THE APPLICATIONS OF INFRARED SPECTROSCOPY TO POLYMERS, PARTICULARLY 1,3 DIENE POLYMERS Joun L. Binver CamuicaL axp Puysieau Resrance Lanonatontra, Tur Finestoxe Tine ‘& Rossen ComPany, AKRON, OHIO CONTENTS I. Introduction . Microstructure determinations... Polybutadienes............ Polyisoprenes....... Polypiperylenes. .... Polydimethylbutadiene... Analyses of various polymers General... = TIL, Structure and spectra. a IV; lsomeriaation V. Crystallinity... VI. Determination of methyl groups VII. Oxidation . VIII. Vulcanization. IX. Rubber derivatives. .... X. References....... I. INTRODUCTION As a result of the discovery of methods for making stereospecific polymers, the whole field of polymer chemistry has broadened considerably from its state in the early post-war years. Infrared spectroscopy has played an important role in the study and development of such polymers and has been applied to the study of polymer features which were not considered before the advent of stereospecific polymers. The present review is concerned with some of these applications, particularly to 1,3 diene polymers, such as microstructure deter- minations, polymer spectra and structures, isomerization, degree of crystal- linity, vulcanization, and rubber derivatives. The survey covers the literature to the end of 1960. "Some of these applications are discussed in a book edited by Clark? and applications of infrared spectroscopy to other types of polymers are also discussed there. _Krimm! has published an excellent paper on the theo- retical analyses of some polymer spectra which leads to assignments of many of the bands in the spectra of the polymers. Diene polymers were not discussed by him but the method he developed should be applicable to such polymers. There are some limitations to the applications of infrared spectroscopy and, since some of them are especially pertinent in connection with polymer studies, it seems worthwhile to mention them here. It is often stated that an infrared spectrum of a substance or compound is a fingerprint of that material. From 8758 RUBBER CHEMISTRY AND TECHNOLOGY this it is frequently concluded that an infrared spectrum will identify an un- known substance. Generally this is correct if the unknown substance is a pure compound and if a spectrum of a known compound can be found which is a duplicate of that of the unknown. If the substance is a mixture difficulties arise which are illustrated by the following example. Suppose a spectrum of a substance has @ band at 10.34 y. If it is quite intense (0-60%, transmission) it can be concluded quite probably that trans CH=CH groups are present and a determination of the unsaturation chemically would, in most cases, make the conclusion certain. If the band is weak (85-95% transmission) it may or may not be due to a trans CH=CH group because spectra of many compounds have weak bands at or near this wavelength and the compounds are known to be saturated. In such a case other evidence is necessary before a decision about the presence of a trans CH=CII group can be made. Another type of limitation arises in quantitative analyses by infrared spec- troscopy. In quantitative analyses it is necessary to make calibration curves, using standard substances, from which the absorptivities of the bands needed for the analyses are derived. If the mixture being analyzed is one of pure compounds the standard substances used are the pure components of the mix- ture. In these cases the mixtures can be accurately analyzed. If the mixture is a polymer the proper standard substances are rarely available and conse- quently the accuracy of the analysis becomes less. The following example will illustrate this difficulty. Suppose it is desired to determine the amount of trans CH=CH in a polymer which contains no other unsaturation. The standard substance required for the calibration curve of the 10.34 w band is a pure all trans CH=CH polymer. If this is available the amount of trrns CH=CH in such an unknown polymer can be determined. (Another con- sideration enters here which is discussed under Microstructure Determinations.) If the purity of the standard polymer is open to question, the certainty of the results of analyses is open to question. This is often the case. Despite these limitations the application of infrared spectroscopic methods to polymers have been fruitful. By quantitative analyses (although the accuracy may be small, the precision can be large), it is almost always possible to say that polymer A has more of one structure than polymer B, which in turn may outrank polymer C. Often this information is sufficient for the polymeri- zation chemist. In qualitative analyses, many band assignments are known well enough that the appearance of a particular band with fair intensity in cates the presence of a definite structure with great probability. ‘These limita- tions are inherent in all of the following discussion but, in many cases, methods of reducing the uncertainty caused by them are also given. II, MICROSTRUCTURE DETERMINATIONS Polybutadienes—Since the article on the determination of the microstru tures of polybutadienes was written for the Encyclopedia of Spectroscop: there have been some developments arising from the preparation of polybuta- dienes containing all, or nearly all, cis CH=CH or trans CH=CH or side vinyl CH, =CH groups. The effect of these on the determination of the micro- structures of polybutadienes has been discussed by Binder, As is shown there the spectra of atactic 1,2 polybutadienes have bands at about 13.7 and 14.4 and cis CH=CH polybutadicnes have a complicated long wave (13-15 u) ab- sorption spectrum. Hence the determination of cis-1,4 by measurements in the 13-15 p region may be subject to considerable error depending upon theINFRARED SPECTROSCOPY 59 amount of 1,2 addition in the polymer and upon the method of preparation of the polymer. It has been shown’ that the 7.64 u and the 7.4 bands in the infrared spectra of polybutadienes are due to cis CH=CH and trans CH=CH respectively. Binder’ described a method by which the cis-1,4 determination was made by measuring the intensity of the 7.644 band. This eliminated the question concerning the source of the long wave absorption in cis-1,4 polybutadienes. Since all nine absorptivities in the three equations of the type Di = (ay'Cy + a2'Cs + asia) where Di is the absorbance at wavelength 4, the a’s are absorptivities of the components at that wavelength, the C’s the concentrations of the components and l the thickness of the absorbing layer, were determined from polymers, it was necessary, in order to determine the cis CH=CH absorptivity at 7.64 u, to assume that C: + C2 + Cs = C, the concentration of the polymer in the solution used for analysis. This assumption is probably unwarranted for the cis polybutadienes used or for any cis polybutadiene known to the writer today but it is necessary. ‘The assumption that C, + C2 + Cs = C is inherent in all methods for determining the microstructures of polybutadienes so far described (or, what is the same thing, that the polymers used for determining the absorp- tivities were 100%, or nearly so, cis CH=CH or trans CH=CH or CH»=CH). This means that the Total Found* values of analyses should be near 100%. If they are not there is either error in the measurements or the polymers are not like those used for the original calibrations. It is surpising that the percentage C(cis) (cis) £ cis (trans) + C2) changes so little (3 or 4 out of 90) even though the Total Found value changes from 80% to 95% when one absorptivity value is changed. In comparing methods the actual values for the concentrations of the components are more meaningful. If the percentage composition is calculated using the concentration of the polymer solution instead of C(cis) + C(trans) + C(1,2), Total Found values are meaningless and possible errors in the measurements are covered up. This is also true whenever specific absorbances or specific absorptivities are uscd since they must be calculated from the known concentration of the polymer solution. If the assumption that C = C(cis) + (trans) + C(1,2) could be elimi- nated, (which would be possible if the proper polybutadienes were available), Total Found values for polybutadiene analyses would be meaningful and im- portant characteristics of the polymers. ‘This is shown below for polyisoprenes. Polyisoprenes.