F334 The Materials Revolution: Amines and Amides: Organic derivatives of ammonia.

nia. Ammonia has three hydrogen atoms bonded to the central nitrogen atom whereas amines have one or more alkyl groups substituted for hydrogen. Like ammonia, the lone pair of electrons on the nitrogen atom is responsible for the 3 main properties of amines bases, nucleophiles and ligands.

Primary, secondary and tertiary amines: In primary amines, the nitrogen atom is bonded to one alkyl (or aryl) group. In secondary amines, the nitrogen atom is bonded to two alkyl (or aryl) groups. In tertiary amines the nitrogen atom is bonded to three alkyl (or aryl) groups.

Naming amines: The amines are named following the general rules. The alkyl groups are arranged in alphabetical order, and placed in front of the suffix amine. For amines with long alkyl chains, it is equally correct to use the prefix amino followed by the name of the parent alkane. Note: an aryl group contains a benzene ring with one hydrogen atom substituted. Examples: CH3NH2 = methylamine CH3CH2NH2 = ethylamine CH3CH2CH2NH2 = propylamine CH3CH(NH2)CH3 = 2-propylamine or 2-aminobutane C6H5NH2 = phenylamine CH3CH2CH2(NH)CH3 = methylpropylamine (CH3)3N = trimethylamine H2NCH2CH2CH2CH2CH2CH2NH2 = 1,6-diaminohexane

Solubility: Like ammonia, amines can form hydrogen bonds to water. Because of this strong attraction between amine molecules and water molecules, amines with small alkyl groups are soluble. Amines with larger alkyl groups are less soluble because the alkyl groups disrupt the hydrogen bonding in water.

Amines as bases: The lone pair on the nitrogen atom can take part in dative covalent bonding. When the electron pair is donated to a H+, ammonia acts as an H+ acceptor and is a base. NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) NH4+ is the ammonium ion. A similar thing happens with amines. Like ammonia they can accept H+ from water. Using propylamine as an example, the reaction with water is: CH3CH2CH2NH2(aq) + H2O(l) CH3CH2CH2NH3+(aq) + OH-(aq) The presence of hydroxide ions makes the solution alkaline. Like ammonia, amines also react with acids. The H3O+ ions in acidic solutions are more powerful H+ donors than water. Their reaction with amines goes to completion and the solution therefore loses its strong amine smell. CH3CH2CH2NH2(aq) + H3O+(aq) CH3CH2CH2NH3+(aq) + H2O(l) The above are both examples of neutralisation reactions.

Amines as Ligands: Ammonia is an effective ligand because the lone pair of electrons on the N atom can bond to metal ions. For example, ammonia forms a deep-blue complex ion, [Cu(NH3)4(H2O)2]2+ Complex ions containing ammonia ligands have their counterparts in amine chemistry. For example, adding butylamine to aqueous copper(II) sulphate produces a dark blue complex ion, [Cu(C4H9NH2)4(H2O)2]2+ With a structure similar to [Cu(NH3)4(H2O)2]2+.

Amines as nucleophiles: Ammonia can act as a nucleophile with the lone pair of electrons on the N atom attacking electrophiles, such as the positively polarised carbon atom in halogenoalkanes: R-Cl + NH3 R-NH3+Cl- R-NH2 + H+ + ClThe product of this reaction is an amine. Amines themselves can behave as nucleophiles. They have a long pair of electrons on the N atom just the same as ammonia. So amines undergo substitution reactions with halogenoalkanes, to form secondary and tertiary amines. R-Cl + R-NH2 [R-(NH2)-R]+ Cl- R-NH2 + H+ + Cl-

Amides: Primary amides have the functional group:

Primary amides are named from the corresponding carboxylic acid: CH3CONH2 = Ethanamide Secondary amides have the functional group:

