studies on Pl€paration o{ stalch succinate by reactive extusion

studies on Pl€paration o{ stalch succinate by reactive extusion

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EWA RIjDNIK, EWA żUKoWSKA
lndlsbbr chmisry R$alch rErib r.
!l,RydygleĘ3,01793Waińw,Poland
enaiL cwa.rudnik@ichp rl
studies on Pl€paration
o{ stalch succinate by reactive
extusion
nA?ID coMMUŃIcAT]oN
slfińaly
lteadllc ghsion wffi aPPlied b oblain the stalch s!.cinJlc'
E*c.jficihon usn8 succili. anhyd de was płfomed using mWl6/25D
tuin-srcv cxrudc Nabiun hy
wem Used d .atalysh The idu.nĆe .f lhm. kind s of *aIó was śud i.d 'I}Ć
6on (D9) hishcr $an 0.6 was obbnred
łoń Potłt *łĆh i'1 th! Ptseice ol N'otj soluiion
rcy wÓ.ds nath eshrificahon, slalcń suc.inaiq r€łdive extusion
Reactivc .xtuŚion PrÓv.d t, bE ł stcasslul and low
to Ć.nlin!Óus Ploducdon of mibt]s Twi'}
Ó*way
adoE ror bulk Po\,n.opolymo Jomi.
bńn.hlng rcichon, .o|full.{ Drclco}
ind Jundlonalizaiion ot IunĆ
tionilSroups modiri.arion n,2t rnchemkby of pory
sac.ha .s rcadive exrusion is usualy lsed to rhc
sralhnB or rhc chemi.al modirica
Ples c lhe reftion Óf poly*yrcnc sżItjng onto distiÓń,
Ć.lPling
or
Iar lveight dcgladihon
solved slłdl in a twin sd.w
latjon of *arh !sn8 r.achv.
!*rdcr
l3l or PhosPhoq'-
cxbu'on l4l.
watr shry alÓng Lvnh NaoH sol
arc slv.nl holrs starch cdcE of modd
EIcc of sub*jfutjon (Ds
= 0'5
o
b lriSh dc
PfPłrtd usjns
]d py dine łs the sÓlvent/caialyś
sysle'n. othcr solvenh Usd fÓr lhc synrhc5n of sti(h
e*ers i|cluded N_meih]rlPJrmlidonc, dĘcthv]'or
ńan jd c and dimdhyla.ciam idc/ Licl. Howc\.i jn ]l
olg ri. soll€nb e.łP.En(, iox
ńove tron śarhso
ahcrnłiiv
fitty hydridcs
2'5) ate
'n
*ai.h Ś!.clnłlc
13,
d b PrcPirc thc
9l' The lesulb rcpo cd aboul a
ralhd loN D5 and/or teacńon cifi c
hrve becn a cnptcd in oder tonodily rheir.hemi.al
DS < 05 and R[ < 30 "r,. Th6c srudics werc !.non
and Physicil propcnies' Fot lramPl! śtnficaho]
wilh organic a.ids .an Ę!k in rhcńopli*ic d hyThe aim or thB work was io rrdy rh. p.sibilir_v ro
droPhÓbicńJtriils Dcpcndi'\E on ihc naiure oI sub*i
obtain the śi(h.sfon, Ź{. sb(h su.cnNtcs by rcactivc
n (Ds' ihc pbpełies
of rhe ńodificd śrRhv y siBnifi.ani]y 15,6l. AŚ Ds
indi. a the żv*aEc nunbo ofsubśiluenb p.r anhy bation, and *ind Óf Ćablyst o| D5 of *arch su.ciluks
droslu.osc unt in *a(h polymeE
rhre hydlo\yl groups per nnit, &
ńuń of Ds G 3. Młjodiv ol rh. $ł.h delivahvs, whicń
arcivailible.ohmrriłnv havclos'd.srmof sub iiu_
tion (Ds = 00l {.2) 16l. Sb h cstms ot motldat. ro
hi8h degt.o of sub*iluhon (Ds = 0.5-2'5) .łn slblv
v€ry diffar.ntiated P.oPc ies such łs hydroPhobi
Mahfuk uŚed lvet as fouows:
cily/ńcltp.ocmsibiIityand i nUm
star.hes
.rch (PocH cliwi.E), .dn'
- pot od wleai
cations su.h is hbrei birdere, hor n
d -d](sĘńa Aldnch)
slal.h (sisńa AldIi.h)
in8s, og cr. riuere, biodlgradabr. plashc and mctil
su.cinic anhydride (analyri.al sladc, sismi
ion ibsorbanb havĆ bcqr Śu8gcścd l7l
starh cle6 ÓI low Ds ale no!ńally p.cPilc,l by
cahly s _ NaoH łńd Naljco] (Jlal],hcil
an aqucous śarclv
3IJs}filt.r ańd th. Icsiduc wa
ploPanol (]00 ńL). Th. *arch \{as rc.dĘPe6cd in
Estriiicatjon
lro€s
was auiomati.łlly
was
pc omcd
rnto]led by
usin8 thc ThcF
Uii? PoIyLłb
dah aqltsirion and
graPhiĆ pl*eńbhon of the full Pocss beń8 run s<$v
dńńer.! \!as ró Bń and Ł/D r.ńo 25l Thc cxtrusion
was pcrfomcd with a rod die (5 nm diameht. Ihe
tenPeiafole prrfilo of tte eitudĆr
lows; ó0/30/B0/30/3s't' Thc rÓ
wm arbitarily s.t ar 70 rpm Thc shrh lvas prem dt
wiih sLĆ.ij'i. łnhydr r (sA) in va
GtłrĆIisA łon r:0 05 to ] o 75) befole the exp€'inents
comPutet
deionized warcr (300 nL), d ihcn dispcBion was
heahd ,n a boilir8 waier bath to
soluiion was tfuared witl1 0 r N Naorl
l,
ł
niiblc Ms
fcd in'o zonc r oa thc cxhdc'usiĘ
loluńet( fccdc. rd lccd ntc wm 47IPm. Thc 25'l'
N'OH solution was iddcd in zonc 2 usi,B th. ProMi.
