Destructive test analysis of varied lengths of polymer chains made of Caprolactone to observe physical properties of polymers By: Marley

Gabel Abstract: To examine and test the physical properties associated with varying chain lengths in polymers made of caprolactone, students from Animas High School used a variety of tests. Students were observing how the physical properties of the polymer changed depending on the amount of initiator and catalyst used to form the polymer. The polymers were molded into rods and pucks and each of the different forms were tested differently. A hanging weight test was used to test the strength of the rod polymers and the pucks were tested by a dropping hammer test to determine their strength as well. Polymers that used different amounts of initiator and catalyst broke at different weights and forces. Separate classes tested the polymers and the data was compiled for all of the students to use. Through multiple tests, the students found a slightly linear trend line for the rod test, establishing the claim that polymers made with more initiator and catalyst will have shorter chains, thus weaker breaking points. The data for the pucks was inconclusive due to widely ranging data, presumably caused by different classes tests. The rod test results imply that the polymers with longer chains are stronger, and the polymers that have shorter chains are weaker, making polymers with less initiator and catalyst a better plastic for durable purposes. Introduction: Materials such as plastics, rubbers and cloths are polymers. A polymer is a made up of many simple molecules stranded together into a long chain of monomers. Monomers are single, simple molecules that make up the polymer. In this experiment, students created polymers using chain-growth polymerization. This means that monomers were added in sequence to one end of the polymer chain, similar to a conga line. Other polymers can be formed by adding monomers to both ends of the chain, but chain -growth polymerization means that monomers are only being added to one side of the chain. For the creation of the polymers, students used catalysts and initiators. A catalyst, in this experiment the stannous octoate complex (Sn(Oct) 2), is used to speed up the reaction rate of a process. Catalysts are not needed to start the reaction, but the reaction will take a longer time to take effect without a catalyst. The initiator, 1-octanol, starts the process of the polymer forming by unraveling the original substances molecules. The more initiator present, the more chains of molecules will form, causing a faster process rate and more chains of molecules that are shorter. However, if there is a lower amount of initiator, then the reaction will take a longer time to come into effect and the chains of molecules will be longer. For this experiment, the starting substance was the monomer caprolactone. When these molecules unwind, it causes unwinding in the neighboring molecule allowing for the two of them to bond to each other. This forms the chain of individual, unwound molecules bonded to each other. As learned in the previous lab, polymers are covalently bonded. Covalent bonds are made up of intermolecular and intramolecular attractions. Intramolecular attraction defines the bond between two atoms of a substance. This attraction is generally very strong and forms

molecules which bond to create intermolecular attractions between the two molecules. This attraction is relatively weak, which means that the polymers have lower melting points and high malleability. Additionally, polymers are made up of long chains of molecules. The longer the chains, the chains are more likely to become entangled with each other and there are also more points for intermolecular attraction where the molecules can be attracted to each other. This means that the polymers made with longer chains are inherently stronger than polymers made with shorter chains. This test used different polymers with varying lengths of molecule chains to determine the durability and strength of the different polymers and observe how that relates to the chain length. Polymers can have varying architectures such as linear, branched or cross linked. Cross linked polymers are formed by long chains of polymers connected to each other with shorter molecule chains in between, forming a pattern similar to the way a brick wall looks. Cross linked polymers are strong, rigid polymers with high melting points because of shorter chains linking together the long molecule chains. In this particular lab, the polymers created were not bonded through cross linking. Methods: In the lab, students were required to wear aprons, gloves and goggles to protect themselves from the hazardous materials. Additionally, students performed all procedures using chemicals under a fume hood to avoid contact with the toxic vapors. Many of the materials used in the process of making the polymers were flammable and reactive, so students had to take extra precautions to ensure the chemicals were contained and dealt with appropriately. One way students prevented accidents was to use a hazardous waste bin instead of dumping any of the chemicals down the sink. Additionally, the stannous octoate was kept in the supply room and administered by the teacher to prevent any accidents with the dangerous chemical. For the polymers to set, students needed to make molds to pour their polymer into. Unevenly sized scoopulas and metal tape were used to form rod molds. Aluminum weigh pans, Santa Claus molds and spoon molds were also prepared for the polyme rs. All the molds were greased with vacuum grease to keep the polymer from sticking to the mold. The students used a 100 ml graduated cylinder to measure the caprolactone and added the chemical to the flask. Using syringes, the 1-octanol was measured and added to the mixture. To determine the amount of 1-octanol to use, students followed Table 1 according to their assigned polymer (A-G) as assigned by their teacher. Groups A-G all were assigned a different quantity of initiator and catalyst which provided students with seven polymers with varied chain lengths so students could observe the physical properties o f the polymers created. Then students obtained their stannous octoate from the supply closet where their teacher measured and added the chemical to the solution.

