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SEMICONTINUOUS EMULSION POLYMERIZATION OF VINYL

ACETATE X. KINETICS OF HOMOPOLYMERIZATION, CO
POLYMERIZATION, AND INITIATOR DECOMPOSITION
IN THE PRESENCE OF SULFOSUCCINATE-TYPE
SURFACTANTS
a a
Dan Donescu & Liana Fusulan
a
Center for Plastic Materials Research , 202 Splaiul Independentei, Bucharest, 77208,
Romania
Published online: 19 Apr 2007.

To cite this article: Dan Donescu & Liana Fusulan (1994) SEMICONTINUOUS EMULSION POLYMERIZATION OF VINYL
ACETATE X. KINETICS OF HOMOPOLYMERIZATION, CO POLYMERIZATION, AND INITIATOR DECOMPOSITION IN THE
PRESENCE OF SULFOSUCCINATE-TYPE SURFACTANTS, Journal of Dispersion Science and Technology, 15:5, 543-560, DOI:
10.1080/01932699408943573

To link to this article: http://dx.doi.org/10.1080/01932699408943573

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 I. DISPERSION SCIENCE AND TECHNOLOGY, 15(5),543-560 (1994)

SEMICONTINUOUS EMULSION POLYMERIZATION OF VINYL ACETATE

X. KINETICS OF HOMOPOLYMERIZATION. COPOLYMERIZATION, AND

INITIATOR DECOMPOSITION IN THE PRESENCE OF
SULFOSUCCINATE-TYPE SURFAcTANTS
Downloaded by [University of Glasgow] at 17:33 22 December 2014

Dan Donescu and Liana Fusulan

Center for Plastic Materials Research
202 Splaiul Independentei. Bucharest 77208 Romania

In the vinyl acetate emulsion homopolymerization

and copolymerization with dibutyl maleate. in the
presence of a surfactant (i.e. disodium salt of the
sulfosuccinic acid monoester with nonylphenol ethoxylate
having 25 moles ethylene oxide). the polymerization and
persulphate decomposition rate increase with the
surfactant concentration. The initiator decomposition
rate decreases with the increase of the nonpolar monomer
concentration, because of the selective interaction
surfactant-monomer-polymer. The dibutyl maleate low
reactivity reduces the copolymer Forma~ion rate, as
compared to the homopolymer one. The average particle
diameter decreases with the inCI"eaSe of the emulsi fier
and dibutylmaleate concentrations in the polymerization
system.

1. INTRODUCTION

The previous papers hav" presented the vinyl

acetate (VAc) emulsion homopolymerization and
copolymerization in the presence of certain protective
colloidsl~. The initiator used for these papers has been
a persulphate. It reacts. during polymerization. with

543

Copyright Ci 1994 by Marcel Dekker. Inc.

 544 DONESCU AND FUSULAN

all reactants existing in the system 2,4,5 because of the

initiator's strongly oxidizing character. Its
decomposition rate is highly changed as compa~ed to the
thermal decomposition in water case. Morris and Parts 6
showed that the monomers or emulsifiers present during
emulsion polymerization increase the persulphate-type
initiator decomposition rate. The only additives that do
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not influence it are fluorinated compounds that do not

contain vulnerable C-H bonds".
Many papers presented so far confirm these
resul ts 5-15.
Starting from these data, we considered it
opportune to study the vinyl acetate homopolymerization
and copolymerization kinetics, together with the
initiator decomposition kinetics, usi rIg an aniordc
surfactant of the sulfosuccinate class. This type of
surfactant has b'<",n little used in vinyl acetate
emulsion polymerization studies 16-18

2. EXPERIMENTAL

2.1. Materials

The vinyl acetate was purified by rectification,

while the dibutyl maleate (DBM) was purified by low
pressure distillation.
The sulfosuccinic acid half-ester with nonyl-phenol
ethoxylated by 25 moles of ethylene oxide-disodium salt
(NFEC-~ 55) was laboratory synthesized 9• The quality of
the surfactant was verified by thin layer
ch.'omatography.
 SEMICONTINUOUS EMULSION POLYMERIZATION OF VAc. X 545

Ultrapure potassium persulphate (KPS) (LOBA-CHEMIE)

was used without any further purification.