Amide formation: Acylation of an amine forms an amide. It is called acylation as an acyl group is added to the amine. For example: NH3 + CH3COCl H2NCOCH3 + HCl Ammonia + ethanoyl chloride ethanamide + hydrochloric acid. The reaction is very vigorous, even at room temperature as acyl chlorides are very reactive. They also react violently with water to form the carboxylic acid, so anhydrous conditions are essential. When ammonia reacts with an acyl chloride a primary amide is formed as shown above. When a primary amine reacts with an acyl chloride a secondary amide is formed: R-NH2 + CH3COCl R-NHCO-CH3 + HCl

Hydrolysis of amides: The C-N bond in amides can be broken by hydrolysis. The reaction is catalysed by either acid or alkali. For the acid hydrolysis, the amide has to be heated under reflux with aqueous moderately concentrated acid. When the amide is hydrolysed using an acid, the NH3 molecule produced acts as a base and accepts a proton from the acid, thus becoming NH4+.

Therefore the product contains ammonium ions.

For the alkali hydrolysis the amide has to be heated under reflux with aqueous moderately concentrated alkali. When it is hydrolysed using an alkali, the carboxylic acid donates a proton to the alkali, changing the carboxyl group into a COO- group. Therefore the product contains carboxylate ions.

Condensation Polymers Polymers are long chains of repeating units known as monomers. Additional Polymers are formed when many identical monomers join together to form a polymer (these polymers can be referred to as A-A polymers), for example:

Condensation polymers are formed when lots of smaller molecules (monomers) join together to form a larger molecule (polymer), resulting in the loss of small molecules. Condensation polymers are examples of A-B polymers.

Polyamides Polyamides are polymers in which the individual monomers are held together by amide linkages. They are made by reacting a diamine with a dicarboxylic acid, or molecules with both an amino group and a carboxylic acid group, for example 1-amino-hexanoic acid. Below is an example of a polyamide:

The polyamide is called Nylon-4,8 (there are four carbons on the amine side of the polymer,

and eight on the carboxylic acid side). The above polymer is formed when 1,4-diaminobutane reacts with octanedioic acid:

These two molecules line up alternatively; forming amide linkages between the adjacent NH2 groups and COOH groups. Each amide bond formed results in the loss of a water molecule.

History of Polyamides- The invention of Nylon Wallace Carothers developed the first ever nylon. He joined the US chemical company Dupont in 1928, where he led a team of investigators working on the production of a polymer that could be used as a fibre. Carothers decided to investigate the polyamides as possible future fibres; however the polyamides formed gummy resins, rather than fibres (due to the presence of water). To get around this problem, Carothers designed a molecular still in which the reaction mixture was heated gently to vaporise the water that was formed. These new polymers were tough, opaque solids; however they melted at low temperatures, meaning that the new fibres could not be ironed. They were also slightly soluble in water. This problem was solved accidentally, when Jullian Hill, a member of Carothers team, removed a stirring rod from the hot polymer mixture. To his surprise he realised that he had pulled out a long, thin filament. On cooling, the filament could be stretched to many times its usual length. This process was named cold-drawing; it produced fibres that were long, pliable and tough. Xray diffraction showed that the undrawn fibres were crystalline, but that the crystals had random orientation. Cold drawing causes the polymer chains to become orientated along the length of the fibre. This means that the chains can get closer together and so there are more points where intermolecular forces can act, thus leading to a large increase in the polymers tensile strength.

When the polymer is cold-drawn, a neck forms. The polymer chains within this neck line up to form a more crystalline region. The process continues until all of the polymer chains are aligned

(except the ends being pulled). Carothers discovered nylon in 1935; he decided that nylon-5,10 had the most potential. However, Elmer Bolton (director of Dupont) argued that nylon-6,6 was the better polymer, due to its high melting point, insolubility in organic substances and its ability to be produced from abundant materials. In 1938, the first product using nylon appeared; a toothbrush with nylon bristles. Nylon stockings were seen for the first time in 1939, along with nylon parachutes.

