JOIJRNAL OF POLYMER SCIENCE VOL.

62, PAGES 197-209 (1962)

Polymer NMR Spectroscopy. VI. Methyl
Methacrylate-Styrene and Methyl
Methacrylate-a-Methylstyrene Copolymers*
F. A. BOVEY, Central Research Department, Minnesota Mining and
Manufacturing Company, St. Paul, Minnesota
The theory of copolymerization of vinyl and diene monomers was
developed many years ago1 and has been tested and st>rongly supported
by a large number of subsequent experimental investigations. However,
nearly all of these studies have dealt with the overall copolymer com-
position, and only a few attempts have been made to verify the predictions
of the theory with regard to the microstructure of the polymer chains,
i.e., the distribution of monomer sequence lengths. Since the equations
that predict these sequence lengths are based on the same assumptions as
those that predict the copolymer composition, without any additional
hypotheses, there is perhaps no very serious question of the correctness of
the predicted structural details. Nevertheless, the absence of experi-
mental verification constitutes a definite lacuna in an otherwise satisfactory
picture. As an example of the efforts made to supply this information, the
work of Marvel2 and Alfrey3 and their coworkers may be cited (see ref. 1,
pp. 137-145). I n their studies the rate and extent of zinc dechlorination
of vinyl chloride copolymers was measured; however, the zinc apparently
did not confine itself to the expected removal of chlorine atoms in 1,s
positions along the chain, and so the results were inconclusive. The infra-
red spectra of copolymers often deviate from a mere summation of the
corresponding homopolymer ~pectra.~ Such deviations are marked
enough to be useful when the immediate environments of the backbone
atoms (most commonly hydrogen) are altered in the copolymer, as, for
example, in copolymers of hydrocarbon monomers with fluorine-substituted
ethylenes. Side-chain absorptions are in any case affected only to a small
degree, if at all. At best, infrared spectra supply only qualitative indica-
tions that the substance concerned is indeed a copolymer, and do not pro-
vide a basis for the calculation of sequence lengths.
For block and graft copolymers, to which the classic copolymerization
equations cannot be applied , there frequently is no theoretical or experi-
mental basis for a prediction of the detailed polymer structure. I n such
cases, new analytical methods clearly are needed.
and Manufacturing Company, St. Paul, Minnesota.
* Contribution No. 219 from the Central Research Depnrtment, Minnesota Mining
197
198 F. A. BOVEY
Finally, nothing at all can be stated or predicted at present concerning
the stereochemical conjiguration of the monomer units in copolymers of any
type, even of the random or alternating types to which the copolymeriza-
tion equations apply and whose structure might therefore be thought well
understood in other respects. It is true that from the practical viewpoint
such information is of less interest than in the case of homopolymers,
because it appears less likely that the properties of copolymers will be
profoundly affected by variations in the stereochemistry of the monomer
units. Nevertheless, some effect on both physical and chemical properties
is certainly to be expected, and in any case the question is of theoretical
interest.
I n this paper are reported preliminary studies of methyl methacrylate
copolymers which indicate that high-resolution NMR spectroscopy of
solutions of copolymers can yield valuable information concerning both
sequence lengths and stereochemical configurations of the monomer units.
At the present stage of this work, it is not possible to disentangle sequence
and configurational effects satisfactorily and therefore the conclusions are
necessarily somewhat tentative and incomplete. Further investigations
are in progress, but it was thought best to publish the present data so t,hat
others may be encouraged to make use of this potentially useful technique.
Experimental
Polymer Preparation
All polymers were prepared in bulk in Pyrex ampules which were swept
with prepurified nitrogen before being sealed. Monomers were vacuum-
distilled before use. I n the methyl methacrylate-styrene copolymeriza-
tions, the total weight of monomer in each ampule was 20 g., the monomer
weights being adjusted to give methyl methacrylate/styrene mole ratios of
10 : 90,25 : 75,50 : 50,75 : 25, and 90 : 10. I n each ampule, 5 mg. of benzoyl
peroxide was dissolved. Polymerization was carried out by immersing
the ampule in a boiling-water bath until the first slight increase of viscosity,
indicative of incipient polymerization, was observed. The ampule was
then quickly cooled in ice water. Monomer conversions ranged from 4.5
to 8.1%. The polymers were precipitated in a large volume of met,hanol
and dried for 16 hr. in vacuo at 75'. Methyl methacrylate-a-methyl-
styrene copolymers were prepared similarly. The methyl methacrylate/ a-
methylstyrene mole ratios were 12:88, 28:72, 54:46, 78:22, and 91.5:8.5.
