Radiation protection in copolymers of isobutylene and styrene By P. Aruxanper: Chester Beatly Research Institute, Institute of Cancer Research, Royal Cancer Hospital, London, 8.W.3 AND A, CHARLESBY* Atomic Energy Research Establishment, Harwell, Berks (Communicated by F. A. Frecth, F.RS.—Received 14 January 1955) ‘Tho effect of ionizing radiations on copolymers of isobutylene and styrene has been studied. Molecules consisting only of isobutylene units degracie under radiation, whereas styrene polymer cross-links. In the copolymer the styrene units offer protection against radiation to tho neighbouring ssobutylene units. An ostimate is given for the extent of this protection. On irradiation the copolymer at first degrades to an extent which depends on the per- centage of styrene, then it cross-links partially into gel. Even for copolymers containing 80% of stytone, protection is only partial, and after high radiation doses specimens separate into a gel and a s0l fraction, Tt is not possible to cross-link such copolymers sufficiently to produce a completely insoluble material. Chemical analysis of the irradiated copolymer shows that the separate units are dis- tributed approximately at random throughout the material, and do not oreur in large blocks rich in styrene or isobutylene, InTROpUCTION ‘The effect of ionizing radiation on solids ean be readily detected in polymers by changes in molecular weight. In many polymers cross-linking oceurs, and the molecular weight increases until a gel structure is formed (Charlesby 1952, 1953). In other polymers the effect of radiation is to fracture the main chain at random (degradation), giving a decrease in molecular weight which can serve as a measure of the efficiency of the radiation in causing molecular changes (Alexander, Charlesby & Ross 1954). Partial protection against these effects of ionizing radiation can be provided both in the liquid and in the solid state. For example, a small percentage of aniline or allyl thiourea incorporated in solid polymethyl methacrylate can reduce the effect of radiation (as measured by the drop in molecular weight) by a factor of 2 or 3, This applies when the protecting molecules are dispersed among, but separate from, the polymer molecules, Protection can also be afforded by the presence of a phenyl group within the polymer molecule, as, for example, in polystyrene. The stabilizing effect of the phenyl group is then shown by the much higher absorbed energy needed to produce a cross-link—about 2000eV as against about 20eV for most other polymers which cross-link. * Present. address 'T.I. Research Laboratories, Hinxton Hall, Hinxton, Cambridge. [136 }Radiation protection in. copolymers of isobutylene and styrene 137 In polystyrene no carbon atom is separated by more than one atom from the protecting phenyl group. An approximate estimate for the distance over which protection. against cross-linking can extend along a paraffin chain was obtained by measuring the cross-linking efficiency of a hydrocarbon carrying a protective aromatic group at various positions (Alexander & Charlesby 1954). In the present paper a study is made of the behaviour under radiation of copolymers containing varying proportions of styrene and isobutylene, with a view to determining the protective effect against degradation, due to the phenyl group. Isobutylene polymer shows a rapid decrease in average molecular weight as main-chain bonds are fractured by radiation. The number of bonds broken is directly proportional to the radiation dose. When styrene units are included in the molecule one would expect to observe a decreased rate of main-chain fracture, largely because of the protection offered by the styrene units to neighbouring isobutylene units. This decrease in degradation rate will depend on the range of protection offered, and on the location and concentration of the styrene units in the molecule, At a certain concentration one might perhaps hope to obtain a co- polymer in which the protection offered by the styrene units extends over sub- stantially all the isobutylene units, and a radiation-resistant copolymer would be obtained in which the small residual degree of degradation of isobutylene units would compensate for the cross-linking of the styrene units. In these experiments the behaviour of irradiated copolymers of isobutylene and styrene, of varying proportions, was compared with that of pure polyisobutylene and of polystyrene. The changes produced by radiation were studied by viscosity measurements, solubility and chemical analysis. EXPERIMENTAL DETAILS Three sets of isobutylene+styrene copolymers were available for study, com- prising respectively 80, 50 and 20°% of isobutylene by weight. Comparative data on the degradation of polyisobutylene and of cross-linking in polystyrene were also available. Specimens of these copolymers were irradiated in the B.E.P.O. pile at Harwell, operating at a constant intensity, and the irradiation doses quoted in this paper are expressed in terms of a pile unit of 107 slow neutrons/em!, plus the associated fast neutron and y-flux, which could not be measured separately. The slow (thermal) neutron