137
157

 

SOME S‘EUDIES 0N THE EMULSION
POLYMERIZA‘E‘EON OF STYREN E

Thesis for the Degrae of M. S.
MICHIGAN STATE COLLEGE

Helen Deborah Morgan
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This is to certify that the

thesis entitled

Some Studies on the Enulsion
Polymerization of Styrene

presented by

Deborah Morgan

has been accepted towards fulfillment
of the requirements for

M. S. _degree m_9rganic Chemistry

WM oi/M

Major professor

 

 

“' -‘ d' .‘(533mmr'mh'u

son STUDIES 0! m EMULSION POLYmIZATIOI at am

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Hahn Deborah torso:

1133818

mitt“ to the School 01’ aunt. Studio: of linkage:
“at. college of Agriculture and input! Science
in partial fulfill-ant at the ”amount.
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IABLE OF COMM”
Introduction
Hiatorieel

Pue-

Port 1: Preparation of Polynere in nnleion 4

Port 11: Chereeterizetion ot the Product
tummy leletionlhipl
Preeipitebility leletionahipe

rheeretioel

Experimental

‘ Port 1: Preparation of the Polymer
interni-
Equipment
Procedure

Port '11: Chareeterisetion or the Polyuer
Vieeoeity determinations
Preeipitebility determination

Dieenoeion
Coneloeione

Bib liogrepb:

6
6
'8
10

81
21
81

84
£4
8!
32
35
36

momentum

. In recent yeere the inreetigetien of polylerieetion reo
ectiene hee beecwe er ntneet inportenee iron the eonereiel
ee well ee the theoreticel eepeet. the prodnete e: theee
reectiowe heweyideepreed neege in the preperetion oi cyn-
thetic rubberl'z
proof tille tor peeheging teed end eeehinery. end new other

_, ehetterpree: treneperent windowe, weter-

prodnete. It ie runner: in the preperetien e: theee wete-
riele to here e nnii’orw prodnet. the propertiee e! the rinel
product derived from o poly-er ‘3 dependent prilerily upon
the noleenler weight of the. polyner, end the woleenler weight
veriee greet]; with the weth of preperetion. It ie deeir-
title to produce eppolner in en eeeily hendled term which
will here the proper woleenler weight te give the deeired
propertiee in the tiniehed product;

lttenpte to eeeoeplieh thie by nee or neee end eolntien
polyeerieetione led to produete in the torn e1 etichy eewente
er large herd lnwpe, difficult to hendlefi" It wee found
thet through the an of emileion polynorieetion prodnete
could be ehteined in e letex tern which could then be precip-
iteted to torn e tine powdered poly-er which wee eeey te
hurdle."6 lhe nee or en ewnleien eyeten. however, intro.
dneed more eeriehlee into the preeeoe. Phie eede it here
difficult to deternine the eiteet eeeh veriehle hed open
the tinel product. flue rete or toreetion or polyetyrene in
en enleion eyeten end the nehenler weight of the prodnet

ere dependent upon the following:' type end enonnt e1

-2-

eetelyet, type of eteoephere, type end eeonnt of enuleifr-
ing egent. retio of lonelier to weter, tenperetnre end rete
ef etirring. 1e deternine the effect of ell of theee veri-
ehlee would be e teeh toe greet for the eeope of one invee-
tigetien. thie etudy wee confined to the investigation of
the effect of two different typee of eetelytie eyetene in
two etnoepheree. neeelp. nitrogen end eir. ill ether con-
ditiene were kept ee eonetent ee wee preetieelly peeeible
in leheretory procedure.
rho enelyticel proceduree for following the rete of

reeotion heve been ieeletion of the polynor’, titretien ef
the weneeer by tree'ine, ehenge in volnee, end weet reeentlr
the ehenge in rotetien' of polynerieetion of cptieelly ee-

10.11 One nethod which hee been widely epplied

tive uneeere.
ie the running of dnplieete reeetioee in ee'eled tnhee, re-
roving the tnhee et verione intervele end ieoleting the
product. lenp verietione of the eceled tnte technique heve
been reported. thie eethed hee not been toe eetiefeetory
ee eeell differeneee hetween the tnhee leede to ineoneietent
reenlte.,"
In thie inveetigetion the retee cf polyurieetiee were
detereined by withdrewing eeeplee free e hoeogeneone poly-

werieing eixtnre et veriene tine intervele end preeipiteting
the eenplemiw-edietely with eleohel. the preeipiteted
polymer wee centrifuged. weehed thoroughly, dried end weighed.

flee neleenler weighte ef the verione polyeerie eenplee were

4-

deternined by vieeeeity eethode neing Stendingere mun."
one. eetieete of the eoleeoler weight dietrihntion
within e eenple nor be node by titrating e eoloticn of en.
eenple with e noneelvent end eeeeoring the ehenge in trenc-
nieeion of light free e con-tent light eonree through the

eolnticn by eeene of e photocell.“

me proeednre wee
eerried out on nneerone eeeplee end ehowed eheerrehle dif-

fereneee in eeepoeition between then.

