Modified Starches:

Properties
and

tlses
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 and
IJSES

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.

u.le.

rrr'

hr

I Sr.r. h I \\ 1;17nyg. (). lt. ll. (.rolrcr. ... ('h.rrlc. \\ Ql).1: I ltsan teti6 5J7.7.1i: N6t.i67l S [t\ tl,5;r) i. ieh-l-.1
I

lrl rrr.lsj1r1111.. JD(l rn(lc\.

hr\ t\\r\ rcnr(,\.nt\ illl cr \\ ,h i*n,,,s\,(x,. ;:"::^:::':l:'H,]l;::l ",1'Illi;llllli*r:"1:.-,i.,,,,:::,;]Iil, h'r\ t\'('rt"ntJdc lrr Sirt'rt'liahlc tlrl.t'rrl rrr.r.r'rr()n. h,t rrrr. autlr.r 'll.n r.\Frrl\rhrlrt\ tirr th(. \.rlr(lit\ trf rll rrrrtcrillr ,,, ,.r, ,ir.j'.aru."q1c1(.c\ 6l-tlr(,irantr trrt puhrishc, crn,lor.ssunrc u\c
I

.j,,(,

-;i:ll:.Til,1;

hxrl' trr irr\ . ,,.:li,';:ll; ,li"",ll,'nJ,.nllt'' '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.. ,
l()Sh
S('(

\\'. llrr;r R:rr.rr. r;r'rirr;r.

.1.1].1

l)flntin{. liruillr l'rIltillr.

Itttcrrrrttrrnrrl Strrrrl;rrrl

.llllr(1

h\ (.R(. I,re .*. lrrt iln(l l)nnlilt!. |(,)s7

l()S7 l()S()

l](xrl Nurrrhr 0

|iJ().t-5()6.1-.1

I tbrrr-r rrl ('rlngrq\\ (';rrtl Ntrrrrpr N6-l l(|7J

l,rrrrir.rl ur t.lre Itrritr,rl St;rles

il

79 ChaPtcr 5

HYDROXYETHYLATED STARCHES
Kenneth

Il. I\toser

TABLE OF CONTENTS

l.
ll.

HistorY...
Chemistry.

80 EI

C.
ilt.

A. B.

Mechanism Subslituent Distribution. AnalYtical Mcthtxls.

8l
82 83
8-1

Metho<ts

A. B.

of

PrcPumtion

...-, """'

Aqueous Slurry Reactions ...

Nonaqueous Reactions

83 8-l

lV. PmprtiesandUscs-... A. Producrs Made by Aquc'ous Slurry Rcuctiops" " t. ProPerries . 2' Uses-B. Prcxlucts Madc by Nonaqucous R!'itctions l. ProPerries. 2. Uses..
Rcferences.

""""'85
"""""

" " ' 85

$6

"''''"85

"""86 """""86
87

80

Modtlied Sturches: propertie.r ttnd

(Jse.r

I.
Srarch has been used in
r

HI.STORY

l:t unrrrtrririctJ',,i1:u:,ypiii..uir,'"illf|'.j|'llilJ.i:T:il")'.ilrrracrivc. wn;rc naiiuc.

both focd applicarions.'.ior"t it;;.;'b;;r:Tt,1id-,T1food applicarions for.many years. tn mosr un'out visc'sitv chilrilcrcrisri* strr'ngrh. Thc rc.tarivc.t), ,i.ri" io'r,ii,J-i"" ;;, ;;;'.;;

urr,"* trl slzrng run' iit "rn.l"nall"'ttt-x H-r'pothloritc

r

:;:fl.i li;iii, - 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 i' ;; il ;; #,',[i I .,?h J:: lff *l,T'* lo leave l.ugh i *, il::i I -ii:.""" ;:: ['Aiil.*' il:,j,:ff
u,,,r"', raun<rry

i"nrJ ,T;);r"XT:jl* i,,.q u i,. J in ;;"T l; jil

-";

*s aqucous sorurions tute u r"n.r..r,.-f ,.,

ffi',{,.;"s

rr,tr"n *;::;;il;. ;i:xihl,';#,ili,,iilT:lr:. x,ruri'n,,, pu,,;; (;;.. riqui<r

*rirch

un.r

istosir.r,

li'n

.-f-srarch bt'

lhc'-r'arn

*'ill

manl,or rhe.e p,obrem,.

thc'-v arc unacceprabre

'rsr'.sir'r'

lHill[Jl:::,:*-l,m:N*
tt.^c'traprers-t-i-J"a

o*,i.i*,#ffi,-;.y-Jil;:r,,J#jl,;.il.#|yo?::.;|i;;,1,J:ffi; r".ii"ny ,."r'*;ur. rt. ,"i."i"" [[,,on rcducrion r"ritor"..r"rt ryr gr,rr;tilffi:." causes a subsranriat 1nd Srso

oxidation of starch inrnro

n,,, srarch pasrc chanrcs ,t""t- nr u'n.r.rrir...l ,.*.ut,ing in lxxlr *"uui,rg

.;;il;;:';ln"

chc'nrical derivatization. of starch but *'ith.ut concontitant."ir"r.i,y ats' yiclds prqtucts which have gtxxt viscosity srabiriry. irr-.'ti.,i'o.",ylu,i.r" and *'as conrnrgrciar.iz"a becn known since rg65 in

,ol.