—Binder and Ransaw showed that as little as 2% balata in a hevea-balata mixture could be accurately determined spectroscopically. Cunneen et al.” questioned the accuracy of this method in analyzing isomeriza- tion mixtures of hevea and described another for determining the amounts of cis-1,4 and trans-1,4 additions in such mixtures. Tobolsky and Rogers® found difficulty with it in analyzing alkali metal catalyzed polyisoprenes. Tabie I gives the analyses of six polyisoprenes, four of which, A-D, were made at the same time, by the same chemist, with the same monomer, solvent composition, calculated by per cent cis-1,4 = etc. Cheis) + Cltrans) +.60.2) * Total Found % = =" G(eone, of sola.) x 100.60 RUBBER CHEMISTRY AND TECHNOLOGY and lithium-based catalyst. Polymer E was also made by the use of the same general type of catalyst and Polymer F was made by the use of a Ziegler type catalyst. It is evident that the values for the components agree remarkably well, including Total Found values. This table also gives the analyses, by two different laboratories, of the two polymers E and F. Here again it is evident that the results for each polymer agree very well especially considering that the measurements for one analysis were made with a Beckman IR2 instrument and, for the other, with a Perkin-Elmer 21 instrument. In the analyses of sodium, potassium and cesium catalyzed polyisoprenes the Total Found values have rarely been 102%, generally about 95%. If a Total Found value of 110-120% is obtained in an analysis the results are considered worthless. It is suspected that many of the difficulties mentioned in (6) and (7) arise from the absorbance measurements. For the determinations involved in these analyses the Beckman IR2 is a superb instrument since the absorbances have an accuracy of 0.003, in the proper range, and can be duplicated easily to 0.001. From personal experience it is known that such accuracy is difficult to achieve with a double beam, null recording spectrophotometer. The deviation of the 100% line and the mismatch of the cells must be known and taken into account. In addition cells of different path length must be used for many analyses, if an Tape I ANaLyses OF PoLyisopREeNrs Sample ciel& ane ta 34% A 0.0 62 B 0.0 6.1 Cc 0.0 6.1 D 0.0 61 E Laboratory 1 0.0 a7 E Laboratory 2 0 54 F Laboratory 1 0 40 F Laboratory 2 0 34 accurate Total Found value is to be obtained. The net result of taking these precautions is that a microstructure determination can generally be made faster with the IR2. It is assumed here that the sample was properly purified as discussed in the above references. The base-line method for emulsion and alkali metal polyisoprenes, described by Binder and Ransaw’, is laborious if transmittance vs. wavelength spectra are used. The time could be reduced considerably if the spectra were recorded in frequency vs. absorbance. No way is known at present by which the addi- tional absorption at about 8.75 u, found in most emulsion or alkali metal cata~ lyzed polyisoprenes, can be taken into account except by the base-line method. It is possible that the effect of this absorption on the cis-1,4 and frans-1,4 bands at 8.854 and 8.684, respectively, could be eliminated by calculating band envelopes at these wavelengths which fit the observed spectrum. The maxi- mum absorbances of these two bands should then give the correct amounts of cis-1,4 and trans-1,4 addition. With the method described by Cunneen et al.” only the amounts of cis-1,4 and frans-1,4 additions were determined and thus the 3,4 and Total Found presumably remain constant. In view of work described later it would be interesting to know if this is so in the isomerization mixtures. The methodINFRARED SPECTROSCOPY 61 involves making measurements at an isobestic point, at 1090 em! in this case, and in this respect it is similar to that described by Richardson*., Our experi- ence was that, in a series of hevea and balata solutions, the isobestic points in the 12 band were not constant to 0.024, which could be read from the wave- length seale of a Beckman IR2. At the same wavelength the absorbances were not always the same, within the experimental error, for solutions of the same concentrations. In synthetic polyisoprenos it is often observed that the band maxima shift. As was pointed out by Brattain, Rasmussen and Cravath®® in an admirable paper on C, analyses, shifting up or down on the side of a band caused large errors in the cis-2-butene determination and the same situation applies to Richardson's method. Consequently this part of it was abandoned in favor of measurements of the 8.68 z and 8.84 4 bands. How well such meas- urements ean be made with the usual recorded transmittance spectra is not known, but any advantage of this method seems doubtful, if the polymers are soluble. In addition the knowledge of the Total Found value is lost. If this method could be used in film analyses for small amounts of trans-1,4 addition, it would be helpful in studying vulcanization, or other reactions which result insoluble products. We have observed, as Golub? has pointed out, that, when frans-1,4 addition appears in a polyisoprene, the 7.65 « band begins to widen with a slight shoulder first appearing on the short wave side. At about 10% trans-1,4 structure this becomes a distinct band. It is easier to recognize the presence of trans-1,4 with those two bands than it is with the 8.84 and 8.68 bands. This difficulty is the main reason why a satisfactory method of analysis using films has not been developed. This is necessary if quantitative experiments are to be done on curing of rubber. A compensation method, similar to that described by Willbourne” for CH; in polyethylene, might be used to detect small amounts of trans-1,4 in a cis-1,4 polyisoprene but this has not been attempted. Binder" has shown that the bands at 13.1 and 13.45 u in the spectrum of hevea are probably connected with the cis CH=C (CH) structure. The band at 13.45 4 was used to verify the results of microstructure determinations of synthetic polyisoprenes®, From a calibration curve relating the absorbances of the 13.45 4 band to the amounts of hevea in the solutions, it was found that the percent “hevea” of a polyisoprene was generally the same as the net cis-1,4% (cis-1,4%X Total Found %). The net cis-1,4% was chosen, rather than per cent cis-l,4 because it was found that there is a direct corrleation between the net cis 1,4 values and the gum tensile strengths. The net cis 1,4 values were more reasonable for such a comparison because a polymer which has 95% cis 1,4 and a Total Found value of 95% must contain more “hevea’” than one which has 95% cis 1,4 but a Total Found value of only 85%. Corish”® determined the amount of cis 1,4 in polyisoprene by measuring the intensity of the 2.46 u band. Since this was the only