flux does not contribute significantly to the energy deposi- tion, while that from the y-rays varies but little with the chemical constitution of these organic materials. The energy obtained from the fast neutron flux arises mainly from the seattering by hydrogen atoms. Experiments on methyl meth- acrylate (C,H,0,),, and isobutylene (C,H,), show that one pile unit as defined above produces thesame degradation as 4-5 x 107rat 20°C (towithina small percentage), in spite of the considerable difference in the proportion of hydrogen. It may therefore be assumed that the energy deposition per pile unit in the various specimens studied will not vary very appreciably owing to the greater hydrogen content of the polymers richer in isobutylene.138 P. Alexande: . Charlesby Resvuts Viscosity measurements Changes in molecular weight due to irradiation were followed by measurements of intrinsic viscosity [7] in carbon tetrachloride at 30°C. For polyisobutylene the relationship between intrinsic viscosity [7] and viscosity average molecular weight MY, is given as follows (Fox & Flory 1949): [y] = 2-9 x 10-4299°, (1) For a polymer which degrades as a result of irradiation (0.g. polymethylmeth- acrylate, polyisobutylene) it has been shown that a linear relation is obtained if [7] is plotted against the radiation dose & on a log-log scale, provided two conditions are met: (i) The initial molecular weight distribution follows a random law, i.e. the type of distribution obtained by random fracture of an infinite chain. [7] CCI, at 80°C ONTO 0T OF Os rt = 0 radiation dose (pile units) Ficurs 1. Inteinsie viscosity of styrene + isobutylen polymers); @, 80/20 isobutylene/styrene; A, 50/ +, polyisobutylene (different Gi, 20/80; ©, polystyrene. (ii) A correction is applied for the initial average molecular weight. This can conveniently be done by adding to the radiation doses 2, a small ‘ virtual’ radiation Ry which is defined as that dose which would be needed to reduce a molecule of infinite molecular weight to a distribution of the same average molecular weight as the original unirradiated material. Where condition (i) is not met the plot will still be approximately linear for high values of 2 (about > 42.) but will deviate from linearity at smaller values of R. Figure 1 shows for each of the specimens studied the experimental values of [7] plotted against R, and figure 2 the corresponding values with an appropriate correction R,. Also shown on the figures are the [7] values for irradiated polyiso- butylene and irradiated polystyrene.Radiation protection in copolymers of isobutylene and styrene 139 ‘The curves for the copolymers show three distinct regions: an initial region in which the intrinsic viscosity falls with increasing radiation dose; a second region in which it is substantially constant, and a third region in whieh it falls very rapidly. It was observed that gel formation first occurs at the transition from the second to the third region, and the intrinsic viscosity of this last region corresponds to the sol fraction only, A rapid fall in intrinsic viscosity [7] of the sol fraction occurs in all long-chain polymers once gel formation takes place, as the higher molecular weight fractions tend by preference to become linked into the gel fraction. In. these experiments the fall in [y} may be further accentuated by main ehain fracture due to radiation. [7] CCA, at 30°C 05 oo 002 005 OT O02 OF 1 2 5 0 radiation dose (pile units) ‘Fraune 2. Intrinsic viscosity of irradiated polymers after correction for initial molecular weight. +, x, polysobutylene (two samples of different initial molecular weight) @, 80/20 isobutylene/styrene; A, 50/50; (1, 20/80; O, polystyrene; |, initial gel formation. In pure polyisobutylene there is no evidence of the second and third regions; this has been confirmed for much longer exposures than those shown in figures 1 and 2. For polystyrene there is no initial drop in intrinsic viscosity, and the rise near the gel point is relatively small because the higher molecular weight molecules produced by cross-linking are branched and have a lower intrinsic viscosity [7] than have linear polymers of the same molecular weight, The intrinsic viscosity measurements above the gel point correspond to the sol fraction only. Gel fraction ‘The variation of sol fraction with radiation dose for each of the copolymers is shown in figure 3. The curve for 80°, styrene copolymer does not tend to zero with inereasing radiation dose as is found to be the case for pure polystyrene but toa value of about 35%. This behaviour is one which has been predicted for a polymer in which both chain fracture and cross-linking occur simultaneously, and at random, and are proportional to the radiation dose R.140 P, Alexander and A. Charlesby The full curve drawn through the crosses (representing the experimental data for the 80 %, styrene copolymer) is the calculated curve when the ratio of chain fracture to cross-linking is 0-0. The data for the copolymers containing a higher proportion of isobutylene are not sufficiently extensive for a corresponding analysis, but it is clear that in these cases the ratio of chain fracture to cross-linking is appreciably greater. The fact that, even when 80% of the copolymer consists of styrene units, protection is only partial, indicates that there is little possibility of producing a completely radiation-resistant copolymer. From this copolymer, which has already lost the useful rabberlike properties of polyisobutylene, extensive radiation will always produce a mixture of about 65% gel material and 35% of a low molecular weight viscous fluid. A more resistant copolymer would contain so little éso- butylene as to be almost indistinguishable from polystyrene, and would cross-link and eventually become very brittle. 