2.2. Working method

The working method similar to the previously

adopted l - 4•
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described one was

The polymerization took place in a glass autoclave
provided with an anchor-type agitator at 200 r/min. In
the autoclave was fed water, 655 g~ various surfactant
amounts, and VAc 100 g. For the copolymerization, there
were fed mixtures corresponding to volumetric ratios of
70/30 and 60/40' VAc/DBM, in the same quantities as used
for the homopolymerization. When the temperature reached
65 -c, 2. 1 g of KPS were introduced under st i rri ng
conditions (Figs 1-3, 5-~). The mixture reacts for one
hour and meanwhile samples for determining the
conversion and nonreacted initiator were taken. The
results presented in Figure 4 correspond to certain
separate eHperiments, where the reactants were used at
half the values in comparison with those presented
above.
At the end of this batch polymerization period, the
temperature reaChed 70°C. At this temperature, 840 g of
VAc and 2.1 9 KPS dissolved in 105 g of water, are
continuously added for 5 hours, and during this period,
at constant intervals, the conversion and unreacted
initiator were determined; the conversion was determined
gravimetrically, while the unreacted initiator by
ceriometry20. Unreacted KPS was reduced with an excess of
standard ferrous sulfate and this is back-titrated with
standard eerie sulfate solution.
The particle diameter was de.termined by the dynamic
light scattering with NICOMP 270.
 546 DONESCU AND FUSULAN

3. RESULTS AND DISCUSSION

The semicontinuous polymerization process has 2

stages: a batch polymerization one, followed by another
where both the monomers and the initiator are fed
continuously. That is why-the two stages are analyzed
separately.
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3. 1. Batch polymerization stage

3.1.1. Effect of emulsifier concentration

The polymerization rate is str~ngly affected by the

VAc/DBM ratio and by the initial emulsifier
concentration (Fig.l).
The polymerization rate increases with the initial
emulsifier concentration. It was a maximum for the
homopolymerization. The comonomer presence reduces the
copolymer formation rate. The lowest rate corresponds to
the comonomers' mixture having a minimum VAc
concentrat ion.
The polymerization rate increase with the
emulsifier concentration is due to the increase of the
particle number, to their total shell weight. This is
the locus where the polymerization- is carried on
according core-shell model for emulsion polymerization.
The particle diameter decreases with the increase of
emulsifier concentration.
The comonomer used, i.e. DBM, has a low reactivity
in comparison with VAc 2! • That is why the increase of DB~
concentration in the initial comonomer mixture results
in the reduction of the total polymerization rate. The
data available in literature on reactivity ratio do not
 SEMICONTINUOUS EMULSION POLYMERIZATION OF VAc. X 547

~
·S
E
10-- ---0----0
~
'--
o
LJ
§
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Q:

--
0)

1,6 1,7 1,8

IgIE10(gl/ )

Fig.l Polymerization rate variation function of the

initial emulsifier concentration. (I-VAc; 2-VAc/DB~
70/30; 3-VAc/DBM = 50/40).

---.S .

E -1
':: -11 --- .J')

~'
(/)-13
Q'
Ct:.~-1,5
5::-1,7
3
1,6 1,7 1,8
Ig1E10 (gil)
Fig.2 Initiator decomposition rate dependence upon
the initial emulsifier concentration. (I-VAc; 2-VAc/DB~
= 70/30; 3-VAc/DBM = 50/40).
 548 DONESCU AND FUSULAN

agree 2! • In our contri but ion we employed VAc/DBM rat ios

which enhaces the reactivity o~ DBM.
The increase in the initial emulsifier
concentration results in an increase in the initiator
decomposition rate (Fig.2). These results are in
agreement with those reported ~or vinyl chloride
polymerizat ions7.
The changes in the initiator decomposition rates
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takes place in a similar manner to the polymerization

ones. The KPS decomposition rate reached its highest
level ~or VAc homopolymer~zation. It was the lowest ~or

the mixture having the lowest VAc level (VAc/DBM =

60/40). The same trend is observed i ~ the quar,t i ty o f
initiator decomposed in an hour is plotted as ~unction

of the emulsifier concentration (Fig.3).

