F o r t s c h r . Ho c h p o l y m. - F o r s c h . , Bd. 2, S.

4 0 1 - - 4 4 1 (1961)
Mechanism of Acrylonitrile Polymerization
By
W. M. THOMAS
Co n t r i b u t i o n f r o m t h e Ch e mi c a l Re s e a r c h De p a r t me n t , Ce n t r a l Re s e a r c h Di v i s i o n ,
Ame r i c a n C y a n a mi d C o mp a n y , S t a mf o r d , Co n n e c t i c u t
Wi t h 4 F i g u r e s
Co n t e n t s
Page
1. I n t r o d u c t i o n . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
2. F r e e - Ra d i c a l P o l y me r i z a t i o n i n Ho mo g e n e o u s So l u t i o n . . . . . . . . . 402
3. F r e e - Ra d i c a l B u l k P o l y me r i z a t i o n . . . . . . . . . . . . . . . . . . 409
4. He t e r o g e n e o u s F r e e Ra d i c a l P o l y me r i z a t i o n i n t h e P r e s e n c e of Or g a n i c
Di l u e n t s a n d Ad d i t i v e s . . . . . . . . . . . . . . . . . . . . . . . 417
5. P o l y me r i z a t i o n i n Aq u e o u s S u s p e n s i o n . . . . . . . . . . . . . . . . 422
6. An i o n i c P o l y me r i z a t i o n . . . . . . . . . . . . . . . . . . . . . . . 428
R e f e r e n c e s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
1. I n t r o d u c t i o n
Thi s revi ew deals wi t h cur r ent ideas on t he mechani sms oper at i ve in
acryl oni t ri l e pol ymeri zat i on. The t opi c is of i mpor t ance i n i t s own f i ght
and also because t he s t udy of acryl oni t ri l e has cast l i ght on het er o-
geneous pol ymeri zat i ons in general. I t is an act i ve field of research and
t he i nt er pr et at i ons are still cont roversi al . We shall l ook first at free-
radi cal pol ymer i zat i on in homogeneous solution, where t he monomer
behaves in a mor e or less classical fashion. Next we shall consi der t he
compl i cat i ons t hat arise where t he monomer is at l east par t i al l y soluble
in t he react i on medi um but where t he pol ymer preci pi t at es. These con-
di t i ons are encount er ed in bul k pol ymer i zat i on and in most aqueous or
organi c diluents. Fi nal l y we shall exami ne t he less ext ensi ve l i t er at ur e
on anionic pol ymer i zat i on and show i mpor t ant differences bet ween t he
radi cal and t he ionic processes.
The general l i t er at ur e on acryl oni t ri l e monomer , its reactions, its
pol ymer i zat i on and t he t echni cal appl i cat i ons of i t s pol ymer s have been
summar i zed in a r ecent book listing 1454 references (1). These t opi cs
will not be discussed her e except as t he y bear on pol ymer i zat i on me-
chanisms. Copol ymeri zat i on is ment i oned onl y as i t t hrows l i ght on
402 W.M. THOMAS:
homopol ymer format i on. The present revi ew covers t he l i t er at ur e up
t o about J anuar y, 1960.
Before discussing details of t he pol ymer i zat i on process, we ma y
consi der t he nat ur e of t he pol ymer itself. Or di nar y pol yacryl oni t ri l e
appears t o have t he nor mal head-t o-t ai l st ruct ure. Pol ymer made in
homogeneous solution or in t he presence of chai n t r ansf er agent s is
pr obabl y essent i al l y unbr anched. Pol ymer made in aqueous syst ems at
t emper at ur es below about 50 ~ is ve r y l i t t l e br anched ( z l l , 67, 9 8 ) . Hi gh
mol ecul ar wei ght fract i ons of pol ymer pr epar ed in aqueous syst ems ap-
pear t o be somewhat br anched ( 9 8 , 1 1 1 ) , especially when made above 50 ~
and when act i ve i ni t i at ors like persul fat e are used. Evi dence for ot her
st r uct ur al modifications ( cyanoet hyl at i on and ket ene i mi ne format i on)
is discussed in appr opr i at e sections below. Recent l y t wo groups of inves-
t i gat ors ( 1 3 8 , 1 2 4 ) have begun t he pr epar at i on and s t udy of low mol ecu-
l ar wei ght oligomers and analogs.
A large number of paper s has deal t wi t h t he quest i on of mol ecul ar
wei ght and mol ecul ar wei ght di st ri but i on in pol yacryl oni t ri l e. Recent
discussions are t hose of ONYON ( 1 0 8 ) , KRIGBAUM and KOTLIAR ( 9 0 ) ,
BOOTH and BEASON ( 3 3 ) , BAMFORD, JENKINS, JOHNSTON and WHITE ( 1 9 )
and KOBAYASHI ( 8 7 ) . The intrinsic vi scosi t y vs. mol ecul ar weight rela-
.tionship of CLELAND and STOCKMAYER ( 4 1 ) is pr obabl y as well suppor t ed
as any. For t unat el y, much of t he mat er i al in this revi ew does not depend
heavi l y on det ai l ed knowl edge of mol ecul arwei ght s or of t hei r di st ri but i ons.
Fi nal l y, t he quest i on of st er eor egul ar i t y and cr yst al l i ni t y must be
ment i oned. The pol ymer has oft en been called cryst al l i ne on t he basis of
X- r ay di ffract i on (37, 1 2 3 ) sol ubi l i t y ( 3 3 ) , spherul i t e f or mat i on (71) and
ot her charact eri st i cs. Some of t he confusion arises from differing defini-
t i ons of what const i t ut es "cr yst al l i ni t y". The best i nt er pr et at i on seems
t o be t hat or di nar y pol yacryl oni t ri l e can exhi bi t good l at eral order
(packing in di rect i ons per pendi cul ar t o t he chai n axis) but except in t he
most unusual ci rcumst ances (106) i t is poor l y or der ed al ong t he chai n
axis. The possi bi l i t y of syndi ot act i c confi gurat i on has been discussed by
several wri t ers ( 2 , 1 0 , 9 0 ) . Pr obabl y nor mal pol ymer is not compl et el y
at act i c, but t he ext ent of r egul ar i t y has not been measur ed reliably.
ARCUS and Bos e (2) were not able t o i nduce cr yst al l i ni t y by t r eat i ng
pol ymer wi t h bases t o i nver t ~CHCN groups. For a ve r y r ecent dis-
cussion of cryst al l i ni t y, glass t emper at ur e and chai n conf or mat i on t he
r eader is referred t o t he paper of KRmBAUM and TOKITA ( 9 1 ) .
2. Free-Radical Polymerization i n Homogeneous Solution
The mai n feat ures of acryl oni t ri l e pol ymer i zat i on in sol ut i on have
been clarified t hr ough a number of i nvest i gat i ons in t he past five years.
The general conclusion t o be dr awn from this wor k is t hat in homo-
Mechani s m of Acr yl oni t r i l e Pol ymer i zat i on 403
geneoussyst ems acryl oni t ri l e is a fai rl y t ypi cal vi nyl monomer. Al t hough
t hi s s t at ement ma y not appear significant in i t sel f, i t becomes i mpor t ant
when vi ewed in cont ext wi t h resul t s on het erogeneous syst ems. The
het erogeneous work, t o be descri bed in a l at er section, preeeeded t he
solution work in t he hi st ori cal devel opment of t he subj ect and pr ovi ded
much of t he i mpet us for under t aki ng solution studies.
I n this revi ew t he el ement ar y st eps and t hei r vel oci t y coefficients are
defined as follows:
Ra t e of I ni t l a t i ou = Ri
Ra t e of Pol ymer i zat i on = Rp
I ni t i a t or = I
Monomer = M
Sol vent = S
Dead Pol yme r ----- X
Gr owi ng Pol yme r = M.
Cat al ys t Ef f i ci ency = f
Degr ee of Pol yme r i z a t i on = P
Radi cal f or mat i on
I - + 2 1 -
I ni t i at i on
I . = M - +M.
Pr opagat i on
M. +M - +M.
Tr ansf er t o sol vent
M. +S - +X +S .
Ter mi nat i on by combi nat i on
2 M. - + X
Ter mi nat i on by met al ion
d I t . ] ~d r : 2 k, [I 3
Ri = 2 f kl [I]
( may depend on M at low f )
- - d [ M ] H t = k2 [ M. ] [ M]
- - d [ M. ] Ht = k~ [ M. ] [S]
- - d [M .]/dt = 2 k, EM.] 2
M" + Fe +a -+ X + Fe +2 - - d [ M. ] / dt = k 5 [iT/.] [Fe +8]
Square bracket s denot e mol ar concent rat i ons. Uni t s are moles, liters,
seconds, degrees cent i grade and kilocalories per mole. E n refers to t he
ener gy of act i vat i on for t he st ep in whi ch k n is t he vel oci t y coefficient,
t he l at t er t er m bei ng used t o avoi d reference t o vari abl e r at e "cons t ant s ".
Since t he pol ymer i zat i on rat e, R, , is commonl y
R~ = - - d [M]/ dt = k~(klf/k4) 1l~ [1] 1/2 [3/]
i t follows t ha t t he over-al l act i vat i on energy, E 0, is in t hi s i nst ance
E o=E 2+ 1/2E l - - 1/2E 4.
The r at i o ks/k~, is t he chai n t r ansf er const ant , C~.
Fortsehr. Hoehpolym.-Forseh., Bd. 2 27
404 w. M. THOMAS:
Much of t he ear l y l i t er at ur e on pol ymer i zat i on in homogeneous solu-
t i on is ci t ed by ULBI~ICHT ( J 3 5 ) and by SRINIVASAN and SANTAPPA ( 1 2 2 ) .
Onl y a few liquids are sui t abl e sol vent s for t he pol ymer, and a gr eat er
par t of t he mechani sm wor k has been concerned wi t h N, N- di met hyl -
formami de, general l y abbr evi at ed as DMF. I n t hi s revi ew we describe
t he react i on in DMF i ni t i at ed by an azo compound and t hen go t o resul t s
wi t h ot her syst ems for compari son.
Cur r ent views on pol ymer i zat i on of acryl oni t ri l e in homogeneous
solution are i l l ust r at ed by a descri pt i on of t he react i on in N, N- di met hyl -
formami de (DMF) as i ni t i at ed by azobi si sobut yroni t ri l e (AIBN) at about
50 t o 60 ~ Pr i mar y radicals f r om t he decomposi t i on of AI BN r eact wi t h
monomer t o s t ar t a growing chain. About one-half of t he pr i mar y radicals
are effective, t he ot hers bei ng lost in side react i ons not l eadi ng to pol ymer.
BEVlNGTON and EAVES ( 32) est i mat ed i ni t i at or efficiency b y use of AI BN
labelled wi t h C-14, whereas BAMFORD, JENKINS and JOHNSON ( t 3 ) used
t he FeC13 t er mi nat i on t echni que. Bot h of t hese met hods requi re t ha t t he
r at e of AI BN decomposi t i on be known, and t he numer i cal val ue of this
r at e has under gone a number of revi si ons t ha t requi re recal cul at i on of
efficiency results. Fr om r ecent l y proposed r at e expressi ons for AI BN
decomposi t i on at 60 ~ ( 2 2 , 1 3 6 ) one calculates an efficiency of about 40~/o
b y t he t r acer t echni que and 60- - 65% by t he FeC13 met hod.
I t has been deduced f r om t he or der of r eact i on wi t h respect t o mono-
mer t hat t he r at e of i ni t i at i on is not i ndependent of monomer ( 7 2 2 ) . One
coul d assume t ha t i ni t i at or and monomer ma y form a compl ex from
whi ch t he act ual i ni t i at or is derived, or else t ha t t he AI BN and its radi cal
pr oduct s are in equi l i bri um wi t hi n a cage of sol vent . Al t hough ki net i c
dat a are consi st ent wi t h such assumpt i ons, i t appears t hat t he resul t s
can be expl ai ned r easonabl y on t he grounds of t er mi nat i on by pr i mar y
radicals (2]). The or der of react i on wi t h respect t o AI BN i ni t i at or in
near l y all of t hese st udi es is t he expect ed 0.50 or possibly sl i ght l y hi gher
( 0 . s s t o 0 . s 9 ) .
Chain gr owt h cont i nues at a r at e dependent on t he concent r at i ons
of monomer [M] and of act i ve sites [IV/.]. Monomer exponent s in t he
range 1.3 t o 1.5 or hi gher had been obser ved ( 7 7 0 , 7 2 3 , 7 2 7 ) especially
at low [M], b u t first or der dependence has now been est abl i shed over
a br oad range of [MJ ( 2 1 ) . A s t at i onar y level of [ M. ] is r eached r api dl y
and is t ypi cal l y of t he order of l 0 -s mol ar. Chains grow r api dl y by
successive monomer addi t i ons unt i l t he pol ymer chai n is t er mi nat ed b y
t r ansf er or by react i on wi t h anot her radical. The r at e const ant for pr opa-
gat i on (ks) at 60 ~ in DMF is 1960 m -1 ls -1 (16), whi ch is a compar at i vel y
hi gh val ue [see Tabl e 1 and ref. ( 1 6 ) ] . On t he ot her hand i t is onl y about
one- t ent h of t ha t f ound for acryl oni t ri l e in aqueous syst ems (Table 6)
Mechanism of Aerylonitrile Polymerization 405
but is much above t he r ange pr oposed (24) for post - pol ymer i zat i on. The
r at i o k J ( 2 k4) 112 has been assi gned a va r i e t y of val ues, t he mos t rel i abl e
of whi ch appear s t o be 0.081 (21, 32). Thi s cor r esponds t o k2/k)/Z = 0.11
1
in our not at i on. The val ue of E 2 - - ~ - E 4 has been gi ven (122) as 7.6 kcaL
per mole.
