Molecular Structure of Styrene= Butadiene Capolymers DYNAMIC MECHANICAL MEASUREMENTS L. E. Nielsen, Rolf Bnohdahl, and 6. C. Claver Monsante Chemical co., Springfield, Mass.
L
1
T h e dynamic shear modulus, mechanical damping, swelling properties in benzene, and infrared spectra have been determined on a series of styrene-butadiene copolymers which were prepared under a variety of polymerization conditions. Evidence is presented which indicates it may be possible to prepare a polybutadienerubber which retains its rubberlike properties down to -120" C. Materials of the same over-all composition were often found to differ greatly in structure as determined by these experimental methods.
Many of these differences can be explained in terms of various types of heterogeneity found in the copolymers. The temperature of maximum mechanical damping is primarily determined by the composition of the copolymer whereas the width of the damping peak is related to the heterogeneityof the material. The work reported here is part of an investigation of the differences in physical properties, of polymers of like composition, that occur as a result of changes in polymerization conditions.
I
T IS well known that the physical properties of a synthetic rubber are markedly affected by changes in the polymerization conditions and ingredients making up the polymerization recipe. These differences in properties in turn can only be the reflection of differences in the molecular structure of the materials. This is illustrated, for instance, by the difference between cold rubber and regular GR-S rubber (6). An even more striking illustration was reported by Schildknecht (1.4)with polyvinyl isobutyl ethers, where by changing the polymerization conditions the polymer can be made t o have either the properties of a rubber or of a rigid solid. At various times during the last few years, differences have been found in materials of the same over-all composition a t this laboratory. I n this preliminary work some of these structural changes have been investigated in more detail,
e
polymerization variables, where known, are given in Table I. The styrene content was determined from the refractive index (8). The extension of the refractometric method to determine the styrene content up t o 75% styrene in a butadiene-styrene copolymer was developed a t Monsanto's Central Research Laboratory. The study of the interrelationships between polymerization conditions, molecular structure, and physical properties is still in its infancy. The many properties of a rubber are a complex combination of both the intermolecular and intramolecular factors making up the structure of the bulk material. Any single experimental technique can be sensitive t o only part of these structural factors so that several types of experiments must be carried out t o characterize a given material. For this investigation three physical methods were chosen which tend t o be charExperimental Methods acteristic of widely different aspects of molecular structure. A series of styrene-butadiene copolymers prepared under a These experimental methods are dynamic mechanical tests, variety of conditions and composition ratios was used for this swelling measurements, and infrared spectroscopy. investigation. These materials were for the most part prepared Infrared spectroscopy can be used t o determine the relative by emulsion polymerization using well known techniques. They amounts of cis-trans isomerism and 1,2 or 1,4 addition in such have a styrene t o butadiene ratio greater than that found in polymers as several investigators have shown (a, 6, 16). This is GR-S. The composition of the copolymers and some of the an especially powerful method of determining the atomic groups and their configuration within the individual molecules. Swelling measurements in Table I. Composition and Properties of Copolymers solvents are useful for determining the percentage of maTemp. of Styrene, % CataReguMa?. terial that has been cross linked Deterlystb, latorc, Conversion, Gel, Swelling [goyf Dam Ing, Copolymera Charged mined % % % % Index Fraction 0 8. t o give a network structure and the closeness of the cross 1 60 60.0 0.3 A 0.2,M 93.6 66.6 65.8 0.639 +7 0.3:A 2 60 57.5 0.8, M 96.3 0 . . . 0.612 +4 links in the network. 0 3 A 3 60 54.2 71.4 0.2,M 0.5-1.0 140 1.53-1,62 -5 0:5:A 44.5 93.5 0.2,M 112 10.4 1.51 . . . Dynamic mechanical tests, 0.5 A 44.5 95.9 0.8,M 124 21.6 1.255 ... in which an elastic modulur 91.2 55.8 0 l b B 0.6,N 8.2 150 1.774 . . . 0 : 15' B 0 . 2 N ... 52.3 34.8 1.38 ... and damping are measured 57.8 0 . 3 , b 1 . o : o 92.2 I 42.5 0.943 ... 58.0 0.3,A 0.5, 0 87.4 2 1 . 6 5 0.181 over a temperature range, are 59.5 0.3,A 0.5,0 90.24 88.4 0.150 23.8 +5 useful for determining the re0 3 A 1.0,o 92.2 86.3 0.653 25.6 ... 0:3: A 0 . 8 ,M 49.1 94.8 0.708 54.3 sponse of various structural ... ... ... 78.5 27.4 ... 0.328 +'io 14 .. 43.5 ... ... 84.1 . . . 0.265 17.3 ... units in a substance t o an ap44.0 ... 80.9 15 50 25.4 ... 0.5725 - 12 plied mechanical force. By 16 85 .. .. .. . . . Yes' . . . ... . . . ... 79 . . . No 17 85 ... ... ... ... ... this method transitions in poly5 Cop01 mers 1-12 were polymerized a t 50' C.; copolymers 13-17 are commercially available. mers and an indication of the b A = 8umene hydroperoxide. B = potassium persulfate. 0 M = mixed tertiary mereapian; N = dodecyl (kerosene) mercaptan; 0 tertiary C I mercaptan. ~ degree of molecular heterogeneity can be established. The ,
..I
t . .
