Experiment 26

Synthesis and Analysis of Commercial Polymers

Introduction A large number of materials of biological and economic importance are polymers. Polymers are very large molecules and are made by adding many small molecules, called monomers, to form large chains. These high molecular weight macromolecules consist of repeating units of much smaller molecular weight. Polymers may be natural or synthetic (see McMurry text, pages 12061218). An example of a naturally occurring polymer is a protein. Proteins are extremely important biologically occurring polymers of amino acids that make up a major portion of our hair, skin, tissue, and cellular contents. A polysaccharide is another example of natural polymer, which is made from smaller carbohydrate units. Starch and cellulose are also examples of naturally occurring polysaccharides. Starch and cellulose are natural polymers, made from repeating units of glucose. In starch the glucose molecules are linked through -glycosidic linkages. In cellulose, the monomers are linked by -glycosidic linkages. Both starch and cellulose can be extensively branched (Figure26.1).
CH2OH O OH O OH O OH
Starch (

CH2OH H OH O O H

CH2OH O OH O OH
(1-4) linkages)

CH2OH H OH O OH
CH2OH O O

CH2OH O CH2OH O CH2OH O OH O OH H O OH

Cellulose (

OH O OH H H

OH O OH H

OH

(1-4) linkages)

Figure 26.1 Glycosidic linkages of starch and cellulose.

A third class of biologically important polymers consists of the polynucleotides such as deoxyribonucleic acid (DNA) and ribonucleic acid (RNA). The materials that contain all the genetic information of a living cell, DNA and RNA, consist of linear chains of smaller molecules called nucleotides. Synthetic polymers are of vast economic importance in manufacturing processes. Some of the best-known types of synthetic polymers are nylons, polyesters, acrylics, polyvinyls, and polystyrenes. Nylons, polyesters, and acrylics are used mainly in the clothing industry. Polyvinyls are used to make plastic sheeting and plumbing materials. Polystyrenes are used
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extensively for insulation materials. Synthetic polymers can be classified in a variety of ways, such as the type of reaction used to make the polymer, the mode of assembly, the structure, or the properties of the polymer. Classification by Reaction type Two common types of reactions used to build polymers are addition reactions and condensation reactions. An addition reaction can occur in which two molecules can combine to form a long chain (linear or branched) polymer. These reactions typically occur in monomers which contain bonds and are also classified as chain-growth polymers due to the method in which the polymerization occurs. For example, in the synthesis of polystyrene, also known as Styrofoam, the linear polymer is produced by a chain-reaction polymerization in which an initiator adds to a carbon-carbon double bond of styrene to yield a reactive intermediate (Figure 26.2). This intermediate reacts with a second molecule of styrene to yield a new intermediate, which reacts with a third unit, and so on. Polystyrenes are used extensively for insulation materials. Tiny bubbles of HCFC gases are trapped between the flat polymer chains during the production of polystyrene. Heat must travel along the polymer chains, making a number of detours around these trapped gases, which are poor thermal conductors thus increasing the usefulness of polystyrenes for insulation materials.
CH CH2
catalyst

CH CH2 CH CH2 CH CH2 CH CH2

Styrene

polystyrene

Figure 26.2 Synthesis of polystyrene.

Condensation reactions can also be used to form synthetic polymers. A condensation reaction is one in which two molecules undergo addition accompanied by the loss of a small molecule as a byproduct. One example of a condensation polymer is the polyamide Nylon 6,10 (Figure 26.3). In this reaction, a diacid chloride is reacted with a diamine, resulting in the formation of a polymer and the release of hydrochloric acid as a byproduct. Each diacid chloride and each diamine is capable of reacting twice, enabling the formation of a polymer. Notice that HCl is generated as a byproduct, characteristic of a condensation reaction. Since each bond in the polymer is formed independently of the others, these reactions can also be classified as stepgrowth polymerizations.
H N H Hexamethylene diamine N H H + Cl Sebacoyl chloride O O Cl

H N

O N H

H N O Nylon 6,10

O N H
n

Cl O

+ 2 HCl

Figure 26.3 Synthesis of nylon 6, 10. 212

Another example of a condensation polymer is a type of linear polyester, formed by the reaction of phthalic anhydride and ethylene glycol (Figure 26.4). In this type of reaction, an anhydride is reacted with a diol to generate a linear polyester, with water formed as a byproduct. This linear polyester is an example of a thermoplastic, which is a type of polymer which is hard at room temperature, but softens upon heating.
O C O C Phthalic O Anhydride + HO Ethylene glycol linear polyester C OH CH3CO2Na O O C OCH2CH2O + 2n H2O

Figure 26.4 Synthesis of a linear polyester.

