POLYMER ENGINEERING (MM 538)

Dr. Kausar Ali Syed Lecture No 1 & 2 June 29, 2012

Review of polymerization, structure, and properties of polymeric materials Although many people probably do not realise it, everyone is familiar with polymers. They are all around us in everyday use, in rubber, in plastics, in resins and in adhesives and adhesive tapes. They are an extraordinarily versatile class of materials, with properties of a given type often having enormously different values for different polymers and even sometimes for the same polymer in different physical states. Nowadays designers and engineers readily turn to plastics because they offer combinations of properties not available in any other materials. Plastics offer advantages such as lightness, resilience, resistance to corrosion, colour fastness, transparency, ease of processing, etc. We are here concerned primarily with synthetic polymers, i.e. materials produced by the chemical industry, rather than with biopolymers, which are polymers produced by living systems and are often used with little or no modification. Many textile fibers in common use, such as silk, wool and linen, are examples of materials that consist largely of biopolymers. Wood is a rather more complicated example, whereas natural rubber is a biopolymer of a simpler type. Since most polymers are organic in origin, we briefly review some of the basic concepts relating to the structure of their molecules. The major bonds that hold atoms together are covalent, where electrons are shared by adjacent atoms, ionic, where electrostatic attraction occurs when electrons are donated or accepted to provide complete electron shells, and metallic, where the atoms donate their valence electrons to form a sea of electrons surrounding the atoms. The valence electrons move freely within the electron sea and become associated with several atom cores. The positively charged ion cores are held together by mutual attraction to the electrons, thus producing a strong metallic bond. There are also secondary bonds that are relatively weak by comparison. These are seldom mentioned when studying metals and ceramics because they are not important. In polymer materials, covalent bonds provide strong, rigid bonding of atoms within a long chain molecule while the secondary bonds provide the attraction forces between long chain molecules and thus held them together. Secondary bonds play an equally important role in the properties of polymers. Now, many organic materials are hydrocarbons; that is, they are composed of hydrogen and carbon. Furthermore, the intramolecular bonds are covalent. Each carbon atom has four electrons that may participate in covalent bonding, whereas every hydrogen atom has only one bonding electron. A single covalent bond exists when each of the two bonding atoms contribute one electron. A bond between two carbon atoms may involve the sharing of two pairs of electron; this is termed a double bond. For example in ethylene, which has the chemical formula C2H4, the two carbon atoms are doubly bonded together, and each is also singly bonded to two hydrogen atoms. H H CC H H

Where and denote single and double covalent bonds. Molecules that have double and triple covalent bonds are termed unsaturated; that is each carbon atom is not bonded to the maximum four atoms.

Polymer molecules

The molecules in polymers are gigantic in comparison to the hydrocarbon molecules. For most polymers, these molecules are in the form of long and flexible chains, the backbone of which is a string of carbon atoms: C C C C C C C C These long molecules, called polymers are formed by linking together a large number of identical units, or mers. These polymers offer a variety of useful properties. Although all polymers contain covalent bonds within the molecules, they may have either primary or secondary bonds bridging the macromolecules. The term polymer is used to mean a particular class of macromolecules consisting, at least to a first approximation, of a set of regularly repeated chemical units of the same type, or possibly of a very limited number of different types (usually only two), joined end to end, or sometimes in more complicated ways, to form a chain molecule. If there is only one type of chemical unit the corresponding polymer is a homopolymer; if there is more than one type it is a copolymer. Here we will deal briefly with some of the main types of chemical structural repeat units present in the more widely used synthetic polymers and with the polymerization methods used to produce them. It should be noted that the term monomer or monomer unit is often used to mean either the chemical repeat unit or the small molecule which polymerizes to give the polymer. These are not always the same in atomic composition, as will be clear from what follows, and the chemical bonding must of course be different even when they are. The simplest polymers are chain-like molecules of the type AAAAAAAAAAAAA where A is a small group of covalently bonded atoms and the groups are covalently linked. The simplest useful polymer is polyethylene CH2CH2CH2CH2CH2CH2CH2CH2 or [CH2] n

wherein a typical length of chain, corresponding to n ~ 20 000 (where ~ means of the order of), would be about 3 mm. A piece of string typically has a diameter of about 2 mm, whereas the diameter of the polyethylene chain is about 1 nm, so that a piece of string with the same ratio of length to diameter as the polymer chain would be about 1.5 m long. It is the combination of length and flexibility of the chains that gives polyethylene its important properties. The phrase typical length of chain was used above because, unlike those of other chemical compounds, the molecules of polymers are not all identical. There is a distribution of relative molecular masses (M r) (often called molecular weights) and the corresponding molar masses, M.

