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Natural rubber is from the monomer isoprene (2-methyl-1,3-butadiene). Since isoprene has two double bonds, it still retains one of them after the polymerization reaction. Natural rubber has the cis configuration for the methyl groups.

Charles Goodyear accidentally discovered that by mixing sulfur and rubber, the properties of the rubber improved in being tougher, resistant to heat and cold, and increased in elasticity. This process was later called vulcanization

Vulcanization causes shorter chains to cross link through the sulfur to longer chains.

Some of the most commercially important addition polymers are the copolymers. These are polymers made by polymerizing amixture of two or more monomers. An example is styrene-butadiene rubber (SBR) - which is a copolymer of 1,3-butadiene and styrene which is mixed in a 3 to 1 ratio, respectively.

More than 40% of the synthetic rubber production is SBR and is used in tire production. A tiny amount is used for bubble-gum in the unvulcanized form.

. At the nipple end of the balloon, there is lots of rubber and therefore many, many polymer chains - still loosely coiled. These chains can be pierced without popping the balloon because the the chains can still be stretched. This is because they allow the skewer in between the chains without breaking the chains or the bonds that connect them. But on the sides of the balloon, these chains are stretched almost to their limit and very far apart. The piercing is too much for the stretched chains and they break apart., and the balloon pops.

Most synthetic polymers are made from the non-renewable resource, petroleum, and as such, the "age of plastics" is limited unless other ways are found to make them. Since most polymers have carbon atoms as the basis of their structure, in theory at least, there are numerous materials that could be used as starting points.

Disposing of plastics is also a serious problem, both because they contribute to the growing mounds of garbage accumulating everyday and because most are not biodegradable. Researchers are busy trying to find ways to speed-up the decomposition time which, if left to occur naturally, can take decades.

n order for monomers to chemically combine with each other and form long chains, there must be a mechanism by which the individual units can join or bond to each other. One method by which this happens is called addition because no atoms are gained or lost in the process. The monomers simply "add" together and the polymer is called an addition polymer.

The simplest chemical structure by which this can happen involves monomers that contain double bonds (sharing two pairs of electrons). When the double bond breaks and changes into a single bond, each of the other two electrons are free and available to join with another monomer that has a free electron. This process can continue on and on. Polyethylene is an example of an addition polymer.

The polymerization process can be started by using heat and pressure or ultraviolet light or by using another more reactive chemical such as a peroxide. Under these conditions the double bond breaks leaving extremely reactive unpaired electrons called free radicals. These free radicals react readily with other free radicals or with double bonds and the polymer chain starts to form.

ifferent catalysts yield polymers with different properties because the size of the molecule may vary and the chains may be linear, branched, or cross-linked. Long linear chains of 10,000 or more monomers can pack very close together and form a hard, rigid, tough plastic known as high-density polyethylene or HDPE

Shorter, branched chains of about 500 monomers of ethylene cannot pack as closely together and this kind of polymer is known as low-density polyethylene or LDPE.

The ethylene monomer has two hydrogen atoms bonded to each carbon for a total of four hydrogen atoms that are not involved in the formation of the polymer. Many other polymers can be formed when one or more of these hydrogen atoms are replaced by some other atom or group of atoms.

Natural and synthetic rubbers are both addition polymers. Natural rubber is obtained from the sap that oozes from rubber trees. It was named by Joseph Priestley who used it to rub out pencil marks, hence, its name, a rubber. Natural rubber can be decomposed to yield monomers of isoprene.

It was sticky and smelly when it got too hot and it got hard and brittle in cold weather. These undesirable properties were eliminated when, in 1839, Charles Goodyear accidentally spilled a mixture of rubber and sulfur onto a hot stove and found that it did not melt but rather formed a much stronger but still elastic product. The process, called vulcanization, led to a more stable rubber product that withstood heat (without getting sticky) and cold (without getting hard) as well as being able to recover its original shape after being stretched. The sulfur makes cross-links in the long polymer chain and helps give it strength and resiliency, that is, if stretched, it will spring back to its original shape when the stress is released.

A second method by which monomers bond together to form polymers is called condensation.

Unlike addition polymers, in which all the atoms of the monomers are present in the polymer, two products result from the formation of condensation polymers, the polymer itself and another small molecule which is often, but not always, water.

One of the simplest of the condensation polymers is a type of nylon called nylon 6.

All amino acids molecules have an amine group (NH2) at one end and a carboxylic acid (COOH) group at the other end. A polymer forms when a hydrogen atom from the amine end of one molecule and an oxygen-hydrogen group (OH) from the carboxylic acid end of a second molecule split off and form a water molecule. The monomers join together as a new chemical bond forms between the nitrogen and carbon atoms. This new bond is called an amide linkage.

