JOURAAL OY lOLYR11511 SCIENCE: I A l i l A-2

V 0 1 7, ~ 897-907 (1969)

Lactone Polymers. 11. Hydrodynamic Properties and

Unperturbed Dimensions of Poly-c-caprolactone

J. V. KOLESKE and R. D. LUNDBERG,* Union Carbide Corporation, Chemicals and Plastics Technical Center, South Charleston, West Virginia 65303

Synopsis
Poly-e-caprolactone prepared by a dibutylzinc-catalyzed bulk polymerization process was fractionated, and the solution properties of the fractions were studied in benzene and in dimethylformamide. I n these solvents a t 3OoC the Mark-Houwink relations were [v] = 9.94 X 10-6 ii?wo.82 and 191 = 1.91 X 10-4 a i U p . 7 3 , respectively. The value of K e was found to vary from 1.1to 1.2 X 10-3 when determined by three known extrapolation techniques. Poly-e-caprolactone chains appear to be quite flexible in solution, and the steric hindrance parameter u had the low value of 1.37. Root-mean-square end-to-end dimensions were approximated from the experimental data and calculated from the Debye-Bueche and the Kirkwood-Riseman theories.

INTRODUCTION
Poly-ecaprolactone (PCL), +O-(CH2)j-CO+,, a t a variety of molecular weights has been known for some time. This paper deals with the solution properties of this linear polymer in benzene and in dimethylformamide. Unlike most condensation polyesters, PCL samples of high molecular weight can be readily obtained. An earlier paper in this series2 described the dynamic mechanical properties of PCL, and in a subsequent paper details of the bulk and solution polymerization will be d e ~ c r i b e d . ~

EXPERIMENTAL
Preparation of Poly-e-caprolactone
Relatively high molecular weight PCL for this study was prepared by a bulk process with dibutylzinc as an initiator a t a temperature of 60C. The resulting polymer was chipped, washed with methanol, filtered, and dried. Intririsic viscosity mcnsuremcnts in benzene and in dimethylform:Lmitlc (1)RIF) :it :30C rcsultcd in v:ilucs of 1.14 : b i d 0.S3 dl/g, res1)ectively. This iritrinhic vi-co4iy correspoiitlrtl to : L WciBht,-:ivt.l:Lg(~ nro1ecul:ir weight of S(i,OOO.
* Present address: Research and Development Department, Union Carbide Corp., Bound Brook, New Jersey. 897

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KOLESKE AND LUNDBERG

Fractionation
A benzene solution with a n initial PCL concentration of 0.7% was used for fractionation. Fractions were obtained by slowly adding n-heptane to the agitated solution at room temperature until turbidity was observed. After warming t o the solution point, the system was allowed to cool slowly to 30C, where it was maintained for 24 hrs. The precipitated polymer was easily recovered by decantation. With the exception of fraction 9, which was recovered by evaporation, this procedure was repeated for all fractions. The first fraction was omitted from the overall study for it contained residual catalyst and gave anomalous results. Fraction 4 contained about 18% of the whole polymer. A portion of this fraction was used for the study and the remaining portion was refractionated into two fractions. One of these fractions, 4B, was used. The other fractions each represented about 10%of the whole polymer.

Molecular Weight Measurement

Sedimentation velocity experiments were made in benzene a t 30C with a Spinco Model E ultracentrifuge and a standard An-D analytical head, a double-sector synthetic boundary cell, and schlieren optics. The centrifugations were conducted a t 50,740 rpm. Average sedimentation coefficients, S, were calculated in a manner described by S ~ h a c h m a n . ~ Values of S were obtained a t three concentrations and extrapolated to zero concentration by plotting 1/S as a function of concentration to obtain the average sedimentation coefficient at zero concentration, So. Viscosity measurements were made in benzene and in D M F with a Cannon-Fenske, modified Ostwald type, size 50, viscometer. The intrinsic viscosity was determined from plots of log (vS,/c) versus c. Weight-average molecular weights were calculated by means of the Flory-Mandelkern e q ~ a t i o n : ~