Table 1: Amount of Stannous Octoate and 1-Octanol for Specific Polymerization Ratio
Group Ratio Volume 1Octanol (ml) Mass 1-Octanol (g) Volume Stannous Octoate (ml) Mass Stannous Octoate (g)

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

1.53 1.15 0.57 0.29 0.19 0.14 0.12

1.332 0.999 0.499 0.250 0.166 0.125 0.100

3.19 2.39 1.12 0.60 0.340 0.30 0.24

4.143 3.107 1.554 0.777 0.518 0.388 0.311

Students assembled their work stations with 125 ml Erlenmeyer flasks, hot plates, magnetic stirring bar and thermometers. The stirring bar was placed in the flask to ensure the solution was constantly stirred and the thermometer was secured in the solution with the reservoir fully submerged to monitor the temperature. Then, the solution was heated to 120C, while students ensured that the temperature did not rise above 120. Once the chemicals reached 120, students frequently assessed the viscosity of the fluid by gently lifting the thermometer out of the mixture and observing the way the mixture dripped back into the flask. Once the mixture reached the consistency of syrup, or had been maintained at 120 for an hour, students took the mixture off of the hot plate and poured into the greased molds. These molds where then baked for 24 hours to allow the polymer to set. In the classroom, students tested the strength and durability of the polymer rod molds and the aluminum weigh pan molds or pucks. To test the polymer rods, a group of students designed an experiment to test the strength of the polymer with brass weights. They used two regular classroom tables spread 2 inches apart and balanced the rod across the gap. Using the brass weights with a hook, they gradually added weight until the rod broke. This measured the polymers ability to hold weight which correlated to the polymers strength. The pucks were tested with a hammer contraption. A hammer was taped to a meter stick and attached, by a clamp, to a classroom table turned on its side. The side of the table was taped with strips of duct tape of specific angles. Then, the puck was placed on the ground at the contact point of the hammer and the hammer was dropped onto the puck from the degree marks that increased by 15. The group testing the pucks strength increased the drop degree, starting at 15 all the way to 90. This test measured the force it took to break the polymer, using the degree measurement as a proxy for force.

Results: Table 2: Test results for polymer rods with two tests. Note: For test two, many of the rods were too short to test, causing gaps in the data. Polymer Group A B D E Test 1 (grams) 650 800 1032 982 Test 2 (grams) 550

Figure 1: Hanging Weight Rod Test

Maximum Mass Rod Witheld (Grams) 1200 1000 800 600 400 200 0 A B D E Polymer Group R = 0.8193 Test 1 Test 2 Linear (Test 1)

The rod hanging test results show that the weight each polymer group withheld. Polymer A was tested twice and held 650 grams the first test and 550 grams the second time it was tested. Polymer B, D and E were only tested once and polymer B held more weight than polymer A. Polymer D held 1,032 grams before the polymer rod snapped. However, when testing polymer E, the rod broke at 982 grams, lower than polymer D. These results represent a slightly linear trend throughout the polymer groups. Table 3: Test results for polymer pucks with varying degrees of hammer drop. Note: Two tests were conducted, creating two sets of results.
Group Letter A B C D E F G Test 1 15 60 30 60 15 15 45 Test 2 n/a 15 15 90 30 30 n/a Angle Degree From Drop Test 3 Test 4 Test 5 n/a n/a n/a 30 n n/a 45 n/a n/a 30 30 15 n/a n/a n/a n/a n/a n/a n/a n/a n/a Test 6 n/a n/a n/a 75 n/a n/a n/a

