Natalie Youssef

Polymerization of Caprolactone Monomers and Analyzing Variable Lengths of Polymers Through Destructive Testing
Abstract: Polymers are macromolecules made of many monomers. Initiators start the polymerization process and catalysts speed up the reaction, by reducing the amount of energy needed for the reaction to take place. By reducing the amount of initiator during polymerization the polymer length can be controlled. The less initiator that is used, the longer the polymer chains will be. Longer polymer chains have more mechanical strength than short polymer chains. Varying ratios of monomer, initiator, and catalyst were used to make rod and puck shaped caprolactone-based polymers. Students performed two different tests, The Rod Hang test and the Angle Degree Drop test in order to find the breaking point of each polymer. We would have expected a correlation between the amount of initiator and the strength of the polymer. It is expected that the polymers containing less initiator would be stronger because these polymers would have longer chains. We did see this trend in the hang-test data, but did not find a strong trend in the angle-drop data. A lack of data supporting the expected correlation could be due to discrepancies while the polymers were being made or while they were being tested. Introduction: A polymer is a macromolecule made up of the same unit formed by the combination of many repeating molecular units. Polymers are organized by linking small molecules called monomers. Monomers are molecules that can be bonded to other molecules in order to form a polymer. When monomers are linked together they form a long chain in the process called polymerization. Polymers occur naturally and can be synthetically produced. Some common synthetic polymers are polyethylene, polypropylene, and polystyrene. Natural polymers include: cotton, wood, DNA, proteins, and latex. Polymer chains can be linear, branched or chain-linked. Polymer structure determines the physical properties of the polymer such as melting point, flexibility, and strength of a polymer. Polymers are covalently bonded, which results in minimal conductivity, and they are held together by intermolecular forces. Cross-linked Polymers have a network type structure and are covalently bonded. They do not soften when heated, but they decompose. Cross-linked polymers are very flexible and have high elasticity. An example of a cross-linked polymer is rubber. Polymers have either an amorphous or crystalline structure. An amorphous polymer has no definite structure. A crystalline polymer has rigid structure. The more orderly the polymer chain, the more crystalline the polymer is. A linear polymer would be considered crystalline. An example of a linear polymer is DNA. A cross-linked polymer, like rubber, is amorphous. Among all polymers, a longer chain length results in greater strength. Intermolecular forces between polymer chains become stronger as the chain length increases, making the polymer stronger.

There are two main methods of polymerization, step-growth and chain-growth. Step- growth polymerization occurs from monomers reacting to form polymers. Through step-growth polymerization monomers react in four different ways before they become polymers. First the monomers react in order to form dimers. Then they react in order to form trimmers. After they form into trimmers, they react again and turn into oligomers, and from there they eventually turn into a long chain polymer. Step-growth polymerization is where all monomers can react with each other. The other method of polymerization is chain-growth. Chain-growth is where unsaturated monomer molecules add onto the active site on a growing polymer chain one at a time. In chain-growth polymerization only monomers that have interacted with the initiator, or already radicalized monomers can add another monomer. These are the reactive groups of the monomer. Polymer chains are made of reactive and nonreactive groups. Reactive groups are involved in the polymerization process by interacting with the initiator and bonding to other reactive groups that have also interacted with the initiator. The initiator begins the process of polymerization. In the polymerization of caprolactone, the monomer changes structure by unwinding. The unwound caprolactone molecule will cause a neighboring caprolactone molecule to undergo the same change. These two molecules will bond together. This process will continue repeatedly in order to create a progressively lengthening molecule. A catalyst can be used to speed up the process of polymerization. However, the reaction can occur without a catalyst, just at a much slower rate. Methods: This experiment uses some hazardous chemicals. All of the chemicals used are considered to be irritants. For this reason eye protection, apron, and gloves were required for this experiment. All work was done under the fume hood to prevent irritated skin and chemical damage to the body. The first thing students were required to do for this lab was to prepare the molds. Students prepared two scoopula molds, one spoon or Santa Claus mold and one aluminum weighing boat mold.. In order to prepare the scoopula mold, students found slightly mismatched scoopulas and set them together like in the first image of Figure 1. Then 85ml of caprolactone, which was the monomer, was placed into a 125ml Erlenmeyer flask, along with a magnetic stir. Next, students added the prescribed amount of 1-octanol using the 1-mL syringes initiating the polymerization of the monomer (see table 1 for the monomer-initiator-catalyst ratios and amounts). Stannous octoate was then added to the mixture, which acted as the catalyst, speeding up polymerization. The mixture was then heated to 120 degrees Celsius using a hot plate. The time the mixture reached 120 degrees Celsius, it was recorded. Once the mixtures viscosity reached that of syrup, then it was poured into the different molds and placed in the oven to bake. After the polymers were made, their strength was tested using a hang test and a drop test, shown in Figure 3. In order to conduct the hang test, students used two regular classroom tables spread 2 inches apart and balanced the rod across the gap measurement of weight and force. Using the brass weight with a hook, students gradually added weight until the rod broke.