constituent measured the method appears to be of limited application. Polypiperylene—When piperylene, CHs- CH= CH—CH = CH polymerizes i ree by 14 addition cis CH=CH and trans CH=CH structures are formed, as in polybutadienes; by 1,2 addition side vinyl groups, CH:=CH, appear, again similar to polybutadiene; and by 3,4 addition cis and trans CHs- CH=CH— groups can form ina side group. As Binder! has shown there are two bands at about 13.4 and 13.7 n which may be due to the two different cis structures but only one trans 1,4 band at 10.34. In the polypiperylenes catalyzed by lithium or lithium compounds in these laboratories there is no 1,2 addition. However,62 RUBBER CHEMISTRY AND TECHNOLOGY the relative intensities of the 13.4 and 13.7 bands, thought to be due to the two kinds of cis structure, change depending upon the catalyst used in making the polymer. The amounts of total trans CH=CH and total cis CH=CH in polypipery- lenes have been determined® in a manner analogous to that for the determina- tion of the microstructures of polybutadienes. The cis 1,4 absorptivity was found, starting with measurements taken from API spectra of pure hydrocar- bons containing cis CHj-CH=CH groups. In general, the trans CH=CH amounts to about 60%, in the polymers studies and the Total Found values are about 95%. Attempts are being made to resolve the two long wave bands so that cis CHs-CH=CH (3,4 addition) and cis CH=CH (1,4 addition) can be determined. Polydimethylbutadiene —When 2,3 dimethylbutadiene-1,3, CH2=C (CHs)— 1 C(CH3) =CHz polymerizes by 1,4 addition cis and trans C(CH3)=C(CHs) 3 ‘ CH; structures form and by 1,2 or3,4 addition side iospropenyl groups, CHe form. The polymers with which we have worked were known from x-ray studies to be trans C(CH;)=C(CHs). As Binder"! has shown, the band at about 8.65 u is due to trans C(CH)—C(CH) (actually a C—CH; vibration of this group) and a band at 11.25, is due to the isopropenyl group. ‘The microstructures of such polymers have been determined in the same manner as for polyisoprenes". ‘The absorptivity of the trans C(CH,)—-C(CH) band at 8.65 is greater than in balata and was found from pure hydrocarbon (API) spectra. Again the validity of the results was judged by the Total Found values. The amount of 1,2 addition varied with the method of preparation of the polymer. Yen" has described both cis and trans poly (2,3-dimethyl-1,3-butadienes), giving X-ray data to indicate the cis or trans polymer. He also reported a band at 8.66 u in the (rans polymer spectrum but said that two bands, at 8.66 and 8.97 u, were observed in the spectrum of the cis polymer. Only one would be expected, near 8.94, and consequently the purity of the sample may be open to question. Analyses of Various Polymers.—Richardson described the microstructures of polybutadienes and polyisoprenes made at high temperatures (mostly emulsion or bulk), at high pressures" and with cationic catalysts! ‘These polymers were analyzed by methods developed by him. While, for the poly- isoprenes, the experimental error was rather large compared with what can be done nowadays, the general conclusions about the effects of temperature and pressure deduced from the experiments probably are correct. In the case of polybutadienes, however, he found the cis-1,4 by difference, i.e. Total Found values were assumed to be 100%, and this procedure is doubtful, especially if the chemical unsaturation is not known. Medalia and Freedman'® also de- scribed the microstructures of high temperature polybutadienes. Measure- ments were made with gelled polymers and rather broad assumptions in their analytical method. In view of the kind of polymers used and assumptions made in the analyses the accuracy of their results and thus the validity of their conclusions may be open to question. Condon"? found the changes in enthalpy and entropy for the reactions, cis > trans and vinyl — trans in polybutadiencs using published valucs for the microstructures of polybutadienes. RichardsonINFRARED SPECTROSCOPY 63 calculated the same quantities from his microstructure determinations. A comparison of their results follows: Richardson, ‘Condon AH tone — AH 3200 cal 2800 + 200 cal Sean ~ OScix 5 eu. 6.8 40.9e.u. AH wane — AHi2 —770 cal 870 + 110 cal ASvrane — AS, —9, 7 eu. 0.46 + 0.47 eu, While the agreement in the enthalpy and the entropy values, given above, appears to be quite good, there are marked differences in the amounts of cis-1,4 addition found or calculated at different temperatures. Thus Richard- son found 43% cis-1,4 at 223°C whereas Condon calculated 42% cis-1,4 at about 147° C (420° K) and about 53% cis-1,4 at 227°C (500° K). Medalia and Freedman found that the amount of cis-1,4 addition, in emulsion polymers, increased from 33% at 125° C to 40% at 200° C and that there was no further increase as the temperature was raised to 270°C. These last results are normalized values. Their Totals changed from 73% at 233°C to 42% at 270° C so that it is evident that a large amount of polymer was unaccounted for by their analyses. All of this work was done before synthetic polyisoprenes or polybutadienes nearly pure in a single structure were prepared. As a result, as shown by Binder’, the amounts of cés-1,4 addition found in the emulsion and sodium polybutadienes are probably too large. Consequently it seems unlikely that about 40% cis-1,4 would be obtained in a polybutadiene made with a peroxide catalyst at about 250° C. The analysis of polybutadiencs, using the bands due to CH stretching and their first harmonics to determine 1,4 and 1,2 was described some years ago"®. With the resolution available today in grating instruments, this might be an attractive method although how well the cis and trans CH=CH, in polybuta- diene spectra, could be separated is unknown. This is probably true of poly- isoprenes also. Side vinyl and isopropenyl groups in polyisoprenes could not, be determined in this region. The analysis of polyphenylbutadiencs also has been described and apparently the bands from the butadiene appear in the same places as in polybutadiene spectra, except for cis CH=CH, which, the authors state, appears at 14.13-14.34 4. The analysis of mixtures of polymers has been studied by several authors. In what should now be regarded as a classic paper on the application of infrared spectroscopy to the analyses of polymers, Dinsmore and Smith® deseribed the determination of the compositions of many mixtures of polymers which were cured, The determination of the compositions of mixtures or copolymers of the ethylene-propylene system, has been described by Therese Géssl’". The mixtures were homopolymers of ethylene and isotactie polypropylene. She reports atactic and isotactic polypropylene in copolymers and the spectra given show some crystalline polyethylene. Thus if the mixtures were actually co- polymers they must have contained large blocks of ethylene and propylene. Ethylene-propylene copolymers have been analyzed? by measuring the ab- sorhances of the 8.6 4 and 13.9 4 bands, and solving simultancous equations of the form, D' = (EC, + By'C3)1._ The E’s were obtained from soluble poly- mers. These were carried over to film analyses for which base-line absorbances were used. Attempts to analyze cthylene-propylene copolymers containing crystalline components were unsuccessful.64 RUBBER CHEMISTRY AND TECHNOLOGY Since ethylenc-propylene copolymers are of considerable interest it seems to be worthwhile to point out features of the spectra of these polymers, some of which have not been mentioned. As has been pointed out by Liang and Wyatt’® and was mentioned