Ter mi nat i on is a bi mol ecul ar process i nvol vi ng t he growi ng chai n and
a second radi cal , usual l y anot her growi ng chain. Ter mi nat i on b y cyano-
pr opyl radi cal s f r om AI BN t akes pl ace t o some ext ent (21). I t ha d been
t hought t h a t t he t er mi -
nat i on st ep i nvol ved dis-
pr opor t i onat i on i nt o an
uns at ur at ed pol ymer and
a s at ur at ed pol ymer ,
but BAMFORD, JENI~IlqS
and JOI-INSTON (20) have
pr esent ed st r ong evi -
dence t ha t t he t wo grow-
ing chai ns coupl e t o gi ve
an i nact i ve pol ymer mol -
ecule. I n t he first place,
t he r el at i onshi p bet ween
degree of pol ymer i zat i on
for coupling. Secondl y,
Table 1. Velocity Coefficients for Acrylonilrile and
Some Other Monomers in Homogeneous Systems
Acrylonitdle 0nDMF) . .
Vinyl acetate . . . . . . .
Methyl acrylate . . . . . .
Methyl methacrylate . . ,
Styrene . . . . . . . . .
k,
1960
3700
2090
367
176
k, (X 10 -7)
39.1
7.4
0.47
0.93
3.6
Data are for 60 ~ C and non-aqueous systems. Except
for acrylonitrile theyare from the summary by FLORY
(5d). In BAMFORD'S notation k 4 is double this amount.
and i ni t i at or concent r at i on is t ha t requi red
when pol ymer is pr epar ed wi t h i ni t i at or
cont ai ni ng f unct i onal groups, i t is possible t o l i nk chai ns s ubs equent l y
t hr ough t hese end groups. The i ncrease in sol ut i on vi scosi t y on end-
l i nki ng is consi st ent wi t h coupl i ng r a t he r t han wi t h di spr opor t i onat i on.
I n t hi s respect acryl oni t ri l e behaves in an unusual manner , since
mos t ot her vi nyl pol ymer i zat i ons t er mi nat e b y di spr opor t i onat i on. The
wor k of BEVINGTON and EAVES (32) general l y confi rms t he combi nat i on
mechani sm. I f t er mi nat i on were b y di spr opor t i onat i on and t r ansf er t o
sol vent occur r ed as has been supposed, t hen t he numbe r of i ni t i at or
f r agment s per mol ecul e woul d be less t ha n t hey found. On t he ot her
hand, soluble gr af t pol ymer s have been made at hi gher t emper at ur es
(100~176 so t er mi nat i on cannot have been l ar gel y b y combi nat i on
in t hese cases. Ei t her t he mechani s m changes at hi gher t emper at ur es or
else t r ans f er r eact i ons pr event crossl i nki ng [see discussion af t er refer-
ence (t 4)].
Dependi ng on t he r at i o of DMF t o monomer , chai ns are s t opped mor e
or less f r equent l y b y abs t r act i on of a hydr oge n a t om f r om t he DMF
sol vent . The poi nt of a t t a c k on DMF was t hought (109, 722, 727, 135)
t o be as in A below, but a paper b y CAMPBELL (36) suggest ed t ha t t he
N- me t hyl gr oup is a t t a c ke d when BF 3 is pr esent and BAMFORD and
27*
406 W.M. THOMAS:
WHITE (18) have now shown t ha t t he DMF r adi cal is i ndeed t he one of
s t r uct ur e B :
O O / CH3
II r l
9 CN(CH3), (A) HCN\ (B)
CH.~"
Radi cal B ma y of course r esul t also f r om a t t a c k b y radi cal s f r o m
AI BN. I n t ha t event or in t he event of t r ansf er f r om t he pol ymer radi cal
t o sol vent , a new pol ymer chai n will be s t ar t ed b y B and t hi s chai n will
have no AI BN f r agment at t ha t end. Coupling of t wo B radi cal s is
assumed t o be a ver y i nf r equent event . Tr ansf er t o monomer , t o pol yme r
or t o i ni t i at or are i nf r equent also. The t r ansf er cons t ant s are appr oxi -
ma t e l y t 10 -5 for t r ansf er t o monome r at 25 ~ (108) and 2.7 10 -4 for
t r ansf er t o DMF at 50 ~ (135). SRINIVASAN and SANTAPPA (126) suggest
t ha t t he val ues for DMF are 1.0 10 -4 at 50 ~ and 2.4 10 -4 at 60 ~
al t hough t hi s requi res an unexpect edl y hi gh act i vat i on ener gy of 18 kcal
per mol e for t ransfer. Hy d r a t e d DMF appear s to be r el at i vel y i ner t
t owar d t r ansf er (84).
The quest i on t hen arises as to how r api dl y radi cal B rei ni t i at es a
growi ng chain. THOMAS, GLEASON and PELLON (127) and t hen ULBRICHT
(735) obser ved t ha t t he pol ymer i zat i on r at e in DMF is sl ower t han in
some ot her sol vent s and t ha t in t he pol ymer i zat i on r at e expressi on t he
monomer exponent is f r act i onal l y hi gher t han uni t y ( l OP, 1 2 2 ) . These
and mol ecul ar wei ght consi derat i ons led t hem t o concl ude t ha t t he r at e
of rei ni t i at i on is r el at i vel y sl ow Csee also ref. (109)~. Ki net i c expressi ons
were der i ved t hat reduce t o t he convent i onal equat i on onl y in t he l i mi t
of hi gh monomer concent r at i on. Rapi d cr oss- t er mi nat i on as in copol y-
mer i zat i on ma y be i nvoked also ( 2 2 , 1 0 9 ) . JENKINS ( 8 3 ) on t he ot her
hand has concl uded t ha t expl anat i ons of t hi s t ype [see also BURNETT
and LOAN (35)] are not l i kel y t o be general in pol ymer i zat i on ki net i cs.
BAMFORD, JENKINS and JOHNSTON ( 21) showed r ecent l y (as ment i oned
above) t hat t he [3/1 ~-~ r el at i onshi p is obeyed at hi gh EM~ and t ha t
devi at i ons at low [MJ can be expl ai ned b y assumi ng t ha t a si gni fi cant
t er mi nat i on st ep is r eact i on of pr i ma r y radi cal s (from AI BN) wi t h t he
growi ng chain. Fur t he r wor k in sol vent s ot her t han DMF will be hel pful
at t hi s poi nt .
Pos t effects have not been exami ned in det ai l in homogeneous syst ems.
ONYON (10Q) a t t e mpt e d t o use t he vi scomet r i c met hod, but t he da t a
di d not va r y in accor dance wi t h t heor y and di d not allow accur at e
det er mi nat i on of i ndi vi dual r at e const ant s.
The general pi ct ur e out l i ned so f ar is pr es umed t o be val i d for ot her
sol vent s, i ni t i at or s and t emper at ur es , but t he evi dence is much less
ext ensi ve. The choice of sol vent s is qui t e l i mi t ed, and at hi gh [M3 t hese
Me c ha ni s m of Ac r yl oni t r i l e Pol yme r i z a t i on 407
liquid mi xt ur es lose t hei r sol vent propert i es. Thi s l i mi t is about 3 mol ar
for DMF at 25 ~ and about 5 or 6 mol ar at 60 ~ Pol ymer i zat i on in et hyl ene
car bonat e and in 4- but yr ol act one is consi derabl y more rapi d t han in
DMF ( 7 2 7 , 7 3 5 ) , suppor t i ng t he idea t hat radicals der i ved from DMF
are r el at i vel y i nact i ve. ULBRICHT ( I 3 5 ) concl uded t hat t he t r ansf er
const ant s t o sol vent at 50 ~ are
Et hyl e ne c a r bona t e . . 3. 9 10 -5
But yr ol a c t one . . . . . 7. 4 l 0 -5
I ) i me t hyl f or ma mi de . . 27. 0 10 -6
CLELAND and STOCKMAYER ( 41) used succinonitrile as one of t hei r
solvents, but is has been suggested since t hat pol ymer i zat i on ma y not
have been st r ai ght f or war d in t hat medi um ( 1 9 ) .
Pol yacr yl oni t r i l e is soluble in a var i et y of concent r at ed aqueous salt
solutions, and t hese solutions ma y be used in acryl i c fiber manuf act ur e.
On several occasions i t has been proposed t hat pol ymer mi ght be formed
di r ect l y in such solutions, t hus avoi di ng t he i nt er medi at e st eps of sepa-
r at i ng and dissolving t he pol ymer. One such reference is a r ecent pat ent
by SCHMIDT ( 1 7 8 ) . HUNYAR and GROBE ( 7 4 ) discussed t he vari abl es in
t hei r phot oi ni t i at i on process, and GROBE and SPODE ( 6 5 ) st udi ed pol y-
meri zat i on as a funct i on of t he wave l engt h of t he light. MILLER ( 9 9 )
has pr ef er r ed aqueous Perchl orat es in graft i ng exper i ment s because t he
sol vent is not a chai n t r ansf er medi um and because it is not at t acked
by oxidizing cat al yst s. Ext ensi ve mechani sm st udi es have not been
carri ed out in t hese aqueous
solvents.
ULBRI CHT (135) cal cul at ed
i ni t i at or efficiencies as follows,
usi ngAI BN. He concl uded t hat
di spr opor t i onat i on is t he more
likely, but ]3AMFORD, JENKINS
and JOHNSTON ( 2 0 ) used et hyl -
Assumed Termination
Mechanism
Combi na t i on . . . .
Di s pr opor t i ona t i on .
Ethylene Butyro-
Carbonate lactone
0. 96 0. 83
0. 48 0. 42
ene car bonat e as well as DMF in t hei r exper i ment s and concl uded t hat
combi nat i on is oper at i ve in bot h solvents. I f so, t he efficiencies of
ULBRICHT seem unr easonabl y high.
Exper i ment s in which i ni t i at ors ot her t han AI BN are used do not
i ndi cat e any unusual effects. Pol ymer i zat i on r at e is near l y al ways pro-
por t i onal t o t he square r oot of t he i ni t i at or concent r at i on or at l east t o
a val ue bet ween 0.5 and 0.6. ULBRICHT ( 1 3 5 ) est abl i shed t he square r oot
l aw for ammoni um persul fat e, AI BN and benzoyl peroxi de in DMF, t he
r at es bei ng fast est wi t h persul fat e, slower wi t h AI BN and slowest wi t h
t he peroxi de. One expect s t ha t persul fat e and per oxi de will be mor e
act i ve t han AI BN in abst r act i ng hydr ogen from ot her component s of t he
syst ems. Ot her i ni t i at ors have been used, i ncl udi ng UV wi t h di - t - but yl
408 W.M. THOMAS:
per oxi de ( 1 0 9 ) and ei t her Ra or Co-60 ( 2 8 ) . Resul t s are in general con-
f or mi t y t o t hose obser ved wi t h AI BN. BE~SASSON and PREVOT-BERNAS
( 2 8 ) f ound t hat wi t h ionizing r adi at i on t he i nt ensi t y exponent in 70 mole
per cent DMF is 0.55, whi ch is subst ant i al l y t he same as t he exponent
for AI BN.
BARSON, BEVINGTON and EAVES have l ooked i nt o t he i ni t i at i on
react i on wi t h azobi si sobut yroni t ri l e and wi t h benzoyl peroxi de, bot h in
di met hyl f or mami de ( 2 3 ) . Wi t h AI BN t he y r epor t ed nor mal i ni t i at i on.
Wi t h t he per oxi de t her e appear ed t o be complications, due t he y t hought
t o hydr ogen abst r act i on f r om monomer or pol ymer . By usi ng per oxi de
labelled in t he ri ng or in t he car bonyl group wi t h C-14 t hey measur ed
t he rel at i ve i mpor t ance of t he t wo st eps:
C6H5COO- -+ C6H~- + CO, (A)
C6HsCOO" + CHi=CHCN ---> CoHsCOOCHaCHCN (B)
and f ound t hat t he rat i o of r at e B/ r at e A is not less t han 8 m 1-1 at 60 ~
Thi s rat i o vari es from monomer to monomer and is gr eat er for st yr ene t han
for acryl oni t ri l e. Thus t he first uni t in a st yr ene copol ymer woul d be
C6HsCOOCH2CHC6H 5 r at her t han a uni t cont ai ni ng acrylonitrile.
Smal l quant i t i es of i nhi bi t ors and r et ar der s give t he expect ed effects.
Most of t he sol vent s for pol yacr yl oni t r i l e are difficult t o pur i f y, and
some of t he l i t er at ur e is based on resul t s obt ai ned wi t h sol vent s cont ai n-
i ng t races of amines and wat er . The growing chai n is an el ect ron accept or
and undergoes t r ansf er react i ons most r eadi l y wi t h el ect ron donors ( l d ) .
Addi t i on of small amount s of agent s like CBr , , whi ch commonl y serve
as efficient chai n t r ansf er agents, is consi derabl y less effective. On t he
ot her hand, t r i et hyl ami ne is a ve r y efficient t r ansf er agent and t hi s f act
has been used as a basis for pr epar i ng bl ock copol ymers ( 1 5 , 2 2 ) .
When cert ai n salts like FeC13 are pr esent t he maj or t er mi nat i on
react i on becomes el ect ron t r ansf er from t he growing chain, reduci ng Fe +a
t o Fe +~. The r at e of Fe +2 f or mat i on can be i dent i fi ed wi t h t he rat es of
i ni t i at i on and t er mi nat i on. BAMFORD and coworkers have used t hi s
principle t o est i mat e i ni t i at or efficiencies and i ndi vi dual r at e const ant s
( 7 2 , 7 3 , 7 6 , 1 9 ) . At 60 ~ t he r at e Constant (ks) for ferric ion t er mi nat i on
was est i mat ed as 6533 1 m -1 s -1 ( 1 3 ) . I n t hese exper i ment s t he i ni t i at or
efficiency f was cal cul at ed t o be in t he range 0.73 t o 0.79, whi ch now
appears high.
