X~prefërably~b.~ to'2-i'.~
~Poss~bly~ôf~gre3ter~signi~facance,2the~'poiyhydrid aico~ol is transvinylated to react with ~rom 10 percent to~90`
pèrcen~ pre~era~y~from ~3D~percënt ~o~80~percent, of ~
t~'e'~Xydr'oxy'~'groups whlch~ar~e prësent~t~ëréoX.~'Thë ~x~ ~' 3~ higher the funotionality of the polyhydric alcohol, the . ~ .
:.:,,--~

W~90/10661 PCT/US90/012~.

.:

hiyher the proportion of hydroxy groups thereon whichshould be reacted by transvinylation.
, As previously discussed, a.palladium (II),.; .
catalyst can be.utilized. Illustrative palladium .
catalysts are PdCl2, tPhCN)2PdCl2, diacetato- ..
(2,2'-bipyridyl)palladium (II), diacetato- .
(l,lO-phenanthroline)palladium (II), diacetato- .
(~,N,N',N'~tetramethylenediamine)palladium (II), diacetato(P,P,P',P'-tetraphenyl-1,2-di-phosp~ino-ethane) palladium-,(II), and the like. ., Diacetato~ o-phenanthroline) palladium (II) is a preferred palladium (II) catalyst.
.The catalyst is usually~present in a range of about O.OOl to about l percent,.,preferably about O.l percent, by weight based on the total weight of the polyhydric alcohol and vinyl ether. ....
. .. The transvinylation reaction is a c~nventional one,. as~previously indi'cated,.and is described in ~he articles,noted.previously., We em~loy,a.closed~vessel.
which is charged..,wlth~the_ap~ropriate,amoJunts,,of~t,he~, ,-polyhydr,io.~,.alcohol,,~vinylyether;and.~catalyst and the mixture~is,stirred.and reacted,at.a~temperature;of.,from about~ro,om;~tëmperature up ,to.about 4~C..~Te..The.reactlon.
proceedsrslowly,.and,~we.*sually permit~it~,to proceed~for 25 an~r.,e,x~t~n,ded-~pAerlo,d,o,$~timeJ"up"~to~about~,3 ,days to(obtaln ~, jt,he;.d,esired~e~ui-li~rium,composition.,~A~ter.,.aboutJ2~days ,.
~we,~fin~d~that~.using,aJ~,20.per*ent~.".stoicplom,e~rlc excess~of ~iny,l,~;et,her with;respectt,tp hydroxy;~func~ionality~i~auses abo,ut,.~h,al~of,the.hydroxy~grou~sJ.~to be ~cpnsumed.ln,~he 30 reac~ion.,~ r ~r ~ ; L~n.~:r ~ .y~ L Q~
Atpréferred.met*odlof~pe~fo~rm~n~g~the r, , $~ransvi~y~lia~t~lo~react~ionùas6to ~t,~lize~p,1l~rasonic en~,ergy ~nce~thei~tr~nsvi-nxl~at~i~on~vInl~tthls~method~an ~
admixture.~,o,f~the ylnyl; ether,:the~polyhydric~.alcohol~and~ ' .': .' the catalyst~is~exposed~to~ultrasonic energy-~for.a;time -~ :

, ,...... . - .

WO90/10661 PCT/US90/012.~
2~

- ~6 -period effective to produce the transYinylation mixture.
The frequency of the ultrasonic energy is about lO to about 850 kilohertz (kHz). The ultrasonic transvinylation reaction is preferably performed at room S temperature and pressure, i.e., about one atmosphere.
An illustrative device for supplying ' ultrasonic energy is a Model B220 ultrasonic'cleaner, commercially available from Branson Corp., Shelton, CT.
This.clea~er has 125 watts of power and provides a frequency of a~out:~0 to about 50 kHz at this power level. In this method the reacta~ts are placed''into a suitable vessel which is then plaoed in the water bath of t~é' cleaner. The cleaner-is then activated to enhance ~he transvinylation reaction~
: :- The transvinylation reaction can be:run for a time period sufficient to'obtain the desired :
tran~svinyl'ation mixture. A m'ethod of dete'rmining if the desired transvinylation mixture has been''obtained is to test~samples by:gas c~ro~atography to'det'erminè:the :
con~ent':'o~ he'::transvinyla't'i'on''m`ixture?~-;'?~
~f-- ! s After the~transvinylation reaction'~is'`''': ''` - .
termlnatëd,~;^it~is-convenienti~o removë the'-catalyst by ::':' filtrati'on,' and:-thè additi'on o~ about l percë'nt'~by'-`:' 'r weic~fh't~'o'f 'cha'rcoal'~can be h'elpful.'''~We aiso'prefér to ' s~lp 'off'any vol'a~tile~:pro'ducts~which':canib'e'ipresé'nt;'~
and;t'~ caWn~ ~ donëV;by's''i'm'p'~ 's'ub'jècting'jth'è"'-r'eàctlon :' ~pr'odUct'-to re'~uc"é'~-.p'ress'ur'ëta't'room'tëmperat'ure`.;~-~This ~-~rémovës!an~y rësidual"al~yl~m'ono'vinyllether~an'd thë.'-'~
~'simple~m'o'n'ohy`d~ri''c'a'lco'~'ol~'b'y-pr'o'duct 'of th-e ~rë`action:,iat .; ' least when methyl or ethyl vinyl ether is used'.-'~ -Wi~
: higher monohydric '~à'~c'oho'ls`~:mo~dest''h'e'ât`,~ e., heat to Y~a'ch'ieveVr~`a'~t'emper`a~turë~rof~a~ou~ o~:to--abbuti:6o C'"'','~can' :
. be ~sed"~o'~el'p~remove voia~i~ës''`':~h'i'lè'~hè~fiIt'rat'i'on step'~ 'is ' prë~'~'era~iy ':~carrie;~ 30u~ prior' to ''?reinov'àl ~of i~
volat1lës~,-'~his sequei~ce~can -be ?reversed. i'-;Whein' i- ~-~: ' , . . ' ' :
. ~ . ~ ' . ', - ' ~ :. . ' ' 'i ' . ' :: . '. ' ' WO9~/10661 P~T/US90/01244 7 ,,~ ~J~

polyvinyl ether~ are used, there is no need to ~ubject the transvinylation reaction product to reduced pressure because there is no residual alkyl monovinyl et~er or slmple monohydric alcohol by-product present, and this is a feature sf this invention.
It is preiferred that the transvinylation polyhydric alcoh~l mixture be liquid at room temperature, but this is not essential since reactive liquid materials can be added, e.g., the aforementioned ~--vinyl ethers such as ethyl vinyl ether or a polyvinyl ether such as ethylene glycol divinyl ether, to permit the further reactions contemplated herein to be carried out. Op~ionally,,any residual,alkyl monovinyl ether~and simple,monohydric alcohol by-product can be retained as a reactive liquid material, but this is usually undesirable since the monohydric alcohol is independently reactlve with poiyisocyanate and functions as a chain-,terminating agent and limlts the attainment of,"t,he;!;deslred mjolecular;we,i~ht., Other,conventional diluents,,e.g.,~N,-~,inyl pyrro~i,d~one,,N-v;iny~
cap;rolactam,~,;and,the,,;like,,c,an~,also be,presen,t. ,, ,,~ ,, ,The unreacted p1olyh~dric alcoh~l and,,partially transviny?a~ed polyhydric~alcohoil are th21n converted;
";in,t,o,,,,a vinyl ,ether,containing olligomer,by,reactlon,wlth the di~:so,cvyana~te,t,o,~or~ ~a,~v~i~ny~lt,e;thr~e'~ cD~ntlalnling~; ~, ;, , ,ollgomer,jpreferjably~hajvl~ng;an~average of l to about l0, mo~r~jp,referabl~,Tabou,t~"2,tjo a~out 5,~vi;n,yl~ether groups ,, per mole,cule.~f,The,polyiso,ic,yjana,te l"s,~,u,tilized~, ln,~,an ;j amount su~ficien~ to substantially eliminate unreacted _~ J~ p,~ pr~sent3~n~t~he~transv nylation mixture.
The ~ r~e~ th;~r~is~ocyanat~f;~coni5umes~s~ul~b~s~tantl~ally~a~
vla~ ablle~.~yd,r~o~y~,gr~u~s~of~,~the~ra1n~s~v,i~nyla~tJlo,n~
mixtlllrc~eL~ f~ e~ e~ss~ thi~n~ a~Jouc.~t~nO;. l~ peFC~en~ f~byj wleLi~ht, ~
,~hydroxy,groups are presentj~in the ~nyl~ether,,containlng ,: " ' ,.' :'.' ' ' , , - ~ , , .' , '. ' ' ' ' ' ~' .