The value of Mr for the chain considered in the previous paragraph would be 280000, corresponding to M = 280000 g mol-1. Commercial polymers often have average values of M between about 100 000 and 1 000 000 g mol-1, although lower values are not infrequent. The flexibility of polyethylene chains is due to the fact that the covalent bonds linking the units together, the so-called backbone bonds, are non-collinear single bonds, each of which makes an angle of about 112 with the next, and that very little energy is required to rotate one part of the molecule with respect to another around one or more of these bonds. The chains of other polymers may be much less flexible, because the backbone bonds need not be single and may be collinear. A simple example is polyparaphenylene, for which all the backbone bonds are collinear and also have a partial double-bond character, which makes rotation more difficult.

Such chains are therefore rather stiff. It is these differences in stiffness, among other factors, that give different types of polymer their different physical properties. The chemical structures of the repeat units of some common polymers are shown in fig. 1.1, where for simplicity of drawing the backbone bonds are shown as if they were collinear. The real shapes of polymer molecules are considered elsewhere. Many polymers do not consist of simple linear chains of the type so far considered; more complicated structures are introduced in the following section.

Fig. 1.1 Structures of the repeating units of some common polymers.

The classification of polymers

Polymers are classified in several ways: by how the molecules are synthesized, by their molecular structure, by their chemical family, by their crystal structure, or by their application. Two other useful classifications are the following. (i) Classifications based on structure: linear, branched or network polymers. A linear polymer consists of spaghetti-like molecular chains. In a branched polymer, there are primary polymer chains and secondary offshoots of smaller chains that stem from these main chains. Note that even though we say linear, the chains are actually not in the form of straight lines. Figure 1.3 shows these types of polymer schematically. It should be noted that the real structures are three-dimensional, which is particularly important for networks. In recent years interest in more complicated structures than those shown in fig. 1.2 has increased.

Fig. 1.2 Schematic representations of (a) a linear polymer, (b) a branched polymer and (c) a network polymer. The symbol represents a cross-link point, i.e. a place where two chains are chemically bonded together.

(ii)

Classifications based on properties: A better method to describe polymers is in terms of their mechanical and thermal behavior e.g., (thermo) plastics, rubbers (elastomers) or thermosets.

These two sets of classifications are, of course, closely related, since structure and properties are intimately linked. A brief description of the types of polymer according to classification (ii) will now be given. The three major polymer catagories are; (1) Thermoplastics, (2) Thermosetting polymers, and (3) Elastomers. Thermoplastics Distinction between two major subclasses of polymers is based on the type of bond between adjacent polymer chains. It may be noted that in contrast to the monomer, the PE polymer chain is saturated, so that there are no additional sites for primary bond formation. Thus, the only mechanism that remains for bond formation between PE chains is secondary bond formation.

H H H H H H H H CCCCCCCC H H H H H H H H Secondary bonds H H H H H H H H CCCCCCCC H H H H H H H H Linear or branched polymers that form melts upon upon heating such as PE, are called thermoplastic polymers. Thermoplasts soften when heated (and eventually liquefy) and harden when cooled processes that are totally reversible and may be repeated. In the

