r.",,.*

PleParation oi new Polyorganosiloxane acrylate and th€ PIoPe ies
of Uv-cured acrylate compositions containing it
sunnary
A nc'!
pliyoĘ 1ośilonn. lrv
la
te
(
llosA
) has
bee| obtained
.y.lohcxvlinD. wtlr m.thyl .nd sroups (McAPs) akl h.xan.dn,l diacrv
r.",,.* '. ,l t.tu' .. "r.' - .;,
h alyyli.Sroups ofnDD^ pOS^ hasbccn
ofN-H Sroups ofMCAMPSw
lale
l .poxv_dia.q,lat! resn'' k
has
loty{dyli. sys.ń
blel
(HDD^ + bu\1a.ry.
łihd d'at .vcn small PosA .onlcnt
(] ]]$l li).a$!ś li8|ifi.atrl d'anlles ofŚlrlac ProPc ics of.urcd.oat
Egs NaltlY .ontict
ind rśhy*crcsjs i]trcłsc' 8lsŚ dc.tĘses jl.
'Ęh
Iijn]hirtlncs docs notdFngc' UsjnAxDsDtthod ił !vłŚ show.d thł !os^
h
td on thc str
Kcy wolds| polyorganosilonne lavlak, cPoxy aÓylic s}.lcms, modih.i.
tiotr,Uv{llinA,fffa.!ptop.łi!ś,\'!hability'
sclcdivc ly .on.cn bi
Th. Uv.umble syslcDt IiId jmPoń tapPli!żtio|!
i,r mafr i'du*rial liclds roi thcp
itcns in rom orfilms, chmi s,.o i',8s, pigDr.r6,
adhcsivś .r Pri't d .irĆuih, altl i'r
ty. Thef lse lcsulb floń th.n u
Iollows h !3 h .u rc sFccd, cncĘ]' .oNcn'a tion solvcn L
'
łlcc fornn]lit]oI and c\.!llcnt Ph],si.al PropUti.s
l)-71
Thc uv-curabrc
s$.nE
gcnualr
ajo' .onrPoneŃ: rca.ti|c poly'nclizable oligom.A,
h l5,el ro obbnr drc
sulfa.c (Btirgs drowin8 lirticuLłr Prc},crhs,lhc us.
ot monomcs an,r oliaomcE coirhnlirg sili.oncs or
si]ox r.s ń vcr], aitacŃt, owing io thc P.n'liit lnam.
brktiś3Ńen b]r th! preseM.of silicDtratom lr0,]rl. Itś
Per publiśhed n11ł,lńe!v"
n2l A
sj]i.on. cońPounds PrcPżĘtjon
oli
od
]s thc
iLi|c
yl funchonil
rcichon of h-V'
to producc
adyliĆ fundi]nal silno|e <,ńPound, With
ń.
Hcl.s i by'
prcdudlr0, lrl Anothcrpro.csolphotopolyncLizabl.
poryorsarosiloxin.s pEpaniion by Lca.rion or hy
drosilonres w h icnliics iir rhcprscn.coraphtnN)
.iial]'* hłs bcc|r ł]sodcs bld ll]]'
h or prcs.r t rm* a ncw pol)'orga nosj roxa m adv
lai. Js synlhcsized by Mi.hłol a
Dkoduccd into ePoxy dj..lvlii. (B|DA) 5],ś.ń5 it
3.ciusc no . ilvśN.s uscn
and noby Pnrducb Wc'c
thcsvnth$śind puriricatiotr r!c!csinplc. Unu$ml
$rrac.prop$hcsorihc
'omcd,
FÓlymdi( nLms obiin]cd l i]? UvcuriĘ hch|iquclfse
Thc
b.s..ompon!!k
oI
IÓrńlla
ol shc]l cpoiy rg\jń5 E 327 Wih a
duct ot]tained ńdń L 327 !!ós dc
avcla8cmÓkĆula!wci8htwis.ssuncdlo],c.quil!)