The first two systems were very slow t,o polymerize, and therefore were
initiated by Co60 yradiation; 17.5 Mrad over a 233-hr. period at approxi-
mately 25' gave 2.8% monomer conversion in each. The system highest
in methyl methacrylate was polymerized with 20 mg. of benzoyl peroxide;
1.6% conversion was reached in approximately 30 min. at 100'. The
54 : 46 and 78 : 22 systems contained 20 mg. of benzoyl peroxide as sensitizer
and were exposed to ultraviolet radiation (275-w. G.E. sun lamp) for 15 hr.;
they gave monomer conversions of 5.7 and 8.8%, respectively. Copolymer-
POLYMER NMR SPECTROSCOPY. VI 199
ization reactivity ratios are somewhat affected by temperature, but the
effect is small and was not considered significant in the present study.
Sample Preparation
Polymer solutions for NMR spectral measurements were prepared by
dissolving 0.100 g. of polymer in 0.5 ml. of solvent containing 29i, of tetra-
methylsilane as internal reference ~tandard.~ For the styrene and a-
methylstyrene homopolymers and for the copolymers made from the
systems having the two highest styrene and a-methylstyrene contents,
carbon tetrachloride was employed as solvent. For the other polymers,
chloroform was the better solvent (i.e., gave spectra of better resolution)
but solutions in carbon tetrachloride were also employed in order to permit
measurement of the aromatic peak positions, which are obscured by the
chloroform resonance. For the methyl methacrylate homopolymer,
chloroform was used. The polymer solutions were transferred to 5 mm.
O.D. Pyrex NMR tubes which were evacuat,ed and then sealed under
about 400 mm. of nitrogen pressure in order to prevent boiling at the
temperature of observation, 90.
Spectral Measurements
A Varian V-4300-2 40 Mcycle/sec. spectrometer, equipped with a Varian
heated probe, Varian field homogeneity control unit, Hewlett Packard
522-B frequency counter, and Varian recorder, was employed. I n the
spectra, the peak for the methyl group of the tetramethylsilane reference
appears at the extreme right and its position is taken as +lO.OOO ppm.
Peak positions on this scale are termed 7-values, as previously describedJ 5s6
and are determined by linear interpolation in these spectra.
Experimental Results and Interpretation
I n Figure 1 the spectra of the methyl methacrylate-styrene copolymers
are shown, together with those of the homopolymers. The spectra of the
homopolymers and of the copolymers from the 1O:OO and 25:75 methyl
methacrylate/styrene feed ratios are shown as recorded. For the other
copolymers, the left-hand portion of the spectrum with the aromatic peaks
is shown as recorded in carbon tetrachloride solvent; the remainder of the
spectrum is shown as recorded in chloroform solvent. The peaks, from
left to right, correspond to the following polymer protons. At the left
(3.0-3.5 7 ) is the resonance of the phenyl protons of the styrene units,
except in Spectrum g, where the chloroform proton resonance appears in
this position. I n the polymers from 90 and 75 mole-yo styrene feeds, the
ortho ring protons can be distinguished as a smaller peak or shoulder at
higher field than that of the meta and para; at lower styrene feed ratios,
only a single peak can be seen. Similar behavior has been observed for
styrene-butadiene copolymer^.^ I n the region 6.4-7.2 7 are the peaks for
the methoxyl protons of the methyl methacrylate units. There are further
200 F. A. BOVEY
Fig. 1. NMR spectra of solutions of methyl methacrylatestyrene copolymers and
homopolymers, 0.10 g. in 0.5 ml. of CHCL or CCl, (see text) with 2% tetramethylsilane
as internal reference ( 7 =10.00): ( a) polystyrene; ( b ) 10:90 (methyl methacrylate-
styrene mole ratio in monomer feed); (c) 25:75; ( d) 50:50; (e) 75:25; (f) 9O:lO;
( 9 ) polymethyl methacrylate.