E: (spoon not puck) F: (square not puck)

Figure 2: Angle of Breaking Point for Puck Test

100 90 80 Angle (Degrees) 70 60 50 40 30 20 10 0 A B C D Polymer Group E F G R = 0.0523 Test 1 Test 2 Test 3 Test 4 Test 5 Test 6 Linear (Test 6)

In Figure 2, the results of the hammer drop test are revealed. Polymer A was only tested once and broke at 15. Polymer B was tested three times and broke at a different degree each time. The first test, polymer B broke at 60 and the second test; the puck broke at 15. The last test of polymer B varied from the other two tests as the puck broke at 30. Then, polymer C was tested 3 times. All of the tests of polymer C are equal or less than the test results for polymer B. Polymer D was tested 6 times These test results varied from 15 to 90 and the only angle that reappeared was 30. Polymers E and F have the same values in both test one and two; 15 and 30, respectively. Lastly, polymer G, was only tested once and the puck broke at 45. The results of the hammer drop test varied widely and no trends were apparent. Discussion: In this experiment, students created and then tested polymers to examine the result of varying lengths of monomer chains. The chain length was dependent on the amount of catalyst and initiator used in the solution to make the polymer. Students then tested the polymer rod molds and puck molds for strength and durability. The data collected by multiple classes was compiled into tables and graphs to demonstrate the test results. Based on the bonding structures of the polymers, the test subjects with shorter chains of monomers should be weaker and the polymers with longer chains should be stronger. Students gathered many data points for the puck test due to an excess in polymer puc ks. However, the data collected from the puck test was too scattered to provide clear evidence to either disprove or support the experiments claim. The polymer pucks were tested for strength by a swinging hammer test. The hammer was dropped from different angles and the angle that the polymer broke at was recorded in the Table 3. In Table 3, the results from the three tests vary and provide no clear evidence to support the prediction. If the results

supported the claim, then the force withheld by the polymer would increase in a linear progression. In Table 3, the data points of the puck test range from 15 to 90 and show no clear pattern. In Figure 2, the puck test results are graphed and the bar graph does not reveal any trends in the polymers either. For example, polymer G used the least amount of catalyst and initiator in the creation process of the polymer. The chains of monomers are the longest in polymer G which would cause polymer G to have the strongest bonds, but the results collected do not support the original claim. The polymers in the puck test did not behave in the same way that was predicted. This uncertainty and unreliability in the tests may have been a product of the testing methods. Test results may have been skewed by the organization of the polymers during the testing period. On several of the wooden classroom tables, the polymers were organized on pieces of paper labeled with the polymer group, A-G. However, with 5 classes utilizing the polymers for tests, the tables became messy and the polymer pucks and rods could have drifted from paper to paper without the students even knowing it. The paper to separate the polymers from each other was overlapping in some cases and if students assumed they were testing polymer D, but were really testing polymer E, then there would be inconclusive results. With the puck test, the uncertainty is too great to rely on as reliable and therefore, the puck test will not be used in the final conclusion. In the reaction, the more catalyst and initiator correlates to more, shorter chains of monomers to make up the polymer. The shorter chains generally mean the polymer is weaker, and the results of the hanging rod test support this claim. In Table 2, the fi rst two tests on polymer A are recorded at lower masses than the rest of the tests on other polymer groups, indicating that the results follow a linear trend line. Additionally, in Figure 1, the linear progression is shown by the data points of hanging rod test. This trend is maintained throughout the different polymer rods, as predicted, due to the bonding structure of the polymers. The polymers with more catalyst and initiator have shorter chains of monomers that are unable to bond solidly to each other. The shorter chains have less points of attraction than the longer chains, causing polymers made with shorter chains to be weaker. In Figure 1, these values are graphed to better examine the trends. One tool that can be used to determine if a trend line is close to linear is the R 2 value. The closer this number is to 1, the more linear the equation is. In Figure 1, the R 2 value is 0.8193. This value is not exactly linear because of the jump between polymer D and polymer E, observed in Table 2, but the general direction of the trend line is linear. The polymers were created by student groups in the lab, so some polymer groups may have been made incorrectly or sloppily. The polymer, as a liquid, was poured into molds that then formed the rods. The discrepancy in values might stem from student groups pouring the polymer into the mold to quickly, permitting air bubbles to form in the final rod , causing it to be weaker when tested. Additional error might have been caused by the testing procedures. The rods were balanced between two tables 2 inches apart. However, some of the rods were too short and so the distance between the tables was reduced to an inch or an inch and a half. This variation in the distance between the two tables might have contributed