Hetanediol dnovl.ic (HDDA) łnd buil]
(BA) as adiYc dih'enb wer. pur
i yliI!
Mcthyl.nded ĆyĆlohrxylańi'l. fl]dj1i!d Polvor
gżnosilox.ne (McAPs' M , = 3r 02' Mi = 379r) l'as 5!F
Plicd by Hcn8zho! DalU lńd!*ł Ltd
2-hydroxt 2,2 d,rdhyl'r Fhc
(Darc.ur 1173, Ciba'Ccisr, switz. and) wis uscd is
Fhobinitńlor lor Uvculilu'
AIr rhe narmiib nr ihis udv . nsed rs re.crv.ir
v houtrunhcr Pu ri. ion
Th. polyorEano5iloxań! i.lvlab (PosA) Was PIc'
ParĆd bv ńŃln8 JlDD^ v h \4c^],s i'] ProPo ion 2 ]
vol/vorGcc Equihof 0)l
,'.,
*,
,,.1
. ,,! .
,
1oln.d in i.tahvdtolurłn solft
talt-vńgd 1o]Aólumtru'dsthc.p."i l
o-u-l l
Th..ontaĆt Źnglc mcłsurcmcnb wcr. pcllo'nd
trsi'u Ema nśrumc|t The meas
i'' ail ar iljon tcmP.rłturc fol clli samFlc l!a* 5i\
ńeisurcmcnb weio Pctf.!ńcd, Fl
dnhucd wai.r il1 dirf.renrprtu ol ihc smptc surfi.c
Th€ di'I!fun.cs jn ivcraAc valucs wclc m morc lhan
2'' 1or
rh.'dlan.iIgłn31ca|d
the
Eedi'l3
ń'.c
of
inaryzed lstus x !,), .n
Eosco$] (xDs, orntrd Is]+300) Thc sŻc ot
t,rDr was
3l.'
U\:.uIcJ
i smph
Hłntn.$ ofUv curcd film wis clah'iicd NijrN aEY
c Tianjb IŃrumdt
comPafy Thc films w.r! appl
(95x3Bx5 ńm)byacoatfi wirha 100!m
s.P
r+\ ,;.,,,L\
25'cU'nga surfa.! fusi*i]rc t$t.rot tyPc Zc3ó lrorn
shan8hailNtuńcntco Thc t.st \oltigcMs ]000v
,r'
ThcsP.Ćllar glosof
tlrlrccdtli
ingshe 60iFFio
shc ln rumetrLśLTD T
tlt glis(rcIla.tjVcindc\ ł!= ] 5ó7)Msdclimdas]00.
fus froń
70'c n'
24 h, wfth
mcchaIi.i]łiiiij]8
Thc l]quid Pro.
IJ N\,lRsp.Ćhn of Pos^ is s]rownin Fig. ] Thcn
łIcih.sigmls l.lit.d to aayli. lroups {5'73ł r0 PPm)
sholn i,r rhe\Pc.rum orihc prodr
pdaks or
by
BEDA (6a wL,D'HDD^ c0 nł''
" ), lros^ (various ltnmnbłtiońs) an.l Phoioiniińtor
l] wt ,]lJ in thc liqlid loinuhtfuńs uscd ln thc rcpo &1
rvs..o
cd onro a gla$ plaie wr
5uPFo 'Thc| th. sanPl.s vs. o'cd usi'rg łhc Ulta
ljoht High PresŚllc !'c!.uł' LJmP 0 k$' 31] W/cń'
Huiyixfu [llcbical Llght souru T.durolÓ8y Devek,r
mcni Lrd, Brijins)
vsii€ated waś ]25 Frc.lilmswcr.obbimd by Pecling
r!
NMR amlysis Ni" Fc.romcd at a Bruklr a00
Nhnn.nt !Śitu cDcl] is solvcni
FTt( łnalvsiŚ \'as Psfum.d usi|E Rrx 65A FTjR
\'tsŻ
sp.drophotonclcr (^nłhct, UsA)
Molrula! wcrshi dlshr,uiiotr (,L1wD) of PosA vis
measllĆd bv gc] Pcmc ion dłomak'graPhr' (cPc)
icyli.
sroups i', thc
pod!
