Chem 109H Fall08

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

Polyethylene terephthalate (PET), or polyethylene terephthalic ester (PETE), is a condensation polymer produced from the monomers ethylene glycol, HOCH2CH2OH, a dialcohol, and dimethyl terephthalate, CH3O2C–C6H4–CO2CH3, a diester. By the process of transesterification, these monomers form ester linkages between them, yielding a polyester

PETE fibers are manufactured under the trade names of Dacron and Fortrel.

Pleats and creases can be permanently heat set in fabrics containing polyester fibers, so-called permanent press fabrics. PETE can also be formed into transparent sheets and castings.

Transparent 2-liter carbonated beverage bottles are made from PETE.

ne form of PETE is the hardest known polymer and is used in eyeglass lenses.

     Polyethylene is perhaps the simplest polymer, composed of chains of repeating –CH2– units. It is produced by the addition polymerization of ethylene, CH2=CH2 (ethene)

HDPE is hard, tough, and resilient. Most HDPE is used in the manufacture of containers, such as milk bottles and laundry detergent jugs.

LDPE is relatively soft, and most of it is used in the production of plastic films, such as those used in sandwich bags.

Polymerization of vinyl chloride, CH2=CHCl (chloroethene), produces a polymer similar to polyethylene, but having chlorine atoms at alternate carbon atoms on the chain.

About two-thirds of the PVC produced annually is used in the manufacture of pipe. It is also used in the production of “vinyl” siding for houses and clear plastic bottles.

is used to form flexible articles such as raincoats and shower curtains.

This polymer is produced by the addition polymerization of propylene, CH2=CHCH3 (propene). Its molecular structure is similar to that of polyethylene, but has a methyl group (–CH3) on alternate carbon atoms of the chain.

olypropylene is used extensively in the automotive industry for interior trim, such as instrument panels, and in food packaging, such as yogurt containers. It is formed into fibers of very low absorbance and high stain resistance, used in clothing and home furnishings, especially carpeting.

Styrene, CH2=CH–C6H5, polymerizes readily to form polystyrene (PS), a hard, highly transparent polymer.

A large portion of production goes into packaging. The thin, rigid, transparent containers in which fresh foods, such as salads, are packaged are made from polystyrene. Polystyrene is readily foamed or formed into beads. These foams and beads are excellent thermal insulators and are used to produce home insulation and containers for hot foods. Styrofoam is a trade name for foamed polystyrene.

eflon is a trade name of polytetrafluoroethylene, PTFE. It is formed by the addition polymerization of tetrafluoroethylene, CF2=CF2 (tetrafluoroethene). PTFE is distinguished by its complete resistance to attack by virtually all chemicals and by its slippery surface. It maintains its physical properties over a large temperature range, -270° to 385°C. These properties make it especially useful for components that must operate under harsh chemical conditions and at temperature extremes. Its most familiar household use is as a coating on cooking utensils.

his important class of polymers is formed by the addition polymerization of an diisocyanate (whose molecules contain two –NCO groups) and a dialcohol (two –OH groups).

Polyurethane is spun into elastic fibers, called spandex, and sold under the trade name Lycra. Polyurethane can also be foamed. Soft polyurethane foams are used in upholstery, and hard foams are used structurally in light aircraft wings and sail boards.

Polyamides are a group of condensation polymers commonly known as nylon. Nylon is made from two monomers, one a dichloride and the other a diamine.

Nylon can be readily formed into fibers that are strong and long wearing, making them well suited for use in carpeting, upholstery fabric, tire cords, brushes, and turf for athletic fields. Nylon is also formed into rods, bars, and sheets that are easily formed and machined.

Polyacrylamide is a condensation polymer with an unusual and useful property.