nm= 1.184 X

1W6 [7]1/2 [709/(1 - sp)]a/2

(1)

where 70 is the solvent viscosity, D is the partial specific volume of the poly, a mer, and p is the solvent density. The buoyancy factor, 1 - ~ p had However, the value of this value of 0.218 f 0.002 in benzene a t 30C. parameter for fraction 1, 0.246, was one of several indications that this fraction was anomalous. We suggest this anomaly is due to the presence of substantial amounts of catalyst residue. If one assumes the following relation t o hold,

a value of 0.223 is obtained for the unfractionated polymer. I n this expression wi is the weight fraction of fraction i and (1 - gp)* is the value of the parameter for the corresponding fraction. This calculated value is in

LACTONE POLYMERS

899

good agreement with the experimental value of 1 - i i p = 0.224 that was obtained for several unfractionated poly-E-caprolactone samples prepared with dibutylzinc as the catalyst. Elemental analysis confirmed that the catalyst was associated with fraction 1. Fraction 1 had a n intrinsic viscosity of 1.61 dl/g and a sedimentation coefficient of 4.02 X 10-13 sec-' in benzene a t 30C. The aw was 134,000 if the experimental 1 - bp was used in the calculations and was 160,000 if the average value 1 - b p = 0.218 was used. It is interesting to note that the higher molecular weight value for Fraction 1, is in agreement with the other data described in this paper.

RESULTS AND DISCUSSION

Table 1 contains the results from the experimental measurements. The Huggins constants k ' fall into the range of 0.34.4, indicating that both solvents are good solvents for PCL. All linear extrapolations in this study were made b y the method of least-squares to obtain the best mathematical fit of the data.
TABLE I Experimental Hydrodynamic Properties for Poly-ecaprolactone at 30C

So x 1013,

[VI,

dl/g

k '
Benzene
0.38 0.38 0.34 0.37 0.33 0.35 0.33 0.36 0.36 0.34

Bw
Fraction
2 3 4 5 4B 6 7 8 9
X

sec-' (benzene)
3.82 3.15 3.30 3.06 3.25 2.77 2.52 2.49 1.45 3.07

Benzene
1.70 1.49 1.31 1.09 1.03 0.91 0.76 0.54 0.26 1.14

DMF
1.19 1.05 0.95 0.81 0.75 0.65 0.56 0.44 0.22 0.83

DMF
0.42 0.40 0.39 0.39 0.42 0.39 0.42 0.39 0.40 0.41

Whole

1.50 1.05 1.06 0.86 0.91 0.68 0.54 0.45 0.14 0.86

The intrinsic viscosity determined a t 30C is shown as a function of molecular weight in Figure 1. These data may be represented by eqs. (3) and (4)
= =

9.94

x 1.91 x

10-5

~ ~ ~ 0 . 8 2

(3)

10-4

Bw0.73

(4)

in benzene and in DMF, respectively. The value of the exponent in the Mark-Houwink equation for benzene is above the Flory-Fox6 upper limit of 0.8. Thus, this factor could be taken as evidence for chain stiffness and draining effects. However, the more recent Kurata-Stockmayer theory7 allows exponents to be as high as 1.0 for flexible, nondraining polymers in

YO0
I.(

kOLESKE AND LUNDBEIIG

0.:

o
-0.5

0 0
J

-I

.o
4.0
45

5.0

5.5

LOG

Mw

Fig. 1. InLrinsic viscosity (dl/g) as a function of molecular weight for fractionated polye-caprolactone (0)in benzene and ( 0 )in dimethylformamide a t 30C.