some years ago by Natta et al.”, isotactie polypropylene can be amorphous as well as crystalline and the spectra of the two are different. ‘The spectrum of atactic polypropylene is even more different. Judging by their spectra most of the ethylene-propylene copolymers seen by the writer always have some isotactie polypropylene in them. Since the polymers have not had any evident crystallinity this must mean that there are scattered groups of isotactic polypropylene in the molecules but not enough to allow crystalliza- tion to occur. The 13.5 4 region of the spectra of these polymers nearly always has weak bands which are associated with various lengths of methylene chains such as (CHz)2, (CH2)s. From the standpoint of deciding whether there is polyethylene crystallinity in the polymer, the band at 13.5 4, duc to (CHz)s, can be troublesome. The band at 13.94, due to (CH2)x, which is always found in polyethylene and ethylene-propylene copolymers, appears as a doublet, at about 13.7 and 13.9, when the polyethylene crystallizes. If the amount of crystallization is small, the 13.7 4 band becomes a small shoulder on the 13.9 4 band but the shoulder may appear at shorter wavelengths. Thus a broadening of, or a weak shoulder on, the 13.9 band may be due to the 13.7 u crystalliza- tion band or the 13.54 (CHz)s band. A study of the spectra in this region should give considerable information about how the polymerization occurred. General—It scems worthwhile to point out here some limitations which are inherent in all determinations of structure or composition by infrared spec- troscopy and which, while recognized by many in the field, are rarely stated. One of these is that such determinations are really comparisons of the unknown polymers with the polymers used to determine the absorptivities necessary for the analyses. These comparisons can be made almost as accurately as one wishes; it is simply a matter of making enough measurements. However, if it turns out that the standard polymers are not as pure as they were thought to be the results will not be as accurate, with respect to the amounts of components as originally thought. For example, if hevea is taken to contain only cis- C(CH;) = CH— double bonds the amount of cis 1,4 in a polyisoprene can be accurately determined. If hevea contains other double bonds, besides cis- C(CHs) =CH, the amount of cis-1,4 found in the polyisoprene will be in error even though the precision is as great. Thus, the precision can be great but the accuracy (truth) is less and may be quite small. This limitation to the accuracy can only be removed, or decreased, by knowing positively the composi- tion or structure of the standard ; something which is not easy to establish. ‘Another limitation has to do with the compositions of copolymers. These may be copolymers of amorphous all cis, all trans and all 1,2 polybutadienes, for example, or copolymers of different monomers. The question is whether, for example, trans CH=CH will absorb at the same frequency and with the same absorptivity in a copolymer, in which it amounts to only 5% distributed along the polymer chain, as it does in a pure amorphous trans CH=CH homo- polymer. It is not known positively that this is, or is not, so because copoly- mers in which the number and location of, in this case, trans CH=CH groups have not been made. It is the opinion of this writer that the absorptivities for various groups which occur in the diene polymers discussed here probably are constant whether they appear at intervals in the polymer molecule or in a sequence of such groups. The position, particularly with cis CH=CH, may shift somewhat. The reasonsINFRARED SPECTROSCOPY 65 for this opinion are that the positions of the side vinyl or side isopropenyl or cis-C(CH;) =CH or trans-C (CHs)==CH or trans CH=CH appear in the same places in the spectra of polymers containing all or nearly all of one of these structures as they do in polymers containing only a small amount of one of them. The side vinyl group in polybutadienes is an example of this. The band appears at the same place in an all 1,2 polymer as it does in an emulsion polymer which is generally considered to be random. Moreover analyses of polymers with the same absorptivities generally yield total found values which agree with the chemical unsaturation, regardless of whether the polymer contains a large amount or a small amount of a particular structure. In addition, it seems that there is considerable validity in the idea of constant integrated band intensities for the bands of these various structures. If the absorptivities are not constant there would be no point in testing an analytical procedure, for analyzing co- polymers, by making mixtures of homopolymers of the various components. However, despite the limitations discussed above there is no doubt that very close comparisons of polymers can be made in any given laboratory. Comparisons betweon different laboratories are more difficult to make since absorptivities change depending upon, among other things, the instrument and operating conditions used. Nor is there any doubt that very real progress in the study of the structures of polymers has been made with infrared spectroscopy. III. STRUCTURE AND SPECTRA Although some work was done on the infrared spectrum of hevea before World War II, (see, for example Williams®*), much of it has been repeated since with better instruments and greater knowlecge of the origin of some of the bands. Some of this is discussed in other sections of this report. The paper by Binder" contains references to the early work. In addition to the work by Natta and his coworkers on various kinds of polybutadienes and polypropylenes*** a paper by Nikitin, et al27 on the spec- trum of trans polybutadiene ascribes the 12.95 band in that spectrum to crystallinity. This has been confirmed by the author, and also it has been observed that the bands at 9.5 1 and 8.0 4 are due to crystallinity. The band at 8.04 decreases in intensity with decreasing crystallinity but does not com- pletely disappear. The polarization spectra of isotactic polystyrene and iso- tactic poly-a,8,8-trideuterostyrene have been described’. These authors state that the 1364, 1314 and 1297 cm~! bands in the spectrum of isotactic poly- styrene may be associated with the three-fold screw axis of the isotactic mole- cule. Similar bands appear at 1358, 1304 and 1167 em~ in the spectrum of isotactic polypropylene and it is thought that these may be connected with the screw axis of this molecule which has a helical structure. This raises the ques- tion of whether some of the bands in crystalline 1,2 polybutadiene may have the same origin. Golub and Shipman™ described the spectra of deutero poly- butadienes. This work confirms the assignment of the 967 cm band to the trans out-of-plane hydrogen deformation. Their spectra show very interesting shifts in the long wave absorption of cis polybutadienes and certainly indicate that there is a cis CH=CH (cis out-of-plane hydrogen deformation vibration) band near 740 emo. The effect of structure on physical properties has been discussed for poly- butadienes™ and for polyisoprenes™: **, For polybutadienes it seems clear that the gum tensile strength, for example, depends very much upon the amount of cis 1,4 or trans 1,4 additions, after a certain amount appears in the polymer.66 RUBBER CHEMISTRY AND TECHNOLOGY There appears to be an intermediate range in which the amounts of cis 1,4 and trans 1,4 in the polymer have little effect on the tensile strength. The effect, of microstructure on the physical properties of