ho\cBoL|L

ho\cBoL|L ),vlN''
Ą
( ''\Ż'') \'|]1 1llAN. '1Aolll:1
Pleparation and proPe ies of try-curabl€
containing silicon
acrylate compositions
_ somc dl and tjacrylates wrm Ślbie.td to Mlchacl iddihon
(cAMs)'
tea.tion wi$ N..yclohcxyĘańinoproPylmdhyldimcthoxvsilmc
FTjR mothod has b.en !s.d to follow lhe co!Ę. of ihc reł.tion oI -NH 8roUP
in cAlvls with doublc bond ń
ioylab Po*jciclion mixiures obbind
uldcfuĆńt tjvĆutilB in ihe PrsPn.c of a Photoiniiiatol (2 hydloxy 2'2 di
ńcthyl ] Phrny1ethane.1_one' hidc nańc ''Daro.ul1173 ) and lormed thin
ńlń5 on rhÓ 8laŚ or Plaśi. subś'at!Dcpcndcl.e of the therńa l shbilit-v ol
ored naleliłl on ib ilritial comPosition wis chancbrjzed usi.g tn.rmo
iernimd thc efteds of nol rcaĆted a.rylic
in
readion
thc
Po$
8IouPś Pi
kroslink ilrg dcgrcc) oi hard ne$ a nd britl€neŚ of rh. odlngs .urcd silrc|
ons Ptekn.c in thc .om'ositions ińProves lhen ch$rit-v but dctc ontcs
summffy
di' rd tiaavlaes, N .ydohe!'l r
phob.ured ÓatingŚ' haidn.s,brild!
iion,
'aminoProPylndhyldimelhoxysilane'
sńrc jb cońńd.ial intmdudion ovcr ]0 ycJG ago,
ndńhononnghas*.łdy8rownindcmandandusgc
and has bc.om. onc of thc fasbr dĆv.loping .oaiin8s
te.hnol%ies in thc wo.ld ll,2] RadiańondlingGnbe
peńormed by eledon bcam (Ell) and ulbaviolei (UV)
c ol lhc
ńo
cfficicńt
ńcthods fot PloduĆin8 4łtriinstanily highly sos'
linkcd Polync! m;tdalŚ D!Ć to ih Uni9ue adMnhges
leni physi.al plopc ics, this i..hnology has fo!ńd
a laĘe numbel of indusbial aPPl
drJriĘ vaniŚhes and inks' opticil fibcn' clc.tonic .oń
Ponrnh and prińtiĘ Plats, and rc
t3
7t
n, pnrdle rhe slrfa.e.oati$s showing pa i.ulir
PÓp.łies, anapproprialeoli8ono functionaliŻcd wilh
ith a polyrundional
to
'aylat
91. Bc.ausc
redledE vtÓlityoaal oli8on€r is uscd l3'
of thc pcolnr charactuii*ic\ 8iv.n b)' sili
trs. ot<\. &ijlts m0N0
".i"-p ;.
h+totr
Ńludc
jńPad
rłĘc
a widc workin8 iempcmtu.c
lncłs.d
sbcngth, 8ood releas. Pbpc ics, hydroPhobi
.ily' 3ood themal ónd ĆhlniĆal sbbilit' (rełihc resisin.Ómp.rlibilitv with
majolity of dganic ońpounds
'n
gr th. siloxanc se3nenb iend
to
mrSrar
o
ih.
in
poLy.
posiblc biońateriak be.alse tlEy arc physiologically
s.Velal Ę.thods of thc PrcPi'itjo
iń3 śjl!Ąa.c monomos d oli8olr
Silancs and siloxmcs mo,lilicd b
halc ben syn8rsized ria rhp hydrGilvlihon oi vnryl
cPoxy rcsim usinE various si_H ń
siloxinG and then.uiinB with.ationic photo,n,hitors
neihod oI th. a.!rl lumiionłl sili.onc .om_
116l
^ preparins n a rcadnn.I hydro{,alkylaq,1itc
pounds
wiih chlorosilan. t. prod!.e the advl rL rtional siloxłne ÓmPo$d with llcl a5 a bl p
Óń fun in thc Prcscncc of in a.
