KINETICS AND MECHANISM OF n-BUTYL METHACRYLATE

POLYMERIZATION UNDER CONDITIONS OF ISOTACTIC POLYMER

FORMATION t

Z. A. AZIMOV, A. A. KOROTKOV and S. P. MITSENGENDLER

Institute of Macromolecular Compounds, U. S. S. R. Academy of Sciences
(Receivexl 23 December 1961)

ON THE basis of a study of the reaction kinetics of the butyl lithium-induced

polymerization [1,2] of methyl methacrylate (MMA), the authors came to the
conclusion t h a t the reaction of the monomer with butyl lithium through the
bond C----C which leads to the formation of active polymer centres, while C----O
reaction leads to destruction of the catalyst, but both reactions proceed via the
formation of exactly the same intermediate compound

k T--* M (BuLi)*
BuLi-t-M ~-~ M. BuLl ,,,
k4
T _, BuMoLi

The reaction of the growth and destruction of the chains also proceed with
formation of quite stable complex compounds of more or less complicated com-
position. In all eases the intermediate reactions are accompanied by a positive
thermal effect.
I f these propositions hold for the polymerization of other esters of the metha-
ery]ie series them the values of the apparent rate constants of the reactions, and
also the activation energy should be markedly dependent on the structure of
the ether group radical.
The present report aims at testing this proposition on the example of the
butyl lithium-induced polymerization of n-butyl methacrylate (BMA) in toluene.
As in the case of MMA, we will assume t h a t BMA polymerization is describ-
ed by the following four elementary reactions. $

Vysokomol. soyed. 5: No. 8, 1144-1151, 1963.

The intermediate reactions of the formation of complex compounds have been left
out of the schemes. The apparent constant values are related to the true ones as shown
below, by the relations: ki----Kk~" where ki is the equilibrium constant of the formation
of the intermediate complex compound and k~'"is the rate constant of the reaction of the
conversion of the latter to the end product.

205
206 Z.A. AzI~ov et aL
1) Formation of the polymerization centres:

BuLi+M ~M[BuLi]*" ' dn*

d--~ = k l m n " (1)
2) Growth of polymer chains:
k2 . • dm
MI[BuLi]* + M --~ M~+I[BuL1 ] ; dr :lc2mn*" (2)

3) Termination of polymer chain growth b y the monomer or polymer

M~[BuL1] + M --* BuMi+IOLI dn* (3)

• ~"" ] =k81n*m +/ca2n*"
M~[BuLi] - - . BuMi_IMOLi dr (3a)
4) Interaction of catalyst with monomer, leading to the formation of in-
active molecules:

BuLl• + M --*
k, BuMOLi, -- dn
d--v-=1¢4n m (4)

For homogeneous catalytic polymerization in the absence of a quasistation-

ary state and under conditions k~ >>kl, kal , ks~ and k 4 the solution of the
system of differential equations will be in the form;
1 + x 'h
----(kl/c=)-'/' (2nomo) -'/~ In 1--x '/, ' (5)

1 (]Q~'/'(2no~ ]~1 -~- ]~4

(6)

where T is the reaction time in min, /c1 , ]c~ and ]Q arc the apparent elementary
reaction constants, m 0 and n o are the initial monomer and catalyst concentra-
tion (mole/1.), x is the relative extent of polymerization and P is the mean
degree of polymerization.

(2homo) r
3
y
j,y
• r3

,,2 o o
b
I

43 A

0 0 1 2 3 4A

FIG. 1. T(2n0mo)½ vs. 2-3 log(l+x½)/(1--x~)(A), a--at--50 °. Experimental points at m~

and no (mole/l.): 1--1.0 , 0.005; ;2--0'5, 0"005; 3--1"0, 0.01; 4--1"0,002; b--at too=0.5;
n=0.005 mole/1. Temperature, °C: 1-- --50, 2-- --35, 3-- --20, 4--0.
 n-Butyl methacrylate polymerization 207

E q u a t i o n s (5) a n d (6) hold for conditions where t h e chain-breaking reactions

(3) a n d (3a) are n o t i m p o r t a n t .
T h e e x p e r i m e n t a l figures on the BMA p o l y m e r i z a t i o n kinetics o b t a i n e d for
different m o n o m e r a n d c a t a l y s t c o n c e n t r a t i o n s (see Fig. l a a n d 2a), a n d also for
different t e m p e r a t u r e s (Fig. lb a n d 2b) p e r m i t the conclusion t h a t e q u a t i o n (5)
a n d (6) satisfactorily describe t h e process. On t h e basis of the dependences
shown in Fig. 1 a n d 2 the a p p a r e n t c o n s t a n t s (see T a b l e 1), a c t i v a t i o n energies
a n d p r e - e x p o n e n t s (see T a b l e 2) were calculated for t h e e l e m e n t a r y reaction.