The explanation o~ the above results resides in the
complex interactions between emulsi~ier-monomer-polymer

as well as in the reaction between the initiator and the

system.reactants.
It is known that in micellar systems, in those
including and solubilizing substances, the
solubilization depends on the partners polari ty 22,2~
During monomer solubilization in sur~actant aqueous
solutions there are selective interactions as a ~unction

o~ polarity. The polar monomers interact with the

micelar hydrophilic part, while the lower polarity ones
wi th the hydrophobic part 24,Cl! The non-polar monomer
solubilization capacity increases in the presence o~ 2
monomers having di~~erent polarities, i~ it is
introduced a~ter the polar one 27, 28. The micellar
solubilization o~ the non-polar monomers having low
water solubility, and interacting with the hydrophobic
part o~ the micelles is higher than that o~ the polar
ones29 •
 SEMICONTINUOUS EMULSION POLYMERIZATION OF VAc. X 549
Downloaded by [University of Glasgow] at 17:33 22 December 2014

01
-42
..
-------.
o o
@------~

40 60 70
1E10(glt)

Fig.3 Modification of the initiator Quant i ty

decomposed within an hOl.Jt.., fUYlctiorl of' the irdtiCtl
emulsifier concentration. (l-VAc; 2-VAc/DBM 70/30;
3-VAc/DBM = 50/40).

The presence of excess monomer in surfactant

aqueous solutions, determines selective interactions at
the monomer-wat.er- interface !6,3~,\33. The interfacial
tension decl'''eases, and the area of an emulsifier
molecule on the monomer droplets surface grows with the
polarity increase, and implicitly with the monomer water
solubi lity.
The increase of the area covered by d surfactant
molecule with the polarity was rendered evident by the
polymer-surfactants aqueous solution systems
too 8,16,30,32,3'-37. In systems including more polar monomers
the sorpt ioY, rate of monon"'" into the polymer is
higher 3e.
 550 DONESCU AND FUSULAN

For the systems studied in Figs.1-3 it may be

concluded that those containing a maximum concentration
of emulsifier and VAc have a maximum quantity of water
solubilized ,'eact ant "'. At the same emulsifier
concentration in mixtures having various VAc/DBM ratios,
the maximum emulsifier concentration on the monomer
particles or on the polymer particles is reached at the
Downloaded by [University of Glasgow] at 17:33 22 December 2014

maximum DBM concentration.

In the case of homopolymerization for example,
there is a maximum water solubilized monomer quantity,
as well as a maximum one of free emulsifier. As
previously pointed out, both reactant types, the monomer
and emulsifier, i~crease the ioitiator decomposition
rate.
This comparative analysis offers an good
explanation of the apparently diverse data presented in
the literatureS-IO • In a system including a high water
solubility monomer, the initiator scisson rate may not
be affected by the emulsifier 9,l1 In other nori-epo Lar-
monomer systems, the decomposition rate may be close to
that in water, due to the very low reactants
concentration in the water S.10,l~ In an aqueous system
including surfactants, the presence of the monomers 13,1~
of certain substances solubilized in the hydrophobic
part 13 or of the polymer surface~1O,15 decrease the free
surfactant concentration and decrease the initiator
decomposition rate.
The above mentioned results were confirmed by other
experimental data, presented in Fig.4. Aqueous solutions
containing initiator and water, surfactant, surfactant
with VAclDBM, respectively, in 100/0; 70130; 60/40 and
01100 ratios were prepared. The initiato,' conversion,
after one hour of reaction, demonstrates that it is a
maximum at the initiator + surfactant + VAc mixture and
it is minimum for the initiator + surfactant + DBM one.
 SEMICONTINUOUS EMULSION POLYMERIZATION OF VAc. X 551

"D
~
o
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Q..
E
o
o(!)
u
(/)
0...
~

Fig.4 Correlation between the reaction mixture

composition and the initiator conversion within an hour.
(rEl a = 58 gIl H 2 m ,

In this last case, the KPS conversion, is similar to the

system containing only KPS dissolved in water.