06ł0o ) Thcnunbo
,.rłgcmo
a!d w.ight łvcrag. mo]ĆĆ|lil
') nEsur.d bv crc !!ci! 3łl7 rJ
PosA
FTIRsp{tum
wejghł (
LccuLiI
wcighł (Mi ) or
,lł26, Hp.chvdl
s
the
MWD Vallc t!Ź5 r 3]
wer? performcd on lhc .ur.d ńlńs Peeled off from
gla$
rsżsl'bcn.dńc
the bsb
P
GIaŚ) sid?'
Tnc oniact anglc of a ńiafute .ÓmP$ed of Pure ePoxy-
i(ylic min
(BEDA), HDDA and
aboui40"onilE gl.ssidcand42oon thcatrsidc when
PosA wa added to $is.ulłblc fomulahon' and ihc
ńixfur. Ms pla.ed on lhe same sub nte (j. 8las) ihe
wdtibil ych rgcd, as evidenced in Fis.2 by the.onrad
an31e lesult' oblańcd wth n'atc. Th. dła d.arly
Ił 3 xDs rs!łs oi't
al
PasAtonc"tdion onnrrdr
rcirs
atbd
r.0wr
'r
ThnPhcooneńoni5 tyPidl
('a
hyd!,Phobic
n,id
lloś
'7A
ol
UV{!{/ Iil
ExccPt for the direĆt mrasuremenb ol conbct
hcr iŃomation.Ón..rnińg
lhe
lained by conh.t ań8l. hyslcl$is, !:
Iu
lween łdvancin8 a.d
Pe'ed
sholled th losA w.s .frc.fi\c o
Uv culcd {j|!ś, whjlc thc 3la5s 5
PoPcrhcs łs ol lhc purc rcsin lt ncłns ihłt ihc lcs
poldiirsideisen chPd wth PosA
]]le.dvan.ing.ontad aĘl€s of Uv rcd lilms in_
.reased lvilh ińdssing of PosA .
Ó1 PosA shows a "PlatełL va]L.'' (]0]'') th l'aŚ
a''
{or
ńajo
t-v
aĘl.'
rc€dln8ing
of thc
miiciik, PinicuLłrly thos
.onhinin8 both hydroPhobiĆ and hydroPhili. 8iouPs ai
the surfa.. For tho Pur. r$lń śvallc as 25'aid 3d'
, rcsP..tivlly on thc
glaŚsidi in rh.Prcs.n(oiPolyolgan6ikxahełdt]ai!,
thc.onhd anglc hyslmsś dd |ot
the ail śidoas Fig' 4 shoq lh4c }'
kr6is. k was ako depend?rt on P
111e rcsuks
can be explain.d by the racr ilmt hydropho.