The
rcni c/4B PumP with 0'3 nl/nin nfu Glarh]Ćahly*
nojar raiio = ]:0 09). ln u'e Ćase wn
bomre was Lsed as a cahlyst, ihe p
eńi' The .abIysr (śa!ch{atily* mo|ir mtio = ]:0 75) was
Pl.ń\cd włh ś .h ind suc.ini. .nhyd dc beforc ihc
cxPelimenb (it lhcsamc olal ntios ś &s^ as ina
cisc of NaoH miĘ) ind th. distilled watel wm a{tded
irzon!2 usinB the same punp and
łdde'l' r.Plł.inE hcr. lvłicr jŃtodu.al in NaoH solu
tion, played lhe9me rcle i'.' dksÓlved th. olalysr żnd
Ilhrc:A
linnliń !a]!ńt o|Naolr nnlli,l
sallnion' w _ dl! wiŚt|
nń"alĘ q NroH
Rt valucs wcrc calculakd by dividing th.
ńeibl Ds and dE teoreiiĆal Ds
spc.i'i. neĆhaniĆal .nerEy GM[) w'5 dcfined as t,
r.l inPui of me.hanical enclsy pc! lnt dry wcishrol
€xtudate l]1l'To ńnd sME valuc an cxhudaic was Ól
l€ded fol30 s and dlicd sME,inwh/Lg'w.5calculitd
aĆĆord nB to
thcc4u ion
."t
ltt:l
śn!sp\d
Nnl),MFR ntl,fl ,ląr.(nI
tIutw\$haldrtdrhe
Fi8
nńilt łfrtl! (1) rfu sklrh gl(ialt
DS ol su..inylation w.s neasurd
tion oI the .arbovl grÓlp aftordi
b_v
alkrlirc tiba
wib.d in lr0l rhe s!..i',ylated 5hrch O
E) was dis
soludon (25 mL) by
peBed in 2.5 N lrcvisopopanot
ŚlininA for 30 ńD Thc djsFcG ion was filic.cd
th
mu gh a
phs htun nd13a s.
re ] lePrcscnś śirchłnd ś .h suc.inaic FI_]R
, (onf'rmjnA lh 5ucdIv a
r7rr.
buhd to eslei €rbÓńyl ErouP *rehjng libżtion
The vab.s of dcsrcc of subsitorion (Ds) d R{tion efi.iency (łE) fo! dificrcni i(h:s^ ntios ind dif_
FTiR spe.hł w4. obl.ined from xBr pelek Jsing
i Pc*in-Elmer FI-IR S?ECTRUM 1000 spedronetei
r|
1_ ąt|ip laĄk (nl
krllI) drxnlnld on ll]l br'l
(ń lplr'
h rcd r mh paaiturnd
spth,
L-l
.".= l!91
\P€d
FiN 1 FT IR
experi
(2)
(glrpb: PsTs A 1]3)
irc givcn in Tiblc I and Tiblc 2 lor
by NaoH and NaHcoł I.sPeĆ
lhe
the
nĘe o10003
surtiniĆ
0ó39' h x]l
tydride Ón.lnba
tion.esulred in an incrcasc in Ds ol rrh sudnahi
fte higher Ds is obtatured wnen NroH solutirn is used
a a caialyst fot all kinds of slanh€s'
bBion Óńdihotr, the hi3h6r sM' js al$
Pohto
shr} t.3aldl6s ol kind Óf thc otalvst uscd' 'or
lt nav be
dPlaincd Ę dt. higher ńcl' viscosiry of potaio *arĆh
than of oth€r sbrchś nulhng ń pł i.ulaĄ high eń
Rea.6vc cxbusion po.ess was lound ro b. npid aM
śimPle mcthod 01pĘParinE of *rrch c cF Eśłiii.ł
hon ol śar.I Jsins sA ln fuiFsf,
in .hemi.ally ńodificd starch wiih
on thc rcmtion conditio
'lependiry
nai€ of D9 hiEher than 0'6 lvas obtaincd Th. rci.tion
dliĆi.nry was aIso hĘh (>30 9ó). Good r6ult ould b.
a.hieved independently oń rhe Lind o' a
.h' How_
ere' rhe hi8hPsl Ds and R. valucs wmc oblłined fol
sleinyIation of polab śarch' FuIlh.I sludies conrnl
ing the optiniŻafion of the Prepal
ś
'1'
byreadiv.dtu onarcunderinvP
Thb @tL
rB
s.nnlłi. RERlll1
kzióFk^
stppr at
R.]
lo&'r'y
R.,
'czióFk
;,
;.
Dc
ł.
;
:
NaoH as a 6bly* in .onpa
Re8aldńs the inf|uence of kind
o1shrch, the hi8heł rea.hliiy is lol Potalo sbrd]' i.' Ds
is above 0 ó and nE gc*ds 35 1''
sME varidd
about 90 lo about 400 wh/Ę. cÓń
p.md wid' orhel'bń
*archc Prmes€d
Gtaf
hlr Prlktt
(KBN) futhi1
lt
p
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ci]1lllrye PrĘ
20m,
Ź,
ł9
wan8 Y ]', Jżnc ] : shrcL 1995, ł7,9ó'
] L : skLhlslńIł
nE is ako higher lor
son wiih NaHco! Ón.'
wt
bl
Patyn
1es,8,55