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Application of NMR spectroscopy in molecular weight determination

of polymers

Article  in  European Polymer Journal · December 1986

DOI: 10.1016/0014-3057(86)90082-0

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Eur. Polvm. J. Vol. 22, No. 12, pp. 1001 1008, 1986 0014-3057,86 $3.(10+ 0.00
Printed in Great Britain Pergamon Journals Lid

A P P L I C A T I O N OF N M R S P E C T R O S C O P Y IN
MOLECULAR WEIGHT DETERMINATION
OF P O L Y M E R S
SUBHASH C. SHIT a n d SUKUMAR MAITI*
Materials Science Centre, Indian Institute of Technology, Kharagpur 721302, India

(Received 20 January 1986)

Abstract Determination of molecular weights of polymers by ~H-NMR spectroscopy is discussed. A brief

survey of application of NMR; both ~H and 13C, in the analysis of monomer sequence, copolymer
composition, polymer microstructure, end-group and relaxation phenomenon is also made. NMR offers
an elegant and simple yet fairly accurate method for determination of molecular weights of polymers.

INTRODUCTION N M R spectroscopy in molecular weight deter-

N M R spectroscopy is now well established as an
important technique for characterization of polymers
[1-3]. Characterization of polymers by N M R spec-
troscopy includes determination of monomer se-
quences in the macromolecule [4-II], copolymer
composition [12 13], monomer reactivity ratios [14],
block copolymer sequence [15, 16], polymer micro-
structure including stereoregularity [17-24], relax-
ation phenomena and end-groups [28]. Formerly
many such analyses were carried out by pyrolysis gas
chromatography, radiometric methods and isotope
analysis, i.r. spectroscopy and chemical titrimetric
methods for end-group analysis. Some of these meth-
ods are of doubtful quantitive validity, others are
time consuming involving elaborate experimental
techniques. N M R methods for polymer character-
ization offers a simple, convenient and rapid method
of analysis,
Determinations of molecular weights of polymers
are usually done by vapour pressure or membrane
osmometry, light scattering photometry, sedimen-
tation equilibrium technique or gel permeation chro-
matography. Although viscometryis the mostwidely
used technique for molecular weight determination, it
is a secondary method requiring the prior deter-
ruination of K and ~ for the polymer solvent pair
used for the viscosity determination. Some of these
methods require certain procedures or materials. For
example, light scattering photometry requires spe-
cially purified dust-free solvents, and gel permeation
chromatography needs standard polymer samples
having M w / Mn close to unity for calibration.
Recently N M R spectroscopy has been utilized for
molecular weight determination of polymers [29-38].
Like all other analyses by NMR technique, this is a
simple, fairly accurate and rapid method. We report
here a brief state-of-the-art on the application of
- -
*Present address: Plant Polymer Research, Northern Re-
gional Research Centre, U.S.D.A., Peoria, IL 61604,
U.S.A.
1001
mination of polymers and discuss some of our results.
'H-NMR VS '3C-nMr
For organic compounds and polymers, ~3C-NMR
is increasingly used for structure elucidation [39 -48].
~3C-NMR possesses obvious advantages over
IH-NMR particularly in monomer sequence analysis
because the latter has weaker signals and con-
sequently less sensitivity than the former to com-
onomer sequence effects. For determination of bran-
ching in polymers, however, both N M R techniques
are equally applicable [41] although it was thought
earlier that 13C-NMR has some limitations particu-
larly when the branches are larger than ethyl or
propyl. IH-NMR offers in some analyses of polymer
structure and composition advantages over
~C-NMR spectroscopy. These are (a) signal in-
tensities of JH-NMR remain unaffected by different
nuclear Overhauser effects; (b) similarly signal re-
sponses are also insensitive to dipolar relaxation
rates; (c) chemical shifts of certain groups in
~H-NMR spectroscopy are better resolved; and (d)
the signal-to-noise ratio in general is better in
~H-NMR [44].
The disadvantages of ~H-NMR arise primarily
from small chemical shifts in stereoregular
configurations, microstructures (head-to-head and
head-to-tail monomer linkages), molecular weight
changes and compositional differences etc. Chemical
shifts due to such molecular effects in ~3C-NMR are
about 20-30 times those of ~H-NMR. Another lira-
itaticn of ~H-NMR is overlap which causes littlc or
no peak resolution in many polymers. Non-
availability of suitable solvents and/or poor solubility
of polymers in NMR solvents are other drawbacks.
They could be largely overcome by solid state
~3C-NMR techniques.
Both N M R methods have advantages and lira-
itations. One technique cannot completely replace the
other. These two, and in fact other nuclear (such as
31p, ~gF)magnetic resonance spectroscopies should be
complementary.
1002 SUaHASHC. Star and SUKUMARMAITI

MOLECULAR WEIGHT DETERMINATIONBY total number of protons in the polymer is calculated.