*ir. ---d

anionic .,rh*, n"guri,..ry .r,u,g",r [:roups reducc subs,iarcs. ,hc ""u textile pruducriin
is grcarty

ar-"iri.iii.",.'"

i.lliJli;"1"'

ha'c linritc'J

;il,;'l;"*ll,r,r,"i,

rrr*.il;* rr,"'iss;.,'iJnir";;;;;;;;"*"r,,,,

*"J"""yiJ'l"u.",r,ore

prtxlucts h hrnd is st:thlc'ro r,1.rr,r1r-ii'"r;J',,,l|:,.f:avrng cxccllc'nl viscosity srahiliry and rhc crhcr sinc(. tet:., hr, ,h;.lt:l!:.T.cr'!'n ilt high pH. Tt"."ik;;i;ir;j;;;:: \' nr'\'L'r *.'r" pr.*r,i:..i havc t*cn kn'*'n in rurg..-r,,,iJ;'"";*:tarch c()sr.

Erhcdlicarion of srarch givcs

used in nrany appri_ unrrc.r arkarinc

",n*:ll;lililil:1:-:tcIi'lrn.f t,,,,tr.'*r"riit;;; :""**nsi'c c'th-r'lc'nc' oritJc i" ,r,.' irJd-. ,ti.,'.1,,u,,,ni"s

(
(

c'!h-rrcnr"':l:r1:':.".r

',"J;';":;"::l;":::
..

lor prrxrucinr

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

i.

**

pi 1iiil:fil#ili.j;*;:,:l * il,J,,fu:# #.t;..ff trr p"*t in ..'ni".li'*lli;';,*i "ttf:j.llt's.classillcation

rn ,i,"
thar c.nrc's

"u

"- " "1.',,,

i.nl

lll,

: J :i :il;.ll

l]*}:1.lllillfffi
burchcr

lft
,

is rttadc b-r rc'cting prrrpl-rcnc. tlritJc. r'ith sr'rch untrc,r:rlk:rlinc 'r-csirahrc'n"'^',.--.; n!i,.,,1..rr,y;.,;,.;; ,,,.c ,,brui,,..l. hur rrrc :ill'.T;';:";.:il; il'li" .irict-n.r:.,,riil_illi:ili,1';::::ll;: ;;;; '*c'. arc approvctr b1, rhc ,f.on l: 'rirccr iixxr addirir.c-s n n('r ri\xr appr icur i.rrs r,r. ";;;";;:il.;r".ljlllli:']fi'l;l:li:n"s i,,, i,il ;;:;:,I1il,::::H +;:HJ, |,r,r.lfi i.Y;;

i,l,i ffi"'j slarch H'rdror'rprop-rl

i

;;o;;;;-,,, b,rrcs) ";;i; l;'fiJ.i[:lX.j'J,.;ll,l,J],'1; i:: l'l ffi; :: ll; :, fl;ii'r.lT i Lg r :i; Iiff :ii n;r.,., r LTr ril *. :l ff n r,. n n-" i ;iil[;il11";,,il:l ;H1;ilH{',_.,m:i$
,:::,
i

;;; 1 as a sizing :rgcnr is

r,,,

.;J

* ;ffi

i-,ffi

:ji;*u;;

t*'

l;,**;,*iili[ip_,cnc,,xi,,.]il jilf

8l
starch was conrnrcrcialir.cd in the 1960,..t'"' Thc'sr' vc'ry lorv-cosl stanch pnxlucls nr'\'!'r "intlustri:tl achic.vcd thc. cgrnnrcr.*ial succcss of hydroxye'thyl starch ht'cuuse lppnrvul as Hydroxyethyl starch remains the prtxluct starch mdified" was ncvcrobtaincd lronr the FDA. is ncc'dc,'l of choice when a low-cosl, premiutu sturch pKduct rr"'siitant to alkaline conditions

for nonfood applicatkms.

II. CHEMISTRY
A. Mechanism
Hydroxyethy,l starch is produced commercially by reacting ethylene oxide and starch undcr alkaline conditions lEquation l).

q{oH

Starch
'llrc gcncrully-ucccPted

Ethrylene

ltttdroxyefid
Starch

OxHe

(l)

ttrs'Chanisnr l'trr fhis tl'.lctittn iri

shpwl in ldUuti6ns

ttr

{'

,c}"

CI{OH

+OH.

+rto
(:)

+ lor cH.-94

OCflCtqO-

(-1)

+
ocH,ctlo-

H.O

OH-

82

Modificd Starches: propertics uncl lJses

,"&:ff:"lrfrom
Lcach et
star'-h'

Tlrc lt-r'droxidc ion abslracls a pr()l()n frrrnr onc 9[ rhg rhrcc av'ilablc hydroryl gnrups tEqirJtion l)' llrr'.sr.rctrrlc i()t gir,*i,,...'i'uii"*r,,n,ti"."i.i'.li*,,rr",," opcning and sintultaneous pnxtuction c.using ri'g .ttl'" ncw allioxidc-ion ia,iuurrun 3). 'xitrc The rarter picks the water tiberating an hydroxide ion for f'rr-h-er,caralysis of rhe reatrion

