Modified Starches:Properties

andtlses

Gditor

O. B. Wur-zburg, M.S.('otts11l1;1111

N:rtion:rl Stlrclr :rnd Chcnric:rl Corp.Brirl{crr:rlr.r. Nr.rl J1sL.1

;\'clY

CRC Prcs.s, Inc.Boca Raion. Florida

EFFIp pta AA

Oo3-t rq44'

Moditied Statches:Properttes

andIJSES

. Editor

O. B. Wurzburg, M.S'('ottstthatlt

Nltitlnll Stirrch and Chc'nricll Co4r'

Brittgcs'atcr. Nr"s Jcrsr'1'

r6PC'

CRC Prcss. lnc.Boca Raton, Florida

l-ibren of ('onRress Cetaloging in publication l)al!

i'irri\nr(.. .il)(l u\.\ l()r nl(\lrftc(, \tJrchr.s.

I rrr' I u.le. hr lrl rrr.lsj1r1111.. JD(l rn(lc\.

... I Sr.r. h I \\ 1;17nyg. (). lt. ll. (.rolrcr.

('h.rrlc. \\Ql).1: I ltsan teti6 5J7.7.1i: N6- t.i67lI S [t\ tl,5;r) i. ieh-l-.1

I hr\ t\\r\ rcnr(,\.nt\ illl. .j,,(, cr \\ ,h i*n,,,s\,(x,. ;:"::^:::':l:'H,]l;::l ",1'Illi;llllli*r:"1:.-,i.,,,,:::,;]Iil, -;i:ll:.Til,1;

'll.n h'r\ t\'('rt"ntJdc lrr Sirt'rt'liahlc tlrl.t'rrl rrr.r.r'rr()n. h,t rrrr. autlr.r antr trrt puhrishc, crn,lor.ssunrcr.\Frrl\rhrlrt\ tirr th(. \.rlr(lit\ trf rll rrrrtcrillr ,,, ,.r, ,ir.j'.aru."q1c1(.c\ 6l-tlr(,ir u\c

. ,,.:li,';:ll; ,li"",ll,'nJ,.nllt'' hxrl' trr irr\

'rrI\ tltctc'trl. rrr* rr(rr lrri rcrrr'(ru(c(r

'r rn\ .).. u.irh('ur \\rirrc'

l)rerr 'rrr rrqr'rc\ r(' (-R(' r'rc\\' r*( ' l(xx) ( {}rr\rrirrc Blrrl.. N \\'. llrr;r R:rr.rr. r;r'rirr;r. .1.1].1 r

, l()Sh h\ (.R(. I,re .*. lrrtS('( iln(l l)nnlilt!. |(,)s7.llllr(1

l)flntin{. l()S7liruillr l'rIltillr. l()S()

Itttcrrrrttrrnrrl Strrrrl;rrrl l](xrl Nurrrhr 0 |iJ().t-5()6.1-.1

I tbrrr-r rrl ('rlngrq\\ (';rrtl Ntrrrrpr N6-l l(|7Jl,rrrrir.rl ur t.lre Itrritr,rl St;rles

il

79

ChaPtcr 5

HYDROXYETHYLATED STARCHES

Kenneth Il. I\toser

TABLE OF CONTENTS

l. HistorY...

ll. Chemistry.A. MechanismB. Subslituent Distribution.C. AnalYtical Mcthtxls.

Metho<ts of PrcPumtion ...-,A. Aqueous Slurry Reactions ... " " " '

B. Nonaqueous Reactions

lV. PmprtiesandUscs-... """"'85A. Producrs Made by Aquc'ous Slurry Rcuctiops" " " " ' 85

t. ProPerries .

2' Uses-- "''''"85B. Prcxlucts Madc by Nonaqucous R!'itctions " " " " " $6

l. ProPerries. """862. Uses.. """""86

Rcferences.

8l82

80

EI

83

8-1

838-l

ilt.

87

80 Modtlied Sturches: propertie.r ttnd (Jse.r

I. HI.STORY

Srarch has been used in both focd rapplicarions.'.ior"t it;;.;'b;;r:Tt,1id-,T1food applicarions for.many years. tn mosrstrr'ngrh. Thc rc.tarivc.t), ;;, ;;;'.;; l:t un'out visc'sitv chilrilcrcrisri* ,i.ri" io'r,ii,J-i""unrrrtrririctJ',,i1:u:,ypiii..uir,'"illf|'.j|'llilJ.i:T:il")'.ilrrracrivc. wn;rc naiiuc.

*s aqucous sorurions tute u r"n.r..r,.-f ,., rr,tr"n *;::;;il;. ;i:xihl,';#,ili,,iilT:lr:.,T;);r"XT:jl* i"nrJ ffi',{,.;"s x,ruri'n,,, pu,,;; (;;.. riqui<r raun<rry *rirch un.ri,,.q u i,. J in ;;"T l;

jil :;:fl.i li;iii, - u,,,r"', i," i i.ilil;i

ntanut:tcrurcn n'"""'*n'o'r't'n thc'ir'rrn i:L:Y;d;iilffi;fi"1:f"::::;;t'J'ltll;ll.,?h J:: lff *l,T'*

i' -"; ;; il ;; #,',[i

i I *, il::i I -ii:.""" ;:: ['Aiil.*' il:,j,:ff

r istosir.r, urr,"* iit lo leave a l.ugh li'n .-f-srarch .;;il;;:';ln" n,,, srarch pasrc chanrcs

"rn.l"nall"'ttt-x

trl€ slzrng run' lhc'-r'arn *'ill bt' ,t""t- nr u'n.r.rrir...l ,.*.ut,ing in lxxlr *"uui,rgH-r'pothloritc oxidation of starch inrnromanl,or rhe.e p,obrem,. o*,i.i*,#ffi,-;.y-Jil;:r,,J#jl,;.il.#|yo?::.;|i;;,1,J:ffi;

thc'-v arc unacceprabre r".ii"ny ,."r'*;ur. rt. ,"i."i"" [[,,on causes a subsranriat'rsr'.sir'r' rcducrion 1nd Srso

r"ritor"..r"rt ryr gr,rr;tilffi:." anionic [:roups reducclHill[Jl:::,:*-l,m:N* *ir. ""u .,rh*, n"guri,..ry .r,u,g",r subs,iarcs. ,hctt.^c'traprers-t-i-J"a ,ol. ---d textile pruducriin is grcarty ar-"iri.iii.",.'"

