Chemical and Geometrical... 105 Figure 5.2B shows a schematic representation of two monomers and two homopolymers and a copolymer made of them. pater TPN alte Miele) felt at td ia lS While the chemical structure of a macromolecule depends on the chemical nature of the monomeric units, the geometrical structure depends on the spatial arrangement of the monomeric units with respect to each other. Polymers having the same chemical structure (i.e., made-up of the same monomeric units) can have different geometrical structures. While discussing the spatial arrangement of monomeric units in a polymer chain, two terminologies are common: configuration and conformation. A configuration is an arrangement fixed by chemical bonding between adjacent monomeric units and between atoms of individual monomeric units. The configuration remains unaltered as long as chemical bonds are not broken or re-formed. A polymeric chain cannot shift from one configuration to another without breaking or re- forming the chemical bonds. A conformation, on the other hand, is an arrangement resulting from the rotation of chain segments (or adjacent monomeric units) around single bonds. It will be noticed that this kind of rotation does not involve any breaking or re-forming of the chemical bonds; a polymeric chain of a given configuration can, over a period of time, assume innumerable shapes or conformations, depending on such external forces as thermal energy, solvent interaction and applied stress. The conformations taken by a polymer molecule depend on whether the polymer is of a flexible- chain type or a rigid-chain type. A flexible-chain polymer is one in which the chain segments can rotate with respect to each other with a sufficient degree of freedom. Polymers composed of non- polar segments or segments with a very low polarity are of the flexible-chain type. Polyethylene, polystyrene and rubber are examples. By contrast, a rigid chain polymer is one in which the rotation of the chain segments is hindered due to steric factors (such as the presence of bulky side groups or of aromatic groups in the chain backbone) or due to strong forces of attraction (such as dipole or hydrogen bonding) between the neighbouring chains. Polyamides, aromatic polyesters and cellulose esters belong to this group. The conformations possible with polymer molecules vary from a linear rigid rod-like structure to that of a flexible random coil. Polymer molecules in the solid state have conformations of interpenetrating random coils (in amorphous polymers), orderly folded chains (in crystalline polymers) and spiralled or helical chains (in biological polymers such as proteins). In dilute solutions, molecules of flexible-chain polymers exist as isolated random coils and those of rigid-chain polymers exist as rigid rods or helixes. In highly concentrated solutions or swollen gels, they form interconnected network or interconnected cell structure (Fig. 5.3). Details of these conformations will be given in appropriate chapters. In the forthcoming sections, we deal mainly with various configurations. 5.3.1 Linear, Branched and Cross-linked Polymers Homopolymers and copolymers can exist in three different types of chain configurations, viz., linear, branched or cross-linked. Consider a PVC homopolymer and a PVC-PVAc copolymer. Their CHAPTER 5LR ES rinsio” Q KR af interpenetrating random coils Folded chains (Solid Polymers Amorphous) (Solid Polymers Crystalline) Spiralled or-helical chains (Polypeptides or Proteins) a hS 0) eo), S Ue (Linear) (Branched) Interconnected network structure |solated random coils (Cross-linked Polymers) (Dilute Polymer Solution) Fig. 5.2 Representative conformations of polymer molecules under different situations. structures, shown in Fig. 5.2, are of a linear chain type. Here, each monomeric unit is linked with two other monomeric units on either side, forming a continuous straight chain. Monomeric units added on to each other, like railway bogies; forming a long train. A linear polymer can schematically represented by a single line. In some cases, however, while the polymer chain is growing in a linear manner, some sid? growth also takes place from the main chain. In such cases, while most of the monomeric units 2 linked with two others on either side, some monomeric units may also be linked with a thif monomeric unit. Such polymer molecules will have an overwhelmingly linear chain, with a few shot side chains or branches attached at random points, These are called ‘branched polymer molecules" the shape of which can be represented by a line with a few branches. During polymerisation, a large number of branched polymer molecules may be formed and, further polymerisation, the side chains from one molecule could possibly interact with those from neighbouring ones. Since there are many molecules present with side chains attached at raneee Ur Kec Us: ec a UL positions, the process of the interuniting of side chains of neighbouring molecules results in a single molecule with a ctiss-crossed network of chain segments in all the threc dimensions. Such a polymer ig called a cross-linked or network polymer, Schematic representations of linear, branched and network polymer molecules are shown in Fig. 54. Linear Branched Cross-linked 9 o0000000000009 — cooooodacanr ‘ Fig. 5.4 Schematic representation of linear, branched and cross-linked polymer molecules. 5.3.2 Random, Alternating Block and Graft Copolymers When two different repeat units in a copolymer are distributed at random throughout the chain, the polymer is called a ‘random copolymer’. In certain copolymers, a more ordered sequence of repeat Units is seen and then these copolymers are termed alternating, block or graft copolymers. When two repeat units are distributed alternately throughout the chain, the polymer is termed an “alterating copolymer’. CHAPTER 5 When a sequence or block of one repeat unit is followed by a block of another repeat unit, which, in turn, is followed by a block of the first repeat unit and so on, the polymer is called a block Copolymer’. Block copolymers are, therefore, linear molecules in which both repeat units are Consecutively distributed in fairly long sequences. Graft copolymers, on the other hand, are branched molecules where the main chain is made Cntirely of one repeat unit, while the branch-chains are made of yet another repeat unit.GL Meta ul este Figure 5.5 shows schematic representations of various copolymers. ee Random copolymer 000000008 0® Altemating copolymer @ Block copolymer Graft copolymer Fig, 5.5 Schematic representation of different types of copolymer structures. 