WO ~fO/10661 PCr/USso/01244 j X ~" ' oligomer. Preferably ~he vinyl ester containing oligomer has a hydroxy number below about 10.
'The reaction with organic polyisocyanates increases the number average molecular weight and the vinyl ether functionality of the resultant vinyl ether containing 'oligomer. ~his is especially true to the extent that polyhydric alcohols having a hydroxy'' functionality in excess of 2 are used since this introduces branching or an increase in the number of vinyl ether or di~inyl ether groups. ~hile the polyisocyanate can have a functionality higher than two, it is preferred to utilize diisocyantes because of their avaiiability and also becausë this minimizes the tendency'to gel'when substantially all of the hydroxy functionality''is'consumed.' .. . .; ...
A stoichiomstric excess of-isocyanate groups, based 'on hydroxy groups, can'be used",~'but a ' , stoich'iometric proportion'is preferred. Excess isocyanatè groups', when prese'nt; can be latér 'consumed by reaction wlth~any 'isoc'y'anat'é rë'act'ive 'group." ~Thus," ' ~ ', one A~an post~rèact'the exce'ss'isocyanate groups of the vlinyl'éth'er conta'lning oli`g'ome'r'with'àn 'alcohol or amine-functiona'l reagent' that~can'~e mono~unctional~or ~
poiyfuncti'onai''"depending upon whëther a~further increase ~'2~ in' mol'ecu}àrnwéight~''o~r~furnctionâîity'~is des;ir`éd.~~`~
'' '~~ '~Thé aforemen~ionèd''polyisocyanates utiIi~ed in the p'roduction'of~the saturatéd`reactant arè'sùitablé;'' ~or use^in~producing the~lvinyliéthër contalning' ;
oligomërs. ''~''~' f~ 7~ A~ ' L ~ ;; In~ theA~ r;ealctlon~étwèen~hyA rA xy ;ànA `? isA cyanate ~ A ,~
L~ ~ ~ r.Aq ~r r .r ~ r '~t~ r'~ 'iA'.;.'~''~.."'1"~.~'~`~ `'i 'i' ~ r~ A~ t~ r groùps~A~ it~~is preferred to~employ a stolchlometrlc baia~r~er7~` hyd~roxy ~andrA~ socyanate funct~i!or~aiityi and ...
~ t,1 rJ~ ~A~ t~ ~Ar ~ ``` h ~ rr l ? A tr d ~ ~ct~o~n~
perature cf at ieast abou~ `4 0C ~ ùntii t ~r~
~5 funA~ tionality is su~stan~cia~lly consumed. I~his also 1l .

6,1 2 ~ 1~ r~ PCT/US90/012~
.

~.
indicates the hydroxy functionality is similarly consumed. one can also use a small excess of isocyanate functionality.
Since diisocyanates are preferably used herein, this ~eans that the polyhydric àlcohol used ., : ~
should contain a proportion of polyol having at least three hydroxy groups. Using a triol as illustrative, transvinylation provides a monovinyl ether having two hytdroxy groups that is reacted with diisocyanates to provide vinyl èther functionality along the length of thé oligomer. Transvinylation al50 provides a monohydr~c divinyl ether which acts as a capping agent.
Such a capping agent supplies two vinyl ether groups wherevér it appears in the vinyl ether containing ollgomer. ~oth of thèse triol derivatives increase the vinyl ether functionality of the vinyl ether containing oligomers. Moreover, unreacted triol has the same function, for it provides three branches which must be capped by the vlnyl ether-contain~ng capplng agent. , Further chain extension, and ~ence increased molecular weight, can be àchievéd by thë addition~ôf ;3 ~-, ? i r t ~i ~ r~ J !'. ~
conventional chain extenders including amine functional rhain extënders. Illustràtive amine funrtional chaln 3 ~ .,r ;~ V .~i ~r, . :~ . .r~ fi ~ z -;--i~t ~ rL ~
extenders lnclude polyoxyalkylene amines and the Jef'amine line ot' products, commercially available from ~; ~c~3~ 3~ JC~T ~3~ lyr~ -s ~ Li~
~Jeff'erson Chemicals.
~ .t~ L~ ;'tl~ o 3,~ 3~t ~
A monohydric ca~ping agent can also be present ~ 3 ~ c~ 7,rl¢~
to prevent gelation. The use, and amount required, of t~ ~,n"r~ rlrv~Lc~ ?. ~ ~,7~ ?~ J . ~.t r; .;; -s~
this agent isJconve~tional; ~ 3 ~ ~hte~iiti.er~al;~eth~an,e~o~r~ur~e~a~grou;pst!aJre,~
- provid`ë~` by the stoichiometry c~ the system. ~r -~
Suktracting the molar pxoportion of the monohydric ~rt~rr~ f~ r~ r~3~J~ c~
~apping agent, i~ such an agent ~s present, from the ~ ~ r ~ ~ s ~ f 4~ y ll ~ 9 ~ ? ` ` - i~ J .~
number of mols of d~isocyanate, ~he equivalent ratio of r ~ C~; L ~ 3 t`~ L~ ('L ; ~ t ~
3~ hydroxy, and/or aminè from the amine func~ional chain : .
. .

WV90/10661 PCT/US90/~12~, extender if one is utilized, to isocyanate in the unrea,cted diisocyanate can be about l:l and can be up to about l.2:l. This ratio increases the ~,olecular weight of the vinyl ether containir.g oligomer and introduces internai urethane or urea yroups therein.
Unreacted isocyanate grr~ups ca~, be present in ~ -.
the vinyl ether containing oligomer, but are preferably ... ., . . :
~inimized to less than about O.l percent by weight.
More particularly, the residual isocyanate content of the vinyl ether containing oligomer obtained by rPaction ,of the transvinylatiDn mixture witn polyisocyanate can be substantial when further reaction, e.g., reaction with an aforemen~ioned amine functional chain~extender, is contemplatèd, but when the v1nyl ether containing oligomer is to be ùsed for coating, it is preferred that .. .~ . , ~ , .. . . . .
there`be no detectabl`e iso,~yanate~ present.
` The vinyl ether containing oligomers can comprisè the reactlon pr~duck of an organic diisocyanate with a transvinylation mixture containing hydroxy groups that is the transvinylation reaction product of a divlny~ ethèr havlng the Formula III, abové, and at least one~àiiphàtic polyhydric alcohol having an average ~of 3 or more hydroxy groups per m~lecule. The diiisôicya`nat,`~^onsu,es substantiaiiy all of the a,7~aliàble 4; "~ i? ~ 3 ~ .à ;~ . - lJ ~ - . 7~
hydtro~xy~grou.psJof ,th~re3transv ~iny,l, atlonimlxture j ~ j The~, 3, , ~ ; .
equi~alènt ratio~of vinyl ether to polyhydrlc alcohol l5 in the range of about 0.5:l to about 5:l. -'~~ Furt~er èxa^mples of suitàble vi!nyl ether ~r` ~ ~ r~r~ t'i S ~ t^'~ r 1 th~rr~polyurét~ànè~
. 01~ ~ ,7 ~ r~ J ~
and saturated polyesters such as those shown in U.S. ~ i ~Pat,ën~ Nos. ~ 472;01^9, 4,749,80?i 4;751,273, and ~ 2 ,s,~ yY~r~ r.~
4l775r732 th~e~r~ ~epresentative vinyl ether oontaining ~ r~r; ,~ J ~ r~t~ lS~ r ~
oIlgomers~ are, o~tain"~d by the metathesis o~ a cycllc ~~olëfln ethér Xav~ng thè fol ~ g generai Fo~mula IV

W090/106~ P~T/US9~tO12~
~ i~ f~ 8 CRI=CR
O--( CR R ) m . . . ........... . . ..
wherein each Rl independently'can be hydrogen or^an ' alkyl, aryl, cycioaliphatic or~haloge~''group and m is a ~umber in t~e range of aibout 2 to about 10, preférably about 5 to about 6.' Metathesis, which'is descri~ed in March, Advanced Or~anic Che~istry, Third Edition, copyright 1985 by John Wilèy & Sons, Inc., pp 1036-103g & lllS, results in the opèning of the ring of the cyolic ,. :
olefin ether to produce an oligomer having the following general Formiula V: ' : ...~:(V) 2.;-~'(CR~R!)m~- O - CRI =.CR~.~ y Z
.