HISIORIOAL:
Pert l: Preperetion of Pelpncre in bullion:

r11. field of enuleion polynorieetion ie one of the
newer fielde of polyeerieetien. yet it ie widely epplied.
lt ie eepeciell: ieportent in epnthetie rubber eenufeeturefl”a
It ice convenient method for otteining en eeeily hendled
product which ie in the fore of e letex. in contreet to the
eticb cencnte end eolid luepe otteincd ee products free
uneeuleificd polyncrieetione. 1t ie more repid end the
rete of reectien ie norc ceeil: controlled then in either
bulk or eolution pollqreerieetionfiv:u

hrh end leff4 give e liet of the ingredients neeee-
eerp for en ceuleicn polyeerieetien ee: heeie pheee er
eeuleion ecdiu, the eei‘n honour. edditionel none-ere.
eeuleifying egcnt or egente, etehiliecr, rcguletor of euro
feec teneion, cetelyet, end chein rcguletor. ihe eere il-
pcrtent of theee ingredients ere the eonoeer, cetelyet, end
enuleifying egente. I '

Ihc eetcriel to be polyeerieed eey eoneiet of one or
nore nenoeere. the eein neneeer builde up the nein pert
cf the polyeer end ie ueuelly $0.8“ of the finel polyeer.
the reeeinder being en edditicnel eonoecr which ie to he

cepolyeerieed with the nein nonoeer. if only one eonoeer

ie to be used it um up 30-357. of the enuleion systoe.‘

the eetelyet eoceleratce the foreetion of polyecriee-

tion nuclei without effecting prepegetion. loot euheteneee

-5-

which have a catalytic effect eleo react toward the tor-in-
etion reaction, thee the eddition of too eueh catalyst re-

eulte in a low eolecular weight product.‘ it has been ehown

by the experimente of Fryling and Harrington,‘ l‘ihcntechcr,1‘
end eleo by lerh.end othcre6'8‘17 that in eyetuee catalysed
by water soluble catalyete eueh ee; inorganic peroxidee.
'pereulfeteo, percarbonetee end perboretee, the activation
eecure in the eQueoue phaee rather than in the eoneeer pheee
or at the interface.

Fryling and Herrington‘

believe that with organic per-
oxidee the initiation probably takes place in the organic
pheee end euggeet that the lecue of initiation of polyeer-
.ieation.eey provide an.ueeful.eethod of elaeeificetion fer
varioue typee of eeuleion.polyeeriaetione. .

ine cnuleifying'egcnt ie an ieportent ingredient of
the eeuleion eyeten for polymerization. 1t nay in acne
eeeee catalyse the reaction ae well ae fore the ceuleion
nediue.z the poly-eriaetion velocity of cone eyetene of
low eeap concentration ie elecet linearly preportionel to
the concentration of the eoep. lhie catalytic effect ep-
peere to favor the theory of initiation of polyeeriaatiee
in the equeoue pheee.‘ lhe eorc ueeful eeuleifying agente
for polynorinatione are theee that exhibit coneidereble
eolubilieetion of the none-er. Sane of the more effective
elnleifying agente ere: aliphatic long chain cerbexylic
and eulfonie acids, eulfoneted long chain alcohole and

-5-

and aninee and aromatic alkyl eulfonic acide. fhc enulei-
fying agent coneiete of free 0.8-“ of the eeuleion eyetcn.‘I

Part ll: Characterization of the Product:
Viecoeity Reletionehipe:

fhcrc ie a definite eimle relation-hip between the
epecifie viecoeity of the eolutiono of different eateriele
and their eoleoular weight. hperinente" chow that with
eolutione cf poly-er honcloge of the cane concentration the
epeeifie viecoeity variee greatly with the noleeular weight,
and that a few long nolcculeo cause a each higher viecoeity
than nuncroue ehort once. being heni colloidal and ncrwal
hydrocarbon producte with known nolecular weight 'I’
Staudinger arrived at the following einple relationehipxn'u

23:21 ek'n

ln thie equation ’c' ie the concentration of the cola-
tion in nolee per liter of the bane unit of the polyner.
'k' ie a characterietic conetant for each ecrice of polyner
honologe. 'n '3' in the epccifie viecoeity which in the via-
coeity of the ablation divided by the viecoeity of the col-
vent einue one. fhie equation ie valid only if applied to
dilute eolutione in which the individual cheinc, branched
or not. are preeent ae independent kinetic unite and deter-
ninc the character of the eolution. Such eclutione ueually

exhibit the property of ncrnel viecoeity, free free eigne

-7-

cf electic eneaaiiee.‘

Ivory natcrial which coneiete of
threadlike noleculce bee in dilute eolution a definite
”0" value, thie value ie dependent upon the cane char-
acteristicc and ceeentially en the aolcculc length. fhie
value ie practically independent of the type of solvent
need}:

In cone caaee the behavior of dilute eolutionc ie alec
a ..i. in.dietinguiehing between straight and branched
cheine and ie eo need. !he 'k' value. ae calculated free
the Standinger viecoeity equation. ueuelly aeeunec ite high-
cet value for etraight chaine and deercaeee gradually ac
branching increaece.“ Polyetyrene fractione of identical
molecuhr weight prepared at low tenperaturce (80%) chow
'k' valuce around 1.6 n 10". while ccrrcepcnding eclecular
weight fraction for canplee prepared at high tenperaturee
(150°C) ehow veluee ae low as 0.5 n 10“. Apparently thie
..... that the capability of a long etreight chain to pre-
ducc viecoeity in a eolution ie greater than that of a
branched eyetcn.

there ie a great deal of controverey ac to the validity
of the Staudinger equation and any correction factore have
been applied to 3.30.21.23.33 Huggine“ givee a ecepreo
heneivc report on the development of eeveral relationehipe
between viecoeity and aolecular eiec, namely then of

Iinetein, Kuhn and Iieeneohita. It ie generally recognised,
however, that the Standinger equation ie a valuable and can.