polyisoprenes has not been investigated as extensively as for polybutadienes. For a limited range at least, there is a direct correlation in polyisoprenes between the gum tensile strength and the amount of cis 1,4 addition or the net cis 1,4. ‘The amount of isopropenyl groups in polyisoprenes also has a great effect upon the physical properti IV. ISOMERIZATION, Golub®* described isomerization of high cis-1,4 polybutadienes to, mainly, the trans-1,4 polymers by a variety of methods such as mercury are radiation with different initiators such as diphenyl sulfide, allyl bromide, bromine, ete. and with gamma radiation. According to him the thermodynamic equilibrium between cis-1,4 and trans-1,4 should be reached and these amounts should pre- sumably correspond to what would be found in a thermal or emulsion polymer made at the same temperature if there were no 1,2 addition. Some of these isomerizations were repeated by us? and, according to our method of analysis, the final composition of the isomerization mixture was not like that of a 50°C emulsion polymer, i.e. about 5% cis-1,4, since more cis-1,4 was left. However, it is not known how the 20% 1,2 addition that is found in an emulsion polymer should be divided between cis-1,4 and trans-1,4 so that the remaining 1,2 would be about the same as in the high cis-1,4 polybutadiene. If it were divided in the ratio of the cis-1,4/trans-1,4 found the cis-1,4 in the final isomerized mixture would still be too large. Unlike Golub we were unable to get enough soluble polymer after isomerizing with gamma radiation to analyze. We found the rate to be slower with allyl bromide than with diphenyl sulfide and slower when hexane or heptane was used for solvent than with benzene solvent. Moreover, a high cis-1,4 poly- butadiene (ca. 85%) made without benzene in the catalyst or solvent did not isomerize as much with allyl bromide, heptane and mercury radiation as did the usual high cis-1,4 polymer in the same length of time. Attempts to isomerize a trans-1,4 polybutadiene did not positively produce much, if any, cis-1,4 as judged by thespectrum. This may or may not refute the idea of an equilibrium resulting in the cis-1,4 isomerization, depending upon what the microstructure of a.50° Cemulsion polymer is. One difficulty with these experiments was that the isomerized polymer gelled so readily that it was difficult, and often impossi- ble, to purify the polymer for analysis. The question of the isomerization of hevea has been discussed in several connections, e.g. vuleanization. A series of papers by Cunnen et al., beginning in 1957, discusses this subject and one of them’ discusses the determination of the amounts of cis-1,4 and frans-1,4 in the isomerized samples as mentioned previously. Various isomerizing agents were used, such as SOs, butadiene sulfone, thiobenzoic acid and dibenzoyl sulfide at 140°C. Golub? also iso- merized hevea with selenium but only gave estimates of the amounts of iso- merization, He used different bands, at 7.68 » and 7.52 x, for estimating the amounts of cis-1,4 and trans-1,4 respectively. Unfortunately, Cunneen et al. did not show these bands in their spectra. Hevea has also been isomerized with the components of Ziegler type catalysts. ‘These included triisobutyl- aluminum, triethylaluminum, diethylaluminium chloride, titanium tetra- chloride, ete. For each of them isomerization, as measured by the change in the 840 cm~ band, was found. With titanium tetrachloride, more 3,4 and 1,2INFRARED SPECTROSCOPY 67 was found than occurs in hevea and in all cases the degree of unsaturation decreased. ‘This decrease was ascribed to cyclization. We have isomerized purified hevea according to Golub’s procedure. The analysis of the isomerized material was 37.1% cis 1,4, 36.2% trans 1,4, 0.0% 1,2, 6.7% 3,4 and 94.2% Total Fouud. The original purified rubber was 97.8% cis 1,4, 2.2% 3,4 and 100.4% Total Found. There was no evidence of oxidation in the spectrum but there was a shoulder at about 8.75 « on the frans 1,4 band and it appeared that there might be more absorption at 10.44 than in the original spectrum. The increase in the 3,4 addition and the probable appear- ance of trans CH=CH show that other reactions besides isomerization of cis C(CH;)=CH to trans C(CHs)=CH occurred. Since there was no change, within the experimental error, of the Total Found valuc it is unlikely that there was much, if any, change in the unsaturation. The 3,4 addition here may actually be CH»=CR,Re where neither R, or Rz is CHs. So far as is known now this would be indistinguishable from CH2=C(CH)R spectroscopically. V. CRYSTALLINITY While a general discussion of polyethylene spectra is not given here, crystal- linity determinations are included for several reasons. First, the determination of the crystallinity of polyethylenc has been studied most. Second, the methods found suitable for polyethylene should be applicable to other crystalline poly- mers. Third, many a-olefins polymerize to form crystalline polymers and the degree of crystallinity is an important characteristic. Since it was observed quite a long time ago that the 13.94 band in the spectrum of polyethylene has a companion at 13.7 1 when the material crystal- lizes, many attempts have been made to determine the degree of crystallinity of this substance, as well as other polymers, by measuring the intensity of a crystallinity band. In a series of papers, Stein and Sutherland®“"' discussed the origins and relative intensities of the 13.7 and 13.94 bands and Synder! has also discussed the splitting of the 13.9 » band, as well as others, in n-paraf- fins. Stein and Sutherland” concluded that the 13.7 4 (730 em™) band is due to crystallites and the 13.9 u (720 em™) band to both amorphous and crystalline material. Krimm! has also discussed the crystallinity of polyethylene. The amount of crystallinity in polyethylene was determined by Tobin and Carrano* who decided that the 1300 cm~! (7.69 u) band is due to an amorphous CH, rock vibration and the 730 cm™ (13.7 4) band due to crystalline CH. ‘They corrected the 13.74 band for the overlap of the 13.9 band and also allowed for the non-methylenic material (for example CH) in the polymer. Unfortunately their results do not agree well with those obtained by X-rays. ‘The difficulty in determining the degree of crystallinity by measuring the intensity of an infrared band (and this applies to other types of determinations as well) is the lack of a known standard or of polymers which are known to be completely erystalline or completely amorphous. The method of Tobin and Carrano would scem to overcome this but it is evident that some factor is omitted in cither the infrared, X-ray or density methods since the results ob- tained by the three methods do not agree. Recently Hendus and Schnell have described another method for deter- mining the degree of crystallinity of polyethylencs. They measured the ab- sorbances of a band at 5.3 # which seems to be due only to crystallization and of the band at 7.7 4 mentioned above. _In this way the contribution of crystal- line absorption to the 13.94 band or of the 13.9 band to the 13.7 # band was68 RUBBER CHEMISTRY AND TECHNOLOGY avoided. The spectroscopic results given by them agree well with their X-ray determinations. It would be interesting to see the same comparisons made by other workers. Heinen“ determined the crystallinity of polypropylene by measuring the absorbance of a band at 846 em™ (11.82 4) which was ascribed to crystalliza- tion. To eliminate the film thickness he also measured a band at 1171 em (8.54 ») which was found to be temperature