4.0

4 . 5

5.0

5.5

LOG

Mw

Fig. 2. Sedimentation coefficient (see-') as a function of molecular weight for fractionated poly-tcaprolactone in benzene at 30C.

good solvents. The corresponding plot of average sedimentation coefficient determined in benzene at 30C. as a function of molecular weight is showri in Figure 2. These data may be represented by the expression

S O
[q] =

3.58 X 10-15

j$fw0.39

(5)

According to the Flory-Fox method,s the exponent in the expression KM" is related to the exponent, in the expression So = KIMb by the relat,ion
h
=

(2 - u)/3

(6)

Using the value a = 0 . U in cy. (4)yields a calculated value for 0 of 0.30 which agrees with the experimental exponent in eq. (6). Thus, the two exponents are consistent.

LACTONE POLYMERS

901

Unperturbed Dimensions
A number of graphical procedures are available for ob tainirig unperturbed dimensions of polymer molecules from intrinsic viscosity and molecular weight measurements in nonideal solvents. I n general all of these methods involve determination of the constant K e for the expression
[qle =

K,M'/'

(7)

In this expression K e is defined as

Ke
=

90 (GZ/M)"/"

with a0 as the asymptotic value of the Flory constant, 2.56 X 1021, and (ro2) as the unperturbed mean-square end-to-end distance. The Stockmayer-Fixman expressiong has a relatively simple form and is given by

[a]M-'/'

Ke

+ 0.51 @o BM"' + 0.950 K,"/Kk'/aM'/'

(9)

where B is a constant related to the specific volume of the polymer, the molar volume of the solvent, and the Flory interaction parameter ai. Another expression is that of Inagaki et al. :lo
[q]4/6i14-'/s = 0.786K,'l6

(10)

I n this equation k = 0.33 BM/(rO")"/". Cowiell has examined and compared the above equations in detail. I n addition, he has modified an expression of Bohdanecky,12and the result has the form
[7,1]1M-~/' = [@(t)/@O]Ke 0.9166 [ @ ( ~ ) / @ 0 ] K e k ' / ' ~ M ' ~ ~ (11)

The parameter @(E) has been dealt with by Ptitsyn and Eizner;13 it is the value of the Flory constant for the particular system being investigated [in a theta solvent @(E) = aO] and is given by
@(E)

= @o

(1 - 2 . 6 3 ~ 2 . 8 6 ~ ~ )

(12)

While the value of e is related to end-to-end dimensions of the polymer coil through the relation
r2 = K , B ( l

+ e)

(13)

it is also related to the exponent a of the Mark-Houwink equation by

E

( 2~ 1)/3

(14)

which allows it to be readily calculated. When expressions of this type are used, it is possible to obtain KO; and with this one may calculate (g)"/" from eq. (8). I n addition, [q]emay be found by means of eq. (7), and the molecular expansion factor atl is then calculable from
a! 2 =

([~l/hlo>'/3

(15)

902

KOLESKE AND LUNDBERG

Mv2

x 10-2

Fig. 3. Plot of the Stockmayer-Fixman expression, [eq. (9)] for poly-rcaprolactone

(0)in benzene and ( 0 )in dimethylformamide obtained by using smoothed data; for comparison, the experimental data in benzene ( X ) are shown by the dashed line.

With this parameter known, it is possible to obtain an estimate of the hydrodynamic weight-average root-mean-square end-to-end distance from
(r2)'/2

(cz)1'2
(16)

= a,, (;F;;i)'/2

itself yields a measure of the molecular size of Either this dimension or a,, the polymer chain in solution. It _ should _ be noted that eq. (16) is only a n approximation unless a,,= a = ( T ~ / T ~ ~and ) ~ / such ~ , an equality has not been established in this work. However, it is equally important to note that this approximation is not of great significance for the study. Equations (10) and (11) are expected to hold only over the range 0.5 6 a 6 0.8; however, eq. (9) should hold for values of a greater than 0.8.9 Since the exponents for the intrinsic viscosity-molecular weight relations determined in this study are less than 0.8 in one case and greater than 0.8 in the other case, it is interesting to compare results obtained by the three methods. The Stockmayer-Fixman expression was first used to evaluate K e as 1.0 X low3 from the experimental data obtained with benzene as a solvent, which are given in Table 1. To facilitate the calculations, the same expression was used on smoothed data obtained by selecting molecular weights and calculating intrinsic viscosities by means of eq. (3). I n this case K e was found to be 1.1 X Since these values were in good agreement, it was decided to use smoothed data for the determinations. Graphical representations of the various equations are shown in Figures 3, 4, and 5, and the K e values are shown in Table 11.

