F332 Advance Notice June 2011 Polymers on the move Types of polymers Thermoplastic polymers: Polymers that soften

n and melt when heated. (This means t hat they are easy to recycle by remoulding into a new item). These polymers only have intermolecular bonds (which are much weaker than the covalent bonds in the rmosets) between chains which can be broken by warming. Thermosetting polymers: Char and burn when heated (so can't be reshaped). These have extensive cross-lin king by covalent bonding. The cross-links prevent the chains moving very much re lative to one another, so the polymer stays in the same shape when it is heated. Elastomer: Polymers that are soft and springy, which can be deformed and then g o back to their original shape. A co-polymer: Is made from two different monomer s. This produces a polymer with properties in between those of the two polymers you would get if you polymerised each polymer separately. ABS Acrylonitrile (2-propenitrile) butadiene styrene is an example of a co-polymer a nd is also a thermoplastic. This material combines the strength and rigidity of the acrylonitrile and styrene polymers with the toughness of the polybutadiene r ubber. The nitrile groups from neighbouring chains, being polar, allow permanent dipole-permanent dipole forces to bind the chains together, making ABS stronger than pure polystyrene (which only experiences Van der Waals forces between chai ns). Monomers in ABS polymer How properties of polymers are linked to uses Polymer Acrylonitrile butadiene styrene (ABS) Fluoroplastics (PTFE, FEB) Use Car facia panels Reason(s) for use -High impact strength improves car safety -Ability to be injection moulded impro ves design flexibility. High maximum use temperature prevents polymer from melti ng when engine heats up. Exceptional anti-stick/low friction characteristics Dur ability and high chemical resistance makes it long-lasting. Rigid, tough, hard-w earing and tear from repeated use. Engine gaskets Bearings Nylons Carburettor parts Gear wheels Poly(propene) Poly(chloroethene) (PVC) Car accelerator pedals Toughness and fatigue resistance reduces wear 'Imitation leather' fabrics -Flexibility allows polymer to be stretched into shape. -High impact strength an d durability reduces wear. 1

F332 Advance Notice June 2011 Polybutadiene buta-1,3-diene polybutadiene Polybutadiene is a highly resilient synthetic rubber (elastomer). Due to its out standing resilience, it can be used for the manufacturing of golf balls. Polybut adiene rubber can be used in water seals for dams due to its low water absorptio n properties. Rubber bullets and road binders can be also produced by polybutadi ene rubber. Polybutadiene can be formed from many buta-1,3-diene monomers undergoing free ra dical polymerisation to make a much longer polymer chain molecule. The propagati on steps in this reaction involve free radicals at the end of growing polymer fo rming a covalent bond with a carbon in the next monomer. (E)-1,4-structure (Z)-1,4-structure The properties of polybutadiene rely on the types of stereoisomers formed when t he double bonds in buta-1,3-diene open up and a new double bond is formed. A pre valence of the E isomers will result in a crystalline plastic whereas a high per centage of Z isomer will result in a flexible elastomer. 2

F332 Advance Notice June 2011 Polyurethane Polyurethane used as an adhesive to bond windscreens in place. This allows the s trength of the glass to contribute to the roll-over strength of the car allowing room to reduce the body weight. Reducing the body weight in this way improves f uel efficiency as less fuel is needed to move a lighter vehicle. Polyurethane fo am replaced rubberised hair in seat cushions. Chlorofluorocarbons (CFCs) were us ed as a blowing agent in foam production, but this was stopped when an internati onal agreement to stop the use of CFCs was reached as they contribute significan tly to ozone depletion. Polyurethane can be classed as an addition polymer becau se many monomers bond together via rearrangement of bonds without the loss of an y atom or molecule. Formation of polyurethane repeating unit from its monomers . .. . .. + + .. + ... . + This part of the polyurethane chain allows hy rogen bon ing to occur. The N-H bo n is polar, provi ing the H atom with a + an an N atom with a - an a lone pair. The C=O bon is also polar an the O atom has two lone pairs. This means O can also act at a hy rogen bon acceptor. .. ... . + + .. + ... . + .. ... . + + Two ways in which hy rogen bon ing can occur between polyurethane chains 3

