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Becky Kriger

Polymer - Condensation polymers - 1 views

  • Polymers are made up of extremely large, chainlike molecules consisting of numerous, smaller, repeating units called monomers. Polymer chains, which could be compared to paper clips linked together to make a long strand, appear in varying lengths. They can have branches, become intertwined, and can have cross-links. In addition, polymers can be composed of one or more types of monomer units, they can be joined by various kinds of chemical bonds, and they can be oriented in different ways. Monomers can be joined together by addition, in which all the atoms in the monomer are present in the polymer, or by condensation, in which a small molecule byproduct is also formed.
  • The importance of polymers is evident as they occur widely both in the natural world in such materials as wool, hair, silk and sand, and in the world of synthetic materials in nylon, rubber, plastics, Styrofoam, and many other materials.
  • Polymers are extremely large molecules composed of long chains, much like paper clips that are linked together to make a long strand. The individual subunits, which can range from as few as 50 to more than 20,000, are called monomers (from the Greek mono meaning one and meros meaning part). Because of their large size, polymers (from the Greek poly meaning many) are referred to as macromolecules.
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  • 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.
Becky Kriger

Scientific Principles:Polymers - 0 views

  • The chemical reaction in which high molecular mass molecules are formed from monomers is known as polymerization. There are two basic types of polymerization, chain-reaction (or addition) and step-reaction (or condensation) polymerization.
  • One of the most common types of polymer reactions is chain-reaction (addition) polymerization. This type of polymerization is a three step process involving two chemical entities. The first, known simply as a monomer, can be regarded as one link in a polymer chain. It initially exists as simple units. In nearly all cases, the monomers have at least one carbon-carbon double bond. Ethylene is one example of a monomer used to make a common polymer.
  • The other chemical reactant is a catalyst. In chain-reaction polymerization, the catalyst can be a free-radical peroxide added in relatively low concentrations. A free-radical is a chemical component that contains a free electron that forms a covalent bond with an electron on another molecule. The formation of a free radical from an organic peroxide is shown below:
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  • 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
Becky Kriger

Chemical of the Week -- Polymers - 0 views

  •  Polymers are substances whose molecules have high molar masses and are composed of a large number of repeating units. There are both naturally occurring and synthetic polymers. Among naturally occurring polymers are proteins, starches, cellulose, and latex. Synthetic polymers are produced commercially on a very large scale and have a wide range of properties and uses. The materials commonly called plastics are all synthetic polymers.
  •    Polymers are formed by chemical reactions in which a large number of molecules called monomers are joined sequentially, forming a chain.
  • If all atoms in the monomers are incorporated into the polymer, the polymer is called an addition polymer. If some of the atoms of the monomers are released into small molecules, such as water, the polymer is called a condensation polymer.
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  • 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:            
Becky Kriger

Emulsion polymerization - Wikipedia, the free encyclopedia - 0 views

  • Emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomer, and surfactant. The most common type of emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer (the oil) are emulsified (with surfactants) in a continuous phase of water.
  • Typical monomers are those that undergo radical polymerization, are liquid or gaseous at reaction conditions, and are poorly soluble in water.
  • A dispersion resulting from emulsion polymerization is often called a latex (especially if derived from a synthetic rubber) or an emulsion (even though "emulsion" strictly speaking refers to a dispersion of a liquid in water). These emulsions find applications in adhesives, paints, paper coating and textile coatings.
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  • 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)
Becky Kriger

Plastics - 0 views

  • lastics are synthetic materials, which means that they are artificial, or manufactured.
  • he building blocks for making plastics are small organic molecules - molecules that contain carbon along with other substances. They generally come from oil (petroleum) or natural gas, but they can also come from other organic materials such as wood fibers, corn, or banana peels! Each of these small molecules is known as a monomer ("one part") because it's capable of joining with other monomers to form very long molecule chains called polymers ("many parts")
  • 1. Crude oil, the unprocessed oil that comes out of the ground, contains hundreds of different hydrocarbons, as well as small amounts of other materials. The job of an oil refinery is to separate these materials and also to break down (or "crack) large hydrocarbons into smaller ones. 2. A petrochemical plant receives refined oil containing the small monomers they need and creates polymers through chemical reactions. 3. A plastics factory buys the end products of a petrochemical plant - polymers in the form of resins - introduces additives to modify or obtain desirable properties, then molds or otherwise forms the final plastic products.
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  • 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.
Becky Kriger