10 % sol fraetion radiation dose (pile units) Frovne 3, Decrease in solubility. +, cross-linking only (applies to polystyrene, previous data); —, 0-9 main-chain fracture per cross-link (theoretical); x, +, ©, experimental -values for 20/80, 50/50, 80/20 isobutylene /styrene copolymers respectively. Chemical analysis ‘The arrangement of the styrene and é#obutylene units in the copolymers is un- Imown, although a random distribution might appear probable. A second possibility is one in which there are relatively long blocks consisting mainly of styrene, followed by other blocks containing predominantly isobutylene units. If the range of protec- tion of the styrene units is much smaller than the average length of the isobutylene block, considerable chain fracture will occur in the latter parts of the molecule, while cross-linking will predominate in the styrene-rich blocks. The irradiated copolymer will then separate into two constituents, a sol fraction with a high isobutylene content, and a gel fraction in which the styrene/isobutylene ratio is higher than the average, This behaviour can be readily traced from a chemical analysis of the gel fraction, since the percentage of styrene can be deduced from the C/H ratio. The experimental results for the gel fractions of a number of irradiated specimens, together with those for the original material, are shown in table 1. The last column gives the percentage of styrene units which would be needed in the gel to account for the observed C/H ratio, and shows only a small tendency for styrene to segregate by preference in the gel. The differences observed should indeed be further reducedRadiation protection in copolymers of isobutylene and styrene 141 (possibly by 1 or 2%) to allow for the loss in hydrogen in cross-linking and for the tendency for cross-links to be associated with styrene so that even for an initially random distribution some increase in C/H is to be expected. It is concluded that the distribution of styrene and isobutylene units in the polymer does not take the form of long blocks in which one monomer predominates, but that the distribution is either at random, or at the most in very small blocks of a few monomers only. ‘TaBLe 1. CHEMICAL ANALYSIS OF IRRADIATED GEL FRACTION initial percentage styrene (%) by weight corresponding —— radiation CE opt to C/H isobutylene styrene (pile units) —_ealeulated observed observed 80 20 0 oT O72 20 80 20 10 — 6-8 0 50 50 0 81 8-10 + 0-05 50 50 50 i ~ 8-87 63 50 50 9 — 8-8 £015 62 20 80 0 10-1 10-08 380 20 80 3 — 105 £04 85 20 80 7 — 10-3 82 20 80 9 ~ 10:37 83 INTERPRETATION OF VISCOSITY-RADIATION CURVES The intrinsic viscosity curves for the copolymers can be usefully compared with those for pure polyisobutylene and for pure polystyrene, which are typical respec- tively for polymers which degrade, and those which cross-link under radiation. In tho first region the decrease in intrinsic viscosity with radiation dose is parallel to that for pure polyisobutylene if suitable values for 2, are chosen (figure 2) showing that degradation takes place in all these copolymers, but to a decreased extent. The small amount of cross-linking due to the presence of styrene does not seriously affect the initial course of degradation, although more radiation is required to achieve the same number of fractures. The rise in viscosity due to cross-linking between styrene units is negligible, as can be seen in the first part of the eurve for pure polystyrene. Except close to the gel point (when cross-linking becomes appreciable), or above it, one would expect a relationship [y]oc KM* te hold for the degraded copolymers, although the constants might be appreciably different from those in (1). On the assumption that the number of main-chain fractures is proportional to the radia- tion dose R, this relation would result in a straight-line plot of [yy] against. R-+ Ry on a logarithmic plot, the slope being —e. The only parameter available is Ry, and this was chosen to make the intrinsic viscosity [7] of the unirradiated material fit the same straight lino as the values for the highly irradiated specimens. Tt is then found that the intermediate values of [7] fall on the same straight line, and that the slope is —0-68, as for pure polyisobutylene. It follows that equation (1) can be expected to apply to the copolymers to a sufficient degree of accuracy, It should be em- phasized that with the exception of the 20%, isobutylene polymer R, is very small,142 P. Alexander and A. Charlesby