5.3.3 Stereo-regular Polymers In stereo-regular polymers, each monomer segment is in a regular configuration, giving a defiie structural regularity to the polymer molecule as a whole, This structural regularity, in a polymer m3) arise due to what are termed as “optical” and “geometric” isomerisms of the main chain atoms 0 substituents in the polymer molecule. The meaning of these two isomerisms is now explained. Optical Isomerism Optical isomerism has its origin in the way different substituents sit on an asymmetric carbon atom a polymer molecule. We will give an example. A polyethylene molecule has fully saturated carbo atoms with the following chemical formula: —CH,—CH,—CH,—CH,—CH,—CH,— We can write this formula in a linear structural way, showing how various atoms are attached (™! without bothering about the bond angles and molecular plane) as follows: It It | | HW de tH 4 oo HOW HO HOH HOH H HOH Pele ke te fl TPT P TPP b G6 e oe | H Let us now assume that the carbon-carbon bonds are all on the plane of this paper and that the boats between the carbon atom and its substituent atoms are either below or above the plane of the P%t The structure of polyethylene in a planar zig-zag configuration is then 2s show i Fig, 5.6. In dom this, of course, we have not bothered about the free rotation around each carbon.carben single al and the various resultant spatial positions of the polymer segment. It is seen from Fig. 5.6 that carbon atoms are attached to each other through single bonds which are arranged in a zig-zag 2" considering their bond angles. All carbon atoms lie in the plane of the paper but hydroge® 2%Chemical and Geometrical. . - 109 to the carbon atoms protrude away, up or down, from the plane of the paper. The hydrogen tached arom above or below the plane of the paper are interchangeable without altering the overall olyethylene structure. This is possible because in polyethylene all hydrogen atoms attached to polpen atoms are indistinguishable. H H 7 S | I I | H | /t | ~ Hon Plane formed by the —C—C—backbone <———! — : Bond projecting above the plane of paper +} Bond projecting below the plane of paper ‘C—atom Planar zig-zag structure of polyethylene molecule. —CH,—CHR—CH,—CHR—CH,—CHR— and its structural formula would be as follows: H H H H H H H H HH A oh a —c—¢—¢—¢—c—c—¢—c—¢—c—c—C— PEEPS SSE eee ect ete Cet H R HR R H RH RH R In such a polymer chain, every alternate carbon atom can be considered to be asymmetric. This means that the alternate carbon atom, which we designate as C*, carries four different substituents —H, R and two polymer chain segments of chain length m and as shown H . I * X—CH,+ Ga— chide CH, — Hex R R R Here, X denotes end groups. Each of these C* atoms provides a si d- or [-type isomerism, depending on whet carbon chain or above. The regularity or the ord molecule. The structures shown in Fig. 5.7 wil groups located on one side of the plane of the gToups located alternatively above and belo Ill, we have them located randomly. Polyme: Structure II are called syndiotactic; while the three types of polymers have the same che use of their differing configurations and But imagine that one of the hydrogen atoms in all ethylene units of this polymer is substituted by |g substituent R (such as CH, Cl or CN). The polymer will then ‘have the chemical formula ite for optical isomerism. Each such site can exhibit either ther the R group is located below the plane of carbon- jer in which the successive asymmetric carbon sites, C*, exhibit their d- or /-form gives rise to three different types of isomeric structure in the polymer Il clarify the concept. In structure I, we have all the R arbon-carbon chain. In structure II, we have the R ww the plane of the carbon-carbon chain and in structure rs having structure I are called isotactic; those having third type are known as atactic or heterotactic. These mical structure, but exhibit entirely different properties the resulting geometrical structure. Atactic polymers are, CHAPTER 5for instance, generally low melting and easily soluble, while isotactic and syndiotactic polymers, high melting and less soluble. He Geometric Isomerism In optical isomerism, while single bond C—C atoms are involved, in geometric isomerism double bond C=C atoms are involved. Geometric isomerism arises from different configurations of jj, substituents on a carbon-carbon double bond and depends on how the substituent TOUS are positioned. For example, let us consider 1, 3-butadiene polymerisation. The butadiene monomer ha, two double bonds in its structure: HoH OH boiot —c=C i H —d—Id_I-d (Syndiotactic) or Hdd —d—d—I—d—I (Atactic or Heterotactic) or Fig. 5.7 Planar zig-zag structure of polymer molecules showing: liotactic al 19: (I) Isotactic, (11 ind (IT) eter Configurations. (Hydrogen atoms are not shown for the purpose of ny. net ns a)fear UC cel ee It can polymerise as shown CH, ‘CH — CH=CH, —» (CH, — CH=CH — CH; The resultant polymer structure has a double bond in each repeat unit of ~{Ch, — CH = CH —cH- Each of these double bonds provides a site for a steric isomerism, depending on whether the CH, groups attached to the carbon atoms on either side of the double bond are close to or away from each other. The two possible configurations (Fig. 5.8) are: (a) where both the —CH, groups are on the same side of the double bond close to each other (called cis-configuration), and (b) where they are on the opposite sides and quite apart (called trans-configuration). = CH: CH —OHe — CH CH CH=CH CH=CH -+H= CH, CH i - Cis-configuration ‘Trans-configuration 1, 2 vinyl configuration Gis-, trans- and 1, 2 vinyl configurations of butadiene units in polybutadiene molecule. A third configuration, called 1, 2 vinyl configuration, is also possible. (see Fig. 5.8). In the case of 1, 2 vinyl configuration, however, the three types of optical isomerism, i.e., atactic, isotactic and syndiotactic configurations, are possible. It may also be seen from this figure that in cis- configuration, there is a bending back of the