ańin. Whń produr iminc hydro
tn undmpańalla um b rcmov. Hcl t]y Produd'as
ii śformcd
9l Another prcccs oI photoPolymcri
zible o€anopolysilox
Es PrrFring by Paction of hy_
'3,
drosiloxanes with allyl acybfoŚ ii tll. pr6cn.c of a
p]atinum .atal'ś has becn d.!ĆribeJ They are mixed
irh Lretlane a-yla.eand.poxy adylaE b be applicd
tÓ thl oPhcal fibcĘ lr7, ]3l
trgJ oP],l\ s oęnci.ry łc hi\żls
ho| ofh)drclv icrhlnłcd d ńGJinPoh'.\ane' \oth
aninvrłerrn.rorBtilto v!h etb
lir
Th.nllurcwa\hcit.duphTol.iidmi'ntahcd
12 holF Tne cqlł'on ]] j
ret
.ouEe on ih. example of DPGDA'llu
+ cAMs Śyslem
thu p:Pcr to vbhnl ihc lońps lon oiidvlitś
!o|b n n3 \ ]!on. ompÓund5, N.rcl"h-'l
l"EPiBlion Órlheo ihBrmPo'tion5 ind lh.n
friPylm.ńJ ]djmdho\ t j]ane (cAlłil *a ,i ""-',*
i.-,+
r
.hac].t],Pe ad.lition read]on was applicd Bc.ausĆ
no
uscd ind no b\ pro
.rnrsL ..ic
truhtcs !ÓnbjnlnAJljconc ob
Pure.lhJn whcn ol}s dhńd. w
Pholop', \nenŻJt on nlsynlhŚLzc
thc
PhotÓ
niIDto
P.fud oN:
vłs di\\ohed
..n(nkitonĆqułł"t .rt.l'
'_
l ins $!rc .iJl€n i nio :
!|iŚ Ph
h i 5rc.jJlfrJńcJśżśupp.łTn- l]"';-"..;..'
'
(ccTŹble Żlu'lns the Ultill'lctHlsh
fured
?ft$Dn,
M.i.urv L:mp r rw ao w/.. H_v.,; Ehd.-r
L'3htsour.TerhnolÓsl
M.lh
d d
s Óf Pro
oslcropmc L]L] ts.i|n!l
du.b .haridelization
Elyo L]E.r] łc {DlcDA]' ncoÓut\l
r,tnE doD,o!mih,
NPCDAl' PmP.\) ed mo; til
F\ 05^ffrRŚ";
glvco] d'ł.rvih lPo NPCDA]
rophobhdł (Ą D d U9Ąl' ĄbsolpholB duc b th.
la'c (rET^l t"mcth'ro|ph'pr'; h*ńl"t lrum.il
ilrJ !!ń!bhbd'J\JPpar l7Żq ri'', brrJld slo
Jho'lJlcJ irjnelhy.lplopżn" ti"-,r.r,ro]
.ń U\ ng 3l0 (nl Lnul o ohne dciorńł'on .
TMI-T^lrłbLhmd'idn.rylitcIBDDA)ohlhalLe
-'
ho|) i b'tsc]jhcmcthod, ńcspE
tr prÓPtlcnc q]y.ol d]id!lil.
LfDTlco^)' dh;*h'd unn8 lhc.łrbony pe| i|
l7i9 cm ó in fbfui
b spltnold ł9 łelEoBPDĄl
l,Ó he\incdLol'lD.rv_
ind nsłUmcn}rclordl g Thu\ th" .h. th.
lpocTA) \!re \upprild b\ T,rnr"" p"tu łd. T"-.
pe} s0ch ]d r72q!ń r !fu dctrmfcdh-rń''
"- -.
";
p\ lnc gl\.ol !laq :tc iTncDĄ),
Drc,rfrl,'d
dnqhbłmDĄ) djE\ord nł"oh
Locoł'ia
u
3lvfu] dF(ylilclTcDĄl $rre 5uDp][.l bv BA
F*'.