al' sh.we<l that nxrsl of thc'alkali in alkalinc starch slurrics is adsorbe.4 by thc This indicalcs lhut al lc'ast un.' uiil " ..ru..n tf.rro*il; ; srrongcr aci4 rhan warcr. ln rhc hldroxl'erhvrarion or,rur.r,. i,"u nu"t"optiti;'r;r;;;", rhe resurring srarchare ion is ablc' lo conrpcle effc'ctively "ti.,i u'i,r, ri" relativety row of hydroxide ions t. gi'e reaction efficiencies of 7b ro s0;. "on."n,ru,ion Thi, i. i.. ougrr rherc arc four ro tinrc's as nranl' nrores of \,r,arer in it.. **"", as thc.re ur" "u"n-rt aquiuot.nts
of srarch hydroxyr. 'vc B. Substituent Distribution When starch is chemicaily modifird. rhe degrc.c of substirurion (DS) is define<J as thc c\'('rusc' nunrb^-r of h1'druxyl gruups rlcri'arized i"r unir.,. Thus, for nrcrhyl ethc'n of starch' the DS is-eq-ual ""rty.r.rsi"lur" a ,rt. ot=rge nunlfr of merhyr subsrituents pcr glucosg unit' Howeler' in anhydrorhe case tirrl'.r-r*y.,hylation. thc crhylene oxide can reacl wirh an1'of the thrce h'dmxyt gmups of rhc:rnhyd..rglu"n*. unli-o'.'*"lr as with suhstitutr'd h'dnrrictlr-r'l'g.i'up.'Ti,': li;"; rc*cri,ir rcsurrs i,, ir^* tin.,,,uri'n an atrea,v prry,rxy'r'th1lc'nc. sirte chain. rr,i, 'r.a oridc'rc'acrin{ u'irh a singre "r,uining:;r;;;; resulr in mrre rhiu itr.l. n,ut".ules of crhylc.ne unir qir:ilg thc' thc.n-tical tttitrintuttt' T."nrr1:anrglu.-or" grss-ibi[irj.""-"pp"r.r, DS of grcarer rhan 3. pruvitlcitirr rhis irr..',lru, nurrar subsriruri.n (MS)
thc t'riat

ffi::.tt.|$ifil,as

nr";r*;,,i

n,ot",. nr ,"og"nr .",",t in..'r wirh rhc srarch

rrr

|.f;:,f;l,:

The most prevalenr commcrciatly prtxJuccd hydroxyethyl starch prtxlucrs havc an MS of lcss than 0'2 and il rhar "noi.lt*..u ln ttl'n* highl-r' rtr'ri'atizcd pnxlucr..',,,".il'"i".tD, r-hc ds i* .r..,'nriary equar ro rhc MS. ,"uai.ui,rr';,;.:;,,,, irr vrr'c'rs. nral' be signiricanrrj higl,":. ,'h;;',i,"

";;'Jil;. *

os au" ,"

rh;;;;;..

'rg.nic u,.s,ryo*ycrhyrcnc sidc

For conrrncrci:r1v prtxluccd 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 nunrro*r 6 h.r'drox1'r groups of rhe number 3 and rr", nor-t".in'"*urirr,"a-n;;;;; ur rgo".enr in rhe r'ariarions in rr',. .,,Jirions uscrl ,.rpr"p,,r" ,rr"ilv.r.o^v.rhvt srrrchcs lji::"ffiJ:1.?..T to :rnrl1'zc tltcrrr. tn !;";;: ;r rhc Ms is incrcascrr. rhe subsrirurion at a' .Li-t'Y:-""d ";y

Thc l*'ation of thc'.hydro*l=tr,yr sr.r;f.'* extensi'el1'by rie*crat t"r.-.n-grou]..'li. ,r," anhydroglui.osc rings has bccn $udicrJ *" r"o.,i'.rn h-r'dror1'ethyt sran'h appcar to affc'cr r'hc disrriburion .,r rrurriiu";;r;. r. ";;i;;", used lo prepare rhe

as describcd Thcrcforc. nrusr be ratcn to derenninc whicrr de'r'iniri,tn",rr"

Thc' use of h1'drox.vethl'l srarch as a blood plasnra exrendc.r hils gcncr:lrcd intcrcst in ln.thcr nleasurc of substitution. nuru"5'. iic nrtltc fr.cti'n of ariiryurogrucosc conrain ar r!'asr onc h1'drox;'errryt unirs rhar 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 rhcsc enz'nles cannol nral!21 c'.q- l.a tinkage of rhc srarch backb.rne if rherc is a subsrirurc, 3 sidc' of anh'r'dru'clucose unil on eithcr t6lo in qucsrion. rrr" ,,,"ai."r rcscarchcrs uscd the ternr degrce of subsrirurion i;:h, rr,i, nr"orur"-,u.ir"fi;r1or;.ally, starchhavr-. cellulose chemists have and rcserved the tc'nn DS to define the degree of hydroxyl subsrilution pcr anh.r'drogrucose unir

il;

*h;;j;ng

auftor is using.

rrrc rirerarure. carc

'fi:';jirt

ffi!.'

p rcc i a b

c s.'

butitrn in h.r'drox1,crh.vt starch have

J ;' J.:: T ::

":*:l

"#" fi',illff U"., p"iiirf,"d.r.r.*.:s

I,

f,

:*f',m*lr :H

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

8-1

C. Analytical

Methods .;.::,:H',n:
1!

