CHEM . RES . CHIN ESE U .

2004, 20( 2) , 232235

Synthesis and Biodegradation of St-g-poly( MMA-co-VAc) Initiated

*
by Manganic Pyrophosphate
1

1* *

ZHU L in-hui , CHEN Mi-f eng , JI Yan , XIA H ai-ping

and DING Ma -t ai
1. Col lege of Chemist ry and Chemical Engineer ing, X iamen Univer sity , X iamen 361005, P . R . China;
2. College of Chemistry and E nvir onmental Science, K ey L aboratory of E nvir onmental
Science and T echnology of H igh E ducation i n H enan Pr ovince,
H enan N ormal Univ ersity , X i nx iang 453002, P. R. China
Receiv ed D ec. 5, 2002
M et hy l methacry lat e( M M A ) a nd v inyl acetate ( V A c) wer e g raft ed o nto co rn star ch w ith ma ng anic pyr ophospha te{ [ M n ( H 2 P 2O 7 ) 3 ] 3- } as the initiato r and w ater as t he rea ction medium . T he influences o f r eactio n
co nditions, including pH v alue, initia tor concent ration, mo nomer concent ration and its composit ion, on percent gr afting and g rafting efficiency wer e investig ated . T he gr aft copolymer was char acter ized by means of IR
spectro sco py , scanning electr on micro gr aph( SEM ) and 1 H N M R spect ro sco py . T he biodegr adatio n ex per iment show ed that the deg r adat ion o f co rn star ch -g -po ly( M M A -co -V Ac ) w as mainly fr om star ch . How ev er ,
aft er poly V A c in the side chain w as tr ansfo rm ed into po ly vinyl alco ho l( PV A ) , bot h st arch and t he gr afted
side chain could be deg ra ded co mpletely .
KeywordsStarch, Gr aft copolymer ization, M ang anic pyr ophosphat e, Biodeg radatio n
Articl e ID1005-9040( 2004) -02-232-04

Introduction
Starch is an abundant nat ural resour ce w hich
is renew able and biodegr adabl e. T he g raft copo lymerizat io n of st arch wit h some v inyl monom ers
pr esent s a pot ent ial w ay f or t he productio n and applicat ion of biodeg radable mat erials, t her eby protecting the env iro nm ent . Various init iat o rs can be
used t o prepar e st arch g raft copolym er s. Ceric ions
[ 1]
are ef f icient but cost ly ; persulf at es ar e nont ox ic
[ 2]
and low -cost but ineff icient ; in some r edox sy stems it is diff icult t o det ermine the suit able propor[ 3]
tio n o f oxidant t o reduct ant . Comparat iv ely ,
manganic py ropho sphat e is an eff icient init iat or
w ith g ood select ivit y, low cost and few side reactio ns. Accordingl y, it can be used inst ead of t he
expensiv e ceric amm onium nit rat e ( CAN ) in mass
[ 4]
pr oduct ion .
In our st udy , MM A w as gr af t ed onto corn
st arch because of t he t ranspar ence of pol y ( M MA )
( P MM A ) . How ev er , it was co nf irmed t hat onl y
t he st arch po rt io n o f t his co pol ymer coul d be biodegraded w hile PM MA por tion could not . In order t o
make PM M A port ion degr aded, poly VAc( PVAc)
segm ent s w ere int roduced int o t he side chain by
co poly merizing VAc wit h M MA . PVAc could be

t ransfo rmed t o PVA under alco ho lysis or f ungal at t ack , and P VA coul d be easily biodegr aded . T hus ,
t he degradat ion o f the g raft ed side chain could be
improved g reat ly . T his art icle present s t he f irst
successful at t em pt to g raft the copolym er of MM A
3and VAc ont o co rn st arch by [ M n( H 2P 2O 7 ) 3] init iat ion and bio degradat ion of co rn st arch-g -P
( M M A-co -VAc) , t he resul ts are sat isfy ing .