3.1.2. Initiator concentration effect

The VAc homopolymerization reaction kinetics

dependence on the initiator concentration range is well
known~ • The experimental data presented above shows
that, besides the ionic strength change with the
initiator concentration, by changing its interactions
with the existing reactants, its decomposition kinetics
can also be modified.
For initiator concentrations of 0.1 - 2.1 g in the
batch stage, the decomposition reaction order with
respect to the initiator concentration is.
 552 DONESCU AND FUSULAN

..c
--
...-
~
0
70
c 60
0
VJ 50
L
QJ
40
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c>
0
o 30
lI)
0.... 20
~
10
1 2
I KPSl o ( 9)
Fig.5 Influence of the' initiator concentrat ion on
its conversion for 1 hour of reaction. ([EJ o 58 gIl
HiP; l-W~c; 2-VAc/DBM 60/40 [EJ? 37 gIl ~O;
3-VAc/DBM = 60/40).

0.7 for VAc, [EJ 0 = 58 gIl t!0

0.66 for VAc/DBM 60/40), [EJ 0 = 58 gIl Hfl
0.5 for VAc/DBM ( 60140 r , [EJ o = 37 gIl H20

The overall reactions order was calculated by

plotting Ig(-d[I] o/dt) versus Ig([1J o).
The final KPS conversion decreases with the initial
initiator concentration increase (Fig.S). These results
agree with those presented in Fig.3. At high initiator
concentration, the E/KPS ratio is low. The decomposition
reactions induced by the interaction with the emulsifier
are lower, just like for low emulsifier concentrations
in Fig. S.
 SEMICONTINUOUS EMULSION POLYMERIZATION OF VAc. X 553

r
-
.--
~
.Q..

§
l/l
L.
(!)
>
C
o
o
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L..
(!)
E
o
c 1 2
o
~
II<PSl o ( 9 )

Fig.6 Fi7lal mc nomer- c,;.nvers i Or-I for batch step

versus initiat~r c or.c-errt :... n.~ ic'~" ([EJ", 58 gIl fi 0;
I-VAc; 2-VAc/DBM = 50/40 CEJ = 37 g/i ~ 0; 3-VAc/DBM
50/40) .

UndeY' the ab..:~ve-mentioned iydtiate'r concei"',tration

corid i t ions, the hOMopolyroerization
copolymeriza~ion reaction order, versus the initiator
concentration is:

0.1 for VAc, rEJ 0 = 58 gIl Ii G

0.31 for VAclDBM 60140 ) , [EJ c 58 gIl Hp
0.33 fo" VAc/DBM 60/40 ) , [EJ o 37 gIl Hp

This order was calculated by

Ig(-drMJ,/dt) vers~s Ig([IJ o i ,
These orders are quite different from those
speci fied fol" the sodium-lauryl-sulphate emulsifier ro •
The overall reaction order with respect to ";he irlitic..tol'''
level was 0.5-1.- A higher react ion "ate o,'der was at the
 554 DONESCU AND FUSULAN

900
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L...
C!J
E
d:
60 120 180 240 300
Time (rnin.)
Fig.7 Evolution of t~e. obtair,ed p.:.lyme,· i t·, th~
peri od of C:-O':'"lt:. nuous feeding." (l-VA~; 2-VAc/CBM 70/30;
3-VAc/DBM =
50/40) ([E) =
33 gIl HcD'.

low~r initiatQt~ leve:. They demonstrate the inlpGrta~ce

of the emulsifie~ nature upon the vinyl a~etate emulsion

po Lyme r Lz.e t il~n kinetics. ThE' di ff'et"eY',ces c,tls.er"ved w:.th
different eMulsifiers are certainly due to the initiator
decomposition kinetics modification. After 0ne hour of
react iOYI, the monomer convet"sioY: the
initiator concentration. It always grows with the KPS
concentratio~ (Fig.6).
The conversion value at the end of the batch

semicontinuous stage. As in the case presented in Fig.!,

the max inn.\rr. c·.:Jn\lers ion is achieve~
 SEMICONTINUOUS EMULSION POLYMERIZATION OF VAc. X 555