peaks, less clearly defined, in the 7.5-7.9 r region. For the present it
appears best to interpret these also as corresponding to methoxyl groups
(see Discussion below), but such an interpretation is tentative, particularly
as corresponding peaks can be seen much Iess clearly, if at alI, in the a-
methylstyrene copolymers. The region 8.1-8.5 corresponds to the CH,
protons of the methyl methacrylate units and the CHCHz protons of the
styrene units. I n three of the spectra (d, el and f), these can be distin-
guished, the styrene protons being at somewhat higher field. Finally, at
highest field (8.8-9.5 r) are the a-methyl groups of methyl methacrylate
units. The peaks corresponding to isotactic, heterotactic, and syndio-
POLYMER NMR SPECTROSCOPY. VI 201
Fig. 2. NMR peak positions for methyl methacrylatestyrene copolymers and homo-
polymers in CHCla or CCl, (see text) as a function of fi, the mole fraction of methyl
methacrylate in the monomer feed: (0) styrene protons; ( 0) methyl methacrylate protons;
(a) not yet assigned with certainty but interpreted in the text as methyl methacrylate
methoxyl protons.
tactic triads6 cannot be distinguished in any of the copolymers, although
the peak shapes (particularly in Spectra e and f) indicate an unresolved
multiplicity. I n Figure 2, peak positions are plotted as a function of the
mole fraction of methyl methacrylate (jl) in the feed. Most of the peaks
move upfield as the proportion of styrene in the copolymers is increased.
This is particularly marked in the case of the a-methyl peaks, and the
methoxyl peak at lowest field. As in the spectra of butadiene-styrene
copolymers, this shielding effect is due to the magnetic anisotropy of the
styrene phenyl groups,8-11 and becomes particularly marked when most of
the methyl methacrylate units are isolated between styrene units.
The spectra of the methyl methacrylate-a-methylstyrene copolymers are
similar to those of the methyl methacrylate-styrene copolymers, and are
not shown. The backbone methylene regions (8.1-8.6 7 ) of the two
comonomer units cannot be distinguished from each other. On the other
hand, the methyl methacrylate a-methyl regions are clearly multiplets
except at the two lowest values of fi. I n the spectrum of the 46 : 54 methyl
methacrylate-a-mcthylstyrene copolymer the shape of the methyl meth-
202 F. A. BOVEY
3 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Fig. 3. NMR peak positions for methyl methacrylate-a-methylstyrene copolymers
and homopolymers in CHCl, or CCI, (see text) as a function of fi, the mole fraction of
methyl methacrylate in the monomer feed: (0) a-methylstyrene protons; ( 0) methyl
methacrylate protons.
acrylate a-methyl resonance is markedly altered from that observed at
higher fi; the peak at lower field (8.83 T), which corresponds to isotactic
triads in the homopolymers and is normally very small in free-radical
polymers, appears to be the most prominent. The a-methyl protons of the
a-methylstyrene units appear at highest field, 9.6-9.8 7. Peak positions
for the a-methylstyrene copolymers are plotted in Figure 3. It can be seen
that the phenyl groups of a-methylstyrene are somewhat less effective than
styrene units in shielding neighboring protons, for most of the peak posi-
tions show a smaller upfield slope with increasing a-methylstyrene
content.
I n both series of copolymers, the methoxyl resonance is surprisingly
complex and appears to offer the best promise of yielding fundamental
information concerning the microstructure of the chains. I n methyl
methacrylate homopolymers the methoxyl protons appear as a single narrow
peak at 6.40 T regardless of the stereochemical configuration of the chains.
POLYMER NMR SPECTROSCOPY. VI 203
I n the copolymers, the methoxyl resonance is evidently very sensitive to
the configuration and proximity of the styrene units, there being in all
spectra at least two, and sometimes three or more, peaks clearly visible.
I n the next section, we shall attempt an explanation of this result.
Discussion
We shall assume that only nearest neighboring styrene units produce
sufficiently marked shielding effects on the methoxyl protons to require
detailed consideration. That this is not strictly correct is shown by the
apparently continuous upfield shift of the methoxyl resonance with
increasing styrene content; but at least there is no reason to believe that
more distant styrene units cause the appearance of separate methoxyl
peaks. It is evident that, considered without regard to stereochemical
configuration, a methyl methacrylate unit ml in a copolymer may exist in
any of three situations with respect to the nearest neighboring units,
mlmlml, mlmlm2, and m2m1m7, that is, only like units as neighbors, one
comonomer unit m2 as neighbor, or surrounded by m2 units. The proba-
bilities of occurrence of these triads may be readily calculated if the re-
activity ratios r1 and r2 for the copolymerization system are known. The
probability that a monomer sequence picked at random will contain nl
and only n1 units (nl being any arbitrary number, and the subscript re-
ferring to monomer 1, which, in the present systems, is methyl meth-
acrylate), is given by the following (see ref. 1, p. 134 et seq.).