Polyesters Polyesters are polymers in which the individual monomers are joined together by ester bonds. They are made by reacting a carboxylic acid with two COOH groups, and an alcohol with two OH groups, or molecules with both a hydroxyl and carboxylic acid group, e.g. 4-hydroxy-benzoic acid. The reaction process is called esterfication. Below is an example of a polyester:

The polymer chain could continue, as the one unit is repeated many times throughout the section. The above polymer is formed when benzene-1,4-dicarboxylic acid reacts with ethan-1,2-diol:

These two molecules line up alternatively, forming ester linkages between the hydroxyl and carboxylic acid groups. Each ester linkage results in the loss of a water molecule:

History of polyesters As with the polyamides, the polyesters were first developed by Wallace Carothers. His polyesters were improved by J.R Whinfield and J.T Dickson, who used benzene-1,4dicarboxylic acid instead of hexanedioic acid. The new polyester they developed was named terylene.

Polyesters today are strong, heat resistant and insoluble in water. They are commonly used to produce trousers, skirts, sheets, boat sails and filling materials. The polyester is produced in small granules, which can be melted and squeezed through small holes; producing long fibres known as Dacron or Terylene. Polyesters are now being used to make drink containers; the polyester granules are melted and stretched around a mould.

Kevlar In the early 1960s, Du Pont were looking for a fibre with the heat resistance of asbestos and the stiffness of glass. The aromatic polyamides seemed to be promising candidates, as the presence of the planar aromatic rings meant that they would form rigid polymer chains, which would require large concentrations of oxygen in order to burn. The first polymeric aromatic amide (aramid) was made from 3-aminobenzoic acid. It could be made into fibres, and whats more it was fire resistant; however it wasnt very strong (zig-zag nature of chain prevented the molecules aligning themselves properly). Eventually Kevlar was produced. It could be made from readily available starting materials and was cheap to produce.

Kevlar had to be produced in concentrated sulphuric acid, as it has a high insolubility and needs to be dissolved in a substance in order for the chains to grow. Kevlar is flexible (due to the fibres it forms), light, flame retardant, strong (five times stronger than steel) and has a high insolubility. Kevlars strength comes from the way the rigid, linear molecules are packed together. The chains align themselves parallel to one another, and are held in place by hydrogen bonds. This leads to sheets of molecules, which stack together regularly around the fibre axis to give a highly ordered structure.

PEEK In the 1960s, John Rose (a chemist working for ICI Platics) decided to investigate high temperature materials. He wanted to find a material that would have a high melting point and also be resistant to oxidation. Him and his team eventually developed Poly(ether-ether-ketone) (PEEK).

PEEK is a polymer which can withstand very high temperatures; it is used to make containers in which you can boil water and as the nose cone of missiles.

Polyhydroxyamine This is a polymer that when strongly heated, turns into a fire-resistant polymer. On burning no smoke is produced, which makes it useful as a plastic for aeroplane interiors. When PHA is heated strongly, it loses water and re-arranges to form PBO. PHA is used as a plastic, rather than PBO, as it is easier to mould.

Properties of Polymers The intermolecular forces between polymer chains can have a huge effect upon the properties of the polymer. In general the longer the polymer chain, the stronger the polymer as there are more intermolecular bonds. In polyamides, the presence of a the amide linkage allows the polymer chains to hydrogen bond with one another, this prevents the chains from sliding past each other as easily, and so makes them less flexible.

In polyesters, permanent dipole-permanent dipole interactions can also occur, which holds the polymer chains together more firmly.

In Kevlar, a combination of the benzene ring (which is hard to rotate) and the presence of hydrogen bonds makes its structure very strong. Kevlar is fireproof, and forms very strong fibres (its fibres are 20 times stronger than the equivalent weight in steel).