:s

:$:dfl:T:.'--,.,}',
is used ro catculare ethylene oxide per

1;d; "J 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 f trytmarornohic mclhtxls.'' or.*Ji. '* "t*if ThJnumber of m.les.t ficat.ron of rhese n,o,"rii6iiiiati.,n."
,n.'i"','*ii*r".", ", ",nr,'.". ".*iitH'9}: follows: trusi is calculated as ""n,l"-t*J;t ""ii
IrlS =

'f

rvith the starch r,,'agent conrbinetl .per -i' *t'i'h re I ies on the conversion
v

,ffi

%c2l.ofound * g ++
irrctrh'rs

(5)

'l cstr.rr. r-thcn. irntr thc' 'n' L.w nxrrccur.r wcight kcr.nr.s.l;cn rrcirrcrr *i,'r,'rrl'.iti.Jic ucid and w'r inrerr'crr' *ith itxridcs ,,r ;;;;the appuratus. v'larirc arkyr u" u'e.r as aids in dryine
analysis. Thereforc. Of even grcarer

ut. capirhrr'

gs'nr'rlrting

.t,"*. ,n"i.,iuls should.not and acetoie are \er'v facr that ,t" io*., alcohols .r";;;;;

dilt-rculr

starch from aqu"r'us to'emover,omsrurcr..-e""nun.t",vacuumatetcvirtedtempenrtures.Sincethesesolsr.nts u" u*"J'o prccipitate' the the *"ro'' io"y *ttot'ta-nor inrerferc with i"*o't: *lu,ion or to aid r"

ll,*$.*[Hi';;:*l*::triiJ"::'iLl'$ ::l"Tr;lJ:ffi t*rt i*fur.JilV i*t"-itytng the.ir aoueous solutions' n*HffiHigh-MS ffiuii,*; i,-'l[r::ri:i$*]:'H*iti;:Hsnl*ffJll-" -filter manv instanc*' onr'
pnxrucr'tr rrurrng unorvrirll'lfi;;;;;;""0,,'o*l',.i.* i.tic"i rr,,npins ,tJ".'r,,iri.. "n.t.orc'rins pnrbrems is in ,iliffi;"',." cflicit'nc1-'r thc trrp rrscd of rhc

dJi;il"

cake.

rhe Zciset

i'ilei*r

in

the Ht

of tht'actrrrl l)s is ,*r"ror". ,i";Sl;cssenrially i* ro"'"'*iion'tit nii' c^tculition.f Jr.tenriirl isrrnlr'rr ' *i u""o"o ,r,.r *"., number b""ou** ir is hard rQ sep.lrure "".'i*r,rii" s vcry dirl.icurt 'ignint'ni-oiJthc'DS aon.io;o"t'* tr't'o eth)'lene orid!- units 0n a sinsh" when one of tlihl'tlnrrl t'th1 I This becomes mor app|rcnt 'l,ln '*'*;;; ; 6 dtil;;;'-t*t'1u'"* i'.. i*on'tcrs DS l '0)'
neelisibte.
anhydrostucose "",, anhydroglucosc. DS considerable oroducrs. but rhe

increased's the nunrber of poll:oryethylene chains is ,J*ir."i,nt Mt' At substiturion *"ti' ;i;;;h"" -0:3 .o;;i; tm pfS' et-trigtrer lVtS levels chatntng
ethylene is

rc*tion.

c""'ll'i'**rfi;i-ilil';tu;,l*t:il

'-tt"tiitt"

*' :**t:'::n: fl ttttti tttt' substitutcd is calculittt'd: unii*

anhytlnrgluco*"

rc'stor**tv,r"'*v"*'vii^'pi'*,*ui-1.:1t*Ili.:;f;'J,:"H:lroU*l$liliT n"'te tnc'li'lrn'lrr T:':';ill!1"i5":itii*:I ilil ;; ;ii'lt'e

DS=l---ti)r dcrcrnrini"*,n.'i-,rin",;;;;-r' :1 rcvicwetl in several aniclcs'r1':"
0.9

* p.*r*. i", been made ," ambiguous':3 ,t'uttural aspc'cts arc still J;;;*.orpt.*-ono'r-ot" *hich arc substituted *'ith ut *ntit.,*r"t"-"-""it' f)r.rr,.mrin.ri.n .f ld.;"iltili1".t

t;il.i;;;;;-icthr-t ont''or.trluc.st" high-l\lS ;.1;.;",i'-;,;.,n,..r* ur jl"ilt rne nne tt*ttu'" of these

We(l6l

+ 44

MS)

(6)

stuch urr' whereWgistheweightof.freeglucoseinasamptr'.:':.on,-)u'p.loAnall'ticaltechniques orirJr.'*1'"th1'l gnrups in hydrtrxl'eth1'l

III. METHODS OF PREPARATION

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

.ttt

8{

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

slum' ai i, i-

u;*ilg agucous slurry reactions. This ,-

i,'il,':il$ilii!::1r.1"..'i:,Y;;' "-l
duc

,;^;;.,::iili'1ll:

.,,nj:.

d<,nc corrrn-*-rcialtv

rrrirrirrs

;0"'"; l:T'!1.:l',...Tifi*;l;::f,::,T:l
rr.:rcri.n

,.,,, ...,.i r ii iiir

ll*li{niin *li*Ii*, r. ;; i;,$".;.:.:.1J.):'l:.lll:tr rn rh.

rr.arcr. _::,, 1.,r rne

_r ;:,*r riltcrcd.gh *iu# andii, u.,, ns : rvashctr. dricd

i

vc,y

ai

$"llill*il1n$},;;{Jtli;1ii*;ui,;,"il':ff 1;.::r":H:rrl: or crhylene oxitle. tirr luo,-n6 t ,,a-,,^lr]] A .,r;";;;j_;::dusc ,u.ili?T#t^1 i:rl,'r;i:'.fi $:ilt:nl;iiTi::,ffi il;,i,}+r.'",."
rne incrca.\ed

ffi

'f "*liun'""i'i1j:t't''' *:[i$:**:*;il]',:i*l,l$rf

corrrnrcrci:rrrr.. 1l' .,*

*nffi ft fil.,pl$':*,''ffi n"

starch so that rt

hish lcrc'ls

ci

i**'firir*lrffi

..i.r".r ,.,

it can bc trrmbincd ;3,*ii.l'#'lir'-.',n"*".ii.".ii'l,."", ,i.'ir'#l*'it"s a"t* ;;;:tuX',',',H."