Ot her salts pr obabl y have similar effects but have not been st udi ed
ext ensi vel y. Li t hi um salts have l i t t l e influence on t he t er mi nat i on r eact i on
but can increase t he pr opagat i on rat e, pr esumabl y b y compl exi ng t he
growi ng nitrile radi cal ( 1 4 ) . Anions compl ex wi t h t he growing chai n in
t he or der C1 > NO3 > CIO,. Compl ex f or mat i on bet ween salt and mono-
Mechanism of Acrylonitrile Polymerization 409
mer appears uni mpor t ant , but sal t -i ni t i at ed anionic pol ymer i zat i on has
been suggested ( 1 4 ) . These salt effects are by no means l i mi t ed t o acryl o-
ni t ri l e pol ymeri zat i on but have been observed wi t h acryl ami de and wi t h
ot her monomers.
Di st ri but i on of mol ecul ar weights in t hese homogeneous syst ems has
been uncert ai n. A recent discussion and review of this t opi c is t hat of
]3AMFORD, JENKINS, JOHNSTON, and WHITE ( 1 9 ) . The y assume a simple
exponent i al di st ri but i on and consider bot h t r ansf er and bi mol ecul ar
t ernfi nat i on. PEEBLES ( 1 1 2 ) obser ved convent i onal pol ymer i zat i on ki-
net i cs but he concl uded from l i ght scat t er i ng results t hat t here are
devi at i ons from nor mal behavi or in t he hi gher mol ecul ar weight fractions.
He associated t hese wi t h t he same mechani sm t hat causes microgel.
3. Free-Radi cal Bul k Pol ymeri zati on
I t mi ght be supposed t hat t he simplest way t o s t udy acryl oni t ri l e
pol ymer i zat i on woul d be to follow t he react i ons of pur e monomer. In
fact , however, this syst em is ver y compl ex and even now af t er ma ny
i nvest i gat i ons t he details are not compl et el y under st ood. Thi s is because
separat i on of pol ymer in an essent i al l y unswollen st at e leads to ki net i c
results t hat have been i nt er pr et ed in a var i et y of ways. The subj ect has
been t r eat ed r ecent l y in a book by BAMFORD, BARB, JENKINS and
ONYON (17).
Pur e monomer is qui t e st abl e t o heat , al t hough t he cyclic di mer
CHzCHCN
I I
CHzCHCN
is f or med at t emper at ur es in t he range of 200 t o 300 ~ (d,/). For most
purposes uncat al yzed t her mal pol ymer i zat i on can t hus be disregarded.
A f ur t her simplification arises from t he fact t hat depol ymer i zat i on is
uni mpor t ant under usual conditions.
Pol ymer i zat i on is i ni t i at ed r eadi l y by light, by azo and per oxy
compounds, by ionizing radi at i on, or in general, by any source of free
radicals. I f a t ube cont ai ni ng pur e acryl oni t ri l e t oget her wi t h a t r ace of
cat al yst is kept at a moder at e t emper at ur e t her e is a peri od of a few
seconds t o mi nut es duri ng whi ch t he sol ut i on remai ns clear and while
t races of i nhi bi t ors such as oxygen are bei ng consumed. At this stage t he
monomer cont ai ns part i cl es r oughl y 100 t o 200 A across. The y are
sl i ght l y fl at t ened spheres not large enough or numer ous enough t o cause
t ur bi di t y (130).
Sudden appearance of a haze signals t he begi nni ng of t he mai n pol y-
mer i zat i on react i on. Ordi nari l y t he haze does not ext end uni f or ml y
t hr ough t he t ube but appears as a cl oud along t he axis of t he t ube
27a
410 W.M. THOMAS:
beginning near the bot t om. Turbi di t y increases rapidly, and if the tube
is shaken, discrete particles can be seen with the unaided eye. If the t ube
is kept still a clear l ayer may persist for a short time. After about 0.2
to 0. 3% of the monomer is convert ed to pol ymer the fine suspension
begins to coagulate to a curdy precipitate and the slurry gradually in-
creases in thickness. By the time half of the monomer has been convert ed
to pol ymer the reaction mi xt ure is a hard, coarse, white solid. Particles
Fig. 1. Polyacrylonilrile. Bulk polymerization at 60~ (127)
are fairly densely packed aggregates porous to nitrogen. They are several
t housand Angst roms across and comprise many smaller particles in the
range of a few hundred Angstroms to 1000 or more (126). Each of the
smaller particles contains many pol ymer molecules. Fig. 1 shows ag-
gregates made at 60~ at 30 ~ t hey are less uni form (130).
A large amount of heat (17 kcal/mole) is given off during polymeriza-
tion (131). The character of the slurry and the speed of reaction are such
t hat this heat is not easily dissipated. Unless the sample size is small
and the rate of initiation is low, the t emperat ure is likely to rise rapidly
and lead to an uncontrolled reaction. These characteristics make bul k
polymerization unat t ract i ve except for l aborat ory experi ment at i on.
First detailed studies appeared in the 1940% not abl y those of KERN
and FERNOW (86) and of KONINGSBERGER and SALOMON (89). Our
knowledge of the mechani sm of bulk pol ymeri zat i on is based largely on
kinetic work of the present decade. Results t urned out to be quite
Mechanism of Arcylonitrile Polymerization 411
di fferent from those general l y obt ai ned wi t h vi nyl monomer s or even
wi t h acryl oni t ri l e itself in homogeneous sol ut i on. The more st ri ki ng
differences are shown i n Tabl e 2 and are discussed i n t ur n below.
A t ypi cal conversi on-t i me curve exhi bi t s a short peri od of accel erat i on
followed by a near l y const ant rat e up to 50% conversi on or more, t hen
followed i n t ur n by a di mi ni shi ng rate. The accel erat i on peri od is some-
t i mes report ed to persist to qui t e hi gh conversi on. Al t hough some
Table 2. Comparison of Bulk with Sohtlion Polymerization
Heterogeneous Hontogeneous
(Bulk) (Solution)
Acceleration period
Monomer exponent in
rate expression
Initiator exponent in rate
expression
Energy of activation
Velocity coefficients
Post polymerization
Mol. wt. vs. temperature
Mol. wt. vs. initiator
Radical concentration
During polymerization
At end of reaction
Present
Not observed
0.7--0.8
Individual values not
known; some appear
to be high
Variable and not known
with certainty
hnportant; shows un-
usual features such as
fast reaction
Maximum at 60~ ~
i - 0. 3
ca. 10 4 to 10 s31
Appreciable fraction
of radicals trapped
Absent
1.0 over must of range
0.5--0.6
Normal
Normal (rather high)
Moderate (does not fit
usual expression)
Normal inverse relation-
ship with chemical
initiation
tr-0.5
Normal, ca. 10 -8 M
l)ecays rapidly to zero
workers (122, 27) have recorded t he usual square root dependence on
i ni t i at or, at least at t he ver y begi nni ng, an i ni t i at or exponent of about
0.8 is observed in t he const ant rat e period. This t ype of dependence
holds regardless of whet her t he i ni t i at i on is by azo compounds, peroxides,
sensi t i zed ul t ravi ol et light or i oni zi ng radi at i on. Wi t h high i nt ensi t y
X-rays t he exponent appears to drop somewhat (31, 39), al t hough ac-
curat e dosi met r y is more difficult i n this range.
Ori gi nal l y it was t hought t hat t he capt ur e of radicals by acrylo-
ni t ri l e is so rapi d t hat t he cat al yst efficiency is near uni t y (3). I n view of
more recent results i n homogeneous sol ut i on, it is perhaps more reasonabl e
to assume t hat t he efficiency is l i kel y to be i n t he range 0.5 to 0.7 (32).
I n or di nar y vi nyl pol ymeri zat i ons, mol ecul ar wei ght vari es i nversel y
wi t h t he square root of t he i ni t i at or concent rat i on. I n t he case of acryl o-
ni t ri l e at 40 ~ i nt ri nsi c vi scosi t y vari es as I -~ whi ch implies t hat mole-
cul ar wei ght varies as i -0. a (126).
412 w.M. THOMAS :
If the source of free radicals is removed, as can be done conveniently
with UV initiation or with ionizing radiation, polymer continues to form
although at a greatly reduced rate. This post-effect is substantial and
may persist for some time. According to MAGAT ( 9 3 ) the rate may not
decay to 1~ of its initial value in 100 days. In one experiment con-
version was 7~ at the end of irradiation and had increased to 11~ at
the end of the post-reaction ( 9 3 ) . The magnitude of the post-effect depends
on the extent of the previous photo-reaction and also on the physical
state of the polymer (7, 2 9 ) . It will be recalled t hat in ordinary homo-
geneous polymerization the post-effect does not depend on the length
of the prior illumination except for very short exposures. For relatively
long post-effect times the post-conversion is a logarithmic function of
time, but the exact functional dependence is a mat t er of some uncer-
t ai nt y ( 2 9 ) . BENSASSON and BERNAS compared polymer before and after
post-polymerization and found t hat the latter was less readily soluble,
gave a lower intrinsic viscosity and a higher HUGGIt;S constant ( 2 9 ) .
They suggested t hat post-polymerization may involve branching. BAWN,
HOBIN and MCGARRY ( 2 4 ) have irradiated monomer at 60 ~ and have
observed the post effect at t hat temperature. They showed t hat the
radical concentration is of the order of 10 -5 molar and t hat radicals may
be kept without loss for a week at - - 80 ~ Assuming t hat k 4 did not vary
(a procedure criticized in the ensuing discussion) t hey estimated k 2 as
about 0.3 1 m- i s -1 and ka as 24 to 51 1 m- i s -I. These are extra-
ordinarily low values.
An interesting consequence of the properties of acrylonitrile is t hat
it enabled BAMFORD and JENI, INS (9) to observe for the first time a
thermal after-effect. A catalyzed polymerization was carried to about
4% conversion at 60 ~ , chilled to - - 80 ~ and then continued at 25 ~ . The
25 ~ rate was about twice the usual 25 ~ rate, indicating t hat the higher
radical concentration at 60 ~ had been preserved at least in part.
The temperature dependence of bulk polymerization shows some
unusual features. BAMFORD and JE~KINS measured initial rates and
obtained an activation energy of about 28 kcal per mole (7). THOMAS
and PELLON found 35 to 37 kcal for the constant rate period up to about
50% conversion ( 1 2 6 ) . These authors used azo and peroxy initiators in
the range 30 to 60 ~ More recently BENSASSON and BERNAS ( 2 9 ) initiated
polymerization with gamma rays and obtained about 5 kcal between 0 ~
and 20 ~ and about 15 kcal between 20 ~ and 50 ~ One expects a drop of
about 15 kcal in going from azo or peroxy initiators to initiation by
radiation, since splitting an initiator molecule is avoided. Normal values
for other monomers in radiation work are 4 to 7 kcal. If irradiation is
at 20 ~ and the post-effect is measured at 40 ~ to 60 ~ , the activation energy
with respect to initial rates is very high (35 kcal). These figures cannot
Mechani sm of Aerylonitrile Pol ymeri zat i on 413
be rat i onal i zed compl et el y because t he val ues for t he i ndi vi dual st eps
can onl y be guessed. I t appears pr obabl e t hat separat i on of solid pol ymer
reduces bot h pr opagat i on and t er mi nat i on rat es al t hough not t o t he same
rel at i ve ext ent s. At t emper at ur es near 60 ~ t her e is a gr eat er effect on
t er mi nat i on t han on pr opagat i on resul t i ng in a maxi mum in mol ecul ar
weight.
Recent work wi t h ionizing r adi at i on suggests t ha t t he pol ymer i zat i on
mechani sm at low t emper at ur es ma y well be anionic ( 9 5 ) r at her t han
free radical. CHEN, COLTHUP, DEICHERT and WEBB ( 4 0 ) have shown t ha t
pol ymer made wi t h X- r ays at - - 78. 5 ~ exhi bi t s an i nf r ar ed band at
2030 cm -1 charact eri st i c of ket ene imines ( ~ C=C=N- ) . The mechani sm
by whi ch t hi s st r uct ur e forms is not cl ear but i t does not seem t o be
i nt r oduced by act i on of r adi at i on on t he finished pol ymer . Accordi ng t o
GRASSIE and McNEILL (64) ket ene imines are f or med in pol ymet hacr yl o-
ni t fi l e by react i on of t he growi ng radi cal in t he f o r m- - CH~ - C= C= N.
i
CH~
BENSASSON ( 3 0 ) has pol ymeri zed acryl oni t ri l e even in t he solid st at e a t
- - 1 9 6 ~ and finds t ha t i t pol ymeri zes mor e r api dl y at - - 196 ~ t han in t he
liquid at - - 78 ~ Ver y r ecent l y SOBUE and TABATA (121) have i nvest i gat ed
pol ymeri zat i on i nduced in bul k by i oni zi ng r adi at i on over t he range q- 15
t o - 196 ~ The y suggest t hat bot h ionic and radi cal pol ymer i zat i on ma y
occur.
Anot her unusual t emper at ur e effect is obser ved in compari ng t he
i nt ri nsi c vi scosi t y of pol ymer pr epar ed wi t h chemi cal i ni t i at ors at a
series of t emper at ur es f r om 25 ~ t o 100 ~ ( 7 , 7 2 6 ) . A di st i nct maxi mum
appears at a t e mpe r a t ur e of pr epar at i on
in t he 50 ~ t o 60 ~ range, whereas one expect s
a monot oni c decline wi t h t emper at ur e.
Typi cal figures are t he following (126) (see
t abl e 3). Ot her t emper at ur e effects are
ment i oned in t he discussion of t he fast
react i on af t er effect.
Not much is known about mol ecul ar
wei ght di st ri but i on in bul k pol ymers. An
intrinsic vi scosi t y of 10 deciliters per gr am
corresponds t o a wei ght average mol ecul ar
Tabl e 3. I nt r i ns i a Vi scosi t y vs.