Polymer Structures - 0 views

    • Becky Kriger
       
      To view the annotated contents of this page, click on the highlighted links to the left.
  • Although the fundamental property of bulk polymers is the degree of polymerization, the physical structure of the chain is also an important factor that determines the macroscopic properties.
  • Configuration refers to the order that is determined by chemical bonds. The configuration of a polymer cannot be altered unless chemical bonds are broken and reformed. Conformation refers to order that arises from the rotation of molecules about the single bonds. These two structures are studied below.
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  • 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.
Becky Kriger

Special Properties of Polymers - 0 views

shared by Becky Kriger on 08 Dec 08 - Cached
  • why these polymers, these macromolecules, act differently from small molecules.
  • Chain entanglement Summation of intermolecular forces Time scale of motion
  • Remember now that most polymers are linear polymers; that is, they are molecules whose atoms are joined in a long line to form a huge chain. Now most of the time, but not always, this chain is not stiff and straight, but is flexible. It twists and bends around to form a tangled mess.
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  • 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.
Becky Kriger

Biopolymers and Bioplastics - 0 views

  • Biopolymers are polymers which are present in, or created by, living organisms. These include polymers from renewable resources that can be polymerized to create bioplastics. Bioplastics are plastics manufactured using biopolymers, and are biodegradable.
  • There are two main types of biopolymers: those that come from living organisms; and, those which need to be polymerized but come from renewable resources. Both types are used in the production of bioplastics
  • Biopolymer Natural Source What is it? Cellulose Wood, cotton, corn, wheat, and others This polymer is made up of glucose. It is the main component of plant cell walls. Soy protein Soybeans Protein which naturally occurs in the soy plant. Starch Corn, potatoes, wheat, tapioca, and others This polymer is one way carbohydrates are stored in plant tissue. It is a polymer made up of glucose. It is not found in animal tissues. Polyesters Bacteria These polyesters are created through naturally occurring chemical reactions that are carried out by certain types of bacteria.
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  • 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.
Becky Kriger

Chemistry - Condensation polymer - 0 views

  • Condensation polymers are any class of polymer formed through a condensation reaction, as opposed to addition polymers which involve the reaction of unsaturated monomers. Types of condensation polymer include polyamides and polyesters.
  • The carboxylic acids and amines link to form peptide bonds, also known as amide groups. Proteins are condensation polymers made from amino acid monomers. Carbohydrates are also condensation polymers made from sugar monomers such as glucose and galactose.
  • Condensation Polymers, unlike Addition polymers are bio-degradable. The peptide or ester bonds between monomers can be hydrolysed by acid catalysts or bacterial enzymes breaking the polymer chain into smaller pieces.
Becky Kriger

How Plastics Are Made - 0 views

  • The term "plastics" encompasses organic materials, such as the elements carbon (C), hydrogen (H), nitrogen (N), chlorine (Cl) and sulfur (S), which have properties similar to those naturally grown in organic materials such as wood, horn and rosin.
  • The plastic production process begins by heating the hydrocarbons in a "cracking process." Here, in the presence of a catalyst, larger molecules are broken down into smaller ones such as ethylene (ethene) C2H4, propylene (propene) C3H6, and butene C4H8 and other hydrocarbons.
  • Other examples of thermoset plastics and their product applications are: Polyurethanes: mattresses, cushions, insulation, ski boots, toys Unsaturated Polyesters: lacquers, varnishes, boat hulls, furniture,  Epoxies: glues, coating electrical circuits, helicopter blades
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  • 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.
Becky Kriger

