pubs.acs.

org/jchemeduc Laboratory Experiment

Exploring Divergent Green Reaction Media for the

Copolymerization of Biobased Monomers in the Teaching
Laboratory
Ethan A. Gormong, Michael T. Wentzel, Boen Cao, Laura N. Kundel, Theresa M. Reineke,
and Jane E. Wissinger*
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ABSTRACT: Polymerization reaction media can have a profound effect on the

physical properties of the resultant polymer. This phenomenon is showcased in a new
experiment for the organic chemistry and polymer science teaching laboratories
wherein the radical copolymerization of biobased β-myrcene and dibutyl itaconate is
performed using a nonhazardous aqueous emulsion solvent and compared to a bulk
reaction. Both procedures demonstrate multiple green chemistry principles and
application to sustainable polymer synthesis. The emulsion copolymerization
produces a tacky, elastomeric cross-linked material, capable of swelling to many
times its original volume in organic solvents, setting the stage for the exploration of
the relationship between solvent polarity and swelling capacity. Conversely, the
polymerization of β-myrcene and dibutyl itaconate in the bulk yields a viscous non-
cross-linked polymer whose 1H NMR spectrum is suitable for student analysis and
estimation of polymer number-average molar mass (Mn), monomer conversion, and
copolymer composition. This inexpensive experiment models the use of renewable feedstocks, the effect of reaction medium on
polymer architecture, the unique properties of cross-linked organogels, and the quantitative analysis of polymer structure using 1H
NMR spectroscopy.
KEYWORDS: Second-Year Undergraduate, Upper-Division Undergraduate, Organic Chemistry, Polymer Chemistry,
Laboratory Instruction, Hands-On Learning/Manipulatives, Green Chemistry, Materials Science, NMR Spectroscopy, Polymerization

■ INTRODUCTION
The impact of polymers on human life cannot be under-
Committee on Professional Training of the American
Chemical Society.23,24
This laboratory experiment features the radical copolymer-
estimated; polymers comprise many consumer goods used
ization of sustainably sourced monomers, β-myrcene and
daily. However, a majority of synthetic polymers are derived
dibutyl itaconate, and illustrates the effect of reaction medium
from petroleum, a nonrenewable source, and are environ- and conditions on the structure of the resultant material
mentally persistent or difficult to recycle. An estimated 8.3 (Scheme 1). An aqueous emulsion copolymerization of these
billion metric tons of synthetic plastic have been manufactured two monomers produces a cross-linked copolymer network,
since 1950, most of which has been relegated to landfills, suitable for gelation studies in various organic solvents to form
incinerated, or leached into the environment.1 As such, the organogels (Scheme 1a). Alternatively, polymerization in the
scientific community is aggressively investigating the synthesis bulk (solvent-less) yields a CDCl3-soluble linear copolymer,
of sustainably sourced and degradable polymeric materials with most likely with branching (Scheme 1b), amenable for study
properties and prices comparable to those of their petroleum- by 1H NMR spectroscopy. Distinguishable proton resonances
derived counterparts.2 for both repeat units allow for calculation of monomer
The chemistry education enterprise is raising awareness of incorporation and copolymer ratio, and an initiator peak can
these research initiatives by introducing sustainable polymers
into the undergraduate teaching laboratory.3−8 Published Received: June 16, 2020
laboratory experiments highlight classic industrially relevant Revised: December 6, 2020
polymers,9,10 materials with advanced architectures and
properties,11−15 and modern polymerization16−19 or character-
ization20−22 techniques. These laboratory activities also help
fulfill the macromolecular requirements put forth by the
© XXXX American Chemical Society and
Division of Chemical Education, Inc. https://dx.doi.org/10.1021/acs.jchemed.0c00688
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Scheme 1. Divergent Reaction Media for the Radical Copolymerization of β-Myrcene and Dibutyl Itaconate: (a) Emulsion
Polymerization Conditions and (b) Bulk Polymerization

be used for estimation of the number-average molar mass procedure to one amenable to the nonstringent conditions and
(Mn). Incorporation of these divergent reaction conditions into time constraints of a teaching laboratory, it was discovered that
a teaching laboratory experiment provides students with the the formation of cross-linked gels could be enhanced by
opportunity to synthesize two tangibly different materials from replacing the carefully controlled reagent additions and stirring
the same monomers, one cross-linked and the other linear/ with aggressive shaking of the monomers with the emulsifiers
branched, and to engage in discussions related to green before initiation of the polymerization.
polymer chemistry.