If more than two hydroxyl groups are present on one of the monomers, the chains can be linked together to form a large, strong three-dimensional structure. These structures are more rigid than their linear counterparts, are often used for paints and coatings, and are referred to as thermosets. Thermosets are very hard and insoluble, even at high temperatures. An example of a cross-linked polymer is that of Glyptal resin, shown in Figure 26.5. This polymer is made using the same phthalic anhydride monomer used to prepare the linear Dacron isomer, however the glycerol monomer contains an additional hydroxyl group (a triol), whereas the ethylene glycol only contains two hydroxyl groups (a diol). The addition of this simple hydroxyl group allows for extensive branching during polymerization.
O O C C O C O Phthalic Anhydride glycerol O C O C O C O OCH2CHCH 2O + HO OH OH CH3CO2Na O C OCH2CHCH 2O O C + H2O O

n Glyptal resin

Figure 26.5 Synthesis of Glyptal resin.

Polymers formed via condensation reactions are also classified as step-growth polymers. Step-growth polymers are produced by reactions in which each bond in the polymer is formed independently of the others. The best known step-growth polymers are the polyamides and the polyesters which will be synthesized in this experiment. Another interesting polymer is the cross-linked polymer commonly known as slime. Slime is the result of the polymerization of poly (vinyl alcohol), commonly referred to as PVA, with sodium borate decahydrate (Borax) in aqueous conditions. PVA itself is an example of an addition polymer built on a carbon-carbon backbone with a hydroxyl (-OH) group on every other carbon. The presence of these hydroxyl groups give it the ability to form hydrogen bonds with other molecules such as the borate ion (B(OH)4-).
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The borate ion results from the dissolution of Borax (Na3BO3) in water. When hydrolyzed, the Borax dissolves to form boric acid (H3BO3). The boric acid will then undergo a condensation reaction with PVA. The hydrogen bonds between PVA and the borate ion lead to a three dimensional network with extensive cross-linking (Figure 26.6). These hydrogen bonds are weak, however, allowing them to form and break easily. For this reason, slime is often referred to as a reversible cross-linking gel. Evidence of this is shown when a sample of slime is placed on a flat surface. It will slowly flatten out as the bonds break, rearrange, and reform, but not fully break apart. If a great deal of force is applied to the gel, however it will break, as some of the bonds are broken permanently.
H O H O B H O H O OH H O O H O H O H HO O H H O
hydrogen bonds

Figure 26.6 Borate ion cross-linking with poly (vinyl alcohol) to form slime.

The physical properties of a polymer, such as melting point and solubility, depend mostly on the intermolecular and intramolecular forces in the polymer. The monomers used to form polymers are generally gases, liquids, or solids, due to their weak intermolecular forces. During the polymerization reaction, the monomers are joined together to form larger molecules, the attractive forces between molecules increase, and the mixture becomes more viscous. Eventually, the molecules become so large that their chains become entangled, and it is this entanglement which gives the polymers their characteristic properties. A common structural feature in all polymer materials is the presence of chain entanglement, but there are other features which give polymers unique properties such as flexibility of individual polymer chains, strength of the forces between the chains, and the presence of cross-linking between chains. Cross-linking restricts the ability of individual polymer chains to slide past one another and depending on the degree and type of cross-linking, various properties result. Materials with a low degree of cross-linking are elastic and deformable, such as rubber bands. Highly cross-linked materials are more rigid and brittle, as in the case of Bakelite, used in cooking pot handles and billiard balls. Temporarily cross-linked materials behave as viscous, liquid-like gels, as seen in the case of slime (Figure 26.7).

Figure 26.7 Linear, branched, and cross-linked polymer chain structures.

Objectives In this experiment, several different synthetic polymers will be prepared. Once synthesized the physical properties of these polymers will be compared to other synthetic polymers and natural polymers. The synthetic and natural polymers will be investigated through solubility testing, as the physical properties of polymers depend mostly on the intermolecular and intramolecular forces in the polymer. Finally, the length of the nylon strand prepared during synthesis will be determined
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Experimental Synthesis of Nylon 6, 10: Pour 3 mL of the hexamethylene diamine solution into a 50 mL beaker. Pour 6 mL of the sebacoyl chloride solution into a 100 mL beaker. Slowly pour the sebacoyl chloride solution into the beaker containing the hexamethylene diamine solution. A white film should form at the interface of the two layers. Reach into the beaker with forceps and grasp the film in the center of the beaker. Slowly pull straight up. Try not to let the thread of nylon touch the sides of the beaker. Pull the nylon from the beaker and wrap the thread around the tip of a large test tube. Rotate the tube slowly, counting revolutions, until no more nylon can be obtained. Record the number of revolutions of the nylon, along with the circumference and diameter of the test tube used in the data section of your laboratory notebook. Place the test tube and nylon in a beaker of tap water for 2-3 minutes. Remove the tube, wrap the nylon with a paper towel, and carefully blot the nylon to remove excess water. Continue to blot the nylon until the sample is fairly dry. Set sample aside for product analysis. Synthesis of Linear and Cross-linked Polyesters: Cover two small watch glasses completely with aluminum foil. Label the watch glasses B and C. Weigh two separate amounts of phthalic anhydride (between 1.2-1.3g each) onto separate weigh papers. Weigh two separate amounts of anhydrous sodium acetate (between 0.50.6g each) onto separate weigh papers. Return to fume hood and transfer the solid anhydride and acetate to the center of each watch glass. Carefully mix the solids together using a glass rod. Heat the solids on the hot plate on a setting of 5. Quickly transfer 0.5 mL of ethylene glycol to the solids on the B watch glass while on the hotplate. Transfer 0.5 mL of glycerol to the solids on the C watch glass. Mix the solids and liquids gently with the glass rod while heating (Be careful not to tear the aluminum foil!) until a white paste forms. Once the mixtures turn to colorless, clear liquids and boil, continue to heat for 5 minutes. Using tweezers, carefully remove the watch glasses from the hotplates (they will be HOT!) and allow the samples to cool to room temperature. Once cool, remove the polyester polymers from the foil and set sample aside for product analysis. Product Analysis: Nylon String Length During the synthesis of nylon, the number of revolutions made as the nylon string was wrapped around the test tube was recorded. Using this information, along with the diameter of the test tube, calculate the length of the nylon string using the following formula: Nylon produced (mm) = (Diameter of test tube) * (
Where = 3.14