The new molecule, just like each of the monomers from which it formed, also has an amine group at one end (that can add to the carboxylic acid group of another monomer) and it has a carboxylic acid group at the other end (that can add to the amine end of another monomer). The chain can continue to grow and form very large polymers.

Polymers formed by this kind of condensation reaction are referred to as polyamides.

Nylon became a commercial product for Du Pont when their research scientists were able to draw it into long, thin, symmetrical filaments. As these polymer chains line up side-by-side, weak chemical bonds called hydrogen bonds form between adjacent chains. This makes the filaments very strong.

Another similar polymer of the polyamide type is the extremely light-weight but strong material known as Kevlar. It is used in bullet-proof vests, aircraft, and in recreational uses such as canoes. Like nylon, one of the monomers from which it is made is terephthalic acid. The other one is phenylenediamine.

Polyesters are another type of condensation polymer, so-called because the linkages formed when the monomers join together are called esters.

Probably the best known polyester is known by its trade name, Dacron.

Dacron is used primarily in fabrics and clear beverage bottles. Films of Dacron can be coated with metallic oxides, rolled into very thin sheets (only about one-thirtieth the thickness of a human hair), magnetized, and used to make audio and video tapes. When used in this way, it is extremely strong and goes by the trade name Mylar. Because it is not chemically reactive, and is not toxic, allergenic, or flammable, and because it does not promote blood-clotting, it can be used to replace human blood vessels when they are severely blocked and damaged or to replace the skin of burn victims.

Advantages of emulsion polymerization include:[1] High molecular weight polymers can be made at fast polymerization rates. By contrast, in bulk and solution free radical polymerization, there is a tradeoff between molecular weight and polymerization rate. The continuous water phase is an excellent conductor of heat and allows the heat to be removed from the system, allowing many reaction methods to increase their rate. Since polymer molecules are contained within the particles, viscosity remains close to that of water and is not dependent on molecular weight. The final product can be used as is and does not generally need to be altered or processed. Disadvantages of emulsion polymerization include: Surfactants and other polymerization adjuvants remain in the polymer or are difficult to remove For dry (isolated) polymers, water removal is an energy-intensive process Emulsion polymerizations are usually designed to operate at high conversion of monomer to polymer. This can result in significant chain transfer to polymer.

The first "true" emulsion polymerizations, which used a surface-active agent and polymerization initiator, were conducted in the 1920s to polymerize isoprene.[6][7]

The Smith-Ewart-Harkins theory for the mechanism of free-radical emulsion polymerization is summarized by the following steps: A monomer is dispersed or emulsified in a solution of surfactant and water forming relatively large droplets of monomer in water. Excess surfactant creates micelles in the water. Small amounts of monomer diffuse through the water to the micelle. A water-soluble initiator is introduced into the water phase where it reacts with monomer in the micelles. (This characteristic differs from suspension polymerization where an oil-soluble initiator dissolves in the monomer, followed by polymer formation in the monomer droplets themselves.) This is considered Smith-Ewart Interval 1. The total surface area of the micelles is much greater than the total surface area of the fewer, larger monomer droplets; therefore the initiator typically reacts in the micelle and not the monomer droplet. Monomer in the micelle quickly polymerizes and the growing chain terminates. At this point the monomer-swollen micelle has turned into a polymer particle. When both monomer droplets and polymer particles are present in the system, this is considered Smith-Ewart Interval 2. More monomer from the droplets diffuses to the growing particle, where more initiators will eventually react. Eventually the free monomer droplets disappear and all remaining monomer is located in the particles. This is considered Smith-Ewart Interval 3. Depending on the particular product and monomer, additional monomer and initiator may be continuously and slowly added to maintain their levels in the system as the particles grow. The final product is a dispersion of polymer particles in water. It can also be known as a polymer colloid, a latex, or commonly and inaccurately as an 'emulsion'.

Both thermal and redox generation of free radicals have been used in emulsion polymerization. Persulfate salts are commonly used in both initiation modes. The persulfate ion readily breaks up into sulfate radical ions above about 50°C, providing a thermal source of initiation.

Emulsion polymerizations have been used in batch, semi-batch, and continuous processes. The choice depends on the properties desired in the final polymer or dispersion and on the economics of the product. Modern process control schemes have enabled the development of complex reaction processes, with ingredients such as initiator, monomer, and surfactant added at the beginning, during, or at the end of the reaction.