For monomer 1:
For monomer 2:
I n the above equations,
Pll and Pz2 are, respectively, the probability that monomer 1 will add to a
growing chain ending in ml and the probability that monomer 2 will add
to a chain ending in m2; fl and f2 are, of course, the mole fractions of
monomer 1 and monomer 2 in the feed. I n order to interpret the spectra,
we require the mole fractions of monomer units involved in specified
sequences rather than the probabilities of occurrence of those sequences.
Of the total ml units in a very long (semi-infinite) chain, the mole
fraction occurring in sequences having a length exactly n1 will be given by:
204 F. A. ROVEY
( 5)
The denominator can he expressed as :
(1 - Pii)(1 + 2Pii + 3Pii' + 4P1l3 + . . .) = (1 - Pll)-'
We therefore have:
F( ml , n1) = n ~ 1 1 ( ~ l - ~ ) ( 1 - ~ 1 1 ) ~
F( m2, nr ) = n~~22( ~*- ' ) ( 1 - ~ 2 2 ) '
(6)
('7)
We may now calculate the mole fraction of ml units having oiily mI neigh-
bors (it should be noted that this is quite different from the mole fractioii of
ml units in sequences for which nl is 3).
and correspondingly for monomer 2:
This quantity will be given by:
FIII = '1'4 I i . ( ml . nl =8) + "4 F ( ml , n l = 4 ) + '//6 F(rnI, n1=6) +
n ! = m
= (1 - PI,)' c (n1 - 2)P11(nl -1)
= P11*(1 - P11)?(1 + 2P1, + 3P,,2 + . . .)
= PllZ (9)
The mole fraction of ml units having one ml and one m2 neighbor is given
by :
n1=3
F211 (or F112)
= F(rnl. n1=2) + ' I ' 3 F( mI , nl =s ) + ' I ' d F( ml . n t =4) +
2
. . . + - F( l nl , nl ) + . . . (10)
nl
nl =-
nl =2
= 2(1 - Pll)2 c Pl l ( nl - l )
= 2P1,(1 - PI])
Finally, the mole fraction of ml units having oiily m2 neighhors is the frac-
tion of ml units in sequences for which n1 = 1 , i.e. :
F Z ~ Z = F( ml , n , = l ) = (1 - Pll)'
(12)
(Obviously, if any two of these quantities are known the third is known,
since F111 + F211 + F212 = 1.) Exactly analogous relationships hold for
m2 units.
The relationships of Flll, F211, and FZl 2 t,o Pl1 appear to be closely analo-
gous-in fact, are identical in form-to the relationships of Pi, Ph, and P,
(the probnlditics of orcurreiicc of isotnctic, heterotartic, and syndiotactic
POLYMER NMR SPECTROSCOPY. V I 204
triads) to u, the probability of isotactic monomer placement in homo-
polymerization.6 However, the analogy is not quite so close as it may
appear at first sight. We may illustrate the difference by pointing out
that whereas the probabilities of occurrence of the triads ldl and dld are
not and need not be distinguished in treating homopolymers, both being
given by (1 - u ) ~ , the probabilities of occurrence of m2m1m2 and mlmzml
will not in general be identical by any means. Such differences must be
C
D
Fig. 4. The mole fraction of ml (methyl methacrylate) monomer units which are in
mlmlml triads ( PI, , ) , mlmlmz triads ( Fzl l ) , and mtmlm:. triads ( F z I ~ ) as a function of
f,, the mole fraction of methyl methacrylate in the monomer feed, in (-) the systems
methyl methacrylate-styrene and (-) methyl methacrylate-a-methylstyrene.
clearly recognized when analogies are drawn between copolymers and
configurational isomerism in homopolymers.
I n Figure 4, F1ll, FZU, and Fzlz are plotted for the copolymer systems
employed in this paper. For the methyl methacrylate-styrene system the
reactivity ratios reported12 are r1 = 0.46 and r2 = 0.52 (see also ref. 1, p.
