Copolymerization of dodecyl methacrylate with oxyethylene glycol

ELżBETAsocH^,!l{A ANDRZE]EWSKA], MACIE'Ar,jDRŻE'EwsKI,
MARrIJszB RocAcKLKATARZ'/NABlELlcKĄ-DAsŻKIEl{lcz
wydŻial TehnÓl%ii cheni.znej
Pl M sklodowskje] c!li. 2, ó0 965 Poznali Poland
Copolymerization of dodecyl methacrylate with oxyethylene glycol
dimethaCrylales: det€rmination of r€activity Iatioś
RAPID COMMUNICATION
_
Thc work prcsc|ts ihe rcŃlh ol dctemil lon of rGrctjvii-v
rłiiG lol vnryl/dlllnyl syścńs ba*d otr dodeĆyl ńcthacyl'h ind lour
oxyethylcnc 8lyco] dmcthrcylates vaiiÓus nethods (bmcd on tcninil
model an.l pcNliinmrc clf.c0 rrcrc uscJ ror cilculiiion or everin.rtal rc.
śulb' The evelimeŃl dab wcm obtiincd by gas chrcmatography (debrni.
re leed) and by NMR ańaly5i5 of lh. Ś)
lublc oPÓly ń ei n wal IÓ! nd that d im€thi yla tes wei! Pre{ctntia ll' bu ili
inio thc.opolyń.r chanr Th$c tsth! wd! i'18q,d agrRmcnt with qu r
summrry
m{mhł|i.ól cilculańoN based
sho {hłinoli8omcE
Key words:.oPolyneńz.iion,,lErcthad]rlaE5,
liry ntios, ternina I n odcl, pcnul t
fu
nonom.t]F.r]'lates' r.ach'
Polyńeliztion oI m ]iifuldionłl nronom8s l.ads
lo thc Iornatfun of hislrly doŚli .d insolL'ble plo.
du ds Thc rcsu ldng Pol]rńel nd\'ork k ]] dło8.rco u s
ndwolk
duc to mio%cl forEatjon. Thc dcfuit-v ń
'hÓ
.an be r%ulałed by łn addtion ol ń
no|Ji'rc..currently'ihercn ]inearmcthodsarc.ś-o[
ncn,lc,l t3]' Althou8h a8reat num
lolcdiodetermiń,tiÓnof!Ćadjviryrariojij1mlioussys
t.ns, o )' a lim .d nuńbgoftl1e
v i''yl /d iviń],l sr,ścnś
lł_6l
Dedeas.ińa.tdsliŃingde$itJ,.llows torci.hhlghcr Thc aE oJ thń work Nas to dctrnrim thcrcichvjry
.oNetion of d oubl. bo nds ańd tÓ Rt ce ihe polvn di nhGofdodP.ylndha.rylaieandlouox}'ethylencgly.
złiion shri .gc' How.vcł r.dudńń ol dÓŚlilkiĘ .o1dineihaĆl}'laE\' differ ]! i'l oiyethyl.nP Rgmens'
dcngq by oFolyńcńzdd o ń With ńon vinyl monomł len8ihs, Ni'B la!ńUs cal.ulatioń
..n lerd to .n inoełsc i]r hchrc8cńcit-v due tlj a .ÓmFo 3l9 rh. prefelcn.cs o' thc lndjvjd
sitionil d fra$o.iitd wth dift.rc
mononers' The nom hetcrolcnm
Polyner .halńs wTc cshmatcd by q
moie likelt, it will sltow a signili.inily rvcikcr sEudur. .rlculations, bascd on thc ulysno
iń some roRions, potonti ly causing lI.natur fiilurcs ofshort(halnoligomPN.
lr1. ThUs, rh. knÓvled8e of thc l.adivity ratios fol
ńÓnovinyl/divin],l sy*rms is vely
ihe fiMl FfuducrPn,PeńjEs.
Iati6, ill oI thcm bascd oń N'ay(E
aiiÓno1rtadili9 M .lials
cIaŚin.dłsdiffcrcntił1orint.Eraloncsl2]Th.codc
sPondiĘ eqlatioN and soluiiol methods ire
'.'''
.'' '_'ar' '''"
^'
linc or
_
_
dode.J'l mdtaclylatc (DD]V''
.thyl.ne 8l!d,ldińĆthaĆrylab (EGDM),
di(ethylen€ glyĆÓl) dimetha.iylab (DEGDM),
id' hy'n"3J'''l)d'ń''}ł'yl .'T'f.DM'
fioń Aldńch conPany
.oluńn .hrcmato€nPhy bcfore usc.
wele Pllchased
and
Pu
fi.d by
2'2_Dinethoxy.2_Pheny1ac.thoph€
iniiiad
of
.oPolynł'atiÓn
was
delivłed by ciba sPe
coPÓlyn.!Śyllh.śigand ledin8
il T!bl.l'nq('ilyolb!dDDv
ar40 oc wiih !h.365 nń light of 1 mw/cm':iŃeEiĘ
rhc rrcscn.e oI 2,2.dimcthoxy.2-phenylaretophenon.
For E.s chrcnar%rrphy investiSaiions, 10
Pl6 wclc irradiai€d for a line ne
ng
sam
convcrsion ol double bonds (as e*isaied by Dsc
melho'l) and łlkr irradiaiion immediaely ke ed by
.hlororon b exiiact rhe unreactu
lubl. polymer was pre.ipibred usinE methanor and un
lea.led hÓnonss włe analyżed by cc iń lhe iitbat.'