-8-

venicnt tool for the coaperieon of different poly-er canplee

- under einilar conditione of preparationezla

Precipitebility lelationehipc:

fhe fact that polyeere of different nelcculer weighte
have different eolubilitiee hae been need to fractionate
polyncr eaeplee and thue deternine the ecleeular weight die-
tribution within the eanple. fhie ie a tine coneuning Job

and ie inpractfcal for a large nunber of coupled}.

um and revere.“ using a nethod deccribed by no lolly
at the Gibeon Inland conference 1948 for neeeuring the tranc-
nieeion (-log III.) of light through a eolution of a cyn-
thetic rcein during precipitation by a noncclvcnt. developed
a rapid nethod for cetineting nolcculer weight dietributicn.
d photronic cell wee need to ncecurc the trenenieeion, which
varied inveraely with the aunt of rcein precipitated.
fhcy detcrnined that the dietribution of pclyncre in e reein
could be cetineted if the trancniecion during precipitation
and the concentration of neneolvcnt were known. 2c corre-
late titration data with polynor dietribution a reein could
be fractionated by partial eolution and the nclecular weight
of each fraction determined. fhe anount of noneolvent necce-

eary to precipitate a known noleculer weight fraction could

then be determined.

dohule86

developed the following rcletionehip:
2“ e a + a]:
3/ " 3 concentration of noneolvent

x 2 degree of polynorioation

d and I are conetante
which ehowe that the about of noneolvent required to pref
eipitate a polyaer ie a ncaeure of ite degree of polyncri-
action. By an of thie dehala equation the range in which
a polymer fraction will be precipitated way be cetinated.
the amount in each fraction nay be eatinetcd by the differ-
entiel of 4.; 111°. ,

Aden and Power-cu aleo found that thin eethod would
neeeure eeell differencce in the oonpceition of eiailer
reein eaaplee. that ie eeeplce that have the cane average
nolecular weight but with different dietributien of eclec-
ular weights within the individual eaeplce would give dif-

ferent precipitebility curvcc.

ERRORETICAL:

the courec of any polyncriaetion reaction and the type
of product for-ed in dependent upon three rate factors. nu»
cleue foneation, propagation.end termination; which will be
deeignatcd ac k1. kg, and k3 respectively.

Doetal end‘larkz' have foreulated and eolvcd the general
differential equations for a chainspolymeriaetion which
occure without breaking of the chain.

luclcue formation in a relatively elow prcecee which
requiree a definite amount of energy. In a hoeegeneoue
eyetem there exiet molecules of the nonoeer '3' which can.
by a certain.preccee, form active nuclei. the formation
of nuclei ie cheraoteriacd'by a velocity conetant k1. Poly-
nere may be formed by either none or diaolecular reactions.‘
the relative amount of activation depende upon the number
of’mononere and the amount of heat added.

If the fornation of nuclei is nonceoleeular the poeei-
bilitiee of activation are photocheeical, catalytieal, or
purely thernel. the photochemical formation of nuclei, k11
ie a acaeurc both of the absorption of active radiation by
the nclecule WE', and of the quantun.yicld of the irradiated
light in respect to nucleus formation. lxperieentelly no
menonolecular thermal activation hae been definitely observed.
However, in the eaee of large eolcculee. the interference
of internal vibrations nay accaaulete euffioient energy to

produce a polyneriaetion nucleue.

It is thought that the biaolocular formation of nuclei
is always the result of an activation due to collision
between.aoncaer nolecules or monomer and catalyst aolecule.
these collisions are induced by theraal agitation and are
represented by the constant klz“

catalysts greatly influence the biaolecular nucleus
formation and it is doubtful whether an unoatalysed thernal
nucleus foraaticn has been obtained. the types of sub-
stances which set as catalysts are metals (ha, I; Ii, re).
halides (Big. 11613. Silk. ZnClgl. and oxygen compounds
angst. peroxides, persulfates, percarbonates, oaonides).

’ our“ points out that n the presence of these sub-
stances the first step in.nuelear formation is the addition
of the catalyst to the none-or. chalners" suggests that
the metal of the catalyst unites with the alpha carbon of
vinyl derivatives to give a half-addition.produet such.as
cantonxongo. This could act as a starter for a polymerisa-
tion.chain reaction. the evolution of the polymeric aoleo
culc nay be regarded as a chain reaction of the sort in
which the units produced coabine instead of maintaining
separate existence. .