35) ; for the methyl methacrylate-a-methylstyrene system the reactivity
ratios reported12 are r1 = 0.50 and r2 = 0.14 (in ref. 1, p. 3.5, r? for this
system is erroneously reported as 0.04). The curves for the two systems
are similar, since they depend only on r1 and not on r2. Conversely, of
course, the curves for F222, FIz2, and Flzl would depend on r2 and not on r l .
206 F. A. BOVEY
When we examine Spectrum b in Figure 1 (fl = 0.10) in the light of
Figure 4, it is at once evident that the copolymer spectra cannot be ex-
plained in terms of sequence probabilities alone. For fl = 0.10, Fzlz is
approximately 0.91 ; that is, over 90% of the methyl methacrylate units
are isolated between styrene units. We see, however, three methoxyl
peaks, at 6.89, 7.17, and (rather poorly defined) at about 7.53 7; their
relative areas are impossible to estimate with accuracy in the present
spectra but appear to be approximately 35 : 45 : 20. We assume that these
resonances correspond to the three configurations possible for an m2mlmz
sequence, that is, dzdldz (or 121112), dzd112 (or 12dld2, lzlldl, and dzlllz), and lzdzlz
(or d,lldz). These configurations might be thought of as corresponding
to the isotactic, heterotactic, and syndiotactic triads in a homopolymer
chain16 but it must be kept in mind that there is a certain arbitrariness in
deciding which copolymer triad is to be called isotactic (or co-isotactic)
and which is to be called syndiotactic (or (co-syndiotactic), since one
must decide which substituents to align along the planar zigzag. Despite
this semantic difficulty, however, the stereochemical differences are very
real, and could easily account for the shielding values observed. It is
noteworthy that, whereas the a-methyl group resonance is markedly
shifted by configurational differences in the neighboring carbomethoxy
groups and not by configurational differences in the neighboring styrene
units, just the reverse is true of the carbomethoxy groups, if the above
interpretation is accepted.
For mzmlml (or mlmlm2) sequences, it is assumed that only two of the
four possible stereochemical configurations are magnetically distinguish-
able; that is, / &I d1 (or dzllll) cannot be distinguished from lzdlll (or dzlldl),
and dzdlll (or 1211dl) cannot be distinguished from dzdidl (or 121111), but 12dldl
and/or lzdlll can be distinguished from dzdlll and/or dzdld,. It is further
assumed that one of these (it is not possible to say which at present) has its
resonance in the 6.4-6.8 r region and that the other appears at 7.0-7.2 r,
and that they occur in the approximate ratio of 0.55:0.45 for those
methoxyl protons giving the lower field resonance to those giving the
higher. Thus, the four types of mzmlml triads, which are distinguishable
in principle, actually appear as only two peaks in most of the spectra. I n
Spectrum d, Figure 1, which corresponds to a 50:50 molar feed ratio, two
peaks can be distinctly seen in the 6.4-6.8 region, although they are not
well resolved.
For the mlmlml sequences it is known, from studies of the homopoly-
mers16 that the stereochemical configuration of the neighboring units does
not affect the methoxyl peak position of the central units, and so these
units in such sequences are assumed to have their resonance near 6.40 r,
except as influenced by the presence of styrene units as next nearest and
more distant neighbors.
If we assume that these same distributions of configurations occur in the
m2m1m2 and mlmlmz sequences wherever they occur in the chain (and this
must be so if the usual assumption is correct, that only the end unit
This is discussed below.
POLYMER NMR SPECTROSCOPY. VI 207
of the growing chain influences the configuration of the monomer unit to be
added), then all of the relative peak areas and positions in the methoxyl
region can be accounted for, except for the occasional appearance of an ill-
defined multiplicity in the 7.6-7.9 T region. For example, in the 50:50
spectrum (Fig. 1, d) the two closely spaced peaks in the 6.5-6.8 r region
would correspond to m2mlm2 (0.17 of the total methoxyl resonance),
m2mlml (0.23), and mlmlml (0.10). As f1 is increased, the resonance
narrows rapidly and, of the two peaks in this region, that at higher field
(6.72 r ) apparently dwindles rapidly. This probably then corresponds to
m2mlm2. I n the fl = 0.75 spectrum (Fig. 1, e ) t,he ratio of methoxyl peak
areas does not correspond at all to the sequence ratios of Figure 4, but can
be consistently interpreted if the above configurational ratios are also
taken into account.