D'pIopY cn.
śkol !lD.Iy]ik
".
Na\dohe'vl_y'rń nopmp\ńclhVldLndh,,..-b-
r'",,r."
o"r, ,ia
*-
T]ic Pł.]hŹrdj Asd lhc0rc
: hvdn'' \ 2 2.il mcthyl |.phcny lthinc l.onś
Dy driwlns th. loilcd lubsfłc u
ru:rc.r rr 7) dcti\scd bl
li:ngeibc ni mh flircfdeLl hiLl, r-"1, a,-r .
w} uęJ is p vio nit olivrW.unnc
q;"--r"
All tlt mihniL r lh^ trd! ire ;cd.L reł.d Mdj es sł.]reld filńh ińłEt tl" nl.
łnd pd\hld awiJ
"t"
-,,l tt" - "r"",
l'hd' th. fil Nó dóetl !'Ń El-a.a
l'"'jl."*
ipP|doj 3l.$ Plilśbyi oibl {t]l abo!ń
synthesis of ihe .onP osiriÓns
lh !l
s
Compu'r,{s r,m i(yLi}e. rr
łc Pl.FTe.l
by
ń 'Ln8 ld.]l."d*Ąl"i"łl'c^MŚ
/o@
Ęoiio
ed.ubśt eand:\
5
nrsiurc.t bv
Ąń lrb tŹry
(ż|! nm
0,._!,,. .8. dr. o_t,,k:.H.
rBf
] |ro
d.b!i' n.iibl!)
to 5 (large
The de.ońPositi{,n
i
Bic of l0
hcahng
amoni
of
temp.nfuP
r/ńiń
d€bń,
very btitd.)
o
hłnal analyzer
and a le$ rangc of 20
at
700'c undcr a n,togcn purss
Asc
ofsili.on conbrjns plodu.b synthcsizcd
by Michael.type a'ld ion rc.dion wcre taNpareni li
1
cs
Typi.al etample of the .hłnEes .Ppeatin8 i'r lR spe.
dion is Bilon i'1Fig.
for DPGDA
PPsene of an .ffc.ńvc photoinilia
ruP or rh*e nabul' whi.h miy
tivity js that biacrylates and dia.iylahs with hiSh part oI
dolble bonds łre Us€d' As it Ćan bĆ se.n łoń Fis 2, thc
uled lilń5lnacłscd
cxEŃjYcly' io 33 o/. for .!Ęd PUrc TMPTA iilnr,13 ,]l' fol
.ucdTMPTA+CAMS(3t)film,43 /, for nedTj\'IPTA
+ cAMs (2]]) ńtm, 50 '11 lol nmd TIIPrAłcAIYls o l )
film afi.r inś5 s of Eidiłiio|' rPsPelively r{]Ftr dr.
iime was growiĘ up to 40 s, there weto 30,12' ]5, ańd
mainins in rhc culcd
Iilms in ihe rour oses, Epshvdy complctc siiurariof
ourb or rhc adyric
may
be
hiddcn
nBide the oGslhrked nefuotlś
3louPs
liÓnal polvńc' mibix
/cAMs syś.n'
-Y-
.::
'--1=--',-/.-,'-'
,.-
'r'*'Ą
-'ż
Fi! 1'
ł nailm ln!! hIa łaI lio rf llx rery.rs
rn@ńbn a| uBd! lkr D| TMPT^ (.), TMPTA +
Efsed
l lh
cAMs o:1,f
ris. 1. rrrR sp(hR aJ DPoDA
tudn , n"t DPcDA + cAMs
FIIR spNba of such a syśem t nd to bc chdńEcd
Nh.n thc mixhtr. was mai' ain.d ar 70 tt Thcrc irc
c\id ent absorp tion pea ks oI N l-l gmp of cAMs łt 3300
dcocas.d wilh mlcisilg tlt readion tińe
as -NH 8rt,uF of cAils vas rei.iil€ wilh the aĆlyli.