insensitive. ‘The degree of crystal linity was calculated from density measurements using an equation due to Natta (see Ref. 44). Plotting Ase/Auz against the per cent crystallinity gave a calibration curve from which the erystallinity of other samples could be de- termined. Another method was described by Luongo‘® who measured the intensities of bands at 974 em™ (10.27 4) and 995 em™ (10.054). A calibration curve was obtained by plotting the ratio of these two measurements against the amount of atactic polypropylene. The atactic and isotactic polypropylenes were obtained by extracting suitable polymers with heptane. While, from his spectra, Luongo’s criticism of using measurement of the 1171 m7! band as. Heinen did appears justified, experience in these laboratories with trying to make a completely isotactic or atactic polypropylene by extracting with heptane or hexane indicates that a pure polymer is not obtained. Therefore, provided Natta’s equation is correct, it would appear that this part of Heinen’s method is more desirable. Measures of the relative crystallinities of polypropylenes were obtained by Abe and Yanagisawa‘* by measuring the dichroism of the 1000 cm (10.0 4) and 975 em (10.26 4) bands which were used by Luongo. They pointed out the changes in the 1170 cme band observed by Luongo. It seems likely that the same difficulties which appear in determining the crystallinity of polyethylene by infrared spectroscopy beset the determination of the crystallinity of polypropylene and other polymers. For these they may be magnified since the number of bands in the isotactic polypropylene spectrum is much greater. If syndiotactic polymer is also present the difficulties may be even greater. No attempts have been made to determine the degree of crystallinity of hevea, balata, trans 1,4 and 1,2 polybutadienes spectroscopically although all have distinct crystallinity bands in the spectra of the crystallized materials. Perhaps, for synthetic diene polymers, this would be pointless because, at present at least, may these polymers contain other structures. This may be true also of other types of hydrocarbon polymers. It has always scemed strange to this writer that, while high cis 1,4 polybutadienes are known to crystallize readily, no distinet crystallization bands, such as are found for trans 1,4 poly- butadienes or hevea or balata, appear in the spectra. Many writers make comparisons between the amount of crystallinity found spectroscopically with that found by other methods such as x-ray diffraction, density measurements, ete. If the current ideas about crystallinity in polymers are correct it is not surprising that different methods do not give the same results since, actually, different features of the crystal are measured by the different methods. If it is desired to measure the amount of crystallinity, any of these methods require standards which are known to be completely crystalline and completely amorphous. Such are not known for polymers of the types discussed here. This lack probably explains, in part at least, the differences in the amount of crystallinity of hevea, determined by the same method, which have been reported. It is possible, however, to measure the relative degree of crystallinity and so arrange a group of polymers in degree of crystallinity.INFRARED SPECTROSCOPY 69 VI. DETERMINATION OF METHYL GROUPS: ‘The question of how many methyl groups are in a polymer is of some interest because, with diene polymers the unsaturation is sometimes less than it should be and, with others, there is no guarantee that only polymerization by simple addition occurred. This subject has been studied extensively for polyethylene and has been described very well by Willbournc, Hughes and’ Martin’® determined the number of methyl groups in polypropylene, polybutene and polypentene. ‘There is a significant difference in the work of these authors which is puzzling. The number of methyl groups (as weight percent methyl or the number of methyl groups per hundred carbon atoms) is determined by measuring the in- tensity of the CH, band at 7.254. A calibration curve relating the absorbance of the 7.25 u band to the number of CHs groups is obtained using pure, known compounds. Willbourne assumed that the methyl absorptivity was constant regardless of the position of the methyl group in the molecule (i.e. at the end of a chain as in a normal paraffin or in the chain as in an iso paraffin) so that the absorbance of this band would give the total number of methyl groups. He also measured the number of ethyl and butyl branches in polyethylenes using other bands in the spectrum. The number of methyl groups found by adding the number of ethyl and butyl branches agreed very well with the number found by measuring the 7.25 4 band. This would appear to substantiate the assumption of a constant absorptivity for the 7.25 4 methyl band. Hughes and Martin, on the other hand, found that the absorptivity of the methyl band at 7.25 4 depends upon the location of the methyl group in the molecule. Otherwise the number of methyl groups in polypropylene was an impossible number. ‘There is considerable evidence that the absorptivity of the methyl band at 7.25 w does depend upon the location of the methyl group in the molecule. In the case of the work of Hughes and Martin it sccms unfortunate that the methylene absorption was not considered in a more direct way than they did. Methylene bands overlap the methyl absorption at 7.25 4 and, in the case of polyethylenes, was taken into account by using measurements of polymethylene. Hughes and Martin, instead of measuring only the absorbance at 7.25 u, used a Kind of integrated (average of measurements at many wavelengths) absorptivity for the 7.05-7.45 4 region which would include much of the methylene bands. How well they accounted for the methylene absorption for the various molecules they studied is not known. If it were, the evidence for the changing methyl band absorptivity would be stronger. We have attempted to determine the number of methyl groups in synthetic polyisoprenes” primarily because Total Found values were sometimes less than 95%. If the Total Found reflects the unsaturation of the polymer, as is thought, the decrease could be duc to saturation of the double bonds which might lead to the formation of methyl groups. The calibration curve was made as for polyethylenes and, similar to the experience of Hughes and Martin, the number of methyl groups in hevea was found to be an impossible number with it. In the light of present knowledge this not surprising since the absorptivity of the methyl group which, in this case, is on an unsaturated carbon would be expected to be different from that found from paraffins. Taking hevea to have 20 methyls per 100 carbon atoms and drawing a calibration curve parallel to the paraffin calibration curve it was found that most of the synthetic poly- isoprenes had about 21 CHa per 100 carbon atoms. ‘The accuracy is probably no greater than 1.0 CH and more points are needed for the calibration curve.70 RUBBER CHEMISTRY AND TECHNOLOGY VII. OXIDATION One of the carliest applications of infrared spectroscopy to the study of hevea was in the investigation of oxidation by air and ozone. Much of this work was done before the spectrum of hevea was very well understood and before analytical methods for determination of the microstructure were avail- able. Consequently most attention was given to the appearance of the C=O and OH bands. As is known now, hevea must be considerably degraded before these bands appear. LeBeau‘? studied some of the reactions occurring during reclaiming and, somewhat suprisingly, found no evidence of C=O, OH or C—O—C. In the oxidation of sodium catalyzed butadiene, i.e. high 1,2 polybutadiene, it was found that the OH and C=O (1720 cm~) bands appear early. With increasing oxidation the absorption in the 7-8-10 gw region increased, with a band appearing at 8.54 which was attributed to an ether C—O—C. The side vinyl bands at 10.05 and 10.98 y decreased in intensity. Assigning the band at 8.54 to an ether (which would be aliphatic in this case) seems a little doubtful. 