The spectra of the methyl methacrylate-a-methylstyrene copolymers
can be explained qualitatively along similar lines, but here the small
differences in sequence probabilities shown in Figure 4 do not suffice to
account for the differences between these spectra and those of the nearest
corresponding styrene copolymers. For instance, in the 54 : 46 methyl
methacrylate-a-methylstyrene spectrum, the methoxyl resonance at
lower field is considerably larger than that at higher field; such is not true
of the 50:50 styrene copolymer. Again, the resonance at 7.6-7.9 r does
not appear clearly, if at all, in the a-methylstyrene copolymer spectra. At
present., a consistent quantitative interpretation of these spectra cannot be
offered, but it will probably he found that the same general treatment will
hold.
To complete the formalism, we note that to define both the sequences
and configurations of the monomer units in a two-component copolymer,
assuming that ((a propagation (see ref. 6) has occurred and that some
convention has been agreed on, as to what the term ((co-isotactic (and
therefore co-syndiotactic and co-heterotactic) shall signify, we need
to define the four monomer placement probabilities ull, u12, uzl, and u22;
ull is the probability that monomer 1 will add in the isotactic configuration
to a growing polymer chain ending in an ml unit, u12 is the probability that
monomer 2 will add in a (co-isotactic manner to a growing chain ending
in an ml unit, etc. We then have the following relationships (in which it is
of course to be understood that all ds may be replaced by 1s and vice versa;
that is, dl dl dl = 111111, lldlll = dllld7, etc.):
All the other spectra can be similarly explained.
where :
208 F. A. BOVEY
F2ll (or F112) = Fdz dl dl (or Fd l dl dz ) + Fl z dl dl (or Fdl dl dl I z )
f Fd 2 d l i I (or Fz l d l d 2 ) f Fi z d l i l (Or Fz l d 1 i 2 ) (17)
where :
Fd l d l d l = 2ull(fl21 + Ulz)P11(1 - Pll)
Fi 2 d l d l = 2U11[(1 - an) + (1 - U I Z ) ] P U ( ~ - p11)
Fd2d, t l = 2(1 - u11)(Uz1 + Ul z) p11( 1 - PII)
(18)
(19)
(21)
Rz12 = Fd 2 d l d 2 f F~~r l ~d ~ (Or Fdz dl i z ) + Fi 2 dl i l (22)
(23)
(24)
( 25)
Fi 2 d l i l = 2(1 - ail) [(I - Uzi) + (1 - uiz) IPii(1 - Pii) (20)
where :
Fd 2 d l d z = azl ~l z( 1 - 1'11)~
F l l f l d z
(Or Fdzd112) = [u12(1 - UZI) + ffzl(1 - U I Z ) ] ( ~ - P11)'
= (u12 - 2UlZUZl + UZl ) ( l - Pld'
F12dl i I = (1 - u21)(1 - ulZ)(l - Pll)'
A corresponding set of equations will hold for triad sequences with central
m2 units. These can be written down by replacing all 1's by 2's and vice
versa in the above equations; ull and uZ2 can be obtained from studies of
homopolymers; u11 is known already.6 One way of evaluating ulz and uz1
for the copolymer systems considered in this paper would be to prepare
model compounds corresponding to central methyl methacrylate units
flanked by styrene units, the styrene units both having the same stereo-
chemical configuration, the relationship of which to that of the central
unit must be known. The peaks in the methoxyl region of Spectrum b,
Figure 1, could then be assigned, and from their areas and any two of the
eqs. (23), (24), and (25) the ~ 1 2 and aZ1 would be known and the micro-
structure of the copolymer chain could be regarded as fully defined.
Clearly, this will be no easy task.
The author is indebted to Dr. G. V. D. Tiers for many stimulating and helpful dis-
cussions, to Mr. R. B. Calkins for the careful operation of the NMR spectrometer, to
Mrs. Kathryn LaCroix for the preparation of polymer samples and tubes, and to Dr.
