Exp.

# 8

Polymers, Polymerization, and Analysis

Alyssa Ference

SCH 211 01

26 November 2018
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I. Abstract:

The purpose of this experiment was to synthesize Cis- Norbornene-5,6-endo-anhydride

and to polymerize dimethyl ester. This was done by reacting maleic anhydride and

cyclopentadiene to obtain the endo-anhydride crystals. The endo anhydride was tested for

melting point range, proton NMR, and IR (0.03 g, 0.90%; NMR: 6 ppm, 4 ppm, 2 ppm; IR:

3011.12 cm-1, 2980.79 cm-1, 1838.83 cm-1, 1449.97 cm-1; MPR: 156-167 °C). The melting point

discovered correlated with the melting point expected with a range from 165-169 °C. After, Cis-

Norbornene-5-6-endo-dimethylester was synthesized. The endo-diester was created by reacting

the endo-anhydride with concentrated sulfuric acid and later, it was refluxed. Seperatory

filtration and rotary evaporation were then performed on the ether. Analysis of the liquid with a

proton NMR and Infrared spectroscopy showed a molecular formula and IR results that

correlated to the structure already known for the substance (1.58 g, 41.15 %; NMR: 6 ppm, 4

ppm, 3 ppm, 2 ppm; IR: 2950.01 cm-1, 1433.89 cm-1, 1339.28 cm-1, 1251.68 cm-1). Then, the

diester was polymerized with the Grubbs second generation catalyst to create the polymer to be

further analyzed with a proton NMR and an Infrared Spectrum that found the functional groups

to match the functional groups in the polymer structure expected (0.31 g, 55.36 %; NMR: 6 ppm,

4 ppm, 3 ppm, 2 ppm; IR: 2949.99 cm-1, 1728.14 cm-1, 1434.59 cm-1).

II. Introduction:

A synthesis of Cis- Norbornene-5,6-endo-anhydride experiment was performed to obtain

crystals to later be polymerized. Maleic Anhydride was reacted with dry cyclopentadiene in

hexane and ethyl acetate to obtain the Cis- Norbornene-5,6-endo-anhydride and the reaction is

shown below.
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This reaction was completed using a Diels-Alder reaction. Diels-Alder reactions involves

a cycloaddition of a conjugated diene and a dienophile to an alkene or alkyne. It results in a

formation of new sigma bonds (Matthey). It is the most effective method of synthesis for an

unsaturated six-membered ring (Matthey). The reaction occurs by an overlap of molecular

orbitals, p orbitals to be precise. The dienophile plays the role of electron-withdrawer (Matthey).

The diene needs to be as electron rich as possible, while a strong dienophile consists of the

following; CHO, COR, COOR, CN, and C=N (Matthey). The product typically favors the kinetic

control due to secondary orbital interactions, but contains a diastereoselective reaction

(Bartelson). These reactions can be used to synthesis organic molecules due to the favorable

thermodynamics and the conversion of two pi bonds to two stronger sigma bonds.

Polymerization is the process by which monomers are covalently bonded together to form

a long polymer chain (Moerdyk). These reactions can occur through heat, pressure, and catalysts

that help alter the chemical bonds of the monomers and turn them into covalent bonded atoms

that form the polymer chain. An example of a linear polymer is Polythylene, commonly found in

plastic bags, toys, and bottles (Kelley). The creation of this polymer includes the free radical

polymerization, which has three stages names initiation, propagation, and termination

(Bartelson). Polymers have numerous usages and are a part of everyday life. The downsides of

polymers are that they are biodegradable, large so they take longer to react, and they easily

precipitate out of solutions (Moerdyk). They can be found in any kind of plastic, some clothing,

and throughout DNA.

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To complete the polymerization, the endo-anhydride crystals were reacted with

concentrated sulfuric acid and refluxed to create the endo- diester. Refluxing is a technique used

to prevent the solvent from boiling away as it allows for the solution to maintain the reaction at

the boiling point of the solvent for an indefinite amount of time (Gillespie, 2018). Refluxing was

completed with two glass columns, one in which cold water ran through to cool the vapor from

the boiling solvent. The cooled vapor solvent then fell back into the solution to continue the

reaction.

The endo-diester was then reacted with THF and Grubbs second generation

catalyst for the polymerization and creation of the polymer. Grubbs catalysts was used to create a

ring opening with metaphysis so that the polymer can be formed as followed.