Polymerization catalysts past, present, and future - 0 views

  • The most common polymers are polyolefins, especially polyethylene (better known as Polythene, although this is a trade name owned by DuPont) and polypropylene. However, efficient ways of producing these vital materials are only the result of recent discoveries and have been dependant on the chemistry of catalysts.
  • Since the 1950s, the production of polyolefins has depended on the use of Ziegler-Natta catalysts.
  • Ziegler-Natta catalysts are based on a mixture of a transition metal, commonly a titanium compound, and an alkali metal, most commonly aluminium oxide.
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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).
Becky Kriger

Rubber Polymers - 0 views

  • Rubber is an example of an elastomer type polymer, where the polymer has the ability to return to its original shape after being stretched or deformed.
  • The elastic properties arise from the its ability to stretch the chains apart, but when the tension is released the chains snap back to the original position.
  • Natural rubber is an addition polymer
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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.
Becky Kriger

Polymer Tutorial - 0 views

  • "Poly" means "many" and "mer" means "parts.
  • The parts are usually the same part used repeatedly in a chain-like manner. Polymers are also referred to as plastics
  • Nature has many examples of polymers. Cotton fibers are made of sugar molecules that are repeated in a chain-like manner. Hair, wool, and other natural fibers are polymers.
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  • 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.
  •  
    A simply explained introduction to polymers.
Becky Kriger

Is Glass a Polymer? - 0 views

  • The highest quality glass has the chemical formula SiO2. But this is misleading. That formula conjures up ideas of little silicon dioxide molecules, analogous to carbon dioxide molecules. But little silicon dioxide molecules don't exist.
  • Instead, in nature SiO2 is often found as a crystalline solid, with a structure like you see on your right. Every silicon atom is bonded four oxygen atoms, tetrahedrally, of course; and every oxygen atom is bonded to two silicon atoms. When SiO2 is in this crystalline form we call it silica.
  • But this silica isn't glass. We have to do something to it first to make it into glass. We have to heat it up until it melts, and then cool it down really fast. When it melts, the silicon and oxygen atoms break out of their crystal structure. If we cooled it down slowly, the atoms would slowly line back up into their crystalline arrangement as they slowed down.
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  • As you can see, there is no order to the arrangement of the atoms. We call materials like this amorphous. This is the glass that is used for telescope lenses and such things. It has very good optical properties, but it's brittle. For everyday uses, we need something tougher. Most glass is made from sand, and when we melt down the sand, we usually add some sodium carbonate. This gives us a tougher glass with a structure that looks like this:
  • So is this a polymer or not? Usually it isn't considered as such. Why? Some may say it's inorganic, and polymers are usually organic. But there are many inorganic polymers out there. For example, what about polysiloxanes? These linear, and yes, inorganic materials have a structure very similar to glass, and they're considered polymers. Take a look at a polysiloxane:
  • So glass could be considered a highly crosslinked polysiloxane. But we usually don't think of it that way. Why not? Probably because even in a highly crosslinked system, you could still trace a polymer chain and see where the crosslinks are. But with glass, it'd be tough to do that.
Becky Kriger

Effects of Temperature on Polymers - 0 views

  • Many polymers have a mixture of ordered (crystalline) regions and random (amorphous) regions.  In the glassy state the tangled chains in the amorphous region are frozen so movement of chains is not possible.  The polymer is brittle.
  • If the glassy material is heated, the chains reach a temperature at which they can move.  This temperature is called the glass transition temperature Tg.  Above this temperature the polymer is flexible. 
  • The glass transition temperature of a polymer can be changed by two different ways: Copolymerisation.  Ethene can be polymerised with propene to give a new polymer with different properties. Plasticisers.  PVC is quite brittle.  Its Tg can be lowered, making it less brittle, by introducing a substance between the polymer chains, allowing the chains to slide over each other more easily.  Such a substance is called a plasticiser.
Becky Kriger