chc'nrical derivatization. of starch ats' yiclds prqtucts which have gtxxt viscosity srabiriry.but *'ith.ut concontitant."ir"r.i,y irr-.'ti.,i'o.",ylu,i.r" rrr*.il;* becn known since rg65and *'as conrnrgrciar.iz"a in rr,"'iss;.,'iJnir";;;;;;;;"*"r,,,,

used in nrany appri_i.lliJli;"1"' ha'c linritc'J ;il,;'l;"*ll,r,r,"i, *"J"""yiJ'l"u.",r,ore

unrrc.r arkarincErhcdlicarion of srarch givcs prtxlucts hhrnd is st:thlc'ro r,1.rr,r1r-ii'"r;J',,,l|:,.f:avrng cxccllc'nl viscosity srahiliry and rhc crhcrsinc(. tet:., hr, ,h;.lt:l!:.T.cr'!'n

ilt high pH. Tt"."ik;;i;ir;j;;;::c()sr. \' nr'\'L'r *.'r" pr.*r,i:..i in rurg..-r,,,iJ;'"";*:tarch havc t*cn kn'*'n

",n*:ll;lililil:1:-:tcIi'lrn.f c'!h-rrcnr"':l:r1:':.".r ',"J;';":;"::l;":::t,,,,tr.'*r"riit;;; :""**nsi'c

c'th-r'lc'nc' oritJc i" ,r,.' irJd-. ,ti.,'.1,,u,,,ni"s lor prrxrucinr

li.l'T,i::);tii::::,::{ii:l&1illl';i'iillrj[1ll',',,'#ill',,f,T{1ffi( ( u dr i r i. n { **

"u "- " "1.',,, i.nl lll, : J :i :il;.ll l]*}:1.lllillfffi ..

.;J 1 i-,ffipi 1iiil:fil#ili.j;*;:,:l * il,J,,fu:# #.t;..ff 1 r,,, * ;ffi ;;;trr p"*t thar c.nrc's in ..'ni".li'*lli;';,*i ,:::, "ttf:j.llt's.classillcation is as a sizing :rgcnrrn ,i,"

";;i; l;'fiJ.i[:lX.j'J,.;ll,l,J],'1; i:: burchcr ;;o;;;;-,,, b,rrcs)

lft Iiff :ii ; i Lg LTr ril *. :l ff :ji;*u;; l'l ffi; :: ll; :, fl;ii'r.lT r :i;, i,l,i ffi"'j

i n r.,., r i n r r,. n n-" i ;iil[;il11";,,il:l ;H1;ilH{',_.,m:i$H'rdror'rprop-rl slarch is rttadc b-r rc'cting prrrpl-rcnc. tlritJc. r'ith sr'rch untrc,r:rlk:rlinc

:ill'.T;';:";.:il; il'li" 'r-csirahrc'n"'^',.--.; n!i,.,,1..rr,y;.,;,.;; ,,,.c ,,brui,,..l. hur rrrc

'*c'. .irict-n.r:.,,riil_illi:ili,1';::::ll;: l;,**;,*iili[ip_,cnc,,xi,,.]il ;;;;

,f.on l: 'rirccr iixxr addirir.c-s ";;;";;:il.;r".ljlllli:']fi'l;l:li:n"s

arc approvctr b1, rhcn n('r ri\xr appr icur i.rrs r,r. t*' r i,,, i,il ;;:;:,I1il,::::H +;:HJ, jilf |,r,r.lfi i.Y;;

8l

starch was conrnrcrcialir.cd in the 1960,..t'"' Thc'sr' vc'ry lorv-cosl stanch pnxlucls nr'\'!'r

achic.vcd thc. cgrnnrcr.*ial succcss of hydroxye'thyl starch ht'cuuse lppnrvul as "intlustri:tl

starch mdified" was ncvcrobtaincd lronr the FDA. Hydroxyethyl starch remains the prtxluct

of choice when a low-cosl, premiutu sturch pKduct rr"'siitant to alkaline conditions is ncc'dc,'l

for nonfood applicatkms.

II. CHEMISTRY

A. MechanismHydroxyethy,l starch is produced commercially by reacting ethylene oxide and starch undcr

alkaline conditions lEquation l).

Starch EthryleneOxHe

ltttdroxyefidStarch (l)

'llrc gcncrully-ucccPted ttrs'Chanisnr l'trr fhis tl'.lctittn iri shpwl in ldUuti6ns I ttr {'

CI{OH o

,c}" o

+OH.

+ H.O

+rto

OCflCtqO- (-1)

+ OH-

(:)

+ lor -

cH.-94 o

q{oH

ocH,ctlo-

82 Modificd Starches: propertics uncl lJses

Tlrc lt-r'droxidc ion abslracls a pr()l()n frrrnr onc 9[ rhg rhrcc av'ilablc hydroryl gnrupstEqirJtion l)' llrr'.sr.rctrrlc i()t gir,*i,,...'i'uii"*r,,n,ti"."i.i'.li*,,rr",," 'xitrc

c.using ri'gopcning and sintultaneous pnxtuction .ttl'" ncw allioxidc-ion ia,iuurrun 3). The rarter picks,"&:ff:"lrfrom

the water tiberating an hydroxide ion for f'rr-h-er,caralysis of rhe reatrionLcach et al' sh.we<l that nxrsl of thc'alkali in alkalinc starch slurrics is adsorbe.4 by thcstar'-h' " This indicalcs lhut al lc'ast un.' uiil

" ..ru..n tf.rro*il; ; srrongcr aci4 rhan warcr.ln rhc hldroxl'erhvrarion or,rur.r,.