"Temperat ure Bu l k Pol ymeri za-
t i on wi t h 0. 008 Mol ar Benz oyl
Peroxi de
Polym. Temp.
*C
30
40
50
60
IntrinsiG Visc~ity
in DMF at 25 ~
11.8
12.7
13.1
11.0
wei ght of perhaps a million, al t hough rel at i onshi ps in t hi s range are
not well established. I t is general l y assumed t ha t mol ecul ar wei ght
di st ri but i on is qui t e br oad and t ha t in some cases t her e ma y be microgel.
Al t hough br anchi ng is not a f r equent react i on, i t ma y be f avor ed some-
what by het erogeneous conditions. Br anchi ng is mor e pr obabl e at hi gh
t emper at ur es and t he most br anches will be found in t he l argest molecules.
414 w. M. THOMAS:
Under a gi ven set of condi t i ons i nt ri nsi c vi scosi t y changes onl y moder -
at el y wi t h conversi on, at l east in t he S t o 55% range. Some dat a of
THOMAS and PELLON ( 1 2 6 ) i l l ust r at e t hi s poi nt (Tabl e 4).
Some a t t e mpt s ha ve been made t o es t i mat e i ndi vi dual vel oci t y
coefficients, mos t r ecent l y b y BENGOUGH ( 2 7 ) . I n vi ew of t he com-
pl exi t i es one mus t r egar d t he resul t s as t ent at i ve. I f t he physi cal st at e
of t he s ys t em does i ndeed al t er vel oci t y coefficients drast i cal l y, t her e is
no single val ue but r at her a whol e s pect r um r el at ed t o t he par t i cul ar
envi r onment of each growi ng chai n. One mi ght expect t ha t condi t i ons
in t he ve r y earl i est st ages of r eact i on woul d appr oxi mat e t hose in homo-
geneous sol ut i on. I f anyt hi ng, t he val ues for bul k pr opagat i on and t er -
mi nat i on are l ower t ha n in homogeneous sol ut i on (DMF) and ve r y much
l ower t han i n wat er . The r at i os k~/(2 k4)1/~
Table 4. I n t r i n s i c Viscosity vs. are consi der abl y less affected, however.
Conversion These ki net i c resul t s have led t o a
% Conversion IntrlnsicViscosity va r i e t y of i nt er pr et at i ons. 1VIAGAT and
associ at es have pr oposed ki net i c schemes
3.4 10.0 based on t he i dea t ha t a s t eady s t at e does
9.4 11.2
14.4 11.1 not exi st and t ha t onl y smal l (pri mary)
27.4 12.0 radi cal s can t er mi nat e pol ymer chai ns ( 5 2 ,
35.0 11.8 93). BAMFORD and JENKINS have criticized
39.6 I 1.8
54.4 12.4 t hi s concept of emul si on- t ype pol ymer i -
zat i on ( 1 1 ) . The y poi nt out t ha t if t he
source of i ni t i at i on were r emoved no mor e smal l radi cal s woul d be
f or med and pol~Tnerization shoul d cont i nue i ndefi ni t el y. The y ci t e a
phot osensi t i zed r eact i on at 60 ~ in whi ch t he l i ght was shut off at about
15% conversi on, wher eupon t he r at e fell t o one-hal f of i t s ori gi nal val ue
in 60 seconds. BAMFORD and JENKINS poi nt also t o evi dence f r om t he
f ast r eact i on t ha t argues agai nst emphasi s on t er mi nat i on bet ween
pol ymer radi cal s and smal l radicals.
THOMAS and PELI, ON ( 1 2 6 ) , ext endi ng a ki net i c scheme of BERNSTEIN
and coworkers ( 3 1 ) , expl ai ned t hei r resul t s on t he basi s of t wo di st i nct
t er mi nat i on st eps. One of t hese was consi dered t o be nor mal bi mol ecul ar
t er mi nat i on, and t he ot her was r egar ded as a uni mol ecul ar process in
whi ch t he growi ng chai n becomes bur i ed and is shi el ded f r om f ur t her
gr owt h. As pol ymer i zat i on progresses monome r is depl et ed mor e r api dl y
t ha n cat al ys t is decomposed, and t he l i qui d phase is enri ched in cat al yst .
A ki net i c scheme post ul at i ng a s t eady s t at e and encompassi ng t hese
consi derat i ons l ed t o sat i sf act or y agr eement wi t h t he dat a, at l east
wi t hi n t he r ange of t hei r exper i ment s [al t hough not necessari l y under
all condi t i ons of l at er wor ker s ( 1 1 5 ) ] .
BAMFORD and JENKINS ( 7 , 8 , 9 , 1 0 , 11) t ook except i on t o t hi s t r eat -
me nt as bei ng an undue si mpl i fi cat i on. They poi nt ed out t ha t bot h t he
Mechanism of Acrylonitrile Polymerization 415
pr opagat i on and t er mi nat i on coefficients are r educed by occlusion and
t hat t he ext ent of r educt i on is dependent on t he physi cal st at e of t he
syst em, compl et e buri al bei ng r el at i vel y rare. Evi dence pr esent ed below
confirms t he vi ew t he syst em is i ndeed compl ex, al t hough i t ma y be
emphasi zed t hat vel oci t y coefficients are not necessari l y const ant pro-
pert i es of a monomer even in syst ems t ha t appear homogeneous on a
macroscopi c scale.
Unt i l vel oci t y coefficients and radi cal concent r at i ons are known wi t h
gr eat er cer t ai nt y one cannot be sure how closely t he t r ue st at e of affairs
is appr oxi mat ed by an algebraic t r eat ment . Fur t her effort t o describe
t hese het erogeneous syst ems by formal ki net i cs does not appear war-
r ant ed at present . Progress is more l i kel y t o resul t f r om det ai l ed i nvest i -
gat i ons i nt o t he physi cal st at e of t hese syst ems. I t seems qui t e possible
t hat pol ymer i zat i on is occurri ng si mul t aneousl y on t he part i cl es and, be-
cause of slow preci pi t at i on, in t he liquid phase as well. Thi s woul d correspond
t o t he si t uat i on descri bed in a l at er section for aqueous pol ymeri zat i on.
Recent microscopical st udi es by THOMAS, THOMAS and DEICHERT
( 1 3 0 ) l end suppor t t o view t hat t hese syst ems share some feat ures of
emulsion pol ymeri zat i on. Duri ng t he ear l y stages of pol ymer i zat i on t he
part i cl es grow as r at her uni form aggregat es (Fig. 1). The number of
t hese part i cl es is fai rl y const ant and is in t he range of 1011 t o 10 TM per cc.
Thi s is approachi ng t he number f ound in t ypi cal emulsion systems.
The concent r at i on of t r apped radicals and t he degree of occlusion
(how deepl y t hey are buried) have been st udi ed ext ensi vel y by BAMFORD
and JENKINS (9). They det er mi ned t he appr oxi mat e radi cal concent r at i on
by swelling or dissolving pol ymer in solutions of di phenyl pi cr yl hydr azyl
( DPPH) , a vi ol et subst ance t ha t becomes colorless on react i on wi t h
radicals. Ni t robenzene was general l y used as t he medi um t o dissolve t he
hydr azyl and t o swell t he pol ymer ; fl-propiolactone, a sol vent for t he
pol ymer, was used also.
The concent r at i on of t r apped radicals in a t ypi cal exper i ment was
est i mat ed as about 3 10 -5 mol/1 of react i on mi xt ur e, or about 2 10 ~6
radicals/ml. Thi s concent r at i on i ncreased wi t h t he r at e of phot opol y-
meri zat i on, but t he number of radicals t ha t became t r apped was a con-
st ant fract i on of t he t ot al number generat ed. I n t hese exper i ment s t ha t
fract i on was est i mat ed at about 1% at 25 ~
More recent l y, el ect ron par amagnet i c resonance has been used in
place of DP P H t o est i mat e radi cal concent r at i ons ( 1 0 , 8 0 ) . Considering
t he uncer t ai nt i es at t endant on t he use of DP P H t he agr eement is rea-
sonabl y good. Under condi t i ons where BAMFORD and JENKINS using DP P H
f ound 5 x 1018 radicals per ml, INGRAM, SYMONS and TOWNSEND r epor t ed
3.5 0.05 x 10 ~7 wi t h e.p.r. ( 8 0 ) . The l at t er aut hor s poi nt out t hat pol y-
acryl oni t ri l e is far more efficient in occluding radicals t han are any of
416 W.M. THOMAS:
the other compounds studied. The e.p.r, spectrum of polyacrylonitrile
shows very little structure. Unfortunately, conclusions regarding poly-
merization mechanism are subject not only to the accuracy of e.p.r.
measurements but also to estimates of catalyst efficiency and number
average molecular weight.
If polymerization is carried to say 20% conversion at 25 ~ and the
reaction mixture is transferred to a 60 ~ bath, there is a sudden fast
reaction followed by the normal 60 ~ rate (7, 9). The fast reaction is
attributed to radicals t rapped at 25 ~ and liberated at 60 ~ . Successive
fast reactions can be observed by preparing polymer at 25, 60, and 70 ~ .
No further reaction occurs at 70 ~ . From this fact, from the much greater
rate at 60 ~ t han at 40 ~ and from the fact t hat maxi mum molecular weight
polymer is made at 50 to 60 ~ it is concluded t hat polymer undergoes
marked changes in the range 40 to 60 ~ .
Table S. T r a p p e d R a d i c a l s i n Polymer heated in alcohol at 60 ~ contracts
]~olyacrylonitrile very slightly (7), but dat a are lacking on
Polymer Relative Radical changes in the polymer in the 20 ~ to 60 ~
Made at Concentration range and on quantitative aspects of swel-
ling by monomer. The glass transition tern-
20 ~ 8
40 ~ 5 perature measured by differential thermal
60 ~ 2 analysis (85) is about 80 ~ t hough other
techniques suggest higher temperatures
( 9 1 , 7 3 ) . The radical concentration was only slightly diminished by heat-
ing at 40 ~ , but the degree of occlusion was probably increased. As the
temperature and consequently the rate of photopolymerization were
increased (15.8 to 44.0 ~ ) the rate of the fast reaction at 60 ~ decreased,
and it was concluded t hat the fraction of radicals trapped had de-
creased also. Experiments with e.p.r, suggest a smaller decrease as shown
in Table 5 ( 8 7 ) .
When polymer was heated in the absence of monomer to 60 ~ no
decrease in radical concentration was observed over a long period of time.
If oxygen is admitted to the e.p.r, tube at room temperature the resonance
decays within 10 rain to less t han one-fifth of its value, but at - - 50 ~ no
change is observed in 24 hours.
If a swelling agent is added to the reaction mixture, a maxi mum rate
is usually noted for some fairly low agent-to-monomer ratio. DMF, which
is merely a swelling agent when mixed with monomer, gives a maxi mum
rate at 10 mol-% in photoinitiated polymerization, at about 25 mol-%
in polymerization catalyzed by benzoyl peroxide (9), and at about
30 mol-% with gamma rays ( 1 1 4 ) , all near room temperature. On the
other hand, as little as 10 mol-% of DMF reduces the rate at 60 ~ by a
factor of about 15. I t decreases also the ratio of the fast reaction at 60 ~
to the 25 ~ rate.
Mechanism of Acrylonitrile Polymerization 417
Assuming t hat DMF is funct i oni ng chi efl y as a swelling agent, r at her
t han as a t r ansf er agent and ret arder, BAMFORD and JENKINS (9) i nt er pr et
t hese resul t s in t er ms of t he degree of occlusion and its effect on t he
pr opagat i on and t er mi nat i on coefficients. Wi t h a small amount of swell-
ing t he effective pr opagat i on const ant is increased. The number of
radicals t r apped ma y be somewhat di mi ni shed but t hose t r apped are
t hought to be bur i ed in a deeper mass of pol ymer. Mild swelling is t hus
compar abl e t o heat i ng at 40 ~ , and such syst ems give t he l argest fast
react i ons on heat i ng t o 60 ~ Beyond a degree of swelling t he t er mi nat i on
r at e is gr eat l y enhanced (especially at hi gher t emper at ur es) and t he
number of t r apped radicals is ve r y small. Reduct i on in t he number of
bur i ed radicals f ar mor e t han compensat es for i ncreased degree of
occlusion. Thus t he effect of occlusion is t o decrease t he t er mi nat i on
coefficient and, t o a lesser ext ent , t he pr opagat i on coefficient. Ei t her no
occlusion or compl et e occlusion will pr event t he fast react i on, of course.
When pol ymer is war med wi t h DMF in t he absence of monomer , par t i al
solution t akes place and t he e.p.r, spect r um vanishes.
Copol ymeri zat i on wi t h small amount s of met hyl acr yl at e produces
resul t s even mor e dr amat i c t han t hose wi t h DMF. As little as 0.03 mol - %
is able t o change t he propert i es of aggregat es enough t o faci l i t at e t er-
mi nat i on (9).
Not much is known about t he det ai l ed mechani sm of occlusion. The
process can be r egar ded as one of local monomer depl et i on in t he vi ci ni t y
of a growi ng chain. Coalescence of part i cl es ma y be a mor e i mpor t ant
f act or t han is t he coiling of chains. Vari ous pi ct ures mi ght be drawn, but
necessary i nf or mat i on on physi cal charact eri st i cs of t he pol ymer is still
lacking. For exampl e, HAM ( 6 8 ) t hi nks i t pr obabl e t ha t in t he ear l y
stages of pol ymer i zat i on monomer adds t o t he growi ng chai n in a syn-
di ot act i c manner. He proposes t hat at t he end of t he " i nduct i on" peri od
t he pol ymer crystallizes and subsequent l y a mor e r api d helical, st ereo-
specific pol ymeri zat i o n occurs on t he particles. The monomer is r egar ded
as havi ng sufficient sol vat i ng power t o pr ovi de t he necessary chai n
mobi l i t y. Unt i l more dat a are avai l abl e t he si t uat i on will r emai n specu-
l at i ve. I nf or mat i on is needed about t he f or mat i on of nuclei, pol ymer
separat i on, coalescence of particles, pol ymer i zat i on loci, radi cal occlusion,
swelling of part i cl es and local monomer depletion.