TABLE 1. VALUES OF APPARENT CONSTANTS OF ELEMENTARY REACTIONS

OF BMA POLYMERIZATION
Reaction
temperature ~4
kl × 10a k~, × 1 0 -4 k4
(°C) kl

--50 0.4 0.18 0.047 117

--35 1.18 0'19 0.103 88
--20 3"75 0.24 0.18 48
0 14.3 0.295 0.75 52

TABLE2. VALUESOFfk,, k~, k, AT -- 50° OFAPPARENTACTIVATIONENERGIESANDPRE-

EXPONENTSFOR ELEMENTARYBMA ANDMI~A POLYMERIZATIONREACTIONS[3]
E
Reaction Monomers k-a°° (kcal/mole) A

Formation of polym- MMA 6 × 1 0 -8 5.5 1.4 × 10a

erization centres BMA 0.4× 10-3 9.2 1.3 × 106
Chain growth MMA 800 10 0.5 X 10TM
BMA 1800 1.6 0.56 × l0 s
Catalyst breakdown MMA 0.05 5-6 1-8 × 104
BMA 0.047 5-3 0.65 × 104

W h e n the r e s u l t a n t k l , k 2 a n d k 4 figures are used, the c u r v e p l o t t e d accord-

ing t o e q u a t i o n s (5) a n d (6) quite satisfactorily describe t h e p o l y m e r i z a t i o n
kinetics for different m 0 a n d n o values (Fig. 3a a n d b), a n d also the d e p e n d e n c e
o f the molecular weight o f the p r o d u c t p o l y m e r s on the d e p t h o f p o l y m e r i z a t i o n
(Fig. 4a a n d b) u n d e r conditions where the d e p t h o f conversion is n o t more
t h a n 70 t o 8 0 % a n d t h e r e a c t i o n t i m e 20 to 25 rain. A t a lower m o n o m e r con-
c e n t r a t i o n (m0=0.2 mole/1.), w h e n the reaction induction period is more t h a n
40 min, the t h e o r e t i c a l kinetic c u r v e will, of course, d e p a r t considerably from
the e x p e r i m e n t a l points (curve 5 Fig. 3a). Due to t h e slowness o f t h e polymeriza-
tion reaction, i f seems t h a t the molecular r e a c t i o n of chain b r e a k i n g (3a) plays
an important part.
208 Z . A . A z r ~ o v et a/.

In the initial period the reaction rate of BMA polymerization is approxi-

mately proportional to the catalyst concentration only where this is low. At
higher concentrations it is virtually independent of n 0 (see Fig. 5). A similar
dependence has been observed in the polymerization of organo lithium com-
pounds and other monomers [1,4-6]. The complex dependence is due to interac-

J~tO~ a

08 A2
~3
04 04

fl I I I

_I. ~to ~ b

~'4" 0"8 3 4 r 2

z~ 1 ~4 ~ x
/2

0.8 0.2 ~,, zx

I I ~ ~ t ,
) 0 20 40 60 0 20 40
0 0-1 0-2 03 A 77me, min

FlO. 2 Fzo. 3
Fie. 2. l i p vs. (2n0/xm0)½(A). a - - a t - - 5 0 °. E x p e r i m e n t a l p o i n t s see Fig. la;
b--at different t e m p e r a t u r e s . F o r c o n d i t i o n s see Fig. lb.
FIO. 3. P o l y m e r i z a t i o n kinetics, a - - a t - - 5 0 ° for m o n o (mole/1.): 1--1"0, 0"02;
2--1"0, 0"01; 3--1"0, 0"005; 4--0"5, 0"005 and 5--0.2, 0"005; b--m0=0.5 a n d
n0=0.005 mole/]. Temperature, °C: 1-- --50, 2-- --35, 3-- --20, 4--0.
Curves p l o t t e d u s i n g the c o n s t a n t s g i v e n in T a b l e 1.

tion between the active chains or with the original lithium organic compounds
[1,4]. Thus the break in the chain growth reaction on MMA and BMA polymeri-
zation with butyl lithium is considerably more complicated than as demon-
strated by equations (3) and (3a), and therefore it is very difficult to draw a con-
clusion regarding a general kinetic equation.
The apparent activation energy of the chain formation reaction E 1 is approx-
imately 1.7 times greater for BMA than for MMA. On the other hand, E2,
the apparent activation energy of chain growth is 6 times less being only 1.6
kcal/mol. At this H l value, polymerization should occur at an ionic reaction
 n - B u t y l methaerylate polymerization 209

rate, however, due to the low pre-exponent values it takes place much more
slowly. However, E~, the activation energy of the reaction of BMA and MMA
with butyl lithium according to C = 0 , differs very little between the two (see
Table 2).