+
-
341
INDUSTRIAL AND ENGINEERING CHEMISTRY
40
Vol. 43, No. 2
Much the same type information can be obtained from a r r w p test as from swelling measurements-for instance, a rubber that is mostly in the form of a gel will deform when a comtant force is first applied, but the deformation will not increase much with time because the network structure prevents viscous Row. Thib is illustrated by curves 1 and 3 of Figure 1. Here compliance rather than deformation is plotted, but for a constant load or stress the compliance is proportional to the deformation. A low molecular weight, noncross-linked rubbei will give a creep curve in 71-hich the deformation increases linearly with time bwause viscous flow can occur. This is illustrated by curve 4 of Figure 1. High molecular weight, noncross-linked rubbrrs or rubbers in which there is only a moderate amount of gel give creep curves between these eutremes. Surh rubbeis are shown in curves 2 and 5 of Figure 1. These creeprurwawrreobtaiiiedwithaparallel
t TIME-SEC.
80
Y
y, I
6C
1000
2000 TIME -SEC.
3000
Figure 1. Creep of Styrene-Butadiene Copolymers Measured 50" C. above Transition Temperature Curve 1 = 13; curve 2 = 3: curve 3 = 15; c u r v e 4 = 2; curve 5 = 1 (Tnhle I)
2
0 IP K 0 v)
m 4
of dynamic mechanical methods for deterniining structure is quite new and is only beginning t o be explored ( 1 , 11, 15). There is still much t o be learned in this field, but in metallurgical fields especially such methods have been of great value ( 1 7 ) . UYB
be
2c
Hesultw Swelling Measurements. Swelling measurements were made in benzene on these rubbers The measurements give three quantities that are characteristic of a material: the ratio of sol to gel, the swelling index of the gel portion, and the intrinsic viscosity of the soluble portion ( 4 , 6). The experimental trchniques used in these measurements have been described in the reports of the Rubber Reeerve Co. (6). Most of the experiments were carried out a t 25" C. (Table I). The results are in general agreement with the findings of other investigators. High conversions in the polymerization stage tend to give rubbers in which most of the material is a gel. l'olymeiieation regulators such as mercaptans decrease thr amount of material in the gel phase and usually decrease the intrinsic viscosity of the sol fraction but not in all cases. If most of thtl material is in the gel phase, then it is possible for the intrinsic viscosity of the soluble portion to actually increase as the amount of regulator is increased. I n general, rubbers having a low gel content also have a high swelling index (4). If the cross-linking ieactions have occurred only t o the extent of giving a small amount of gel, then this gel, itself, will have a low concentration of cross-linking points so that it is capable of swelling t o a very large volume. This general trend, however, is quite dependent on the catalyst, regulator, and other polymerization conditions so that there is not a unique value of the swelling index for a given gel content.