4, He t e r o g e n e o u s F r e e Ra d i c a l P o l y me r i z a t i o n i n t h e P r e s e n c e of
Organic Diluents and Additives
The general feat ures of bul k pol ymer i zat i on are r et ai ned in syst ems
t o whi ch non-sol vent s have been added. Microscopical st udi es (130)
demonst r at e t ha t t he st r uct ur e of t he part i cl es can be var i ed from ver y
418 W.M. THOMAS:
dense to ver y loose by pr oper choice of diluent. Fig. 2 shows t hat pol ymer
made in benzene is mor e densel y packed t han t ha t made in undi l ut ed
monomer (Fig. 1). On t he ot her hand Fig. 2 shows t hat pol ymer made
in benzene- DMF mi xt ur es ma y be ver y loosely packed. When t he
monomer is di l ut ed t o 20% b y wei ght in acet one t he numbe r of part i cl es
f or med is l arger t han in bul k and t hese part i cl es are less densel y ag-
gregat ed.
Overal l r at es of pol ymer i zat i on are gener al l y r at her i nsensi t i ve to t he
presence of di l uent . DAS, CHATTERJEE and PALIT ( 5 0 ) compar ed r at es
at 50 mol e per cent concent r at i on in a va r i e t y of liquids. I n t he r ange
of t hei r exper i ment s, pol ymer i zat i on r at e was near l y i ndependent of t he
choice of di l uent . BAMFORD, JENKINS and WHITE ( 2 2 ) poi nt out t ha t
t r ansf er agent s reduce t he mean degree of occlusion. Since t he t er mi na-
t i on r at e is i ncreased under t hese condi t i ons, t he overal l pol ymer i zat i on
r at e is reduced. The ext ent of pol ymer swelling will va r y f r om one l i qui d
to anot her ( 3 2 , 7 3 0 ) , and t hi s obscures t he i nt er pr et at i on t o be made
f r om l i mi t ed dat a.
Gener al l y t her e is a peri od of accel erat i on up to a few per cent con-
versi on, and t hi s is oft en followed b y a const ant r at e peri od ext endi ng
to fai rl y hi gh conversi on. Ki net i c dat a are consi der abl y less ext ensi ve
in t hese syst ems t han in bul k, and i nt er pr et at i ons are open t o t he
cri t i ci sms t ha t were ci t ed for bul k work. The anal ogy t o emul si on pol y-
mer i zat i on seems qui t e reasonabl e in syst ems cont ai ni ng organi c di l uent s.
Concur r ent pol ymer i zat i on in bot h t he l i qui d medi um and t he part i cl es
is a possi bi l i t y. Monomer adsor pt i on b y pol ymer and ext ent of aggrega-
t i on and swelling mus t be i mpor t a nt fact ors.
St udi es in benzene were r epor t ed b y IMOTO and TAKATSUGI ( 7 7 ) .
Wi t h AI BN at 50 ~ t hey found an i ni t i al accel erat i on followed b y a con-
s t ant r at e peri od ext endi ng t o 20% conversi on or more. Rat e in t he
monomer range bel ow one mol ar var i ed as about [M} 1.~ and in t he hi gher
r ange as about [71//] 3.~ A si mi l ar si t uat i on pr evai l ed in respect t o
i ni t i at or, t he exponent bei ng 0.6 at low AI BN levels and 1.0 at hi gher
concent rat i ons. I f DMF was pr esent also, t he l ower figure was 0.8. An
al gebrai c t r e a t me nt empl oyi ng spont aneous t er mi nat i on (uni mol ecul ar
burial) and t he s t eady s t at e assumpt i ons led t o a r at e expressi on mor e
near l y in accor d wi t h t hei r dat a t han is t he si mi l ar l y der i ved expressi on
of reference (126).
Exper i ment s in t ol uene are i ncl uded in t he paper of SRINIVASAN and
SANTAPPA ( 1 2 2 ) . The y wor ked wi t h AI BN, chi efl y at 50 ~ and at 60 ~ The
i ni t i at or exponent s were 0.62 (50 ~ ) and 0.64 (60 ~ ) and t he monomer
exponent was about t wo. The aut hor s concl uded t ha t bot h t he i ni t i at i on
st ep and t he t er mi nat i on- s t ep are compl ex in t hese pr eci pi t at i ng syst ems.
The y es t i mat ed t hat cat al ys t efficiency in t ol uene is onl y about 56% at
Me c ha ni s m of Ac r yl oni t r i l e Pol yme r i z a t i on 419
Fig. 2a- - c. Polyacrylonitrile (127) Benzene-Dimethylformamide Media: 60 ~ C; AI BN 3 10 3, mononmr 20%
by volume, a) 100% Benzene; b) 3: 1 Benzene : Ditnethylformanfide; c) 1: 1 Benzene. Dinlethylforinamide
Fortschr. Hochpolym.-Forsch., Bd. 2 28
420 w. M. THOMAS:
50 ~ and about 22% at 60 ~ Val ues of k 2 / ( 2 k 4 ) 1/2 a r e recorded al ong wi t h
t he correspondi ng act i vat i on energies, and t hese quant i t i es are compar ed
for pol ymer i zat i on in bul k, in DMF and in t ol uene. The hi gher r at i o of
k~/(2 k4) 1/2 in t ol uene as compar ed wi t h DMF ma y mean a decrease in
t er mi nat i on (k4) in t ol uene. Since da t a in t ol uene are r est r i ct ed t o 50 ~
and 60 ~ not hi ng can be sai d about t he ma x i mu m in k4/(2 ka) 1/2 t ha t t hese
aut hor s r ecor ded for bul k pol ymer i zat i on or t ha t ot hers (7, 126) not ed
1
for mol ecul ar weight' . Act i vat i on energies for E ~ - - ~ - E 4 were 8.0, 7.6
and 4.9 kcal / mol e for pol ymer i zat i on in bul k, in DMF and in t ol uene,
respect i vel y.
NAKATSUKA and coworkers (104) meas ur ed pol ymer i zat i on r at es in
t ol uene wi t h benzoyl per oxi de at 30 ~ and at 68 ~ Exponent s in t hei r r at e
expressi on were :
Per oxi de 0.85 at 30 ~ 1.0 at 68 ~
Monomer 1.1 at 30 ~ 2.0 at 68 ~
A cat al ys t - monomer compl ex and spont aneous t er mi nat i on were post u-
l at ed.
More compl ex cat al ys t s have not been st udi ed in detail. An except i on
is t he wor k of IMOTO and TAKEMOTO ( 7 5 ) who i nvest i gat ed pol ymer i zat i on
r at es in benzene usi ng a series of s ubs t i t ut ed benzoyl peroxi des al ong
and wi t h di met hyl ani l i ne. The y f ound a r ough l i near r el at i onshi p bet ween
log ( R / R E ) and o, where R and R~I are r at es wi t h t he s ubs t i t ut ed and
uns ubs t i t ut ed per oxi de and a is t he HAMMETT const ant . The overal l r at e
depended on t he monome r t o t he first power and peroxi de and ami ne
each t o t he one-hal f power. The y concl uded t ent at i vel y t hat t he benzoyl -
oxy r adi cal is t he i ni t i at i ng species.
Syst ems cont ai ni ng monome r and DMF but no ot her di l uent were
di scussed in t he previ ous section, and i t was not ed t ha t a ma x i mu m r at e
is associ at ed wi t h i nt er medi at e monomer - DMF composi t i ons. IMOTO (79)
obser ved a si mi l ar effect wi t h monomer - benzene- DMF mi xt ur es. A shal-
l ow mi ni mum in pol ymer i zat i on r at e was found at a low benzene l evel
and t hen a ve r y pr onounced ma x i mu m at a hi gher benzene cont ent .
Mol ecul ar wei ght i ncr eased monot oni cal l y, however, wi t h t he benzene/
DMF rat i o. I n t hese t e r na r y s ys t ems t he a mount of DMF was not
enough t o keep t he pol ymer in sol ut i on but consi derabl e swelling mus t
have occurred. THOMAS, THOMAS and DEICHERT ( 130) show el ect ron
phot omi cr ogr aphs of pol ymer made under t hese condi t i ons.
NAKATSUKA (104) meas ur ed r at es and mol ecul ar wei ght s in mi xt ur es
of DMF and t ol uene at 30 ~ t o 50 ~ Benzoyl per oxi de was t he i ni t i at or .
Mol ecul ar wei ght dr opped as t he t emper at ur e was rai sed and as t he DMF
cont ent i ncreased. Mol ecul ar wei ght di st ri but i on, for whi ch t he aut hor
Mechanism of Acrylonitrile Polymerization 421
relied on a met hanol pr eci pi t at i on met hod, was sur pr i si ngl y narrow.
Pol ymer i zat i on r at e at 30 ~ was pr opor t i onal t o t he per oxi de concent r a-
t i on and t o t he squar e of t he monome r concent r at i on, j ust as had been
f ound for t ol uene alone. A s ubs t ant i al aft er-effect was obser ved in
t ol uene- DMF when acri fl avi ne was used as a phot osensi t i zer, and i t was
concl uded t ha t t he radi cal l i fet i me near 20 ~ is of t he or der of 10 mi n.
To expl ai n t hese resul t s NAKATSUKA pr oposed t ha t occlusion is i mpor t ant
near 30 ~ , t he r at e bei ng cont rol l ed b y t he st age before occlusion and t he
mol ecul ar wei ght b y t he st age af t er occlusion. At hi gher t emper at ur es
occlusion was r egar ded as uni mpor t ant , but nni mol ecul ar t er mi nat i on
was i nvoked in t he ki net i c scheme.
Usi ng t he same t ol uene- benzoyl per oxi de s ys t em NAKATSUKA ( 1 0 5 )
meas ur ed pol ymer i zat i on r at e and mol ecul ar wei ght as funct i ons of
t emper at ur e (40 ~ and 58 ~ ) and of t he concent r at i on of t hr ee r et ar der s:
p-ni t rophenol , 2, 4-di ni t rophenol and pi cfi c acid. Resul t s were consi st ent
wi t h a ki net i c scheme post ul at i ng ( among ot her things) bi mol ecul ar
i ni t i at i on i nvol vi ng per oxi de and monomer and spont aneous uni mol e-
cul ar t er mi nat i on of growi ng pol yme r chains.
OKAML'RA, t{ATAGIRI a nd TAKEMOTO ( 7 0 7 ) added surface act i ve
agent s t o monomer cont ai ni ng benzoyl peroxi de. Al t hough t he da t a do
not per mi t st r i ct compar i sons, i t appear s t ha t bot h pol ymer i zat i on r at e
and mol ecul ar wei ght were r educed b y t hese agent s. Var i at i ons were
not ed wi t hi n each class of agent I non-ionic, cat i oni c and anionic. When
a pol ygl ycol l aur at e was pr esent , t he dependence of r at e on per oxi de
concent r at i on dr opped f r om 0.7 t o appr oach 0.5. The aut hor s fel t t ha t
surface act i ve agent s pr event adhesi on and gr owt h of pol ymer par t i cl es
and also pr event radi cal occlusion.
The r adi ot r acer me t hod for est i mat i ng efficienc~z of i ni t i at i on was
appl i ed b y BEVINGTON and EAVES ( 3 2 ) t o pol ymer i zat i on in benzene
and in car bon t et rachl ori de. Wher eas t hey had cal cul at ed t ha t about
47% of t he radi cal s f r om AI BN i ni t i at e pol ymer chai ns in DMF sol vent ,
efficiency in benzene was about 50% and in car bon t et r achl or i de about
30%. Thi s low efficiency in car bon t et r achl 0r i de is at t r i but ed t o a t t a c k
of radi cal s f r om AI BN on t he car bon t et r achl or i de sol vent , especi al l y
at hi gh concent r at i ons of sol vent . Chai ns i ni t i at ed b y s econdar y radi cal s
der i ved in t hi s wa y f r om t he sol vent woul d not be det ect ed b y t he t r acer
met hod.
The mos t ext ensi ve chai n t r ansf er st udi es are t hose if DAs, CHAT-
TERJEE and PALIT ( 5 0 ) , who st udi ed near l y t hi r t y liquids. These i ncl uded
ar omat i c and al i phat i c hydr ocar bons, alcohols, ket ones and hal ogenat ed
compounds. The monomer i t sel f has a l ow t r ansf er const ant (C = 2.6 x 10 -s
at 60~ Most ot her liquids are in t he r ange f r om 1 x 10 -4 t o 1 x 10 -3 but
s - but yl alcohol has a t r ansf er const ant of 9.7 10 -3. Eas e of t r ansf er t o
Fortschr. Hochpolym.-Forsch., Bd. 2 28*
422 W.M. THOMAS:
amines was ment i oned in a previ ous section, and IMOTO (76) gives 1.04
for N, N-di met hyl ani l i ne. The absol ut e val ue of all t hese number s must
be accept ed wi t h some r eser vat i on because t he basic equat i ons rel at i ng
intrinsic vi scosi t y t o number average mol ecul ar wei ght have undergone
revision. Het er ogenei t y of t he pol ymer i zat i on medi a ma y cause uncer-
t ai nt i es also. I t is clear t hat t he rel at i ve val ues do not parallel those for
ot her monomers (e. g. st yrene). BAMFORD, JENKINS and JOHNSTON (ld)
show t hat this difference is rel at ed t o t he powerful el ect ron accept i ng
char act er of t he pol yacryl oni t ri l e radical.
Tel omers have been pr epar ed by pol ymeri zi ng acryl oni t ri l e in t he
presence of agent s like CC14. F o x and FIELD (58) have revi ewed this
whole subj ect recent l y.