( # test tube revolutions)

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Physical Property Analysis On a small piece of aluminum foil, draw a 2X3 grid with a permanent marker. Number the areas 1-6. Place a small amount of each polymer from Table 26.1 into the appropriately numbered section on the foil grid. The polymers not synthesized in lab will be provided in the supply hood. Observe the transparency of each polymer. Record whether the polymer is CLEAR or OPAQUE in Table 26.2. Observe the elasticity of each polymer by attempting to pull and stretch on the polymer. If the polymer stretches without breaking apart immediately, record the elasticity as HIGH in Table 26.2. If the polymer breaks apart quickly when stretched, or you are unable to stretch it at all, record the elasticity as LOW in Table 26.2 Finally, observe the hardness of each polymer. Attempt to penetrate the polymer with a microspatula. If you are able to penetrate the polymer, record the hardness as SOFT. If you are unable to penetrate the polymer, record the hardness as HARD in Table 26.2. Solubility Testing Place 18 small test tubes in a test tube rack. Label 6 tubes with the number 1, 6 tubes with the number 2 and the final 6 tubes with the number 3. Next, label the first 6 test tubes with the letter A-F. Repeat with the next two sets of test tubes. These number/letter combinations will represent the solvent used for testing (1-3) and the polymer to be tested (A-F). Add 2 mL of toluene to the first 6 test tubes. Add 2 mL of acetone to the next 6 test tubes. Add 1 mL of methanol to the final 6 test tubes. Add a small amount of the appropriate polymer to the test tubes containing the toluene (about the size of a pencil eraser). Mix the contents to the tube carefully with a glass rod. Clean the glass rod between each polymer by simply wiping it thoroughly on a paper towel. If the polymer does not dissolve completely in the solvent, record the solubility as INSOLUBLE in Table 26.2. If the polymer does dissolve completely, record the solubility as SOLUBLE in Table 26.2. Repeat the solubility testing with acetone and methanol. Record all solubility results in Table 26.2. WASTE MANAGEMENT Pour the remaining contents of the beaker in which you synthesized the nylon and any liquids used during the solubility testing into the container labeled LIQUID ORGANIC WASTE located in the waste hood. Place solid nylon product and aluminum foil in yellow solid waste can.

References McMurry, John. (2008). Organic Chemistry, 7th ed. Belmont: Thomson/Brooks/Cole. Hart, Harold, Craine, Leslie E., and Hart, David J. (1999). Organic Chemistry Laboratory Manual: A Short Course, 10th ed. Boston, MA: Houghton Mifflin Company.

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Final Lab Report Due Date_______

Names______________________________ ______________________________ Exp. 26: Synthesis and Analysis of Commercial Polymers EXPERIMENTAL RESULTS (Tables in INK only!)
Table 26.1 Nylon Fiber Results Test tube diameter (mm) # of test tube revolutions Length of nylon (mm) Table 26.2 Physical Property and Solubility Results

Polymer Type

Physical Properties Transparency Elasticity Hardness (clear/opaque) (high/low) (hard/soft)

1 Acetone (Sol/Insol)

Solubility 2 Toluene (Sol/Insol)

3 Methanol (Sol/Insol)

Synthetic Natural

polyamide linear polyester cross-linked polyester polystyrene cellulose Starch

A B C D E F

DISCUSSION/CONCLUSIONS
(Briefly answer the following questions. Use structures and numerical values where applicable.)

1.

Differentiate between an addition reaction and the condensation reactions used to produce the polymers described in this experiment. Give an example of a polymer produced using each method.

2.

List the intermolecular forces present in polystyrene, toluene, and nylon 6,10. Explain, in terms of intermolecular forces, why polystyrene is soluble in toluene, but nylon 6,10 is not.

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3.

Which co-reactant produced the more brittle polymer when treated with phthalic anhydride, ethylene glycol or glycerol? What is the major difference between these two co-reactants, and how does this affect the physical properties observed?

4.

In the space below, draw the repeating unit for the polymers indicated:

Nylon 6,10

Linear Polyester

Cross-linked Polyester

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