bic mononEr lÓrms
ł hłdÓ8rml
Thc sclcdivc modiri.ation of filn surfa.c was on'
limcd by xDs r6ulb. Thcy allowcd rhc cstimarion ol
ihe rn.enbation or si elem.nt in th
UV{[cd
As slmwn m FĘ 3
'iln
surfacc rmPosiiion
between the air sid€ łnd lhe 8laŚ
sidc wm notcd. Nam.ly, thc absorpiion pe* or si elemeni on the glaŚ side r'as lety ]ow on tlP Óntary an
evident absorPtiÓn Feak ol si
s
gl.n
IrosA <,n.cnrahon in uv olabl
ofS, clcncnt on thc an sdc ircrcrfd. So wctabilily ls
dearry coirelatud b si (i.. PosA)
FiŚ'
4 rffnt
hwkl{iŚ tl
o|
thć
PosA aldnnń;on d| nI
żi, sią. rł Uv..llll
ti't\
ańrl
h.r.rÓgoneiry inĆrcased ai fiEt, tl'€n, as previously, kePt
a coĄśhnt valle o wt' 'r' o1 ?06A) indj.łii$ lhe foma_
hon ofin cqu $riuń surIaĆe layĆr
Hadncs was onc of lhc imPo an'Pop..ńelofUv
.!ied films lor nany apPlicalions' łnd ii was r.lihd io
thcqoŚslinkiń8fu8vdkdemii-va
icy]i. gfuuPs iI th. ńole.!lal ch
Table 1 shÓUŚ th. sJrlace rĆŚńta
the air side of rhc LrVrled filń is en
ri.l,ed with PosA and ros^ n b.tu
tl'an thc ot)rs r.rylic omPoncnś, thc vłlLlśoI surli.c
rc'śin.c of rmPositions .ÓnhniĘ FosA wcn highcl
thinth one of Plle adyliĆ filń
lilłrs' Be.aLse
filldry'jlms.rc
ako sńParcd ń Tablc 1' fiis Pbpcny ol Purc aol]lr
Iilń was ibout ]17'6, whil€ PosAintodudion siBnil
a new PosA, which .an b. i smd idd ivc
,!..,
MCAI'S with
nr krdars
dffd n'fun
uvrrtu littF
.I Poś,{
aJ
a
prolo|s.ho| of thc Frdńbo| iiń.
in hirdncss to som. linit bc.rus
.auses higher conyeNion of acrylic Sroups. Unfo unatell,, nrrdn$s d Lw dr.d riln w
ińal śa3ąśo1ifadia
hon' with Prolongłtion of trk dń ńon iim.' hird ńcs of
rrL\eprueneor effsti!.phobiniiiaroriheaolir.
ic5i(s {dc rapidly dGdink d am
Pol)frÓdatiÓn ń€hłńiln oui rs
oI
uv
Michaela
spc.hosopi. mlsis .ofrirn.d
ł0]
=t
Fł 5 qr|dl
HDDA
for
hatdn6s .an bc dPlaincd
fusP
b},
solubiliĘ of Po6A in pure
ofrjv
nbl.liqJ lohn
en.y
]ition dNcmcd, whrh lc'ds b thc lows cIńc]cn.y oa Uv
itridńtion. At tjr $mc hmc' only a ltlc anount of PosA
miy Lt nrfudu..d iŃo orcd fiLn' so th. chłnfc o( thc
ooślinkin8 deNilt of łh. ńLns was liltlq whió lcd lo thc
rcŚjn Thai n' rhc
d
grcups of McAPs lith rhe aÓyliĆ siouPś .l IIDDA
Uv .urahlc Ęsin ńlńs wc'c Prcparcd by urtoducho| of
l,06A inro thc fomut.hon. xDs D
that Pos^ cnńchcd ihe łir side of
rhcn surfaes show sha9ly r lincd hydiophobi. dm
radcr (i'r spit€ .I the Pl*en@ of ńań]r Polal ol I grÓLFs
in d'e Polymcic nctuork) ind i h
ra.t angrc Thc hlglrGr conhd in8lc of uv-amd films
włh Nato rach€d 1010. Uv{nrcd fitms with Pos^
showhishcr$trraccr6ishrcc d rorrcrspcd,r 31cs,
l
Blrak L. / ce,'
2'
cÓjdĆnR:/
{.
Lrvorchak N! J, nrb.ri
Trł Novcnb.
orJ t.,!
1997,69,No 37],33
3. YtQ',NauFąns.,sanhrEl'll,Żha s. l ĄPl lr
B
Dekel ch., MÓUsa K':
H
/.
I
/ crrr
rdr
o{,
Irnouc,sordatA,crvczz,n J: I c,D,
rdob
roneui
^.,
c, roslli M:
/. L{fr,,
BołliĘ K'' Adańs J'sbucksi /
cI l'
^PPl
Błtc! R
,ąn
J.,
rer2, 61,
cr,
rd
ree5,
fo,r s.i
T.tl
]996,
9ci 1997,66,1997'
Dłvidson R s ' El1js R J,
w
krjEon
s