Lab 3: Degradable and Non-Degradable Polymers

Ryan Betz
Group Members: Rima Viradia, Cristina Rascoll, Stephanie Cherry, Alexander Long, Sana
Suhail

BME 3700- 001L

March 22, 2017

1
Introduction: Polymers are composed of many mer units. There are three different synthesis

methods that can allow mer units to become polymers. The three different types of synthesis are

addition polymerization, condensation polymerization, and ring opening polymerization. These

different techniques allow for polymers to be synthesized and created in a way that will allow for

researchers to have properties necessary for a certain application.

Polymers can be seen in everyday life. From the soda bottles made out of PETE to high

density polyethylene for milk bottles, polymers are all around. Polymers can also be used for

applications other than just storing liquids for human consumption. One application of polymers

used in the body involves drug delivery. These small units localize the drug potency to a specific

region of the body. This is in comparison to taking a drug orally that will affect other areas of the

body in comparison to where the drug is actually needed. Also, the drug delivery devices can

have antibodies that attach to the pathogens surface. This will cause the drug to be internalized

and it can kill the cells. If the polymer has these antibodies and is only absorbed by the pathogen

the drug can also be in a larger concentration dosage as other parts of the body will not be

affected just the cell being targeted.

Another use for polymers in the body is for articulating surfaces. One example of this is

for a hip replacement surgery. The ball and cup is made out of metals such as cobalt-chromium,

but these materials are not wear resistant. To solve this issue, ultra-high molecular weight

polyethylene is placed on the surfaces of the cup. This reduces the wear between the femoral

head and acetabular cup. Polymers, based on the structure and processing can vary the

mechanical loading and wear that a material can withstand.

Another great aspect about polymers is they can be biocompatible and biodegradable.

Biocompatibility is extremely important as this means that the body will not react to the polymer

2
inserted into the body. This means that there will be no foreign body response which could lead

to the polymer degrading prematurely or create inflammation that will affect how the implant sits

in the body. Due to the biocompatibility aspect, polymers are an ideal choice of a material to

implant into the body. Biodegradability in the body is also important. This means that the

material could be implanted into the body then be degraded into material the body can use or

excreted from the body. This type of polymer can be used with drug delivery device as the

polymer could be a hydrophobic material that will allow for the polymer to undergo surface

erosion. With surface erosion, the material will degrade like an onion peeling which will allow

for the drug to be released in a zero order manner. Once the material degrades completely, the

materials can be absorbed into the body or made into materials that exist in nature that the body

can dispose of.

Polymers can exist as either synthetic or natural polymers. Synthetic polymers are ones

that engineers create in a lab while natural polymers can be found in nature such as cellulose or

silk. The goal of this lab was to create four different polymers in a lab setting to understand how

polymers can be synthesized. This is important as it allows the students to have an understanding

of how polymers are synthesized and different techniques to alter the polymer for specific

applications. These different tools can be applied to real world situations and allow the right

polymer choice to be made and synthesized correctly.

Methods: Materials for the Lab

1. Polycaprolactone (PCL) (80K mw)

2. Polycaprolactone (PCL) (40K mw)
3. Poly(glycerol dodecanedioate) (PGD)
4. Chitosan (80% deacetylation)

3
5. Methyl methacrylate
6. Ascorbic acid
7. Ammonium persulfate
8. Ethanol (100%)
9. Methylene Chloride
10. H2So4 (1% aq)
11. HCl (1% aq)
12. Sodium Chloride
13. 30ml scintillation vials
14. Incubator set to 37 Celsius
15. Glass pipettes with rubber bulb
16. Weigh boats
17. Balance
18. Glass petri dish
19. Small spatulas
20. Parafilm

The first step of the lab was to create Polymethylmethacrylate (PMMA). The way to synthesize

PMMA was to first grab a Petri dish and label it with the group number and date. After labeling

the Petri dish, weigh the dish and record the mass. Next, get a 30 mL scintillation vial with 2mL

if methyl methyacrylate. Make sure not to open the vial until necessary as the fumes are odorous

and are bad for the health of the individual. The amount of initiator that is added to the methyl

methyacrylate depends on the group number. If in group one add 10 milligrams of Ammonium

persulfate and 7 milligrams of Ascorbic acid into the same weighing boat. Make sure to tare the

scale after the boat has been added to the scale to get the correct reading for Ammonium

persulfate and Ascorbic acid. If the incorrect amounts are added, the polymer will not be correct.

