POLYMERIZATION OF CAPROLACTONE AND ANALYSIS OF VARIABLE LENGTH POLYMERS BY DESTRUCTIVE TESTING Abstract: The intent of this study was

to find the ideal ratio of catalyst to initiator in creating the fast reaction of polymerization. Caprolactone was heated in the presence of stannous octoate (catalyst) and 1-octonal (initiator) at varying ratios from 75:1:1 all the way to 1000:1:1. The resulted polymers were tested for tensile strength. The results showed that the ideal ratio of catalyst to initiator was 400:1:1 as demonstrated by having the highest tensile strength in the Breaking Point test and the highest compressibility in the Average Degrees test. The tensile strength correlates with the length of the polymer chain, which also correlates with the most rapid rate of reaction. However, there comes a point when adding more catalyst does not speed up the reaction any further. This information can assist additional polymerizations by knowing the ideal concentration of catalyst to have. Introduction: A monomer is a molecule that can be bonded to other identical molecules to form a polymer (many parts). The purpose of this lab was to polymerize monomers by controlling the ratio between catalysts and initiators, in order to change the chain length of the polymer. A catalyst is a substance that speeds up a chemical reaction without changing its own properties. The initiator begins the process of chemical change. It unwinds the monomer to therefore make it available to bond with other monomers. Polymers are long chains of molecules, and are either natural or synthetic. Natural polymers consist of cellulose, starch, nucleic acids, and proteins. Synthetic polymers are created in either one of two processes, chain growth and step growth. Step growth is where bi-functional or multifunctional monomers react to form dimers and trimers, and eventually long chain polymers. Chain growth is where a monomer binds to another monomer in one direction at one monomer at a time, resulting in a polymer. In this experiment a catalyst, being stannous octoate complex (Sn(Oct)2), and the initiator, being 1-octanol, were used in the polymerization of e-Caprolactone. ECaprolactone is biodegradable, but is not commonly found in materials because of its cost and low melting point, making it hard for it to be used in temperatures above 50 degrees Celsius. The reaction of polymerization will create covalent bonds between monomers. The intermolecular forces in a polymer are important for the following reason. Because a polymers chain length is especially large, their intermolecular forces are a lot stronger. This can greatly affect its physical properties. The intermolecular forces of a polymer can determine if they are brittle, flexible, or have high or low melting points. In addition, longer chains have higher tensile strength, have higher crystalline melting points, and have higher melting points because of their higher intermolecular attraction, like hydrogen bonding.

Most polymers have the following general properties: they are resistant to chemicals, they can be thermal and electrical insulators and they are light in weight with varying degrees of strength, depending on their ratio of catalyst and initiator. This is because of the intermolecular forces based on the length of the polymer chain. When polymer chains are linked together by cross-links, it means that they lose some of their ability to move as individual polymer chains. This can affect the properties of the polymer. Low cross-link densities decrease the viscosity of a polymer, whereas high cross-link densities can cause materials to become rigid or glassy. The properties are also strongly dependent on the length of the chain. As the chain length is increased, the melting and boiling temperature increase quickly. Viscosity also increases with chain length. Increasing chain length decreases the chain mobility and increases the strength and toughness. Methods: Safety Procedures The chemicals used in this experiment are irritants and flammable liquids and therefore should not be inhaled or ingested. Throughout this lab, commonly used safety measures were followed. Safety goggles and gloves were worn at all times because of the hazardous nature of the chemicals used in this experiment. The experiment took place in the fume hood; therefore, common fume hood safety protocols were followed. Mold Preparation A mold was made to hold the polymer after it had been polymerized. To create the mold, two slightly uneven metal spatulas were held together with oven safe tape, and then greased on the inside. This mold resulted in the polymer being in the shape of a rod. There were also premade Santa Clause and puck molds that were used in the experiment. Polymerization A magnetic stir bar was placed in a 125 mL Erlenmeyer flask. 85 mL of Caprolactone was measure in a 100 mL graduated cylinder and then added to the Erlenmeyer flask. .19 mL of 1-octanol (initiator) was then added to the mixture using a 1 mL syringe. .34 mL of stannous octoate was added to the mixture (ratio 600:1:1) in the fume hood. There were multiple groups that all had different ratios of catalyst and initiator; Groups A G. The Erlenmeyer flask was attached to a clamp and placed on a hot plate with a thermometer submerged in the reaction mixture. The mixture was slowly heated to 120 degrees Celsius with rapid stirring of the magnetic stir bar. The reaction was monitored until it reached its viscosity point (point of becoming like syrup) and no longer than an hour at its temperature of 120 degrees Celsius (Figure 1). The reaction was poured into the molds and precautions were taken not to have any air bubbles or overflow. The molds were then placed in the oven and then examined at another time.