carbon-carbon chain, whereas, in trans-configuration, there is a straightening out of the carbon-carbon chain. During the polymerisation of 1, 3-butadiene, if all repeat units take cis-configuration, we get a 100% cis-polybutadiene and due to bending back of. all the successive carbon-carbon chain segments, the molecule as a whole assumes a shape of a Spring (Fig. 5.9) and exhibits good elongation. On the other hand, during polymerisation, if all the repeat units take trans-configuration, the resultant polymer is a 100% trans-polybutadiene and due to the straightening out of all the successive carbon-carbon chain segments, the molecule assumes a Straight and stiffened rod-like structure (Fig. 5.9) and exhibits lower elongation. In practice, however, polymerisation of butadiene to 100% cis or 100% trans is extremely difficult, and we usually obtain mixtures of cis- and trans-configurations, randomly distributed throughout the chain length (presence of 1, 2-vinyl structure is also possible) (Fig. 5.9). Depending on the ratio of cis- to trans-chain segments present, the polymer can exhibit either high or low elongation. CHAPTER 58 f bang CH OCH dH, oH Y Y cc ae HH Hoe (Cis-polybutadiene) HoH HH AKAK oe WY LAAN HoH HH (Trans-polybutadiene) HOH WOH Ai te carcgre wee Ee. "cH HeCHH Gute, (1, 2-polybutadione) 5:2 Configurations of 100% cis-, 100% trans- and 100% 1, 2-Polybutadiene molecules, Books for Further Reading Natta, G. and Damusso, F., Stereoregular Polymers and Stereospecific Po Oxford, 1967. Bovey, F.A., Polymer Conformation and Configuration, Academic, New Koening, J.L., Chemical Microstructure of ‘Polymer Chain, ymerisations, Pergamon, York, 1969, Sons, New York, 1980. John Wiley &We have studied so far the chemical aspects of polymerisation reactions. The terminology includeq terms such as polymerisation system, catalyst system and solvent system. These refer to the physica] pects of polymerisation reactions which decide whether the monomer is polymerised in its velensed or gaseous state, whether it is polymerised as such or along with other inert components ch as solvents and non-solvents. Factors such as the nature of the monomer, the type of polymerisation mechanism chosen, the required physical form of the polymer and the viability of the process for industrial production are some of those dictating the physical conditions under which polymerisation is to be carried out. These varying physical conditions lead to different polymerisation techniques, as enumerated in the following sections. 2.5.1 Bulk Polymerisation ¢ and the initiator is dissolved in the monomer. The chain the molecular weight, is also dissolved in the monomer mogeneous phase. The reaction mass is heated or lymerisation and is kept under agitation for proper The monomer is taken in the liquid stat transfer agent, whenever used to control itself, The whole system is, therefore, in a ho exposed to radiation source for initiating the pol mass and heat transfers. As the polymerisation proceeds, the viscosity of the medium increases and mixing becomes progressively difficult, leading to products with very broad molecular weight Gisribution, Another disadvantage of bulk polymerisation is that as the medium gets viscous the diffusibility of the growing polymer chains becomes restricted, the probability of chain collision termination becomes difficult, active radical sites accumulate and the rate of becomes less. d ‘autoacceleration’ am: polymerisation increases enormously. This whole phenomenon is calle sometimes, the uncontrolled exothermic reaction can lead to an explosion. nd the product obtained has a high purity since her additive that could contaminate the prodv! Bulk polymerisation, however, is quite simple ai m other components except the initiator and the chain transfer agent, no ot] is used. The polymer obtained can also be used as such since no isolation fro involved.Chemistry of Polymerisation 53 Finally, the bulk polymerisation technique is used in the free-radical polymerisation of methyl methacrylate or styrene to get transparent moulding powders and cast sheetings and also of vinyl chloride to got PVC resin, 2.5.2 Solution Polymerisation In solution polymerisation, the monomer is dissolved in a suitable inert solvent along with the chain transfer agent, whenever used. The free-radical initiator is also dissolved in the solvent medium, while the ionic and coordination catalysts, can either be dissolved or suspended. The presence of the inert solvent medium helps to control viscosity increase and promote a proper heat transfer. ‘The major disadvantage of the solution polymerisation technique is that, however, inert the selected solvent may be, chain transfer to the solvent cannot be completely ruled out and, hence, it is difficult to get very high molecular weight products. The polymer formed will also have to be isolated from the solution either by evaporation of the solvent or by precipitation in a non-solvent, and removal of their final traces is always extremely difficult. Solution polymerisation techniques, nevertheless, can advantageously be used where the polymer is used in its solution form, as in the case of certain adhesives and coating compositions, or in systems where the polymer formed is insoluble in its monomer or solvent and precipitates out as a slurry and is amenable for easy isolation. Coming to the practical applications, industrial production of polyacrylonitrile by free-radical polymerisation and that of polyisobutylene by cationic polymerisation, use the solution technique. Block co-polymers are also made exclusively by this technique. 