molten state they consist of a tangled mass of molecules. On cooling they may form a glass (a sort of frozen liquid) below a temperature called the glass transition temperature, Tg, or they may crystallise. The glass transition will be considered later on. If they crystallize they do so only partially, the rest remaining in a liquid-like state which is usually called amorphous, but should preferably be called non-crystalline. These materials are normally fabricated by the simultaneous application of heat and pressure. On a molecular level, as the temperature is raised, secondary bonding forces are diminished (by increased molecular motion) so that the relative movement of adjacent chains is facilitated when a stress is applied. Irreversible degradation results when the temperature of a molten thermoplastic material is raised to the point at which molecular vibration become violent enough to break the primary covalent bonds. In addition, thermoplastics are relatively soft and ductile. Most linear polymers and those having some branched structures with flexible chains are thermoplastic. Thermosetting polymers Thermosets are network polymers that are heavily cross-linked to give a dense three-dimensional network. Thermosetting polymers become permanently hard when heat is applied and do not soften upon subsequent heating. During the initial heat treatment, covalent crosslinks are formed between adjacent molecular chains; these bonds anchor the chains together to resist the vibrational and rotational chain motions at high temperatures. Crosslinkling is usually extensive, in that 10 to 50 % of the chain mer units are crosslinked. Only heating to excessive temperature will cause severance of these crosslink bonds and polymer degradation. In other words, thermosetting plastics formed into a permanent shape and cured or set by a chemical reaction cannot be remelted and reformed into another shape. Thermosets polymers are generally harder, stronger, and more brittle, than thermoplastics, and have better dimensional stability. The name thermoset arises because it was necessary to first heat the polymers of this type in order for the cross-linking, or curing, to take place. The term is now used to describe this type of material even when heat is not required for the cross-linking to take place. Examples of thermosets are the epoxy resins, such as Araldites, and the phenol- or urea-formaldehyde resins. Elastomers Rubbers, or elastomers, are network polymers that are lightly crosslinked and they are reversibly stretchable to high extensions (>200%). When unstretched they have fairly tightly randomly coiled molecules that are stretched out reversibly by applying a force. This causes the chains to be less random, so that the material has a lower entropy, and the retractive force observed is due to this lowering of the entropy. The cross-links prevent the molecules from flowing past each other when the material is stretched. On cooling, rubbers become glassy or crystallise (partially). On heating, they cannot melt in the conventional sense, i.e. they cannot flow, because of the cross-links.

Classical polymerization processes

The chemistry of polymer molecules

The structurally simplest polymers are synthetic, or man-made. As an example, consider the linear polymer polyethylene, or PE, for which the monomer is C 2H4 molecule that has the following structure: H H CC H H PE polymer chain is formed by opening the double bond between the C atoms in an individual monomer and linking a series of monomers together to form the linear molecule. An examination of bond energies associated with single and double covalent bonds between carbon atoms shows that the breaking of one double bond and the formation of one single bond (per monomer) result in a decrease in the free energy of the system. Thus, the formation of a PE polymer chain from a collection of identical monomers is a thermodynamically favored reaction. Functionality of a monomer In order for a monomer to polymerize, it must have at least two active chemical bonds. When a monomer has two active bonds, it can react with two other monomers, and by repetition of the bonding, other monomers of the same type can form a long-chain or linear polymer. When a monomer has more than two active bonds, polymerization can take place in more than two directions, and thus three dimensional network molecules can be built up. The number of active bonds a monomer has is called the functionality of the monomer. A monomer which utilizes two active bonds for the polymerization of long chains is called bifunctional. Thus ethylene is an example of a bifunctional monomer. A monomer which utilizes three active bonds to form a network polymeric material is called trifunctional. Phenol, C2H5OH, is an example of a trifunctional monomer and is used in the polymerization of phenol and formaldehyde.

Polymer Synthesis
In polymerisation, monomer units react to give polymer molecules. In the simplest examples the chemical repeat unit contains the same group of atoms as the monomer (but differently bonded), e.g. ethylene polyethylene n(CH2 CH2) (CH2CH2)n

More generally the repeat unit is not the same as the monomer or monomers but, as already indicated, it is nevertheless sometimes called the monomer. Some of the simpler, classical processes by which many of the bulk commercial polymers are made are described below. These fall into two main types, addition polymerisation and step-growth polymerisation.

Addition Polymerization or Chain Growth Polymerization

The sequential addition of monomer units to a growing chain is a process that is easy to visualize and is the mechanism for the production of an important class of polymers. For the most common forms of this process to occur, the monomer must contain a double (or triple) bond. In chain-growth polymerization, the only chain-extension reaction is that of attachment of a monomer to an active chain. The active end may be a free radical or an ionic site (i.e., anion or cation). Chain Polymerization Steps It can be divided into three steps: (1) initiation, (2) propagation, and (3) termination. Initiation In the initiation step an activated species, such as a free radical from an initiator added to the system, attacks and opens the double bond of a molecule of the monomer, producing a new activated species. Initiators are the source of free radicals. A free radical can be defined as a group of atoms having an unpaired electron (free electron) which can covalently bond to an unpaired electron of another molecule and usually denoted in its chemical formula by a dot. Usually organic peroxides are used as free radical formers. For example hydrogen peroxide, H2O2, can decompose into two free radicals, as shown below H O O H 2H O Benzoyl peroxide is an another organic peroxide which is used to initiate some chain polymerization reactions and decomposes into free radicals as illustrated below:

When the ethylene gas (monomer) is subjected catalytically to appropriate conditions of temperature and pressure, one of the free radicals created by the decomposition of the organic peroxide can react with ethylene molecule to form a new longer-chain free radical (an active mer is formed by the reaction between an initiator or catalyst species (R ) and the ethylene mer unit). The double bond between the two carbon atoms is opened up, the double covalent bond is replaced by a single covalent bond as shown below H H H H Free electron RO + CC ROCC H H H H
Free radical Ethylene Free radical

The organic free radical in this way acts as an initiator catalyst for the polymerization of ethylene.

Propagation The process of extending the polymer chain by the successive addition of monomer units is called propagation. The double bond at the end of the ethylene monomer unit can be opened up by the extended free radical and be covalently bonded to it. Thus, the polymer chain is further extended by the reaction R CH2 CH2 + CH2 CH2 R CH2 CH2 CH2 CH2 The polymer chains in chain polymerization keep growing spontaneously because the energy of the chemical system is lowered by the chain polymerization process. Although this process may continue until thousands of monomer units have been added sequentially, it always terminates when the chain is still of finite length. Termination Termination can occur by the addition of a terminator free radical or when two chains combine. Another possibility is that trace amounts of impurities may terminate the polymer chain. Termination by coupling of two chains can be represented by the reaction R (CH2 CH2)m + R' (CH2 CH2)n R (CH2 CH2)m (CH2 CH2)n R'

The simplest type of addition reaction is the formation of polyethylene from ethylene monomer: (CH2)nCH2CH2* + CH2 CH2 (CH2) n+2 CH2CH2*

There are basically three kinds of polyethylene produced commercially. The first to be produced, low-density polyethylene, is made by a high pressure, high-temperature uncatalysed reaction involving free radicals and has about 2030 branches per thousand carbon atoms. A variety of branches can occur, including ethyl, CH2CH3, butyl, (CH2)3CH3, pentyl, (CH2)4CH3, hexyl, (CH2)5CH3 and longer units. High-density, polymers are made by the homopolymerization of ethylene or the copolymerization of ethylene with a small amount of higher a-olefin. Two processes, the Phillips process and the ZieglerNatta process, which differ according to the catalyst used, are of particular importance. The emergence of a new generation of catalysts led to the appearance of linear low-density polyethylenes. These have a higher level of co-monomer incorporation and have a higher level of branching, up to that of low-density material, but the branches in any given polymer are of one type only, which may be ethyl, butyl, isobutyl or hexyl. 1.3 The chemical nature of polymers 13 Polyethylene is a special example of a generic class that includes many of the industrially important macromolecules, the vinyl and vinylidene polymers. The chemical repeat unit of a vinylidene polymer is (CH2CXY), where X and Y represent single atoms or chemical groups. For a vinyl polymer Y is H and for polyethylene both X and Y are H. If X is CH3, Cl, CN, C6H5 or O(C O)CH3, where C6H5 represents the monosubstituted benzene ring, or phenyl group, and Y is H, the well-known materials polypropylene, poly(vinyl chloride) (PVC), polyacrylonitrile, polystyrene and poly(vinyl acetate), respectively, are obtained. When Y is not H, X and Y may be the same type of atom or group, as with poly(vinylidene chloride) (X and Y are Cl), or they may differ, as in poly- (methyl methacrylate) (X is CH3, Y is COOCH3) and poly(-methyl styrene) (X isCH3, Y is C6H5. When the substituents are small, polymerization of a tetra-substituted monomer is possible, to produce a polymer such as polytetrafluoroethylene (PTFE), with the repeat unit (CF2CF2) , but if large substituents are present on both carbon atoms of the double bond there is usually steric hindrance to

polymerisation, i.e. the substituents would overlap each other if polymerisation took place. Polydienes are a second important group within the class of addition polymers. The monomers have two double bonds and one of these is retained in the polymeric structure, to give one double bond per chemical repeat unit of the chain. This bond may be in the backbone of the chain or in a side group. If it is always in a side group the polymer is of the vinyl or vinylidene type. The two most important examples of polydienes are polybutadiene, containing 1,4 - linked units of type (CH2CH CHCH2) or 1,2-linked vinyl units of type (CH2CH(CH CH2) ) , and polyisoprene, containing corresponding units of type (CH2C)CH3)CH CH2) or (CH2 C(CH3)(CHCH2) ) Polymers containing both 1,2 and 1,4 types of unit are not uncommon, but special conditions may lead to polymers consisting largely of one type. Acetylene, CH CH, polymerises by an analogous reaction in which the triple bond is converted into a double bond to give the chemical repeat unit (CH CH). Ring-opening polymerisations, such as those in which cyclic ethers polymerise to give polyethers, may also be considered to be addition polymerisations: nCH2(CH2)m-1O (CH2)mO)n