"ti.,i i, u nu"t"optiti;'r;r;;;", rhe resurring srarchareion is ablc' lo conrpcle effc'ctively u'i,r, ri" relativety row "on."n,ru,ion

of hydroxide ionst. gi'e reaction efficiencies of 7b ro s0;. Thi, i. i.. "u"n-rt

ougrr rherc arc four ro 'vc

tinrc's as nranl' nrores of \,r,arer in it.. **"", as thc.re ur" aquiuot.nts of srarch hydroxyr.B. Substituent Distribution

When starch is chemicaily modifird. rhe degrc.c of substirurion (DS) is define<J as thcc\'('rusc' nunrb^-r of h1'druxyl gruups rlcri'arized i"r ""rty.r.rsi"lur" unir.,. Thus, for nrcrhylethc'n of starch' the DS is-eq-ual a ,rt. ot=rge nunlfr of merhyr subsrituents pcr anhydro-glucosg unit' Howeler' in rhe case tirrl'.r-r*y.,hylation. thc crhylene oxide can reacl wirhan1'of the thrce h'dmxyt gmups of rhc:rnhyd..rglu"n*. unli-o'.'*"lr as with an atrea,vsuhstitutr'd h'dnrrictlr-r'l'g.i'up.'Ti,': li;"; rc*cri,ir rcsurrs i,, ir^* tin.,,,uri'n

'r.a prry,rxy'-r'th1lc'nc. sirte chain. rr,i, "r,uining:;r;;;; resulr in mrre rhiu itr.l. n,ut".ules of crhylc.neoridc'rc'acrin{ u'irh a singre

"nrr1:anrglu.-or" unir qir:ilg ""-"pp"r.r, DS of grcarer rhan 3.thc' thc.n-tical tttitrintuttt' T. pruvitlcitirr rhis grss-ibi[irj. irr..',lru, nurrar subsriruri.n (MS)

ffi::.tt.|$ifil,as thc t'riat nr";r*;,,i n,ot",. nr ,"og"nr .",",t in..'r wirh rhc srarch rrrThe most prevalenr commcrciatly prtxJuccd hydroxyethyl starch prtxlucrs havc an MS oflcss than 0'2 and

"noi.lt*..u il ";;'Jil;. * rhar r-hc ds i* .r..,'nriary equar ro rhc MS.ln ttl'n* highl-r' rtr'ri'atizcd pnxlucr..',,,".il'"i".tD, ,"uai.ui,rr';,;.:;,,,, irr 'rg.nic vrr'c'rs.

|.f;:,f;l,: nral' be signiricanrrj higl,":. ,'h;;',i," os au" ," rh;;;;;.. u,.s,ryo*ycrhyrcnc sidc

Thc' use of h1'drox.vethl'l srarch as a blood plasnra exrendc.r hils gcncr:lrcd intcrcst inln.thcr nleasurc of substitution. nuru"5'. iic nrtltc fr.cti'n of ariiryurogrucosc unirs rharconrain ar r!'asr onc h1'drox;'errryt gr,,up. rr,ir-i, inrJnrtant ,, ir,"lrr".ri*r rcscarchcrs sincc!'nz'nres in rhc' bltxrd can hy<rrory-2. un,uJin"o ilr.h-;;;"dJi"i,, uir.oriry. bur rhcscenz'nles cannol nral!21 3 c'.q- l.a tinkage of rhc srarch backb.rne if rherc is a subsrirurc,anh'r'dru'clucose unil on eithcr sidc' of t6lo in qucsrion. rrr" ,,,"ai."r rcscarchcrs havr-.uscd the ternr degrce of subsrirurion i;:h, rr,i, nr"orur"-,u.ir"fi;r1or;.ally, starch andcellulose chemists have rcserved the tc'nn DS to define the degree of hydroxyl subsrilutionpcr anh.r'drogrucose unir as describcd il; Thcrcforc. *h;;j;ng rrrc rirerarure. carcnrusr be ratcn to derenninc whicrr de'r'iniri,tn",rr" auftor is using.Thc l*'ation of thc'.hydro*l=tr,yr sr.r;f.'* ,r," anhydroglui.osc rings has bccn $udicrJextensi'el1'by rie*crat t"r.-.n-grou]..'li. *" r"o.,i'.rn

";;i;;", used lo prepare rheh-r'dror1'ethyt sran'h appcar to affc'cr r'hc disrriburion .,r rrurriiu";;r;. r. For conrrncrci:r1vprtxluccd starches of le-ss than 0.1 trts. rtre nunrbcr 2 hydroxyl is by far thc mosr rcactivc.accounting lbr 76 to 85% of the substituti"r.l.r.rr" rerariue *".,i"iiy of rhe number 3 andnunrro*r 6 h.r'drox1'r groups rr", nor-t".in'"*urirr,"a-n;;;;; 'fi:';jirt ur rgo".enr in rhelji::"ffiJ:1.?..T ffi!.'

r'ariarions in rr',. .,,Jirions uscrl ,.rpr"p,,r" ,rr"ilv.r.o^v.rhvt srrrchcsrhe subsrirurion at a' .Li-t'Y:-""d

to :rnrl1'zc tltcrrr. tn ";y

!;";;: ;r rhc Ms is incrcascrr.p rcc i a b r c s.' e J ;' J.:: T ::

":*:l

"#" fi',illff

"1ll.,';::*,;'J;

I, f, :*f',m*lr :Hbutitrn in h.r'drox1,crh.vt starch have U"., p"iiirf,"d.r.r.*.:s

8-1

C. Analytical Methods :s 'f r,,'agent conrbinetl rvith the starch

.per

:$:dfl:T:.'--,.,}', .;.::,:H',n:

1! 1;d; "J v -i' *t'i'h re I ies on the conversion

il';i;;;;;;v.c,tryr;r1c;y:ilXlli,.J.:f d;Tl.i:lf l:f r!l$F:::.'J*,'f ti;li

or mixlures of ethYl itt

ficat.ron of rhese n,o,"rii6iiiiati.,n." '* or.*Ji. "t*if f trytmarornohic mclhtxls.'' :"

is used ro catculare ,n.'i"','*ii*r".", ", ",nr,'.". ".*iitH'9}: ThJnumber of m.les.t

ethylene oxide per ""n,l"-t*J;t ""ii trusi is calculated as follows:

%c2l.ofound * g,ffi ++

(5)IrlS =

L.w nxrrccur.r wcight kcr.nr.s. cstr.rr. r-thcn. irntr irrctrh'rs 'n' ut. capirhrr' 'l

gs'nr'rlrting

v'larirc arkyr itxridcs ,,r ;;;;- l;cn rrcirrcrr *i,'r,'rrl'.iti.Jic ucid and w'r inrerr'crr' *ith thc'

analysis. Thereforc. .t,"*. ,n"i.,iuls should.not u" u'e.r as aids in dryine the appuratus.

Of even grcarer .r";;;;; facr that ,t" io*., alcohols and acetoie are \er'v dilt-rculr

to'emover,omsrurcr..-e""nun.t",vacuumatetcvirtedtempenrtures.Sincethesesolsr.ntsinrerferc with the *"ro'' io"y *ttot'ta-nor u" u*"J'o prccipitate' the starch from aqu"r'us

*lu,ion or to aid r" dJi;il" i"*o't: ll,*$.*[Hi';;:*l*::triiJ"::'iLl'$n*Hffi ::l"Tr;lJ:ffi i,-'l[r::ri:i$*]:'H*iti;:Hsnl*ffJll-"-filter

cake. High-MS ffiuii,*; t*rt i*fur.JilV i*t"-itytng the.ir aoueous solutions'

rhe Zciset unorvrirll'lfi;;;;;;""0,,'o*l',.i.* i'ilei*r in manv instanc*' onr'

of rhc pnrbrems is in ,iliffi;"',." rr,,npins ,tJ".'r,,iri.. i.tic"i "n.t.orc'rins

pnxrucr'tr rrurrng

the Ht rc*tion. c""'ll'i'**rfi;i-ilil';tu;,l*t:il '-tt"tiitt" cflicit'nc1-'r thc trrp rrscd

,J*ir."i,nt ethylene is increased's :oryethylene chains is

At substiturion *"ti' ;i;;;h"" -0:3 Mt' the nunrber of poll

neelisibte. ,*r"ror". ,i";Sl;cssenrially .o;;i; tm pfS' et-trigtrer lVtS levels chatntng

*i u""o"o 'ignint'ni-oiJthc'DS i* ro"'"'*iion'tit nii' c^tculition of tht'actrrrl l)s is

s vcry dirl.icurt b""ou** ir is hard rQ sep.lrure "".'i*r,rii" ,r,.r *"., number .f Jr.tenriirl isrrnlr'rr '

This becomes mor€ app|rcnt when one aon.io;o"t'* tr't'o eth)'lene orid!- units 0n a sinsh"

anhydrostucose "",, 'l,ln '*'*;;; ; 6 dtil;;;'-t*t'1u'"* i'.. i*on'tcrs of tlihl'tlnrrl t'th1 I

anhydroglucosc. DS ;.1;.;",i'-;,;.,n,..r* ur t;il.i;;;;;-icthr-t ont''or.trluc.st" DS l '0)'

considerable p.*r*. i", been made ," jl"ilt * rne nne tt*ttu'" of these high-l\lS

oroducrs. but rhe J;;;*.orpt.*-ono'r-ot" ,t'uttural aspc'cts arc still ambiguous':3

f)r.rr,.mrin.ri.n .f ld.;"iltili1".t *ntit.,*r"t"-"-""it' *hich arc substituted *'ith ut

rc'stor**tv,r"'*v"*'vii^'pi'*,*ui-1.:1t*Ili.:;f;'J,:"H:lroU*l$liliT

*' :**t:'::n: fl T:':';ill!1"i5":itii*:I ilil ;; ;ii'lt'e n"'te tnc'li'lrn'lrr

anhytlnrgluco*" unii* ttttti tttt' substitutcd is calculittt'd:

0.9 We(l6l + 44 MS) (6)DS=l----

whereWgistheweightof.freeglucoseinasamptr'.:':.on,-)u'p.loAnall'ticaltechniquesti)r dcrcrnrini"*,n.'i-,rin",;;;;-r' orirJr.'*1'"th1'l gnrups in hydrtrxl'eth1'l stuch urr'

rcvicwetl in several aniclcs'r1':" :1

III. METHODS OF PREPARATION

^.ffTr"";:r:1uuilt",i:.:*:ti;ltr.,r.rr.'*u.,t yr srurch protlucrs is nrost con'r'nienrl' curri''tl .ttt

8{ Modilied Slcrr.lrcs: pro;rt,nics crrd Uses

u;*ilg agucous slurry reactions. Thisslum' ai i, i- ,;^;;.,::iili'1ll: .,,nj:. ,- d<,nc corrrn-*-rcialtv 9

i,'il,':il$ilii!::1r.1"..'i:,Y;;' "-l rrrirrirrs ;0"'"; l:T'!1.:l',...Tifi*;l;::f,::,T:l

,.,,, ...,.i r ii iiir ll*li{niin *li*Ii*, ;:,*r i vc,y h i gh *iu# _r ii, u.,, ns

duc r. ;; i;,$".;.:.:.1J.):'l:.lll:tr rn rr.arcr. rh. rr.:rcri.n : riltcrcd. rvashctr. and dricd ai

$"llill*il1n$},;;{Jtli;1ii*;ui,;,"il':ff ffi 1;.::r":H:rrl:tirr luo,-n6 t ,,a-,,^lr]] _::,, 1.,r

rne crhylene oxitle. A .,r;";;;j_;::dusc or rne incrca.\ed

,u.ili?T#t^1 i:rl,'r;i:'.fi $:ilt:nl;iiTi::,ffi il;,i,}+r.'",."