2.5.3 Suspension Polymerisation Only water-insoluble monomers can be polymerised by this technique. The monomer is suspended in water, in the form of fine droplets, which are stabilised and prevented from coalescing by using suitable water-soluble protective colloids, surface active agents and by stirring. The size of the monomer droplets formed depends on the monomer-to-water ratio, the type and concentration of the stabilising agents and also on the type and speed of agitation employed. The initiators are monomer soluble. Since each monomer droplet is isolated and independent of the other droplets, it can be visualised to act as an independent bulk polymerisation nucleus. The continuous aqueous phase separating the monomer droplets acts as an efficient heat transfer medium and, hence, the exothermicity is well controlled. Since water is used as the heat transfer medium, the process is also economical as compared to solution polymerisation. As the entire bulk of the monomer is divided into innumerable tiny droplets, control on the kinetic chain length* of the polymer formed is also quite good, resulting in a fairly narrow molecular weight distribution of the product. Polymerisation proceeds to 100% conversion and the product is obtained as spherical beads or pearls. (For this reason, this technique is also known as bead or pearl polymerisation). Isolation of the product becomes easy as this involves only filtration of the beads and removal of the surface active agents and protective colloids by water Washing. The water-washed and dried product can be used as such for moulding purposes or can be dissolved in a suitable medium for use as adhesives and coatings, n on ‘kinetic chain length’, see Section 4.2.1 CHAPTER 2bela Expandable polystyrene beads (from which polystyrene foams are made), styrene.diyin benzene co-polymer beads (for the preparation of ion-exchange resins) and polyvinyl acetate (for further conversion into polyvinyl alcohol) are produced by the suspension technique using fy radical initiators, 2.5.4 Emulsion Polymerisation As in the case of suspension polymerisation, in emulsion polymerisation too, the monomer i dispersed in the aqueous phase not as discrete droplets, but as a uniform emulsion. The emulsion ig stabilised by surface active agents (surfactants), protective colloids and also by certain buffers, The surfactants can be anionic (alkali salts of fatty acids and of aryl and alkyl sulfonic acids), cationic (alkyl amine hydrochlorides and alkyl ammonium halides) or non-ionic (alkyl glycosides ang saccharose esters of fatty acids), Surfactants serve the purpose of lowering the surface tension at the monomer-water interface and facilitate emulsification of the monomer in water. Owing to their low solubility, surfactants get fully dissolved or molecularly dispersed only at low concentrations. Beyond a particular concentration, the excess quantity does not get molecularly dispersed, but forms molecular aggregates known as ‘micelles’, and an equilibrium is set up between the dissolved surfactant molecules and the aggregated ones. The highest concentration, wherein all the molecules are in a dispersed state, or the concentration beyond which only micelle formation is possible, is known as the ‘critical micelle concentration’ (CMC). Typical examples of surfactants and their CMC values are given in Table 2.6. We know that emulsifier molecules are made of two parts: a long not- polar hydrocarbon chain to which is attached a polar group such as—COONa, —SO;Na, —NH,H( or —NBr. In micelle formation, the emulsifier molecules aggregate in such a way that the polar end Table 2.6 List of surfactants and their critical miscelle concentration (CMC)” aed TCD) Temp (°C) Anionic CH,(CH,)gCOONa 6.5 x 10" 20 CH,(CH,),,COONa 56 20-70 CH,(CH,),0SO,Na 3.0 x 107 25-50 CH,(CH,),OSO,Na 26 25-60 CH,(CH,)sCoH,SO.Na 98 5 (CH,(CH,))CgH,SO,Na 4.0 «10% 50-75 Cationic CH,(CH,)NH, HCI 85 25 CHY(CH,) ,NH,HCI 27 30-50 CH,(CH,))N(CH,),Br 7.8 «10! 25 (CHACH,) N(CH), 54 25 Non-ionic (CHy(CH,}/CyH 110 25 CraHyOglC gH, O2), 20 CHy(CH,) (SOOT 7H} y0 50 “Data from Polymer Handbook, Eds. Brandrup J and Immergut EH. John Wiley & Sons, New York, 1975:oer ete eae ul eld) of the molecules align themselves outward and the hydrocarbon ends come close to each other at the interior (Fig. 2.3). ‘Aqueous phase ow Z 2 te! [ * | e , 4 | s | i <- e a we < =x oO Individual surt c Line Individual surfactant ‘Aggregated surfactant molecule molecules (micelles) ee: Non-polar hydrocarbon chain of the surfactant molecule » : Polar head of the surfactant molecule Fig.2.3 Schematic representation of surfactant molecules distributed in water: (A) completely dissolved at low concentration and (B) dissolved as well as aggregated beyond critical micelle concentration (CMC). Due to the close proximity of the hydrocarbon ends of all emulsifier molecules, the interior of the micelle acts as a hydrocarbon phase where the monomer can be solubilised. Now, when the monomer is added and agitated, emulsification takes place. The resultant emulsion is a complex system: A molecular solution of the emulsifier in water is the continuous phase wherein the monomer droplets and micelles (having the solubilised monomer at their interior) are uniformly dispersed (see Fig. 2.4). If the monomer is slightly soluble in water, then the aqueous emulsifier solution phase will also contain a part of the monomer dissolved in it. O ‘Monomer molecule or monomeric unit in the polymer chain e Surfactant molecule Fig. 2.4 Schematic detalls of the various components present in an emulsion polymerisation system. S,, S,, S,, MM and, represent respectively the empty micelle, monomer-filled micelle, micelle with growing polymer chain, monomer droplets and latex particles containing monomer as well as growing polymer.POLYMER DEGRADATION WHAT IS POLYMER DEGRADATION ‘You may have noticed that a plastic bucket left for long in the sun and rain loses its lustre and strength. This deterioration in Properties is due to a phenomenon called ‘polymer degradation’. “sch is characterised by an uncontrolled change in the molecular weight or constitution at the mer. Conventionally, the term ‘degradation’ is taken to mean a reduction in the molecular weight of the polymer. A polymer can suffer degradation mainly at two sta; 0cess and secondly, durin; oulding involve heating, ust degrade. Similarly, in TESSeS, solar radiations, at ,__ While polymer degra fat eample, when a spa ‘nt to melt the met ted by a ‘heat shi Derature on re-entry, and thus Protects tl ges of its life. First, during the fabrication g its daily usage. Many of the fabrication processes such as extrusion or which the polymer may not be able to endure and as a consequence, may the hustle-bustle of modem life, plastic ai ticles have to face mechanical itmospheric oxygen, moisture, etc. and this can degrade the polymer. dation is generally undesirable, it can sometimes be put to advantage also ‘cecraft re-enters the earth’s atmosphere, intense heat is generated, which