III. Experimental:

To create the endo-anhydride, maleic anhydride (2 g, 20.4 mmol) and ethyl acetate (6

mL) were mixed and placed in a hot bath. Hexane (6 mL) was added and the solution was placed

in the ice bath. Dry cyclopentadiene (2 mL, 24.36 mmol) was added to the mixture to create the

exothermic reaction and form the white cloudy substance. The solution was then heated to

dissolve the white cloudy solid and set aside to cool for recrystallization. The crystals were

suction filtered, rinsed with cold methanol, and weighed to be analyzed (2.42 g). 0.100 g of the

crystals were set aside to be analyzed with a melting point range, proton NMR, and Infrared

Spectrum.
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The synthesis of Cis- Norbornene-5,6-endo-dimethylester was performed by the addition

of the endo-anhydride (2.30 g) to methanol (9 mL) and concentrated sulfuric acid (0.45 mL). The

mixture was then refluxed for an hour. After, it was cooled and transferred to a seperatory funnel

with water (15 mL) and tert- butyl methyl ether (15 mL) to extract the dimethyl ester into the

ether layer. Saturated aqueous sodium bicarbonate (15 mL) and saturated aqueous sodium

chloride (15 mL) were then used separately to extract the ether layer into a dry Erlenmeyer flask.

Once extracted, anhydrous pelletized CaCl2 (0.51 g) drying agent was added. The dry solution

was decanted into a round-bottomed flask (50 mL) and the tert-butyl methyl ether was rotary

evaporated. The left over diester (1.58 g) was analyzed with a proton NMR and an Infrared

Spectrum.

During polymerization, the diester (0.51 g) was added to an Erlenmeyer flask (125 mL)

with THF (4 mL). Once the Grubbs second generation catalyst (0.004 g) was added, the mixture

was heated at 60 degrees Celsius for seven minutes. After the solution was cooled, THF (20 mL)

was added again. In order to precipitate the polymer, methanol (50 mL) were added and then the

solution was suction filtered. A pale pink solid polymer was formed. The dried, washed, and

weighed polymer (0.31 g) was collected for further analysis with a proton NMR and Infrared

Spectrum.

IV. Results and Discussion:

Endo-Anhydride

The endo-anhydride crystals were weighed at 0.03 g. The i07 ATR iS5

Thermoscientific IR was used to analyze the crystals. The analysis showed an alkene double

bonded C at 3011.12 cm-1, a C-H stretch at 2980.79 cm-1 and 2955.50 cm-1, a C double bonded to

O stretch at 1763.49 cm-1, and a C-C stretch at 1449.97 cm-1.

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Figure 1: Infrared Spectrum for endo-anhydride crystals.

These functional groups match up with the functional groups found in the structure of endo-

anhydride, which is pictured below.

Figure 2: Endo-anhydride structure (Moerdyk).

The proton NMR was performed with the EM 360-Eft-60 proton NMR. It explained the

amount of hydrogens that were located at each carbon and on the carbon adjacent to be eight in

total. The molecular formula found for the endo-anhydride was C9H8O3. The chemical shifts

correlate to the types of carbons that the NMR showed the Hydrogens were attached to. The

NMR hydrogens labeled A were found on the carbons that were double bonded to each other.
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Hydrogens at point B were located on the top, bottom, and two right points of the hexagon while

the hydrogens labeled C were located on the middle carbon.

Figure 3: A labeled proton NMR for the endo-anhydride crystals.

The melting point range was also analyzed for the endo-anhydride. The voltage was at 50

volts for this substance, which shows how high of a melting point it could be expected to have.

The expected melting point was range found was 165-169 ° C (Sci-Finder). The found melting

point range was 156-167 ° C, which proves that the analysis was completed correctly and the

synthesis experiment was successful due to the expected range falling in between the

experimental range.

The percent yield for endo-anhydride was extremely low at 0.90 %. This could have been

caused by an incorrect transfer of the crystals from when they were originally collected. The
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beaker was not completely dry when the crystals were placed in it, which could have dissolved

some of the crystals obtained.

Endo- diester

The endo-diester liquid was analyzed with an IR. The functional groups found in

the IR were a C-H stretch at 2950.01 cm-1, a C-C stretch at 1433.89 cm-1, a C-H rock at 1339.28

cm-1, and a C-O stretch at 1251.68 cm-1.