Colloidal stability is a factor in design of an emulsion polymerization process. For dry or isolated products, the polymer dispersion must be isolated, or converted into solid form. This can be accomplished by simple heating of the dispersion until all water evaporates. More commonly, the dispersion is destabilized (sometimes called "broken") by addition of a multivalent cation. Alternatively, acidification will destabilize a dispersion with a carboxylic acid surfactant. These techniques may be employed in combination with application of shear to increase the rate of destabilization. After isolation of the polymer, it is usually washed, dried, and packaged.

Ethylene and other simple olefins must be polymerized at very high pressures (up to 800 bar).

Copolymerization is common in emulsion polymerization. The same rules and comonomer pairs that exist in radical polymerization operate in emulsion polymerization.

Monomers with greater aqueous solubility will tend to partition in the aqueous phase and not in the polymer particle. They will not get incorporated as readily in the polymer chain as monomers with lower aqueous solubility.

Ethylene and other olefins are used as minor comonomers in emulsion polymerization, notably in vinyl acetate copolymers.

Redox initiation takes place when an oxidant such as a persulfate salt, a reducing agent such as glucose, Rongalite, or sulfite, and a redox catalyst such as an iron compound are all included in the polymerization recipe. Redox recipes are not limited by temperature and are used for polymerizations that take place below 50°C.

Selection of the correct surfactant is critical to the development of any emulsion polymerization process. The surfactant must enable a fast rate of polymerization, minimize coagulum or fouling in the reactor and other process equipment, prevent an unacceptably high viscosity during polymerization (which leads to poor heat transfer), and maintain or even improve properties in the final product such as tensile strength, gloss, and water absorption

Anionic, nonionic, and cationic surfactants have been used, although anionic surfactants are by far most prevalent.

Examples of surfactants commonly used in emulsion polymerization include fatty acids, sodium lauryl sulfate, and alpha olefin sulfonate.

Some grades of poly(vinyl alcohol) and other water soluble polymers can promote emulsion polymerization even though they do not typically form micelles and do not act as surfactants (for example, they do not lower surface tension). It is believed that these polymers graft onto growing polymer particles and stabilize them.[12]

Other ingredients found in emulsion polymerization include chain transfer agents, buffering agents, and inert salts. Preservatives are added to products sold as liquid dispersions to retard bacterial growth. These are usually added after polymerization, however.

Polymers produced by emulsion polymerization can be divided into three rough categories. Synthetic rubber Some grades of styrene-butadiene (SBR) Some grades of Polybutadiene Polychloroprene (Neoprene) Nitrile rubber Acrylic rubber Fluoroelastomer (FKM) Plastics Some grades of PVC Some grades of polystyrene Some grades of PMMA Acrylonitrile-butadiene-styrene terpolymer (ABS) Polyvinylidene fluoride PTFE Dispersions (i.e. polymers sold as aqueous dispersions) polyvinyl acetate polyvinyl acetate copolymers latexacrylic paint Styrene-butadiene VAE (vinyl acetate - ethylene copolymers)

Thermoset materials are generally stronger than thermoplastic materials, and are also better suited to high-temperature applications. They do not lend themselves to recycling like thermoplastics, which can be melted and re-molded.

Examples Natural Rubber Bakelite, a Phenol Formaldehyde Resin (used in electrical insulators and plastic wear) Duroplast Urea-Formaldehyde Foam (used in plywood, particleboard and medium-density fibreboard) Melamine (used on worktop surfaces) Polyester Resin (used in glass-reinforced plastics/Fibreglass (GRP)) Epoxy Resin (used as an adhesive and in fibre reinforced plastics such as glass reinforced plastic and graphite-reinforced plastic)

Table 7 shows that the composition varies from chains of only monomer A (homopolymer A) to chains containing only monomer B (homopolymer B).

In many of the structures no regularity can be detected, although there will be short sequences of one type of unit, and the copolymer can be regarded as completely random; such copolymers are usually said to be ideal copolymers. These possible copolymer structures are shown schematically in Table 7.

It can be shown that the rate of change of monomer concentration in any copolymerization is given by the equation where [M1] and [M2] are the concentrations of monomers 1 and 2 at any instant and r1 and r2., are reactivity ratios. The reactivity ratios represent the rate at which one type of growing chain end adds on to a monomer of the same structure relative to the rate at which it adds on to the alternative monomer. The copolymer equation can be used to predict chain structure in the three different ways, already mentioned.

An ideal copolymer will tend to form when each type of chain end shows an equal preference for adding on to either monomer. In this case, and the copolymer equation becomes Hence composition depends on the relative amounts of monomer present at any time and the relative reactivities of the two monomers.