4
After both the Ammonium persulfate and Ascorbic acid have been added to the boat 200

microliters of distilled water are needed. To measure out the 200 microliters first grab a

microliter pipette and add the plastic tip to the end. Change the dial to 200 microliters and place

the plastic tip into the solution of deionized water. Press down to the first point and release. This

will cause the distilled water to be taken into the pipette. After 200 microliters has been obtained,

bring the pipette over to the weighing boat and add to the Ammonium persulfate and Ascorbic

acid. To release the water, press the injector button all the way down and this will release all the

water from the plastic tip. The next part involves adding 800 microliters of 100% ethanol to the

weighing boat. To complete this change the dial to 800 and do exactly the same thing that was

completed for the distilled water.

If in group two the amount of Ammonium persulfate added to the weighing boat is 20

milligrams and the amount of Ascorbic acid is increased to 14 milligrams. In group three the

amount of Ammonium persulfate added to the weighing boat is 30 milligrams and the amount of

Ascorbic acid is increased to 21 milligrams. Finally in group four the amount of Ammonium

persulfate added to the weighing boat is 40 milligrams and the amount of Ascorbic acid is

increased to 28 milligrams. The same amount of distilled water and 100% ethanol are added to

the weighing boats for all four groups.

Once all the ingredients are added and dissolved, the next step is to transfer the initiation

solution to the scintillation vial. Change the micropipette to 1000 ml and gather the initiator

solution. After the initiator solution has been acquired by the pipette, open the cap of the

scintillation vial and place the initiator solution inside. Close the cap quickly. After closing the

cap, place the vial in a 37 degree Celsius incubator for 60 minutes. After the 60 minutes shake

the vial occasionally. The changes need to be recorded. Afterwards the TA will add 80% ethanol

5
to the vial if not all of the precipitate has dissolved. Once all the precipitate forms it needs to be

added to a Petri dish and left to dry. The Petri dish should be under a fume hood when drying.

Calculate the efficiency of polymerization a week after.

The next part of the lab involved creating Polycaprolactone (PCL) film. The first PCL

film that was created was 80 K molecular weight PCL. Weigh 1.25 grams of PCL 80 K

molecular weight onto a weighing boat and transfer to a 20 mL scintillation vial. The next step

involves getting two labels and writing the group number and date along with whether the vial

will have 80 K molecular weight or 45 K molecular weight. These labels should also be placed

on the bottom of the Petri dishes that will be used. Add 10 mL of methylene chloride to the

20mL scintillation vial. After mixing let the solution sit for around 40 minutes until the mixture

is completely distributed throughout the polymer solution. Pour the solution into the respective

Petri dish which is under a fume hood and let the solvent evaporate. This same procedure needs

to be completed with the 45 K molecular weight PCL.

Another part of the lab was to create porous Poly(glycerol dodecanedioate) (PGD). To

create this polymer the first thing to do is to weigh out 2 grams of PGD onto a weighing boat.

Next add 10 mL of 100% ethanol into a 20 mL scintillation vial. Once the ethanol has been

added to the vial, the PGD needs to be added to the vial. The scintillation vial will then be

covered and placed in a 37 degree Celsius incubator. The mixture will be mixed thoroughly

while in the incubator and can take up to 30 minutes. Write a label with the group number and

date and add to the bottom of the Petri dish. Once the label has been added, salt is uniformly

spread to the bottom of the Petri dish. Group one will add 15 percent of dry weight salt

concentration to the Petri dish. This salt needs to be spread uniformly. If in group 2, add 25% dry

weight salt concentration to the Petri dish. If in group 3, add 35% dry weight salt concentration

6
to the Petri dish. Finally, if in group 4, add 45% dry weight salt concentration to the Petri dish.

After the salt has been added, pour the polymer solution into the Petri dish and let the solvent

evaporate.

Finally, the last polymer created was a Chitosan thin film. Weigh 1 gram of chitosan

flakes. Once this has been weighed, add 20 mL of 1% hydrochloric acid to the vial. Add the

chitosan slowly to the HCl solution. Place the solution in the vortex to allow for the solution

stirred so that all the chitosan has been dissolved. Place a label on the bottom of a Petri dish with

the group number and date. Pour the solution into the Petri dish. If in group 2 or 4 add 2 mL of

1% Sulfuric acid to the solution. Let the water evaporate from the solution.

Results:

𝑌𝑖𝑒𝑙𝑑 𝑜𝑓 𝑝𝑜𝑙𝑦𝑚𝑒𝑟 0.076

Percent Polymerization: % 𝑌𝑖𝑒𝑙𝑑 = 𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑌𝑖𝑒𝑙𝑑 ∗ 100 = ∗ 100 = 4.04% To find the
1.88

theoretical yield multiply the mL of methyl methacrylate by the density which is 0.94 g/mL =

1.88 grams.