I
10.0 10.5 11.0 WAVE LENGTH I N MICRONS
Figure 2. Infrared SDectra o € -Styrene-Butadiene Rbbbers (Table I) A = sol fraction; B = gel fraction; each curve displaced about 5 % ; bottom one i n proper position
plate plastometer (2) a t a temperature of 50" C above the transition temperature of each rubber The method of obtaining th1transition temperature %ill be discussed later As Moonej (9) has pointed out, therr are certain advantages in making comparative teats a t equal temperatures above the transitioii temperatures rather than a t a single temperature for all t h r rubbers. Infrared Spectra. Infrared spectra of these copolymers have been determined from 2 . 5 t~o 16p using a Perliin-Elmer Model 12B spectrometer. The most interesting differences appeared in the neighborhood of 11p The initial work was done on thin films, but later solutions of the rubbers in carbon disulfide were found t o be more satisfactory. Some of the infrared absorption curves are shown in Figures 2 and 3. I n rubbers 1, 13, and 17
INDUSTRIAL AND ENGINEERING CHEMISTRY
February 1951
both the gel and sol fractions were studied. For rubber 1, the ratio of styrene t o butadiene was the same in both the sol and gel fractions; however, there was less 1,2- and trans 1,caddition in the gel portion. This means t h a t relatively more of the butadiene was in the cis 1,4-configuration (3, 6, 16). The gel fraction of rubber 13 contained a considerably higher ratio of styrene to
343
t o twipt and untwist as it carries out free vibrations. The oscillatory motion of the specimen is converted into electrical potentials by means of a linear variable differential transformer on a torque measuring device attached to one of the specimen clamps. The electrical potentials are eventually recorded on the chart of a direct writing magnetic oscillograph. The shear modulus is calculated from the frequency of the oscillations and the damping is determined from the logarithmic decrement or rate a t which the oscillations die down. The frequency was not constant during the course of a test but was roughly 0.2 cycle per second.
Table 11. Amodnt of 1,2- and trans 1,4-Addition of Various Copolymers Copolymer No.
Styrene/ Butadiene
l,2-Addition,
Trans 1,4-Addition,
%
% 48 37 28 37.8 24.8 21
IO 0 WAVE
IO 5 110 LENGTH IN MICRONS
Figure 3. Infrared Spectra of Styrene-Butadiene Copolymers (Table I) A = sol fraction: B = gel fraction; P = polystyrene; each curve displaced about 15%; bottom one in proper position
'
e
butadiene than the sol portion. It appeared that the reverse was true for rubber 17, but it was impossible t o make a n accurate determination to check this point with certainty. The absorption spectrum of rubber 10 showed that there were considerable
\
amounts of -C-0
/
\
and C-0
/
linkages in the material.
Figure
3 shows part of the absorption curves of rubbers 16 and 17, which had the same styrene t o butadiene ratio but which were quite different in physical properties because of differencesin polymerization conditions such as regulator concentration. One of the differences in absorption spectra was a shift in the 1 1 . 0 ~band to 11.1~ for copolymer 16 and the sol portion of copolymer 17. Vinyl compounds ( 1,2-addition) are characterized by a n absorp tian band a t 11p whereas polystyrene has an absorption band a t about 11.1~. The observed shifts might be explained by the polystyrene band overlapping the vinyl band in a product which has only a small amount of 1,a-addition. Data on the percentage of 1,Z- and trans 1,4-addition, based on the amount of butadiene in the rubbers, are presented in Table 11. Dynamic Mechanical Properties. A recording dynamic mechanical tester based on the principle of a torsion pendulum was used t o determine the shear modulus and damping over a temperature range (IO). I n this apparatus the plastic or rubber specimen is attached t o a moment-of-inertia disk and is allowed
-2 0
I
0,
,
,
,
20 ,
,
TEMPERATURE OC.
Figure 4.
Dynamic Shear Modulus of Styrene-Butadiene Copolymers 0 = 15; X = 13; 0 = 2; A = 3 (Table I)
Tho variation of the shear modulus with temperature is illustrated in Figure 4 for four rubbers. All the rubbers change from the rubbery state t o a hard, rigid state over a narrow temperature range. I n the temperature range where the modulus is rapidly changing, the damping goes through a maximum as is shown in Figures 5 and 6. The dynamic properties of a material can for the most part be characterized by the temperature at which the damping is a maximum and by the width of the damping peak. The temperature of maximum damping has been shown for various types of high polymeric materials t o occur in the neighborhood of the second order transition temperature. I n general at low frequencies the temperature of maximum damping is a few de-
INDUSTRIAL AND ENGINEERING CHEMISTRY
344
Vol. 43, No. 2
temperature region for many polyniera. J The difference between these figures, -120" C. and -70" C., must partly be due to the large amount of cross linking, crystallinity, and other differences in molecular structure that occur as more and more butadiene is added t o the rubber. The question immediately arises; is it proper t o use this linear plot t o extrapolate t o a pure polybutadiene rubber? Experimental work on other copolymer systems and on plasticized polymers indicates that a plot of temperature of maximum damping against volume fraction of one of the components is linear throughout the whole of the composition range ( 1 2 ) .