The simplest type of polyether, polyoxymethylene, is obtained by the similar polymerisation of formaldehyde in the presence of water: nCH2 O (CH2O)n

Step Growth Polymerization

Consider the following simple organic molecules: R OH RNH2 R C OH O Acid

Alcohol

Amine

R is used to indicate an organic root (eg, CH3, C2H5 etc.). OH, NH2 & COOH are functional groups. These functional groups can react with each other forming water and a linkage. The formation of an amide and an ester is shown below. Note that water is a by-product of both reactions. These types of reactions are called condensation reactions.

Fig. 1.4

Fig. 1.5

However these reactions would not form polymers because in these reactions each reactant has only one functional group. If each reactant has two functional groups, then it is possible to form a polymer. In stepwise polymerization, monomers chemically react with each other to produce linear polymers. The reactivity of the functional groups at the end of a monomer in stepwise polymerization is usually assumed to be about the same for a polymer of any size. Thus monomer units can react with each other or with produced polymers of any size. In many stepwise polymerization reactions a small molecule is produced as a byproduct, so these types of reactions are sometimes called condensation polymerization reaction. An example of stepwise polymerization reaction is the reaction of hexamethylene diamine with adipic acid to produce nylon 6,6 and water as a by-product, as shown in the figure below:

Fig.1.6 Two reactants that could form a polyamide

Fig. 1.7 The reaction of a difunctional alcohol and a difunctional amine

Fig. 1.8 Formation of a poloyamide

This reaction is very similar to the one shown in Fig. 1.4 & 1.5. The amine functional group (NH2) and the acid functional group (COOH) will react and form an amide linkage NHCO and water. The reaction will not cease in this case. There is no possibility that one and only one HOOC(CH2)6COOH molecule reacted with one and only one H2N(CH2)NH2 molecule. Therefore, more than one of the product molecules formed. The product molecule has an amine functional group (NH2) and an acid group (COOH). These can react to form an amide linkage NHCO and water. The reaction will continue, and a molecule of n units enclosed in [ ] is called a mer, and because the molecule has many mers, it is called a polymer. In the labeling of these nylons the first number is the number of carbon atoms in the amine residue and the second the number of carbon atoms in the acid residue. Two nylons of somewhat simpler structure, nylon-6 and nylon-11, are obtained, respectively, from the ring-opening polymerisation of the cyclic compound e-caprolactam: nOC(CH2)5NH (OC(CH2)5NH)n and from the selfcondensation of -amino-undecanoic acid: nHOOC(CH2)10NH2 (OC(CH2)10NH)n + nH2O The most important polyester is poly(ethylene terephthalate), ( (CH2)2OOC C6H5COO)n, which is made by the condensation of ethylene glycol, HO(CH 2)2OH, and terephthalic acid, HOOC C6H5 COOH, or dimethyl terephthalate, CH3OOCC6H5COOCH3, where C6H5 represents the para-disubstituted benzene ring, or pphenylene group. There is also a large group of unsaturated polyesters that are structurally very complex because they are made by

multicomponent condensation reactions, e.g. a mixture of ethylene glycol and propylene glycol, CH3CH(OH)CH2OH, with maleic and phthalic anhydrides (see fig. 1.9).

Fig. 1.9 The chemical formulae of (a) maleic anhydride and (b) phthalic anhydride.