Figure 4: The Infrared spectrum for endo-diester liquid

The C=O, C=C, C-O, and C-H all appear in the structure expected for the endo-diester, as shown

below. This confirms the success of the reaction in forming the correct structure of the endo-

diester.
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Figure 5: Endo-diester structure (Moerdryk)

To analyze the endo-diester further, a proton NMR was performed. The molecular

formula of the endo-diester correlated with the structure expected, C11H14O4. Two hydrogens on

the NMR were the most upstream and occurred around 1.7 ppm. Due to oxygen’s

electronegativity, it pulled the other hydrogens further downfield. Two hydrogens occurred

around 6 ppm, six hydrogens occurred around 4 ppm, four hydrogens were around 3 ppm, and

the last two hydrogens occurred around 1.7 ppm. After analyzing the structure of endo-diester

and the chemical shifts, the NMR was performed successfully because the hydrogens found

correlated with the expected structure of the endo-diester. At point A, the two hydrogens on the

carbon double bond were labeled. The six hydrogens labeled point B are located on the carbons

attached to the single bonded oxygen atoms. Hydrogens labeled C are located on the two right,

top, and bottom points of the cyclohexene and the point D hydrogens are found on the middle

carbon.
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Figure 6: Labeled proton NMR of the endo-diester liquid.

Polymer

An Infrared Spectroscopy was used to identify the functional groups in the

polymer solid. The functional groups found were a C-H stretch at 2949.99 cm-1, a C=O stretch at

1726.14 cm-1, and C-C stretches around 1434.59 cm-1. These functional groups all matches the

ones in the polymer structure that is shown below.

Figure 7: Structure of the Polymer (Moerdyk).

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Figure 8: Infrared Spectrum of the polymer solid.

A proton NMR was also conducted to determine the amount of hydrogens and find the

molecular formula. Two hydrogens were found around 6 ppm and were labeled A to be found on

the first carbons attached to the cyclopentane. Hydrogens labeled B were found around 4 ppm

and appeared on the carbons single bonded to the oxygens. The fours carbons located around 3

ppm were labeled C and were found on the four corners of the cyclopentane. Lastly, the

hydrogens labeled D were located at 2 ppm. They appeared on the point of the cyclopentane.

Therefore, the NMR verified the structure and the success of the polymerization.
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Figure 9: Proton NMR for the polymer.

Calculations

Theoretical Yield= Amt reactant ∈Moles × mole ratio ( reactant

product )
× molecular weight of product

1 mol 1 mol Endo− Anhydride 164.16 g

Theoretical Yield Endo− Anhydride=2 g Maleic Anhydride ( 98.06 )( )(
g 1 mol Maleic Anhydride 1 mol Endo− An

ActualYield
Percent Yield= ×100 %
Theoretical Yield

0.03 g
Percent Yield Endo− Anhydride= ×100 %=0.90 %
3.35 g

1 mol 1 mol Endo−Diester 210.23 g

Theoretical Yield Endo− Diester=3.0 g Endo−Anhydride ( 164.16 )( )(
g 1 mol Endo− Anhydride 1 mol Endo−die

1.58 g
Percent Yield Endo−Diester= × 100 %=41.15 %
3.84 g
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1 mol 1 mol polymer 234.25 g

Theoretical Yield Polymer=0.5 g Endo−Diester ( 210.23 g )( 1 mol Endo−Diester )( 1 mol polymer )
=0.56 g

0.31 g
Percent Yield Polymer= ×100 %=55.36 %
0.56 g

The percent yields for all substances were not as high as desired, but the reactions were

still completed successfully. The lack of yielded endo-anhydride was due to the lost product

during the collection of crystals into the wet beaker. The endo-diester and polymer yielded

around 50% for both, showing some impurities during the experiment, but overall the experiment

was successful.

V. Conclusion:

Each analytical technique was used to determine if the substances collected matched the

substances expected to obtain. According to Sci-Finder, the melting point, molecular formula,

and molecular structure all matched the expected endo-anhydride. The IR results all showed

correct functional groups for each structure given like C=C, C=O, and C-H stretches. The proton

NMR’s showed more of a chemical shift for the polymer solid, but the amount of hydrogens still

matched the structure. In the end, the experiment was successful with the proper structure of a

polymer being synthesized and polymerized.

VI. References

Gillespie, Claire. (2018, May 15). What is the Difference Between Reflux &

Distillation? Sciencing. Retrieved from https://sciencing.com/difference-between-reflux-

distillation-5953384.html

Kelley, F. N. (n.d.). How are polymers made? Retrieved December 6, 2018, from

https://www.scientificamerican.com/article/how-are-polymers-made/
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Matthey, J. (n.d.). Diels-Alder Reaction. Retrieved December 6, 2018, from

https://www.organic-chemistry.org/namedreactions/diels-alder-reaction.shtm

Polymer Synthesis. (n.d.). Retrieved December 6, 2018, from

https://www.nature.com/subjects/polymer-synthesis

SciFinder. (n.d.). Retrieved December 6, 2018, from

https://scifinder.cas.org/scifinder/view/scifinder/scifinderExplore.jsf