5. Polymerization in Aqueous Suspension
Aqueous syst ems have been st udi ed by a ver y large number of
i nvest i gat ors. Economy, safet y, conveni ence and qual i t y of pr oduct have
combi ned t o make this t he met hod of choice for commerci al pr oduct i on
of copol ymers. The i ndust ri al i mpor t ance of such end pr oduct s as
el ast omers and acryl i c fibers has been a special i ncent i ve to r el at ed
f undament al studies. Fur t her mor e, t he rel at i vel y high sol ubi l i t y of
acryl oni t ri l e monomer in wat er coupl ed wi t h i nsol ubi l i t y of t he pol ymer
make it a conveni ent t est monomer for st udi es of i ni t i at i on by r edox
syst ems (6, 2 5 , 102). Large number s of homogeneous chemi cal i ni t i at ors
and some het erogeneous i ni t i at ors have been st udi ed as well as i ni t i at i on
by phot ochemi cal means, by ul t rasoni cs and by ionizing radi at i on. I t will
not be possible here t o revi ew t he enormous world l i t erat ure. Several.
publ i cat i ons (1, 9 2 , 117) refer in some det ai l t o t he ol der papers, and we
shall rest ri ct our comment s t o recent i nt er pr et at i ons t hat have recei ved
suppor t from several quart ers.
I f radicals are pr oduced in an aqueous solution of acryl oni t ri l e t here
ma y be a short i nduct i on peri od duri ng which ai r or i mpuri t i es are
bei ng consumed. SMELTZ and DYER (120) have shown t hat pol ymeri c
peroxi des are formed but t hat none of t he or di nar y high pol ymer is
pr oduced duri ng this period. Onset of pol ymer i zat i on is evi dent from t he
devel opment of a haze, followed r api dl y by t he preci pi t at i on of whi t e
pol ymer. The sl ur r y increases in thickness, and by t he t i me pol ymeri za-
tion is compl et e it ma y be qui t e stiff, looking much like cot t age cheese.
The pol ymer general l y filters readi l y but holds about four t i mes its weight
of wat er in t he filter cake. Thi s sequence of event s is t ypi cal , but at low
el ect rol yt e concent r at i on and at slow rat es of st i rri ng t here ma y be
formed a r el at i vel y stable suspension t hat passes t hr ough or di nar y filter
paper.
Me c ha ni s m of Ac r yl oni t r i l e Pol yme r i z a t i on 423
Furt her knowledge of the events taking place is gained by micro-
scopical study. Rapid motion of individual particles makes it difficult
to observe the changes directly, but samples may be withdrawn periodi-
cally for examination by the usual techniques of light and electron
microscopy. Fig. 3 and 4 show some of the stages in typical experiments.
Fig. 3. Polyaerylonitrile prepared in aqueous emulsion. Electron micrograph, negat i ve print, shadowed with
urani um at a 30 ~ angle. M. C. BOTTV and F. G. ROWE, American Cyanamid Company
More quant i t at i ve microscopical studies are reported by THOMAS,
GLEASON and MINO (128) and by NAGAO and UCHIDA (103). During the
early stages of polymerization, particles separate as dense, slightly
flattened spheroids occasionally joined by filaments or by partial fusion.
The particles are often surprisingly uniform in size. They are known to
have a high surface area, but details of their structure have not been
disclosed. By the time the first observations have been made (about 1~)0
conversion) the particles may have reached a diameter of 200 to 500.4.
From this point t hey grow until at high conversion the average diameter
may be 1500 to 2500 A. Few new particles, if any, are formed during
28a
424 \V. M. THOMAS:
this growth period, and in many experiments there is relatively little
agglomeration. Particles are t hought to be stabilized by a negative
<
,4
.o
8
v
o
charge and by hydration. Thus the number of particles per unit volume
is often fairly constant during an experiment. This number nearly always
lies between about 1012 and 1014 per cc., which is in the lower end of the
Mechani sm of Acr yl oni t r i l e Pol ymer i zat i on 425
t ypi cal range for emul si on pol ymer i zat i on in general. New part i cl es
appear if a second qua nt i t y of i ni t i at or is i nj ect ed near t he s t ar t of a run.
The ext ent of aggr egat i on is i ncreased b y addi t i on of salts, or organi c
liquids, b y agi t at i on and b y i ncreased t emper at ur e. Aggregat i on is
mi ni mi zed b y addi t i on of surface act i ve agent s, and t he numbe r of
part i cl es per cc is i ncreased b y such addi t i ves. Recent exper i ment s by
YUGUCHI and WATANABE (/37) show t hat agi t at i on reduces t he pol y-
mer i zat i on r at e wi t hout affect i ng t he i nduct i on peri od or t he aver age
degree of pol ymer i zat i on. As mor e sodi um l aur yl sul fat e is added t he
effect on r at e becomes less. Under condi t i ons where t he suspensi on
aggr egat es wi t hout agi t at i on t he r at e const ant s for pol ymer i zat i on could
not be det er mi ned ( 4 9 ) .
The general r esembl ance of t hese syst ems to t ypi cal emul si on pol y-
mer i zat i on has been st ressed b y several i nvest i gat ors. Thus t he numbe r
of part i cl es per cc can be var i ed b y al t eri ng t he concent r at i on of i ni t i at or
or di spersi ng agent , but t he r at e per part i cl e is r easonabl y const ant so
l ong as aggr egat i on is avoi ded. Dependence of pol ymer i zat i on r at e on
soap concent r at i on has been est abl i shed empi r i cal l y in several cases.
PALIT and GUHA ( l l 0 ) drew f ur t her at t ent i on t o t he connect i on
bet ween pol ymer i zat i on r at e and t he colloidal nat ur e of t he pr eci pi t at i ng
pol ymer . They found t hat as t he a mount of r edox i ni t i at or i ncreased t he
pol ymer i zat i on r at e first i ncreased, t hen decreased and finally i ncreased
agai n. These regions cor r esponded t o a fine sol, a mi l ky dispersion and
a coarse pr eci pi t at e. Gener al l y t he r at e of pol ymer i zat i on r an paral l el
t o t he a mount of el ect rol yt e requi red t o pr eci pi t at e t he colloid.
Under sui t abl e condi t i ons a r easonabl y st abl e l at ex ma y be f or med (/).
Al t hough ma n y of t he fact ors r el at i ng t o pol ymer i zat i on rat e, mol ecul ar
wei ght and part i cl e size in emul si on have been st udi ed [reference ( 1 3 4 1 )
is an exampl e] t he l i t er at ur e on homopol ymer s is b y no means as
ext ensi ve as t ha t per t ai ni ng t o copol ymers. At t e mpt s t o pr epar e bead
homopol ymer s have not been ve r y successful.
As is commonl y t he case, t he deepest i nsi ght i nt o t he react i on me-
chani sms has been gai ned f r om ki net i c st udi es. All of t he usual t echni ques
have been used, but t hat of DAINTON and SEAMAN ( 4 7 ) deserves special
notice. These aut hor s devi sed a di l at omet er par t i cul ar l y sui t abl e for t he
necessar y deaer at i ng, mi xi ng, filling, st i rri ng, pol ymer i zi ng and cl eani ng
st eps. The per cent pol ymer i zat i on vs. t i me cur ves oft en show a bri ef
accel erat i on, followed b y a near l y cons t ant r at e peri od and finally a
region of reduced rat e. The const ant r at e peri od ma y ext end f r om a few-
t ent hs per cent up t o 10- - 20% or even hi gher conversi on dependi ng on
t he i ni t i at or s ys t em and ot her fact ors. Under some condi t i ons t he
accel erat i on peri od ma y be undet ect abl e (d7). I n t he case of phot o-
i ni t i at i on or i ni t i at i on b y ionizing r adi at i on t here is a pr onounced aft er-
Fortschr. Hochpolym.-Forsch., Bd. 2 281)
426 w. M. THOMAS:
effect. When i l l umi nat i on ceases t he r at e drops r api dl y at first, t hen more
slowly ( 4 8 ) . I f t he aft er-effect is obser ved at a t emper at ur e hi gher t han
t he original react i on (50 ~ vs. 25 ~ t her e is a bur st of act i vi t y followed
by a decay peri od ( 4 9 ) , similar t o t hat occurri ng in bul k pol ymer i zat i on
but much less mar ked.
The most significant ki net i c analysis is t ha t of DAINTON and coworkers
( 4 6 - - 4 9 ) . Under condi t i ons where t er mi nat i on by met al ions was not
i mpor t ant , R~ var i ed as [3/ ] ~ at l ow monomer concent r at i ons and as
[Ml at hi gh concent rat i ons. The cri t i cal monomer concent r at i on for
t r ansi t i on from one region t o anot her vari ed wi t h t he r at e of i ni t i at i on,
first decreasi ng and t hen increasing as t he r at e of i ni t i at i on increased.
Dat a in t he l i t er at ur e gi vi ng exponent s of [3/] of ei t her one and t wo
are appar ent l y reconci l ed in t hi s way.
Because of t he het erogeneous nat ur e of t he pol ymer i zat i on i t is cl ear
t ha t or di nar y homogeneous kinetics cannot appl y. Despi t e this, a me-
chani sm l eadi ng t o a s t at i onar y st at e can be devel oped ( 4 6 ) based on t he
obser vat i on ment i oned above t hat a const ant number of growing par-
ticles is f o r me d n e a r t he s t ar t ( 7 2 8 ) . The s t eady r at e of pol ymer i zat i on
is t hen t he sum of t he r at e in t he aqueous phase and t ha t of monomer
adsorbed on t he pol ymer particles. When pol ymer i zat i on is chi efl y in t he
aqueous phase (i. e., at hi gh [M]), t hen t he r at e R~ depends on [21//] [Il 1/2.
When t he part i cl es are t he pri nci pal locus (i. e., at low [M]), t hen R~ will
v a r y as [M] 2 [ I ] x , where 0.2 < X < 0.9. I f t he r at e of i ni t i at i on is ve r y
hi gh t hen R~ will depend on [M~ ~ because of pr i mar y radi cal t ermi nat i on.
Analysis of t he aft er-effect suggests t hat radicals on t he part i cl es dis-
appear slowly by mut ual i nt er act i on and have a half-life at 25 ~ of about
5 min. Radi cal s in sol ut i on have a correspondi ng half-life of about one
second. Agi t at i on faci l i t at es t he i nt er act i on of part i cl es and so diminishes
t he after-effect. At t he s t ar t of r eact i on radicals are pr oduced in solution,
where t hey grow unt i l t er mi nat ed in pairs. These unst abl e pol ymer mol e-
cules aggregat e unt i l t he y form part i cl es havi ng a size and charge such as t o
make coalescence of part i cl es unlikely. Radi cal s ma y ent er t hese particles,
however, and cause pol ymer i zat i on of monomer adsor bed on t he particles.
Uni mol ecul ar t er mi nat i on has been suggest ed by some st udi es ( 1 3 2 ) .
The general quest i on of pol ymer i zat i on on or in t he part i cl e vs. pol y-
mer i zat i on in t he t r ue aqueous phase has been discussed for a number
of years. Evi dence ot her t han t hat ci t ed above suggests t ha t bot h sites
ma y be i mpor t ant dependi ng on conditions. Pol ymer chai ns mi ght be
i ni t i at ed in t he aqueous phase and t hen grow f ur t her af t er t r ans por t t o
t he particles. Unr epor t ed work in t hi s La bor a t or y suggests t hat pol y-
mer i zat i on in t he t wo sites concur r ent l y, ma y account for some resul t s
on mol ecul ar wei ght di st ri but i on and on copol ymeri zat i on. MINO ( l O 0 )
has shown from his own exper i ment s and t hose of ot hers t ha t t he pat t i -
Me c h a n i s m of Ac r y l o n i t r i l e P o l y me r i z a t i o n 427
t i on of acryl oni t ri l e bet ween t he t wo phases mus t be t aken i nt o account
in copol ymef i zat i on wi t h st yr ene.
Pr ef er ent i al wet t i ng of pol ymer b y monomer was demons t r at ed qual i -
t at i vel y some year s ago ( 6 0 ) . Monomer adsor pt i on has been conf i r med by
MILLER ~cited in reference (128)], but quant i t at i ve i nf or mat i on on t he
ext ent of adsor pt i on is l acki ng. DAINTON makes t he r easonabl e as-
s umpt i on t ha t t he concent r at i on of monome r on t he par t i cl e is pr o-
por t i onal t o t ha t in sol ut i on.
By means of t he sect or t echni que DAINTON and EATON (49) det er -
mi ned t he absol ut e val ues for t he vel oci t y coefficients appl i cabl e t o t he
aqueous phase. Tabl e 4 lists t hei r resul t s, whi ch ma y be compar ed wi t h
t hose of Tabl e 1 for pol ymer i zat i on in DMF. I t appear s t ha t in aqueous
medi a pol yacr yl oni t r i l e radi cal s pr opa ga t e ve r y r api dl y ( compar abl e t o
pol yacr yl ami de) and t er mi nat e qui t e r api dl y. I t will be not ed t ha t t he
act i vat i on ener gy for t er mi nat i on is hi gher t ha n t h a t for pr opagat i on.
The f r equency f act or is hi gher for t er mi nat i on t han is usual l y t he case
in pol ymer i zat i on react i ons, but t he f r equency f act or for pr opagat i on is
nor mal . The l arge differences bet ween coefficients in wat er and in DMF
has not been expl ai ned adequat el y [see reference ( 4 6 ) , p. 2283. Unf or t u-
na t e l y t her e ar e no da t a for ot her homogeneous sol vent s. The wor k of
BAwN ( 2 4 ) in het er ogeneous s ys t e ms cer t ai nl y suggest s t ha t k S is hi ghl y
sensi t i ve t o t he envi r onment . On t he ot her ha nd in t hi s event one woul d
expect copol ymer composi t i ons t o be mor e sensi t i ve t o t he choice of
r eact i on me di um t ha n t hey seem t o
be (/33).