If a polyreaction consists of nucleus fornation. growth,
and tornination without branching of chains, the following
relationships between tins and concentration of monomer say

be derived.‘

-12-

For nuclear fcnaation:

fi‘s x11. 0

dc‘

It " kin-o
#

21% ' I“is"

'c? designates the molar concentration of the inactivated

3

nonoaer ‘33. 'o“ the concentration of the activated nuclei
Hi. Eh. it; if it is assumed that the activation alwnys
proceeds in one definite nanner. the possibility of the
simultaneous occurrence of two activation reactions of dif-
ferent orders being excluded, the process of growth is rep-

resented by:
"' 5% ’ t2:""'°

fhis is a second order reaction between nuclei or chain-
c‘ and the aonoaer c.

the growth process uses up aoncner but the concentrap
tion of nuclei raaains unaltered. This condition is ac-
counted for by the fact that the activity of the nuclei,
i.e. the velocity constant of the growth reaction, is inde-
pendent of the length of the nuclei.

fhe chain-breaking reaction, which consumes nuclei,

can be of the first or the second order. in the fonaer case

it can consist of the migration of a hydrogen aton.along
the chain to cause saturation of free valenoes. in the

latter case, it can consist either of a reaction between

a nucleus and a nolecule ef‘acnonsr or between two nuclei:

_’dc*

’ ‘31.}.

dc’
"’ It 3 “2520'”8

" it" ‘31)?"

If there is a possibility of tenninaticn reactions of
the first and second order occurring simultaneously, then
the fonner would predoninate at low concentrations and the
latter at high concentrations.

these reactions describe the total conversion of none-
aer into polmner in the following way:

rho starting reaction uses up nonmaer and produces
active centers (or nuclei) in the systen.

The propagation uses up more nonaner. but leaves the
nuaber of the active centers unchanged becousc of the fact
that the growth is of a type which regenerates the reactiv-
ity of the chain end after the addition of each new link.

fhe termination reaction destroys the active centers.
It any or.nay not use up moncncr for this purpose. but it
does use up the nuclei.

the velocities of the different steps contribute to
the rate of the total conversion. If k1<1k34§kz each nucleus
produced by the slow reaction k1 will be caught imaediately
by the fast propagation process It and extended into a long
chain until this chain is stabilized by k3. Ehc rate of

the conversion will depend only on k1 and ha; the distribu-

-14-

ticn.curve of the polymer will be determined by kg and k3.
lha average aolecular weight will remain practically con-

stant during the reaction because the average life-time of
the chains does not change; it is detorained by the ratio

of kg and k This case has been observed in the theraal

3.
pclyaerisation of different vinyl derivatives. It has been
called the radical chain nechanisn.

If ti>>k£§>k3 nuclei are rapidly produced by k1. only
slowly extended into chains by kg and slowly used up by k3.
fhus due to the ever growing nuaber of active centers, no
high polymeric material can be produced. It is possible
by photocheaical or catalytical action to produce very rap-
idly a certain number of active centers, and then to observe
how they are gradually extended into chains by kg. and how
these chains are slowly converted into inactive aoleeules
by ha. the average life-tine of the growing chains is long;
the mean.nolecular weight of the naterial increases as the
reaction proceeds; the distribution curve depends upon the
interaction of h; and :3 and the rate of total conversion
is given by k2. Ibis type of polymerisation follows the
double bond chain mechanics.

ihe double bond nechanimn is highly insensitive to all
kinds of disturbances; it leads to extreaely long chains.
but the growth is very slow. the free radical ne'chanisa is
auch faster, the high polymeric state is reached acre rapidly,

but the highly reactive inter-edicts products are very sensi-

~15-

tive to external influences and chains are easily terninated.

lorrish and Brock-Lon}9 upon investigation of the cat-
alysed thernal polynerisatien of styrene and nethacrylate,
drew the following conclusions. the nolecular weight of
the polyner obtained will be proportional to the tins of
the reaction, and inversely proportional to the concentra-
tion of the catalyst. this substantiates the earlier eon-
olusions of Kart and Raff.“o

the eonpounds which undergo chain polymerisation reac-
tions are those which contain unsaturatien. she types of
unsaturation which any produce pelynerisstion are ~csc-;
431; 4336-; 86:0; and scab. Rho proxinity of two or acre
of such groups is an inportant factor in deternining the
ease with which a eonpound will polynerise.

the analysis of the -¢.‘:¢- double bond according to
cusntua noehanics gives rise to the following concept: each
valence dash of this linkage represents a pair of electrons
in the sense of the Lewis valence theory. for each of these
electron pairs there, is a corresponding charge distribution
which can be nathenatically represented by suitable eigen-
functions.‘ the eigenfunctions cf the two electron pairs
can be characteristically distinguished. so sake the dis-
tinction between the two clear. the terns; electrons or
eigenfunctions of the first order (cru- functions), and clccé
trons of the second order (1f «- functions) have been intro-

d‘QCQQ

-15-

fhqu'eigenfunetion is that of the inner electrons,
and closely corresponds to a normal single carbon to carbon
bond. the TF eigenfunction is that of the outer electrons,
and is the decisive factor in the behavior of the double
bond during polymerization.

the eigenfunctions of the second order any correspond
to electrons of either antisparallcl or parallel spin. In
the fonaer ease the double bond is closed and represents
the fundaaental state of ethylene; in the latter, the double
bond is open and represents an excited state of ethylene.
rne double bond nay be represented by the following synbcl
>c E c: in.whieh the electrons of the first order are des-
ignated by points and those of the second order by saall
circles.

for thernal polymerisation.in the absence of added
catalytic agents. it has been suggested that the activation
process night consist in the fornation of a biradieal’
either unflaolecular or binoleoular.