grcJP of DI.CDA FEduJ]y Thc rcid ol o śynthe.ś
}Jd ben r n shcdłhcnth!it'sorp
l'ad ĆonPlebl)'dE'Ppc''cd ilto 12ll'
The silnon-.ont i n]q acrylai€s ł! rapidl]r dGs
lnrkcd by frcc{adi.al polymeri2lion ń(haiisń in thc
at 3300 Ćm
L
foned l21l'
), TMP'|^ +
cAMs ł2:1,^) rhl TMPTA
+
Tl'sc rcsulb would indi.at-A rhe sll(onconhinurS
adylahs rorm hckjr. lilms it sh
cir dui, wirhh ihc
lb.fu.c of dre pdlynglzu8 s]h.on{oniaiŃ1g ady
la16, lhcr. łte sDm. doUble bonds !c
cAMs ]d .onforńahonal nobilily is 8lc ci urer.by
arlowing dr. radicar ar the 8rowtuF .hair ro .xpldc
a greater vÓltńc than is lhe case oI TM?TA cÓNe
quentltala.lerpropo ionoracrylnErolpsisuscdup.
PTA lcd io so much
shnnkaSe rhat rhc tilns cxhibit.d severe reri.ulatioi
mPosible b subńit
stand d physi.łl testins PntgdJld
The r$ulb of Tca anaryscs or u
thcm ło ih.
exańPlc
. shown ilr Fig 3
dP.omp$irion Ó
mir*ably deocakd with indease
iion in adylahŚ The renperature o
TMPTA
oIśłtof thmmal
tiÓn beginnin8 oI
Lrvtuftd TMFIA ńIń5
js 2011
'c,
tŁ
.:
rl
_{
F|'.3' Thl
cAus
cŁus
ntd
TMPTA la), TMPTA
'pdłi'n
+ CAMS l2:1,.) tnd TMPTA
111,8), TMPI:A
ł3|1,.)) ann$ tn Ż 4a Ś
Óf
+
":
!
+
how.vei the Uvtlred TMF|A + cAMs ol) filń sbt
b de.ońPos. ł l3l.4 \: Tnc lBllts ń'y bc inhĘ.chd
ihn way: C'C and C-o bonds (342 and 343 kllmol rcsPmhvely) are .oBiderably śónB€r lhan c N ańd si c
bonds (293 łnd 3]3 k'/hol tesptliv.ł) in silicrń$n
tajniĘ aĆryIats l9l' c N and sic bond6 sta* to dfun
PN€
at
lrwł t.mPerabre
thań c_c and
l
;
c.o
*
:l
1ł .:
ElI
1l
lt
t!
łI Il
Tablc I prsenh th. resrlrs oI t
analyscs of thre seleded types
ol.ońpBitions, namcly
onc błsed on łiaĆlylat. (TMITA) and fuo bóed on
dircrylat€ NPGDA (!oo PtPoxyklcd _ NPGDA or
ProPoxylatd - Po'NIrcDA)' cAMs ptAenĆe iń the
.ońPGihon deteriorłb $€rhal shbility of rhe sysEń
(Jp to 20 7J o1 diżoy'
Beglńnin8 of the
'l€
r
mFositioń
lat bas.d compNihon is plaĆed i
rrn8e llran of tiadylate bascd onc ProPoxylłtion of
dia..yIate siEnifi.ańtly shift this Iangc to hiEhcr ien_
cha.ad.ristiĆ o1fulctional Pmpohc o' thc rfiIEs
oblłined frrm various Pośjea.iion mixiuH is 8ivPn in
Table 2 Th€se mai€ ils rc'c .olcd onb a 8laŚ plate ot
a PlasiĆ Pić. and $€n gxPosed to UV ladDhon The
fi lńs Iorned w€re subniiled b Ph}.ica l tcshn8 Thc rc
sulb of tcdins or pen.il tardnes and briitlencs arc .ol.
lRbd in Table 2 In our dse rhey ar. only a gunt. b ilp
propdries or rilns bccausc !r is d
1Órń Óae.ig]r6 of thP filns' Th. Pcncil ha.dns is one
of lhe ińpońant PtÓpełies of Uv rued filTs ind it is
rclarcd to rhc s6linkinS neeork deffiry and the convcrsion of a.rylic 8louPs in the no
pcncil hadncs ol our filńśd.P.nd
ll cn b. sccn thł ifadńtion tińe plÓlon8atiÓn usua]ly
leads b rn ,na..sc in the p.ncil ha
1i3hi eneĘI .iusG hi!he. onversjon ol aclylic 3lo!Ps.