is ‘tal and even make the craft explode. To avoid such a situation, jeld’, which is a polymer-based material. As the heat shield enc the material chars and degrades and in the process, takes a\ he spacecraft. the spacecraft ounters a high way the severe ors Eye Ca degradation j the f 's broadly of two types: (i) chain-end degradation and (i) random degradation, OSL type. th “Se ina, Le Seeradation starts from the chain ends, resulting in successive release of the Alymerice ls (Fig. 10.1). This phenomenon is actually the reverse of the propagation step in chain ation. For this reason, this type of degradation is also called ‘depolymerisation’. We may © propagation step in polymerisation to represent the ‘c ‘losing of a zip’ anddepolymerisation the ‘opening of the zip’. Indeed, this type of degradation is also ‘unzipping’. The scission is almost like cutting off successively a long strip of paper into from its end. The result is that the molecular weight of the polymer decreases slowly a quantity of the monomer is liberated simultaneously. termed ,, Small bj, + + (oH eee HCH HoH + + | o- SoH } +24} Fig, 10.4 Schematic representation of a polymer molecule undergoing chain-end degradation. (Each block inthe dagen represents one monomeric unit). A good example of unzipping or chain-end degradation is provided by the therms! depolymerisation of non-terminated (i.e., living) poly o-methylstyrene synthesised through the anionic mechanism. This polymer in a solvent such as anhydrous tetrahydrofuran, upon heating fon ~70°C to +60°C, undergoes degradation from the chain end carrying the active carbanion in sucha manner that, at 60°C, the entire polymer is converted into the monomer (cf. depropagation at th ceiling temperature in Section 4.2.5). The important precaution to be taken is that the system should be kept free from moisture and other impurities such as oxygen and carbon dioxide. The process interestingly enough, reversible. Hence, by simply cooling the system back to ~70°C, the polymer sit be obtained qualitatively. Polymers formed by chain reaction polymerisation are more susceptible unzipping (or chain-end degradation). But here again, all such polymers do not undergo unzippins straightaway. For example, it is well known that polymethyl methacrylate, when heated to 300°C under vacuum, depolymerises to give back the monomer in an almost quantitative yield The unzipping, however, sets in only after a weak link somewhere in the polymer backbone is broke? under the influence of heat to generate a chain end carrying a free-radical: Tt Heat Ll The unzipping now starts from the active chain ends formed, In fact, depolymerisation isa se! method for recovering the monomer from waste polymethyl methacrylate with a recovery of aims 100%. Polystyrene, polybutadiene and polyisoprene also undergo depolymerisation to give back monomer, although t0 limited extent. Polyeaprolactam (nylon 6), which is not a ‘chain reat polymer, can also undergo depolymerisation to a limited extent, giving back the caprols! " monomer up to 6%. In genera, it can be said that chain-end degradation occurs when the backbo™ bonds are weaker than the bonds of the side groups and only with polymer molecules carrying 2°" chain ends with a free-radical, cation, anion, etc. Schematically, we can write this as follows: Ind a latye | | |Deeg tl M; > M*\+M Mi. M*_,+M and so on here M is the monomer and M7, M}_, and so on represent the polymer chain made up of so many Tponameric units and carrying an active end group. The enzymatic degradation of certain natural products also follows the ‘unzipping’ mechanism: For example, the enzyme called B-amylase degrades starch to maltose, beginning with the chain ends. The second type of degradation occurs at any random point along the polymer chain instead of at the chain ends (Fig. 10.2) and hence, the name ‘random degradation’. This type of degradation could be thought of as the reverse of the polycondensation process as illustrated by the following equation: M, > M,+M, i HOH HoH (HOE + io C +4 Hoo 4 +o Fig, 10,2 Schematic representation of a polymer molecule undergoing random degradation. (Each block in the diagram represents one monomeric unit). CHAPTER 10 Here, the polymer degrades to lower molecular weight fragments but (unlike in chain-end degradation) practically no monomer is liberated. Almost all polymers can undergo random degradation. Polyesters, for example, undergo hydrolytic degradation, resulting in chain scission: meson ~~ HO — ~—~E—0H +HO-RA~~ ] ° ° Further, in random degradation, of polyethylene for instance, a hydrogen atom may migrate from one carbon to another and yield two fragments, as shown: “CH, — CH, — CH, — CH, — CH, — CH, — CH, — CH, — CH, — CH, — CH, — CH, ~~ *. Fee [si scission “> CH, — CH, — CH, — CH, + CH= CH — CH, — CH, — CH, — CH, + CH, — CH, ~~ | | 5 | For random degradation to occur, the polymer chain need not necessarily carry any active site. tCA ee Sul esl It would thus be noted, that the polymer molecule breaks up while degrading. The process op breaking up is decided by the type ofthe degradation. In chain-end degradation, the molecular weigh drops very slowly and a large quantity of the monomer is released; in random degradation, there i sudden drop in the molecular weight with little or no release of the monomer. Degradation of polymers may be brought about either by physical factors (such as hea, light op mechanical stress) or by chemical agents (such as oxygen, ozone, acids or alkalies). In the following sections of this chapter, we will study how these factors or agents bring about degradation, 3. THERMAL DEGRADATION Thermal degradation of polymers may follow either ‘unzipping’ or the ‘random’ route The ‘unzipping’ mechanism gives the pure monomer, while random degradation leads to the formation of a host of products, depending on the structure of the polymer, Since many polymers have a carbon-carbon (C—C) chain as the backbone, their thermal stability is dependent on the stability of the C—C bond. So, let us examine the factors which affect the stability of such a bond. 10.3.1 Factors Affecting the C—C Bond Stability Several factors can affect the C—C bond stability in a polymer. Consider the following example: it hi i ot a a or ~~ o—o-~ I | i I | HoH HCH, HCH, Polyethylene Polypropylene