*nffi ft fil.,pl$':*,''ffi i**'firir*lrffistarch so that rtn" "*liun'""i'i1j:t't'''

hish lcrc'ls 'f ci

*:[i$:**:*;il]',:i*l,l$rf ;3,*ii.l'#'lir'-.',n"*".ii.".ii'l,."",

corrrnrcrci:rrrr.. 1l' .,* ..i.r".r ,., ,i.'ir'#l*'it"s a"t* ;;;:tuX',',',H."

it can bc trrmbincd

;i# ,,:il*l,:;firi{tt','l,?;: ffi #ili lii;liiillii1,,'tffi ;'J:::fiiitT;

*i;I^*Hlffi iltlliti'.;1j;';';;#drilJ[lT.'':=']arc''lr^u'-u'i"i*"'"'tr'c. rt ac r i'n i.l i1"" I:" r,""ii r,'

" ".r -ftl'ilf" il ffi #::""1T';

":il;if

:tlfi: ffi;;.1":l:,::h[ixH::,,1]rf,Hr:1.{;m{l;:fi :H:x.i:::.:,:,,yrcsu,,inswc,,ing

fl'.':,#x;1.1;T:11::!:'ilifi:ffir[:;il";"1.:[;:;j1'.',.*,:iiiT!::];.,}:[il il f-"Hl;1: yl''{*#:fi lilff -': o rb r','! hiffil

Jiii l:hi:|n i;:{. aricr.rh. nro^,^rJii1,'""'il* iilr'ff$.:"T*1.'ll,lf.1;,'f,l':::"':""".,ir iru.-r"l'nr,rr ir urv,irriilltjltitl;.^ L: r . ._

- - t-"rlu t'ul o' rh(r slurry cithc'r h.t.u." ,,,

$**TrumM*I hr. pnduct is xrlu. High-IlS h1.dro1,

( t. lo .l% srarch vrliu'rth a considerablcthts u'1;p1. tr

8., )o.n19u*us Reactions

-. n.rgh-J\lS hl,droxrr

rl picarr-r . ,n" .*; iilll:iil:lu';il:l,iliTl.:i1"",,, prcparc'd by rc.acri,n in arcohl)r. r , ,r.,;:rt\)ur 7ri adtJirional ,,;,;.; .:^];'l::rcr ts slunicd in an c.luai *"i,,1,,',,,1,

;*,nlmlJ,,[iL1i*xiJ:tT,*,,,:,,ffi ;t*ll;nnm*lm:. *fuii r**i'5d.l;;;iil#ffi ffi tl,l'# ,1'r'**ti:'iJ;:l';ffi ,;ll.l:*ii;l*:ri:r,l.,"::'i,i,jjx"';:{illi;i':lf l;;*';*'lit

. . ra rc n r

" ,r. r i n.] .li ru ir.,, :11 y;,

;ii.,, I i:":1",.,:f

85

s:l"to:""..T*.I,:j'T'fi l*':l'.;:5iil::T::I,.1.";t'"X"*IJT'$[l:;*".ffichloride reacts wlth a I

crrronrhydrin una *.*',ril'iy.irr*iJ". pi r1"r i.it.'-o.,u"t caratysr in the sysrenr' The

starch rctains ir* g'unt'it* it"tlt in rlris prt*:i"t*" " f-lS lcvels shere the pnxlutt is

co.rplcrcly ..rld *or"r''rnr"ii". ii""r.rnut of uy-pr.*tuct lk.tn rvuter-scnsitive prulucts is

;:'.ffi;-iJ t'v wastring with.a suitablc solvcnt'

IV. T}ROPERTIES AND USES

A. Products Made by Aqueous Slurry Reactions

l. Pntpcrtics ----._r.- .,i- ry. is vcry similar in up-

Llw-MS hytlroxyc'thyl starch' rrrlttt' vil oquL\)us slurry rcactton'

Dcaruncc ro unmoditic'tili;J';";;il,o,o .tiii.t grcatly -in

many.of their othcr Pnrpcrtr!'s'

Th" pr"r.n"" or nvo*'*y"rivi'g-"ry oir*pr,r,.i;l;;g.l boniing between sta*h nrol('-

cutcs thcrcby ,"au.ing'iir" or.,-un, rf cncrgy ;;",ii; siiubilizc rhe stan-h in rvutc'r' Thus'

hydroxyethyt *tu'ttt ttu* u loo'er pa*ting-temPeruture than unmodified starch'

tn addition. on." *.iruiiiir.J. ,.urr.iiu,i"iitli'lt tiuittt ttt"int is inhibited' soluti.ns'f

hyctroxyethyl sur.r, n"J"'irp*""c viscosity ;;ilii;,)'. morcclarity' a reduced tendencl- to

rcrr()grudc. tctrcr rrec?.c'Lo* .,Ji6,y. oni in"r"o*tltt c'hesiveness' Filnrs i*e c1'nr!'r :rnd

nrore flcxible rtrun rtro*l ;il;fi;o *tuor,.-rt.v erhibit improved erease brrrier proP'

ertics bccaus. ,t.y uJ*nr.Jil;J ir* "f pi;;.,1"-. All of these inrirovcrl xrturion und

fihn proprric* ,"*ur,'rl.r,r, iniit i,inn .rr ,rr. iy,r.sc'n bonding betwcen slarch nrtrlecuL's b1'

thc hydroxyethyl gntups' hvdroxyethyl starch does not cause l*x'culation-'