■
The phases of emulsion polymerization were first articulated
BACKGROUND by Harkins32 and elegantly summarized by Lovell and Schork
in a recent review.33 During 0−5% conversion (interval I),
β-Myrcene (myr) is a naturally occurring terpene obtained particles are nucleated within the aqueous phase and begin to
from the pyrolysis of β-pinene, commonly derived from
form oligomeric radicals. At 5−40% monomer conversion
turpentine,25 whose 1,4-butadiene subunit has a structural
similarity to isoprene. Such diene substructures are highly (interval II), polymerization occurs at a constant rate in the
amenable to free-radical polymerization, and the resulting presence of monomer-rich micelles. At 40−100% conversion
rubbery materials abound in the commercial marketplace. The (interval III), the polymerization is characterized by a decrease
US Department of Energy has listed itaconic acid, the parent in propagation rate as monomer concentration within micelles
chemical of dibutyl itaconate (dbi), as a “Top Value-Added decreases. Cross-linking due to chain-transfer events during
Chemical from Biomass”.26 This platform chemical is interval III is likely as dibutyl itaconate is incorporated due to
industrially relevant as a drop-in replacement for monomers its easily abstractable H atom α to the ester carbonyl,
such as acrylic acid, and more than 40,000 tons are produced generating a midchain stabilized radical. A high concentration
annually by fungal fermentation of glucose.27 The dibutyl ester of polymers within the micelle bearing a midchain radical leads
of itaconic acid is inexpensive and has long been known to to cross-linking. A student handout regarding polymer chain-
polymerize well in emulsion systems.28 Recently, the emulsion transfer and termination mechanism is available in the
copolymerization of myr and dbi was reported.29 The authors
Supporting Information (SI).
synthesized a range of linear copolymer compositions of
In contrast to the originally reported 20 h of heating, the
number-average molar mass (Mn) up to 65 kg/mol with glass
transition temperatures (Tg) between −60 and −33 °C. The new reaction conditions gave a good yield of cross-linked
authors utilized slow addition of the two monomers to the materials in 2 h, a suitable time frame for a teaching lab
aqueous emulsion (formed with sodium dodecyl sulfate (SDS) experiment. Precipitation and drying yielded tacky, stretchy
and sodium bicarbonate) to encourage formation of the linear copolymer gels that could not be melt-pressed even under
polymer with a low gel fraction (minimized cross-linking). 8000 lbs of force at 150 °C (well above the highest possible
Emulsion Polymerization Tg) and recovered back to their original shape. This provided
In a continuation of our efforts to design laboratory evidence toward extensive cross-linking. Furthermore, during
experiments that teach polymer science, use green synthetic preparation of a 1H NMR sample in deuterated chloroform,
methodologies, and illustrate modern approaches to sustain- the copolymer quickly swelled to a gel in the NMR tube. This
able polymers,5,8,30,31 this reported emulsion polymerization observation was a catalyst for development of an organogel
appeared to be an attractive lead to pursue. In the course of experiment showcasing differential swelling capacity of the
investigating the translation of the published experimental network in a range of organic solvents.
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Figure 1. Addition of the propagating chain (P•) to myr: (a) major pathway through 1,4- or 4,1-addition to diene and (b) minor 1,2- or 4,3-
addition resulting in dangling alkenes available for branching or cross-linking.