to uncertainty in the results of the polymers. Though there was uncertainty, I believe the results from the hanging weight test on the rods to be reliable. The group of students that tested the rods all tested one rod together so all the students knew the procedure and the set up of the test. Then, one group broke off and tested the rods that the first group hadnt tested yet. Through this method, both stations of testing were set-up the same so there was little room for mistake in the actual procedure. By using the results of the rod tests, I can conclude that polymers increase in strength as the amount of initiator and catalyst used to make the polymer decreases.

Honors Extension: 1. Landfills are full of all sorts of polymers, ranging from plastic bags to rubber tires. Due to the polymers stable state, they are unlikely to biodegrade rapidly, if at all. However, some polymers, such as polycaprolactone, are able to biodegrade overtime, unlike polymers such as polyethylene. Polyethylene is a polymer made from a simple chain with carbon electrons at each point where the chains of polyethylene are connected. Many polyethers are polyethylene glycols or PEGs and are used in pharmaceuticals. However, because of their structure, they are close to nonbiodegradable, meaning they degrade at an incredibly slow rate. In order to degrade, polyethylene must lose one glycol unit at a time after each oxidation state (Premaj). On the contrary, polycaprolactone has a different structure that allows it to be biodegradable. A chain of polycaprolactone has two oxygen atoms attached to the polymer chain. In the atmosphere of biodegrading, the enzymes and microorganism can degrade the polycaprolactone because of the oxygen atoms. The enzymes and microorganisms need oxygen and when they use that atom, it slowly unwinds the monomer chains, allowing for the polymer to degrade. This means that when a polymer has oxygen bonded to the chains of monomers, the polymer is biodegradable. 2. Because there are so many different types of polymers, they all can be designed to serve different purposes. Some polymers are enhanced by adding molecules called plasticizers. The plasticizers increase the flexibility of the polymers by creating space in between the polymer chains, limiting intermolecular attractions. However, plasticizers are not chemically bonded to the polymer they are added to. This causes concern for leaching. Leaching means that the toxic plasticizers are coming out of the polymer and onto the person it is touching or into the product it is holding. In water bottles, take Nalgene for example, plasticizers have been used to create a long lasting, shatterproof product. For water bottles, plasticizers can be used with the chemical called bisphenol A (BPA). These chemicals can, over time, find a way out of the product they were put in and cause negative affects to a persons overall health. Many of these chemical effects can cause cancer and other ailments. Water bottle companies, like Nalgene, have manufactured water bottles that are BPA free, easing the worries of the consumers. Though their products are free of BPAs, many products such as food jars, plastic toys and drinking cups may contain BPAs that could be leaching onto our skin or into the water we are drinking.

Sources Used: Premaj & Doble: Biodegradation of Polymers http://www.babycentre.co.uk/a1037227/plasticizers-phthalates-and-bisphenol-abpa#section1