Chem 109H Fall08

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.)

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. 

To form polypeptides and proteins, amino acids are joined together by peptide bonds (def), in which the amino or NH2 of one amino acid bonds to the carboxyl (acid) or COOH group of another amino acid as shown in (see Fig. 2). Animation showing the formation of a peptide bond.

The actual order of the amino acids in the protein is called its primary structure (def) (see Fig. 3) and is determined by DNA.

it is commonly said that the order of deoxyribonucleotide bases (def) in a gene determines the amino acid sequence of a particular protein. Since certain amino acids can interact with other amino acids in the same protein, this primary structure ultimately determines the final shape and therefore the chemical and physical properties of the protein.

In globular proteins such as enzymes, the long chain of amino acids becomes folded into a three-dimensional functional shape or tertiary structure (def).

In some cases, such as with antibody molecules and hemoglobin, several polypeptides may bond together to form a quaternary structure (def) (see Fig 6).

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.

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.

Polysaccharides make ideal storage molecules for energy for a number of reasons; a) they are large, this makes them insoluble in water and therefore they exert no osmotic or chemical effect on the cell; b) they fold into compact shapes; c) they are easily converted into the required sugars when needed.

Glycogen is a branched polysaccharide found in nearly all animal cells and in certain protozoa and algae.

In humans and other vertebrates it is principally stored in the liver and muscles and is the main form of stored carbohydrate in the body, acting as a reservoir of glucose

Starch is similar to glycogen, however it is found in plant cells, protists and certain bacteria.

The starch granules are made up of two polysaccharides, amylose and amylopectin. Amylose is an unbranched molecule made up of several thousand glucose units, coiled helically into a more compact shape. Amylopectin is also compact but has a branched structure and is made up of twice as many glucose units as amylose.

For example, peptidoglycans, which are a combination of protein and polysaccharide and are found in the cell wall of certain bacteria. Glycolipids, a combination of polysaccharides and lipids are found in the cell membrane.

The 9 atoms that make up the fused rings (5 carbon, 4 nitrogen) are numbered 1-9. All ring atoms lie in the same plane.

The deoxyribose sugar of the DNA backbone has 5 carbons and 3 oxygens. The carbon atoms are numbered 1', 2', 3', 4', and 5' to distinguish from the numbering of the atoms of the purine and pyrmidine rings. The hydroxyl groups on the 5'- and 3'- carbons link to the phosphate groups to form the DNA backbone

A nucleoside is one of the four DNA bases covalently attached to the C1' position of a sugar.

Nucleosides differ from nucleotides in that they lack phosphate groups. The four different nucleosides of DNA are deoxyadenosine (dA), deoxyguanosine (dG), deoxycytosine (dC), and (deoxy)thymidine (dT, or T).

A nucleotide is a nucleoside with one or more phosphate groups covalently attached to the 3'- and/or 5'-hydroxyl group(s).

The DNA backbone is a polymer with an alternating sugar-phosphate sequence. The deoxyribose sugars are joined at both the 3'-hydroxyl and 5'-hydroxyl groups to phosphate groups in ester links, also known as "phosphodiester" bonds.

DNA is a normally double stranded macromolecule. Two polynucleotide chains, held together by weak thermodynamic forces, form a DNA molecule.

Two DNA strands form a helical spiral, winding around a helix axis in a right-handed spiral The two polynucleotide chains run in opposite directions The sugar-phosphate backbones of the two DNA strands wind around the helix axis like the railing of a sprial staircase The bases of the individual nucleotides are on the inside of the helix, stacked on top of each other like the steps of a spiral staircase.

Within the DNA double helix, A forms 2 hydrogen bonds with T on the opposite strand, and G forms 3 hyrdorgen bonds with C on the opposite strand.

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

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

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

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

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

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

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

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

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

call Styrofoam. Polypropylene (PP) is used in dishwasher-safe containers

You'll often find polyethylene terephthalate (PET) in soda bottles, and it is sometimes recycled into fleece, upholstery fabrics, and other useful materials. And then of course there's polyvinyl chloride (PVC)

about 4 percent of the world's annual oil production of some 84.5 million barrels per day is used as feedstock for plastic, and another 4 percent or so provides the energy to transform the feedstock into handy plastic.

drilling. Recycling, however, does cut into energy use. According to the U.S. EPA, manufacturing new plastic from recycled plastic requires two-thirds of the energy used in virgin plastic manufacture. I have more numbers, too: one ton of recycled plastic saves 685 gallons of oil.

A five-carbon sugar (hence a pentose). Two kinds are found: Deoxyribose, which has a hydrogen atom attached to its #2 carbon atom (designated 2') Ribose, which has a hydroxyl group atom there

A nitrogen-containing ring structure called a base. The base is attached to the 1' carbon atom of the pentose. In DNA, four different bases are found:

The combination of a base and a pentose is called a nucleoside.

One (as shown in the first figure), two, or three phosphate groups. These are attached to the 5' carbon atom of the pentose.

The nucleic acids, both DNA and RNA, consist of polymers of nucleotides. The nucleotides are linked covalently between the 3' carbon atom of the pentose and the phosphate group attached to the 5' carbon of the adjacent pentose.

Most intact DNA molecules are made up of two strands of polymer, forming a "double helix". RNA molecules, while single-stranded, usually contain regions where two portions of the strand twist around each other to form helical regions.

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.

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.

For sugars with more than one chiral center, the D or L designation refers to the asymmetric carbon farthest from the aldehyde or keto group. Most naturally occurring sugars are D isomers.

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.