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their products have variable physical properties. To this day, the systems are little understood, but the monomers (polymer starting materials) react through a number of reaction sites on the catalyst. Unfortunately, this means the polymer can grow from many sites and at different rates, leading to a very wide distribution in the molecular weight, based on the polymer chain length.

Modern life has demanded more of the humble polymer. We want polymers that are stronger than steel, lighter than aluminium, and can be dyed any colour imaginable

Metallocenes are positively charged metal ions, most commonly Titanium or Zirconium, sandwiched between two negatively charged cyclopentadienyl rings (see fig). Their big advantage over the Ziegler-Natta systems is that they catalyse the reaction of olefins through only one reactive site. Due to this “single site” reaction, the polymerization continues in a far more controllable fashion, leading to polymers with narrow ranges of molecular weight and, more importantly, predictable and desirable properties.

it has been found that changing the ligands (functional groups attached to the metal) upon the metallocene molecule can controllably affect the properties of the polymer.

The drawback of metallocene catalysts is that they are unable to polymerize polar molecules, such as common acrylics or vinyl chloride. This is due to the metallocenes’ oxophilicity – their propensity for binding to oxygen.

Catalysts using late transition metals – those metals from groups 6 and higher in the Periodic Table – have become increasingly utilized. These compounds have good polymerization activity, although slightly less than metallocenes. However, crucially they can polymerize reactions with polar monomers.

The most commercially advanced of this type of catalysts are the Brookhart catalysts [6], which are diimine complexes of palladium or nickel (see fig).

Today, Ziegler-Natta catalysts are used worldwide to produce the following classes of polymers from alpha olefins: High density polyethylene (HDPE) Linear low density polyethylene (LLDPE) Ultra-high molecular weight polyethylene (UHMWPE) Polypropylene (PP)--homopolymer, random copolymer and high impact copolymers Thermoplastic polyolefins (TPO’s) Ethylene propylene diene monomer polymers (EPDM) Polybutene (PB)

One such molecule is the ethylene monomer, the starting point for a variety of plastics. Ethylene is a small hydrocarbon consisting of four hydrogen atoms and two carbon atoms.

Polymerization is often started by combining the monomers through the use of a catalyst - a substance that aids a chemical reaction without undergoing any permanent chemical change itself. During the chemical reaction, hundreds or thousands of monomers combine to form a polymer chain, and millions of polymer chains are formed at the same time. The mass of polymers that results is known as a resin.

Polyethylene is made from just ethylene monomers - but it's also possible to create polymers from two or more different monomers. You can make hundreds of different polymers depending on which monomers and catalysts you use.

Cellulose, the basic component of plant cell walls is a polymer, and so are all the proteins produced in your body and the proteins you eat. Another famous example of a polymer is DNA - the long molecule in the nuclei of your cells that carries all the genetic information about you.

lastics are classified into two categories according to what happens to them when they're heated to high temperatures. Thermoplastics keep their plastic properties: They melt when heated, then harden again when cooled. Thermosets, on the other hand, are permanently "set" once they're initially formed and can't be melted. If they're exposed to enough heat, they'll crack or become charred.

Thermoplastics have long, linear polymer chains that are only weakly chemically bonded, or connected, to each other. When a thermoplastic object is heated, these bonds are easily broken, which makes the polymers able to glide past each other like strands of freshly cooked spaghetti. That's why thermoplastics can readily be remolded. The weak bonds between the polymers reform when the plastic object is cooled, which enable it to keep its new shape.

The linear chains are crosslinked - strongly chemically bonded. This prevents a thermoplastic object from being melted and reformed.

The most common method for making plastics is molding. To make a thermoplastic object, plastic granules known as resin are forced into a mold under high heat and pressure. When the material has cooled down, the mold is opened and the plastic object is complete. When making plastic fibers, the molten resin is sprayed through a strainer with tiny holes.