This produces a network of polymer chains, rather like a tiny sponge. The free, unlinked amide groups, because they contain –NH2 groups, can form hydrogen bonds with water. This gives the tiny cross linked sponges a great affinity for water. Polyacrylamide can absorb many times its mass in water. T

his property is useful in a variety of applications, such as in diapers and in potting soil. The polyacrylamide will release the absorbed water if a substance that interferes with hydrogen bonding is added. Ionic substances, such as salt, cause polyacrylamide to release its absorbed water.

Over the past few decades, the use of polymers in disposable consumer goods has grown tremendously. This growth is proving to be taxing on the waste disposal system, consuming a large fraction of available landfill space.

To help sort wastes by type of polymer, most disposable polymeric goods are labeled with a recycling code: three arrows around a number above the polymer's acronym. These are intended to help consumers separate the waste polymers according to type before disposing of them. In the city of Madison, currently only type 1 (PETE) and type 2 (HDPE) polymers are being recycled – see below. The recycling of polymers is not a closed loop, where a material is reformed into new products repeatedly, such as in the case with aluminum. Most polymeric materials are recycled only once, and the product made of recycled polymer is discarded after use

General Rules Remove and discard all lids or caps. Rinse all containers. Remove and discard sprayer tops. CRUSH all plastic bottles to save space. No 5 gallon pails. No containers with metal handles.

What can be Recycled?Plastic Code Number Recyclable Containers Soda Bottles Water Bottles Juice Bottles Cooking Oil Bottles Soap/Detergent Bottles Shampoo Bottles Clear Liquor Bottles Food Jars (Peanut Butter etc.) Plastic Code Number Recyclable Containers Milk Bottles Water Bottles Juice Bottles Cooking Oil Containers Windshield Washer Fluid Bottles Shampoo Bottles Butter/Margarine Tubs Cottage Cheese Containers Ice Cream Containers Without Metal Handles Baby Wipe Containers Do NOT Recycle This Plastic 1. Automotive Product Containers Including: Motor Oil Bottles Anti-Freeze Containers Gasoline and Oil Additive Bottles 2. Brown Liquor Bottles 3. All Containers Marked With The Following Codes:            

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.

Now be aware that one of the connecting sticks can spring open. To see animation of this, move cursor over the image. As long as cursor is over image, animation repeats

1) We start with several pairs of balls each with two connecting sticks. 2) Something causes one of the connecting sticks to fling open. It then connects to another ball, but in doing so, causes one of its connecting sticks to fling open. 3) In moments all of the pairs of balls are now connected. Move cursor over image to see animation.

Sometimes heat, high energy light, or something else causes the double-bond to break and two of the middle 4 electrons split up and end up on the two outer ends of the molecule. These electrons are unpaired, which makes them eager to join with another electron.

(place cursor over the image to see animated version)

The unpaired electron triggers the ethylene molecule that bumps into it, to shift the inside electron to pair with it. That then causes the newly unpaired inner electron to move to the outside and it is now an unpaired electron ready to cause the next ethylene molecule to repeat the process.

The name of this polymer is appropriately called, polyethylene.

This is called high density polyethylene (HDPE).

High density polyethylene HDPE is used for bottles, buckets, jugs, containers, toys, even synthetic lumber, and many other things.

Sometimes the chains get up to 500,000 carbons long. Here they are tough enough for synthetic ice, replacement joints and bullet-proof vests. This is called Ultra High Molecular Weight PolyEthylene or UHMWPE.

low density polyethylene (LDPE).

It is made by causing the long chains of ethylene to branch. That way they cannot lie next each other, which reduces the density of the polyethylene. This makes the plastic lighter and more flexible.

Low density polyethylene is used to make plastic bags, plastic wrap, and squeeze bottles, plus many other things.

The favorite properties of plastics are that they are inert and won't react with what is stored in them. They also are durable and won't easily decay, dissolve, or break apart. These are great qualities for things you keep, but when you throw them away, they won't decompose.

The answer is to recycle the plastics. Here we see a bunch of CDs getting recycled.

Here are two recycle code drawings. You already know about HDPE and LDPE.