'H-NMR SPECTROSCOPY Percec et al. [30] used this method to determine the
Principle for ~,1, determination DP of the ct, fn-dihydroxy polyethersulphone (Fig.
la). He obtained 1H-NMR spectra of
Currently there is growing interest in the use of 3,5-dinitrobenzoyl terminated polyethersulphone
~H-NMR for determination of molecular weights of (Fig. lb) and 4-cyanobenzoyl terminated poly-
polymers. The principle lies in the fact that, in the ethersulphone (Fig. lc). The three aromatic protons
~H-NMR spectrum of a polymer, the whole molecule of the 3,5-dinitrobenzoyl group were used as internal
is reflected in terms of the occupied area of the standard for determination of M. of (la). In both
protons of the monomer units at a particular chem-
ical shift. Since each proton of a given monomer end-groups, actually six protons are of this type.
Similarly two protons of the 4-cyanobenzoyl group
occupies a fixed area with respect to the standard are used as internal standard. DP was calculated from
proton, the total number of such protons at a fixed the following relationship by proton NMR integra-
chemical shift can be calculated from the peak area tion:
for the particular shift. From the total number of
protons available from a particular monomer, the D'--~+l=IcH3/l(~rom~tic)
number of repeat units of the polymer can easily be 6/ g
calculated. (when the 3,5-dinitrobenzoyl end-group is used
For determination of the molecular weight of a as internal standard)
polymer, the following three conditions should be
satisfied by the ~H-NMR spectrum of the polymer: Similarly,
(1) The peak area of intensity due to the same kind ~-~+ l=Icn3/ll,ro__m~tic,
of protons at a particular chemical shift in the 6 / 4
~H-NMR spectrum should be additive. (when the 4-cyanobenzoyl end-group is used as
(2) Overlapping of peaks for protons in different internal standard)
groups should be absent. There is a chance of over-
lapping when the molecular weight of the polymer is where I indicates the peak intensity at the particular
large. This limitation is, however, absent in 13C-NMR chemical shift of the respective protons present in the
because of the wide range of chemical shifts, group (Table 1).
(3) Resolution of protons of the different segments The DP of the copolymer (Fig. ld) prepared by
of a copolymer should be similar. However, different polycondensation of 1,4-dichloro-2-butene with bis-
resolution patterns of the protons of the comonomers phenol A was calculated by the same authors with the
are frequently observed, help of the following equations (here 2-terminal
allylic protons are used as internal standard. The
Because of these limitations, determination of molec- total number of protons of this kind is four) [31]. The
ular weight of polymers by ~H-NMR spectroscopy is D----Pnvalues obtained by ~H-NMR peak integration
limited to polymers of relatively low molecular method agree well with the values obtained indepen-
weight (A~tn < 20,000). dently by GPC.
Methods Jor determination of ~'I,
There are three methods for determination of /~n b-P=tlcn--cn/IcH2c']
- / / ' 2
of polymers via. (1) by introducing characteristic \ 2 / 4 ]
end-groups with known number of protons, (2) by or
using a specific single group with a fixed number of = [/IcH20[/lcH2o \
protons as internal standard, and (3) by expressing D-fi - !
the peak areas due to two or three specific types of \ 4 / 4 ]
prominent protons at corresponding chemical shifts or
in terms of the total number of such protons and =/I-"/IcH2o\ll't:n3/~
solving the equations. ~ \ 6 / 4 J
Method I. After introducing a group with known
number of proton at the end of a polymer, the or
intensity of the various protons in the monomer unit ( ~ / ~ )
of the polymer at different chemical shifts is corn- DP-- - 1
pared with that of the known proton and thus the

Table 1. ~H-NMRassignmentused for DP calculation

Chemical shift range of 6 ppm
Ortho to Ortho to
C-~-N nitro
Polymer aromatic aromatic
in Fig. 1 CH3 ~H2CI ~ H 2 0 - - --CH~-----CH-- protons Phenylene protons
(a) 1.6 . . . .
(b) 1.6 . . . . . 9.2
(c) 1.6 -- -- -- 8.2 -- --
(d) 1.6 4.52 4.08 6.05 -- 6.9 --
 NMR spectroscopy of polymers 1003