Figure 2. Formation of a midchain radical intermediate present in emulsion and bulk polymerization systems.

Swelling of Network Polymers alkene cross-linking or branching. Regardless of reaction

According to eq 1, the degree to which a network swells is medium (emulsion or bulk), the majority of myr monomers
controlled by the free energy of the swelled network (ΔG), add in a 1,4- or 4,1-fashion, producing cis- or trans-
proposed by Flory and Rehner.34 This term is composed of the trisubstituted alkene subunits in the polymer backbone, as
free energy of mixing of the polymer and solvent (ΔGm) and depicted in Figure 1a. Cross-linking and branching can arise
the free energy of elasticity (mechanical distortion of the from a minority fraction of 1,2- or 4,3-additions of myrcene
network, ΔGel). onto a propagating chain, affording a dangling vinyl or geminal
disubstituted alkene (Figure 1b). This phenomenon is
ΔG = ΔGm + ΔGel (1) commonplace in free-radical polymerization reactions.36
Similar to the emulsion polymerization, albeit with different
This experiment demonstrates the tremendous effect the outcomes, several termination and chain-transfer events
identity of the solvent has on the contribution of the ΔGm term characterize free-radical bulk polymerization, the most
as related through the Gibbs free energy equation. Favorable common being disproportionation (through α-H atom
solvent−repeat unit interactions increase swelling capacity abstraction) and chain−chain coupling (Figure 2). Bulk
(“like-dissolves-like”) by enhancing the enthalpy of mixing polymerization gives predominantly branched polymer
(ΔHm), a component of the free energy of mixing. Students
through chain-transfer events and does not lead to extensive
can also visualize how networks swell to at least a minimal
cross-linking because of decreased proximity of midchain
degree in any solvent due to entropy (ΔSel, the primary
radicals due to high monomer concentration.
contributor to the ΔGel term) as chains gain degrees of
The 1H NMR spectrum of the linear/branched polymer
freedom to access more conformations. Cross-linked networks
obtained from radical bulk polymerization has distinguishable
swell much more extensively when immersed in a good solvent,
proton resonances suitable for analysis by students in both
that is, one with a relatively favorable enthalpic mixing
introductory and advanced laboratory courses. As an initial
parameter with the repeat units.35 Phrased another way, the
polymer segments between cross-links are solvated by introduction to the NMR calculations, student are instructed
molecules of similar polarity. to assume that each polymer chain formed in the bulk medium
contains only one initiator. With this assumption, the spectrum
Cross-Linking and Branching Mechanistic Considerations allows determination of copolymer: (i) overall Mn relative to
Suitable for student instruction with this experiment is study of the benzoyl initiator; (ii) percent conversion of each
the radical mechanism and discussion of potential sites for monomer; and (iii) the relative ratio of myr and dbi repeat
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units in the backbone. In reality, chain−chain coupling events, emulsion formed using sodium dodecyl sulfate (SDS) and
both along the backbone and at branch points, complicate an sodium bicarbonate. The polymerization is initiated by an
accurate 1H NMR end-group analysis (EGA) calculation of Mn aqueous solution of ammonium persulfate (APS) (0.1 mol %)
for the polymer. Student assignments explore the mechanistic and then stirred vigorously at 70 °C for 2 h on a vial heating
events that could lead to chains bearing more than one initiator block. Proper stirring is critical for maintaining a proper
in the upper division polymer laboratory course. emulsion; when significant phase separation is observed, the