1
3
0)
2
uQ) 3
2
lf)
0
Q..
E
Downloaded by [University of Glasgow] at 17:33 22 December 2014

0
o
Q)
u
~ 120 100 300 350
~

Time (min)
Fig.8 Decomposed initiator quantity increase duri~g
t he i nUCU$
COr-It :r-e.El,ct arlt 5 feed i rIg. (! --V~c; 2-VA~/DB~
70/30; 3-VAc/DBM = 50/40) ((EJ c. = 33 g/1 Hi').

homopolymeriza~ion. In the presence of DBM it decreases

with the concentration increase in the monomer mixture.

3.2. Continuous stage

Effect of emulsifier concentration

The aqueous initiator solution and the monome~s are

continuously fed in this stage.
The way bhe polymer quantity obtained evolves is
repre~ented in Fig.7.
In the first continuous feeding stage, the polymer
formation rate is low. As with other systems studiedl~,
the Yfonreacted monomer concentratioYI increases in this
period. As the process advances, the part icles' shell
 556 DONESCU AND FUSULAN

..........
-c
<0
<,

~
0
90
'--
c::
.....0
V)
L... 80
Cl.J
:::..
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c::
0
o 70
fr
~
60
40 50 60 70
IEI(gll)
Fig.9 Initiator final conve~siun functiun of the
emulsifier- c'"·,,cer,tt'ation. (1-'JAc; 2-VAc/DBM 70/30;
3-VAc/DBM 60/40). =

grows. The polymer par"icles offer a large surface for

the reaction and the process passes into another stage.
This a linear stage; the rate of monomer feed becames
sufficiently low to control the polymerization rate.
Here too, the VAc containing systems have a higher
reactivity. The minimum polymer- quantity is obtained at
a VAc/DBM ratio 60140.
At a constant initiato~ feedi~g rate, the consumed
initiator quantity ~aintains the characteristics of the
batch stage (Fig.B).
The decomposed initiator- quantity grows with the
comonomer-s mixture polarity.
The final initiator conversion, at the end of the
continue.us feeding stage, is similarly affected by the
reaction conditions. The maximum conversion is achieved
 SEMICONTINUOUS EMULSION POLYMERIZATION OF VAc. X 557

20 0 r - - - - - - - - - - - ,

IQ 100
•
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40 50 60
IE I (gil)
Fig.10 Decrease of the average particle diameter
with the emulsifier concentration. (1-VAc; 2-VAc/DBM =
70/30; 3-VAc/DBM = 60/40).

at the maximum emulsifier concentration and at

homopolymerization.
The explanation of this behavior is the one given
for the batch stage. The cOYlclusion., which clearly
follows is that the monomer polymerization and initiator
decomposition must be studied together for the emulsion
polymerization system characterization for the whole
process a, 16,30,32,34-37 dur-a t ion,
The emulsifier-polymer iy,teractions affect the
particle size obtained a~ the end of the process
(Fig. 10>-
The particle diameters decrease with the increase
in emulsifie~ co~centration. The minimum diameters are
obtained for the maximum hydrophobic monomer
COYlcentrat ior\ SY'5tems. The S l.1t" face that can be
stabilized for similar polarities grows with the
emulsifier concentration, so that the posSibility of
getting a greater number of lower diameter particles
 SSg DONESCU AND FUSULAN

OC'':':-U'f'S. Th e Y"~OYI-pcll6.l'~ comor.omer-s introductiot'l makes i t

possible to obtain some low polarity polyme~s, having on
thei1''' s ..r.. ·face slJr"factants of a lO\,fJer specific at~Ea.