LACTONE POLYMERS TABLE I1 Comparison of Calculated Values of K e for Poly-ecaprolactone from Smoothed [7]-M Data Obtained in Two Solvents

903

K e X 108
Solvent Benzene Dimethylformamide
~ ~~

Eq. (9)" 1.1 1.2

Eq. (10)b 0.8 1.2

Eq. (lip 0.5 1.0

Data of Stockmayer and F i ~ m a n . ~ b Data of Inagaki e t al.10 0 Data of Cowie.I1

a

With the intrinsic viscosity values obtained in dimethylformamide, all three methods gave good agreement. However, when the intrinsic viscosity determined in benzene is used, only eq. (9) results in a K e in agreement with the values obtained from the dimethylformamide data. Equations (10) and (11) used with the benzene data yield results that are not in agreement with the other values of Ke. It is to be emphasized that the exponent of the Mark-Houwink equation is 0.82 when benzene is the solvent, and consequently it is not expected that these expressions should result in proper K e values, as was indicated above.

0 X

1 0

20

30

M 113

40

50

60

Fig. 4. Plot of the expression of Iriagaki et al.I0 [eq. (lo)] for poly-e-caprolactone (0)in benzene and ( 0 )in dimethylformamide.

TABLE I11 Configurational Parameters for Poly-ecaprolactone Calculated from K e Evaluated from Equation (9) I 7 1e
ffll

[71a

(rOz)'/',

(c)l/z, A
DMF
Benzene
73 103 163 230 325 7<5 106 167 237 334

aw
Benzene
0.11 0.16 0.25 0.33 0.49 1.10 1.17 1.2.; 1.32 1.40 0.12 0.17 0.27 0.38 0.54 1.20 1.29 1.42 1.53 1.64

Benzene

DMF
Benzene

DMF
DMF

Benzene

DMF
88 133 232 332 536
83 124 209 313 4.55

1 x 2 x 5x I x 2 x

104 104 104 105 105

0.19 0.34 0.71 1.25 2.21

0.16 0.27 0.53 0.88 1.47

* Calculated from Eqs. (3) and (4).

LACTONE POLYMERS

905

0 0
20

40

60

80

1 0 0

M1/20

Fig. 5. Plot of the Cowie expression [eq. ( l l ) ]for poly-ecaprolactone (0)in benzene and ( 0 )in dimethylforrnamide.

were calculated. With the K e obtained from eq. (9), a,, and Table I11 contains these results. Comparison of the values of ($)'/'obtained in benzene and in dimethylformamide indicates about only a 3% difference in the two solvents. The similarity of the unperturbed dimensions indicates that these two solvents have little or no effect on this parameter. Unless there is a complexing interaction between the solvent and the polymer, the unperturbed molecular coil dimensions are not expected t o vary from one solvent t o another. As would be suggested from the intrinsic viscosity measurements, a,, is greater in benzene, which is the better solvent. I n both benzene and dimethylformamide, a* is of the magnitude to be expected for polymer molecules in good solvents. The unperturbed mean-square end-to-end distance for the free rotation model of a polymer chain 3is given by
-

rof2 =

d 2 ( 1 - cos e)/(i

+ cos e)

(17)

where n is the number of carbon atoms in the chain, 1 is the bond length, and 8 is the valence angle. Assuming the ester group may be counted as 2 carbon atoms and taking 1 = 1.54A and 0 = 109.5", values of Tof2 were calculated. The ratio of [(ro")/(3)]1'' = u, which may be taken as a measure of the hindrance to rotation, was equal to 1.37. The low value for this hindrance parameter indicates the chain is a very flexible coil. Values of the end-to-end distance were calculated from the Debye-Bueche theoryI4 and the Kirkwood-Riseman theory15 t o attempt to visualize the shape of the molecular chains in solution. Debye and Bueche have pictured the polymer molecule as a permeable sphere containing the molecular segments in a uniform distribution. Within the sphere the molecular seg-