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)

Biopolymer Natural Source What is it? Lactic Acid Beets, corn, potatoes, and others Produced through fermentation of sugar feedstocks, such as beets, and by converting starch in corn, potatoes, or other starch sources. It is polymerized to produce polylactic acid -- a polymer that is used to produce plastic. Triglycerides Vegetable oils These form a large part of the storage lipids found in plant and animal cells. Vegetable oils are one possible source of triglycerides that can be polymerized into plastics.

Using Fermentation to Produce Plastics Fermentation, used for hundreds of years by humans, is even more powerful when coupled with new biotechnology techniques.

Today, fermentation can be carried out with genetically engineered microorganisms, specially designed for the conditions under which fermentation takes place,

Fermentation, in fact, is the process by which bacteria can be used to create polyesters. Bacteria called Ralstonia eutropha are used to do this. The bacteria use the sugar of harvested plants, such as corn, to fuel their cellular processes. The by-product of these cellular processes is the polymer.

Lactic acid is fermented from sugar, much like the process used to directly manufacture polymers by bacteria. However, in this fermentation process, the final product of fermentation is lactic acid, rather than a polymer. After the lactic acid is produced, it is converted to polylactic acid using traditional polymerization processes.

Plants are becoming factories for the production of plastics. Researchers created a Arabidopis thaliana plant through genetic engineering. The plant contains the enzymes used by bacteria to create plastics. Bacteria create the plastic through the conversion of sunlight into energy. The researchers have transferred the gene that codes for this enzyme into the plant, as a result the plant produces plastic through its cellular processes. The plant is harvested and the plastic is extracted from it using a solvent. The liquid resulting from this process is distilled to separate the solvent from the plastic.

Currently, fossil fuel is still used as an energy source during the production process. This has raised questions by some regarding how much fossil fuel is actually saved by manufacturing bioplastics. Only a few processes have emerged that actually use less energy in the production process.

Energy use is not the only concern when it comes to biopolymers and bioplastics. There are also concerns about how to balance the need to grow plants for food, and the need to grow plants for use as raw materials. Agricultural space needs to be shared. Researchers are looking into creating a plant that can be used for food, but also as feedstock for plastic production.

Biopolymers and bioplastics are the main components in creating a sustainable plastics industry. These products reduce the dependence on non-renewable fossil fuels, and are easily biodegradable. Together, this greatly limits the environmental impacts of plastic use and manufacture. Also, characteristics such as being biodegradable make plastics more acceptable for long term use by society. It is likely that in the long term, these products will mean plastics will remain affordable, even as fossil fuel reserves diminish.

These methods recover some of the value from the plastic. Recycling recovers the raw material, which can then be used to make new plastic products. Incineration recovers the chemical energy, which can be used to produce steam and electricity. Landfilling plastics does neither of these things. The value of landfilled plastic is buried forever.

A recycling plant uses seven steps to turn plastic trash into recycled plastic:

1. Inspection  Workers inspect the plastic trash for contaminants like rock and glass, and for plastics that the plant cannot recycle.  2. Chopping and Washing  The plastic is washed and chopped into flakes. 3. Flotation Tank  If mixed plastics are being recycled, they are sorted in a flotation tank, where some types of plastic sink and others float. 4. Drying  The plastic flakes are dried in a tumble dryer. 5. Melting  The dried flakes are fed into an extruder, where heat and pressure melt the plastic. Different types of plastics melt at different temperatures. 6. Filtering  The molten plastic is forced through a fine screen to remove any contaminants that slipped through the washing process. The molten plastic is then formed into strands. 7. Pelletizing  The strands are cooled in water, then chopped into uniform pellets. Manufacturing companies buy the plastic pellets from recyclers to make new products. Recycled plastics also can be made into flowerpots, lumber, and carpeting.  

Because plastics are made from fossil fuels, you can think of them as another form of stored energy. Pound for pound, plastics contain as much energy as petroleum or natural gas, and much more energy than other types of garbage. This makes plastic an ideal fuel for waste-to-energy plants.