~ o CH3 7
H /~X /~X J /~XI
s-~L ) ) - - o - - ~ ))---c---~( )z~i-O--R
R 0 J, X ~ / c
X ~ J IH,X~/|o J
o
Ea]
R~H
O2N

R~ (O> COCk [b]

/----
O2N
R ----- NC ~ - - ~ - - - C O C L [C]

ct c.2 c . = c . c . 2 o c oc.2c, cHc.2o-/ y- o c . 2 c . = c.cH2 CL

',~/ I k~/Jo
CH3 CH 3

rd]
Fig. 1. (a) ~,eo Dihydroxy terminated aromatic polyethersulphone. (b) ~,e3 Di(3,5-dinitrobenzoyl)
terminated aromatic polyethersulphone. (c) ~,~o Di(4-cyanobenzoyl) terminated aromatic poly-
ethersulphone. (d) Polymer prepared from bisphenol A and 1,4-dichloro-2-butene.

Method 2. When a polymer contains a single group that they can be clearly expressed in terms of the
with a fixed number of protons, these protons may b_~e number of protons of the monomer at corresponding
used as internal standard for determination of DP chemical shift [32]. For example DP can be calculated
from the 1H-NMR spectrum. For example, the termi- for polymer (Fig. 2b) as shown below:
nal OCH 3 group (methoxy protons) was used for the
determination of DP of the copolymer (Fig. 2a) P~ = 4n
rp_Le.pared from L,L-lactide and E-caprolactone [48]. P2 = 4(3n + 2)
DP of the copolymer (Fig. 2a) calculated from the
P3 = 6(n + 1)
intensity of the end-group signal was in good agree-
ment with DP calculated from monomer/initiator P = peak intensity or area, n = number of
ratio according to the following relation repeat units DP.

M x % conversion The Mn values obtained from GPC were lower than

DP = I x 100 those obtained proton NMR analysis, i.e. by calcu-
lation ofn from the above equations. It is claimed this
Method 3. Sometimes the peaks in the ~H-NMR difference arises from impurity of the polyether sul-
spectrum of a polymer are so prominent (Table 2) phone.

CH3
I
H -(-OC~CO--O--CH2--CH2--CH2--CH2-.-.-CH2--CO4~-nOCH 3
i-a]

(P2)

cH3 cH3

c.3 L \o/
(P~)
t
(P3)
[b]

Fig. 2. (a) Copolyester prepared from LL-lactide and E-caprolactones. (b) 2,c~ Dihydroxy terminated
aromatic polyethersulphone.
1004 SUBHASH C. SHIT and SUKUMAR MAITI

Table 2. Number of protons (three types) in structural unit of polyethersulphone

NMR peak Pi P2 P3
Type of proton Ortho to Ortho to ether Methyl protons
sulphone and ortho to
(aromatic propyl (aromatic
protons) protons)
Number of protons
under each 4 12 6
peak area