THOMAS and WEBB ( ' / 2 9 ) , usi ng
an emul si on pol ymer i zat i on model ,
cal cul at ed k S f r om R~ and t he num-
ber of part i cl es. Thei r val ue at r oom
t e mpe r a t ur e was 2 104 1 m- l l -x, in
good agr eement , per haps fort ui -
t ousl y, wi t h DMNTON and EATO,'~
Ta b l e 6. Rate Constants iv Aqueous
Polymerization (49) (Values Appli-
cable to the Aqueous Phase)
Propagation
Temp. (~ kt ( 10_l) k~{ 10 -D)
15 2. 3 2. 8
25 2. 8 3. 7
30 3.2,5 4. 4
( 4 9 ) . Thi s t r e a t me nt assumes t ha t t he monome r : wat er r at i o at t he
par t i cl e is t he s ame as in t he cont i nuous phase. I f al l owance were made
for adsor pt i on of monome r t hi s val ue of k s woul d fall t o appr oach mor e
cl osel y t he l evel obser ved in DMF.
A r r h e n i u s P a r a m e t e r s
k S = 3.7 10 7 e-4, l~176
k 4 = 3.3 10 lz e -5,4~176
Pol ymer i zat i on of acryl oni t ri l e in wat er b y means of ionizing r adi at i on
has been st udi ed b y a numbe r of peopl e over t he pas t 15 years. The
l i t er at ur e was revi ewed in 1955 b y CHAPIRO and cowor ker s ( 3 8 ) . More
4 2 8 W.M. T,,O~AS :
r ecent r epor t s ar e t hose of BENSASSON and PREVOT-BERNAS ( 2 8 ) , CHA-
PIRO and SEBBAN-DANON (39) and ARTHUR, DEMINT and PITTI~AN (4)
among ot hers. I ni t i at i on is b y H at oms and OH radi cal s deri ved f r om
t he wat er. I t was t hought ori gi nal l y t ha t t he pol ymer i zat i on ki net i cs
demons t r at ed a non- uni f or m spat i al di st r i but i on of i ni t i at i ng species (42).
The pr esent i nt er pr et at i on is t ha t r adi at i on does i ndeed yi el d pr i ma r y
radi cal s in t r acks and clusters, but t ha t t he pol ymer i zat i on ki net i cs do
not reflect t hese effects and can be expl ai ned adequat el y on t he basi s of
t he general pi ct ur e gi ven above (28, 47). The i nt ens i t y exponent is in
t he nei ghbor hood of 0.8 vs. 0 . 5 5 for monomer in DMF (28). Pol ymer i za-
t i on r at e depends in a compl ex way on t he wat er cont ent of t he s ys t em
(4, 2 8 , 4 2 ) . Pol ymer made at hi gh i nt ensi t i es in wat er ma y undergo
cross-l i nki ng and degr adat i on (4).
Cont i nuous met hods of pol ymer i zat i on have been st udi ed ext ensi vel y
in i ndust r i al l abor at or i es (96, 116). Advant ages i ncl ude gr eat er pr oduc-
t i on r at es and much closer cont r ol of mol ecul ar weight. Al t hough det ai l ed
knowl edge of t he mechani s m is still l acki ng, MINTZER and COMA~ (101)
have suppl i ed da t a on t he influence of such var i abl es as i ni t i at or, t em-
per at ur e, resi dence t i me and pR. Condi t i ons descr i bed b y MALLISON (Q6)
l ead t o slurries wi t h much di fferent physi cal char act er i st i cs f r om t hose
encount er ed in or di nar y bat ch oper at i on. Wi t h pr oper agi t at i on he
obt ai ned fluid slurries wi t h 40% pol ymer or more, and t hese slurries
coul d be cent r i f uged t o a wat er cont ent as l ow as 25% of t he cake wei ght .
These f eat ur es are cor r el at ed wi t h t he f or mat i on of dense, r ounded par -
ticles oft en 10 t o 50 mi crons across r a t he r t ha n t he loose aggr egat es
f ound in mos t bat ch processes. Rapi d react i on r at es in such s ys t ems
suggest t ha t a maj or f r act i on of t he pol ymer is f or mi ng on t he pol ymer
part i cl es.
6. An i o n i c P o l y me r i z a t i o n
I t has been known for ma n y year s t ha t acryl oni t ri l e pol ymer i zes
r eadi l y in t he presence of st r ong bases, but t he det ai l ed mechani sms are
not well under st ood. Some of t he difficulties are t hose common t o all
ionic pol ymer i zat i on st udi es, while ot her s are due t o t he het er ogeneous
condi t i ons and side r eact i ons t ha t are somet i mes encount er ed. I n t he
l ast t wo or t hr ee year s i nt er est has i ncreased consi der abl y and sub-
s t ant i al progress can be ant i ci pat ed.
Acryl oni t ri l e is subj ect t o i ni t i at i on b y bases because t he st r ongl y
el ect ron wi t hdr awi ng CN gr oup cr eat es an el ect ron-defi ci ent doubl e bond.
The r esul t i ng ani on is st abi l i zed b y t he CN group. One woul d expect
t ha t in a series of vi nyl monomer s, CHz =CHX, t he ease of ani oni c pol y-
mer i zat i on shoul d v a r y as t he el ect ron accept i ng abi l i t y of X. Conversel y,
wi t h a gi ven monome r t he overal l pol ymer i zat i on r at e mi ght v a r y as t he
Mechanism of Acrylonitrile Polymerization 429
base strength of the initiator. Bot h of these surmises are true, at least
in general, but are not yet supported by extensive quantitative dat a for
the acrylonitrile case. The order of reactivity among common monomers
in anionic polymerization appears to be CHe=C(CN)z > CH2=CHNO 2
CHs CH~
/ /
> CH2=CHCN > CH2=C\ > CH2=C\ > CH2--CHCnH v
CN COOCH a
Correlations of initiator base strength with polymerizability of several
monomers are found in the work of HIGGINSON and WOODING (70). All
of their bases were strong enough to polymerize acrylonitrile and so do
not define a range.
FURUKAWA and coworkers (63) have shown this dual relationship in
the form of a chart. They use the e-value in copolymerization as a measure
of the electron deficient character of the double bond and the electro-
negativity of the metal as a measure of base strength of the organo-
metallic initiator. Although these guides are useful t hey are only ap-
proximate. Temperature, solvent, side reactions and nature of the
organic part of the initiator will be critical in each case.
Table 7 lists a number of agents t hat appear to initiate true anionic
polymerization of acrylonitrile. Many more agents have been proposed,
Table 7. Examples of Presumed Anionic Initiators
Initiator
Type Example Reference
Alkoxides
Amides
Alkyls or aryls
Salts
Alfin catalyst
Grignard reagents
Phosphines
Ketyls
Sodiomalonic ester
Ionizing radiation
Modified Ziegler
Quaternary ammonium
hydroxides
Phosphites
Hydrocarbon salts
9 NaOC2H 5
KNH~
LiC4H~
CaZn(C2Hs) 4
NaC~Hlz, etc.
C2HsMgBr
P(C2Hs)a
N a ( C ~ H s ) ~ C O
N a C H ( C O O E t ) ,
Species unknown
Cr acetylaeetonate plus ZnEt~
+
CgHsCHzN(CH~)~OH
( E t O ) 3 P
NaC--:CH
34, 141
34, 53
34, 78
82
57, 78
125, 26
72
140, 81
~5
95
106
119
51
70
but most of these are poorly understood or else appear on further st udy
to be free radical sources. It is quite difficult to demonstrate t hat the
growing chain end is a carbanion, particularly since classical methods
like copolymerization studies are now known to be ambiguous. Reliance
is usually placed on the chemical nature of the initiator, the low tern-
430 W. M. THOMAS:
pe r a t ur e r ange t h a t is sui t abl e, i nhi bi t i on b y wa t e r a n d CO 2 b u t n o t b y
h y d r o q u i n o n e a n d t he l i ke a n d s ome t i me s on t he col ors one obser ves.
I n a t ypi c a l ani oni c pol yme r i z a t i on of acr yl oni t r i l e t he f ol l owi ng char ac-
t er i st i cs ma y a ppe a r :
Polymerization may be rapid or even explosive at room temperature and may
be fairly rapid at dry ice temperature.
The polymer may be white (if made at low temperature) but is often yellow
or yellow-brown.
Molecular weights are often very low (1000 or less) but may be in the 50,000
to 1000,000 or even higher range under special conditions.
Polymer is sometimes wholely or partly soluble in acetone and other polar
liquids t hat are not solvents for free-radical polymer.
Initiator fragments are sometimes incorporated.
The spectrum is often normal but may show evidence of alpha cyanoethylation
and other structural differences, particularly in the case of acetone-soluble polymers.
One of t he fi rst det ai l ed st udi es on t hes e s ys t e ms was t h a t of BEAMAI~
( 26) , who s howe d t h a t me t ha c r yl oni t r i l e pol ymer i zes b y an ani oni c chai n
me c h a n i s m when t r e a t e d wi t h var i ous bases, i ncl udi ng Na i n l i qui d
a mmo n i a at - - 7 5 ~ C. He not e d al so t h a t l ow mol ecul ar wei ght pol yme r s
are obt a i ne d f r om r eact i on of acr yl oni t r i l e wi t h b u t y l ma g n e s i u m br omi de.
FOSTER (56) e xt e nde d t he l i qui d a mmo n i a me t h o d t o e opol yme r i z a t i on
s t udi es i n whi ch acr yl oni t r i l e was c ombi ne d wi t h s t yr ene, wi t h me t h y l
me t h a c r y l a t e a n d wi t h vi nyl b u t y l sul fone. Sa t i s f a c t or y d a t a wer e ob-
t a i ne d o n l y wi t h t he sul fone, i n whi ch case t her e was s ome t e n d e n c y f or
al t er nat i on.
HIGGINSON a n d WOODING (70) s howe d t h a t acr yl oni t r i l e pol ymer i zes
r e a di l y i n t he pr es ence of a l ar ge n u mb e r of bases b o t h i n e t he r at 20 ~
a n d i n NH 3 at - - 3 3 . 5 ~ Thes e bases cover ed a p K r ange of 17 t o 36 a nd
t he wo r k d e mo n s t r a t e d t h a t acr yl oni t r i l e is pol yme r i z e d b y bases t oo
we a k t o i ni t i at e me t h y l me t h a c r y l a t e or s t yr ene. The pol yacr yl oni t r i l es
wer e sol ubl e i n NH 3 a n d s par i ngl y sol ubl e i n acet one a n d i n pyr i di ne.
Al t h o u g h t he a ut hor s t h o u g h t t h a t s ol ubi l i t y mi ght be as s oci at ed wi t h
l ow mol ecul ar wei ght , i t seems f ar mor e l i kel y now t h a t t hi s was due t o
s t r uc t ur a l di f f er ences s uch as c ya noe t hyl a t i on. HIGGINSON a nd WOODING
t h o u g h t t h a t t he col or of t hei r pol yme r s mi g h t be a r es ul t of c o n j u g a t e d
s t r uc t ur e s ar i si ng f r om pol yme r i z a t i on t h r o u g h t he ni t ri l e. Thi s 1,4 pol y-
me r i z a t i on has been pr opos e d i n ot he r s ys t e ms f or me t ha c r yl oni t r i l e (64)
a nd f or acr yl oni t r i l e (4/0, 86) b u t i t s r el at i onshi p, if a ny, t o col or is n o t
est abl i shed.
Ki net i c s t udi es ha ve been i nf r e que nt b u t CUNDALL ( 4 / 5 ) r e por t e d
r e c e nt l y on t he s y s t e m a c r yl oni t r i l e - DMF- s odi um di e t hyl ma l ona t e .
De s i gna t i ng t he di et hyl ma l ona t e ani on as C- a n d t he DMF s ol vent as
XH he s howe d t h a t t he r a t e expr essi on i s:
- - d [ M] / d t = k [M] 2 [ C- ] .
Mechanism of Acrylonitrile Polymerization 431
The dat a are consi st ent wi t h t he scheme:
C- + M --> CM- (1)
CM- + M ---> CM~ etc. (2)
CM~+M --+ CM~+ M- (3)
CM: + XH --> CM, + X (4)
The average degree of pol ymer i zat i on is l i mi t ed t o about 20 by t he t r ans-
fer react i on (equat i on 3). Ther e is about one doubl e bond per pol ymer
molecule, and i nf r ar ed evi dence suggests some i ncor por at i on of mal oni c
est er fragment s. Onl y t he addi t i on compound was f or med in alcohol and
t et r ahydr of ur an gave an i nact i ve compl ex wi t h t he mal onat e. I n general
resul t s were paral l el t o t hose on st yr ene in t he pi oneeri ng ki net i c s t udy
by HIaGINSON and WOODING ( 7 0 ) . I n t he st yr ene work KNH~. was t he
i ni t i at or and NH s was t he sol vent . Then t er mi nat i on was l argel y by
t r ansf er t o sol vent .
Recent l y, some det ai l ed i nf or mat i on has been pr ovi ded on several
classes of i ni t i at ors in het erogeneous syst ems. One of t hese is a sur vey
of ZILKHA, FEIT and FRANKEL (7,/1) Of sodi um alkoxides. Acryl oni t ri l e
in l i ght pet r ol eum at - - 15 ~ (two l i qui d phases) was t r eat ed wi t h sodi um
al koxi de solutions in t he par ent alcohol. The yi el d of pol ymer was hi gher
and t he i nduct i on peri od was shor t er in t he case of t he mor e st r ongl y
basic alkoxides, i. e., t hose der i ved f r om less acidic alcohols like i -propyl
and n- but yl . Similarly, t he addi t i on of i - pr opyl alcohol t o met hanol i c
sodi um met hoxi de i ncreased t he act i vi t y of t he met hoxi de. Lar ger
amount s of cat al yst gave gr eat er yields unt i l t he t ot al amount of alcohol
pr esent became excessive and t he yi el d dr opped.