,c§c< ”oeg'nce

>o;c<
7c:c<-
. 1 a c c a I , n e t
st :5: 3.,» c 99.9.}: o ......9 e o.c:c:o:o:o o
leohanicm.l

lbr the bensoyl peroxide catalysis of the polyneriaa-
ticns of styrene. sehula and Hoseaann’ conclude that the

propagation and teraination reactions remain unaffected by

-17-

the oatalyst. the catalyst serves nerely to increase the
rate of the initiation reaction. Schnla suggests a nechanp
.f'. for the initiation reation in the presence of peroxides
involving'the equilibrina.fornaticn of a complex between
the catalyst and styrene, this then deocnposes to give an
activated styrene noleculs. His data shows the rate to be
proportional to the wquare root of the catalyst concentraa
tien. Price and xeii1° postulate that the specific nature
of this uninclecular chainpinitiating reaction ef’peroxides
is nest probably their deco-position into free radicals.
Ibis suggestion offers an excellent explanation for many
of the unusual catalytic effects of peroxides.
fhe free-nradiealaechanisn of peroxide catalysis nay
be illustrated by the following sinple equations. in which
'1' represents the nonener nolccule. and the circle indicates
the odd electron of the free radical:11
Initiation: '
' (D603) “9 2: nos, e
”am. a) cog + i: e
lpopagation: , 2
Ar o {fill -;> dr4l_e
dr-l s «i» n ...) tin-Ita o
ir-Iz c {t n -..) trail 13.
fernination: é
- . l l . I
n-s, c +Lr-tf-g-(l: e «9 u—sx-n + u-sy-orcK
or
s.dréli c -9> irélilivir
lechanisn.ll

-18-

the nature of addition polymerisation in the presence
of such catalysts as boron fluoride, aluainun chloride.
stannic chloride, or antinony pentachloride involve a dif-
ferent sort of nechanisn.

Polymerization under these conditions nay involve a
polar chain nechanisn, initiated by reaction of the catalyst

with a noncner nolecule. Hunter and Yohe31

have suggested
that the chain-einitiating action of such catalysts depends
upon their electrophilic nature. and consists in the acqui-
sition by the catalyst of a pair of electrons fron the

double bond of the noncner.

A

o
[$1x 4-)0 3 x

.1

l l
-- e +
9 all.?:?
.I -- .I I l '1,
:9 Wit-worm
I

on + oiIt 1sou} : [oh-E:

I :
cin'c:o++ n
3": I .

‘0‘

l
6

Cu.

Kechanisn Ill
this nechanisn is analogous to the one suggested by Whit-
nore38 for acid-catalysed polynerisation. in which the
electron-deficient catalyst consists of a proton. Under
conditions in which propagation is rapid conpared with the
loss of a proton free: the active poly-er, long-chain poly-
ners will result; under conditions in which the reverse is
true. diners and triaers will be forned.

In general. there have been two essentially different

-19 -

viewpoints on the nature of the propagation reaction of
polymer formation. that originally proposed by Staudingeraz
and supported by others“ indicates a specific mechanism
involving addition of an active free radical to the double
bond of a.mcnmner.moleculc generating a new free radical,
which can in turn add again to another monomer molecule.
(Bee mechanisms 1 and II) is a free radical chain reaction,
polymerisations of this type should be aubJect to strong
inhibition by small aaounts of such substances as hydro-
quinone er diphenylmaine. these substances are capable of
preserving such.mcnmaers as methyl methserylate, styrene,
vinyl acetate. and dienes.

the second viewpoint regards the propagation reaction
as an 'encrgy chain,‘t in.which an 'activated' noncner.mole-
cule adds to a normal molecule yielding an activated dimer
which canradd another monomer molecule the process continue
ing until the activation is nullified in some manner. taco
mechanism 111)

Individual active polynerie chains may be terminated
into stable polymer noleeules in several ways. the free
radical may lose a hydrogen atom iron the adjacent carbon
atom to give a polyner nolecule terminated by a double bond,

or it nay acquire a hydrogen.atom.frcm some other molecule
in the reaction mixture to give a saturated polymer. Either

of these processes, is merely a transfer of the active free

radical. not its destruction, since one of the products in

-20-.

each case is a radical capable of generating a new active
chain. ather ways by which termination.nay occur are; by
the reaction of one chain end with another chain end, (see
nechanism ill the reaction of a chain end with impurities,
and the formation of polymembered rings in the molecule.11
the observation of Williams,3‘ that the rate is directly
dependent upon catalyst concentration, while the degree of
polynorisaticn is independent of catalyst concentration.
would be accounted for if the termination.reacticn were the
unimoleeular loss of a proton. The poly-er would be an
crganometallic compound, which might account for the diffi-

culty encountered in freeing such polymers from the catalyst.

