POLYMER L E T T E R S VOL. 3, PP.
569-571 (1965)
COPOLYMERIZATION OF STYRENE AND METHYL
METHACRYLATE WITH LITHIUM AS INITIATOR
We h a v e been studying t h e anionic copolymerization of s t y r e n e and
methyl methacrylate. A s one p h a s e of t h i s study we u s e d lithium disper-
s i o n a s initiator and tetrahydrofuran as solvent. S i n c e previous d a t a of
Tobolsky (1) were available, h i s r e s u l t s h a v e been reinvestigated. H e
proposed a radical-anion mechanism for t h i s polymerization claiming
that at t h e radical end s t y r e n e and methyl methacrylate were copolymer-
i z e d while at the anion end methyl methacrylate w a s almost exclusively
polymerized. T h i s h y p o t h e s i s w a s forwarded to explain t h e unusual fact
that more s t y r e n e w a s found i n the initially formed copolymer than would
b e expected by a c l a s s i c a l anionic copolymerization. If t h i s mechanism
is correct, then t h e copolymer must b e a block copolymer which c o n s i s t s
of a poly(methy1 methacrylate) part a n d a random styrene-methyl meth-
a c r y l a t e copolymer part. George and Tobolsky h a v e also s t a t e d “we
cannot rule out completely the possibility that t h e propagation is a pure-
ly anionic one. If t h i s is s o , our experimental r e s u l t s indicated’that a
more s u b t l e explanation i s required than that offered by the present theo-
r i e s of ionic copolymerization. ”
T h e monomer unit s e q u e n c e in styrene-methyl methacrylate copolymers
I may b e conveniently studied by NMR spectroscopy. Bovey (2) found that
t h e absorption of methoxyl protons which a p p e a r s at 6.4 r in poly(methy1
methacrylate) is shifted to higher field a n d split into s e v e r a l p e a k s in
styrene-methyl methacrylate copolymers. T h e a-methyl p e a k is also
shifted to higher field in the copolymers. T h e s e facts were attributed t o
the shielding effect of a d j a c e n t phenyl groups.
An NMR spectrum of a copolymer h a s been taken in deuterochloroform
solution at 9OoC. T h e copolymer containing 45.3% of styrene w a s pre-
pared from a 70:30 (on molar b a s i s ) mixture of styrene and methyl meth-
a c r y l a t e u s i n g lithium dispersion as initiator. T h e conversion w a s 3.6%
and t h e intrinsic viscosity w a s 0.11 (chloroform solution, 25’). In com-
parison, two model polymer mixtures having t h e s a m e composition were
prepared. One w a s a mixture of polystyrene a n d poly(methy1 methacryl-
a t e ) and t h e other w a s a mixture of poly(methy1 methacrylate) and a co-
polymer prepared from a 70: 30 styrene-methyl methacrylate mixture u s -
ing azobisisobutyronitrile as initiator. T h e homopolymers were prepared
u s i n g lithium dispersion as initiator. T h e NMR s p e c t r a of t h e s e polymer
mixtures were obtained in t h e same way a s before. T h e s p e c t r a a r e
shown i n Figure 1.
T h e mixture of poly(methy1 methacrylate) and random copolymer h a s
methoxyl proton p e a k s at 6.70,7.07, a n d 7.63 r and a-methyl proton p e a k
569
r
d
1 I I 1 I I I I
3 4 5 6 7 0 9 10
T
Fig. 1. NMR spectra: (a) a copolymer of styrene and methyl methacrylate prepared by lithium dispersion a s initiator; r
M
(b) a mixture of poly(methy1 methacrylate) and a copolymer of styrene and methyl methacrylate prepared by atobisiso- d
butyronitrile a s initiator; (c) a mixture of polystyrene and poly(methy1 methacrylate); and (d) methoxyl and a-methyl 4
n
peak positions a t higher fields for the copolymer reported by Bovey (2). E
POLYMER LETTERS 57 1
a t 9.44 r, a s well a s those at normal positions. The positions of these
peaks at higher fields exactly coincide with those values reported by
Bovey . Neither the copolymer prepared using lithium dispersion nor the
homopolymer mixture has these peaks a t higher fields. In the latter two
spectra the absorption of methoxyl protons appears only at 6.40 T and
that of a-methyl protons a s a triplet a t around 9 r. These facts suggest
that there is no random sequence of styrene and methyl methacrylate in
t h e copolymer prepared using lithium dispersion and therefore indicate
the absence of radical propagation, although the existence of radical-
anions at the beginning of polymerization seems to be certain from the
work of Szwarc ( 3 ) . It is more plausible that styrene molecules are pre-
ferentially initiated and/or polymerized at the early stage of chain prop-
agation.
Recently, Yamashita (4) studied the NMR spectra of styrene-methyl
methacrylate copolymers which were prepared by anionic initiation. The
spectrum given i s quite the same a s o u r s in that there are no methoxyl
and a-methyl peaks at higher fields.
Further study on the mechanism of t h i s copolymerization i s being car-
ried out and will be published in detail.
References
(1) (a) O’Driscoll, K . F., R. J . Boudreau, and A . V. Tobolsky, J .
Polymer Sci., a 115 (1958). (b) O’Driscoll, K . F., and A . V. Tobolsky,
ibid., 31, 123 (1958). (c) O’Driscoll, K. F., and A. V. Tobolsky, ibid.,
37 363 (1959). (d) George, D. B., and A . V. Tobolsky, ibid., B2, 1
z64).
(2) Bovey, F. A . , J . Polymer Sci., 62, 197 (1962).
(3) Szwarc, M., Makromol. Chem., 35. 132 (1960).
(4) Ito, K., and Y. Yamashita, J . Polymer Sci., B, in press.
C. G. Overberger
Naoki Yamamoto
Department of Chemistry
Institute of Polymer Research
Polytechnic Institute of Brooklyn
Brooklyn 1, New York
Received March 18, 1965