A. R. Shults for reviewing the mathematical development.
References
1. Alfrey, T., J r., J. J . Bohrer, and H. F. Mark, Copolymerization, Interscience,
2. Marvel, C. S., G. D. J ones, T. W. Mastin, and G. L. Schertz, J . Am. Chem. Soc.,
3. Alfrey, T., Jr., H. C. Haas, and C. W. Lewis, J . Am. Chem. Soc., 73,2851 (1951).
4. Meiklejohn, R. A., (Central Research Dept., Minnesota Mining & Mfg. Co.)
5. Tiers, G. V. D., J . Phys. Chein., 62, 1151 (1958).
6. Bovey, F. A., and G. V. D. Tiers, J . Polyiner Sci., 44, Ii3 (1960).
7. Bovey, F. A., G. V. D. Tiers, and G. Filipovich, J . Polymer Sci., 38,73 (1959).
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64,2358 (1942).
private communication.
POLYMER NMl i SPECTROSCOPY. VI 209
8. Waugh, J . S., and R. W. Fessenden, J . Am. Chem. SOC., 79.846 (1957).
9. J ohnson, C. E., J r., and F. A. Bovey, J . Chem. Phys., 29,1012 (1958).
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netic Resonance, McGraw-Hill, New York, 1959, p. 180.
Organic Chemistry, Pergamon, 1959, pp. 112-113, 125-129.
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Synopsis
The NMR spectra of methyl methacrylatestyrene and methyl niethacrylate-a-
methylstyrene copolymers exhibit, among other features of interest, an unexpected
multiplicity in the 6.4-7.8 7 region, characteristic of methoxyl protons. This multi-
plicity is believed due to magnetic shielding by styrene units. By comparing the results
of a statistical analysis of monomer sequence probabilities with the relative areas of the
methoxyl peaks, it is shown that the degree of shielding of the methoxyl protons is
dependent not only upon the presence of styrene units as nearest neighbors along the
chain but also upon their stereochemical configuration with respect to the methyl metha-
crylate units. By means of reasonable assumptions it is possible to explain the copoly-
mer spectra and to give a partial description of the stereochemical configuration of the
methyl methacrylatestyrene copolymers. The NMR method should be valuable in
the analysis of other copolymers, particularly block and graft copolymers.
R6sum6
Le spectre de resonance magnetique nucleaire des copolymkres de methacrylate de
rnethyle-styrkne et de methacrylate de rn6thyle-a-rn6thylstyrkne montre parmi
dautres propri6t6s intbressantes une multiplicite inattendue dans la region de 6.4-7.87,
caracteristique des protons m6thoxyles. On croit que cette multiplicite est due B lbcran
magnetique crE6 par les unit& du styrkne. En comparant les resultah de lanalyse
statistique des probabilites de sequence de monomkre avec les surfaces relatives des pics
m6thoxyl6, on montre que le degre de recouvrement des protons rnethoxyles depend non
seulement de la presence des unites styreniques au voisinage imniediat de la chaine, mais
aussi de leur configuration stereochimique par rapport aux unites de methacrylate de
methyle. En faisant des suppositions raisonables il est possible dexpliquer le spectre du
polymhre et de donner une description partielle de la configuration sterbochimique du
copolymkre methacrylate de methyle-styrkne. La mbthode de la r6sonance magnetique
nucleaire serait precieux dms lanalyse des autres copolymkres, surtout tlans le cas des
copolymkres B bloc et greffes.
Zusammenfassung
Die NMR-Spektrcn von Methylmethacrylat-Styrol und Methylmethacrylat-a-
Methylstyrolcopolymeren zeigen, neben anderen interessanten Ziigen, eine unerwartete
Multiplizitat im 6,4-7,8 7- Bereich, der fur Methoxylprotonen charakteristisch ist.
Diese Multiplizitat wird auf eine magnetische Abschirmung durch Styrolbausteine
zuruckgefuhrt. Durch Vergleich der Ergebnisse einer statistischen Analyse der Wahr-
scheinlichkeit von Monomersequenzen mit dem relativen Flacheninhalt der Methoxyl-
maxima wird gezeigt, dass der Abschirmungsgrad der Methoxylprotonen nicht nur von
der Gegenwart von Styrolbausteinen als niichste Nachbarn Ian@ der Kette sondern auch
von ihrer stereochemischen Konfiguration in bezug auf die Methylmethacrylatbausteine
abhangt. Auf Grund plausibler Annahmen konnen die Copolymerspektren gedeutet
und eine teilweise Beschreibung der stereochemischen Konfiguration der Methyl-
methacrylat7Styrolcopolymeren gegeben werden. Die NMR-Methode sollte bei der
Analyse anderer Copoly mcrer, besonders Block und Pfropfcopolymerer, wertvoll sein.
Received October 27, 1061