M~IO-~i a
G!-

2 •

i I I I • s,102
I2

M'10"sF[ b I •
2 • 2 a

I .I i
~ t I I I . 5 fO f5 2O
0 0.4 08 x no " I 0 '~
FIG. 4 FIG. 5
FIG. 4. Mean molecular weight vs. depth of polymerization, a - - a t - 5 0 ° for
m 0 a n d n o (mole/L): 1--1.0, 0.05; 2: &--0.5, 0.005; D - - I ' 0 , 0"01; 3--1.0,
0.02. Curves plotted using the constants in Table 1; b - - a t different temper-
atures. For conditions see Fig. 3b.
FIG. 5. Reciprocal transformation time for 30% BMA (l/z) vs. initial b u t y l
lithium concentration; / - - i n i t i a l BMA concentration 0.1; 2--0.5 mole/l.

To explain these differences we must use a scheme developed for the course
of polymerization reactions: 1) Formation of polymerization centres:
BU Bu

H2C O I-l~C . . . . Li . . . . 0 L'i 0 - C,H.

I If R, I" "1 r' I
Bu : L i + C - - C ---> C C ---* CH~ - - ' C - - C - - C = O
I [ I
CH8 CH3 OC,H9 CH3
I II
 210 Z. A. AzIMOV et al.

2) Growth of polymer chains

R
/:i ~C--CH R--CH,
H,C--"C<+H~C=C< ~ R : I~'i k:" I (III)
H,C "'c/. i2i
HsC "'C<
3) Termination of polymer chain growth by monomer or polymer -
R -- CH s R -- CH s
I ! I I I i
-c- +co~ - - C - -

I~'i I 0 I~'i C
"i "t '
>c"c~, >c c<
R-- OH,

k,, O Li C---~ R--CHs--~,--CHs--~=~--0Li-

• i" :el i
4) Interaction of catalyst with monomer, leading to the formation of in-
active molecules,
Bu
,.

HsC O HsC . . . . Li . . . . O
Jl It ~, L" -I k4'
Bu : Li + C -C 13• -C
i i
CIH, ; C , H , CHa 0C4H 9
Bu
CH 3 Li CHaBu
I i
--~ CI-Is=C--C-- ~ --~ C H s = C - - ~ - - O L i --+ :
i I
O--C4H9 OC,H~
CH a O
I it
--~ CHs--C -- C--Bu+C4HsOLi
With this representation of the mechanism of the course of the reaction,*
e a c h e l e m e n t a r y reac%ion m a y be r e f l e c t e d b y t h e f o l l o w i n g g e n e r a l s c h e m e :
k'
]C" t

* The proposition regarding the mechanism of polymerization :via the formation of

ingermediate, quite stable, compounds of the lithium ester type has been experimentally con-
firmed [7], in which it was found ghag complex compounds of isoprene and piperyleno were
formed with butyl lithium.
 n-Butyl methacrylate polymerization 211

For each type of reaction, the following equalities hold:

k' [{MN}] k'
K k" [M] IN] or [{MN}] = K [ M ] [N] =/~,; [M] [N],

k'k'"
W =k'"r~MN~]
L¢ #J = - - ktp [M] [N] = k ' " K [ M ] [N] =k[M] [N]

k'k'"
k = - ]g"
- =/~'"K,

where Wis the reaction rate, K is the equilibrium constant of the first reaction
and k is the apparent rate constant of the total reaction. After substituting
the k', k " and k ' " values from the Arrhenius equations we get
A'A'"
k, ~ ~ • e -(1~''' "g' - ~")I-~T .

A"

As the different E " - E ' is equal to the thermal effect of the reverse reaction,
Q, t h e n
A'A'"
1¢ = • e-(E'"-Q)II~T .
A"

Thus, the determined values for the apparent rate constants of the elemen-
t a r y reactions are the products:
klkT k;k;
kl-- k1 ' ks= k; and /Q= k~-

the activation energy values are the differences:

E ~ = E'~ -+ E'~"- - E'~ = E'~" - - Q ~ , E ~ = E'2 + E'£' - - E ; = E'£" - - Q 2
and E4=E'4-+E'4'--E'~=E'~'--Q 1
and the preexponents are the products,