Polyisobutylene Here, as we proceed from left to right, the number of substituents increases and the stability of the polymer backbone bond decreases. The result is that while polyethylene is thermally stable, polypropylene is less stable and polyisobutylene the least stable. In the above example, one H atom in ethylene is substituted by a methyl group to form propylene. The same H atom in ethylene can also be substituted by a phenyl group to give styrene, which will obviously be thermally less stable than ethylene. Now, if one hydrogen atom in styrene is, in turn, substituted by a methyl group, we get methyl styrene which, with one more substituent than in styrene, is thermally the least stable among the three compounds: ny im fe a aoe ~~o-o 3 I | 1 | I | HOH HGH, Ho C,H, Polyethylene Polystyrene Poly c-methyl styrenece i ed ‘The effect of substituent groups on the stability of the backbone CC bond ipparent from a comparison of the bond dissociation energies (in kcal/mol) for CC in CH,—CH, ~ 88, CH CHs— CHs = 85, (CH) CCH, = 80 and CgH CH; —CHy = 70 A word of caution would be in order. All substituents do not always reduce the thermal stability of the polymeric system. For ‘Instance, Polytetrafluoro ethylene (Teflon) has all the hydrogen atoms of ethylene substituted by fluorine, but is one of the most stable polymers: a—o—n F | —ce | F aon F | ~c~— | F m™—O—n7 m—o—n a—o—n7 F | —t~s | F (Tefion) Teflon can withstand temperatures as high as 400°C, without undergoing degradation; this property incidentally makes Teflon highly useful for domestic and industrial applications. Its high thermal stability is attributed to the very high dissociation energy (108 kcal/mol) of the C—F bonds. Besides, the highly electronegative nature of fluorine protects the C+-C bond in Teflon from an external attack. 10.3.2 Other Factors Affecting Thermal Stability = Generally, the aromatic groups in a polymer backbone increase the thermal stability. Polycarbonate is a case in point: wl a < is 5 f-O-5-Orosh CH, ° (Polycarbonate) A substance like polyphenylene, where the chain backbone is formed entirely of aromatic t0ups, is, by the same token, thermally more stable than polycarbonate: ~©-O-©O-O-© (Polyphenylene) The high thermal stability of polytetrafluoro ethylene and that of polyphenylene are combined in Polyterafluoro phenylene, which is a relatively new polymer, capable of withstanding temperatures P to 500°C,bet (Poiytetraftuoro phenyiene) The branching and the presence of oxygen atom in the polymer chain are other important Factor which make polymers susceptible to thermal degradation. The easy degradability of the polyethyj. y ethyl oxide molecule, for instance, is attributable tothe presence of the oxygen atom in the polymer eit backbone: ~~.0 —CH, — CH, — O— CH, — CH, — 0 — CH, — CH, —O — CH, — CH, ~ (Polyethylene oxide) 10.3.3 Polymer Degradation Involving Substituent Groups There are some reactions involving polymer degradation by breaking the substituent groups but not the main chain. A typical example is PVC which degrades around 200°C, giving HCI. Although the mechanism of PVC degradation is highly complex in nature, the free-radical path seems to play a major role. What apparently happens is that some free-radical (R), produced either from impurities or because of the reaction temperature being reached, attacks the methylene group and abstracts aH with a simultaneous transfer of the free-radical site on to the chain: ~~ CH, — CH — CH, — CH — CH, — CH ~~ +R | | | cl a a RH a a ~~ | | a a a The labile chlorine atom, which is at a B-position with respect to the free-radical carbon atom, is now released as a free-radical so as to stabilise the structure: ca cl ci | Gie-—~- CH=CH — CH, — GH— OH, — BH ~" CH GH Ci, — GH Gt — FH mr a aGrout ed | hlorine free-radical can now attack a met! 7 me ile chlorine atom: thylene group, abstract a H and produce yet apoter WF CECH Cha — EH — Cy — man cl a co | HOl+““~ CH=CH — CH, — CH — GH — cH aii oO OH Cl (Epoxidised oil) w"[R—c—o] + 2HcI — MG" +76 — OH I ° ° (Metal salts)EAU oN esta uls) Although PVC has a tendency to degrade around 200°C, it is stil the world’s most wig, ey plastic. 4 MECHANICAL DEGRADATION A simple compound such as water or benzene cannot be broken up by subjecting it to mMechanig stresses arising from, say, high-speed stirring or milling. But a polymer such as polystyrene disse in a solvent, when subjected to vigorous stirring or beating, undergoes considerable molec degradation or fragmentation. In fact, in the rubber industry, rubber is masticated by Passing i through two rotating rollers to reduce its molecular weight and make it more processable, This mastication converts hard and tough rubber into a soft, supple and even semisolid mass. Now, wha happens to the rubber at a molecular level when it is so masticated? Let us first remember that rubber is polyisoprene with the following structure: CH, CH, CH, | | i ~~ CH, — C=CH — CH, — CH, — C=CH — CH, — CH, — C=CH— CH, ~~~ (isoprene unit) (soprene unit) (lsoprene unit) (Polyisoprene) In polyisoprene, the bonds which are most vulnerable for scission are the CH,—CH, links between the isoprene units. These bonds in the susceptible regions cleave when the polymer is subjected to mechanical stresses in the form of milling or mastication, The net effect is that the big molecule is broken or scissioned into small parts. This scission at the molecular level reflects on the gross properties of the polymer. Besides milling and mastication, other mechanical methods also make the polymer molecules degrade. For example, when a polymer solution or melt throttles through a small orifice under a fait) high pressure, fragmentation of the polymer molecule can occur. Agitation, grinding or extrusion a other well-known methods for effecting the mechanical degradation of the polymer. The bast phenomenon in all these is the same; namely, to subject the polymer to a very powerful shearing for that breaks the molecule. Many interesting observations have been made by researchets °° mechanical degradation. For instance, the bigger molecules are found to be affected much more tht? the smaller ones during mechanical degradation. This means that the larger the initial molec! weight, the greater the molecular weight drop due to mechanical degradation. The way in which