Thermosets are produced in two steps: 1. Linear polymers are formed. 2. The linear polymers are forced into a mold where "curing" takes place. This may involve heating, pressure, and the addition of catalysts. During this process, a cross-linked or networked structure forms, creating a permanently hard object that is no longer meltable or moldable.

For most applications, the ideal polymer is a long, straight chain with a highly regular molecular structure. Early synthetic polymers, however, often exhibited odd little branches and other irregularities. In the 1950s, German chemist Karl Ziegler (1898–1973) discovered that an entirely different type of catalyst - a combination of aluminum compounds with other metallic compounds - could solve some of these annoying problems and increase the length of a polymer chain, producing superior plastics.

olymers often have short side chains, which can occur on either side of the main chain. If side branches occur randomly to the left or right, the polymer has an irregular structure. Italian chemist Giulio Natta (1903–1979) discovered that some Ziegler catalysts led to a uniform structure in which all the side branches are on the same side.

Firstly, there is an environmental impact from plastics production; however the plastics industry has worked hard to reduce energy and water use, as well as waste generation during the manufacturing processes.

Secondly, during their lives, plastic products can save energy and reduce carbon dioxide emissions in a variety of ways. For example, they're lightweight, so transporting them is energy efficient. And plastic parts in cars and airplanes reduce the weight of those vehicles and therefore less energy is needed to operate them and lower emissions are created.

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)

The first step in the chain-reaction polymerization process, initiation, occurs when the free-radical catalyst reacts with a double bonded carbon monomer, beginning the polymer chain. The double carbon bond breaks apart, the monomer bonds to the free radical, and the free electron is transferred to the outside carbon atom in this reaction.

The next step in the process, propagation, is a repetitive operation in which the physical chain of the polymer is formed. The double bond of successive monomers is opened up when the monomer is reacted to the reactive polymer chain. The free electron is successively passed down the line of the chain to the outside carbon atom.

Thermodynamically speaking, the sum of the energies of the polymer is less than the sum of the energies of the individual monomers. Simply put, the single bounds in the polymeric chain are more stable than the double bonds of the monomer.

Termination occurs when another free radical (R-O.), left over from the original splitting of the organic peroxide, meets the end of the growing chain. This free-radical terminates the chain by linking with the last CH2. component of the polymer chain. This reaction produces a complete polymer chain. Termination can also occur when two unfinished chains bond together. Both termination types are diagrammed below. Other types of termination are also possible.

This exothermic reaction occurs extremely fast, forming individual chains of polyethylene often in less than 0.1 second.

Step-reaction (condensation) polymerization is another common type of polymerization. This polymerization method typically produces polymers of lower molecular weight than chain reactions and requires higher temperatures to occur. Unlike addition polymerization, step-wise reactions involve two different types of di-functional monomers or end groups that react with one another, forming a chain. Condensation polymerization also produces a small molecular by-product (water, HCl, etc.).

As indicated above, both addition and condensation polymers can be linear, branched, or cross-linked. Linear polymers are made up of one long continuous chain, without any excess appendages or attachments. Branched polymers have a chain structure that consists of one main chain of molecules with smaller molecular chains branching from it. A branched chain-structure tends to lower the degree of crystallinity and density of a polymer. Cross-linking in polymers occurs when primary valence bonds are formed between separate polymer chain molecules. Chains with only one type of monomer are known as homopolymers. If two or more different type monomers are involved, the resulting copolymer can have several configurations or arrangements of the monomers along the chain. The four main configurations are depicted below:

They can be found in either crystalline or amorphous forms. Crystalline polymers are only possible if there is a regular chemical structure (e.g., homopolymers or alternating copolymers), and the chains possess a highly ordered arrangement of their segments. Crystallinity in polymers is favored in symmetrical polymer chains, however, it is never 100%. These semi-crystalline polymers possess a rather typical liquefaction pathway, retaining their solid state until they reach their melting point at Tm.