Experimental
1Materials
Corn st ar ch( F ood grade) w as dr ied at 80 t o
a const ant w eig ht . M M A, fro m Beijing Chem ical
Reagent Company , w as washed w it h a 5% sodium
hydr ox ide so lut ion and dist illed wat er befor e dist illat io n at a reduced pressure in t he at mospher e of
nit ro gen, t o remo ve t he inhibit or hydr oquinone.
VAc w as dist il led at at mospheric pressure t hrough
a 30 cm Vig reux column . Bot h t he m ono mers were
st or ed in a r ef rigerat or f or f uture use . T he init iat or
w as prepar ed according to lit erature [ 4] . Pepto ne
w as supplied by Shanghai Medical Fact or y , and
bacillus subt ilis f rom t he Bio logy Depart ment of
Henan No rmal Univ ersit y .
2Grafting Procedure
Dried st ar ch ( 2 g ) w as dispersed in 70 mL of

* Suppor ted by the N atura l Science Fo undatio n of Henan Pr ovince( N o. 97150010)

* * T o w ho m cor respondence shoud be addr essed.

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Z HU Lin -Hui et al .

acidif ied w at er in a f our -necked f lask , preheat ed at

80 under t he at m osphere of N 2 for 30 m in t hen
co oled to the desired temperature . T he initiat or solut ion of 10 mL w as added t o t he react ion vessel,
fo llow ed by t he addit ion of VAc. Five minut es lat er , M MA w as dropped int o t he mix t ur e w it hin
30 min . T he react ion w as carried out under t he at mosphere of nitr ogen fo r 4 h . At t he end of t he react ion , the mixt ure was poured into et hano l,
w ashed w it h et hano l and dist illed w at er , f ilt er ed ,
dr ied and w eig hed . T he crude pr oduct w as ex t ract ed w it h acet one in a Sox hlet apparat us fo r 48 h t o
remov e homo pol ymers P MM A , P VAc and copo lymer P ( M MA -co -VAc ) .
3Acid Hydrolysis of Graft Copol ymer
T he starch graf t ed co pol ymer ( approx imat el y
1 g) w as w eighed accurat el y and hydr olyzed in 150
mL of 0. 5 m ol/ L hydr ochlor ic acid solut io n at 95
97 f or 3 h, all t he st ar ch w ent int o the sol ut ion,
leaving behind the gr af t ed side chain. T he per cent age of g raft ing and gr af t ing eff iciency were calculated by m eans of t he f ollow ing equat io ns:
G( % ) = m [ P ( M MA -co-VAc) g raft ed] /
m( st ar ch react ed) 100
E g ( % ) = m [ P( MM A-co -VAc) gr af t ed] /
m ( mo nom er react ed) 100
4 Biodegradation
Corn st arch -g -P ( M M A -co -VA c ) ( E g = 60% )
and t he correspondent side chains w er e used as
sam ples . T he graf t copolym er w it h 5% pol y chlor oethylene w as dissolved in dim et hylsul fox ide
t hen spread on t he sheet of polyt et rafluroet hylene
t o obt ain a film . T he g raft ed side chain w as dis-

sol ved in acet one and made int o a film in the same
[ 5]
manner .
4. 1T he Degradation of Cor n St arch-g-P ( M MA co-V A c) and the Side Chain
Pepto ne o f 0. 5 g, 0. 25 g beef gr ease and 0. 5 g
so dium chloride w er e dissolv ed in 100 mL of dist ill ed w at er. T he pH value of t he solution w as adjust ed t o 7 w it h NaOH. Bacil lus subt ilis to gether
w ith 0. 5 g graf t ed copolym er or t he side chain were
added t o t he solut io n at roo m t emper at ure.
4. 2 Degradation of Corn S tar ch -g -p oly ( M MA co -V A ) ( V A Ref er s to V iny l al cohol ) .
Corn starch -g -P ( M MA -co -VAc ) of 1 g w as
added t o 20 mL of a 5% NaOH solut ion of
met hanol and st irred f or 12 h at r oom t emper at ure .
PVAc in t he side chain chang ed into PVA . T he
pr oduct w as dispersed in 500 mL o f nat ural w at er
and put in a shady place .