How are polymers made? : Scientific American - 0 views

  • Synthetic polymers are produced by chemical reactions, termed "polymerizations."
  • but such reactions consist of the repetitive chemical bonding of individual molecules, or monomers. Assorted combinations of heat, pressure and catalysis alter the chemical bonds that hold monomers together, causing them to bond with one another. Most often, they do so in a linear fashion, creating chains of monomers called polymers.
  • The monomer ethylene is composed of two carbon atoms, each bonded to two hydrogen atoms and sharing a double bond with one another. Polyethylene consists of a chain of single-bonded carbon atoms, each still carrying its two hydrogen atoms.
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  • 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.
Becky Kriger

Carbohydrates and Polysaccharides - 0 views

  • Disaccharide Monosaccharides sucrose from α-glucose + α-fructose maltose from α-glucose + α-glucose α-lactose * from α-glucose + β-galactose * Lactose also exists in a beta form, which is made from β-galactose and β-glucose
  • A condensation reaction takes place releasing water. This process requires energy. A glycosidic bond forms and holds the two monosaccharide units together.
  • Carbohydrates (also called saccharides) are molecular compounds made from just three elements: carbon, hydrogen and oxygen. Monosaccharides (e.g. glucose) and disaccharides (e.g. sucrose) are relatively small molecules.
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  • a source of energy
  • building blocks for polysaccharides (giant carbohydrates
  • components of other molecules eg DNA, RNA, glycolipids, glycoproteins, ATP
  • Monosaccharides are the simplest carbohydrates and are often called single sugars.
  • Monosaccharides have the general molecular formula (CH2O)n, where n can be 3, 5 or 6.
  • n = 3 trioses, e.g. glyceraldehyde n = 5 pentoses, e.g. ribose and deoxyribose ('pent' indicates 5) n = 6 hexoses, e.g. fructose, glucose and galactose ('hex' indicates 6)
  • Molecules that have the same molecular formula but different structural formulae are called structural isomers.
  • Monosaccharides containing the aldehyde group are classified as aldoses, and those with a ketone group are classified as ketoses. Aldoses are reducing sugars; ketoses are non-reducing sugars.
  • in water pentoses and hexoses exist mainly in the cyclic form, and it is in this form that they combine to form larger saccharide molecules.
  • There are two forms of the cyclic glucose molecule: α-glucose and β-glucose.
  • Two glucose molecules react to form the dissacharide maltose. Starch and cellulose are polysaccharides made up of glucose units.
  • Galactose molecules look very similar to glucose molecules. They can also exist in α and β forms. Galactose reacts with glucose to make the dissacharide lactose.
  • However, glucose and galactose cannot be easily converted into one another. Galactose cannot play the same part in respiration as glucose.
  • Fructose reacts with glucose to make the dissacharide sucrose.
  • Ribose and deoxyribose are pentoses. The ribose unit forms part of a nucleotide of RNA. The deoxyribose unit forms part of the nucleotide of DNA.
  • Monosaccharides are rare in nature. Most sugars found in nature are disaccharides. These form when two monosaccharides react.
  • The three most important disaccharides are sucrose, lactose and maltose.
  • Disaccharides are soluble in water, but they are too big to pass through the cell membrane by diffusion.
  • This is a hydrolysis reaction and is the reverse of a condensation reaction. It releases energy.
  • Monosaccharides are converted into disaccharides in the cell by condensation reactions. Further condensation reactions result in the formation of polysaccharides. These are giant molecules which, importantly, are too big to escape from the cell. These are broken down by hydrolysis into monosaccharides when energy is needed by the cell.
  • Monosaccharides can undergo a series of condensation reactions, adding one unit after another to the chain until very large molecules (polysaccharides) are formed. This is called condensation polymerisation, and the building blocks are called monomers. The properties of a polysaccharide molecule depend on: its length (though they are usually very long) the extent of any branching (addition of units to the side of the chain rather than one of its ends) any folding which results in a more compact molecule whether the chain is 'straight' or 'coiled'
  • Starch is often produced in plants as a way of storing energy. It exists in two forms: amylose and amylopectin
  • Amylose is an unbranched polymer of α-glucose. The molecules coil into a helical structure. It forms a colloidal suspension in hot water. Amylopectin is a branched polymer of α-glucose. It is completely insoluble in water.
  • Glycogen is amylopectin with very short distances between the branching side-chains.
  • Inside the cell, glucose can be polymerised to make glycogen which acts as a carbohydrate energy store.
  • Cellulose is a third polymer made from glucose. But this time it's made from β-glucose molecules and the polymer molecules are 'straight'.
  • Cellulose serves a very different purpose in nature to starch and glycogen. It makes up the cell walls in plant cells. These are much tougher than cell membranes. This toughness is due to the arrangement of glucose units in the polymer chain and the hydrogen-bonding between neighbouring chains.
  • Cellulose is not hydrolysed easily and, therefore, cannot be digested so it is not a source of energy for humans.
Becky Kriger