Step growth copolymerizations produce ideal (random) copolymers since in this special case r 1 = r 2 = 1.

The main reason for copolymerizing different monomers is to adjust the physical properties of a given homopolymer to meet a specific demand. SBR elastomer, for example (Table 1), based on 24 wt% styrene monomer shows better mechanical properties and better resistance to degradation than polybutadiene alone

A second reason for copolymerization is to enhance the chemical reactivity of a polymer, particularly to aid crosslinking. Conventional vulcanization in rubbers is brought about by forming sulphur crosslinks at or near double bonds in the chain

To show the dramatic effect of copolymer structure on physical properties, consider the change from random SBR copolymer to a block copolymer of exactly the same chemical composition but where the styrene and butadiene parts are effectively homopolymer chains linked at two points: The material behaves like a vulcanized butadiene rubber without the need for chemical crosslinking since the styrene chains segregate together to form small islands or domains within the structure. Such so-called thermoplastic elastomers (TPEs) today form an important growth area for new polymers because of the process savings in manufacture that can be achieved with their use.

The two types of polymer configurations are cis and trans. These structures can not be changed by physical means (e.g. rotation). The cis configuration arises when substituent groups are on the same side of a carbon-carbon double bond. Trans refers to the substituents on opposite sides of the double bond.

Three distinct structures can be obtained. Isotactic is an arrangement where all substituents are on the same side of the polymer chain. A syndiotactic polymer chain is composed of alternating groups and atactic is a random combination of the groups. The following diagram shows two of the three stereoisomers of polymer chain.

The ability of an atom to rotate this way relative to the atoms which it joins is known as an adjustment of the torsional angle. If the two atoms have other atoms or groups attached to them then configurations which vary in torsional angle are known as conformations.

different conformation may represent different potential energies of the molecule. There several possible generalized conformations: Anti (Trans), Eclipsed (Cis), and Gauche (+ or -). The following animation illustrates the differences between them.

The geometric arrangement of the bonds is not the only way the structure of a polymer can vary. A branched polymer is formed when there are "side chains" attached to a main chain. A simple example of a branched polymer is shown in the following diagram.

One of these types is called "star-branching". Star branching results when a polymerization starts with a single monomer and has branches radially outward from this point. Polymers with a high degree of branching are called dendrimers Often in these molecules, branches themselves have branches.

A separate kind of chain structure arises when more that one type of monomer is involved in the synthesis reaction. These polymers that incorporate more than one kind of monomer into their chain are called copolymers. There are three important types of copolymers. A random copolymer contains a random arrangement of the multiple monomers. A block copolymer contains blocks of monomers of the same type. Finally, a graft copolymer contains a main chain polymer consisting of one type of monomer with branches made up of other monomers. The following diagram displays the different types of copolymers.

In addition to the bonds which hold monomers together in a polymer chain, many polymers form bonds between neighboring chains. These bonds can be formed directly between the neighboring chains, or two chains may bond to a third common molecule.

Polymers with a high enough degree of cross-linking have "memory." When the polymer is stretched, the cross-links prevent the individual chains from sliding past each other. The chains may straighten out, but once the stress is removed they return to their original position and the object returns to its original shape.

In vulcanization, a series of cross-links are introduced into an elastomer to give it strength. This technique is commonly used to strengthen rubber.

Elastomers,or rubbery materials, have a loose cross-linked structure. This type of chain structure causes elastomers to possess memory. Typically, about 1 in 100 molecules are cross-linked

Natural and synthetic rubbers are both common examples of elastomers. Plastics are polymers which, under appropriate conditions of temperature and pressure, can be molded or shaped (such as blowing to form a film). In contrast to elastomers, plastics have a greater stiffness and lack reversible elasticity.

Take a piece of copper wiring," says Meddick. "It is encased in plastic - a kind of hydrocarbon material. We release all the hydrocarbons, which strips the casing off the wire." Not only does the process produce fuel in the form of oil and gas, it also makes it easier to extract the copper wire for recycling.

Autofluff is the stuff that is left over after a car has been shredded and the steel extracted. It contains plastics, rubber, wood, paper, fabrics, glass, sand, dirt, and various bits of metal. GRC says its Hawk-10 can extract enough oil and gas from the left-over fluff to run the Hawk-10 itself and a number of other machines used by Gershow.

Because it makes extracting reusable metal more efficient and evaporates water from autofluff, the Hawk-10 should also reduce the amount of end material that needs to be deposited in landfill sites.