Amorphous polymers do not show order. The molecular segments in amorphous polymers or the amorphous domains of semi-crystalline polymers are randomly arranged and entangled. Amorphous polymers do not have a definable Tm due to their randomness

At low temperatures, below their glass transition temperature (Tg), the segments are immobile and the sample is often brittle. As temperatures increase close to Tg, the molecular segments can begin to move. Above Tg, the mobility is sufficient (if no crystals are present) that the polymer can flow as a highly viscous liquid.

Thermoplastics are generally carbon containing polymers synthesized by addition or condensation polymerization. This process forms strong covalent bonds within the chains and weaker secondary Van der Waals bonds between the chains. Usually, these secondary forces can be easily overcome by thermal energy, making thermoplastics moldable at high temperatures.

Thermosets have the same Van der Waals bonds that thermoplastics do. They also have a stronger linkage to other chains. Strong covalent bonds chemically hold different chains together in a thermoset material. The chains may be directly bonded to each other or be bonded through other molecules. This "cross-linking" between the chains allows the material to resist softening upon heating.

Compression Molding This type of molding was among the first to be used to form plastics. It involves four steps: Pre-formed blanks, powders or pellets are placed in the bottom section of a heated mold or die. The other half of the mold is lowered and is pressure applied. The material softens under heat and pressure, flowing to fill the mold. Excess is squeezed from the mold. If a thermoset, cross-linking occurs in the mold. The mold is opened and the part is removed. For thermoplastics, the mold is cooled before removal so the part will not lose its shape. Thermosets may be ejected while they are hot and after curing is complete. This process is slow

Injection Molding This very common process for forming plastics involves four steps: Powder or pelletized polymer is heated to the liquid state. Under pressure, the liquid polymer is forced into a mold through an opening, called a sprue. Gates control the flow of material. The pressurized material is held in the mold until it solidifies. The mold is opened and the part removed by ejector pins. Advantages of injection molding include rapid processing, little waste, and easy automation.

Transfer Molding This process is a modification of compression molding. It is used primarily to produce thermosetting plastics. Its steps are: A partially polymerized material is placed in a heated chamber. A plunger forces the flowing material into molds. The material flows through sprues, runners and gates. The temperature and pressure inside the mold are higher than in the heated chamber, which induces cross-linking. The plastic cures, is hardened, the mold opened, and the part removed. Mold costs are expensive and much scrap material collects in the sprues and runners, but complex parts of varying thickness can be accurately produced.

Extrusion This process makes parts of constant cross section like pipes and rods. Molten polymer goes through a die to produce a final shape. It involves four steps: Pellets of the polymer are mixed with coloring and additives. The material is heated to its proper plasticity. The material is forced through a die. The material is cooled.

Blow Molding Blow molding produces bottles, globe light fixtures, tubs, automobile gasoline tanks, and drums. It involves: A softened plastic tube is extruded The tube is clamped at one end and inflated to fill a mold. Solid shell plastics are removed from the mold. This process is rapid and relatively inexpensive.

In 1989, a billion pounds of virgin PET were used to make beverage bottles of which about 20% was recycled. Of the amount recycled, 50% was used for fiberfill and strapping. The reprocessors claim to make a high quality, 99% pure, granulated PET. It sells at 35 to 60% of virgin PET costs. The major reuses of PET include sheet, fiber, film, and extrusions.

Of the plastics that have a potential for recycling, the rigid HDPE container is the one most likely to be found in a landfill. Less than 5% of HDPE containers are treated or processed in a manner that makes recycling easy.

There is a great potential for the use of recycled HDPE in base cups, drainage pipes, flower pots, plastic lumber, trash cans, automotive mud flaps, kitchen drain boards, beverage bottle crates, and pallets.

LDPE is recycled by giant resin suppliers and merchant processors either by burning it as a fuel for energy or reusing it in trash bags. Recycling trash bags is a big business.

There is much controversy concerning the recycling and reuse of PVC due to health and safety issues. When PVC is burned, the effects on the incinerator and quality of the air are often questioned. The Federal Food and Drug Administration (FDA) has ordered its staff to prepare environmental impact statements covering PVC's role in landfills and incineration. The burning of PVC releases toxic dioxins, furans, and hydrogen chloride.