Condensation Polymerization - 0 views

  • The monomers that are involved in condensation polymerization are not the same as those in addition polymerization. The monomers for condensation polymerization have two main characteristics:. Instead of double bonds, these monomers have functional groups (like alcohol, amine, or carboxylic acid groups). Each monomer has at least two reactive sites, which usually means two functional groups. Some monomers have more than two reactive sites, allowing for branching between chains, as well as increasing the molecular mass of the polymer.
  • Let's look again at the functional groups on these monomers. We've seen three: The carboxylic acid group The amino group The alcohol group
  • You might have learned in chemistry or biology class that these groups can combine in such a way that a small molecule (often H2O) is given off. The Amide Linkage:When a carboxylic acid and an amine react, a water molecule is removed, and an amide molecule is formed. Because of this amide formation, this bond is known as an amide linkage. The Ester Linkage:When a carboxylic acid and an alcohol react, a water molecule is removed, and an ester molecule is formed. Because of this ester formation, this bond is known as an ester linkage.
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  • Example 1:A carboxylic acid monomer and an amine monomer can join in an amide linkage. As before, a water molecule is removed, and an amide linkage is formed. Notice that an acid group remains on one end of the chain, which can react with another amine monomer. Similarly, an amine group remains on the other end of the chain, which can react with another acid monomer. Thus, monomers can continue to join by amide linkages to form a long chain. Because of the type of bond that links the monomers, this polymer is called a polyamide.
  • Example 2:A carboxylic acid monomer and an alcohol monomer can join in an ester linkage. A water molecule is removed as the ester linkage is formed. Notice the acid and the alcohol groups that are still available for bonding.
  • Because the monomers above are all joined by ester linkages, the polymer chain is a polyester. This one is called PET, which stands for poly(ethylene terephthalate). (PET is used to make soft-drink bottles, magnetic tape, and many other plastic products.)
Becky Kriger

Addition Polymers - 0 views

  • Addition polymers are usually made from molecules that have the following general structure: Different W, X, Y, and Z groups distinguish one addition polymer from another.
  • In the first stage, a substance is split into two identical parts, each with an unpaired electron. (Peroxides, which contain an O-O bond, are often used in this role.) A molecule with an unpaired electron is called a free radical. The free radical then initiates the reaction sequence by forming a bond to one of the carbon atoms in the double bond of the monomer. One electron for this new bond comes from the free radical, and the second electron for the new bond comes from one of the two bonds between the carbon atoms. The remaining electron from the broken bond shifts to the carbon atom on the far side of the molecule, away from the newly formed bond, forming a new free radical. Each half-headed arrow indicates the shift of one electron.
  • The chain begins to grow--propagate, stage two--when the new free radical formed in the initiation stage reacts with another monomer to add two more carbon atoms. This process repeats over and over again
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  • 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.
Becky Kriger

Polysaccharides - Chemistry Encyclopedia - 0 views

  • Polysaccharides are long polymers of monosaccharides and their derivatives. Unlike proteins or nucleic acids, these polymers can be either linear or branched, and they can contain only one type of monosaccharide (homopolysaccharides), or more than one (heteropolysaccharides)
  • Starch is a homopolysaccharide and has two forms: amylopectin and α-amylose. In nature, starch is approximately 10 to 30 percent α-amylose.
  • Starch is the main energy reserve in plants; glycogen is the main energy reserve in animals
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  • 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
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