Since ttre trydroxycthyl group is nontontc'.r'il;i:';t'ilti- ""4

n"r. .trter th:rn Pasl('s o[

*j:mH"T'il; ft :];;::*H i'lI i, *ir" n, ac itrs and basl' *o it ur t vo*x v ethl r

srarch can bc used o"", u wide pH r"ng" r*i,"hili*"iir"i"s its desirable propertir's' Thc

hytlrcxycrhyl sutstitu..-nr ..rniuin* a rcuClty t.-i--in* pti"tui' trytt1t^yl gmup which olit'rt

iRcreases rhe reacrrvrry of hydroxyerhvr ".J *'i.n-tttl"putttr *'ith unnrtxlitic'd stlrch' Tht'

low cosr of hydmxycihyl srarch nrlkcs it esfcia'y allmcti't' in nrany applic'ti'ns'

3' uses in pa1^*rnraking' ln the granular lonrr' it is ust'tl

Hytlroxyethvl srarch is usett extensivclv i:*f,T]:Tl:*L[:.:ilil,. ilii;-,i'tr. rhr"

as a r.urnish ao.titi"e u.*."usg of its l'rv gcratiniz:rti'n tc'rrr**ralttrt'

srarch pasrcs in rn. iJ"r,**rion ot'rhclal)c;'r*'ii;t to pnrvidc adti"d strr"ngth to tht'shcel'

The low getatinizarion-i"rf*r",r* tf f,l',f,o^V",ftyl *tan:h ensu.res that pasting txcur: in the

sr*het bclbre *utt' "'*t'*i'it-tlt'ntptt'tt"'M"t;i;;

l-.*t'd cln bc' incrclsc'tl s'ht'n h1r'lrtrrlcthl I

-i'*';.,;;*1""i:|;;;':1,lll'J;*:['[1;'1i]*irir1 or fir'rs r{'tr1'trrogcthl-r 3..rchc's 'ukr'

them cs;rciaily uoi.ii t'.n sizing on,t "nntinf-pu*lr.

tu,ptttvcd gloss' printabilitl" rnd r'*-

siilancc ro o'y nrur"riof- ,"*fr *i*n f,y.fro*il,itii .i*tt' i: ":1li *"se applicatitrns' Thesr'

;r'pcrrics or" "*."nii i tor nign-qualir.v s,riiing puJ*r. nt*guzint'.sltxk' and pa1^*r ftitt is ttt

r** uo-d in c.ntacr rvith grc-itsc'or oil-tt"'g" b*i'i* tttup' ilstry b*txcs' r'uargarinr'c'lnons)'

Thc viscosily srabilit-v ,if hydro*yettyt *tu'J-postc facititates y.niform apptication on the

pa1^-r during sizin.c and coating..Hyd-^r.iiitlr,"r.t .it compatible t{ith mos{ comJ*'tnentt

trfctrtrttrtcrciitllyusctlsizc.ftrnrrulatinn.ond-.n"tingctrltrnt^\.cau.sr".ofitsnonionicchirrirr.ler.(irxrtl lilm c.nrinuiry is rcslxrnsiblc lb, ,1..' ;t..'i;t'itt g"'u*t' barricr propcrtir's .[ papc'r sizt'd

"'||iti:Iilii1*:.',Tl rvi!.etr usr.d ro size yarn in rcxrirc manuracturini rhe .:11::srh

anrl llcxibility u1,il.:.,,,r.h lilrrr provirtt- i;;ilt'':tl ahrasion rcsislancc'durin! 11'3r'ittg' lt

crhilrifs ad'csiorr r,, ,".r-, fihr.rs rihic' t,.'..i*,,., it'pr.r'cd fibt'r t.'lir*\'r txr.ding' t'.t'11 *hco

86 Modilied Snrchesiproperties qnd l)ses

tlillicuh blc,nds arc sizcd. Thc vixrrsir,add,on which als

:*l;fj'*l#$'i:l:l*.i".';N1ffil*;fi{[*#.*t#tjnishc's u hr'rc rhc'.hi-crr "r.tit,ir.

',u:*"

","u""i iil"j"",nj **"r- wirh rhc rhcnnosc*ing

;;l;::.'t bt'ncllcial' tn rtrit

"ppil'",i*t. i,," srrrch inrparr-..rl,riir" hanrr nxxtiticari'n ro rhe.

nr,*;*''J::': iJl.:i:'::^:l"bilir1' of h.rrlroxverhvt srarch atso nukes ir vatuabre in rexritc

., p," pi *r,,; il: : i ::[J:,ff ,l.:.,,illiii

..i,ii:,,ffi il! ;ff ',iil i;i jl;.x

_ __::thc' lttrr r'r sc'latinizati.n '"rtr*;;ii;,iiiiir";.1,,,1r sranh iJr..n*i.iur. bc.causc rhc. gr.nurcsprsrr'

'.rc readirf in rhe rJrier rton uii,rxlif*':,"*i;ffi;", do. A nrore <lerairc<r de-x'riprion nt

"o-tl,r,ng oor,"ri*, i.'**"*o in secrion rt, chaprer r5.'lhc.

abi lir-r, ol. h.r,tlrrx),c.,f,yf ."r.fi'i., krnn continu()us. n()nnsuhsr'rL's nukr's ir us".fui in ir,ui""ii"s'".r,i-.ir".l'i,_ "-l'';,iil'ffi:ll'lf"ll}:,;l,,:;ff::spcc'ds hc'causc less arthc'sivc ir d;:;;.J.'*r,i"rr ,rurn in il';;*, renrovar in rhc ttricn.The intprovcd adhesive propcrties nf h1,,tro*y"rhyl srarch nrof" ilricuhre nrarrer. one such

"rfii.;r* r;rt. ori *rir-i";;;;;;;il::firJ:,Hrr:l*il1ilgtxrr rhcrrrog,"u, q-*li:i n,, uppii.:u,i,,n..,,r rhc j;iil ;;;;il; ancr. 'ncc

dry. ir x,rvcs:rs an cxcc'tL'nt binder u'hile provirllngu .;nin"..,ha;i* ,r;;t'r""ulr. tn ad<tirion. rhc rrcc.zr:rli)"::rrr'::;r;i:::'.H*i:ull*,*iiiii,ilr"ffi:"J'il:Id c,rn,pound i* *ti".i".rB. I'roducts Illade by Nonaqueou.s RcaclionsI . Pnryt<'rtieS u'! 'rsilrlll,ll.s

N.naqueous *""r,:::.T..generat1' "*{: prcp.:rc high MS prutucrs. Thesc pnxrucrsharc c'rcc'ttc'nr

'isc.siry sratririry or-. o *ia" rn!" .riorn.ri,i"gr. i** abour 0..5 Ms thcvarc vrtubre in cord warer.'' rr,. "i*.,iir'iiL:tlr": hyrrroxl,erhyi srarch sorurion is quircsrabte r. shear. chaneer_1ry. ;;j gi;;;;:

",,""k. sarrs r,"u. ririri.n cr on ftesc producrs.Freezc rhaw stabirirj' inrproves ona ui.rr.!.udabiriry a""**"r.'"--,n"

", is increased.