1D’Orand Kassler® followed the changes in bands due to C=O, C—O, RC(CH3;)=CHR, C=C, CH; and CH in the oxidation of hevea and found that the intensity of the OH band increased at first and then decreased. However, they put the C—O band at 1130 em™ which is where cis C(CH;)—=CH absorbs. They also reported that, at first, two D bands, at 5.654 and 5.854, appear which become one as the oxidation increases. Ina series of papers Tkac and coworkers studied various aspects of the aging of natural rubber®-*, They likewise observed two C=O bands at 5.66 4 and 5.80 p, said to be duc to carboxyl and aldehyde and ketone, respectively. The C=0, OH and CH bands were found to increase in intensity and the CH: and CH; bands to deerease. The rate of oxidation was followed by measuring the intensity of the C=O band. In one of the papers® the 5.66 u band is attributed to an ester and in another the physical properties of the rubber were reported to be considerably changed without any changes in the spectrum appearing. These and other studies of the oxidation of rubber are complicated by the fact that very often impure hevea was used in the investigation. It seems fairly certain now that the bands at about 6.5 4 and 3 w in the spectrum of pale crepe are due to protein. Thus one wonders if one of the two C=O bands observed in oxidation may be due to the protein or some degradation product of an im- purity, (it is realized, however, that neither of the two amide bands appears at 5.664). Because of this doubt it would seem desirable to make such studies with synthetic polymers. Field, Woodford and Gehman®§ made a very extensive study of the oxidation of butadiene and isoprene polymers of various types. The amount of oxygen taken up by the polymer was measured and the infrared spectra of polymers containing various amounts of oxygen were recorded. They make no mention of two C bands, mentioned above, but did observe the C=O and OH bands as others have. The most striking feature of most of their spectra of oxidized polymers is the gradual washing out of almost all of the bands beyond 8 » and the persistence of the C=C band at 6u. It was suggested that the absorption in the 10 4 region is due to a variety of ethers and esters. For polybutadicnes and butadiene-styrene copolymers the intensity of the trans CII=CH band at 10.34 w does not change to the extent that would be expected on the basis of the amount of cis-1,4 and 1,2 in the polymers and the amount of oxygen absorbed. This appearance may, however, be due to increasing background absorption.INFRARED SPECTROSCOPY 71 Evidently the side vinyl, CH»=CH, group oxidizes faster than trans CH=CH. It would be desirable to have some quantitative measurements if such were possible. It has been our experience that in solution trans polyisoprenes and pol: butadienes degrade, thus presumably oxidize, faster than the cis compounds. Thus, finding the trans CH=CH band relatively unaffected is surprising. We have found no references to the oxidation of balata or of trans polybutadiene but it seems that a comparison of the cis and trans polymers, with respect to oxidation, would be interesting. Quantitative measurements should be possible with polyisoprenes, at least, since they degrade rather than crosslink, as a rule. No marked differences wore observed by Field, Woodford and Gehman in the spectra of polymers treated with ultraviolet light and with the ordinary thermal oxidation procedures, but adding iron to the polymer resulted in the appearance of new bands at about 13.6 and 13.84 and the absorption in the 10 u region appears more complex. This scems to indicate that the iron causes other reactions to occur rather than that of catalyzing the simple oxidations. Since the intensities of the cis-1,4, trans-1,4 und 1,2 bands do decrease with increasing oxidation the persistence of the C=C band at Gu would indicate that other unsaturated structures are being formed. This question has not been explored. One wonders if the compensation technic used by Willbourne to show the CH band in polyethylenes might be used with these substances to unravel the absorption between 8 4 and 10 p. In a paper on the aging of rubber in solution®, it was found that there was a loss of about 19% of double bonds. This loss was attributed to reaction with the solvent or, perhaps, cyclization. Unfortunately this work was done, evidently, with a single beam instrument and the solvent bands were not eliminated. Allison and Stanley® studied the reaction of ozone with various polymers such as hevea, SBR, NBR, butyl and neoprene. They measured intensities of the C=O and OH bands and attempts were made to calibrate with these two bands. Calibrations of the 2.7-2.9 » OH band are subject to many pitfalls In addition, if these bands absorb in polymers as does, say, the trans CH=CH, calibrations made with model compounds are not likely to yield the correet polymer absorptivities. Kendall and Mann’ studied the ozonization of hevea and Hycar OR-15 and found that, instead of the spectrum assuming a washed out appearance as Field, et al. observed, it became rather complicated. While the intensities of the 840 cm™ and 1130 em~ bands decreased, new bands appeared at 1110 cm™! and 1084 em™, which they attributed to the formation of ozonides, when ozonized oxygen was used with a solid sample. If the rubber was dissolved a band was also obscrved at 1170 em-+, the origin of which is unknown. When ozonized air was used with solid samples, bands were found at 1624 cm! and 1290 em™ in addition to the 1720 cm! C=O band. The first two are thought to be due to nitrate groups formed by the reaction of NO» and alcoholic OH. Salomon and van der Schee# investigated the oxidation of natural rubber and the reaction with ozone. Their results are essentially what has been reported above, except that they noted that the C=O band appears first and then the OH band. They identified the band at 11.25 as CH: due to a —CHy—C—CH—CH-— structure rather than the isopropenyl CH2=C(CHa)—.72 RUBBER CHEMIS (RY AND TECHNOLOGY These experiments on the oxidation of hevea and other polymers have not answered the question of what happens during the process but they do show that reactions apparently occur which could not be detected by other means. VIL. VULCANIZATION The study of vulcanization of natural rubber by infrared spectroscopy is as old as the study of oxidation by this means, beginning with the early work of Williams” ® and Sears®. The literature on this subject has been summarized very well by Linnig and Stewart®. Their work is very thorough and forms the basis of the following discussion. Before discussing the work of Linnig and Stewart some comments on the rubber samples used by various investigators seem pertinent. If smoked sheet or other similar commercial rubber is used, it is, based on our experience, almost impossible to completely remove the protein. Rubber from coagulated latex also contains protein. It has been found that if the rubber is sufficiently purified the bands at 3.0 and 6.5 disappear in the spectrum. Hence these