;i# ,,:il*l,:;firi{tt','l,?;:
ac
r

ffi #ili lii;liiillii1,,'tffi ;'J:::fiiitT;

*i;I^*Hlffi iltlliti'.;1j;';';;#drilJ[lT.'':=']arc''lr^u'-u'i"i*"'"'t -ftl'ilf" il ffi #::""1T'; :tlfi: ffi;; r'c. rt i'n i.l i1"" I:" r,""ii r,' ".r .1":l:,::h[ixH::,,1]rf,Hr:1.{;m{l;:fi :H:x.i:::.:,:,,yrcsu,,inswc,,ing ":il;if
"

.
I

f-"Hl;1: yl''{*#:fi lilff -': Jiii l:hi:|n i;:{ aricr.rh. nro^,^rJii1,'""'il* iilr'ff$.:"T*1.'ll,lf.1;,'f,l':::"':""".,ir iru.-r"l'nr, - - t-"rlu t'ul o' rh(r slurry cithc'r rr ir urv,irriilltjltitl;.^ L: r . ._ h.t.u." ,,,

il

fl'.':,#x;1.1;T:11::!:'ilifi:ffir[:;il";"1.:[;:;j1'.',.*,:iiiT!::];.,}:[ o rb

il

r','!

hiffil

$**TrumM*
( t.

u'rth a considerablc thts u'1;p1. tr 8.,

. High-IlS h1.dro1, lo .l% srarch vrli

hr. pnduct is xrlu

.*; iilll:iil:lu';il:l,iliTl.:i1"",,, prcparc'd by rc.acri,n in arcohl)r. , ,r.,; slunicd in c.luai *"i,,1,,',,,1, ,,;,;.; .:^];'l::rcr ;*,nlmlJ,,[iL1i*xiJ:tT,*,,,:,,ffi ;t*ll;nnm*lm:
picarr-r . ,n" :rt\)ur 7ri adtJirional
ts

-. rl

n.rgh-J\lS hl,droxrr

)o.n19u*us Reactions
an
r

. *fuii

i:'iJ;:l';ffi ,;ll.l:*ii;l*:ri:r,l.,"::'i,i,jjx"';:{illi;i':lf l;;*';*'lit y;,

..

r**i'5d.l;;;iil#ffi ffi
ra rc n

tl,l'# ,1'r'**t
ru

r ,r. r i n.] .li

"

ir.,,

:11

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

85

s:l"to:""..T*.I,:j'T'fi wlth a

I chloride reacts crrronrhydrin una *.*',ril'iy.irr*iJ". it"tlt in rlris starch rctains ir* g'unt'it*

l*':l'.;:5iil::T::I,.1.";t'"X"*IJT'$[l:;*".ffi in the sysrenr' The pi r1"r i.it.'-o.,u"t caratysrshere the pnxlutt is f-lS lcvels
prt*:i"t*" " ii""r.rnut of uy-pr.*tuct
lk.tn rvuter-scnsitive prulucts

is

co.rplcrcly ..rld *or"r''rnr"ii". ;:'.ffi;-iJ t'v wastring with.a suitablc solvcnt'

IV. T}ROPERTIES AND USES

Slurry Reactions A. Products Made by Aqueous similar in upl. Pntpcrtics ----._r.- .,i- oquL\)us slurry rcactton' is vcry vil ry. -in hytlroxyc'thyl starch' rrrlttt' Llw-MS .tiii.t grcatly many.of their othcr Pnrpcrtr!'s' Dcaruncc ro unmoditic'tili;J';";;il,o,o boniing between sta*h nrol('or nvo*'*y"rivi'g-"ry oir*pr,r,.i;l;;g.l Th" pr"r.n"" ;;",ii; siiubilizc rhe stan-h in rvutc'r' Thus' ,"au.ing'iir" or.,-un, rf cncrgy cutcs thcrcby starch' pa*ting-temPeruture than unmodified hydroxyethyt *tu'ttt ttu* u loo'er ttt"int is inhibited' soluti.ns'f ,.urr.iiu,i"iitli'lt tiuittt to tn addition. on." *.iruiiiir.J. ;;ilii;,)'. morcclarity' a reduced tendenclsur.r, n"J"'irp*""c viscosity c1'nr!'r :rnd hyctroxyethyl Filnrs i*e .,Ji6,y. oni in"r"o*tltt c'hesiveness' erease brrrier proP' rcrr()grudc. tctrcr rrec?.c'Lo* improved *tuor,.-rt.v erhibit xrturion und nrore flcxible rtrun rtro*l ;il;fi;o ir* "f pi;;.,1"-. All of these inrirovcrl nrtrlecuL's b1' ,t.y uJ*nr.Jil;J ertics bccaus. betwcen slarch i,inn .rr ,rr. iy,r.sc'n bonding fihn proprric* ,"*ur,'rl.r,r, iniit
thc hydroxyethyl