Figure 1: The reaction being stirred and heated

Testing Polymers Two tests were conducted to assess the polymers strength. The first test involved suspending a polymer rod from different groups (ex. Group A, Group B, etc.) across two tables and adding weight via a spring until the rod broke. This test measured the strength of the polymer rod. The second test conducted was a test on the polymer puck. Different groupings of pucks (ex. Group A, Group B, etc.) were smashed from controlled heights with a hammer. Depending on the height of the hammer being dropped, there was correlation with the strength of the polymer (Figure 2). In both tests the amount of force was increased incrementally until failure was achieved.

Figure 2: Assessment of puck strength

Results: Table 1: Average Breaking Point of Polymer Rod With Suspended Weight Added/Breaking Point Test

Figure 3: Average Breaking Point of Polymer Rod With Suspended Weight Added/Breaking Point Test

Table 2: Average Degrees of Hammer Height to Fall and Compress Polymer Puck/Average Degrees test

Figure 4: Average Degrees of Hammer Height to Fall and Compress Polymer Puck/Average Degrees test

In both sets of results, Polymer Group D is the strongest, and Polymer Group A is the weakest. In the Average Degrees test, Polymer D required an average angle of 50 degrees, whereas Polymer A required an average angle of 15 degrees. Similarly, in the Breaking Point test, Polymer D had 1032 grams added to it before it broke, whereas Polymer A only had 600 grams of weight added to it before it broke. As a result, there was a trend that followed the ratio of stannous octoate and 1-octanol. Generally, there was a trend as follows: the lower the ratio, the weaker the polymer, and the higher the ratio, the stronger the polymer. This trend in the Breaking Point test follows until after Group D (400:1:1) when the strength no longer increases. Similarly,

there is a drop in increase in the Average Degrees test when the spoon and square were tested. Ignoring these data points because of the difference of shapes, the trend still mirrors the trend in the Breaking Point test as Group G is decreased from Group D. Groups E and F (Spoon and Square) were relatively weak, based on their Average Degrees, being 30. Discussion: In this lab the intent was to conduct and understand polymerization with a use of a catalyst and an initiator. Adding a variety of ratios of catalyst helped gain an understanding of the ideal amount of catalyst to maximize the speed of reaction. Although the speed of reaction wasnt directly measured, it was inferred that it had correlation to the strength of polymer. Caprolactone was heated at constant temperature of 120 degrees Celsius at a maximum of 1 hour (or until viscosity was achieved) in the presence of stannous octoate and 1-octonal to create a polymer. The strength of the polymer was then assessed using two tests: Breaking Point and Average Degree. The strength of a polymer can be correlated with the length of the polymer chain. The purpose of the catalyst is to speed up the reaction of creating the polymer without getting altered in the reaction. The polymer will grow in length more quickly with the presence of a catalyst. When the polymer chain is longer, it is also stronger. Therefore, the ideal amount of catalyst added to the reaction will make the strongest possible polymer. The reaction is still rate limited past a certain ratio of catalyst and initiator. As seen in the results, there is no increase in strength in the polymer beyond adding stannous octoate in excess of 400:1:1. It has been shown that there are more intermolecular forces in polymers with longer chains. These intermolecular forces result in a higher tensile strength. For example, Group A had a ratio of 75:1:1 and was the weakest polymer group out of every polymer group. For example, in the Breaking Point test, it only needed 600 grams for the rod to break. This means that the polymer chain length was most likely shorter and had less intermolecular forces. One of the difficult parts of this experiment was keeping the temperature constant at 120 degrees Celsius. There were a lot of fluctuations in the temperature control. The problem with this, is that if there are not perfect conditions for the reaction to occur, may be slowed down. Generally, the measurements of the reagents were precise, so there wasnt much of a source of error. The widest variable was testing for tensile strength. In the Average Degree test, the measurements were fairly imprecise and the degrees varied because of a subjective point of view. Also, each group of polymers had variability within the test. As seen in Table 2, Polymer Group D had degrees ranging from 90 degrees to 15 degrees in each different test. This made it difficult to determine the actual compressibility of a certain polymer group.

If this experiment were to be conducted again, it would be interesting to test a completely different reaction and see if it still followed the same trends. I would hypothesize that if you were to change the initiator, catalyst, and monomer, the polymer would still follow the trend of being stronger if it has a long polymer chain. Again, it would also follow the trend that there needs to be a perfect amount of catalyst, and at a point, adding more catalyst will not speed up the reaction any more and make the polymer chain any longer. It would also be interesting to see if there was a more sophisticated way to test strength.