-31-

mama-nun:
Part 1: Preparation of the polymer:
tutorials:
deroecl O!
Pchvinyl‘slcchcl (Dupcnt 521-28)
Dupcncl 9 fl
Potassin peroulfate
Sodiu- bisulfite
‘ Ethyl alcohol 95$
Styrene ens-tun 3.19. chow/m}
the styrene was distilled from hydroquinone into a
receiver containing hydroquincne collecting the fraction
lib-1406]?“ as. this fraction was then uninhibited by
washing with cold 6% sodiun hydroxide solution until the
wash solution was colorless. the styrene was then washed
until neutral with distilled water, dried with anhydrous
sodiun carbonate and stored in a refrigerator. The unhib-
ited noncner was not allowed to stand for more than three

days before use.

Iquipnent:

the polynerisation reaction was carried out in a three
necked roundobottcn flash with 24/40 ground glass Joints.
the flask was equipped with a water sealed aechanical stir-
rer, a vacuun sanpler, a theraonetor and reflux condenser,
which were attached to the acne neck of the flash: by means
cf an offset adaptor. ihe flask was set in a constant taup-

-32-

erature water bath which was kept at 40°c by means of a

knife blade heater and a thcrnoregulator.

Irocedure:

the basic ingredients of the emulsion system, which
were kept constant, consisted of a water to.monomer ratio
of eight to one, and an emulsifying system consisting of
0.a$.derosol 0!, 0.3fijpolyvinyl alcohol and 0.3filnupcnsl c.
ihis systea was selected fron many which were tried because
it see-ed to give the best emulsion throughout the reaction;
that is, it kept both the noncner and polymer phases in an
emulsified form. All percentages were based upon.tho water
content of the system» the tenperature was kept standard
at 46'6 and all reactions were stirred continuously during
the polymerisation reaction.

the enulsifying agents were added to 680 cc. of dis-
tilled water in the flash and the mixture stirred until a
clear solution was obtained. 'lighty cubic centflmeters of
styrene were then added and the mixture stirred until an\
emulsion was formed. the catalyst was dissolved in twenty
cubic centimeters of distilled water and added immediately
to the emulsion. time of reaction was measured from the
addition.ef the catalyst. Samples were withdrawn at various
intervals during polymerisation by means of a vacuum sampler.
the couples were precipitated immediately by pouring than
into 96} ethyl alcohol. they were then centrifuged, washed

-23-

at least six times with water and six times with alcohol,
filtered by suction and dried. The precipitation was car-
ried out directly in graduated fifty cubic centimeter cen-
trifuge tubes. The tubes were filled to thirty-five cubic
centimeters with¥alcohol and fifteen cubic centimeters of
the emulsion.poured into them. Each sample taken has a
volume of sixty cubic centimeters so four tubes were used
for each sample. After the samples were dried they were
then.weighed and the percent polymerisation calculated.
total polymerization would give a yield of six grams of
polymer in sixty cubic centimeters of emulsion.

the variations in conditions used were: 1% potassium
persulfatc (0.023 molesI640 cc water) in an atmosphere of'
air, 1} potassium persulfatc in an atmosphere of nitrogen.
lfirpctassium persulfatc with an equal molar quantity of
sodium bisulfitc (0.023 moles) in an atmosphere of air, and
lfijpotassium persulfatc with and equal.molar quantity of
sodium bisulfitc in an atmosphere of nitrogen. A few runs
were made using smaller amounts of the catalytic systems
and were recorded in Table l.

In.the use of the nitrogen atmosphere the nitrogen was
bubbled through an aqueous solution of pyrogallio acid to
remove all traces of oxygen and then into the reaction mix-
ture through the sampling tube. The nitrOgen was bubbled
through the reaction mixture before addition of the monomer

for approximately fifteen.minutes and continuously during

the reaction period.

IPart ll: Characterization of the Polymer:

‘ the dried samples were ground in a mortar and sifted
through a fine screen in order to make them go into solution
more readily. Solutions of the polymer samples were made

up in volumetric flasks at a concenrration of 0.02 molar
(0.24%) in toluene which had been redistilled and collected
at ioséioe°c at 743 mm. on. viscosities were determined at
20.6 by means of a Cannon-Fenske-Ostwald viscosity pipette
and the molecular weights were calculated according to the

Staudinger equation:

- 77s
11-52
In which
' ‘h.: molecular weight

77., c specific viscosity

c 8 concentration in moles per liter of the
basic unit of the polymer.

k 3 constant . 1.8 x 10"
the specific viscosity was determined by dividing the
time of flow of the solution by the time of flow of the pure

solvent and substracting one.
Ihe molecular weights determined are tabulated in
“‘1. I a

in.cxample of data and calculation of molecular weight
of a typical sample.
Sample: Run! V’o 00.8$ polymerisation.

time in Sec.

 

77.5

Solvent Solution Relative Viscosity : 2.5628
' 32.8 ’ 77.5 Specific Viscosity m 1.3588
\ 33.6 77.4 Concentration : 0.08 I
32.7 77.5 r m 1.s x 10"
32.8 77.5 n.= )752 . *1.3628
6 1.8 x 10-1; 0.02
32.8 77.6
n s 878.500
cz.s 77.5

-26-

 

 

‘_ ‘ Esble I
Rgn Catalyst ‘ 9:2: filPolymer. M0l;§::::1:;:ght
1. 7:39.308 1% 1 10.0
W on c 27.3 33,500
11: 17 82.0' 37.200
20 65.3
11 range; 11L 2 8.0
“ ' ' in 3 9.6
11: 9 1/4 27.1 23.600
25 37.0 27,000
as 76.3 33,800
111 138203 .57. c 3/4 75.0
"‘ ‘ “ in ' 10 . 8.s
Air 23 114 31.0 28.700
28 no.1 32.110
33 3/4 00.0
It racgoa 1g 2 1/6 84.0 398,000
' ’ ' in 2 3/4 83.5 345,300
nitrogen 4 87.0 281.300
_ 7 98.0 182,000
-.....-------..------..----------------------------------
v ranges 1f 3/. 17.3 180,000
' N ' in 1 1/2 50.8 378,300
nitrogen 2 110 57.5 331,900

Some small lumps formed in the emulsion

6 90.0

139,100

-C--- ......... .-------------------------------------.---.