F332 A vance Notice June 2011 Sticky problems Solvents Vehicle paints were tra itionally base on several layers of ifferent high molecular mass polymers issolve in solvents but have been replace ue to concerns about solvent emissions. Organic solvents are volatile organic compoun s (VOCs), many of which are harmful to health. They can also un ergo chemical r eactions causing the formation of groun -level ozone, an air pollutant. High con centrations of ozone can be etrimental to human an animal health. They can als o cause amage to buil ing materials, forests, vegetation an crops. Problems wi th paint: Vehicle must be heate to >150C to increase the mass of some of the lay ers or to melt others. This consumes large amounts of energy an there is no obv ious alternative as lowering the bake temperature woul lea to problems with th e performance of the a hesive. Polymer-base paints require protection against u ltraviolet light, otherwise they will egra e. Paints esigne to a here to meta ls will generally a here much less well to polymeric substrates. Bon ing Polyalk enes In the following equation X represents a free ra ical (tra itionally C6H5C(C H3)2O). A ra ical is a particle with an unpaire electron an is therefore highly reactive. X + nCH2=CHCO2R X(CH2CHCO2R)n reaction 1

Acrylic a hesives bon a wi e range of plastics, for instance polycarbonate or AB S, but are ineffective on poly(ethene) or poly(propene) because they cant get a c hemical grab on the unreactive surfaces. The phrase can t get a chemical grab ref ers to the fact that only weak instantaneous ipole-in uce ipole bon s can for m between poly(ethene) an the a hesive. Polycarbonate an ABS can form permanen t ipole-permanent ipole an hy rogen bon s, respectively, with the a hesive. S urfaceH + R Surface + RH reaction 2 Reaction 2 is a more effective a hesive with R representing the alkyl ra ical CH3 CH2). This ra ical is much more reactive than the alkoxy ra ical use in equation 1. However, long-term ata urability of the bon s in both metho s is non-exist ent as the processes are relatively new. (Both of these reactions are examples o f propagation reactions as there are ra icals on both si es of the equation.) 4

F332 A vance Notice June 2011 Scrap heap challenge Unlike steel, polymers are not easily recyclable. Thermoplastics: As the polymer chains separate on heating, simple thermoplastics, such as nylon or polycarbona te can be melte own an reuse albeit in less stringent applications. Thermoset s: Thermosetting plastics (such as polyurethane foam) char on heating an so can not be recycle in the same way as thermoplastics. What is the best way to recycle polyurethane foam? Approach Digest the foam in ethylene glycol (ethane-1,2- iol) to yiel polyols s uitable for synthesising rigi insulating polyurethane foam. A vantage -Can be u se to make a large range of pro ucts. -Ethylene glycol is cheaply available. Di sa vantage -Requires market for the pro uct -Ethylene glycol is toxic an theref ore nee s to be han le carefully. Chop the foam up an e, carpet backing. compress it, an use the resulting material in, for instanc

-Cheap -Easy, as it oes not require any chemical expertise -Requires market for the pro uct -Limite uses. -Carbon ioxi e, carbon monoxi e an nitrous oxi es are forme . -Carbon ioxi e is a greenhouse gas an contribu tes to global warming -Carbon monoxi e is poisonous -Nitrous oxi es lea to aci rain (which can kill wil life an vegetation). Recover some of the energy use The heat generate by to make the foam by burnin g it in incinerating polyurethane coul an incinerator. be use to generate elec tricity in a power station. 5

F332 A vance Notice June 2011 Long-term forecast Oil base plastics Most plastics are oil-base . The monomers use to form oil-ba se polymers are extracte from cru e oil by fractional istillation an /or crac king. This is a significant problem as the supply of petroleum is being eplete an it takes millions of years for cru e oil to form. This will result in highe r fuel costs in the future, prompting the search for alternative plastics. Vehic les of the future High fuel costs will create the nee to maximise fuel efficien cy, by using lightweight polymers. However, these polymer themselves are ma e fr om oil so this isn t a long-term solution. The ifficulty of recycling plastics is also an issue an alternatives will nee to be investigate . 6