EXPERIMENTAL (one end hydroxyl and the other N,N'-diethyl amine

Materials terminated) (Fig. 3a) by the use of the standard
protons (methyl protons) peak integration method.
Polyethylene terephthalate (PET) with one end hydroxy The ~H-NMR spectrum of polyethylene terephthalate
terminated and the other end diethyl amine terminated was (Fig. 4a) exhibits the following peaks: a simple sin-
prepared by the procedure already published [34]. glet, centered at 8.1 ppm due to four aromatic pro-
~,to-Dihydroxy terminated PET-Ill polyester was prepared
from terephthaloyl chloride and ethylene glycol by main- tons present in the repeat unit of the polyester chain.
taining their stoichiometric ratio in the presence of pyridine. Protons of the - O C H 2 - C H 2 - O - moiety give a singlet
Polyethylene isophthalate (PEI) with two hydroxy end- at 4.6ppm; a peak at 1.3 ppm corresponds to six
groups was prepared by condensation of isophthalic acid methyl protons. There is also a quartet at 2.4 ppm
and excess ethylene glycol [33]. Both the polyesters (PET due to the four - N - C H 2 protons. In the following
and PEI) were purified by reprecipitation from DMF solu- discussion, I is the peak intensity at the particular
tion in methanol. DMSO (E. Merck, India) was kept over chemical shift of the particular proton present in
anhydrous MgSO4 for 24hr and then distilled under re- group as shown.
duced pressure. Pyridine was dried by the usual procedure.
The both end acetylated polyethersulphone polymer and Dp_/(aro__matic)/iCH
3/r
ABA block copolymer of aromatic polyester amide (pre- 4 / 6
pared frOmsegment
end
terephthaloyl~,e~.dicarboxyChloride
and
and p-aminophenol)poly-aS
terminated
A
_ I(ocn24:H2-o)
/lcn 3
(butadiene-coacrylonitrile) rubber (CTBN) as middle seg- 4
ment B were used as obtained by following the published
procedure [36, 37]. All other reagents were used as received. However the/~tn values of two PET polyesters (PET-I
and PET-II) (Table 3) obtained by ~H-NMR peak
Techniques integration method were not compared by other
The 90 MHz ~H-NMR spectra of the polymers PET and independent method. But the inherent viscosity value
PEI were recorded on Varian EM-390 spectrometer using of PET-III (Table 3) of about 1152 molecular weight
DMSO-d6 as solvent and TMS as standard. The ~H-NMR (~tn) as determined from the following equation
spectra of acetylated polyethersulphone (one end hydroxy 1+ r
and the other end amine terminated) and aromatic DP=--
polyesteramide CTBN rubber based triblock ABA co- 1- r
polymer were also recorded on the same instrument using
CDC13 as solvent and TMS as standard. End-group analyses (where r is the mole ratio of terephthaloyl
of PEI and PET-Ill were done according to the method chloride to ethylene glycol)
described for the determination of ~n [33]. indicates that the M. values of PET-I and PET-II
Viscosity measurements were performed on 0.5% (w/v) (Table 3) by IH-NMR technique are correct. The Mn
solution of both type of polyesters (PET and PEI) in
N-methyl-2-pyrrolidone at 30°C using an Ubbelohde sus- of the PET-Ill was also determined by end-group
pended level viscometer, analysis. The fixed amount of PET-Ill was acetylated
with an acetic anhydride-pyridine mixture in DMSO
media and the subsequent titration of the reaction
RESULTS AND DISCUSSION
mixture with methanolic NaOH of known strength
Recently Shit and Maiti determined the molecular (N) gives the hydroxyl number from the following
weight of polyethylene terephthalate (PET) polyester relationship.

CH3CH2
> N -('- c- ~ ' - ) ~ T nCII-OCH2CH2I0 I
CH3CH2 O O
Eel]

HO-- CH2-- CH2-- O4- ~ ~ O ~ r - - ~ -- O-- CH2-- OH2-- O-)'ffH

O ~ O
[b]
Fig. 3. (a) Mono diethyl amine terminated polyethylene trephthalate (PET). (b) ~,o) Dihydroxy
terminated polyethylene isophthalate (PEI).
 NMR spectroscopy of polymers

a'
H O - - CI'12--CH~-0-4- C - - ~ C - - O -- CH2--CH2-- 0 .)--H
IIbL.y.P II
0 c" 0

ClinCH2\
N -(- C "t/O~r C --0 C H2 --CH20-~_ H
ru-t~u / II ~ / II m
~r~3 ~'r~z 0 0

I I 1 1 I I I I I
10 9 8 7 6 5 4 3 2 1
ppm 8

Fig. 4. (a) M o n o diethyl a m i n e terminated trephthalate ( P E T ) . (b) ~,o) D i h y d r o x y terminated poly-

ethylene isophthalate ( P E I ) .

Hydroxyl equivalent
(strength of methanolic NaOH in normality)
= x (titre blank - titre sample)
Sample weight (PET-III)
Then the Mn of PET-III was calculated from the
following relationship
2 x 1000
M'o=--
Hydroxyl equivalent
Similarly M', ofc~,~o-hydroxy terminated polyethylene
isophthalate (Fig. 3b)was determined from ~H-NMR
spectrum (Fig. 4b) analysis by using the terminal
protons of the OH group as an internal standard. A
sharp singlet at 8.3 ppm, a broad singlet at 8.0 ppm
and a multiplet at 7.5 ppm are due to three kinds of
aromatic protons a', b' and c' respectively. A singlet
peak of very low intensity at 4.9 ppm is due to OH
protons in the terminal group of polyester molecules
(Fig. 4b). Another sharp singlet was found at 4.6 ppm
due to -OCH2CH 2 0 protons. The following re-
lationship was used for the determination of Mn of
PEI.
DP + 1 . A(ocH,
. . . CH, O~ /A (OH)
4 / 2
where A is the area at a particular chemical shift
for the respective protons present in a group. Mn
obtained by this ~H-NMR method was in good