AI= A1 ' A2-- A'£ and A~-- A~ '

where k', /d' and k'" are constants, E ' , E " and E ' " are the activation energies
and A', A " and A ' " are the pre-exponents of the reactions of the formation,
degradation and isomerization respectively of the intermediate complex com-
pounds and Q', Q " are the heats of formation of the complex compounds I and III.
Only the presence of equilibrium reactions for the formation of intermediate
complex compounds, which occur with a positive heat effect, can account for
such low apparent activation energy values for the elementary reaction, partic-
ularly chain growth as compared with ordinary bimoleeular reactions.
As the reaction of butyl lithium with a monomer, leading to the formation
of alcoholates (reaction (4)) has the same activation energy and pre-exponential
(see Table 2) for BMA and MMA, it can be taken that the reaction for the for-
212 Z.A. AZlMOVet al.

marion of complex compound I proceeds with the same thermal effect in both
cases. This means that the difference between the apparent activation energy
values and the pre-exponentials of the polymerization centre formation reaction
in the cases of MMA and BMA, is only due to the second stage of the reaction,
isomerization of complex compounds I to final product II. I n other words,
the low value of the positive induction effect in BMA
CHa
CHs=C~

d\
CHs - C H I - C H s - C H s
gives the intermediate compound I high stability in the reaction of its isome-
rization on the side of the bond see CHa-----C(.
I n the case of complex II, this same conjugation stabilizes, and therefore
there m a y be a considerable increase in its heat of formation and, as a result,
a reduction in E 8 the apparent activation energy, because E~=E'~'--Q.
Finally it is not impossible t h a t the lower E 2 value for BMA as compared
with MMA is also due to a lower E~' value.
As can be seen from Table 2, a t - - 5 0 ° the rate constant of the formation
of polymerization centres is 7 times lower t h a n the chain growth constant and
half t h a t of the catalyst breakdown reaction constant. The first fact once again
confirms our previous proposition, t h a t active polymerization centres are differ-
ent in nature from the initial organometallic compound [2,4]. This determines
the prolonged induction period of the polymerization reaction, particularly at
low m 0 values, which is considerably greater than in the case of MMA //¢BMX 1 -- 50°
~
=
0.07 km~Xo ~
1--50 /
here.
The second kl<<k4 means t h a t a smaller a m o u n t of catalyst participates in
the polymerization reaction and consequently, the polymer formed has a high-
er degree of polymerization, approximately 10 fold change in MMA polymer-
ization (0.43 × 105 and 0.55 × 104 at m o = l . 0 ). At --20 and 0 °, due to the approx-
imate halving of the k4/k 1 value (see Table 1) the product polymers have con-
siderably lower molecular weight (see Fig. 45).
I t is suggested that when intermediate complex compound I I I is formed,
forces of an electrostatic nature are found to be in operation between the remain-
ing groups of the addenda, for instance

~ CHa C
\ C .""
.. cH; i
b \ -L,-/
\ CH, .... C--CHa C¢H9
H9C4 "':'0 ~-~( ~ / O /
 n-Butyl me~haeryiate polymerization 213

I t is for this r e a s o n t h a t in t h e p o l y m e r i z a t i o n of MMA a n d B M A t h e condi-

tions are c r e a t e d for t h e f o r m a t i o n o f a n isotactic p o l y m e r [2,8,9].
:[he e x p e r i m e n t a l p r o c e d u r e h a s a l r e a d y been described [8].

CONCLUSIONS
(1) T h e kinetics o f b u t y l l i t h i u m - i n d u c e d BMA p o l y m e r i z a t i o n in toluene h a s
b e e n s t u d i e d a n d t h e a p p a r e n t a c t i v a t i o n energies a n d p r e - e x p o n e n t s o f t h e
e l e m e n t a r y r e a c t i o n h a v e b e e n calculated.
(2) T h e r e s u l t s h a v e b e e n considered in the light of the h y p o t h e s i s t h a t a l l
t h e e l e m e n t a r y r e a c t i o n s p r o c e e d w i t h t h e f o r m a t i o n of i n t e r m e d i a t e c o m p l e x
compounds.
(3) I n B M A p o l y m e r i z a t i o n , as c o m p a r e d w i t h MMA, m o r e s t a b l e i n t e r m e -
d i a t e c o m p l e x c o m p G u n d s are f o r m e d ; this leads to a n increase in t h e induction
period, g r o w t h r a t e o f t h e c h a i n a n d t h e m e a n m o l e c u l a r w e i g h t of t h e p o l y m e r .
(4) A t - - 5 0 ° t h e r e a c t i o n r a t e c o n s t a n t o f p o l y m e r i z a t i o n centre f o r m a t i o n
is 7 t i m e s less t h a n for c h a i n g r o w t h a n d h a l f t h a t for c a t a l y s t b r e a k d o w n .
Translated by V. ALFORD

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