, wherein.R~...and m are as prev,iously described, y is a , ,. ,, i ~ , i . . . . . . . .. . .
number.in the.,range of.,about 2.to about.50, preferably .,."J2 ;to ~,abjo~uj1t~ 25~caind~each~ Z3is~a ~termlr,al ,group~ ~
e.g., hydrogen, a vinyI group. The vinyl ether;,.~"~.. ~;. -containing,oligomers,~,o~,Formula.,V,can~be blended with ~ thenother~yinyl .ether containing oligomers of the ,;,..~.
~: .,present,~invention~r.,those,disclosed,in U.S...Patent.Nos.
`4 ~ 472~ 019"f 4 !~7~49~ 81~07 f~ 273~ a~ 4;! 7.75 ~ 732 ~
~ The oligomers~having an average.of.,j,at;........... least;
: : one electr,on-.ri~h~ethylenically unsa$urated,group per ...
.~:,3~m,o,1e~culetof,~ol1~om~r,,p~refera~.1y.r,cont;aln~.an.average,..o~.
about l~to,about lO,i~more~.preferably about 2~.~to a~out 5, ,.ele5ctsonl-rich.ethy.lenlcally.. ,uns,atur *edJ.~grioups ~e~r ~.. -j .^,,. . -molecule of:~ollg~omer~ ?
.h~e. ~ :~ ~erà~e~.mole,~ula,r~weig~t o~ the~
35 ~ ;oli~g,om~el~s ~a~ ng;~ànl~ay~er~age of~ atj~eas~t one~electro~n-, . , ~
rich ethylenically;~unsaturated group per,.molecule.of. ' ::

WO'~OJ1066~ PCT/US90/01244 2 ~3 ~

oligomer is preferably a~out 500 to about 8,000, more preferably about 1,000 to about 4,000, daltons.
. ~hen the compositions of the present invention are utilized as a primary coating for optical g~ass fi~er the equivalent weight o~ the oligom~rs having an ', average of at least one electron-rich ethylenically , unsaturated group per molecule o~ ollgomer is preferably about 500 to about l,500, more preferably about 800 to about 1,200.
When the compositions of the present in~ention .. .. ~ .
are utilized as a secondary coating for optical glass fiber the equivalent weight of the oligomers having an ..- , . . . . . .
average of at least one electron rich ethylenical?y unsaturated group per molecule of oligomer is preferably lS a~out 300 to about 1,000, more preferably abou~ 400 to ' , about 800.
The present compositions preferably contain ' "
the (meth)acrylate oligomer in an'amount in'the range of '' about'1 to about 70,i more preferably about 20 to about , 40,~weightipercentibased on~thè~totai welght of the~
composition. ~
~ 'The present'compositions preferably contain the s`inglé functionality diluent in' an amount~ln thè
rangè"of'about'o to â~,ou-t- 4oi, 'more préferably about;5;to about 30,~weight'percent ba'sei 'on the total waight of' thei-comp~osition~;4~ r~ ,r,;;~ 2'~3C~C~
~ F~ ?The'presë~t-icompositions preferably c'ontain~
the ~ùai'~unctional~'mon'ome'r ~n an ^amSunt in the' rangëtof ~ abou't7 O~to àbout~ io ~more p,ra'~e'rably a~outi5'to aboùt' 3C,, wéic,~ht;~percent;~bas~e~o~ é''to~a'l~-w'eight~~o~'the ~~' compos lt l on . ~ -r ~ r~ X ~ t s~rre~er~ablY coT~tain ~elsaturatë~ réa8tar~t in an~3amount~iri~Xèi rangé''of Lo 2 abou~o~o~bout 60,~more~prëférably-abouk 30 ~o àbou~

.

. " . ~. . . ; ~ ., . . , . . ............... . : . .: , .. . . ., . .. . . . -. . . . . ,,, .. . ; . . .

WO 90/10661 ~ r,~ , P~/IUS90/01244 -- 33 ~

50, weight percent based on the total weight of the composition. .~ - - . ~.
The present compositions preferably con ain the vinyl ether'containing oligomer in an amount in the range of about 0 to about-50, more preferably about 10 to about 30, weight percent based on the total weight of the composition.
The YisCOSity of *hP present compositions is preferably about 200 to about 100,000, more preferably about aOO to about 4,000, oentipoise (cP).:
: The oo~positions of the present.invention are preferably solvent free.. .. . :
The.compositions.of the.present invention can be cured upon exposure to.energy such.as..ionizing radiation, actinic:energy.,~i.e., ultraviolet and visible iight, a~d heat, i.e.,.thermal cure. ' Conventional ionizing radiation.sources include electron~beam deYices.. The amount.of ionizing . radiati-o~.~!required.for.:cure;of.a.3.mil thick.. film ~is .~ j ':about.'lcto.abou't 5;!megarads.~ t ..-- :t.~
h~hen cure of this composition-by exposure to actinic energy--of~appropriate:wavelength,.such as ultraviolet light, a photoinitiator~can be.admixed.5with the composition.~ The photoinitiator is preferably selected from the group.consisti~g'of (1) hydroxy- or . alkoxy-functio~al-acetophenone derivatives, pre~erably hydroxyalkyl phenones, and (2)~benzoyl diaryl phosphine oxides. Materials having the two different ~ypes of .; l .'.
ethylenically"unsa~uration!, i.e.,~th,e vinyl.etheri,gr;oup l .
and the ethylenically.unsa~urated group, copolymerize rapi~dly~ in3 the~resence~of the ,~!speei~f ied:gro~ups~ OLf ,~ r ,j photoinitiato~s ~o provide a rapid.photocure~and also. ~ . .
interact~,~Jrapidly,~upon exposur~e ~o other types i.~ener~y ~ - :
when,no polymer.ization initiator is present. ~. r................... '-' ':

WO90/106~1 PCT/US90/012~i % ~ ~ 7 ~ `!J ~ ~ ~
.
- 34 - ~

Ethylenically unsaturated dicarboxylates ' respond poorly to photocure using, for example, ultraviolet light when the photoinitiator is an ordinary aryl Xetone photoinitiator, such as ~enzophenone. .Also, the vinyl ethers do not exhibit any substantial curing response to.ultraviolet light when these aryl ketone photoinitiators are utilized. Nonetheless,. these two ~ ' types of ethylenically unsaturated atoms in admixture respond to ~he photocure very rapidly when the photoinitiator is correctly selected.. The photocure, and the;cure upon exposure to other types of energy when ~ .. ...
no initiator is present, is especially rapid and effectiYe when both of.the~described types of unsaturation ~re.provided in.polyfunctional compounds, .particularly. those . of . resinous character...The fastest cures are obtained when:the respective functionalities are present in about:,the same equivalent amount.
~ Preferred photoinitiators are.(l)........ hydroxy- or ~ , alkoxy-functional acet,ophenone derivatives ,. more.:: .............. ' "' preferably hydroxyalkyl phenones,~and (2).~enzoyl diaryl !~
phosphine:oxides.~
-; !m.The acetophenone.derivatives :that ~ay :be :used ..have..the;Formula...VI ..~ ,,r. ~

VI ). ~ ; r~ 4.~ C~ X ~ `
t~.~, r -" ~ ~, ." ; . .t~rt~ t ~'; ix ~ i -''ln`whlch' Rm `ls an'optionai' hydirocarbon sub5tituënt ; contain'ing~;~from~ toilO'cir ~ ~;atoms`aind whii~ ~ay bèi ~ , alkyl~or ~ ,`^~é~. ~ methyi,3~ethyl~ ylt;J octyl or ~i~
p~enryf~ X 'i`s'~sèle ~ erd ~rom't~e grou~~~onsi~ing of ..
~hy'droxy,'C1~~to C~lkoxy,~C~ to`C8~aikyl,~'cycloalXy~
: halogen, ind p~enyi, or 2iXs-!together arë cycloailkyl,;r j 1, :

:
- . , WO90/10661 PCT/US90/012~
^ ~ ~3 ~ ~ 3~ t~3 and at least one X is selected from the group consisting of hydroxy and C1 to C4 alkoxy.
M~y compounds have the ret~uired i6tructure.
The alkoxy groups are prefera~ly methoxy or ethoxy, the alkyl group is preferably methyl or ethyl, the cycloalkyl group is preferably cyclohexyl, and the halogen is preferably chlorine. One commert~ially available compound is t~e Ciba-Geigy product Irt~acure 651 which has the Formula VII: .

(VII) ~ C - C

OC~3 ,, : , .. . ,. ,. , : .
Irgacure ld4, also from Ciba-Geigy, is another useul acetophenone derivative, and it has the F~r~tula , ., . ..! . . . ~ . .. ' . .
VIII: .