a polymer sample attains a constant limiting molecular weight subjected to a mechanical stress for a sufficiently long time, can be seen from Fig. 10.3. M degradation can reduce the average molecular weight, give a narrower molecular weight di and make the polymer easily processable. value, whet Mec! stributo! instants Studies have provided some interesting clues on the degradation mechanism. For eto degradation is found to be almost totally absent when rubber is masticated in an atmos! _ .aed ee ed Molecular weight —> Oo Duration of mastication —> Fie. 10.5. Effect of mastication time on molecular weight of a polymer undergoing mechanical degradation. nitrogen at an ambient temperature. However, when the Process is repeated in the presence of a small quantity of oxygen or air, degradation is very quick and significant. The reason for this is simple. During degradation free-radicals are produced at the end of the scissioned fragments of the chain. In the inert atmosphere of nitrogen, these radicals recombine to form bigger molecule, thereby almost totally nullifying the effect of the degradation. When, however, oxygen is present, due to its radical nature, it readily reacts with the free-radicals formed at the fragmented ends of the polymer molecule and renders the chain break permanent. SLi aU Yel Toms Have you heard of a ‘silent’ sound? Sounds paradoxical, doesn’t it? But this is how ultrasonic sound waves are sometimes referred to because of their very high frequencies (say, above 20,000 hertz) which is beyond the audible range of the human ear. When a dilute solution of a high molecular weight polymer is subjected to ultrasonic waves, the polymer begins to degrade, thereby reducing its molecular weight. A close look at the process taking lace at @ molecular level shows that ultrasonic degradation is a special case of mechanical degradation as the polymer here is subjected to very high vibrations, which are only mechanical forces. As ultrasonic waves pass through the solution, the localised shear gradients produced tear off ‘he polymer molecules leading to chain scission. As a result, the average molecular weight of the Sample goes down. Another point of resemblance between ultrasonic and mechanical degradations is th + : : c the decrease in the molecular weight of the polymer does not go below a certain value even after ng exposure to ultrasonic or mechanical stresses. _ iia, both in mechanical and ultrasonic degradations, bigger molecules are affected more le small degrada et ones. This can be seen from Fig. 10.4, which shows the pattern of ultrasonic Sradation with time in the case of two polymeric samples with different initial molecular weights, CHAPTER 10210 Polymer Science Reduced viscosity of the polymer solutions, Tay/c Duration of ultrasonic exposure ——> Foi. 10.4 Effect of ultrasonic degradation of two samples of the same polymer with different inital molecule weigis Here, molecule weight is represented in terms of reduced viscosity (see Section 12.6.1). & PHOTODEGRADATION Do you recall an old, domestic, laundry problem—a dazzling white synthetic garment yellowing after long use? The yellowing was not always due to a ‘lazy’ laundryman, but due to a phenomenon called ‘photodegradation’—a molecular degradation process brought about by ultraviolet igh The yellowing, and the embrittlement on storage, of some of the transparent plastics or coloured rubber articles are also due to their interaction with ultraviolet light. An interesting example of photodegradation by ultraviolet (UV) radiation is of polymety! methacrylate (PMMA). This polymer in a molten state gives on ‘irradiation with UV rays an almost quantitative yield of the monomer. It is generally believed that free-radicals are initially formed duitg photodegradation, and in many cases, the subsequent course of the reaction of the free-radicels depends on the physical state of the material. Thus, while the molten polymer gives a quantitate yield of the monomer, the solid polymer does not give any significant quantity of the monom®’. Small quantities of methyl formate are, however, formed during the photodegradation of the soll PMMA, as shown here: | htt oe | | hy Oc to ee ea ci co om | | | | | | c=0 c=0 c=0 | | | ocH, OCH och,Polymer Degradation 211 CH, CH, o=C—OCH, + ~~~ CH,—C ~~. + Ho—ocH + ~~ CH | Il | es ° c=o | OCH, ocH, CH, CH, CH, CH, | a a — He 8 aN > A CH, — CCH, HO | = c=o | ocH, OCH, A similar type of photodegradation is observed in the case of poly-c-methyl styrene also. Ithas been shown that polyethylene molecules, due to structural defects or impurities, quite often contain a C=C or C=O linkage, which makes the nearby bonds susceptible to photodegradation as follows ° ll > CH, — CH, — CH, — CH, — C — CH, — CH, — CH, — CH, — CH, — CH, — CH, ~~> CHAPTER 10 | (UV rays) ° ll “CH, — CH, — CH, — CH, — C — CH, + CH,==CH — CH, — CH, — CH, — CH, — CH, ~~ 10.6.1 Photostabilisers iststabilsers Protect polymers from the deteriorating effects of light to a considerable extent. bee Salicylate, known as ‘Salol’, is one of the early stabilisers. Stabilisers such as 2, 4-hydroxy ‘aone (Uvinul 400), 2-hydroxy, 4-methoxy benzophenone (Virnul M 40) and 2-hydroxy, ‘*cyloxy benzophenone (DOBP) are used in the plastic industry. Shy function of a photostabiliser (or photoabsorber) is to absorb the UV radiation and dissipate atemine thus absorbed to the environment in some harmless form. The absorbed energy is In doing <4 2K as heat or radiations of a longer wavelength (consisting of quanta of lesser energy). Tolecut te the stabiliser acts as a filter and does not allow the radiation energy to attack the polymer iePau ed Stabilisers usually are molecules with aromatic rings having hydroxy groups and ketonic Broup, The following is an example: oO ° i I ‘OH HO! (substituted 2-hydroxy benzophenones) Most stabilisers have the hydroxyl and ketonic groups in the ortho-position, which encourage, the formation of the hydrogen bond. In addition, stabilisers have an absorption coefficient higher than that of the polymer in the near ultraviolet range of the electromagnetic radiation. Hence, th absorb most of the light and subsequently convert it into heat. This is effected through the following simple reversible reaction: ys o OH o 0 I | olb-« olbh« Normal structure Hydrogen bonded structure