Results and Discussion

1Identifi cation of Grafting
T able 1 show s t he IR spect ral dat a of corn
st arch, starch-g -P ( MM A-co -VAc ) and gr aft ed
side chain. It could be seen t hat t he gr af t ed st arch
show s bot h t he char act er ist ic abso rpt ion of st arch
- 1
at 38003000, 850, 750 cm and t hat o f carbonyl
- 1
at 1735 cm ; t he gr af t ed side chain show s bot h
t he charact erist ic absorption of PM M A at 1243,
- 1
1192, 1149 cm and t hat o f PVAc at 1375, 1243,
- 1 [ 6, 7]
1022 cm
. It co uld also be seen f rom t he SEM
phot os ( F ig. 1) t hat t he surface of st arch w as
sm oot h and it is g ranular w hile the surf ace of St -gP ( M M A -co -VAc ) w as rough and irregular . Ag ain
t he incidence of gr af t ing w as t est if ied .

Table 1IR spectra data

Sample

~
/ cm - 1

St arch
St -g -P ( M M A -co -V A c)

37203040, 2930, 1630, 915, 850, 755, 560

P ( M M A -co -V A c)

3420, 2999, 2952, 2854, 1735, 1447, 1378, 1243, 1192, 1149, 1076, 1022,

37203060, 2931, 1735, 1638, 1378, 1245, 1154, 1022, 932, 856, 762, 707

Fig. 1SEM images of corn starch( A) and St-g-P( MMA-co-VAc ) ( B) .


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CHEM . R ES . CHIN ESE U .

2 pH Val ues
Fig . 2 show s t he ef fect of pH v alues on G and
E g . On t he one hand , w hen pH is below 2. 7, a
po or g raft ing y ield is obtained. T his could be ascribed t o t he foll ow ing react ion of init iat or :
[ M n( H 2P2 O 7) 3 ] 3- + 2H + + e
2[ M n( H 2 P2 O7 ) 2 ] + H 4P2 O 7
T he new ly produced M n ( ) ions have no ini+
tiat ing abilit y . Besides , t he ex cessive H hol ds
back t he product io n of t he st arch f ree radicals,
w hereas t he st ar ch f ree r adicals are t he key t o pro duce st arch gr aft co pol ymers . High acid concent ratio n also leads t o part ial hydroly sis of st arch and
t he m onomers . On the ot her hand , w hen pH is
over 4. 0, G and E g are low because o xidat ion -re3+
duct ion pot ent ial of M n is reduced, t he initiat ing
eff iciency decreases according ly . T he pro per rang e
of pH v al ues is bet ween 2. 7 and 4. 0.

Fig. 2Ef fect of pH values on G( a) and Eg ( b ) .

3Ini tiator Concentration
Fig . 3 show s t he ef fect o f init iat or concent ra3+
tio n on G and E g . When [ M n ] is bel ow 0. 2
10- 3 mol/ L , G and E g are low because of t he poor
3+
react ing rat e . Wit h t he increase o f [ Mn ] f rom
- 3
- 3
0. 210 mo l/ L to 0. 810 mol / L , G and E g increase and reach t he max im um . T he decrease in
3+
- 3
t he graf t ing yield , w hen [ M n ] is over 0. 810
mol / L , m ight be due t o t he accelerat ion of ho mopoly merization and t er minal react ions .

Fig. 3Ef fect of [ Mn3+ ] on G( a) and Eg ( b) .