So, should we burn plastics or recycle them? It depends. Sometimes it takes more energy to make a product from recycled plastics than it does to make it from all-new materials. If that’s the case, it makes more sense to burn the plastics at a waste-to-energy plant than to recycle them. Burning plastics can supply an abundant amount of energy, while reducing the cost of waste disposal and saving landfill space.  

A study by Canadian scientist Martin Hocking shows that making a paper cup uses as much petroleum or natural gas as a polystyrene cup. Plus, the paper cup uses wood pulp. The Canadian study said, “The paper cup consumes 12 times as much steam, 36 times as much electricity, and twice as much cooling water as the plastic cup.” And because the paper cup uses more raw materials and energy, it also costs 2.5 times more than the plastic cup.

scientists have figured out two ways to make plastics degrade: biodegradation and photodegradation.

Photodegradable plastics are a different matter. They use no organic additives. They are made with a special type of plastic that breaks down and becomes brittle in the presence of sunlight. Of course, that means photodegradable plastics do not break down when they are covered by leaves or snow, or when they are buried in a landfill. 

Since only a fraction of certain types of plastic could realistically be captured by a curbside program, the net impact of initiating curbside collection could be an increase in the amount of plastic landfilled. The Berkeley pilot program showed no reduction of plastic being sent to the landfill in the areas where the curbside collection was in operation.

A chasing arrows symbol means a plastic container is recyclable. The arrows are meaningless. Every plastic container is marked with the chasing arrows symbol. The only information in the symbol is the number inside the arrows, which indicates the general class of resin used to make the container.

Packaging resins are made from petroleum refineries’ waste. Plastic resins are made from non-renewable natural resources that could be used for a variety of other applications or conserved. Most packaging plastics are made from the same natural gas used in homes to heat water and cook.

Using plastic containers conserves energy. When the equation includes the energy used to synthesize the plastic resin, making plastic containers uses as much energy as making glass containers from virgin materials, and much more than making glass containers from recycled materials. Using refillables is the most energy conservative.

Our choice is limited to recycling or wasting. Source reduction is preferable for many types of plastic and isn’t difficult. Opportunities include using refillable containers, buying in bulk, buying things that don’t need much packaging, and buying things in recyclable and recycled packages

Plastic packaging has economic, health, and environmental costs and benefits.

Plastic container producers do not use any recycled plastic in their packaging. Recycled content laws could reduce the use of virgin resin for packaging. Unfortunately, the virgin&endash;plastics industry has resisted such cooperation by strongly opposing recycled -content legislation, and has defeated or weakened consumer efforts to institute stronger laws.

Processing used plastics often costs more than virgin plastic. As plastic producers increase production and reduce prices on virgin plastics, the markets for used plastic are diminishing. PET recyclers cannot compete with the virgin resin flooding the market.

1. Reduce the useSource reduction Retailers and consumers can select products that use little or no packaging. Select packaging materials that are recycled into new packaging - such as glass and paper.

2. Reuse containersSince refillable plastic containers can be reused about 25 times, container reuse can lead to a substantial reduction in the demand for disposable plastic, and reduced use of materials and energy

3. Require producers to take back resins

Make reprocessing easier by limiting the number of container types and shapes, using only one type of resin in each container, making collapsible containers, eliminating pigments, using water-dispersible adhesives for labels, and phasing out associated metals such as aluminum seals.

4. Legislatively require recycled content Requiring that all containers be composed of a percentage of post-consumer material reduces the amount of virgin material consumed.

5. Standardize labeling and inform the public The chasing arrows symbol on plastics is an example of an ambiguous and misleading label. Significantly different standardized labels for "recycled," "recyclable," and "made of plastic type X" must be developed.

Number 6 goes on polystyrene (Styrofoam) items such as coffee cups, disposable cutlery, meat trays, packing “peanuts” and insulation. It is widely accepted because it can be reprocessed into many items, including cassette tapes and rigid foam insulation.