In the Ćase o{NMR jnvesh8atjoń,0533amPl6 wcrc
Polyń*izcd to .onycEion iko śwt' l' łnd lhe solub]e
Thc ractivity raiios were eslimaied Using PtocÓP
conPulm pD€rłm l2]' Two nelho
modcl, Kclcn-Tiidos (KT, lin.at
(TM, nonlin.ar), and a meihod taking inroa@rnrpe
nuhimai.er{t (PIM) w.r. Lsod.
The Pbbabiljly o' fońation of short oligomcri. .o.
polyńd .haiN' dif'łing ilr the nunber and lhe position
of Mo lyPś of monomer Uni6, wa
basis ol geomeĘ' ÓPtihizatiÓń, whi.h eńabkd calolaiion o1the PłĆtiÓn ĆńthalPy (M') troń rhc followin!
Ń'=4''(!Hłl r4)
sh{c,t-ttrtuaru irs.N',-tE ofh nti\rof
llka u'^H'-lwlafln kr0fIhliI ninl 1ł.
0)
uL
crlcuIations lvere perfoth€d bv semi€mpti.al
ńcihod PM3 uing HyPerch€m 7 0 .omPufur Pro8ran'
The lower
value' the ńÓĘ Probabh n thc olisomcl
^''
stu.fure Ćofuistińg
ol
a
givcn numbs of uniis'
DD}'l lFornlla (l)] lvas .oPo|rnelizd wiiń four di.
methadylabs lrormlla (lI)1.
|ł
o
Thccal.ulied nonomerr&Ćtivily
In ałnNi all Ćas6 (one $ePtion: Ł dcc b r ob.
tained by TM method Itr DDM/DEGDM syścm) Ą va-
ru* aft h,Eher rhan I and r
3ugE6hn3 hj8het adivity ofdivin}l ńonońcrs iddcd
b ihc.opolynd.hain Thn in turn ndicarcs that ihc
Polymcr formed at rhc bcginnin! o' thc rci.hon will b€
more denśoly oGsIinkcd dmn tha
work rhe frd thai onc of rhe rwo
.
(rlis łPPrÓad1
6D.Iihough some works łppEłrrd,
Unt
is mote PoPular t5'
j'1
which monomer funĆtionaliry h
inbodu.cdioih.eiprssiondsarbingrhcredivitynThc .omPosihon diasrłms of DDM/DEGDM anLr
DDIVI/TEGDM systcms e ples€ned in Fi8' ] and Ł
respedivcly ThP fitud ruv* SLBB
rain.d ro! DDM/TEGDM sysr.m land DDM/TIECDNI,
iot shown here) aĘ hetld deKlib.d by PTM modcl (tak_
jry'nioaccount$arUńlb beforc thclł*oncniyłIfel
lhc rc&tiviiy of .hain !adi.al)' whcrcłs ń th. oŚc of
'
tuo sho .r dimerhadtrars
thc both modcls, i. ulii(a$uńin8
male orc
that th. rełdivity oI thc proFag
in8 sFe.ics śdepend€ni only on d
lh. .nd ol thc chain) and PTM 8iva very Śińil.r
The lcsulis of ĆalĆdatn,ń5 of r
DDM/TIEGDM syslem łr. gjven j
r$Uls
2
ś ..l
!
Fą' 1. copal9nt nńposłan l| uEA anno - ftźn
nnPosłllu (F) Fl DDM|DEGDM s!
ta| dala ftafi sft tba|nalayaph!,
żtpernnłłaldaIa
^
7.7adł
thaĘ,ical
ćufl6
NMR,
LinćŚ
ąkllabl froh
fldn
rfulbily ńliń Ł łnahd fu Nr l1) nnd rM @ fulh^ls lnd
naii.allyshoM
in
Fis.3 Thi.k lins indi.aic ihc prcIeleŁ
reńtia] addition of the .ononomer io ihe .oPol)'mel
'._/:
ńinal !ńn' The resulb show &at i
values ar lowel lor th€ additirn ofdinethadylatethan
rhosc lo. DDM, indePenden y on t
Unit in the.opolyńer ĆhaiĄ whiĆ
to' Thus' tne Euhs oi thŃrtia
Bood aBreem.nr wi th ih ose obtai ne,l dn{ y 6on r?ac
tivily tńG ddłminations
Ę o.+
:
/{C{NOIłT,'DCMENTS
E$.2. copr]|]'"t frfrpaŚłbn łJ) u6nŚ ńdlńł fkd
dnp6ili.ń (F) |dl DDMITEGDM s!3lfn1l da1rldlibas 6 n1
Tht
@,kuŚ
ŚuPPa .d
|ol sci.nlifu R1 dth
ilpq, b! Pd5ł skk
nsań
prck l
no. 4
mgB
crnłłt
a13 2z).
1' YÓuĘ J s,
2.
'Y
*,/ *B
Fl{'
3
P65;blc
':
+^/
.-,/\u
@.lb
af
,A/ 38
Mdldnll
ńd; lc lh prłtrulful addłiln o| ,ht
palwł kniral ,nł, A
B furck
"rd
xannurpati A' R.
Nndrfr Ól ctan Phvs. 1993' 199, la4]
Hi8iÓpÓl c: ''coPo1ym.ńz io!
łic Approa.Ii,' X]us.r AGdemiĆ/Plenub P!bl'
.+s
3. MonetD,
$^.r
4.
MeodezJ., AbrżhaF
RomanJ s.
T]ieĄ
AndYcjewska^łnm'idJ.
E ; P',ł'l'
' 19ł'
ó.
Ajzenbcrg N', RiÓrd A ; l' Appl P
żddłinrc' Thkt lnles
mol\nł b
lhe
a
ł
s'ł' 2002,5'
4
55
'9.
r,I. Mmmrioi.d,rs
PPmNA:n]'y,ul