-27-

fable I (Con't)

 

 

R? f Catalyst 13:?“ ' {Polyheb reggaziigfefi
ti 1723308 .31: 1 5.1 ' A
‘ ’ in. 1 1/2 19.0
litregcn. 2 23.3 153,000
3 43.3
c 53.3 229,300
3 85.0
3 1/2 35.3 182.000
311 K232°s 1f 1 20.0 13.200
" ‘eien, ' 2 23.0 ,
scans3 .3; 3 41.3 17.000
in 3 33.1 18.500
11: s 32.3
7 23.3 33.200
7111 1.3.5. 1i 1 1/e 11.7
"' ‘with ' 2 1/2 17.7
37.3803 .3; c 37.7 22.700
in 3 1/2 31.7 23.400
Air 7 93.5
e ‘ 34.3 33.300
11 13330. .31. 3/3 23.0 «.300
' :iggbz .23$5 1 1/2 41.3 71.100
in Lumps formed and the reaction did not

iir remain in an emulsion.

.----------------------..------.'-----------O. ------------

-23-

!ablc I (Ccn't)

A;

 

 

Inn fl time - ' ' ' Iolecular height
.f Catalyst Hr. $ Polymer. (Viscosity)
111 ‘xgszoa .1233 1 3.0
" with
la3303 .05233 3 70.000
in Lumps formed and the reaction did
dir not remain in an emulsion.
1111 [38303 .032375 1 0
‘--- ~with
in .
‘Jr 4 91.3 131.900
1 range. 13 1/2 10.1
with .
3.2303 .33 1 1/2 21.3 24.300
in
'1‘r08.n 4 3/4 81.3 30.400
5 1/4 93.7
7 1/4 97.3 30,400
11 ‘392°e 1; 3/5 14.3
- with
losses .3$ 3 1’3 37:1
31:292937 4 3 1/3 ' 43.0 47.400
*4 1/3 34.3 31.400
3 1/3 93.3 43,700

--m------“---- --.-------.- 9 .-...........u............

0ne run made with lfi sodium bisulfitc resulted in only
12$ polymerisation in 30 hours. the product was sticky and
very hard to filter and wash as it adhered to the filter
paper.

One run.madc using 1%:xgszoa in.an atmosphere of oxygen
gave very little polymer in 80 hours. The product was sticky
and very difficult to handle.

rrecipitability measurements were made cn‘the various
samples following a proceedure described by ideas and Boaters?M
She apparatus used consisted of a light source. a specially
constructed cell. a photocell. and a galvancmeter.
the cell was constructed of stainless steel and measured
seventeen centimeters in height. and was approximately four
centimeters square. There were windows on two opposite
sides which were held in place by special brass fittings.
one of which fitted the lens of the light source and the
other fitted the photocell. Ihe other two sides and the
bottoILwere enclosed with a water Jacket through which water
was circulated from a constant temperature bath which was
kept at 20.0. When in use the light passed through the
solution in the cell and struck the photocell on the apps-
site side. Ihe photocell was connected to a galvanometer
by means of a variable resistance as that the deflection
of the galvancmeter could be adjusted to stay on the scale.
through the top of the cell was inserted a mechanical
stirrer which was adjusted so that it gave thorough mixing
but caused no bubbling in the solution; a thermometer. and
the tip of a siphon burette which contained the nonsolvcnt.
Samples of the some solutions which were made up for
the determination of viscosity were used. One hundred sixty.
cubic centimeters of the solution were placed in the cell.
the light passed through and the galvanometer adjusted to
a deflection of approximately one hundred by means of the

variable resistance. Upon the addition of nonsolvent. 90$
ethyl alcohol. an immediate turbidity scoured which was
due to the mixing of the alcohol and toluene alone and not
due to the precipitation of any of the polymer. After
approximately tyenty cubic centimeters of alcohol were
added the solution again became clear and the galvanometor
was readjusted to approximately one hundred and the 1.
reading taken. The solution was then titrated with the
nonsolvent and deflections of the galvanometor recorded.
which were the I readings. the factor olog III. was then
calculated and plotted against the percent nonsolvent. this
resulted in the precipitability curve of the sample.
Tangents were then drawn to these curves at numerous
points and these tangents plotted against percent nonsolvent.
Ehe tangent curves formed a peah.at that percent nonsolvent
which represented the greatest increase in extinction per
unit of nonsolvent added. that is where the greatest amount
of polymer precipitated with the addition of one unit of
nonsolvent. Different molecular weights would precipitate
at different concentrations of nonsolvent therefore. these
peaks indicate the point at which the largest molecular
weight fraction of the sample precipitated.