There is possib~e to bond an i~creased surfacta~~

quantitJ on the same polymer surface that is parti<::les

well stabilized against agglomeration.
These results are in a~reement with th~lse obtained
the vinyl acetate copolymerization with bu t y I
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the ave."age latex particle diamete.· decreasQs ~it~ ~he

bLI.tyl aC'rylate '~o1'lte'nt i~"lc:reas(" in cl;)polymers I.,~;.

the
i~i~iat~r ~eccmposition rat?s increase witM the
emulsif:or conc~~tratiw~. The dibutyl m~leatE ty~~

introductio~ reduces the system r·eac~ivit/,

ini':iate.t"'
de~omp~sition are concer~ed.

initiatc,r t'saction w~th the reactants in the aqu20u~

sol u:; iOl~.

REF ERE NeE S

1. D.r":"Ytt;:£.=I_l, K. Ge,sa, A. C.i'_tpitc·:'u, "" .. Lai'.;:.l.i.... i ,

J. Mac::r or», 0 1 Se i , C!'1 em., A ZZ, 931, \ ~ ge:;; . .
D. Donescu, K. Gosa, J. Langut-i, A. C:~pitoiuJ
J. Ma.:'ro!Jlol. Sc·i. Chem., - ~, '3/i!, (19.'35).
3. D. D,:.r,E;lscu... K. Gosa, J .. Larl;:o..lr"'i, A·::t6. PO:.y;ner'·:.::a,
ll. 210, (1990).
4. D. Dcq"jescu, L. Fu s u Lan , ACt2 Polym2t··~c='., ~, 5:J,
c i 991).
5. D. D':n·12sc::u., L. F·.!sulan,. Mat. Plast ice . . a3., 31,
( 1986) •
C. Moris., A.G. Parts, Makt"'omol. CheM., 212, ~19SS~.
7. J. Neelse~, w. Jaege:~, G. Reinisch, H.~L Schneide~,
A::~~ Pc:olymer.i,=a, ~, 1, (1'387}.
B. N . Ct.-.ubo, ~. j F u Lmu r e , T . t'ie-":"i, ce.i i cs e, P o L y m .

Sc i ., 2.53, 121, (1 '3'31) ..

 SEMICONTINUOUS EMULSION POLYMERIZATION OF VAc. X 559

9. N.H. Litt, K.H.S. Chang i~ : ~r~ul£ion PoliMeri~aticl~

of Vinyl Acetate (Eds. J.W.Vanderh0ff, M.EI-Ad55er)
London ~ App~ied Science P~bl. 1ge1, p. 1~7.
10. M. Okubo, T. Mori, ~akroMol. Chern., Ma=romol.
Sy,op., ai, 143, (1990).
11. S. S~t'ka~~, M.S. Ad~ikari, M. Barnerjee, R.S.
Kona,·, J.PoLym, Sci.,
Appl. as, 1061, (1990).
12. I.M.Kolt0ff, P. 0' Connor, J.L. Ha~se;~, J. ~01ym.
Sci., ~, 459, (1955) ..
13. M. S. Riac·'':-Vc1.!J S. N. Sau.t iY"l, N.!. Smi~"nc"I, .. Pr~}.:l.
Him., ~, 632, (1982).
Downloaded by [University of Glasgow] at 17:33 22 December 2014