An important example of a reaction employed in step-growth polymerization that does not involve the elimination of a small molecule is the reaction of an isocyanate and an alcohol which produces the urethane linkage RNCO) HOR RNHCOOR One of the most complex types of step-growth reaction is that between a di-glycol, HOROH, and a di-isocyanate, OCNRNCO, to produce a polyurethane, which contains the structural unit ORO(CO)(NH)R(NH)(C O). Several subsidiary reactions can also take place and, although all of the possible reaction products are unlikely to be present simultaneously, polyurethanes usually have complex structures. Thermoplastic polyurethanes are copolymers that usually incorporate sequences of polyester or polyether segments. Formaldehyde, H2CO, provides a very reactive building block for step-growth reactions. For example in polycondensation reactions with phenol, OH, or its homologues with more than one OH group, it yields the phenolic resins, whereas with urea, O C(NH2)2, or melamine [see fig. 1.6 (a)] it yields the amino resins. The products of such condensation reactions depend on the conditions employed but they are usually highly cross-linked. Acid conditions lead to the formation of methylene bridged polymers of the type shown in figs. 1.6(b) and (c), whereas alkaline conditions give structures containing the methylol group, CH2OH, which may condense further to give structures containing ether bridges, of the form ROR (fig. 1.6(d)).

Fig. 1.6 The chemical formulae of (a) Melamine; and (b), (c), and (d) various bridging structures in phenolic resins

Newer polymers and polymerisation processes The polymerisation processes described in the previous section are the classical processes used for producing the bulk commercial polymers. Newer processes have been and are being developed with a variety of aims in mind. These involve the production of novel polymer topologies (see box); precise control over chain length and over monomer sequences.

Degree of polymerization The general reaction for the chain polymerization of ethylene monomer into polyethylene may be written as

The repeating subunit in polymer chain is called a mer. The mer for polyethylene is [CH2 CH2] and is indicated in the above equation. The n in the equation is known as the degree of polymerization (DP) of the polymer chain and is equal to the number of subunits or mers in the polymer molecular chain. The average DP for polyethylene ranges from about 3500 to 25,000, corresponding to average molecular masses ranging from about 100,000 to 70,000 g/mol. Average Molecular weight for polymers Let's think about a small molecule, say, hexane. Hexane has a molecular weight of 86. Every hexane molecule has a molecular weight of 86. Now if we add another carbon to our chain, and the appropriate amount of hydrogen atoms, we've increased our molecular weight to 100.

That's fine, but the molecule is no longer hexane. It's heptane! If we have a mixture of some molecules of hexane and some of heptane, the mixture won't act like pure heptane, nor will it act like pure hexane. The properties of the mixture, say, its boiling point, vapor pressure, etc., will be neither those of pure hexane nor pure heptane. But polymers are different. Imagine polyethylene. If we have a sample of polyethylene, and some of the chains have fifty thousand carbon atoms in them, and others have fifty thousand and two carbon atoms in them, this little difference isn't going to amount to anything. If you really want to know the truth, one almost never finds a sample of a synthetic polymer in which all the chains have the same molecular weight. Instead, we usually have a bell curve, a distribution of molecular weights. Some of the polymer chains will be much larger than all the others, at the high end of the curve. Some will be much smaller, and at the low end of the curve. The largest number will usually be clumped around a central point, the highest point on the curve. So we have to talk about average molecular weights when we talk about polymers. And we're not going to stop there. The average can be calculated in different ways, and each way has its own value. So let's talk about some of these averages, why don't we?

The Number Average Molecular Weight, Mn

The number average molecular weight is not too difficult to understand. It is just the total weight of all the polymer molecules in a sample, divided by the total number of polymer molecules in a sample. _ Mn = or in terms of mole fraction xi,

Ni Mi / Ni _ Mn = xi Mi

where xi is the mole fraction of molecules of molar mass MI and is given by the ratio of Ni to the total number of molecules.

The Weight Average Molecular Weight, Mw

The weight average is a little more complicated. It's based on the fact that a bigger molecule contains more of the total mass of the polymer sample than the smaller molecules do.

Demographics
A good way to understand the difference between the number average molecular weight and the weight average molecular weight is to compare some cities /towns of Sindh.. Let's take four cities, say, Sukkur, Dadu, Tando Jam; and Ghulab Laghari. Now we'll take a look at their populations. City Sukkur Dadu Population 700,000 12,000

Tando Jam Ghulab Laghari

10,000 1,500

Now let's calculate the simple average population of the four cities: 700,000 + 12,000 + 10,000 + 1,500 723,500 / 4 = 180,875 = Wow 723,500