V ol . 20

4Monomer Concentration and Its Compositi on

F ig . 4 show s t he eff ect of t he t ot al m onomer
concentrat ion on t he graf t ing . G and E g increase as
t he m onomer concent ratio n is increased, i . e . , t he
increase of local monomers in o r around t he
sw ollen st arch granules . With furt her increase of
t he mo no mer concent rat ion , G and E g decr ease because of t he enhanced rate o f the homo pol ymerizat ion . F urt her st udies also disclosed t hat w it h increasing MM A content in t he t w o m onomers , G
and E g incr ease r apidly and reach almo st a const ant
v alue w hen t he molar rat io of MM A t o VAc is over
60/ 40, as is show n in Fig . 5. T his is due t o t he diff er ent compet it ory poly merizatio n rat e ( r ) bet w een
M M A and VAc. F or example [ 8] , at 60 , r MM A =
20, r V Ac = 0. 015, w hich show s t hat MM A is much
m ore active than VAc.

Fig. 4Eff ect of monomer concentration on

G( a) and Eg ( b) .

Fig. 5Ef fect of molar ratios of MMA to VAc

on G ( a ) and Eg ( b) .

5Composition of Graf ted Side Chains

As is show n in F ig . 6, t he 3. 6 peak o f PM M A unit and the 1. 82. 1 mult iplet o f PVAc unit w ere int eg rated fo r det erminat ion according t o
t he fol low ing equat ion : n ( M MA ) / n ( VAc ) = S 3. 6 /
S 1. 82. 1 ( S refers t o t he proport ion of t he peaks ) .
T he result s are given in T able 2. It could be seen
t hat the molar r at io of M MA t o V Ac in the po lym er v ar ies slight ly w ith t he variat ion o f t he m olar
r at io o f M M A to VAc in mo nom er , t he value approx imat es t o 2/ 1. How ever, t he possible reason

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Z HU Lin -Hui et al .

is st ill under f urt her st udy .

Fig. 6 1 H NMR spectrum of graf ted chain

[ P( MMA-co-VAc) ] .
Table 2Composition of monomer and polymer
n( M M A ) / n( V A c)
in monomer

20/ 80

40/ 60

50/ 50

60/ 40

n( M M A ) / n( V A c) 1. 97/ 1 1. 99/ 1
in polymer

2. 00/ 1

2. 01/ 1

80/ 20
2. 01/ 1

easily , w hil e t he side chain could hardly be deg raded .

2 Biodegradation of Starch-g -P ( MMA -co -VA) in
Natural Water
F ig . 8 show s t he deg radat ion rat e of starch -g P ( M MA -co -VA ) in natural w ater . It coul d be
seen t hat t he mass loss of t he sam ple increases
r apidly as deg radat ion t ime increases . A ft er 30 d
t he mass loss is o ver 80% . T his indicat es starch -g P ( MM A -co -VA ) could alm ost be deg raded completely . Since P VAc could be also t ransf ormed int o
P VA via f ung al at t ack , st ar ch -g -P ( M MA -co VA c ) could be degraded under cert ain condit io ns .
T her ef ore , t he mat erial s made f rom it w oul d
demonst rat e a g ood propert y of biodeg radat io n.

Biodegradation
1 Biodegradation of Starch-g-P ( MMA -co-VAc )
and Pol y MMA-co-VAc through Bacil lus Subtilis
Attack
Fig . 7 illust rat es t he deg radat ion behavio r of
st arch -g -P ( M M A -co -VAc ) and P ( M M A -co VAc ) in the presence o f bacillus subt ilis . It is obvious t hat t he g raft copo lymer dem onst rat es a rapid
degr adat io n rat e, t he m ass l oss is 9% af t er o ne day
and it reaches a max im um of 61% aft er 28 day s.
How ever, t he mass loss of the side chain is less
t han 8% aft er 28 d. It is pr obable that bacill us subtili s could pr oduce st arch enzym e, so t he st arch
po rt io n of t he g raft ed copolym er co uld be deg raded

Fig. 8Degradation in soil lixivium.

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[ 7 ] Hat ada K . , O t a K . , Y uki H . , J . Polym . S ci . P art B ,

Fig. 7 Degradation of starch-g -P( MMA -co-VAc) ( a)

and P( MMA-co-VAc) ( b) .

P oly m. L e tt . , 1967, 5, 225

[ 8 ] Pan Z . R. , M acrom ole cular Chemi st ry , C hem ical Ind ust ry
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