J. t/.sc.r

:..:,' ;*1n k 1m;::'r iJ T:,,: ff# Hi,,,:y,,:l ilt: ::, lT:, ::,: ie:,..

{ r a nd ils a

.lTil::.,ffi ..'f ,',',,T,:"1il#$ili"Iffi fi iili.l"l'll'Lil-;il;'I:f U*";;

_ ln hltxrl applications. u,arl,slarch is usc.d

"_'Ur" ""*, sr.rr,.L r_- ---_

;lHl;:il,,i*:*l:'"r"'"iv * f^;;'r;i,il'i:'i:;'il:"i:'*Jl'::,rffi:;1";;;fr:::ri,,u*r;.;;',**,"":l,l#:t"il,#:li,:fi11l;,**;:irt*[lri"*#{#tp'.\'!'nr cnz-r'nraric arrack in rrrc utaxrsrre""i.r';.:Jni"r,"*,."ir.r'rlrries

arc conrrored bvh1'drol1'zing rhe srarc'h to.thc desirecr,r.r1."r". weight with a suitabrc acir..,:.{F.r cn oprorc'cr i vr' nppr i.'x, i.rnt. ir,.j il'j.*y"rnyr srarcrr has ad van rdinrcrh-rr surroritre in rrrar i,; il;;;;n"''"","* d*s.nor ,".r;;;*";T1,,r."il"*"JfiIl\\'hc'n ccrts arL' p^)rL.crcd *i,r,ir," i"*'",ri"."r,"r.*"rer,i".;;;i,rr.,.*,.nriue

washing ofthc cclls is r'-quirr"d ltl gp;;gs-' corrrplctc n,rr.ruat ,rrin" p..-r'r'a.;.u-,i",,*"", from within thccc'tts' '{ rrrt';rar subsrirurion .rro-.ir;;:;;- lll!1,::q* iulit,..

"nnl,..,"riun.* Hytrroxyerhyrslars-hc's ol' high IrtS ar'- "l"t tuut.'.J *'ir.r"i,ri"r rhic.kcncrs. tii,i..* protectivc coroi<Js.lllnr lbnrtc'n' and sizing !*enls. bur rhc

",rinun, uscd in thcse apprications is very snrar.

87

REFERENCES

I . Degcrins, E. 1'., Dr.rivativs's of $arrch. in c/t(,ni.rtrr rrrttl lrritrtrl- o! sl(dlreh' Kcn' R' w " Ed" Acldcntic

Prcss. Nc* Yorli. 1950. c'hap- lO'

2. lljcrnr.slrd. }:. T.. Pnxlnrirn Ind ust's of hytlruxycthyl rtarrch. in strrn'ft cft.Trrsrn t'4; n't fp11rl'r1r" \'ol'

2.Whistlcr.R.L.andPurhall.E'.F..F-ds..AcattcnricPn'ss.NcwYork.1967.ch!p.17.3. Kedcr. C. C. rnd lljcrmslrd. E' T'. U'S' p11311 1"516'631' l95O'

4. C|rL. of frrlcrul Rcgrrllrirms. Tirlc 11. cFlt l7g..l5:o. U.S. c$rcmni.-nt ltintins ()ilisr'. \\';rshin$trttt.

D.C.. l9ll-1. Ix.5.Thompson.}V.t..'llriltlrn.J.J..ulldll'rllon.R.l'..|'cnirt:rnr.cofslirn.hdr.riruli\'l.rilnddcrlranrrhcn

infu:*rl rficr ht'nr<rrhage- J. Ph.Lluucol' Erp'Thcr" l-16' ll5' 196l'

6. Thompson. lY. 1... llbl-l. D. tl.. rnd lvriton. R. lt.. llL'crting rrilun* in&'rt's ol hlrlntrlcthll stln'h'

.lcrrr.rn. bkxxl urxl lluco:*'. Prrx" J'rtr" E'tp' Eiol' rtlcrl'' Il5' l7'l' lgtrl'

7. Thompsoo. rv. 1.. rnd (irdsdr.n. R. ll.. Pnrlongr.d bh;rrting tinrc urrl hrptlihrinogr'nr'n1i1 in {ogr rlk'r

infu.Lnofhl,tlnrrl'cth1.Islu'th:!ftld!.\lr.ln.Tnu1|itliottPhihuh'lphiltt'5..1J(}.196.r.t. Pr.rclnll, D. ]'. rnd llinkcmr. ll'. ll'. U'S' Pulcnl :'i)65'6'U' lgflr'

9. ycrt6, T. 8.. Crrr. lu. ll.. rnd tuchttrcttcr. C. t... tl.S. Plrcnl .1.:f,{.tlgl. 1965.

10. Potcr.s. R. tlt.. U.S. Prtt'nt -l.Jll7.t).l8. l96lt'

l].lrrch.ll.lY..Sichrrh.T.J..rndChcssmrn.}1.}...Arlxrrpritrnrrrnirlkirlitndurr.hd:rsltjr\c\rrnr.I)ic.Srrir&c. 13. :0O. lr)61.