and has little effect except at low radiation levels. By comparing the radiation doses needed to produce the same reduction in viscosity as for pure polyisobutylene, an estimate can be made of the susceptibilities to degradation of the copolymers relative to that of the pure polyisobutylene. For the 80°%, isobutylene it is about 55%), and for the 50% isobutylene about 25% of that of pure polyisobutylene. For the 20% isobutylene polymer no definite value can be given, butit is obviously much lower. ‘The second region can be ascribed to a continued reduction of [7] resulting from degradation of the isobutylene parts of the chain, together with an increase in viscosity which is due to cross-linking and branching of the styrene units near the gel point, the two opposing tendencies compensating one another approximately. The continued degradation due to isobutylene units only can be evaluated by extending the approximately linear first region, while the increase due to cross-linking can be estimated by studying the appropriate curve for pure polystyrene. If the rise in {y] due to the latter is subtracted from the full [y]] curve for each copolymer, as @ cor- rection for cross-linking, a smooth continuous curve is obtained which is approxi- mately linear over regions | and 2 and represents the continued degradation of the isobutylene units up to the gel point. The radiation doses at which gel formation begins are represented in figure 2 by vertical lines, These doses are greater than for pure polystyrene, since the average molecular weight of the copolymers has been considerably reduced by radiation, and in these short chains not all units are available for cross-linking. One may con- sider separately main-chain fracture and cross-linking. At the gel point the average molecular weight M, of each sample, allowing for protection and fracture, but not for cross-linking, may be estimated very approximately from the viscosity, by extrapolating the linear portion of the curve. The radiation dose R, which would be needed for cross-linking such molecules to the gel point can then be ealeulated. On the assumption that these molecules contain only styrene units, the calculated values are roughly as follows: 80% isobutylene polymer M,= 4000 R, = 10-units, 50 20000 21 20 60.000 0-7 The actual radiation doses needed to promote gel formation are 6-5, 4 and 0-9 units respectively. The agreement between calculated and observed values, while poor, is probably as good as can be expected. This agreement has, however, been obtained by assuming that all units in the degraded molecule can cross-link as well as styrene, whereas in fact they include isobutylene units which would normally degrade rather than cross-link. If allowance is made for these non-cross-linking units, the calculated radiation doses are greatly increased, and no agreement is possible with the observed values, at least for the 80%, isobutylene copolymer. It is therefore tentatively suggested that where an isobutylene unit is protected against fracture by a neighbouring styrene, it may be able to undergo the corre- sponding process of cross-linking.Radiation protection in copolymers of isobutylene and styrene 143 The rapid drop of viscosity after the gel point has been shown. to occur for all cross-linking polymers. No analysis of this portion of the viscosity curve has been attempted. RANGE OF PROTECTION On the assumption of a random distribution of styrene and isobutylene units throughout the polymer molecule, it is possible to deduce from the reduced degrada- tion rates of the copolymer the degree of protection offered by the styrene unit. For this purpose let § represent a styrene unit, B an isobutylene unit, and let us consider the relative probabilities of various configurations about a given iso- butylene unit B as a function of the concentrations of B and 8 in the copolymer. Only the two nearest neighbours on either side of the B unit will be considered. In the configurations of table 2, f represents the proportion of isobutylene (B) units to the total number of units. The numerical values for three values of f are given corresponding to 80, 50 and 20% of isobutylene by weight. Let us now assume, for example, that an isobutylene unit B is only protected against degradation if one of more of its immediate neighbours is a styrene S unit. In the 80% isobutylene copolymer (f = 0-88) the protection factor is then 0-211 +0-014 or 225%. Moreover, only a fraction f or 88% of the units in the molecule are available for radiation fracture (the styrene units not being capable of degradation). As compared with pure polyisobutylene we would then expect radiation to produce only (1—0-225) x 0-88 or 68% of the degradation effect in 80°% isobutylene copolymer. The corresponding figures for 60 and 20%, isobutylene polymers are 20 and 32%, for the same range of protection. If, however, protection is also afforded by styrene units placed farther away, say at next-but-one neighbour, the degradation ratios as compared to pure polyisobutylene are further decreased. For the 80% isobutylene copolymer the probability of a given B unit being pro- tected is