The effect of temperature change on polymers When substances made of small molecules are heated, they simply melt and form a free-flowing liquid; however with polymers the process is more complex. When polymers are cooled, they will often become very brittle. This is because cooling gives a higher percentage of crystalline regions thus making it stiffer

When heated, the polymers will first become flexible before melting. This is due to their structure. In some polymers, there are areas of crystalline and amorphous regions. In the glassy state, the tangled polymer chains in the amorphous region become frozen, which prevents easy movement of the chains relative to each other. If the polymer is forced to change shape, it does so by breaking. When the glassy material is heated, the polymer chains will reach a temperature at which they can move relative to each other (the glass transition temperature Tg). On further heating of the glassy polymer, it becomes flexible and shows the more conventional properties expected of a plastic. Eventually, if the polymer is heated enough, the melting temperature Tm will be reached (the plastic becomes a viscous fluid). This process is reversible for thermoplastics.

Today, polymers are designed to have Tg and Tm values which are related to the desired properties of the substance. Flexibility can occur when the chains are not tightly packed and some freedom of movement is possible (bulky side-groups, for example, may reduce the flexibility of a polymer, as they prevent the chains sliding past each other). Bulky side-groups also affect the amount of rotation that can occur around the linking bonds. Intermolecular forces may also have their effect upon flexibility; stronger intermolecular forces will mean that the chains are held together more tightly and are therefore less able to move relative to each other.

Designing Polymers When looking for a substance for a particular application, it is sometimes possible that there will not be a polymer available that will have all the characteristics that are required. Techniques such as co-polymerisation, the use of plasticizers and the possibility of producing polymer alloys can make a polymer more suitable to its application.

Co-polymerisation This involves incorporating two different monomers into a polymer chain during the polymerisation process. For example, polypropene has a Tg of around -10oC; for some purposes a lower Tg would be

more suitable. One way to lower the Tg of polypropene is to add ethene to the polymer during the polymerisation process; co-polymerisation. Introducing monomers with larger side groups pushes the polymer chains further apart weakening the bonds between them. A section of the chain would be represented as:

Plasticisers Adding plasticisers also lowers Tg. Plasticisers can be used to make polymers more flexible; they are basically a molecular lubricant that allows the polymer chains to slide past each other easier.

Plasticisers are carefully selected so that they are compatible with the polymer they are used with. Di-(2-ethylhexyl)adodate (DEHA) is commonly used as a plasticiser for PVC; however there is growing concern that plasticizers added to PVC film used for wrapping food can migrate into fatty food and may be harmful to health.

Green Chemistry and Recycling: We generate vast amounts of rubbish, much of which goes to landfill. Although only a small percentage by mass is plastics, these take a very long time to decompose. One alternative to burial is to recycle plastics, but identifying and sorting different polymers from domestic waste is expensive. New technology to sort plastics automatically is being developed. Many thermoplastics are made from more than one type of monomer and may be suitable only for remoulding. Another approach is to turn the polymers back to the original monomers by cracking. The recovered monomers can then be turned into new plastics or used in other parts of the chemical industry. A third option is to design degradable plastics. We could use biopolymers (molecules made by living organisms such as bacteria or plants), synthetic biodegradable plastics or photodegradable plastics.

All of these materials break down in the environment, although the speed of this process may still prove to be problematic. A less favourable option is to burn the plastics to release energy. However this may cause environmental problems such as increased CO2 emissions.

Reducing carbon emissions: The energy consumed in producing a tonne of material by recycling is much lower than producing a tonne of the same substance from new raw materials. If less fossil fuel is burned, this leads to a reduction in the emissions of carbon dioxide. For example, over 15 tonnes of carbon dioxide are saved for every tonne of aluminium produced from recycled metal. It is now common to measure carbon emissions over the entire life cycle of a material. A life cycle assessment measures emissions during the extraction of raw materials, the manufacture of the product, the distribution to its customers and its eventual disposal. This cradle-to-grave approach should allow chemists to evaluate better the impact of producing any material, and to design processes that have a lower impact on the environment.

Minimising hazardous waste: Green chemistry involves designing chemical processes that reduce or eliminate waste and the use of hazardous materials. Refer back to AS work for the main principles behind green chemistry.