Polymer Science U.S.S.R. Vol. 27, No. I1, pp. 2637-2641, 1985 0032-3950/85 $10.00+.

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Printed in Poland ~[~ Pergamon Journals Ltd.

KINETIC FLEXIBILITY AND STRUCTURAL

TRANSFORMATIONS OF POLYSACCHARIDE
MACROMOLECULES*

YE. V. ANUFRIEVA, T. N. NEKRASOVA, YE. YE. BRAUDO, M. G. KRAKOVYAK,

V. B. LUSHCHIK,V. B. TOLSTOGUZOVand V. P. YUR'EV
Polymers Institute, U.S.S.R. Academy of Sciences
(Received 2 April 1984)

Structure formation has been studied in polyuronide solutions, using polarized lumines-
cence. It has been shown that intramolecular hydrogen bonds, with participation of COOH
groups or ionically coordinated bonds with participation of COO- groups and Ca 2 + ions,
play an essential role in the formation of an intramacromolecular structure. The substitution
of carboxyl by methylcarboxylate groups prevents structure formation. In conditions pro-
moting intramacromolecular hydrogen bonds, the polyuronides have a kinetic flexibility, com-
parable with that of PMMA.

THE kinetic flexibility of polysaccharide macromolecules and its change due to the
action of various factors, presents considerable interest since the character of polymer
functionality depends on the dynamic characteristics of the macromolecules. The most
modern determination of the molecular characteristics of the functional properties
has wide practical applications for polymers.
The difficulties of determining the kinetic flexibility of polymer chains, under condi-
tions excluding formation of inter-unit contacts (intra- or intermacromolecular) are
related to features of the chemical structure. In fact, the presence in each unit of a large
number of OH groups, susceptible to hydrogen bonding, and the combination of units
carrying OH groups by an oxygen link, causes formation of hydrogen bonds (intra- or
intermolecular) under all possible conditions. Consequently, to determine the kinetic
flexibility of polysaccharide chains, it is necessary to find conditions, in which the prob-
ability of hydrogen bonding would be the least. Determination of the kinetic flexi-
bility, linked with small scale relaxation processes occurring in a nanosecond period,
would allow use of this parameter for studying structures in polysaccharide solutions,
by virtue of the sensitivity of such nanosecond relaxations to structural changes in
polymer chains [1, 2].
The aim of the present work was the study of the killetic flexibility (intramolecular
mobilit3~) of polysaccharide macromolecules in conditions which promote structure
formation or decay of the intra- or intermolecular structure.
To determine the relaxation time z, characterizing the intramolecular mobility,
polarized luminescence [2] was used. Methods were developed for covalent addition
of luminescing anthracene-containing groups (markers) to the various functional groups

* Vysokomol. soyed. A27: No. 11, 2347-2350, 1985.

2637
2638 YE. V. ANUFRIEVAet al.

of the macromolecule: to the carboxyls the anthranylacyloxy methane group (marker I}

and to the hydroxyls (marker II). In the present work, marker I was used. The lumines-
cent group content of the polymer did not exceed 0.3 mole ~o. The polyuronide pectate,
pectinate (58 ~ COOHa groups) and alginate were used for the study.

The following polyuronide samples were used for the work.

Sodium pectate, from the Sigma Co., (U.S.A.), containing 88 ~o of galacturonic acid residue.
Sodium pectinate (citrus) from Koch-Light (U.K.) 88 ~o content of residual galacturonic acid;
degree of esterification of carboxyl groups, 0.58, ester group distribution in blocks, [3], hl,~= 1'8 x
x 105 (in 0"1 i NaCI).
Sodium alginate from British Drug Houses (U.K.). Content of mannuronic acid blocks,
30~, guluronic acid, 20~, blocks consisting of alternating mannuronic and guluronic acids, 50~o,
Mn. D= 1.5 x 10s (in 0.I M NaC1 solution).
The analytical methods and polyuronide purification are described in reference [4].

The macromolecules of these polyuronides are formed by units, differing in chemical

and sterochemical structure. In the units with a 5 carbon atom pyranose ring are found
carboxyl (pectate) or methylcarboxyl (pectinate) groups. In the pectate or pectinate
macromolecules, the hydroxyl groups are all arranged on one side of the pyranose ring.
The alginate is a copolymer, containing mamluronic and guluromic acids, in which
all the OH groups are disposed on the same or different sides of the plane of the
pyranose ring.
We note that a comparison of data for the pectate and the pectinate permits evalua-
tion of the nature of the substituents in the 5 carbon atom ring in structuring and a com-
parison of the data for pectate and alginate, and the features of the mutual disposition
of the hydroxyl groups. To diminish the effect of intermacromolecular interaction on
the kinetic flexibility of the polymer chains, this study was carried out at a small (0.04 ~o)
polyuronide content in solution. To determine the role of intermacromolecular inter-
ations in changes in the dynamic characteristics of the chains, polyuronide solutions
of various concentrations (0.03-1.8~) were used.
In aqueous solutions, the intramolecular mobility of the pectate, pectinate and
alginate macromolecules, even at' low polymer contents in solution, appears to be
appreciably retarded (see Table), compared with that in heterogeneous polymers with
bulky groups with oxygen bridges, for example, polyamidoacids based on pyromellitic
anhydride and diaminodiphenyl ether, in an organic solvent (DMFA). In the latter
case, z < 1 nsec. The high • value for polyuronide macromolecules in water indicates
the substantial role of intramolecular interaction in decreasing intramolecular mo-
bility.
In aqueous-organic solvents, in water-DMFA (50 : 50) mixtures, the intramolecular
mobility of polyuronide macromolecules is increased and reaches a value, similar
to that of carbo-chain polymers, P M M A or PS, in thermodynamically good solvents
[1, 2]. This shows that the polyuronide polymer chains are characterized by a high
kinetic flexibility, which is observed in conditions which promote rupturing of the
intramolecular c o n t a c t s - t h e hydrogen bonds and hydrophobie interactions.
 Structural transformations of polysaccharide macromolecules 2639

The higt kinetic flexibility of the pectate and pectinate macromolecules may be due to
the fact that the determining relaxation process in solvents, weaking the hydrogen
bonds or hydrophobic contacts of non-polar methyl groups, becomes the rotation
~of the pyranose ring around the oxygen bridges.
However, it is known that dilution of organic solvents by water ( > 5 0 ~ ) does not
crease weakening of the intramcromolecular hydrogen bonds compared with the intra-
macromolecular hydrogen bonds in water, but their strengthening, stabilization [5]
and to further weakening of the hydrophobic contacts. The study of intramolecular
mobility ofpolyuronides in water-DMFA mixtures with a high (90 ~) DMFA content,
permits an understanding of yet another important results, the revelation of features
,of structuring in these macromoleeules with differing chemical structure and the part
o f the substituent in the 5 carbon pyranose ring. It appears that with a high DMFA
content in the pectate macromolecules, an intramaeromolecular structure is formed.
Its formation is indicated by the high r value (150 nsec) for the pectate and the co-
.operative character of the change in T with that of the DMFA solvent--water composi-
tion. Substitution Of carboxyl group by methylcarboxyl in the pectate molecules pre-
vents structure formation (~'<20nsec) (see Fig. 1).

oo /

I I I
20 60 DMFA ,w~ %

'FIG. 1. Dependence of r on D M F A content in H a O - D M F A mixture for pectate (l) and pectinate

(2).

A comparison of results for pectate and pectinate in other examples shows that
substitution of the COOH group by COOCH3 is a factor preventing intramolecular
linking. Thus, as the degree of polarization of the COOH groups in pectate molecules
is decreased, a structure is formed and z increases to 150 nsec. No structure is formed
in the pectinate molecules and z increases insignificantly, from 35 to 50 nsec (see Fig. 2).
The substantial effect of substituting part of the COO- groups (58 ~ ) by COOCH3
groups on structure formation in polyuronide macromolecules was also revealed when
metal ions were introduced into the aqueous solution, forming ionically coordinated
2640 YE. V. ANUFRIEVAet aL