Discussion:

Below is the chemical structure of two polymers created in the lab. The first one on the left is

PMMA while the polymer on the right is Chitosan. This shows that PMMA can be synthesized

through addition polymerization while Chitosan is a ring structure. The Chitosan is harder to

break down as it is a ring. This means that the mer unit will need to undergo ring polymerization

which the ring has to open before the polymer can start to go through addition polymerization.

7
 [3] [1]

The FTIR specific group frequencies for both PMMA and Chitosan can be determine

through the use of examining the FTIR spectrum. Have not finished!

PMMA can be used for a variety of different applications from biomaterials to everyday

life. A couple applications for a biomaterial would be contact lenses and intraocular lenses. One

use of PMMA in everday life would be acrylic glass that can be used for windows or other

applications. One advantage of using PMMA is the clarity component along with UV resistance.

If used to make a contact lens, this clarity will allow the user to see clearly and the UV resistance

will help to protect the eye from the sun. One of the disadvantages of using PMMA is the fact

that it has a poor fatigue resistance. This means that it can not undergo cyclic loading as it will

deteriorate and breakdown. This causes the use for PMMA to be extremely limited in what

applications that the material can be used for.

An advatage to introducing pores into PCL or PGD is cells can integrate into the material

once implanted into the body. This means that the body can start to integrate into the implant so

it can degrade and the body will regenrate the affected area. This is a big goal of tissue

engineering going forward is not to just replace, but have the body regenerate and regrow. This

can be aided through the use of growth factors that will cause the tissue around the implant to

start to regenerate and work as if there was no damage to the body. One disadvantage of

introducing pores to PCL or PGD is the mechanical properties of the implant will be

8
significantly compromised. This will lead to the implant needing to be combined with another

material to make a composite to increase the mechanical strength or ductility. If no other material

is used to strengthen the porous polymer, then the applications in which the material can be used

will be diminished.

The native form of Chitosan is like the picture above where it is a ring structure. This

type of structure is very stable and hard to break down. The way to break it down is to expose it

to an acid with a pKa that is less than that of chitosan. Acids such as hydrochloric acid can cause

this ring to breakdown. The non native form of Chitosan is used as it takes less time for

polymerization to occur. The native form of Chitosan can be turned into non native through a

degradation process, but this process can take days to occur. With the non native form the

process to form the polymer will occur when needed in the lab. This is why the non native form

was used. The chemical process of changing the native form of Chitosan to Chitosan involves

breaking down the ring structure of the Chitosan.

Conclusion: Polymers can be used for a multitude of applications in the body as biomaterials.

These polymers can be used as part of a composite to change the properties of the implant or be

the delivery device for a certain drug. Another application can be contact lenses for individuals

who are near or far sighted. Polymers are extremely important in biomedical applications and

help millions of people every day. This is why learning how to synthesize polymers in a

laboratory setting is so important for biomedical engineers. This lab allowed students to

experience the polymer creation process along with the many challenges that are involved.

Some sources of error in the lab deal with measuring the materials. An example of this

deals with measuring the dry materials. The scale was not accurate and when tared would not

stay at zero. This means that the Ammonium persulfate and Ascorbic acid measured would not

9
have been correctly which can affect the outcome of the polymer. Another example of error

associated with the lab deals with the micropipettes. If the user did not use the pipette correctly

then the total amount of liquid added into initiator solution would be incorrect which can

influence the polymer in the wrong way. Another error can be associated with the scales. Since

the scales were not calibrated correctly, the measuring of the Petri dishes were not correct. This

can affect the percent polymerization as the scale could not read a correct value to the user.

A way to fix these issues is to fix the scales. If the scales were better and calibrated the

amount of reactant added to the initiator would be more correct. This would lead to the best yield

possible for each polymer. To fix the pipette problem one fix could be to automate the pipette to

get a certain amount of liquid that the user wants. Another fix would be to teach the user how to

use the pipette before lab.

10
References:

[1] "Chitin/Chitosan Fibers For Anti-Bacteria Textile Products". Swicofil.com. N.p., 2017. Web.
10 Mar. 2017.
[2 ]Huang Yen-Chih, Ph.D. “Lab#1 Synthesis of Hydroxyapatite.” BME 3700 Lab. Bronwell,
Storrs. 01 March. 2017. Lab
[3] Van De Walle, Elke. "Youth Views On Sustainability: PMMA, From Plexiglass Window To
A Packaging For An Implantable Glucose Sensor". N.p., 2017. Print.

11