5-
TEMPERATURE 'C. Figure 5 . Mechanical Damping (Logarithmic Decrement) of Styrene-Butadiene Copolymers
0 = 15; X
= 13;
0 = 2 (Table I)
grees higher than the second order transition as determined by volumetric measurements.
Discussion The temperature of maximum damping of various styrenebutadiene copolymers is plotted against the percentage of butadiene in the copolymer in Figure 7. The butadiene, of course, lowers the temperature of maximum damping as it increases in concentration. The polymers were made over a wide range of polymerization conditions, yet the points do not scatter much from a straight line. The one rubber showing the greatest deviation might be expected to behave in this way because of its broad and unsymmetrical damping peak. An interesting point about the data given in this graph is that they extrapolate t o - 120 C. for pure polybutadiene &hen replotted on a volume fraction basis rather than a weight fraction basis. This would indicate t h a t i t should be possible t o prepare a butadiene rubber which still retained its rubbery characteristics down t o -120' C. Polybutadiene as it is normally prepared begins to harden in the neighborhood of -70" C. [Wiley (16) lists the second order transition of polybutadiene at -85" C. and its brittle point as -66" C. It is known that the maximum in damping occurs in the same O
i
-20
,
20
0
TEMPERATURE
'G.
Figure 6. Mechanical Damping (Logarithmic Decrement) of Styrene-Butadiene Copolymers = 3;
x
= 1:
0
= 10
(TableI)
J
I
IO
Figure 7.
2,o 30 40 % BUTADIENE
5p
\
Transition Temperature of StyreneButadiene Copolymers
The temperature of maximum damping can thus be predicted quite accurately, in general, from the composition of the copolymer. However, the width and general shape of the damping peak cannot be predicted from the over-all composition of a material. Rubbers of about the same over-all composition but polymerized under different conditions show marked differences in the width and shape of the damping peak. The results plotted in Figures 5 and 6 bring out this variation. The causes of these differences are not completely understood, but certain facts are becoming clear. For instance, rubbers poIymerized in the presence of considerable amounts of regulators will have sharper damping peaks than those prepared under the same conditions but without a regulator. It is also a general charaeteristic of high polymeric materials that sharp damping peaks are accompanied by correspondingly sharp changes in the modulus with temperature. This is illustrated by Figures 4 and 5 which give the damping and moduli for the same three rubbers. The effect of polymerization regulators is illustrated further in Figure 8. Both of these materials contain about 85% styrene. In Figure 8 the entire damping peak is not shown but only a part of the low temperature portion where the damping rapidly increases with temperature. At temperatures higher than those shown, the damping goes through the same kind of a maximum as the curves shown previously. These materials have such a high styrene content that they are not rubbers at room temperature. The regulated copolymer was hard and very brittle a t 2 5 ° C . It had a small mechanical damping a t room temperature and a
INDUSTRIAL AND ENGINEERING CHEMISTRY
February 1951
very sharp transition region from a hard t o a rubbery material starting a t about2 55” C. The unregulated copolymer, on the other hand, was hard but very flexible a t room temperature and had a milky appearance. The damping was higher even a t temperatures considerably below room temperature. The transition region from a rigid material t o a rubbery material was broad and ended a t a temperature well above t h a t of the regulated copolymer
”
0
Figure 8.
6,O
OC.
Mechanical Damping of Styrene-Butadiene Copolymers
=I.