'

gntups'

group is Since ttre trydroxycthyl

*j:mH"T'il;
low cosr

""4 ur t vo*x v ethl r i, *ir" n, ac itrs and basl' *o it ft :];;::*H propertir's' Thc pH r"ng" r*i,"hili*"iir"i"s its desirable olit'rt can bc used o"", u wide srarch t.-i--in* pti"tui' trytt1t^yl gmup which Tht' sutstitu..-nr ..rniuin* a rcuClty stlrch' hytlrcxycrhyl *'i.n-tttl"putttr *'ith unnrtxlitic'd of hydroxyerhvr iRcreases rhe reacrrvrry ".J esfcia'y allmcti't' in nrany applic'ti'ns' of hydmxycihyl srarch nrlkcs it

cause hvdroxyethyl starch does not nontontc'.r'il;i:';t'iltin"r. .trter th:rn Pasl('s o[

l*x'culation-

i'lI

3'

uses granular lonrr' it is ust'tl in pa1^*rnraking' ln the Hytlroxyethvl srarch is usett extensivclv ilii;-,i'tr. rhr" of its l'rv gcratiniz:rti'n tc'rrr**ralttrt' as a r.urnish ao.titi"e u.*."usg strr"ngth to tht'shcel' ot'rhclal)c;'r*'ii;t to pnrvidc adti"d pasting txcur: in the srarch pasrcs in rn. iJ"r,**rion tf f,l',f,o^V",ftyl *tan:h ensu.res that s'ht'n h1r'lrtrrlcthl I The low getatinizarion-i"rf*r",r* l-.*t'd cln bc' incrclsc'tl *utt'

i:*f,T]:Tl:*L[:.:ilil,.

sr*het

"'*t'*i'it-tlt'ntptt'tt"'M"t;i;; -i'*';.,;;*1""i:|;;;':1,lll'J;*:['[1;'1i]*irir1

bclbre

or

fir'rs r{'tr1'trrogcthl-r

sizing on,t them cs;rciaily uoi.ii t'.n *"se applicatitrns' Thesr' "nntinf-pu*lr. ,"*fr *i*n f,y.fro*il,itii .i*tt' i: siilancc ro o'y nrur"riofand pa1^*r ftitt is ttt i tor nign-qualir.v s,riiing puJ*r. nt*guzint'.sltxk' r'uargarinr'c'lnons)' or" ;r'pcrrics tttup' ilstry b*txcs' "*."nii oil-tt"'g" on the r** uo-d in c.ntacr rvith grc-itsc'or *tu'J-postc facititates y.niform apptication Thc viscosily srabilit-v ,if hydro*yettyt t{ith mos{ comJ*'tnentt compatible pa1^-r during sizin.c and coating..Hyd-^r.iiitlr,"r.t .it

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

3..rchc's

":1li

b*i'i*

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

"'||iti:Iilii1*:.',Tl

manuracturini rhe rvi!.etr usr.d ro size yarn in rcxrirc .:11::srh lt ahrasion rcsislancc'durin! 11'3r'ittg' u1,il.:.,,,r.h lilrrr provirtt- i;;ilt'':tl anrl llcxibility txr.ding' t'.t'11 *hco fibt'r t.'lir*\'r
crhilrifs ad'csiorr r,, ,".r-, fihr.rs

rihic'

t,.'..i*,,.,

it'pr.r'cd

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# ',u:*" iil"j"",nj

tjnishc's u hr'rc rhc'.hi-crr

;;l;::.'t

"r.tit,ir. bt'ncllcial' tn rtrit

i,," srrrch "ppil'",i*t. ","u""i inrparr-..rl,riir"

**"r-

hanrr

wirh rhc rhcnnosc*ing nxxtiticari'n ro rhe.

'.rc x'riprion nt
'lhc.

nr,*;*''J::': iJl.:i:'::^:l"bilir1' h.rrlroxverhvt srarch atso nukes ir vatuabre in rexritc ., p," pi *r,,; il: ,l.:.,,illiii ',iil i;i jl;.x thc' lttrr r'r : i ::[J:,ff _ __:: sc'latinizati.n ..i,ii:,,ffi il! ;ff prsrr' '"rtr*;;ii;,iiiiir";.1,,,1r sranh iJr..n*i.iur. bc.causc rhc. gr.nurcs readirf in rhe rJrier rton uii,rxlif*':,"*i;ffi;",
abi lir-r,

of

ir,ui""ii"s'".r,i-.ir".l'i,_ spcc'ds hc'causc less arthc'sivc ir d;:;;.J.'*r,i"rr ,rurn"-l'';,iil'ffi:ll'lf"ll}:,;l,,:;ff:: in il';;*, renrovar in rhc The intprovcd adhesive propcrties ttricn. nf h1,,tro*y"rhyl srarch nrof" ricuhre nrarrer. one such il gtxrr rhcrrrog,"u, "rfii.;r* r;rt. ori *rir-i";;;;;;;il::firJ:,Hrr:l*il1il
:rs an cxcc'tL'nt

suhsr'rL's nukr's ir us".fui in

"o-tl,r,ng oor,"ri*, i.'**"*o in secrion rt, ol. h.r,tlrrx),c.,f,yf

."r.fi'i.,

krnn continu()us. n()nn

chaprer r5.

do. A nrore <lerairc<r de-

n,, uppii.:u,i,,n..,,r rhc binder u'hile provirllngu .;nin"..,ha;i*

q-*li:i

rli)"::rrr'::;r;i:::'.H*i:ull*,*iiiii,ilr"ffi:"J'il:Id
I

j;iil ;;;;il; ancr. dry. ir 'ncc ,r;;t'r""ulr. tn ad<tirion. rhc x,rvcs rrcc.zr:
c,rn,pound i*

*ti".i".r

B. I'roducts Illade by Nonaqueou.s Rcaclions u'! . 'rsilrlll,ll.s

Pnryt<'rtieS

prcp.:rc high MS prutucrs. Thesc pnxrucrs abour 0..5 Ms thcv rr,. hyrrroxl,erhyi srarch sorurion srabte r. shear. chaneer_1ry. is quirc sarrs r,"u. ririri.n cr on Freezc rhaw stabirirj' ftesc producrs. inrproves ona ui.rr.!.udabiriry ",,""k. a""**"r.'"--,n"

N.naqueous *""r,:::.T..generat1' harc c'rcc'ttc'nr sratririry or-. o 'isc.siry arc vrtubre in cord warer.''