in example of the data obtained from a typical precip-
itation of a toluene solution of the polymer with 95% ethyl

 

 

.lCOhGIe
Sample: Run # VIII - 51.7% polymerization
Solution concentration: 0.02!
0 OK: Deflection
. . _ - log IIIo 16 3235011

49 93 s 10 30.52
50 94 .00459 51.25
52 92 .01593 52.50
54 88 .05534 55.75
56 79 .0800? 55.00
58 71 .12546 56.25
60 66 .15817 57.50
58 50 .1995? 38.75
64 55 .25755 40.00
65 50 .27875 41.25
60 47 .50568 42.50
70 45 .52451 45.75
75 41 .55494 45.68
75 50 .59794 47.50
7! 55 .45565 49.57
82 52 .47257 51.25
85 . 89 .51552 55.75
90 86 .56275 56.85
95 24 .59751 59.57
100 23 .65550 62.50
110 22 .65550 58.75

120 22 .65550 75.00

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-33-

DIBCpSSIOE:
‘ Iran a study of Table 1.and Fig. 1 it develops that
there is a great difference in rate of reaction along the
different catalytic eyetene. Sodiun bioultite alone hoe
very little catalytic effect but increases the rate of poly»
nerization greatly when used with potaeeiuILpereulthte.
the replacement or air with an atmosphere of nitrogen in-
creases the rate even.turther. The molecular weighte of
the final products however are of the lane order of nagni-
tune.
litrogen atnoephere, need with potaoeiun pereulfate
without the preeence or eodiun bieultite. gives the meet
rapid reaction; The molecular weight of the final product
ie many times greater then that forned in the other eyetene.
It is also intereeting to note that in the formation
or very large molecules the greeteet aeerageinoleoullr
weight occurs at approximately fifty percent polymerization.
This would eeen to indicate that the decrease in the amount
or noncner available toward the end of the reaction cwueee
the formation of low molecular weight compound: which reduce
the total average molecular weight or the final product.
ihie type of.nexilnn deee not reel to occur in the formation
of thelower molecular weight compounds. This could be
explained by the fact that although there ie the cane decreaee
in the amount or scanner available. the chain length through-

out the reaction in low so that there is not the contrast

between the molecules formed at the beginning and end of
the reaction.

Fig. VIII shows the molecular distribution curves of
the samples taken from a run using potassium.persulfate in
nitrogen. it agrees with the molecular weight determina-
tions in that the first and last samples which have approx-
imately the same molecular weight have also almost identical
distribution curves. The intermediate sample, however. which
has a larger molecular weight has its peak at a smaller per-
sentage of nonsolvent.

If an atmosphere of molecular oxygen is used with
potassium persulfatc practically no polymerisation occurs
over a long’period of times

The fact that an atmosphere of nitrogen gives rapid
polymerisation with the formation of long chains indicates
that oxygen acts as an inhibitor and possibly a chain term-
inator. The running of a reaction under an oxygen atmosphere
confirmed this idea.

The rapid rate of polymerization using potassium per-
sulfate with sodium bisulfite could be accounted for if the
sodium bisulfitc, acting as a reducing agent, took.up the
oxygen present in the emulsion. This would remove the
inhibitory and chain terminating effect of the oxygen. The
presence of the sodium bisulfitc in the system, however.
could act as a chain terminator so that low molecular weights
would be obtained.

-34-

The fact that placing this system under a nitrogen
atmosphere gave little increase in the rate of polymerisa-
tion seemed to support this conclusion.

By examining Fig. II it is apparent that there is little
correlation between preeentage polymerisation and molecular
distribution. This is not surprising considering the dif-
ferent rates at which the products were formed.

1y plotting the molecular distribution curves of samples
haveing approximately the same molecular weight on the same
axis as in Fig. 111, it can be seen that samples of the
same molecular weight may not have the same molecular dis-
tribution. However, the peaks for these curves all occur
at approximately the same percentage of nonsolvent.

By studying the various graphs on precipitability and
molecular distribution it can be seen that the molecular
weight and the molecular distribution change considerably

as polymerisation.proceeds.

-afio

CONCLUSIONS:

1. Potassium persulfatc catalyst in an atmosphere of
air gives slaw polymerisation and a product with a molecular
weight of approximately 35,000.

2. Potassium persulfatc catalyst in a nitrOgen atmcl-
phere gives rapid polymerization and a product with a molec-
ular weight of approximately 200,000at total polymerization.
At fifty percent polymerization it gives a product of approx-
imately 380,000 molecular weight.

5. Potassium persulfatc with sodium bisulfitc in an
atmosphere of air gives rapid polymerisation and a product
with a molecular weight of approximately 40,000.

4. Potassium persulfatc with sodium bisulfitc in an
atmosphere of nitrOgen gives rapid polymerization and a
product with a molecular weight of approximately 40,000.

5. Sodium bisulfite alone is ineffective in the sat-
alysis of polymerization.

6. Molecular oxygen has an inhibitory effect upon
polymerization in this systmms

7. The smaller the amount of catalyst used in the
potassium persulfate - sodium bisulfite system the higher
the molecular weight of the product.

-35-

BIBLIOGRAPHY:

1.

2.
3.

4.

5.
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