PVC is used in food and alcoholic beverage containers with FDA approval. The future of PVC rests in the hands of the plastics industry to resolve the issue of the toxic effects of the incineration of PVC. It is of interest to note that PVC accounts for less than 1% of land fill waste.

PS and its manufacturers have been the target of environmentalists for several years. The manufacturers and recyclers are working hard to make recycling of PS as common as that of paper and metals. One company, Rubbermaid, is testing reclaimed PS in service trays and other utility items.

Table 3: Major Plastic Resins and Their Uses Resin CodeResin NameCommon UsesExamples of Recycled Products Polyethylene Terephthalate (PET or PETE) Soft drink bottles, peanut butter jars, salad dressing bottles, mouth wash jars Liquid soap bottles, strapping, fiberfill for winter coats, surfboards, paint brushes, fuzz on tennis balls, soft drink bottles, film High density Polyethylene (HDPE) Milk, water, and juice containers, grocery bags, toys, liquid detergent bottles Soft drink based cups, flower pots, drain pipes, signs, stadium seats, trash cans, re-cycling bins, traffic barrier cones, golf bag liners, toys Polyvinyl Chloride or Vinyl (PVC-V) Clear food packaging, shampoo bottles Floor mats, pipes, hoses, mud flaps Low density Polyethylene (LDPE) Bread bags, frozen food bags, grocery bags Garbage can liners, grocery bags, multi purpose bags Polypropylene (PP) Ketchup bottles, yogurt containers, margarine, tubs, medicine bottles Manhole steps, paint buckets, videocassette storage cases, ice scrapers, fast food trays, lawn mower wheels, automobile battery parts. Polystyrene (PS) Video cassette cases, compact disk jackets, coffee cups, cutlery, cafeteria trays, grocery store meat trays, fast-food sandwich container License plate holders, golf course and septic tank drainage systems, desk top accessories, hanging files, food service trays, flower pots, trash cans

One way to produce polyethylene is called "free radical polymerization." As in other polymerizations, the process has three stages, known as initiation, propagation and termination. To begin, we need to add a catalyst to our supply of ethylene. A common catalyst is benzoyl peroxide, which when heated has the habit of splitting into two fragments, each with one unpaired electron, or free radical. These fragments are known as initiator fragments.

The unpaired electron naturally seeks another and finds a convenient target in the double bond between the carbon atoms in the ethylene molecule. Taking an electron from the carbon bond, the initiator fragment bonds itself to one of the monomer's carbon atoms.

The new radical also seeks a partner. And so ethylene monomers begin attaching themselves in a chain, creating new radicals each time and lengthening the chain. This stage is called propagation.

Eventually, free radical polymerization stops due to what are called termination reactions. For example, instead of stealing an electron from double-bonded carbons or a nearby propagating chain, the carbon atom with the free radical sometimes steals an entire hydrogen atom from another chain end. The polymer end--robbed of its hydrogen--easily forms a double bond with its adjacent carbon atom, and polymerization stops.

Because every part of the ethylene monomer is included in the finished polymer, the free radical polymerization of polyethylene is referred to as an addition polymerization

Polymerizations that use only portions of a monomer, however, are known as condensation polymerizations. The monomers that condense with each other must contain at least two reactive groups in order to form a chain.

For example, poly(ethyleneterepthalate), a polyester known as PET that is commonly found in soda bottles, forms from a reaction of two monomers: ethylene glycol and terephthoyl chloride. At the reaction's end, an atom of hydrogen and an atom of chlorine are left out of each PET molecular junction, resulting in a by-product of hydrogen chloride (HCl) gas.

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.

Other examples of thermoplastics are: Polyethylene: packaging, electrical insulation, milk and water bottles, packaging film, house wrap, agricultural film Polypropylene: carpet fibers, automotive bumpers, microwave containers, external prostheses Polyvinyl chloride (PVC): sheathing for electrical cables, floor and wall coverings, siding, credit cards, automobile instrument panels

These monomers are then chemically bonded into chains called polymers.