"*{: *ia" rn!" .riorn.ri,i"gr.

;;j"i*.,iir'iiL:tlr": gi;;;;:

i**

J.

t/.sc.r

",
T:,,:

is increased.

:..:,'

;*1n k 1m;::'r iJ

ff#

Hi,,,:y,,:l

ilt: ::, lT:, ::,: ie:,..

sr.rr,.L r_---_

r a nd ils

.lTil::.,ffi ..'f ,',',,T,:"1il#$ili"Iffi

ri,,u*r;.;;',**,"":l,l#:t"il,#:li,:fi11l;,**;:irt*[lri"*#{#t
p'.\'!'nr cnz-r'nraric arrack in
rrrc

"_'Ur" ""*, ;lHl;:il,,i*:*l:'"r"'"iv * f^;;'r;i,il'i:'i:;'il:"i:'*Jl'::,rffi:;1";;;fr:::

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

iili.l"l'll'Lil-;il;'I:f U*";;

ol' high IrtS ar'tuut.'.J lllnr lbnrtc'n' and sizing "l"t !*enls.

slars-hc's

h1'drol1'zing rhe srarc'h arc conrrored bv 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 dinrcrh-rr surroritre in has ad van rrrar i,; d*s.nor \\'hc'n ccrts arL' p^)rL.crcd *i,r,ir," i"*'",ri"."r,"r.*"rer,i".;;;i,rr.,.*,.nriue thc cclls is r'-quirr"d washing of ltl gp;;gs-' corrrplctc n,rr.ruat ,rrin" p..-r'r'a.;.u-,i",,*"", from cc'tts' '{ rrrt';rar subsrirurion within thc .rro-.ir;;:;;-

utaxrsrre""i.r';.:Jni"r,"*,."ir.r'rlrries
r

il;;;;n"''"","*

,".r;;;*";T1,,r."il"*"JfiIl
tii,i..*

Hytrroxyerhyr rhic.kcncrs. "nnl,..,"riun.* protectivc coroi<Js. bur rhc uscd in thcse apprications is very snrar. ",rinun,

*'ir.r"i,ri"r

lll!1,::q*

iulit,..

87

REFERENCES
o! sl(dlreh' Kcn' R' w " Ed" Acldcntic . Degcrins, E. 1'., Dr.rivativs's of $arrch. in c/t(,ni.rtrr rrrttl lrritrtrllO' Prcss. Nc* Yorli. 1950. c'hapin strrn'ft cft.Trrsrn t'4; n't fp11rl'r1r" \'ol' 2. lljcrnr.slrd. }:. T.. Pnxlnrirn Ind ust's of hytlruxycthyl rtarrch.
I

1"516'631' l95O' 3. Kedcr. C. C. rnd lljcrmslrd. E' T'. U'S' ()ilisr'. \\';rshin$trttt. Tirlc 11. cFlt l7g..l5:o. U.S. c$rcmni.-nt ltintins 4. C|rL. of frrlcrul Rcgrrllrirms.

2.Whistlcr.R.L.andPurhall.E'.F..F-ds..AcattcnricPn'ss.NcwYork.1967.ch!p.17.
p11311

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' ol hlrlntrlcthll stln'h' 6. Thompson. lY. 1... llbl-l. D. tl.. rnd lvriton. R. lt.. llL'crting rrilun* in&'rt's Eiol' rtlcrl'' Il5' l7'l' lgtrl' .lcrrr.rn. bkxxl urxl lluco:*'. Prrx" J'rtr" E'tp' in {ogr rlk'r 7. Thompsoo. rv. 1.. rnd (irdsdr.n. R. ll.. Pnrlongr.d bh;rrting tinrc urrl hrptlihrinogr'nr'n1i1
9. ycrt6, T. 8.. Crrr. lu. ll.. rnd tuchttrcttcr. C. t... tl.S. Plrcnl .1.:f,{.tlgl.
10. Potcr.s. R.
.Srrir&c. 13.

t. Pr.rclnll, D. ]'. rnd llinkcmr. ll'. ll'. U'S' Pulcnl :'i)65'6'U' lgflr'
tlt.. U.S.
:0O. lr)61.
Prtt'nt -l.Jll7.t).l8. l96lt'

infu.Lnofhl,tlnrrl'cth1.Islu'th:!ftld!.\lr.ln.Tnu1|itliottPhihuh'lphiltt'5..1J(}.196.r.
1965.

l].lrrch.ll.lY..Sichrrh.T.J..rndChcssmrn.}1.}...Arlxrrpritrnrrrnirlkirlitndurr.hd:rsltjr\c\rrnr.I)ic
12. Robcrls.
t

ll. J.. Srln-h

dcrivulirr's. in.st.lrci c/rr'rnirtrr rorrl hTltnolr'.(.t'

\irl' :' \\'histlt'r' R' L'

Jnd

l.