Two imPo ant functionłl lc'folc
Mn.ł peń.il hardnes d briitlcnc$, dcPcnd on thc
Ćd^tiĘ doslinkin8 de8ree Platcd io lhcpańofnon_rc'
acbd adyln gmlPs i[ ihe ÓmPosition. Thehighcr ihis
part (= increisc in .nu\linkinE d.8re) rho bigBer values
of pcn.il hirdnss and britrlcneŚŚ
when ińe .omPosiiions cilhcr mad
nenb but wiih hiBhcl ł.rylatcs' .on..|ba6ons GańPlB
2baM 2c) or or ite sinc molarritio ol thc omponcnb
butbasedondi
ortia
ylahsk.{ sampbsr d5b).re
leadslolhłma]sbbilitydeteliożń
the .ołinEs obtained wcrc atbibuicd
Pt*en.e in thc lIoducb investi€at.d.
1.
,.
LuFan
B'] ].
RŻmld c':
ĆeJ T..[
D9,vł'D.
/' c'iJ n.[ Dr7,y1,s.
3. Yu4.,Na!ffi n s.,sankrf
4
to sih.on łtonr
zhu s. I
I. n,
MihadJ.,Dvorcha*B,Ribsi
^ppt.
h
H :/
5' chn hn D'' }3ulil Il; l' c.il ł.'
6' Pnou c, so]dłi A ' cłvezzł']: ].
7'
BongiÓvanni R', Mżluclll G, M
hiol! A ' Tonelli c, ToRni M; / /},p,' lo.,!łi' s.i
e. B
J., Davidsn R s., Ellis R t, wilkinsn s
PoĘ ł 19l)2, Ś,3ca7
r0. ^
wus B,MarkD.s.:/ cdr.rr,, rees,s8z53
rr KaIąB.,Jay^'su$nncs:/ ctr/ ł 1996,354,
bn R.
12BIueA'WiMd','ł'łcńr9{,Ż,3{'
r3. chbng w Y, shu W l'i
Mił
^'ś
Mi.hael_lype adLlitio|
was
oricd
out in thc
'cłclionThe readiviiy o1-NH
abs.Me of sohent and catłlysl
8!o!Ps of cAMs with th! adyliĆ EmlFs o1diadylahs
Eiaffylats rclld b! ańalyzed by dt .hańge .f the
'nd
.hrriJqEr c ibsorpron p.rl rh
rlnĆtional prÓpe ies of the oretl films nanely pen.
e changed by iradia
Yłry]nA.]hc
a
ho| tin.
curing dt
YcEion incrcascd w h thc cAMs a
als .łn be dmd ai sho timc lo glvc (oPpo9tcly to
affylates łhemselves, wiihoui cAMs) hid' flcxiblc
ionw.snotł(ompł
11 Ming l' c'' Ficd D o, Elt R. P, PhilbeńE'R.,Anb
nio c, valeri. B.i I cd,.7k, reez 370,13
r5. Dtksc: PrcJ. ?ory .s.r r9t6,!1,393
16 clntllo J \r,, Bo A, Kjm w 6: Po,uł 5.. .łJ A
'
]7 shenc X,Qux N,shcw N,Yux M,suno'Ż,
chen H N / Ćdl' Tdi r'99, 3'1, 93
]3 sun Y P.' zh€ry c R;ł.cłxiL!
"
YŹhaya
2r
shi
/'
lPPl
sl
c
o, Brisdon B. j., ]VlŹxw.ll M'' E|lhnd R
5.r r00l,3ż,30s
'o,
F'' Ranby B': /
/}rj. ldŁl]. s.i 1994
',
rr29'