The resulting resins may be molded or formed to produce several different kinds of plastic products with application in many major markets. The variability of resin permits a compound to be tailored to a specific design or performance requirement.

Polymers are created by the chemical bonding of many identical or related basic units and those produced from a single monomer type are called homopolymers. These polymers are specifically made of small units bonded into long chains. Carbon makes up the backbone of the molecule and hydrogen atoms are bonded along the carbon backbone.

In order to achieve a commercial product, the plastic is subject to further treatment and the inclusion of additives which are selected to give it specified properties

Additives are incorporated into polymers to alter and improve their basic mechanical, physical or chemical properties. Additives are also used to protect the polymer from the degrading effects of light, heat, or bacteria; to change such polymer properties as flow; to provide product color; and to provide special characteristics such as improved surface appearance or reduced friction.

Types of Additives:     antioxidants: for outside application,      colorants: for colored plastic parts, foaming agents: for Styrofoam cups,      plasticizers: used in toys and food processing equipment

A Thermoset is a polymer that solidifies or "sets" irreversibly when heated. Similar to the relationship between a raw and a cooked egg, once heated, a thermoset polymer can't be softened again and once cooked, the egg cannot revert back to its original form.

A Thermoplastic is a polymer in which the molecules are held together by weak secondary bonding forces that soften when exposed to heat and return to its original condition when cooled back down to room temperature. When a thermoplastic is softened by heat, it can then be shaped by extrusion, molding or pressing. Ice cubes are a common household item which exemplify the thermoplastic principle. Ice will melt when heated but readily solidifies when cooled.

In this method, a separate molding and cooling station on the equipment allows the parison to be continuously formed.  This technique is used mainly for small thin-walled parts ranging up to containers with five gallon capacities.  Parison programming can be used to vary the wall thickness.  Continuous extrusion also allows the use of heat-sensitive materials due to streamlined flow areas and die designs.

This technique is performed in three basic ways --reciprocating, ram accumulator, and accumulator head systems.  All three vary in machine design and the flow of molten resin through the die for parison forming.  However, each system is designed to produce larger, heavier, and thicker parts than continuous extrusion.

Blow moldable grades of material are initially injection molded into preform shapes.  These preforms are then thermally conditioned and then stretched (utilizing pneumatically operated stretch rods) low pressure air, followed by high pressure air up to 40 bar to form axially oriented parts with molded in necks.  The process is used to manufacture PET bottles.

This process utilizes various thermoplastic materials in a solid pelletized state and converts these materials by way of heat, pressure and compressed air into a finished good stat.The pellitized raw material is conveyed to the feed section of a plasticating extruder by way of a vacuum loader or auger screw.  The raw material is then conveyed forward through the extruder and is plastisized to a molten state of between 350 degrees and 500 degrees F. by way of a feed screw and external heating elements.The material in a melt state is then reshaped into a round hollow geometry termed a parison.  This parison is then extruded vertically from the head section of the machine through a round die at various outside and inside diameters.After extrusion of the parison between the two halves of a mold the press section closes encapsulating the parison inside the mold halves.  Upon mold close compressed air is entered into the parison by way of a centrally located air pipe or by piercing air needles.The molds are chilled with cooled water which transfers the hear form the now formed part inside the mold.  Upon complete part cooling the press section opens and the finished product is removed.  The material which is pinched off outside the mold cavity, or the flash, is then fed into a granulator which cops the flash into a granule size which can be fed back to the feed section of the extruder.

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)

It can be terminated--stage three--when any two free radicals combine, thus pairing their unpaired electrons and forming a covalent bond that links two chains together.

Polyethylene molecules made with the free radical initiation process tend to form branches that keep the molecules from fitting closely together. Techniques have been developed that use catalysts, like Cr2O3, to make polyethylene molecules with very few branches.

yielding a high-density polyethylene, HDPE, that is more opaque, harder, and stronger than the low-density polyethylene, LDPE, made with free radical initiation.