.c
‘
40 TEMPERATURE
16; X = 17 (Table I)
because some of the molecules contained more than their share of butadiene, leaving the larger portion depleted in butadiene. These differences between the two materials can largely be explained in terms of a molecular homogeneity. In the regulated copolymer it seems nearly all the molecules have about the same ratio of styrene to butadiene. However, in the unregulated copolymer some of the molecules are almost entirely made up of styrene; some contain a large amount of butadiene, and other molecules have all types of composition ratios between these extremes. In other words, the unregulated material is heterogeneous on a molecular scale. It is known that regulators tend to lower the molecular weight of a polymer and t o make the molecular weight more uniform (4, 7). The evidence presented here indicates t h a t in some instances they also can have the additional effect of making the polymer more uniform with respect t o molecular composition. These results indicate that various kinds of heterogeneities must exist in styrene-butadiene copolymers. The swelling measurements show the existence of one type of heterogeneity in which the copolymers are a mixture of a gel portion and a soluble portion. A comparison of the swelling measurements with the dynamic tests shows that there is a trend toward broad damping peaks with high gel content in the rubber, but there are exceptions. Above the temperature of maximum damping, the rubbers with low gel content and low intrinsic viscosity have lower than usual shear moduli. The modulus of noncross-linked rubber which has a high intrinsic viscosity, however, gives a normal shear modulus comparable t o t h a t of a cross-linked material. This indicates that dynamic modulus need not depend on the degree of cross linking. However, even in noncross-linked material, a certain degree of compositional heterogeneity must exist. All the molecules do not contain the same ratio of styrene t o hutadiene, so there is a distribution in molecular composition. The width of this distribution can be varied considerably by changing the polymerization conditions. For instance, this distribution can be made quite narrow by polymerizing t o low degree of conversion by the presence of a regulator ( 7 ) . Still another type of
3 45
heterogeneity arises from the distribution in molecular weights of the soluble molecules or the distribution in molecular weight between cross links in the gel portion of a rubber. The effects of these types of heterogeneity on the physical properties of a rubber have never been thoroughly investigated except for molecular weight. Dynamic mechanical tests offer one method of studying these effects. There are definite indications t h a t the width and general shape of the damping versus temperature peak are closely related t o compositional heterogeneity. For instance, copolymers 2 and 3 in Table I are much more homogeneous than copolymers 15 and 17. The damping peaks for both copolymers, 15 and 17, are so broad and unsymmetrical t h a t the transition is shifted t o higher temperatures than what would be expected on the basis of their over-all composition. The differences found by dynamic tests and by swelling measurements cannot be detected by infrared spectroscopy in general. The percentage of styrene in a copolymer can be determined from bhe absorption spectra, and the composition, of course, usually determines the transition temperature range where the damping goes through a maximum. It is t o be expected t h a t 1,Saddition on a copolymer would givc B different transition temperature than one containing either all cis or trans lJ4-addition. However, the variation in these configurational factors was not great enough in the rubbers that were studied t o be able t o detect them definitely by means of shifts in the transition temperature. The differences between normal and cold GR-S give indications of what can be expected along this line, but more work is obviously needed in this field. There is a n indication t h a t low amounts of 1,2addition give broader damping peaks than larger amounts of this type addition. Finally, no correlation was fouqd between the swelling properties and the infrared spectra. The concentration of cross links giving rise t o gel formation is so small t h a t any differences in absorption due t o them are very difficult t o detect.
Acknowledgment Most of the copolymers described here were prepared by George Wesp and Forrest Norris.
Literature Cited (1) Ballou, J. W., and Smith, J. C., J . A p p l i e d phus., 20, 493 (1949). (2) Dienes, G. J., and Klemm, H. F., Zbid., 17, 458 (1946). (3) Field, J. E., Woodford, D. E., and Gehman, S. D., I b i d . , 17, 386 (1946). (4) Flory, P. J., J . Am. Chem. Soc., 69,2893 (1947). ( 5 ) Hart, E. J., and Meyer, A. W., I b i d . , 71, 1980 (1949). (6) Hulse, G. E., Hobson, R. W., Wall, F. T., Johnson, B. L., Yanko, J. A,, and Flory, P. J., Office of Assistant Rubber Director for Research and Development of Synthetics; General Report No. 4 (January 1944). (7) MacLean, D. B., Morton, M., and Nicholls, R. V. V., IND. ENG.CHEM.,41, 1622 (1949). (8) Madorsky, I., and Wood, L. A., National Bureau of Standards Rept., Procedure for Measurement of Refractive Index of GR-S (January 1946); unpublished data of Monsanto Chemical Co. (9) Mooney, M., and Black, S.,C a n . J . Research, 28F,83 (1950). (10) Nielsen, L. E., Rev. Sei. Instruments, to be published. (11) Nielsen, L. E., Buchdahl, R., and Levreault, R., J . A p p l i e d Phys., 21, 607 (1950). (12) Nielsen, L. E., Pollard, R. E., and MoIntyre, E., J . Polymer Sei., in press. (13) Nolle, A. W., Ibid.,5,1 (1950). (14) Schildknecht, C. E., Zoss, A. O., and McKinley, C., 1x1).ENG. CHEM., 39, 180 (1947). (15) Treumann, W. E., and Wall, F. T., A n a l . Chem., 21,1161 (1949). (16) Wiley, R. H., Brauer, G. M., and Bennett, A. R., J. Polymer Sci., 5 , 609 (1950). (17) Zener, C., “Elasticity and Anelastibity of Metals,” University of Chicago Press, 1948. RECEIVED October 4, 1950.