In order to conduct the drop test, the polymer was placed on a skateboard. The hammer was pulled back at a variety of degrees starting at 15 degrees all the up to 90 degrees, which increased force. After the puck survived a 15-degree drop, the hammer was raised up another 15 degrees. This was done until the polymer puck broke. These tests were recorded when the rod failed and when the puck broke shown in Table 1 for the Rod Hang Test. Table 1: Stannous Octoate and 1-Octanol Volumes, Mass & Ratio for Specific Polymerization Group Ratio Volume 1-Octanol (ml) 1.53 1.15 0.57 0.29 0.19 0.14 0.12 Mass 1-Octanol (g) 1.332 0.999 0.499 0.250 0.166 0.125 0.100 Volume Stannous Octoate (ml) 3.19 2.39 1.12 0.60 0.340 0.30 0.24 Mass Stannous Octoate (g) 4.143 3.107 1.554 0.777 0.518 0.388 0.311

A B C D E F G

75:1:1 100:1:1 200:1:1 400:1:1 600:1:1 800:1:1 1000:1:1

Figure 1: Procedure of preparing the scoopula mold

Figure 2: Preparing the beaker and final product

Figure 3: Drop test apparatus

Results: The hang test results (Table 2 and Figure 4) for polymer A were 650 grams in test one and 550 grams in test two. Polymer B was able to hold 800 grams before breaking. Polymer C was able to hold the most mass at 1,032 grams. Polymer D was able to hold 982 grams of weight. In the hang test it can be seen that the force-resistance of the polymer goes up as polymer chain length increases. Although there is some variation in the data, with polymer E holding slightly less than polymer D, a general trend exists. Table 2: Rod Hang Test Group Letter Test 1 (grams) Test 2(grams) A B D E 650 800 1032 982 550 n/a n/a n/a

Table 2: Angle Degree Drop Test Results Group A B C D E F G Test 1 15 degrees 60 degrees 30 degrees 60 degrees 15 degrees 15 degrees 45 degrees Test 2 n/a 30 degrees 45 degrees 90 degrees 30 degrees 30 degrees n/a Test 3 n/a 30 degrees 45 degrees 30 degrees n/a n/a n/a Test 4 n/a n/a n/a 30 degrees n/a n/a n/a Test 5 n/a n/a n/a 15 degrees n/a n/a n/a Test 6 n/a n/a n/a 75 degrees n/a n/a n/a

The results of the Angle Degree Drop test can be seen in Table 3 and Figures 5 & 6. Polymer A broke after an impact from a 15-degree angle. Polymer B broke after impact from a range between 30-60 degrees. Polymer C broke after impact from a range of 30-45 degrees. Polymer D’s range of degree of impact was 50 degrees before breaking. Polymer E and F broke in a range of 15-30 degrees. Polymer G broke at 45 degrees of impact. These results from the angle degree drop test gave us no certainty on any specific trends. Since there are a wide variety of results for each polymer tested there was no clear trend that was determined.

Figure 4: Hanging Rod-Test on Caprolactone based polymers
1200 1000 Mass in Grams 800 600 400 200 0 A B Polymer C D

Figure 5: Maximum degree drop angle per polymer
100 Degree of Angle 80 60 40 20 0 A B C D Polymer E F G

Figure 6: Average degree drop angle per polymer
Degree of Angle 60 40 20 0 A B C D Polymer E F G

The rod and puck data was presented in a variety of line graphs in order to better observe trends in the data