TABLE I V Comparison of Root-Mean-Square End-to-End Distances from Hydrodynamic Theory and Experiment
Benzene
(?)XE/
(Q)%a

R
P

DMF
be

ill

MU

(G2)1/28

(7)DB2

(p)DBvz

E
(T7)KRL/2

be

z
74 111 151 238 325 105 158 269 401 600 11.3 11.9 12.8 13.5 14.3

1x 2 x 5 x 1x 2 x 130 200 347 527 803 13.9 15.1 16.5 17.8 19.2 83 124 209 313 455

104 104 104 105 106

88 133 232 352 536

91 139 24 1 368 560

2 2

8
0

Calculated from eq. (16).

LACTONE POLYMERS

907

ments offer a variable resistance to flow. From this theory, the end-to-end distance is given by where C is a constant and cp(u) is a hydrodynamic parameter that is a function of the resistance to flow within the sphere. This parameter depends on the magnitude of the exponent in the Mark-Houwink relation. Kirkwood and Riseman took the polymer molecule t o be a random coil. The theory accounted for hydrodynamic interaction of the monomer units of the polymer and the effect of inhibited flow through the chain. The endto-end distance is expressed as
-

(1.2)KR1/2

b,(M/Mo)"~

(19)

where be is an effective bond length and M Ois the molecular weight, of a monomeric unit. The value of be is obtained from

be

C'{ [q] M~/'/M'/2XFo(X))'/s

(20)

where C' is a constant and X F o ( X )is a hydrodynamic parameter that depends on the draining characteristics. The value of XFo(X) may be obtained from the exponent in the Mark-Houwink expression and the revised tables of values given by Kurata and Yamakawa.I6 The results of these calculations are summarized in Table IV along with values of from eq. (16) and the experimental values of a7.

(c)'/'

References
1. W. H. Carothers, U.S. Pat. 2,071,250 (1937). 2. J. V. Koleske and R. D. Lundberg, J . Polym. Sci. A-.2,7,795 (1969). 3. R. D. Lundberg, K. B. Wischman, and J. V. Koleske, to be published. 4. H. K. Schachman, Methods in Enzymology, Vol. 4, Academic Press, New York, 1957, pp. 33-103. 5. L. Mandelkern and P. J. Flory, J . Chem. Phys., 20,212 (1952). 6. P. J. Flory and T. G Fox, J . Amer. Chem. SOC., 73,1904 (1954). 7. M. Kurata and W. H. Stockmayer, Fortschr. Hochpolym. Forsch., 3,196 (1963). 8. P. J. Flory, Principles of Polymer Chemistry, Cornell Univ. Press, Ithaca, N. Y., 1953, p. 629. 9. W. H. Stockmayer and M. Fixman, in First Biannual American Chemieal Society Polymer Symposium ( J . Polym. Sci. C, l), H. W. Starkweather, Ed., Interscience, New York, 1963; p. 137. 10. H. Inagaki, H. Suzuki, and M. Kurata, in US.-Japan Seminar in Polymer Physics ( J . Polym. Sci. C, 15), R. S. Stein and S. Onogi, Eds., Interscience, New York, 1966, p. 409. 11. J. M. G. Cowie, Polymer, 7,487 (1966). 12. M. Bohdanecky, J. Polym. Sci. B , 3,201 (1965). 13. 0 . B. Ptitsyn and Yu. E. Eizner, Soviet Phys. Tech. Phys., 4,1020 (1959). 14. P. Debye and A. M. Bueche, J . Chem. Phys., 16,573 (1948). 15. J. G. Kirkwood and J. Riseman, J . Chem. Phys., 16,565 (1948). 16. M. Kurata and H. Yamakawa, J. Chem. Phys., 29,311 (1958).

Received September 20,1968 Revised January 7,1969