14. H. Ba!.:2'l'''', :'T:. Ortelt, W. Fur,ke, Mak'!""":'f'l01. Cher,l., .l..9.9.,

4CS, (1988>.
:5. B.W. Brooks, B.D. Makanjuola, Makromol. Chern. Rapid
C,:.n1fl1:"':',..., ~, 69, (1 '381) ..
:~. B.R. 'Ji~ayandran, T. Po~e, c. Ga~"ji&~ i~ E~:ulsic~
~~lymeri=ati0n ~~ ')inyl Aeeta~~ CEds. J.W ..
...... 2l.n~2't"h;:.fr, ~. El···P.~sser· j , L.::·:".::'e.,n,. .~p~.]. i ;?:! S:,: ~enc..i:.'~
Publ. 1381 p.253.
17. l<' S~hrl,',J';z:(~l'~, .~cta P,:,limerica, ZZ., 4St.., (1982).
:3~ , .. Diy.ge~"~ P. HautJtrnan, R. Sa!.Jter~.ich, P:aste unc.:
Kal_t'tch...;j"., ~, So£S, ~.1 "3B3).
13. N. Sllsat~, :octor4t The5~5, P01yt~chnic Ins~.
Buch5....'est, 1987 ..
20. r .. M. Koltoff, E. ~:. Ca:'~", Ar~al. Cherl1., ~, 2'3B,
( :.'3'33) ..
21. I.V. Er,il('::".I,3., .'.. .l.. 3ris:.:':=, Z. I. Vc,~o,.kit-;:3., I.N.
~~I~t ..\~':IV.:'.} R. E. r:i~":'c:e·(Jko, Vys,::koli101. S,:.edir•. B, ..l3.,
369, (1,,77>.
22. J. H. :=-eY'Jdl~I""', ::. J. F"endle:-'" : Catalysis :Yi ;·1': ce 1 a!'""
arid i't"ac:t'"':(I:':J:ec:-tla!''' Sjstell1~, New Y':J°:-"'k/Sil.n
Francis2~,'London, ~cadeMi= Press 1975.
23. ? t"il~;'(8~"jeE', Pu(e App:oa Chem .. , sz:., 12.17, (1380).
2~. O.?a !~~:c~s~.~~ V.~. Ko~cv~.lova, A.V . Beli~ev,
L.V. Tsailir,gold, Kolloidn. Zh.,~, 391,(982).
2~. V.P. Ko~ovalo"a, O.P. Iablonski~ A.V. Beliaev, L.V.
Kolodidnii Zl->., !t5., 333, (1983).
Tsailin;j.:.::J,
26. D. Do~escu, H. Caldararu, A. Caragheorgheopol, I.
Dra;utan, !UP~C-Ma=ro'a3, Bucharest, 630.
27. L.!. Do~torova, A.F. Moskvin , LaA. Sadovn~cia, D.P.
!ablvYlski, L.V. Tsai!irlaold, Ko Ll oi dr», Zh., ~,
1051, (1987).
2Sa L.P. KQ~oval~va T.D. ZhukoVd, V.P. Iablonski, O.K.
Shvetsc.v, L. V. 7sai 1 i. ngold, Kollo: dr-I. Zh. ~ 52, 143,
(1988) •
23. E.V .. Gul~ekian, J. Polymer Sci. , A-I, ~, 2265,
(~9e;S).

30. V.!. ~liseeva, Polymer ~ispErsions (in ~ussian',

if,Qskvc~, !-1ird".a, i 980.
31. v. I. Eliseeva, A.. 1./. Z'...lik,:,v, Polymer Preprints, li,
143, (:i.?7S).
32. V. I. ::lis8eva, Acta Polyrnerica, aa, 355, (19B!).
 560 DONESCU AND FUSULAN

33. B.R. Vijaendran, T. Bone, C.J. Garjia, J. A~pl.

Polymer Sci.,~, 1351, (1981).
34. J. Snuparek, Acta Polymerica, 32., 368, (1981>.
35. :J. Snupar'ek, Mak"omo:,l. Chern. Supp 1., .lQLll, 129,
(1985) •
36. N. Sutterlin, H. J. Kurth, G. Market, Makromol.
Chern., 122. 1549, < 1977).
37. 1\1. Sutterl ';'" ~Iacro",ol. Chern., 1.QLll, 403, (1985).
38. K. Hornig, W.D. Hergeth, K.G. Haus:er, S. Wartewig,
Acta Polyme,'ica, sa, 174, (1991).
Downloaded by [University of Glasgow] at 17:33 22 December 2014

39. R. L. Zollars .. in "Emulsior. Polymerization o~ Vinyl

Acetate ( Eds. J.W. Vanderhoff, M. El-Aasser),
London, Applie~ Science Publ. 1981, p. 31.
40. M.S. El-Aasser, T. Makgawinata, S. Misra, J.W.
Vanderhoff, c. Picho~. M:.. F. La.uro in "Emulsion
Polymerization of Vinyl Acetate" (Eds. J.W.
Vanderhoff, ~. El-Aasse,') Lor.dori, Appl~2d Science
Publ. 1981, p.215.

Received 7/28/93