Table 3. Physical properties of polyesters (PET and PEI)

~. /1~ (End-group Inherent

Polyester (~H-N M R) (Theoretical) analysis) viscosity
PET-I 2880 -- -- 0.17
PET-II 2112 -- 0.13
PET-I I I -- 1152 1200 0.08
PEI 2000 -- 1940 0.09
1006 SUBHASH C. SHIT and SUKUMAR MAITI

agreement with the value calculated from end-group
analysis (Table 3).
The JH-NMR technique has been used for molec-
ular weight (Mn) determination of aromatic poly-
ethersulphone prepolymers. The polymer is syn-
thesized by the activated nucleophilic displacement
reaction between bis(4-chlorophenyl) sulphone and
bisphenol-A in the presence of sodium methoxide and
p-amino phenol in anhydrous conditions. The details
of synthesis have been described [36]. For N M R
analysis, this polyethersulphone prepolymer was
acetylated to obtain the following polymer,
The following relationship was used for the calcu-
lation of DP of polyether sulphone.
IICH3-C)/6
DP =
I~cH3-co)/6
where I indicates the peak integration of the re-
spective methyl protons of CH3CO and CH3-C
groups. The /~r obtained from 1H-NMR spectral
analysis (M, = 1768) agrees well with the value from
nitrogen analysis ( ~ t = 1900) of the following ABA
copolymer of molecular weight 7122 (/l~t determined
from vapour pressure osmometry). (See Scheme on
page 1007.)

CH3

,,
0 CH3 O

The IH-NMR spectra of the polymer is shown in
Fig. 5. The appearance of two almost symmetrical
peaks at 2.03 ppm and 2.07 ppm indicates that the
Triblock (ABA type) copolymers, having aromatic
polyesteramide segment as the hard A block and
polybutadiene-co-acrylonitrile as the soft B block,
were prepared by interracial polycondensation [37].
The copolymers have the following structure:

~"/F ( ~ - - - ~ ~1- 0 ' - - ' ~ NH ""~m~1- Xp- C-(-"

]] NH - - < ~ O - ~1~ ~ -~n
O O O 0 0 O

CN

polymer contains the

CH3__ C _ The degree of polymerization of the polyesterimide
[] segments at both the terminal ends of the copolymers
O (i.e. m + n ) and the number of poly(butadiene-co-
acrylonitrile) block (i.e. p) in the copolymers were
group at one end and the calculated from ~H-NMR spectra of the copolymers
__NH__C__CH 3 by the following relationships.
II 12 x I l
0 re+n=
9xl 3
group at the other end. These two methyl proton 12 x 12
peak integrations in the ~H-NMR spectrum were p _ _ _
used for the calculation of D---Pof polyethersulphone. /3 x 100

~L ~ CH3, -In 0

"l - i i" 'i

I0 9 6 7 6 5 t, 3 2 I 0
ppm
Fig. 5. LH-NMR spectrum of ct,o~-diacetyl terminated aromatic polyethersulphone.
m

CH 3

L CIH3 L CH3 _jm

I II
0 CN 0

Z
K

,O
-,.<:

\
CH3CH2. /--~ ~ ~ ~ ICH3CH2
..~C-~C~¥C--O-~C~N-)-C--X~-C -~ ~O--C-~C~-C-)-N
ClinCH2 II k'~JII k~/I roll II 1 k~/ II k ~ / i i A n xCH3CH2
0 0 H 0 0 H 0 ~/
X -- CHz--CH----CH--CH~)~'5 CI-I2--CH

I I I I I I I I I
10 9 8 7 G 5 I, 3 2 1 0
ppm
Fig. 6. ~H-NMR spectrum of diethyl amine terminated polyesteramide and poly(butadiene-co-acrylonitrile) rubber based ABA copolymer.
 1008 SUBHASH C. SHIT and SUKUMAR MAITI
where I~, 12 a n d 13 are peak intensities o f p r o t o n s of
the a r o m a t i c region at 7-8.4 ppm, double b o n d re-
gion at 5.4 p p m a n d methyl region at 1.3 ppm, re-
spectively in the 1 H - N M R spectrum o f d i e t h y l a m i n e
t e r m i n a t e d A B A c o p o l y m e r (Fig. 6).
Acknowledgement--Financial support under grant No.
HCS/DST/814/80 from the Department of Science and
Technology, New Delhi is gratefully acknowledged.
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