Usually imprinted with a number 7 or nothing at all, these plastics are the most difficult to recycle and, as such, are seldom collected or recycled.

when a polymer is molten, the chains will act like spaghetti tangled up on a plate. If you try to pull out any one strand of spaghetti, it slides right out with no problem. But when polymers are cold and in the solid state, they act more like a ball of string.

intermolecular forces affect polymers just like small molecules. But with polymers, these forces are greatly compounded. The bigger the molecule, the more molecule there is to exert an intermolecular force. Even when only weak Van der Waals forces are at play, they can be very strong in binding different polymer chains together. This is another reason why polymers can be very strong as materials. Polyethylene, for example is very nonpolar. It only has Van der Waals forces to play with, but it is so strong it's used to make bullet proof vests.

This is a fancy way of saying polymers move more slowly than small molecules do. Imagine you are a first grade teacher, and it's time to go to lunch. Your task is to get your kids from the classroom to the cafeteria, without losing any of them, and to do so with minimal damage to the territory you'll have to cover to get to the cafeteria. Keeping them in line is going to be difficult. Little kids love to run around every which way, jumping and hollering and bouncing this way and that. One way to put a stop to all this chaotic motion is to make all the kids join hands when you're walking them to lunch. This won't be easy rest assured, as there's always going to be a lot of little boys who are too macho to hold the hands of the girls next to them in line, and some who are too insecure in their manhood to hold anyone's hand. But once you get them to do this, their ability to run around is severely limited. Of course, their motion will still be chaotic. The chain of kids will curve and snake this way and that on its way to eat soybean patties disguised as who knows what. But the motion will be a lot slower. You see, if one kid gets a notion to just bolt off in one direction, he or she can't do it because he or she will be bogged down by the weight of all the other kids to which he or she is bound. Sure, the kid can deviate from the straight path, and make a few other kids do so, but the deviation will be far less than you'd bet if the kids weren't all linked together. It's the same way with molecules.

So then how does this make a polymeric material different from a material made of small molecules? This slow speed of motion makes polymers do some very unusual things. For one, if you dissolve a polymer in a solvent, the solution will be a lot more viscous than the pure solvent.

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.

In contrast to amylopectin, which comprises 70 to 90 percent of natural starch, α-amylose is a branching polysaccharide.

Branches occur at every twelve to thirty residues along a chain of α (1→4) linked glucoses. As a result, amylopectin has one reducing end and many nonreducing ends.

Amylopectin and α-amylose are broken down by the enzyme amylase. In animals, salivary α-amylase begins the digestion process in the mouth. Pancreatic α-amylase continues the process in the intestine.

Glycogen is the energy storage carbohydrate in animals. Glycogen is found mainly in the liver (where it is responsible for up to 10 percent of liver mass) and skeletal muscle (1 to 2 percent of skeletal muscle mass)

However, glycogen branches more abundantly than amylopectin, with branches at every eight to twelve residues. As a result, it has many more nonreducing ends. Glycogen is broken down at these nonreducing ends by the enzyme glycogen phosphorylase to release glucose for energy.

The primary structural homopolysaccharides are cellulose and chitin. Cellulose, a major component of plant cell walls, is the most abundant natural polymer on Earth.

Like α-amylose, cellulose is a linear polysaccharide composed entirely of glucose. However, in cellulose the glucose residues occur in β(1→4) linkage rather than α (1→4) (see Figure 1).

In addition, individual cellulose strands can form hydrogen bonds with one another to provide additional strength. Most animals, including humans, lack the enzymes necessary to dissolve α(1→4) linkages and so cannot digest cellulose

The animals that can (such as ruminants) do so via a symbiosis with bacteria that secrete cellulose-degrading enzymes.

The second most abundant polymer on Earth is chitin. Chitin comprises much of the exoskeletons of crustaceans, insects, and spiders, as well as the cell walls of fungi. Structurally, chitin is very similar to cellulose, except that its basic monosaccharide is N-acetylglucosamine