( VI I I ) ~ C -- f -- CH2 -- CH2 2 5 , -1 CH2 -- CH2 -- CH2 : `:
l; j , .. ;. :
StiIl another commercially available usefùl acetophenone derivative is diethoxy acetophenone, availa~le from ~pjohn Chemicals, Nor~h Haven, CT, which :
has the Formula,Ix. n 5 `{ ~ -~ .V~t~''tq9_ ;'1'.. ~,r, ~,~r ~.3 ~ .J

IX , .~.~3~.{~crJ .~ c ~ ~ L1,;V 1CH2c~H3 u~
~ z~ s~ ~.. i~ ,<~ ~C . C~ S ~-'~ t'~_~.. f~nt~ yx''~ is'~ S-S"2~ H.ICH 11~ Q.
,~c,~ ~,3~ r~3~ g ~r~ .15~, ~When the photoinitiator is a s ' ') ~ ~ 3 ;. ,# ~ d ',' ' ,~, .t ~ 2 ~ . ", ~ ~ 2~- _r ' ~?~
hydroxy-fun~tional comp~und, one can define ~he useful acetophenone derivatives in a somewhat different manner.
' ', - . : . . : - ..

wosotl~66l PCT/U~90/012 7~ J~

.. . ....
Thus, the hydroxyalkyl phenones which are preferred herein have the Formula X:
. .

(X ) ' ' ' Rn _~ ' ' . ' , 1~ ' ' in whic~ R is an alkylene group containing fro~ 2-8 - :

carbon atoms and R" is an optional hydrocarbon :-substituent containing fro~ 1 to 10 carbon at~ms and which ruay be alXyl or aryl, e.g., methyl, ethyl, butyl, octyl or phenyl. ~~ _ .

It is particularly pre~erred that the hydroxy group be in the 2-position in which case it is preferably a tertiary hydroxy group which defines a hydro~y gro~p carried by a carbon atom that has its .

remaining three valences connected to other carbon atoms. Particularly preferred co~pounds have the . . .

Formula XI~

(XI) ~ C ~ C ~ OH

r~Of~ ~!7 `~ r 'L~ 3 r3 2 ,r 3 ,~ ,t ,:~ ;, .31~ ?~
: in which each RP is independently an ,al~.yl,grpup ~
containing from 1 to 4 car~on:a~oms. In the com~ercial :~ `
~: product Darocur.ilt3~avai1able~from E-M Company, Hawthorne, N.Y.,,~each RP~is ~ eth ~ . This provides a .: :.
35: compound which can,j~be descrl~ed'~as 2-hydroxy-2-me~hyl-phenyl propane:i-one. ~The "propane" is replaced by -: - .
bu~ane:or hexane to descri~e the corresponding . r~ r~ s~ r ~ J -3-~
compounds, and thas`e will furt~er illustrate preferred.
compounds in-this inventi~n` : : . : .

The benzoyl diaryl phosphine oxide photoinitiators which may be used herein have the Formula XII:

- (Rq) ~ ~(Rq) x (XII~ ~ C - p ~

, (~ (R~ X

In Formula XII, Rq is an optional hydrocarbon -, . .
substituent containing from l to lO carbon atoms and may be alkyl or aryl as previously noted, and each x is independently an 1nteger from 1 to ~. In preferred : :
practice, a 2,4,6-trimethyl benzoyl cor.~pound is use:d, and the two aromatic groups connected to the phosphorus atom are phenyl groups. This provides the compound :~
2,4,6-tr1methyl benzoyl diphényl phosphine oxide which .
is available from B~SF under the trade deslgnation Lucirln~T~0,-~, r ~ , . t , :?. _ ~ .
. When utillzed, the photoinitiator ist preferably present in an amount in the range of about O.Ol to àbout lO.0, more preferably about O.l to about 6.0, weight percent based on the total weight of the c,o~r~ p~OS;~i; i" t~. 5,~ r ~ ~; r 3~ J ~ f~ ; r~ t~
. Suitable sourcës of~actinic enërgy includes t5t~ L? C ~ .: . 3~ o ~t 2 U ~ I !' L' . -! ~ C ~
lasers and other conventional light sources having an 3~ ef~ective energy output; e.g.~ mercury lamps.~ ' .
. r ~q"~ J~ r~ ~. r~ ? ~ ~ C`~ 'J ~ 7~
The wavelength of the actinic energy sultable for use herein ex~ends from the ultravioiet range through the visibie ligh~ range and into t~e infrared ~a ~Fi'*~ 'r~ 3`~ ,1 r3~J,,,;,~ pr~ .7~i~r range. Preferred wa~elengths are aibout 200 to about L."i ~ ~'t~JLX E~-~r~ L ~ 1'1!3Z~ Jr.'~
2,000, more prefèrably a~oUt~250 to about l,000;
. ~f~ *.^~.*~r~
nanometers (nm).
The amoUnt of actinic eneryy utilized to .
. solidify a 3 mil thick film is a~out 0.05 to about 5.0, :' WO90/10661 PCT/US90/012~
, j S t pseferably about 0.1 to about 1, Joules per square centimeter (J/sqcm).
The compositions alsio~can be thermally cured in the presence of a conventional thermal free-radical initiator, e.g., benzoyl peroxide, cyclohexanone peroxide, N,N' azobis(isobutyrylnitrite), metallic dryer systems, redox systems, and the like.
The use of (meth)acrylate oligomers and the single fun~tionallty diluent and~or the dual functional monomer in the co~positions of the present invention result in a r duction in toxicity as compared to convëntio~al compositions that contaln only (meth)acrylate oligomers and diluents. The ' (meth)acr-ylate oligomers result ln improved physical' properties, e.g., toughness, abrasion resistance, tear rësistance and flexibility in products produced from the c~mposltions as compared to non (meth)'acryia'te containing compositions. The reduction in'toxicity and '' ` 'improved physlcal propërties enhances thë p the compositions of the present lnventlon as' coatlngs for optical gl~ss fibers, coatings for substrates;'`''e.g., .. ~ f. '~ .' rFi t ~ , S ` _r _ r ; ~, rl ~ j ~ ' ' . .', ~/ U ~ ~ t ; , ~ :
glass paperl wood, rubber, metal, concrete, fabrlc, anu ~ n~ -t~ c1 ~ i i '7''i'r`te'''''''`~ nd'ë'is in :''' r, ; r 3 ~ C,~, ;t 'I~"F ~ ,- "~
the manufa2turing'of composites, and ~he l ke. The same results are achi~ved when the saturated rea~tant and/or vinyl ether containing oligomer are prese ~ ''i'n'`t~'e"`
?3~ti~ r~J tih~ e~O~ t~-e!J~met~h~)acry~l~ate oligom,erS
'' in;the c~or,posltions'of'"t~e`~pr'es'ënt invëntion also lowers t~t~ LS'l r~ T ~ ompared to ~imiiar r~ y~ ~t~ fh~t~d '`not~^ut~l` ~ thë (mëth)acrylate T~è ~ôllowing Ex~=p~'ès^arë'pres~nt''~y way of r~pre~ n~tà~tio~n ~ an9d~'not~'~l'?l~m~l~t'atîon, of ~e présent - ~ r~ O t~ r.~r.~. ~.r~ :r~ Q ~ $ ~r L ~ ` r ~ 1 ~3 ~ 1 0 ~ S ~J, '-inv'-ntion~ r. ~ t l~;t .:

,', ~ ': ' ' ' ', ', , . ' ' ' , .. ., - ,?

WO90/10661 PcT/usso/ol2~
~ 3l~ J~

EXAMPLE l: pre~a~atiqn of t~e Dual_Funçtional ~onomer Into a one liter 4-neck ~'lask were intr~duced 298.3 grams ~g) (1.732 equivalents) of diethylmaleate, commercially available ~rom Aldrich Chemical Co., ~ilwaukee, WI, 201.2 g (1.732 equivalents~ of 4-hydroxybutyl vinyl ether (HBVE), commercially available from GAF under the'trade designation Rapicure HBVE, 0.5 g of tetraoctyl titanate, a ~onve~tional .
esterification cataylst commercially available from DuPont under the trade designation TYZOR TOT, and 0.22 g of p~enothiazine, a conventional inhibitor commercially available from ICI Chemicals, Wilmington, DE. The flask was fitted with a variable speed stirrer! thermometers, a snyder column, a condenser with a trap, a nitrogen 15 sparge and a heating'mantle~
The temperature of t~e contents-of the flask and the temperature at:the top:of the.column, i.e., a thermometèr is placed -in the condenser at the top of the column to measurë"~the temperature of~.distillatej were,, ~et~to'dis~ la~out 80.,~g~'of~ethanol;in,a3timeiperiod,of about 2.S hours. The resultant product was the dual. _ ~unctional monomer that--had a yiscosity,~at-,25C.:.:of , about~ `c'ëntip'oise'(cP)~.'~ -7~ . n i ~ , EXAMPLE 2: ~ComPosition~_~f the ~resent Invention r 1 ;~3;~ ; Comp"ositi'ons'were prepared:and~.~ested.~,5~Eac~ , composition comprised a ~meth)acrylate,oligomer.1and,~at ;; .. ..
least one o~ a single ~unctionality diluent and a dual ~unc~ional ~onomer o~ 'EXAMPLE 1; !i ~hesformulations of 30 ~'the~compositionis~àreIpresent~in~ABLE~ 7 !,`. '.'.. '. '~
-" ~ "; ~ r, C . `~ T~-if;Jd~i r~ 3 ~
3~ J~ .O ~ 3 ~ fi S~ F~ r~.tJ t ~ J r~3~