12. Robcrls. ll. J.. Srln-h dcrivulirr's. in.st.lrci c/rr'rnirtrr rorrl hTltnolr'.(.t' \irl' :' \\'histlt'r' R' L' Jnd

Pust'hirll. E. F.. F.dr,.. Acudt'nric Pn'ss. Ncw lorli' 1967' l9'l't l. li1rslcr. c. c. rnd l$trnrsled. li.'f .. llydnrrycrhyl- :rntl h1-dror)PnPytsrrR'h' in llcrfurrLr ir (ivh'htlnilc'

thr^irtr',. Vol. {. Whistlcr. R. L.. Ed.. Aculcmic Prcrs' Nr'n Yrxt' ltXrl' ch:rp' ?l'

14. lft.y..Beeskc.D. lll..udcrrlcr.J.E..Detcnninationoflhcnnrlarsub:titutionrJli(ttrfhlrlnr\)cthllstanchr's by grs chnrrrltrlSr.lphy. Am/,' Chtm" 55' '1'U' l9tl'1'

15. llrnks. ri..-cr.n*,.A] ci i.. rnd ttluir. D. D.. A rrtis'w of thc cht'nristry of h-r-dnrr1-tth1l stirnsh.

with n:ft'n'ncc l(t ils ulrc lr I hhrrxJ plasnrir volunr crprndcr' Dic Stiilrlc' lf' l8l' l9?:'

16. tlrnls. lV.. (irccnrrxrd. C. T.. rni [luir. [t' D'! Thc rlructun* of hydnrryt'thtl $ilNh' 8r' J ' Plwrnur'"! '

47. 172. 197-r.

ll. lluscmrnn. E. rnd Krftr. Ift.. Utr.r tlic. vencilun$ rlcr sutxtitucntcn in snrcrtislichen amllosr'ithc'rn-

Mocrtnnol. Cftcn.' Jl. :{)lt. 1960.

l tt. k lt. (1. 1;. rnd 8rotxl. K. flt.. (iirs chrrrnnrrgr.rphic inlr'stigittion rf hyrlnrll-cthyl url-hxr' hltlntll zrtr'r'

Anol. Chen.,.rt. 1767. 11166.

19. Srivestrvr, H. C. rnd Remellngrm. K. V., Distribution of hyrtnrrycthyl gnxrps in commersial hlrlror-

ycthyl $an'h. Dic Stiirke^ 19. 295. 196?'

20. Dc Bcldcr. A.. N. rnd Ro-rn. 8.. Thc sutr:iriturirm prn!.ms of o-l!-h;-dror;-ethll) sr:rn'h lnrl ()-rl-

hydmxycthyl) rtextnn. Carhilt;-lr.8cs" 10. 391' 1969'

2 t . Bollenbrk, G. N.. Golik, R. i.. anA P$rlsh. F. lV.. Dirtribution of hydrurycthl-l gnrupr in h1..tlnrtl-cth) I

starch. Ccrcol Cftcnr.. '16. -1O1. 1969'

22. Mourltr, J. ly., t\lerkus, H. G.. rnd dc Gtlrn, L.. Grs chnrmatographic dctcrmination of hldnrrl'eth1l

dcrivalivcs of glucocc. Anal. Chem-,4t. 1557. 1976'

23. Mcrkus, H. G., trlourlts. J. lY.. de Grlan, L.. rnd deJonS. lV. A.. Substitrrnt distribution in h1-

dmryahyl stach. Dic Stdrkc.29.4()6. 1977-

2a. lrri. (i.. lrrs.orr. li.. end Thcrnder. o.. cu:*'hnrrutogruptric lnrllsis ol lhe sutrrtitution prtt!'rn rrf

hyrlnrxycrhyl starch. l)ir Sr(irlr. -1f. lr0. l9tll'25, Grccnwood. C. T.. Slrrlics of thc' prr'panrtion. ;n1^-rtit's und physicr*hcnticEl shur'rr'tr:n?llittn \)l'ht'

drorycthyl staruh frrr u:r!. a\ ir volunrc.-r.rlr.ndr'r for bhxd plilsnra. Final Rcp. NUnl{'7O-C-0lOl' t"s-

Depnrtrrcnr of thc Nuvy. Officc of Naval Rc:*arch' U"S' N'f'''S' AD Rcp" 7'1:7E5' 19?l '

26. Ven dcr Bii. J. R,. Mrdeme analy:itnnrcrhrxlcn fiir st:irlir\Jcrivate und sidiehldntlysatc. Orr .$trirtr. 19.

256. 1967.

27.Mor8en,P.lV..Dt.rcrminati()nttfclhcrs|ndcslcnofcth}-lcncgll.col.h/.fn3.(.lclrr..{lrrr/.f-rl..1s.5(n. 19{6.

2tl. l,orlz. ll. J.. Dctc.mtinrtion of h1-droxyultyl gnrups in low'suhstilutcd stan'h cthen' Ano/' ('/rcrn ' ltl'8e2. 1956.

19. Grtr.nwood. C. T.. Stutlics of thc.prr.pirrurtrn, pr({\'nir's lnd ph1-sicochcnric:rl shamtteri,ltion ol h)-

Jr,rxycthyl sirrch. Final Rcp. NOml4-71-C-O:Stl. U.S. l)tpurtnrcnt of thc Nav;-. Officc of Navirl Rcs'lru-h'

U.S. N.I.r.S. AD Rcp.. A0ltl{J?. 1976'

.10. luermslad, E. T., U.S. Patt'nt -l.J-ill.9t-1' lt)tr9'

.rt. Kkhr. C. C. rnd tljt'rmstod. l:.'l'.. U'S' p"jt'nj r'6'15'117' 1958'

.ll. (ircenwood. C. T.. tltulr. t). l).. end ll'hitclrer. ll' ff " A n(rvcl nr('lh({ lir thc pre*plr'rtitrn trl h}'

droxlcthyl sh[.h f()r thc cr\opn)lcclion ol'hutrran n-d hl'r\l cctls. I)ir Srrlrlt' 17' l()a)' l97S'