as well as bands near 4.8 u are due to impurities, not to the pure rubber. The bands at 6.25 y, 6.34 and 6.65 u reported by Linnig and Stewart in the Coral polyisoprene spectrum are certainly due to inhibitor, not the polymer. ‘The most striking result of the work of Linnig and Stewart is the difference between the spectra of hevea cured by different methods. Since vulcanization is considered to be a matter of forming crosslinks between polymer chains, with only a few being required for cure, it would scem that the changes in the spectra observed are really not due to the curing reaction but to secondary, accompany- ing reactions. On this basis the spectrum of the reaction product of hevea with sulfur given by Linnig and Stewart is analogous in some respects to the iso- merization of hevea with selenium reported above. ‘The difference is that sulfur causes mainly a double bond shift, since the trans CH=CH band at 10.34» is so much stronger, whereas selenium causes a cis-trans isomerization and cis-isopropenyl reaction. There also seems to be no doubt that conjugated double bands are formed, due either to double bond shift or the formation of a new double bond, but the bands at 6.5 4 and 3.0 u are most likely due to protein. It is regrettable that the reaction products are insoluble in ordinary solvents, so that the microstructures cannot be determined, and that we do not have accurate methods for determining microstructures of polyisoprenes using films. It would be interesting to know if the 6.0 u band is really weaker or if the 6.1 « band is stronger in the spectrum of the sulfur cured sample, compared to hevea, and it would be interesting to know if the unsaturation changes. If the 6.1 4 band did increase in intensity it would be expected that the 11.25 » band would too, if both bands are due to CHs==C(CHs), and as was found in the isomeriza- tion experiment. The apparent increase may be due to the presence of the bands at 6.13 4 mentioned by these authors. ‘The intensity of the 11.9 u band has not changed markedly but the appearance of the 8.95 » band has changed considerably. If both are due to vibrations of the cis C(CH;)=CH structure it is difficult to see how the intensity of the one can change without the other changing. Since the absorptivity of the 11.9 band is about 3 times that of the 8.95 u band it may be that the intensity of the 8.95 u band does correspond with that of the 11.9u band. The band at 7.65 ,which is also due to a vibration of the cis C(CH,)==CH group, appears to be weaker in this spectrum than it is in the spectrum of hevea. All of those changes in the spectrum of the sulfur cured hevea can be ex-INFRARED SPECTROSCOPY 73 plained on the basis of the double bonds in the cis C(CH,)=C structure being removed with the formation of cis and trans CH=CII and a shift of two double bonds to give a conjugated system or the formation of new double bonds. Such changes probably would, also, account for many of the changes observed in the long wave spectra. By contrast the changes in the spectrum of hevea cured with tetramethyl- thiuram disulfide, S02 and H.S or di--butylperoxide are almost insignificant. It is suspected that the spectra of rubber cured with these three curing agents would be practically the same if the film thickness and state (roughness) were the same. The bands at 3.0 u and 6.5 are probably due to protein but it is difficult to understand why they appear so much more intense in these spectra. However, this is speculation and will remain so until quantitative measurements are available. The unusual feature of these spectra is the intensity of the 6.1 1 band which is greater than in the hevea spectrum. One wonders if there are really two bands present, as found in the sample of the sulfur cured material. ‘To sum up this discussion it scoms that none of the spectra given by Linnig and Stewart, or other workers, disclose anything about the curing reaction itself. They do indicate, particularly with sulfur curing, the occurrence of some other reactions. Here again one wonders if the compensation technique would disclose differences not evident now. For example, if the di-t-butyl- peroxide cured rubber sample were used as compensation for the tetramethyl- thiuram disulfide cured material, some bands might be found which could be due to C—8 or C-S—8—C, ete. Very recently Golub and Shipman” reported some interesting experiments on the reactions of sulfur with polyisoprencs and polybutadiencs which, it seems, necessitate changes in the interpretation of some of the bands in the spectrum of sulfur cured hevea. Apparently the band at 10.4p is due to a variety of structures among which are mentioned saturated ring structures, conjugated double bonds and, to some extent, structures arising from shifted double bonds. In cis polybutadienes cured with sulfur considerable cis-trans isomerization apparently occurs as well as the formation of ring structures and conjugated double bonds but little or no double bond shifting. Further details of this important work should be very interesting. IX, RUBBER DERIVATIVES The chlorination of rubber, either with chlorine or hydrogen chloride has been studied spectroscopically by Salomon and coworkers® © and by Ramak- rishnan, Desgupta and Pande. During chlorination, Salomon, et al. found that the bands at 6, 10.3, 11 and 11.94 ,all of which were attributed to double bonds, changed in intensity. The 11.94 band became weaker and a band at 10.9-11.2 4 appeared. ‘This band was attributed to CH: & —c—C—C—c— which is in accord with their assignment of this band in oxidation studies but is now regarded as isopropenyl, CH:=C(CHj)-—~. The relative intensity (relative with respect to CHz band) of the 7.25 CH; band increased with the addition of Cl, or HCl. The decrease in the intensity of the 6a and 11.9p bands is to be expected, if the addition takes place at the double bond. The74 RUBBER CHEMISTRY AND TECHNOLOGY increase in intensity of the 11.2 band was attributed to the reaction This seems somewhat strange as is the increase in the relative intensity of the 7.25u band. Unfortunately, this work was done with a single beam instrument and incomplete spectra are given, Considering the interest in this subject it would be desirable to repeat some of the experiments with modern instruments. Ramakrishnan, et al., found that at 6% chlorine content all of the rubber bands in the 8-11 # region were removed. Maynard and Mochel® analyzed polychloroprenes and found the 1,4 addi- tion to vary, with polymerization temperature, from 99% at ~40° C to about 84% at 100° C with the cis-1,4 structure varying from 35-13% of this amount over the same temperature range. The maximum amounts of 1,2 and 3,4 were 2.5%. The accuracy of these measurements is questionable since the necessary absorptivities were obtained from model compounds. The cis and trans values were determined at 1653 em and 1662 cm}, respectively. In view of the frequency with which cyclized hevea has been mentioned, in various connections it is unfortunate that satisfactory spectra of such materials have not been published. Those available, (sec Salomon’s papers) were made a long time ago with single beam instruments and do not show as much detail as is desirable. The same is true of cyclized polybutadienes. While Shelton and Lee® described cyclized polybutadiene, they only state that vinyl and trans CH=CH unsaturation decreased and that there was evidence of @ con- jugated acid. In view of the structure proposed for such substances a speetrum would be desirable. X. 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