Heat energy If we represent the stabiliser by A and its hydrogen bonded structure by B, the overall reaction may be represented as follows: hv A > B B > A+ Heat This absorption of energy and the subsequent dissipation as heat will take place even at extremely low concentrations of the stabiliser and this is precisely how the polymer is protected from the harmful effects of the UV rays. There are some stabilisers, such as 2-(hydroxy phenol) benzotriazole, which do not contait # ketonic group but are still capable of forming a hydrogen bonded structure as shown: ' H-o cal 7 a i N Nm Photostabilisers are normally used to protect polymeric products of bright colours. They should therefore, be of ‘non-staining’ character so that they do not introduce any unwanted colouration discolouration of the product. This is an important consideration in selecting a photostabiliseeae et cu mL lack, for instance, is a very good photostabiliser but obviously, cannot be used for ‘objects with a bright colour. Non-toxic nature and chemical inertness are other important po derations for the stabiliser if the final product is to come in contact with skin or food. cons DEGRADATION BY HIG UTStar Vel vite) x-rays, gamma Trays, alpha rays and beta rays are among the well-known high-energy radiations. ti ike UV rays, X-rays and gamma rays are electromagnetic radiations, but their energy level is much higher than that of UV rays. Beta rays are fast moving electrons, and alpha rays are fast moving felium nuclei. Degradation by the high-energy radiations is more massive than that by the lower energy (UV) radiations. We can say that high-energy radiations smash a polymer molecule to tiny fragments like what a fast moving cricket ball can do to a sheet of glass. When high-energy radiations are so ‘grutal’, the polymer responds in a complex manner. It lets all sorts of things to happen: from breaking of its bonds or scission of its chain to cross-linking. If the molecule is scissioned, the polymer degradation is obviously associated with a reduction in the molecular weight. On the other hand, cross-linking can take place between polymer molecules, building up the polymer network with @ resultant increase in the molecular weight. Polymers which degrade on irradiation are polyisobutylene, polytetrafluoro ethylene, cellulose, polymethacrylates, poly o-methyl styrene, etc. On the other hand, polyethylene, polypropylene, polyamides, polyacrylates, polyisoprene, polybutadiene, etc. get cross-linked when subjected to high-energy radiations. Many polymers, on being exposed to radiation, give out gases such as H,, CO,,CO, CH,, NH; and (CN). For example, polyethylene and polystyrene, when subjected to high-energy radiations, give out hydrogen which comes from the nearby macromolecules as shown by the following structure (the removal of bydrogen leads to cross-linking of the polymeric chains): peers Ne esas ered +3H, CHAPTER 10When, however, polyisobutylene is subjected to high-energy radiations, methane and hydro, are evolved, The IR spectrum of the irradiated sample shows the presence of double bonds ee simultaneous reduction in the number of methyl groups. The reaction could be given as CH, CH, i CH | | | ~~ C— GH — Co GH G— CH, — C— OH ~~ | | | CH, CH, CH, CH, | High-energy radiation cH, cH, CH, cH, | | ~~ C—CH,— C= CHC — CH, —C— CH, cH, cH, cH, cH, +H cH, CH che cH, | | te C—CH,—C CHC —CH, CCH, | cH, cH cH, +CH, As against this, the behaviour of polymethyl methacrylate towards high-energy radiation interesting in some other ways. First, its molecular weight decreases considerably (with the evolution of gases such as (CO,, CO, Hy and CH,), which means that the polymer undergoes degradation during irradiation. Secondly, the polymer develops a yellow colour, which turns some what reddish brown with a higher radiation dosage. The colour is retained in vacuum but vanishes when expos to air, Disappearance of the colour starts from the periphery of the polymer block and moves tos interior at room temperature. If the temperature is raised to 80°C; the discolouration phenomeno® becomes faster. This discolouration is attributed essentially to the formation of free-radicals Sus the polymer irradiation) which, when trapped in the polymer bulk, react with oxygen amd destroyed. Enhanced mobility of these radicals at elevated temperatures is said to be the 72500 the disappearance of the colour when the polymer is in a molten stage. Although the presene® © free-radicals in the solid polymer (after irradiation) has been established by spectroscopic ™ ne the way in which the radicals are created and ultimately destroyed has not been complete? understood. ol pPolymer Degradation 215 ie EUS » degradation usually te : Onulative deneatation usually leads to hardening, discolouration as well ay surface changes. The ease dation of the polymer, of oxidative d lepends primarily on its structure. ‘Thus, unsaturated polymers such as polyisoprene ot polybutadiene containing double bonds are easily attacked by oxygen The early stage of oxidative degradation is the formation of free-radical sites on the chain 6F some free-rdical produced by the thermal ules trapped inside the polymer matrix) backbone by the attack of molecular OXyREN, OZONE decomposition, of some additives (say, initiator molec bob Where P represents the polymer chain, Onee the tre al sites are formed, attack b binadical nature, adds on at the free-radical s Y oxygen becomes easier, Oxygen, because of its c, forming a peroxide radical P10, pod The peroxy radical can now attack the neighbouring segment, abstract hydrogen and form a hydroperoxide and a new free-radical s POO + Ps Poon F It can also attack a neighbouring double bond: POO +> Cag ——+ Roepe \ The hydroperoxide formed can lead to the formation of several new free-radical sites: CHAPTER 10 POOH > PO + OH B + POOH > Pd + POH PO + POOH > POH + POS With so many free-radicals formed, their recombination can occur and result in the termination of the chain reactions: 2P06 — POOP + 0, 2P6 ~ POOP P41 On pon 2P +P Prete. 10.8.1 Mechanism of Rubber Oxidation Rubber, on oxidation, yields a variety of products. One common product is levulinaldehyde; other Products being formic acid, acetic acid and carbon dioxide. The following scheme will explain the Oxidative degradation of rubber: