Molecular weight - viscosity relationships for a broad molecular weight

distribution polymer
H. K H . M A H A B A D
A NI D L. ALEXANDRU
Xerox Research Centre ($Cotlnrlrr, 2660 Speokr?lntl Drive. Mi.s.si.r,srrrrgrr.0111..
Cnrlrr(lr1 L5K 2Ll
Received February 28, 1984
This poper is rledicrrterl to tile 10th c t t ~ t ~ i v e ~of'
s ~the
r r ~Xerox
~ Resetrrr.il Centre qf' Cotlrrrln

H. KH. MAHABADI and L. ALEXANDRU. Can. J . Chem. 63, 221 (1985).

A novel and simple method is described for evaluation of molecular weight - viscosity relationships for a polymer whcrc
only broad molecular weight distribution samples arc available. The method demands measurement of the intrinsic viscosity
and GPC chromatograms of several samples. Results of applying the procedure to bisphenol A - Diethyleneglycol (50:50)
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copolycarbonate are prcscnted.

H. KH. MAHABADI et L. ALEXANDRU. Can. J . Chem. 63, 221 ( 1985).

On dkcrit unc nouvelle mCthode simple permcttant d'Cvaluer Ies relations poids molCculaire vs viscositk de polymitres pour
lesquels on ne dispose que des Cchantillons pour lesquels la distribution des poids molCeulaires est large. La mCthode implique
des mesures de viscositi intrinstque et des ehromatogram~nesen phase gazeuse de plusicurs dchantillons. On rapporte les
. .
rksultats obtenus lorsqu'on a appliquC la mCthode i un Cchantillon de polymi-re de bisphCnol - A/didthyltneglyeol (50/50).
. . [Traduit par Ie journal]

Introduction
In order to interpret a gel permeation chromatograph (GPC)
of any polymer sample in terms of its molecular weight distri-
bution, it is necessary to establish a quantitative relationship
Can. J. Chem. 1985.63:221-222.
where o;and [q]; are the weight fraction and intrinsic viscosity,
respectively, of all species which exit the GPC columns with
elution volume vi. The denominator in eq. [ I ] is equal to the
intrinsic viscosity [q], of the whole sample GPC solvent. The

between molecular weight M and elution volume v. It is well- values in numerator are available from GPC chromatogr;~mand
known that well-characterized narrow distribution polymer universal calibration curve. Jj = [q],Mi can be read ditectly
samples are the most appropriate for GPC calibration purposes. from the universal calibration curve and wi is equated to the
Such samples are, however, difficult to prepare with the excep- ratio of the area of the GPC detector response at elution volume
tion of polystyrene, for which good standards are readily avail- vi to the total area under the GPC chromatogram.
!
i
!
able. The M-11 relationship for any other polymer can be
obtained using the familiar universal calibration procedure
For a polydisperse polymer, the Mark-Houwink equation
relates [q] to the viscosity average molecular weight M,.
(1, 2) and a reliable pair of k and a constants for the Mark-
Houwink- Sakurada equation.
The evaluation of the Mark-Houwink constants k and a for If the whole polymer is considered to be con~posedof a
a particular polymer-solvent system normally requires the mixture of monodisperse species each with molecular weight
preparation of a series of samples having a wide range of Mi, weight fraction o , , and intrinsic viscosity [q]; in GPC
molecular weights and their subsequent characterization by solvent, then
light scattering and dilute-solution viscosity. However, gel
permeation chromatography (GPC), i.e., size exclusion chrom- [3] M,. = (Cwj~:)llU
atography can provide a convenient alternative route to k and and
a (3- 10). In this case k and a can be estimated using un-
fractionated polymer samples of known M,, or M,,,and intrinsic [4] J, = [rl],M, = KM," '
viscosity. Equation [2] can be written in terms of M,
In this work a new and simple method which permits the
facile determination of the Mark-Houwink constants using
hydrodynamic average molecular weight. M , ( 1 I ) , is where 6 is given by ( 12)
presented. The method described uses a combination of gel
permeation chromatography and intrinsic viscosity measure-
ments for several broad molecular weight distribution samples. If the parameter 6 remains constant through the change of [q]
As an example of the use of this method, molecular weight and M,, then a log-log plot of [q] vs. M, gives the expected
- viscosity relationships for bisphenol A - diethyleneglycol straight line relationship. The constants a and K , can be
copolycarbonate were found. obtained from the slope and intercept of such lines, re-
spectively. Then constant k = K , / 6 can be estimated utilizing
Theory
e q PI.
In a recent publication by Rudin et L I ~ .(1 I), the use of a new As reported earlier (12) 6 , for polymer samples having the
molecular weight average, M,, to characterize polymer samples same polydispersity or having very broad M W D (M,,./M,,2 4),
of heterogeneous composition have been proposed. M,, the is constant.
hydrodynamic volume average, is defined according to
Experimental
Cw,[ql,M, - Cw,J,
[I] a;r,
=
I w , [.ll,
--
[TI
Copolyc.trrbor~nte.syt~the.si.s
Bisphenol A (BPA) - diethyleneglycol (DEG) copolyearbonates
 222 CAN. 1. CHEM. VOL. 63. 198.5

TABLE1. Calculated values of 6 and k

Copolycarbonate
samples 6" l@'kh (dL/g)

" 6 calculated from eq. [6] using a = 0.68.

" K calculated from K = k,/6 using K , = 0.00022 dL/g.
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TABLE
2. Viscosity results of copolycarbonate samples

Copolycarbonate [TI [TI %

samples measured (dL/g) calculated (dL/g) Difference
CPC 121 0.740 0.764 +3.2
CPC 108 0.139 0.130 -6.5
FIG. I. In [TI VS. In M, for cpc in THF at 35°C (M,,/M,, 2 4.5).
ten as:
were synthesized by solution polycondensation of BPA and DEG
bischloroformate using CHZCIZ as solvent and pyridine as the acid
acceptor. The polymerization was carried out at low temperature and
Using this relationship and universal calibration curve any av-
Can. J. Chem. 1985.63:221-222.

atmospheric pressure. The polyn~ermolecular weight was changed by

varying the concentration of DEG bischloroformate. All polymers erage molecular weight of this copolymer can be calculated.
synthesizedare linear and have very broad molecular weight distribu- The precision of the proposed methods which use M,-[q]
tion (M,,./M,, 2 4.5). data to calculate K and a is tested here by comparing measured
Gel pertneotion clirornntogrophv and calculated [q] Two additional copolycarbonate samples
A Water Associates GPC equipped with a high pressure solvent were used for this purpose. Using the estimated values of K and
delivery (model 150C) was used. THF solutions of concentration less a and GPC chromatogram, M,.and then [q]of these two sam-
than 2 mg/mL were used. The flow rate, through a set of six p ples were calculated. Good agreement is observed between
styragel packed columns was I mL/min. The nominal size (in A) of measured and calculated [q]values as shown in Table 2. The
p styragcl packings were 100, 500. lo', lo4, lo5. 10". A calibration difference between corresponding [q]values are small consid-
curve based on elution volumes of I I polystyrene standards from ering possible experimental uncertainties.
Pressure Chemical Company was constructed. The relation between In summary, the proposed method for determination of mo-
molecular weight of PS and elution volume was obtained using a third
degree polynomial. The coefficient of this polynomial was adusted for
lecular weight viscosity relationship outlined in this report has
axial dispersion effects using an optimization method reported in the the advantage of being fast, convenient, and eliminates all
litcraturc (13). Then, the corrected relationship between molecular fractionation problems related to monodisperse sample prepa-
weight of PS and elution volume was transferred to a universal cali- ration and should be very useful for the characterization of
bration curve using the intrinsic viscosity of PS standards. highly specialized polymer products.
Intrinsic vi.sc.osity mea.surernerzt.s
The intrinsic viscosities were determined using a Canon-Ubbclohde I. Z. GRUBISIC, P. REMPP,and H. BENOIT. J . Polym. Sci. B, 5, 753
( 1967).
viscometer. All viscosities were obtained in THF and at 35OC (GPC
conditions). 2. A. RUDINand H. L. W. HOLGY. J . Polym. Sci. A-I. 10, 217
(1972).
~ e s u l t sand discussion 3. A. R. WEISSand E. C. GINSBERG. J . Polym. Sci. B, 7, 349
(1969).
The hydrodynamic volume average molecular weights of the 4. A. L. SPATORICO and B. COUTLER. J . Polym. Sci. Phys. Ed. 11,
polymer, M , , were estimated using eq. [I]. The right-hand side 1139 (1973).
of eq. [I] was evaluated by treating the normalized GPC chro- 5. H. K. MAHABADI and K. F. O'DRISCOLL. J . Appl. Polym. 21,
matogram data in a computer program. The calculated values 1283 (1977).
of M , along with [q]data were applied to eq. [5] and using least 6. C. J . B. DOBBIN, A. RUDIN,and M.F. TCHIR. J . Appl. Polym.
square analysis K, and a were estimated. A log-log plot of [q] Sci. 25, 2985 (1980).
vs. M , for BPA-DEG polycarbonate is shown in Fig. I . Using 7. X. ZHONGDE, S. MINGSHI. N. HADJICHRISTIDIES, and L. J . FET-
GPC chromatogram and estimated value of a along with eq. TERS. Macromolecules 14, 159 1 ( 1981 ).
[6], 6 and therefore K for each sample was estimated. The 8. M. SZESZTY and F. TUDO'S.Polym. Bulletin. 5. 429 (198 I).
results are summarized in Table 1. It is clear that variation for 9. P. SZEWCZYK. J. Appl. Polym. Sci. 26, 2727 (1981).
10. H. KH. MAHABADI. J . Polym. Sci. Phys. Ed. 22, 449 (1984).
the calculated values of 6 is less than 3%. The fact that 6 is 11. J . M. GOLDWASSER, A. RUDIN, and W. L. ELSDON. J . Liquid
independent of MW and MWD of these samples indicate an Chromatogr. 1-5, 2253 ( 1 982).
accurate K and a estimation. The calculated values of K and a 12. H. KH. MAHABADI. J . Appl. Polym. Sci. In press.
can be used to establish a relationship between [q]and molec- 13. J . N. CARDENAS and K. F. O'DRISCOLL. J . Polym. Sci. Polym.
ular weight of copolycarbonate. This relationship can be writ- Lett. Ed. 13, 657 (1975).
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Can. J. Chem. 1985.63:221-222.