Now we see that of these four cities, that average population is 180,875. But we could look at it a different way. Until now we've been worried about "the average city". What is the population of "the average city"? But let's forget about cities for a moment, and think about people. What size city does the average person among the populations of these four towns live in? If you look at the numbers you can see that the average person doesn't live in a town of a population of 180,000. Take a look there. Most of the people in the combined populations of the four towns live in Sukkur, a town with a lot more than 180,000 people. So how do we calculate the size of town that the average person lives in, if the simple average doesn't work? What we need is a weighted average. This is an average that would account for the fact that a large city like Sukkur holds a larger percentage of the total population of the four cities than Ghulab Laghari. Doing this involves a little bit of math that looks scary but really isn't. All we do is take the total number of people in each city, then multiply that number by that city's fraction of the total population. Take all the answers we get for each city and add them up, and we get an answer that we'll call the weight average population of the four cities. Let's walk through this to show what I mean. Take Sukkur. It has a population of 700,000. The total population of our four cities is 723,500. So the fraction of people who live in Sukkur is...

...0.9675, or we might say, 96.75% of the people live in Sukkur. Now let's take our fraction, 0.9675, and multiply that by the population of Sukkur:

And we get an answer of 677,273.3. Now let's do the same thing for all the cities, and add up the answers: So our weight average population of the four cities is about 677,600. We can say from this figure that the average person lives in a city of about 677,600. That is more believable than saying that the average citizen lives in a city of 180,000. We do the same thing with polymers. We calculate, with the same formula as we used for the weight average population of our four cities, the weight average molecular weight and is shown mathematically as:

_ Mw =

wi Mi / wi = Ni Mi2 / Ni Mi

where

wi

Ni Mi

Or in terms of weight fraction fi, the weight average molecular weight of the polymer is described as the sum of the weight fractions times their mean molecular weight for each particular range divided by the sum of weight fractions. Thus it is written as: _ Mw = where _ Mw Mi fi = fiMi / fi ( fi = Ni Mi / Ni Mi )

average molecular weight for a polymer

= mean molecular weight for each particular molecular weight range selected = weight fraction of the material having molecular weight of a selected molecular weight range

The average molecular weight can be determined by the measurement of various physical properties such as viscosity and osmotic pressure. One method commonly used for this analysis is to determine the weight fractions of molecular weight ranges.

Example Problem Calculate the degree of polymerization in a sample of nylon 6,6 having a molecular weight of 120,000 g / mol. H H O [N (CH2)6N C(CH2)4C] O (nylon mer) Mol. Wt. of repeat unit or 1 mer = 2 x 14 + 22 x 1 + 12 x 12 + 2 x 16 = 226 g / mol DP = 120,000 / 226 = 531 ( Note that chain contains 531adipic acid and 531 HMDA molecules).

Example Problem Consider a sample of polypropylene, that is composed of only three types of chains. 60 % of the chains in this sample have a degree of polymerization (n) of 10,000, 30 % of the chains have n = 15,000, and 10 % of the chains have n = 100,000. Calculate the polydispersity for this sample. Solution: First we must calculate the weight of a single PP mer (m), then we calculate the molecular weight each type of chain (Mi). Next we determine the two measures of average molecular weight (M n and Mw), and finally we can determine the polydispersity of the sample. PP mer is [CH2CH] CH3 m(PP) = [ 3 x 12 + 6 x 1] = 42 g /mol / mer No. of chains ( Ni ) 60 30 10
Ni = 100

DP

Mol.wt of each type of chain (Mi)

= DP x Mmer

NiMi (wi) 252 x 105 189 x 105 420 x 105

NiMi

fi = wi / NiMi 252 x 105 / 861 x 105 = 0.2926 189 x 105 / 861 x 105 = 0.2195 420 x 105 / 861 x 105 = 0.4878

fi x Mi

10,000 15,000 100,000

420,000 630,000 4,200,000

0.2926 x 420,000 = 122,892 0.2195 x 630,000 = 138,285 0.4878 x 4,200,000 = 2,048,760 2,309,937

= 861 x 105 Mn = NiMi / Ni = 861 x 105 / 100 = 861,000 g /mol Mw = fi Mi =

2,309,937 g/mol &

PD. = Mw / Mn

= 2309937 / 861000 = 2.68

Assignment Problem: Following data was obtained for a Polyvinyl Chloride (PVC) sample : No. of chains or polymer molecules 1000 4000 5500 6000 6500 2000 Mol. Weight range (g / mol) 5,000 10,000 10,000 15,000 15,000 20,000 20,000 25,000 25,000 30,000 30,000 35,000

For this material compute (a) the number average degree of polymerization & (b) polydispersity.