, ' .
'. ' j:
~ , Woso/10661 - PCT/US90/0~244 2 ~ ~ ^9~

TAsLE I
Ca:~osi t i ons calpoS i t i Dn Equiv~nt Con~onent ~t. A e, C D E ~ ~ G H I ..
Oligr~rRr 1 60~U.3 - ~0.~ 73.4 Oligo~ner22 2030 -~ --- 92.~ 81.9 8Z.9 ~
Oli~laner 33 2829 --- --- --- --- .~-- ---. 80.3 --- ---CDr9 j l l .
0 157034Unreported -~- --- --- --- --- --- --- 75.0 75.0 DVE~35101 -1l.810~1 1$.3 ~, a.2 4.1 2.9 : 8.0 2.5 Diethyl m3~e~s~ - 6.9 ---~.9 --- --- 13.6 4.3 Mor~omer6 2~3 --- 26.1 --- --- --- 9.9 13.8 ~-- 14.8 Photoinitittor7 20L 2.9 3;0 3.4 3.0 ', 0 3.1 3.0 3.~ 3.~ -.. .:, . , " . , :, 1 The (meth)acrylate oligomer l of;this Example 2 The-(meth)acrylate oligomer 2.of this Example 3 The.(meth)acrylate.oligomer 3 of.this.Example.' , . '.
'4~An acrylate oligomer.:.that is a diacrylate ester of ,~, Bisphenol~A;epichlorohydrin~:epoxide.!resin and is ... ~. .................. .
~ commercially~availableifrom~Cargill,-rj.C,arpentersville!.,. . ~'' 5 T,ri'ethyleneglycol:divinyl~ ether,~comme~r~icially~,~i-~.. ; '' : available from GAF under the trade,designation Rapicure ..
DVE-3.
6 The'~dual~,,unct:i,o~al,r.,,m,onomer,o~,EXAMP ~ l. , ,~.,,~.,,~,,,jr,.;,,;~7 ,,.
7~ Irgacu~re~l84,5.commercially.~ayailab,le ,f,rom,Ciba-Geigy ' corp~;Ardsley~ Ny~ f~ '9 ,~ ,";J, ,,l J
.r j j j~J~I L~ L.~ ~ ir ~;. .C~i~i;c -;~ L`?r,i ,r'~ t.;
~ J~ (Meth)acr'ylate ~ligom,e,r-,,l wac,~pr,epare,d,.bx.~
; ~ reacting 80.8~wèight.-~percent-.3Adipren.e L-,200~emmerclally , available ~rom Unircyal, iMiddlebury, CT,~O.'l weight percent o~ dibutyltin dilaurate, O.l weight percent . ,, buty~ated hydr~xy~toluene and l9 weiyh~ percent 2 hydroxyethyl acrylate.
:

: ~ , .
.
: ~ ~ : j ~,, -WO90/10661 PCT/US90l01~
2 !Js ~
.

(Meth)acrylate oligomer 2 was prepared by reacting 3 mols of IDPI and 3 mols of 2-hydroxyet~yl acr~late which was then reacted with 1 mol of Jef~amine 'r5000, commercially available from Jefferson Chemicals.
(Meth)acrylate oligomer 3 was-prepared by reacting 18.65 weight percent Desmondur ~, commercially available from Mobay Chemical Co., 0.01 weight percent P2N, 0.03 weight percent butylated hydroxy toluene, 0.07 weight percent dibutyltin dilaurate and 35.9 weight percent NIAX PPG 1025 commercially availa~le from ~nion Carbide which was then reacted with 4 weight percent hydroxyethyl acrylate which was ~hen reacted with 30 weight percent phenoxyethyl arrylate, 7.3 weight,percent N-vinyl'pyrrolidone and 4 weight percent Jeffamine D230 commercially available from Jefferson Chemcials.
The results'''for"'t'ests conducted-on- --Compositions A to I, and cured films prepared therefrom, are presented in TABLE II~ The test'prb~edures are presented a~ter TABLE II.

~J ~ J ~ r r rr~ -r~ r ~rc~, ~ ! ~ S~ . Y ~ ~ ;r~2.~

' ,;";lr,,~ tj:~ j ~ - ~ ? ?~r~ Sl, ~ r z ~ ) q ~ S ~ r t.~ '3 i."( I' ~t o C~ ~' 3 ~ C1 ~i 'J ~

` V, ~ ~,;"~ ,r,, ",r ~!' .

' .
l :, , ~ :' :: .
' ' : ' '' ' ' ' ' '' - :
, . , . ~ . , , - . ,, ; . . ., . ., . '. ' :

.,. . :,, .. ' ' ~ . '' ', '. ' .~'' ', '' ' ', ' '. ' - ' "' '' '. ' . . ' ' .

WO90/10661 PCT/US90~012M
6l~ `L~

- 4 ~ ~ .

TA~LE
Test Results ~ -ProDertY Composition: A B C D E F G
APPe~rLnCe ~ter yell~u, ~ter c~ear, clear, ye~to~, ye~lou, ~tr-u, yello~, . :-- uhite clear u~te vory very very . e~ear very clear . slight s~i9ht sli~ht ~ ht h3ie h~ie h~ze h~e . ,. . ~ .
Viscosity ~cP) 12,200 2100 9200 .~750 2900 ~700 S0~0 esoo 19,100 1 0 ~ensil~ Properties `;~~
Tensile ~HPA~ 9.4 13 10 . 2.3.. 2.0 2.s 6.2 32 37 Elorlg~tior~ tX) ~8 ~ 49 75 St 53 71 3.3 3.0 ùs~P-) 2s ~1 24 3.7 3.6 4.9 7.7 933l 1113 ~ater ~clsorption t%) -2.8 -1.4 -2.5 1.~ 3.6 -uo o.s ~1.9 ,~31 . ~.
1 5 ~ater r~trActables t%) . -~ , - L . a -2.8. .-4.7 ~ F2.~ -2.7 -0O7 ~D
~ - : . -.. . .. .. .

1 ND = Not determine~d~

The films, cured at a dosagë of l Jouie per square centimeter,~prepared from Compositions A to I
exhibited no odor.: Films~prepared from C~mpositions A, : 25 B and C were clear and exhibited no tack and go~d adhesion and toughness. Films prepared ~rom Compositions D, E and F exhibited slight tack. Film prepared from Composition G exhibited slight tack, good .
~ toughness and ~air adhesion. Films prepared from :Compositions H and I exhibited no tack, were strong and stl~f.Silms.
A~eara~ce T~e~;~appearance of the }iquid composi~ion was determined ~isually. :. - :
5~ ~ v~scosi~y The viscosity, expressed in centipoise (cP), :
was me2sured ~sing a:Brookfield Model RVTD viscometer op~rated in accorda:nce with the:instructionc provided ::

:
.- : ~ ~ , WO 90/10661 PCI/US90/012~4 r~ J~

... .

therewith. Th~ temperature of each sample tested was .25C. . . . ..
Tensile Properties A film for determination cf the tensile properties, i.e., tensile strength [Megapascals (MPa)], percent elonga~ion at break (%) and modulus.(MPa),-of-:
the coating was prepared by drawing dQwn a 3 mil c~ating on glass plates using a ~ird bar, commercially available from:.Pacific Scientific, Silver Springs, MD~ An - -automatic draw.down apparatus like a Gardner AG-3~60 .
commercially available from Pacific Scientific, Gardner/Neotec Instrument Division, Silver Springsj MD, can be.utilized.. The.coating was cured using a "D''..lamp from Fusion Curing.Systems, Rockville, MD. The "D" lamp : .
emits radiation having.a wavelength of about 200 tD
. about 470 nanometers with the peak radiation being at about 380 nanometers and the power output-thereof:is .
....about.300 watts per linear inch. The coatin~ was cured ................ . . . . .
~ at.ajdose,o~ about l~J/sqcm which~provided,complete;~r ;~
cure. The ~ilm was then conditioned-at.23~+~2~C; and J50 + 3~ relative humidity or a minimum time period of 16 ~ hours. .j ~1! . -. ,' ,'-~ ~'~^ .' ,' "............ ~-.-.~r i `.'.' '" ' .-Six, O..~ inch wide..~test.spe.cimens.were cut from the,~ilm..parallel~to.~the,~direction of;the..:draw.down.and ..rem~oved.from the glas~s-~plate.~lTriplicate m.easur.ements ofrthe~ dimensio~s of~.each~specimen;~were-.taken.and the~ :
: average utilized. The tensile properties ofIthese~.r specimens were then determined using an Instron Model 4201 from Instron Corp., Canton, MA operated in . .
~ acoordance with t~e.instructions provided therewith.
Wa~èl~-Resi~n~
To determine the water resistance a :~O:mil draw-down of the composition was m3de on a glass plate : utilizing a Bird bar. The composition was cured .
atilizing the "D" lamp at~a dose of 1.0 J~sqcm. ~hree .

. . .
% ~ ~, rJ l ~

test samples each having dimensions o~ l/2" x l" x l/2"
were cut from the cured coating. Each sample was weighed utilizi7n~ an analytical balance to obtain weight measurement A and then immersed in separate containers of deionized water. After a time period of 24 hours, the samples were removed from the water, blotted to remove excess water on the surface and reweighed to obtain weight measurement B. The samples were then ' placed in aluminum pans and maintained therein at ambient conditions, i.e., am,bient temperature (about 20 - 30C.) and ambient humidi~y, for a time period of 120 hours. The samples were then reweighed to obtain weight measurement C. The following equations were utilized to calculate the water:'absorption a~d the extractables;
(I) ~ water absorption-= [(~ - A)/A] x lO0 ~ extractables = [(C - A)/A] x lO0 It is preferably to have relatively low % water absorption and % extractables. ' ~ A negative value obtained for % water a~sorption indicates~water.solublej-"low'''molecular' weight materials '~ were leached`out~of;the fïlm~

EX~MPLE 3: Tox_ itY St~dies - -~ Toxicity tests-'w'ere-per~ormed''on commercially ~iavaila~le~tmeth)acrylate;oligomers;and di'luent's~'and';on -commercially avail!abI~é~vin`y'l;ièther'~andfmalë'ate `d~lùénts.
Th'e results'-of~these'~'t'-o'x`i'c'i'ty:tests a'r'e`'p`rov'ided''in '' .~ Lr,t~ "3CIr~l "~r~ ~ r ,~ F~
,~ -F '~ r ~ ,~ t` r. ~ ,?~ F~ ',;, t ` ~J'X ' ',~ r~ 3, r; .

-~ L I~ t~ ,r,~ ~ ,3 '~ trt E3 ~

. .

:
:: :

WO 90/10661 Pcr/usso/01 2 44 7 ~

J,S

, .. . .
TAaLE 11 1 Toxicity Tcsts .
Irhalation Skin Ey~
Or~l D50 S~in LD50 ~ill Irrita~ion Irri~ation ~l~terie~l ~r~a./kq.~ (mq./kq,~ tanimals~ (rux.-8~ ~nul.=lQ~ -ACTOI~IER
X 701 . 23.8 16 0 of o ` 2 10ACTOME2 . ~ .
X-~O~ ZO 16 0 of S 3 ~eopen~yl-~ty~ol ~ ' ~ .
ditcrylate2 5.19 0.35 .. ~ 1 o- d ~ 5 8 1 52-hydroxy~
ethyl ", .. . ..
~~ciylatè~ 0.65 0.1~ l Df 6 6 9 Pentaery-thri~ol 2 0triacryla~e 2.46 4 0 of ~- 2 10 2~phenoxyetnyl ..
Dcryl~lte 4.~>6 2.5~ ' O of 6 3 Diethj~ene- ... . .... :.. - ;-- - -- - ---- -- - --- .
glyc~ol __ _ ~- ;,- ;~, - - .
2 5 di~crylrt~ 0.77 o.la o Df o 5 9 .. _._. .~ .. _ .. ~.. .. ~ ... __. .__ . .. _ _ ~.. ..... _ 1 ,6-heJ~Pnediol diacrylat~ 4.76 O.71 ~O c,t o 3 2 ~' -Tri~thy~ène; .~ . .. ::: . , g~yeol,;;-~ 3 .- .~ 3~?.
3 0 ~ divinyl ther ~ 7~j00 : 7?000 NA3 0.25 none Dim~thyl :
.,ldYi!~ite Lf; ~ 1410 i ;-i - ~530"tJ Ni ~ -; ;5.47 ~ moderate : ~ .
D~othy~3 rtr,~ J ~ J;~ s! ~ r~?~
3 5 ruleat~ ~;3200 ~ 000 ~ ;,"~A,~ I 3,;,~ ," 3~, Dibutyl : .mal~it~ !r~ 5~0 ~ J i~'160`0o' ~ r~ A

S~ ~ 35s~ ~L~5-~ '.L~ .. -l3 r a ~ ::3 ~$~ r~ r'~:s~1~39r~ SI~ t~ .#.C~ .Ct~lC''~;~955 ~a~
1`The Actomer products, commercially:~available ~rom ~ rJ ~ n~ 'r ; ~ 3 ~ L~ 5 ,~rr~ 7~
Union Càrbide,:are acrylate ollgomers prepared byl.the .
: ~: addi~ion o~ acrylic acid to epoxidized soy or linseed .

:
.

WO90/10661 ~ r~ - PCI/US90/01244 ,. ~ .
.
~6 oils. These are relative}y high molecular weight materials containing up to three to six acrylic groups respectively per molecule.
2 Neopentylglycol diacrylate was found to be an experimental tumor causing agent.
3 NA = Not available.
. .... .::. .. . . . ~.
The skin irritation and eye irritation tests were condu~ted according to the procedure to catagorize the 1~ cDmpositi~ns under the Federal Hazardous Substance Libeling Act ~16 C.F.R. 1500).
A composition representing the present invention (Co~position J) was tested for skin irritation and eye irritation. The test results are presented in TA~LE IV, j belo~.

TABLE IV
Toxicity Study of Compositions cem20sition Skin irritation ~PI)1 Eve irritation J 1.8 non-irritant t ~ ' t~ ' ~ , 5 1 PI = Primary irritation index. A PI of 1.8 indicates the composition of the present invention (Composition J) is oniy a mi}d irritant.
r'~
3~'ilO~ TABLEjIV indicates,~that therpresent compositions result i~ a significant reduction in irritation as'~'~
compared to conventional (meth)acrylate compositionsj `~
,u The reactant, a branched malea~e termin *e,d~
ester, of Composition J was prepared utilizing a glass flask equipped with a re~lux condenser,-.-Dean-Stark-~ube for azetropic ~eparation of water, a heating man~le" a rl~ ? '~ 9 t:~ ~.{5~ s yL.!f~ 'S~lT;~ r.~J~ C?f~L
thermometer, and a~mechanical stirrer. A mixture of .c~ r ~ 3 ~ gllto o ' .~' o ~ 3^~ 3 . '.~
maleic anhydride ~0.8 mols) an~ butyl carbitol (0.84 ~ ' ' `' ' ' ' ' .

.' .
', ' ~ ' ' ' . ' ~ ' . ' .

WOsn/10661 PCT/US~0/01244 !. 2 ~ 3 ~

mols) was heated in the flask to 80-C.. An exothermic reaction occurred and the temperature rose to 120-C.
where it was held for a time period of 2 hours.
Trimethylol propane (0.23 mols)~ 1,6-pentane diol (0.3 mols), azelaic acid (0.2 mols), Fas~at 4100 a catalyst commercially available from M & T Chemical Co. (0.3%) and 40 ml o~ xylene were then added to the flask. The '.
contents of the flask were heated and stirred while the water of reaction was removed by azetropic distillation.
When an aoid value of 16.5 was reached, the xylene was distilled out. The resulting branched maleate -terminated ester had a Brookfield viscosity of 392 cP.
~ omposition J comprised Novacure 8805, a urethane acrylate oligomer cor..mercially available-from Interez Inc., Lou'isville, K~ ~40 parts), Rapicure DVE-3, commercially available from GAF (11.7 parts), the maleate ~erminated ester described above ~55.9 R.arts)j Darocur 1173, commercially available from ~ ~ M Company (5.0 parts), and Phenothiazine,.commercially.available from Eastman (0.2 parts) were blended together at roo~
temperature under yello~.~-.safety.:.lights.until~
homogeneous. The resultant':Composition:J had a~
YisCosity of 1,830~cP',''-a~weight per-gallon of~~8;'6~ ' pounds, and a closed~'oup ? fla~h pbint;of-greater:than 212-F., .~.~ ~ .................................. 7 .. ~
~ Composition''J~wa~s:drawn~down;~oh ahpaper~;sheet ,'iwith~'a '#~'20.wire)wound`rod;Cplaced:on a~U';V. cure:-~. ' .' apparatus ~commercially available from Fusion Systems) to cure. At an exposure of 1 Joule/s~uare centimeter, the re's.ultant.L:coating~.was:~completely;~cured~l25~.ME~;~'' i~A.
Do~blei^rubs)-;With a~oughvhar.d.~surf~ace." The~same~
: ~cdating'curéd-~wit~.~5~.megara'ds!of elect'ron beamïexposure.
Removal30f thèDarocur:~1173 from'~;Compos'ition''Jtp~rmitted much lower electron ~eam doses for ~otalrcure'~a'bo~t'~'2-3 megarads).
: .-.. ....

, . .
~ . .. . . . .

' ' , .

WO90/10661 P~T/US90/012~

-- q~3 --EXAMPLE 4: ComParison of Comp-osit~2 , A (meth)acrylate ~ligomer containing..composition (Composition K) was compared to a similar composition that did not i~clude a (meth)acrylate oligo~er tComposition L). The formulations of Compositions L and M are provided ln TABLE V. ....

. TABLE V .
Compositions ComPonent . Composition (wt): K L
Novacure B8051 . , 36.2 Saturated Reactant 12 . ~-- 76.9 Saturated , , - "., . : , .: .
: Reactant 23.~ . ,. :.50.5 DVE-3~ : . ,13.3 1g.:2 Photoinitiators , , 5.0 : -3.9,-Phenothiazine ,,, .. 0.2 ---:
-` - . r . ......... ..
.. ....

,A urethane acrylate oligomer.commercially-aYailable ..
from Interez,.Inc., Louisville;,KY;~
2 Saturated Reactant.:l of.,this;EXAMPLE.
3 Saturated Reactant;2.-~of.~his.EXAMPLE...~ ., ,,;-: ~..-";~
~ Triethyleneglycol divinyl ether commercially available j-, from;GAF,~under~he~,trade~designation,~,Rapicure~DVE-3.
5 Darocur 1173,~commercially~available.~from~.E-M .Company, Hawthornej"NY~ 3 r~ 3~ ...L ~ r~ r^~ qit.
, --, 9:5 31'T.~ i 3 .~
. Saturated~Reac,tant~ iwas,~preparedtby.~i~eacting the ....
diisoçyana~e commercially,aYailablq under~the,~radeoc, ,e-~desl.gnation pes~odur W.,iwith~,rthe,;~buty,l.~cellosolve~esiter o~"~ma~eic,;.an,hydride,which had:be.en1reacted witb~ or~
pr~pylenei~oxide.~ 9~ t ~ t'i'`'~ ? ~

' , . .
. .

.
:, . :~ , '. :
'', - ~

Wo90~1066~ PCT~US90/012~
2 o ~ ~ u~ J 3 Saturated Reactant 2 was prepared by reacking1,5 pentane diol and maleic anhydride ~ollowed by reacting butyl carbitol therewith.
Properties of Compositions L and M, and coatings produced therefrom, were tested and the results are..;
provided in TABLE VI. , . - :
, .
~A~LE Vl ~est Results y - Composition: ~ : L
Viscosity ~P) t,~30 3,50~ - -. ~EK Double Rubs ..
~ure ~ose: 0.5 J/sq~m ~Z~ 175 1 5 ` 1.0 J/sqcm ~hD0 181 dhesion to Polycarbonate substr~te ~ 0 0 fl~ixibility Stifl Stift ~ith 2 0 - - - sligh~ ..
i : . , ... , . : ~. ... : ... . . fleribility Fl~sk point ~? ~ ;" ~ 212-F ~ 163~F r . - i !'.' ~
Eye irrit~tion ~ ~ , non~ on , ; , jrritant irritant 2 5 S~in irrit~tion ~Pl) t.8 2.3 '~ J
~miId) ~mvderate) .The-procedures'.for~:determining viscosity, eye -- ' ,, .. , . ., ; ,.~ .~ ; .. ,, .. ~ .. . ... ... ... ... ... . .
~ irritationj;and skin,irr.itationj~pave~been ~rev,iou,sly.,~
dis~,u~s,s,ed,-,;,~ `' '3L~ ' - 'J
The MER Double Rubs test consists of curing a ,.
~ilm of the composition,at,~!a cure dose of either 0.5 ~ , , ,J/is~cm or l ~/sqcm.,~ ,The!su~fac~e of the film was then, ~, ; "
rubbed with a_clothAsoaked~in methyl~ethyl~ketone..(MEK). ' 35 ,~A section of~the sur~ace wa~s rubbed:in one dire~tio`n and : ~''"
~),r~ ~ tl.;.5 1~,~5 'r~3YU
: ~hen in the~opposite direction over the same,~sect,lo,n to constltute one double rub.i,~ The number providedrris~he ~?
number of th'e''double rub at~ which deterioration'of the ::
ilm was first noted., `'''` , ''' - , ,: : : ........................................ : , ... , ... . . .. , . , . .-, , , ,. . - . , .. .. -. ~ ... : . - - . -~ ,, .

WO90/10661 PCT/US90/012~ .

- 50 - ..

The adhesion t~ a polycarbonate substrate was determined by curing a film of the composition on the substrate at a cure dose of 1 J/sqcm. -A first adhesion test was conducted by making a : cross-hatching of lO parallel cuts, equally spaced apart' in the film down to the substrate~ Then,~
parallel cuts, also equally spaced apart, were made perpendicular to the first 10 cuts. The cut section was then covered with Scotch brand 610 tape commercially available from 3M Company that adhered to t~e surface.
Th tape was removed and the number of squares of film remaining adhered to the:substrate is the percent adhesion. None of the film adhered to the substrate.
A second adhesion.test was conducted but n~ cuts were made in t~e film. Again, none of the film remained adhered-to the substrate The adhesion and flexibil.ity of these compositions can be improved by reducing the cross-link density of the cured films. This reduction can be achieved by increasinglthe amount of single functionality diluent and?or dual functional monomér utilized.
., ~, , ; ;; ~
EXAMPLE 5: Paper Co tina Compositions : 25 ~ Compositions~u~Itàble;as~ipaper côating co'mp~o's"it'i'o''n's'wér'é prepa'r'ed`a'nd~~~es~ê'di r3'Thé3~fo^rs~sui'ations of these compositions are presented in TABLE~

.. t.l .. ~ TAE~LE Vi i ~ r ~,~Q~ o ,5 ,~ r 1 3 0 ~ 3 ~ ~* . 3 ~3 .~ " ~ l . P~pOr .Co~t~'n9 Co~pos ~ ~ ~ onS~ ~C~
. !~{.~.~ Con~osie~on.~t) 4n~ 3.{~ t.,~ ~f~ L .
ii fi R~ tr~nt~ L.r j.'J'3~ J'~ ';-L_ ~ ~
DVE~3 Z3.0 ~ 23.0 . 23.0 ~.
th~ t~ff~ S~ C) ~ ~13~ rQq~i3 ~phrJtrJ~nlt~trJr3s~;c~ T 7.0~ .. 7;0.uc~ ~7.0~ 9 ::P~henoth~ no ~ ? ~ ;r 0.1 , ~ o.~ 0.
b~vir~ pyrrol ~done S.O ~ .r ' -'' :: : ' ; . . " .,., ~. '. . . ,' ' i ,,,',', , .. , , , ' ' , ' ' ', ,,, .. , ' . ' ,,, ', . . .. .

DEA/~ 4 0 ~ O
~ 19085 --- 10 --- -DC 576 0.5 0.5 0-5 ` :
. .
The product of the reactLon of trishydroxyethyl ~ .
isocyanurate with the butyl carbitol ester of maleic anhydride. ::~
10 2 Triethyleneglycol divinyl ether commercially available from GAF under the trade designation Rapicure DVE-3. :.
3 Darocur 1173, commercially available from ~-M Company, Hawthorne, NY. :
~ Diethyl amine.
15 5 An acrylate-terminated mela~ine derivative commercially available from Monsanto under the trade designation Santolink AM 1908.
6 A sur~actant available from Dow Corning.

The Compositions N to P, and films produced :-: therefrom, were tested. The test results are provided in TA8LE VIII.