equal to 40%, for the 50% isobutylene copolymer it amounts to 81° and for the 20% isobutylene copolymer it rises to 99 %, The probability of degrada- tion would therefore be 53, 125 and 03%. TABLE 2. CONFIGURATION PROBABILITIES probability configuration probability f= 088 0-66 0-317 (i) BBBEB 6 0-00 019 0-01 (ii) BBBBS aa ide sopap} sus) 0-164 0-195 0-043 (iii) SBBBS sa-sy oon 0-050 0-047 iv) BBS as 2 449 . sap} afl—f) Onl O49 0-433 (v) SBS aan ort ons 0-467 ‘The observed reduction in the rate of degradation as compared with pure poly- isobutylene can be obtained from figure 2 (region 1). The observed ratios for the protection offered by the presence of styrene units in the molecule are summarized in table 3. These values are only to a small extent dependent on the values chosen144 P. Alexander and A. Charlesby for the correction factor Ry. The protection offered in the 20°%, isobutylene eopoly- mer is too considerable to be estimated at all accurately, and the degradation observed, which is only a small percentage, is possibly not significant, Comparing these experimental values for protection with those calculated, it appears that each styrene unit is capable of protecting against radiation-induced fracture between one and two isobutylene units on either side. The assumption made in the analysis that protection is eitherfull or non-existent isobviously anover- simplification, and the units involved are themselves not symmetrical. The range of protection of about four main-chain carbon atoms appears to be in approximate agreement with the results previously obtained for the protection against radiation cross-linking by naphthyl groups (Alexander & Charlesby 1954). Tarrz 3. COMPARISON OF PROTECTION OBSERVED IN /SOBUTYLENE + STYRENE COPOLYMERS WITH VALUES CALCULATED ASSUMING DISTANCE OVER WHICH ONE STYRENE UNIT PROTECTS % degradation relative to pure polyisobutylene for copolymors containing, ———————— 20% styrene 50% styrene 80% styrene observed from viscosity change 55 25 — observed from gel fraction _ 1s calculated values for protection 68. 29 10 over one éaobutylene unit calculated values for protection 53 125 1 over two isobutylene units * Cannot be calculated reliably. From the solubility curve (figure 3) for the 20% isobutylene copolymer it was deduced that there is about 0-9 chain fracture per cross-link formed by irradiation. ‘The energies required to produce a cross-link in pure polystyrene, or to fracture the main chain in pure polyisobutylene, are approximately in the ratio of 100 to 1. ‘To produce the observed ratio of fracture to cross-linking, the ratio of unprotected isobutylene units to styrene units must therefore be in the ratio of 0-9, and the ratio of unprotected to total isobutylene units 18%, This figure lies between the values calculated assuming that (i) styrene units protect the immediate neigh- bouring isobutylene units only (10%) and (ii) they protect the two nearest iso- butylene neighbours on either side (1%). Thus the gel data confirm the degree of protection deduced from the viscosity data. ConcLUsIONS Ina copolymer of styrene and isobutylene it has been shown that the styrene unit is able to offer partial protection to isobutylene units against radiation-induced fracture, The extent of this protection extends over between one and two neigh- bouring isobutylene units on either side, i.e. about four carbon atoms in the main chain. This range of protection is very close to that provided against cross-linking. It is also shown that the units in these copolymers are distributed at random, ratherRadiation protection in copolymers of isobutylene and styrene 145 than in large blocks. As a result protection is not complote, oocasional isobutylene units being unprotected (because of the lack of a neighbouring styrene unit) even for a copolymer containing 80%, of styrene. Such copolymers therefore show both cross-linking and degradation, and after adequate radiation separate with a gel and a sol fraction. It is therefore not possible to produce a copolymer of this character which will be resistant to radiation changes. Even for a copolymer with only 20% isobutylene content, radiation will eventually produce a 35%, viscous sol fraction. It is tentatively suggested that an isobutylene unit, when suitably protected by a neighbouring styrene unit, may undergo cross-linking rather than chain fracture. We wish to thank Miss J. Lazar for experimental assistance, and Dr L. Williams, of the Polymer Corporation, Sarnia, Canada, for the provision of the copolymers. The investigation has been supported by a special grant from the Anna Fuller Fund and by grants to the Chester Beatty Research Institute from the British Empire Cancer Campaign, the Jane Coffin Childs Memorial Fund for Medical Research and the National Cancer Institute of the National Institutes of Health, U.S. Public Health Service. REFERENCES Alexander, P. & Charlesby, A. 1954 Nature, Lond., 173, 578. Alexander, P., Charlesby, A. & Ross, M. 1954 Proc. Roy. Soc. A, 223, 392. Charlesby, A. 1952 Proc. Roy. Soc. A, 215, 187. Charlesby, A. 1953 J. Polym. Sei. 11, 513. Fox, T. G. & Flory, P. J. 1949 J- Pllys. Chem. 83, 197.