Discussion: We did this experiment in order to bond monomers into variable length polymers by controlling the amount of catalyst and initiator, practice design testing methods to assess physical properties of polymers, and to demonstrate and explain the differences in physical properties based on structure and particular length of each polymer. In order to do this, caprolactone based polymers were made using varying ratios of initiator, catalyst, and poured into molds to form rods and pucks. Rod hang test results were measured in grams and can be seen in Table 2. Angle degree drop test results can be seen in Table 3. I would have expected to see a clear relationship between the monomer-initiator-catalyst ratio and the force resistance of the polymer. I would have thought that as the amount of initiator in the mixture decreased, that the strength of the polymer would have increased. Less initiator means that fewer reactive groups will interact and initiate polymerization, this results in fewer, longer polymer chains. The longer the polymer chain, the greater the mechanical strength of the polymer, due to increases in intermolecular forces as molecular mass increases. Some of the results from the hang-test suggest this, however the trend is not clear, and data is lacking. Shown in Table 2, the hang test results seem to show a trend. As the amount of initiator and catalyst decreases, the amount of stress resistance increases from Polymer A - Polymer C. Polymer A withstood the lowest amount of pressure and it had the most amount of initiator and catalyst. Polymer B had a greater tolerance of pressure than Polymer A, and had smaller amounts of initiator and catalyst. The chains in Polymer B should have been longer than Polymer A and therefore stronger. Polymer C was able to hold the most amount of pressure out of all the Unknowns, and had less initiator and catalyst than Polymer A and B. It is difficult to determine if this trend would continue as the initiator and catalyst amounts decreased, or if the force resistance begins to decrease at a particular amount of initiator and catalyst. I would have expected Polymer D to hold more force than Polymer C, following the trend. However, Polymer D actually held less force than Polymer C. After observing Figures 4 it was noticeable that as the initiator amount went down and created longer polymer chains, the stronger the polymer was. The first three polymers shown in Figures 4 are a visual for this trend. In the drop angle test the data is unclear since there is a variety of test results for each polymer that do not create any specific trend. This may have happened because of error during the polymer creation. To confirm the expected trends, tests should be conducted on Polymer E, F, & G and the tests should be repeated multiple times. After analyzing Table 3, I did not notice a specific trend. I would have expected that as the initiator and catalyst amounts decreased that the force resistance of the polymer would have increased. Figures 5 & 6 shows the maximum force resisted by each polymer and there is no clear trend. Figures 5 & 6 shows the average force resisted by each polymer and has a trend similar, but not identical to the hang test. Since all the groups except for Group D, had less than three test results this created a lack of information to determine any specific trend. After taking the average degrees from all tests for each group there still remained no significant trend that could be used to draw conclusions. Comparing Figures 5 & Figure 6 Polymers C & D were able to withstand the most force. Perhaps this suggests an optimal ratio of initiator and catalyst to

create the strongest polymer. If this is true than the strongest caprolactone based polymers will have a ratio between 200:1:1 & 400:1:1. There are several different errors that could have taken place while performing our experiment. The initiator and catalyst could have been inaccurately measured which would cause inaccuracies in our results. It could have been possible that the polymer was not brought up to the correct temperature for the exact amount of time. If molds were not poured slowly enough, air bubbles may have been present. The presence of air bubbles would create points of weakness in the polymer. One question I have is, if the mold was poured when the viscosity was low would that affect the force resistance of the polymer after it was baked? Overall I am not very confident in our results because there were several areas of possible errors and the results did not show any specific trend that was predictable with the limited amount of test results we had for each group.

Honors: 1. First of all there are approximately 140 tons of synthetic polymers that are produced worldwide every year. Because polymers are extremely stable they don’t break down quickly, which leaves the sitting in landfills or the ocean. Polyethylene has a more crystalline structure than polycaprolactone. Polyethylene has a symmetrical molecular shape creating stronger intermolecular forces, increased density, crystalinity, and rigidity. This makes this polymer more resistant to degradation. Polycaprolactone is less symmetrical in shape. This polymer is made of many methylene groups, with esters forming in between. Esters are molecular groups containing -COOH- (carbon, oxygen and hydrogen). This polymer structure creates an asymmetrical shape, which results in less efficient "packing" of the polymer chain. This means that polycaprolactone is less dense, less rigid, less crystalline, and more likely to degrade. Polycaprolactone has a longer chain so it is more biodegradable than polyethylene. Polycaprolactone has a trimer structure similar to Cutin. Cutin is a naturally occurring polymer found in plants. Obviously plants can biodegrade. The polymer Cutin is broken down in nature by Cutinases, which are enzymes that come from fungal pathogens. Because of similarities and structure between Cutin and Polycaprolactone, natural occurring enzymes can break down this synthetic polymer. 2. The physical properties of monomers can be altered by the addition of plasticizers. Plasticizers reduce interaction between segments of the polymer and increase flexibility. They also lower the melting point of a polymer. A natural plasticizer is tall oil, which comes from pulped wood, and contains many fatty acids. By adding a plasticizer to a polymer, the polymers applications are increased. Overtime plasticizers can evaporate out of the polymer they have been added to. This causes the treated plastic to become cracked and lose elasticity. UV light degrades polymers by adding any antioxidants to a polymer this degradation can be reduced. An antioxidant is a molecule that can counteract the damage done by oxidation. This is true in polymers and in our bodies, which is why we eat antioxidants. They react the same way in our body as they do to the polymer. However, like the plasticizers, these molecules don’t bond to the polymer so overtime they can evaporate and the resistant to UV degradation is lost. Sources Used:  Premaj and Doble: Biodegradion of Polymer