But yl l i t hi um as an i ni t i at or was r epor t ed in anot her paper from t he
same l abor at or y ( 5 9 ) . Wor ki ng agai n in l i ght pet r ol eum a t - 15 ~ t he y
f ound t hat a cert ai n t hr eshol d concent r at i on of C, HaLi was needed, but
t ha t t hi s was less t han for met hyl met hacr yl at e. Lar ger amount s of
C4HgLi gave mor e pol ymer , but t he mol ecul ar wei ght di d not change
much. Under t hese condi t i ons t he i nt ri nsi c vi scosi t y was about 0.4
(molecular wei ght about 20,000). A hi gher yi el d was obt ai ned at t hi s
t emper at ur e t han at - - 50 ~ at 10 ~ or at 35 ~ but mol ecul ar wei ght was
r el at ed i nversel y t o t emper at ur e. Quant i t at i vel y t hi s corresponded to a
difference of 4 kcal per mole bet ween t he act i vat i on energies for pro-
pagat i on and t er mi nat i on. Use of t et r ahydr of ur an or et her as sol vent
led t o l ower yields t han were obt ai ned in l i ght pet r ol eum. These aut hor s
were able t o pr epar e what appear s t o have been a bl ock copol ymer by
addi ng acryl oni t ri l e t o a "l i vi ng" st yr ene pol ymer i ni t i at ed by C,HoLi.
I n a t hi r d r epor t ZILKHA and associates ( 7 4 0 ) regarded met al ket yl s
as species havi ng bot h a free radi cal and an ani on in t he same molecule.
4 3 2 w. 1~. THOMAS:
These t wo i ni t i at i ng sites mi ght be consi dered t o compet e for monomer ,
but it appear s t ha t i ni t i at i on is at t he ani oni c site. I n t hi s s t udy sodi um
benzophenone was used as i ni t i at or in t et r ahydr of ur an at 0 ~ Anionic
pol ymer i zat i on was suggest ed b y i nf r ar ed evi dence, b y t he r api d pol y-
mer i zat i on and b y obt ai ni ng near l y pur e pol yacr yl oni t r i l e in a t t e mpt e d
copol ymer i zat i on wi t h st yr ene. I N O U E , TSURUTA and FURUKAWA (8)')
show t ha t i ni t i at i on is sensi t i ve t o specific r eact i on condi t i ons. I n t hei r
exper i ment s sodi um and pot as s i um benzophenone gave pol ymer , but t he
l i t hi um compound was ineffective.
Many or gano- met al l i c compounds of t he second, t hi r d and f our t h
gr oups of t he peri odi c t abl e have been suggest ed as i ni t i at ors. I n some
cases t hese have been t hought t o be ani oni c but t he evi dence is of t en
not cl ear and in cer t ai n cases i t poi nt s t o a free-radi cal mechani sm.
Te t r a e t hyl lead, for exampl e, requi res l i ght at r oom t emper at ur e, sug-
gest i ng a radi cal process (97).
Convent i onal Ziegler cat al ys t s are not sui t abl e for use wi t h acr yl o-
ni t ri l e because, a mong ot her reasons, t he monome r r eact s wi t h t he
cat al ys t or f or ms compl exes wi t h it. Recent l y, modi fi ed cat al yst s have
been devel oped in NATTA'S l abor at or y ( 7 0 6 ) , usi ng such combi nat i ons as:
Chromium acetylacetone plus dibutyl zinc,
Triethoxyvanadyl plus diethyl zinc,
Chromium acetylacetone plus triethy! aluminum.
React i on t akes pl ace at moder at e t emper at ur es (40 t o 80 ~ in a hydr o-
car bon or even in DMF. The pol ymer is descri bed as a whi t e or sl i ght l y
col ored pr oduct cont ai ni ng chai n segment s t ha t show a syndi ot act i c
confi gurat i on of monome r uni t s. I t is pr es umed b y anal ogy wi t h ot her
Zi egl er - Nat t a cat al ys t s t ha t t he mechani s m here is anionic.
I ni t i at i on b y Lewi s acids, al t hough superfi ci al l y cationic, mus t be
di smi ssed as free-radi cal . I f acryl oni t ri l e di ssol ved in di met hyl f or mami de
is heat ed wi t h a l i t t l e BF 3, fai rl y r api d pol ymer i zat i on occurs. Ot her
ami de t ype sol vent s cont ai ni ng t he N- met hyl gr oup can be used, and
ot her acidic subst ances such as H2SO 4, SnC14, A1C13 and SOa can be sub-
s t i t ut ed for BF3. Al t hough t hese are t ypi cal ionic cat al yst s, CAMPBELl. (36)
showed t hat a free-radi cal pol ymer i zat i on is i nvol ved. Evi dence i ncl udes
t he fact s t ha t oxygen is essent i al and t ha t r a t he r l arge amount s of wat er
ma y be present . I ni t i at i on is t hought t o i nvol ve i nt er medi at es like:
-BFa:O
I
9 O,CH2N=C-H + HO2.
I
CH3
The t r i al kyl bor ons compr i se a class of i ni t i at or s t hat had been
r egar ded as ionic ( 5 , 6 2 , 8 8 ) . However , i t seems mor e r easonabl e now t o
l ook on t hese compounds as free-radi cal i ni t i at ors ( 5 5 ) . I f pol ar monomer s
Mechanism of AcryIonitrile Polymerization 433
iike vi nyl acet at e, vi nyl chloride, met hyl met hacr yl at e or acryl oni t ri l e
are t r eat ed in solution wi t h t r i et hyl boron at room t emper at ur e, pol ymers
are obt ai ned in r easonabl y good yield. In some cases, at least, t he
pol ymers seem t o be more hi ghl y or der ed t han are t hose der i ved from
convent i onal i ni t i at ors, but wi t h acryl oni t ri l e t he evi dence for high or der
is not convincing. The i ni t i at i ng species appear t o be par t i al l y oxi di zed
compounds like R2BOOR der i ved from small amount s of air or from
addi t i ves such as met al oxides. FORDHAM and STURM ( 5 5 ) poi nt out t hat
all monomer s pol ymeri zed by t ri al kyl borons are pol ymeri zed also by
convent i onal free-radi cal i ni t i at ors, but not all of t hese monomer s are
suscept i bl e t o convent i onal ionic i ni t i at ors. Fur t her mor e, t he bor on
compounds are said t o be effective in aqueous syst ems, where an ionic
mechani sm is unl i kel y. As a t hi r d piece of evidence, t hese aut hor s
pr esent copol ymeri zat i on dat a for acryl oni t ri l e and for st yrene, wi t h
met hyl met hacr yl at e as t he comonomer in each case. Copol ymer com-
posi t i on for i ni t i at i on by B(C4Hs) 3 and b y B(C2Ho) a is in line wi t h t hat
of copol ymers made wi t h peroxides.
I n cont r ast t o t he boranes, t he t er t i ar y phosphi nes appear t o funct i on
as t r ue anionic i ni t i at ors (43, 72). Evi dence for this vi ewpoi nt includes
t he following observat i ons:
1. Monomers with electron wi t hdrawi ng groups are polymerized by phosphines
(acrylic and methacrylic esters, acrolein, met hyl vinyl ketone, fl-nitrostyrene, nitro-
ethylene, acrylonitrile), whereas t he phosphines have no effect on monomers more
susceptible to acid catalysts (isobutylene, styrene).
2. Polymerization is vigorous even at -- 70 ~
3. Oxygen has no effect ot her t han to oxidize t he phosphine.
4. Wat er lowers t he yields of pol ymer and leads to low molecular weights.
5. Stable 1 : 1 adduct s are formed if t he monomer has very strong wi t hdrawi ng
groups, e. g., CH~=C(CN)v
Unf or t unat el y t her e seems t o be no suppl ement ar y evi dence on copol y-
meri zat i on i ni t i at ed by phosphines. I n a t ypi cal exper i ment , a sol ut i on
of acryl oni t ri l e in pet r ol eum et her is t r eat ed wi t h a little t r i et hyl phos-
phine. A greenish-br0wn pr oduct settles on t he walls of t he flask. I t is
soluble in acet one, furfnral , met hyl et hyl ket one and DMF. Pol ymer
pr eei pi t at ed from acet one b y t ol uene is of low mol ecul ar wei ght and
cont ai ns per haps 0. 5% combi ned phosphorus. I n similar exper i ment s i t
is possible t o obt ai n pal e yellow pol ymer s wi t h number average mole-
cul ar weights of ar ound 30,000 and wi t h about one at om of P per pol ymer
chain. On t he basis of t hese results HORNER and coworkers proposed t he
scheme (72):
Initiation CH2=CHCN ~ CHa-CHCN -+ R3PCHICHCN
| 0 * 0
Propagat i on R3PCHzCHCN ---> R3P(CH2CHCN)~CH~CHCN
@ O O @
Termination R3P(CH2CHCN).CH~CHCN + H~O--> HOR3P(CH~CHCN).CH~CH~CN
4 3 4 w . Iv[. THOMAS:
Pr esumabl y, t he growing chai n woul d have a cyclic conf or mat i on or in
some ot her way woul d avoi d excessive charge separat i on.
HEISENBERG and JURGELEI T ( 6 9 ) prefer t r i et hyl phosphi ne as t he
i ni t i at or but find ot her al kyl phosphi ne t o serve also. Aromat i c phos-
phi nes are less effective, and one assumes t hat t he r at e of pol ymer i zat i on
is di r ect l y r el at ed t o t he base st r engt h of t he phosphi ne. These investi-
gat ors find t hat hi gh mol ecul ar weight, pur e whi t e pol ymers can be ob-
t ai ned by addi t i on of dr y CaCI~ t o t he react i on mi xt ure. The role of
CaCI~ is not si mpl y to act as a dr yi ng agent. Possi bl y i t removes i mpuri t i es
t ha t woul d l ead t o discoloration.
DICKEY and COOVER ( 5 1 ) showed t hat al kyl phosphi t es are capabl e
of i ni t i at i ng pol ymer i zat i on of monomer s beari ng el ect ron accept or
groups. Pol ymer i zat i on is rapi d at moder at e t emper at ur es and, in t he
exampl es given, t he pol yacryl oni t ri l e is soluble in acetone.
The most recent and most puzzling exampl e of anionic i ni t i at i on is
t hat whi ch seems t o t ake pl ace when monomer is subj ect ed t o ionizing
r adi at i on at low t emper at ur es. Acryl oni t ri l e pol ymeri zes r api dl y at t em-
per at ur es well below 0 ~ (and even in t he solid at - - 196 ~ when i r r adi at ed
wi t h X- r ays or wi t h electrons. Since it is now known t hat cat i oni c pol y-
mer i zat i on ma y be i nduced by radi at i on, t here has been specul at i on t hat
similar anionic pol ymer i zat i on mi ght be occurri ng wi t h acryl oni t ri l e
( 8 7 , 1 2 1 ) . Thi s subj ect has been discussed r ecent l y by MAGAT (QS) who
quot es unpubl i shed work of BENSASSON and of TABATA and HIROSHI.
A per t i nent quest i on is whet her t he st r uct ur e of base-i ni t i at ed pol ymer
corresponds t o t he idealized head-t o-t ai l ar r angement t hat seems charac-
t eri st i c of radi cal -i ni t i at ed pol ymer. General feat ures of t he i nfrared
spect r um are i dent i cal for t he t wo t ypes. However , unr epor t ed work in
this l abor at or y ( 1 1 9 ) suggests t hat st r uct ur es of t he t ype
CH, CHCN
/
/ \
--c-CH2C~v
\
CN
are oft en pr esent in base-i ni t i at ed pol ymer. Thi s woul d account for
sol ubi l i t y in acetone, l ower soft eni ng poi nt s and t he presence of a band
at 1420 cm -1 in t he i nf r ar ed spect rum. I f pol ymer made wi t h X- r ays at
low t emper at ur e has followed an anionic course, t hen t he presence of t he
ket ene i mi ne st r uct ur e (40) must be regarded as a poi nt of difference.
I n t hi s connect i on i t ma y be not ed t hat BENSASSON ( 3 0 ) s a w no i nfrared
or X- r ay di st i nct i on bet ween pol ymers made wi t h 1 m. e. v. el ect rons at
20 ~ and at - - 196 ~ Ther e is general agr eement t hat i ni t i at or fragment s
are oft en more pr omi nent in base-i ni t i at ed pol ymer. Color of pol ymer
made ani oni cal l y is general l y (t hough not always) at least pale yellow.
Thi s is of t en ascribed t o t he presence of condensed pyr i di ne- t ype rings
Mechanism of Acrylonitrile Polymerization 435
similar to those postulated in polymer that has been heated strongly,
or to 1,4 polymerization ( 7 0 ) .
Until recently there was little conclusive evidence regarding the
degree of stereospecificity of base-initiated polymer. Generally speaking
the products varied from completely amorphous to moderately well
ordered in two dimensions (i. e., perpendicular to the chain axis) but
poorly ordered in the chain direction. It was assumed that a tendency
existed toward syndiotactic configuration but t hat the sequences were
probably short. This situation existed despite the fact t hat much of the
recent work on anionic polymerization had been inspired by the hope of
making crystalline polymers and that claims to crystalline polyacrylo-
nitrile had been put forth from time to time. Recent work in several
laboratories, including that of NATTA ( 1 0 6 ) , shows that polymer with
varying degress of order can be prepared by presumably anionic pro-
cesses. So far there is little evidence that one can make either completely
random or completely ordered polyacrylonitrile in this way. Syndiotactic
sequences of varying length and frequency appear to have been made,
but X-ray and microscopical criteria for crystallinity are lacking.
11. - - - -
12. - - - -
Fortsehr. Hochpolym.-Forsch., Bd. 2
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