(ivh'htlnilc' c. c. rnd l$trnrsled. li.'f .. llydnrrycrhyl- :rntl h1-dror)PnPytsrrR'h' in llcrfurrLr ir Prcrs' Nr'n Yrxt' ltXrl' ch:rp' ?l' thr^irtr',. Vol. {. Whistlcr. R. L.. Ed.. Aculcmic
li1rslcr.

Pust'hirll. E. F.. F.dr,.. Acudt'nric Pn'ss. Ncw

lorli'

1967'

l9'l'

14.

lft.y..Beeskc.D. lll..udcrrlcr.J.E..Detcnninationoflhcnnrlarsub:titutionrJli(ttrfhlrlnr\)cthll
stanchr's by grs

cht'nristry of h-r-dnrr1-tth1l stirnsh. 15. llrnks. ri..-cr.n*,.A] ci i.. rnd ttluir. D. D.. A rrtis'w of thc plasnrir volunr crprndcr' Dic Stiilrlc' lf' l8l' l9?:' with n:ft'n'ncc l(t ils ulrc lr I hhrrxJ $ilNh' 8r' J ' Plwrnur'"! ' 16. tlrnls. lV.. (irccnrrxrd. C. T.. rni [luir. [t' D'! Thc rlructun* of hydnrryt'thtl

chnrrrltrlSr.lphy. Am/,' Chtm" 55' '1'U' l9tl'1'

ll.

snrcrtislichen amllosr'ithc'rnlluscmrnn. E. rnd Krftr. Ift.. Utr.r tlic. vencilun$ rlcr sutxtitucntcn in Mocrtnnol. Cftcn.' Jl. :{)lt. 1960. (iirs chrrrnnrrgr.rphic inlr'stigittion rf hyrlnrll-cthyl url-hxr' hltlntll zrtr'r' l tt. k lt. (1. 1;. rnd 8rotxl. K. flt..
Anol.

47. 172.

197-r.

hydmxycthyl) rtextnn. Carhilt;-lr.8cs" 10. 391' 1969' gnrupr in h1..tlnrtl-cth) I G. N.. Golik, R. i.. anA P$rlsh. F. lV.. Dirtribution of hydrurycthl-l 1969' starch. Ccrcol Cftcnr.. '16. -1O1. hldnrrl'eth1l 22. Mourltr, J. ly., t\lerkus, H. G.. rnd dc Gtlrn, L.. Grs chnrmatographic dctcrmination of glucocc. Anal. Chem-,4t. 1557. 1976' dcrivalivcs of distribution in h123. Mcrkus, H. G., trlourlts. J. lY.. de Grlan, L.. rnd deJonS. lV. A.. Substitrrnt
2 t

gnxrps in commersial hlrlrorSrivestrvr, H. C. rnd Remellngrm. K. V., Distribution of hyrtnrrycthyl 196?' ycthyl $an'h. Dic Stiirke^ 19. 295. prn!.ms of o-l!-h;-dror;-ethll) sr:rn'h lnrl ()-rl20. Dc Bcldcr. A.. N. rnd Ro-rn. 8.. Thc sutr:iriturirm 19.

Chen.,.rt. 1767. 11166.

. Bollenbrk,

2a.

prtt!'rn rrf end Thcrnder. o.. cu:*'hnrrutogruptric lnrllsis ol lhe sutrrtitution l)ir Sr(irlr. -1f. lr0. l9tll' hyrlnrxycrhyl starch. physicr*hcnticEl shur'rr'tr:n?llittn \)l'ht' 25, Grccnwood. C. T.. Slrrlics of thc' prr'panrtion. ;n1^-rtit's und t"sstaruh frrr u:r!. a\ ir volunrc.-r.rlr.ndr'r for bhxd plilsnra. Final Rcp. NUnl{'7O-C-0lOl' drorycthyl U"S' N'f'''S' AD Rcp" 7'1:7E5' 19?l ' Depnrtrrcnr of thc Nuvy. Officc of Naval Rc:*arch' und sidiehldntlysatc. Orr .$trirtr. 19. 26. Ven dcr Bii. J. R,. Mrdeme analy:itnnrcrhrxlcn fiir st:irlir\Jcrivate

dmryahyl stach. Dic Stdrkc.29.4()6.

1977-

lrri. (i.. lrrs.orr. li..

256. 1967.

27.Mor8en,P.lV..Dt.rcrminati()nttfclhcrs|ndcslcnofcth}-lcncgll.col.h/.fn3.(.lclrr..{lrrr/.f-rl..1s. 5(n. 19{6. stan'h cthen' Ano/' ('/rcrn ' ltl' 2tl. l,orlz. ll. J.. Dctc.mtinrtion of h1-droxyultyl gnrups in low'suhstilutcd
ph1-sicochcnric:rl shamtteri,ltion ol h)19. Grtr.nwood. C. T.. Stutlics of thc.prr.pirrurtrn, pr({\'nir's lnd U.S. l)tpurtnrcnt of thc Nav;-. Officc of Navirl Rcs'lru-h' Jr,rxycthyl sirrch. Final Rcp. NOml4-71-C-O:Stl. 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'

8e2. 1956.

r'6'15'117' 1958' .rt. Kkhr. C. C. rnd tljt'rmstod. l:.'l'.. U'S' p"jt'nj (ircenwood. C. T.. tltulr. t). l).. end ll'hitclrer. ll' ff " A n(rvcl nr('lh({ lir thc pre*plr'rtitrn trl h}' .ll. l()a)' l97S' droxlcthyl sh[.h f()r thc cr\opn)lcclion ol'hutrran n-d hl'r\l cctls. I)ir Srrlrlt' 17'