TAeLE Vl l l irst Results o~os i t i or~ o ViseQsity ~cP) l~0 2~û 210 Adhes~on to Pl~per Substr~te:
~10 100 100 100 ~10 trossh~tch 95 85 95 S~otch 100 95 100 ~ ~ HEI~ ~oublo Rubs :
:~ eur~ cio~ei 0.5 .l~qcm ; ~ - ~ 100 ~9 /s~ 0 107 85 ., The test procedure ~or determination of ~he iSCosity has been discussed~previously S ~ The adhesion to a paper substrate tests was similar to the previously~discussed adhesion~test. The WO90/1066] PCT/~Sso/0~2~
~ ~ ~ 7 ~

.- 52 -cure dose ~or these adhesion test was 0.5 J/s~c~
Furthe~more, a third adhesion test was conducted using scotch tape on an uncross-hatched film.
The MEX Double Ru~s test was conduc~ed on a film cured to an aluminum Q panel.
. . .
; :

. .

....
.. . .. : . . : . , , .. - .... .
., .

, .. , .. ~ .. .... _ . .. ... . . . ... ..

; . : - ; ' ,._ r ~ "~ .~
: ' "`ll~ ','~l,.i' ` .~.~ 1 ~1 r1~ri:rl~ h .t i ; .~
~æ .: ~'? .17!;,.~ 3~
, a ~;t .t~ trJ~
- ~ E , .t ~ ~ t ~. 3 ~ .. ~.. ... ~ .L q .t ~J ~ ) C. ~
, . ~ - f ~ r,J~ , ,f,~ ,r~ 3 ~ , J ~ ,i J
~ ri a~,'.? ' '3C'';~; ;.' '.~ 3.~ r- ;- r .:

Claims

WE CLAIM:
1. Free-radical curable compositions comprising a (meth)acrylate oligomer and at least one of a single functionality diluent, a mixuture of single functionality diluents, and a dual functional monomer, wherein the ratio of electron-rich double bonds to electron deficient double bonds in the compositions is in the range of about 5:1 to about 1:5.

2. The compositions in accordance with claim 1 wherein the ratio of electron-rich double bonds to electron deficient double bonds is about 2:1 to about 1:2.

3. The compositions in accordance with claim 1 wherein the ratio of electron-rich double bonds to electron deficient double bonds is about 1:1.

4. The compositions in accordance with claim 1 wherein the (meth)acrylate oligomer has a number average molecular weight of about 1,000 to about 15,000 daltons.

5. The compositions in accordance with claim 1 wherein the (meth)acrylate oligomer has a number average molecular weight of about 1,200 to about 6,000.

6. The compositions in accordance with claim 1 wherein the dual functional monomer has the Formula:
wherein Ra is selected from the group consisting of H, C1 to C10 alkyl or allyl groups, C5 to C10 aryl groups, metal ions, heteroatoms and combinations of carbon and heteroatoms; Rb is absent or selected from the group consisting of O, C(Ra)2, heteroatoms, or substituted heteroatoms; Rc is an aliphatic, branched or cyclic alkyl group or an arylalkyl group that contains 1 to about 10 carbon atoms, and can contain heteroatoms; and Y is selected from the group consisting of:

; ;; and wherein each Rd is independently selected from the group consisting of H, C1 to C4 alkyl groups, C5 to C10 aryl groups and electron withdrawing groups.
7. The compositions in accordance with claim 6 wherein Ra is a C1 to C4 alkyl group, Rb is O, Rc is a C2 to C8 alkyl group and each Rd is H.

8. A substrate coated with a composition of claim 1.

9. The coated substrate in accordance with claim 8 wherein the substrate is selected from the group of glass, paper, wood, rubber, metal, concrete, leather, fabric, and plastic substrates.
10. A substrate coated with a cured composition of claim 1.

11. The compositions in accordance with claim 1 that comprise the (meth)acrylate oligomer and the single functionality diluent.

12. The compositions in accordance with claim 1 that comprise the (meth)acrylate oligomer and the dual functional monomer.

13. The compositions in accordance with claim 1 that comprise the (meth)acrylate oligomer, the single functionality diluent and the dual functional monomer.

14. Free-radical curable compositions comprising a (meth)acrylate oligomer, at least one of a single functionality diluent, a mixture of single functionality diluents, and a dual functional monomer, wherein the single functionality diluent contains either electron-rich or electron deficient groups and the dual functional monomer contains electron-rich and electron deficient groups and the ratio of electron-rich double bonds to electron deficient double bonds in the compositions is in the range of about 5:1 to about 1:5, and at least one of an oligomer having an average of at least one electron-rich vinyl ether monomer or polymer having a vinyl group adjacent to an ether group per molecule of oligomer and a reactant having a saturated backbone and at least one electron deficient ethylenically unsaturated end group per molecule of reactant.

15. The compositions in accordance with claim 14 wherein the (meth)acrylate oligomer has a number average molecular weight of about 1,000 to about 15,000 daltons.

16. The compositions in accordance with claim 14 wherein the (meth)acrylate oligomer has a number average molecular weight of about 1,200 to about 6,000 daltons.

55a 17. The compositions in accordance with claim 14 wherein the oligomer having an average of at least one electron-rich ethylenically unsaturated group has an average of about 1 to about 10 electron-rich ethylenically unsaturated groups per molecule and the reactant has an average of about 1 to about 10 electron deficient ethylenically unsaturated end groups per molecule.

18. The compositions in accordance with claim 14 wherein the oligomer having an average of at least one electron-rich ethylenically unsaturated group has an average of about 2 to about 5 electron-rich ethylenically unsaturated groups per molecule and the reactant has an average of about 2 to about 5 electron deficient ethylenically unsaturated end groups per molecule.

19. The compositions in accordance with claim 14 wherein the ratio of electron-rich double bonds to electron deficient double bonds is about 2:1 to about 1:2.
20. The compositions in accordance with claim 14 wherein the ratio of electron-rich double bonds to electron deficient double bonds is about 1:1.

21. The compositions in accordance with claim 14 wherein the dual functional monomer has the Formula:

wherein Ra is selected from the group consisting of H, C1 to C10 alkyl or allyl groups, C5 to C10 aryl groups, metal ions, heteroatoms and combinations of carbon and heteroatoms; Rb is absent or selected from the group consisting of O, C(Ra)2, heteroatoms, or substituted heteroatoms; Rc is an aliphatic, branched or cyclic alkyl group or an arylalkyl group that contains 1 to about 10 carbon atoms, and can contain heteroatoms; and Y is selected from the group consisting of:

29. The compositions in accordance with claim 14 that comprise the (meth)acrylate oligomer; the dual functional monomer; and the oligomer having an average of at least one ethylenically unsaturated group.

30. The compositions in accordance with claim 14 that comprise the (meth)acrylate oligomer; the dual functional monomer; and the reactant.

31. The compositions in accordance with claim 14 that comprise the (meth)acrylate oligomer, the single functionality diluent, the dual functional monomer, and the oligomer having an average of at least one ethylenically unsaturated group.

32. The composition in accordance with claim 14 that comprise the (meth)acrylate oligomer, the single functionality diluent, the dual functional monomer, an the reactant.

33. The compositions in accordance with claim 14 that comprise the (meth)acrylate oligomer. the single functionality diluent, the oligomer having an average of at least one ethylenically unsaturated group, and the reactant.
34. The compositions in accordance with claim 14 that comprise the (meth)acrylate oligomer, the dual functional monomer, the oligomer having an average of at least one ethylenically unsaturated group, and the reactant.
35. The compositions in accordance with claim 14 that comprise the (meth)acrylate oligomer, the single ; ; ; and wherein each Rd is independently selected from the group consisting of H, C1 to C4 alkyl groups, C5 to C10 aryl groups and electron withdrawing groups.

22. The compositions in accordance with claim 21 wherein Ra is a C1 to C4 alkyl group, Rb is O, Rc is a C2 to C8 alkyl group and each Rd is H.

23. The compositions in accordance with claim 14 that further comprise a photoinitiator.
24. A substrate coated with a composition of claim 14.
25. The coated substrate in accordance with claim 24 wherein the substrate is selected from the group of glass, paper, wood, rubber, metal, concrete, leather, fabric and plastic substrates.
26. A substrate coated with a cured composition of claim 14.

27. The compositions in accordance with claim 14 that comprise the (meth)acrylate oligomer; the single functionality diluent; and the oligomer having an average of at least one ethylenically unsaturated group.

28. The compositions in accordance with claim 14 that comprise the (meth)acrylate oligomer; the single functionality diluent; and the reactant.

functionality diluent, the dual functional monomer, the oligomer having an average of at least one ethylenically unsaturated group, and the reactant.

36. The compositions in accordance with claim 14 wherein the electron-rich ethylenically unsaturated group is a vinyl ether group.

37. The compositions in accordance with claim 14 wherein the electron deficient ethylenically unsaturated group is a dicarboxylate group.