"CVALUES OF POLYURONIDE MACROMOLECULES IN AQUEOUS SOLUTIONS AT p H = 6"0 AND IN DMFA

Polyuronide T, n s e c
Polyuronide concentration H20-DMFA
in solution, H20 DMFA (50 : 50)
Sodium pectate 0'04 23 140 7
Sodium alginate 0'1 16
Sodium pectinate 0'05 35 14 9

bonds with the carboxyl groups. The relation of v for pectate and pectinate to the
Ca 2+ ion content in aqueous solutions shows a cooperative increase in r to 500 nsec
for pectate as the Ca 2 + content changes by an order from 0.5 × 10- 3 to 0.5 x 10 -2 mole/1,
i.e. from 0.5 Ca 2+ ions to 5 for each pectate units and a smooth change in from 26 to
50 nsec for pectinate (see Fig. 3). ff in each unit, there is a earboxyl group (pectate),
reacting with Ca 2 +, a structure is formed; if it is only in 42 ~ of the residues (pectinate)
then no structure is formed. The observed changes of v with the p H of the solution
or Ca 2 + content do not depend on the content of polymer in the solution, in the range
o f 0.5--0-4~, which indicates the intramolecular nature of these changes.

175ec
5-

5~ !

30
I ~l 77 o I r
3 5 7 2H q -l°S/.c~,. ]
Fm. 2 Fm. 3
Flu. 2. Dependence of T on pH of solution of pectate with e=0'4 mg/ml (1) and pectinate with
3 mg/ml (2), CN=Cl=0"IN.
FIG. 3. Dependence of r on Cu ~+ ion concentration for pectate (1) and pectinate (2), pH 6-0, CN,ci
=0-1 N; c=0.02~.

As the polymer concentration in water increases by 50 times, no appreciable changes

in the r values are observed. For all the polyuronides, a smooth increase in r occurs
in the chosen concentration range, from 16-23 to 30 nsec (alginate, pectate) or from
35 to 60 nsec (pectinate).

Translated by C. W. CAPP
 Carbonization of polyimides 2641

REFERENCES

1. Ye. V. ANUFRIEVA and Yu. Yu. GOTLIB, Advances Polymer Sci. 40: 1, 1981
2. Ye. V. ANUFRIEVA, J'. Pure Appl. Chem. 54: 2, 533, 1982
3. V. P. YURYEV, Ye. Ye. BRAUDO and V. B. TOLSTOGUZOV, Coll. Polymer Sci. 261: 3,
210, 1983
4. V. P. YURYEV, I. G. PLASHCHINA, Ye. Ye. BRAUDO and V. B. TOLSTOGUZOV, Carbo-
hydrate Polymers 1: 2, 139, 1981
5. T. N. NEKRASOVA, Dis. na soiskaniye uch. st. kand. khim. nauk, p. 139, Polymers Institute,
U.S.S.R. Academy of Sciences, Leningrad, 1970

Polymer ScienceU.S.S.R.Vol. 27, No. 11, pp. 2641-2648, 1985 0032-3950]85 $10.00+ .00
Printed in Poland © PergamonJournals Ltd.

THE CARBONIZATION OF POLYIMIDES*

A. V. GRIBANOV, N. A. SHIROKOV, YE. F. KOLPIKOVA, G. N. FEDOROVA,

T . I . BORISOVA, A. I. KOL'TSOV, N. V. MIKHAILOVA, L. G. GLADKOVA, T. SEKEI a n d
Y u . N. SAZANOV

Polymers Institute, U.S.S.R. Academy of Sciences

(Received 2 April 1984)

Pyrolysis products of PM polyimide film (both volatile and solid) have been analyzed
by spectroscopy, electrical conductivity and by thermal and elemental analysis. The nature
of the structural changes occurring in the polyimide as the temperature was raised from 500
to 900 ° was determined. Part of the data permits the properties of pyrolyzed PM to be com-
pared with graphitic materials. A suggestion was made concerning the role of the imide ring
nitrogen in the process of condensed structure formation.

DURING studies of high temperature degradation of carbonized, thermally stable

polymers, especially of various polyheteroaromatic compounds, attention has been
turned to determination of the similarity of the kinetic characteristics of degradation
of these polymers and a series of graphite materials.
Actually, it was shown [1-3] that in directed PM pyrolysis [2-5], in a non-oxidising
medium, the formation of definite carbon structures occurs. Accordingly [4-6], the
conditions of polymer synthesis, their chemical structure, branching and heating rate
during pyrolysis all substantially affect such an important property as the degree of
graphitization [7].

* Vysokomol. soyed. A27: No. 11, 2351-2356, 1985.