■ EXPERIMENTAL SECTION
Materials and Instrumentation
yield suffers substantially, and only linear polymer is formed,
due to a low monomer concentration in the aqueous micelles.
After the 2 h heating period, the emulsion copolymerization
mixture is poured into acidified ethanol (Figure 3a) to
The dibutyl itaconate (≥98%), benzoyl peroxide, and sodium
dodecyl sulfate were purchased from Millipore Sigma and used
without further purification. The β-myrcene (90% with 1000
ppm BHT inhibitor) was purchased from Millipore Sigma. The
inhibitor, butylated hydroxytoluene, was removed from the β-
myrcene by transferring it to a separatory funnel and washing it
with an equal volume of 2 M NaOH, and the neat monomer
was dried with a small amount of magnesium sulfate.
Ammonium persulfate and sodium bicarbonate were pur-
chased from Fisher Scientific and used without further
purification. All solvents used in the swelling tests were those
found in each of the teaching laboratory courses, purchased in
bulk from various suppliers, and used without purification.
Polymers were synthesized in 20 mL scintillation vials stirred
at 70 °C on a vial heating block resting on a hot plate. A
vacuum oven (60 °C) was used to dry the emulsion
polymerization polymer under reduced pressure after transfer
to small aluminum pans (2−3 in.).
Student 1H NMR spectra were obtained on a Varian Inova
300 MHz spectrometer at University of Minnesota or a Bruker
FourierHD 300 MHz at Augsburg University. Spectra of the
monomers, available in the SI, were obtained on a Bruker
Avance III HD 400 MHz spectrometer. 1H NMR chemical
shifts in CDCl3 were referenced to residual CHCl3 (7.26 ppm). Figure 3. (a) Precipitation, (b) coagulation, and (c) final appearance
Concentrations of ca. 10 mg/0.5 mL CDCl3 are suggested for of cross-linked poly(myr-co-dbi) from the emulsion polymerization
good signal-to-noise in student polymer NMR spectra. reaction.
Experiment Overview
Two laboratory periods are required for completing the protonate the surfactant, thus breaking the emulsion. The
experiment. The first day is the longer of the 2 days, for which resulting milk-white latex suspension is vigorously stirred with
instructors should allot 3−4 h. All courses used for trials were 3 a spatula or glass stirring rod, and the polymer coagulates into
h and 50 min in length and comfortably fit the described a rubbery mass (Figure 3b). After rinsing the mass with
procedure. The emulsion polymerization is started first to deionized water, excess water and residual ethanol are kneaded
allow the recommended 2 h of heating. Theoretically, the out, and the material is dried under vacuum at 60 °C for a
emulsion polymerization could be heated for 1.5 h to fit into a minimum of 24 h.
2 h and 50 min lab period, but the yield will be reduced. After During the second laboratory period, students examine the
heating, the product is readily isolated in one step and resulting elastic, lightly colored material (Figure 3c). Swelling
transferred to an aluminum dish for vacuum oven drying for experiments are performed using five or more solvents that
minimally 24 h. range in polarity from nonpolar to polar by tearing five small
During the heating of the emulsion polymerization, the pieces (20−30 mg each) of dried cross-linked polymer and
reactants for the bulk polymerization are combined and heated placing each in a 2 dram vial. Approximately 1.5 mL of any of
on a vial heating block until the next laboratory period. For the five solvents ranging in polarity is added to each vial, and
courses meeting once a week, the bulk polymerization was qualitative observations of the swelling behavior are made over
heated for 1 week out of convenience even though 48 h is the course of an hour.
sufficient time for completion. Bulk Polymerization Procedure
The second day of the experiment, requiring about 1.5−2 h,
is dedicated to exploring the swelling properties of the cross- While the emulsion copolymerization mixture is stirring, the
linked copolymers and preparation of a 1H NMR sample of the bulk polymerization is performed. Student pairs are assigned
copolymer from bulk polymerization. the synthesis of one of three possible copolymers, which vary
in mole feed ratios from 1:1 to 3:1 myr to dbi, respectively, for
Emulsion Polymerization Procedure a total of 5 mmol of the combined monomers. After thorough
The synthesis of the cross-linked myr and dibutyl itaconate mixing of the monomers in a 20 mL scintillation vial, the
copolymer network is conducted in a 20 mL scintillation vial polymerization is initiated by adding 4 mol % benzoyl
with 20 mmol total monomer (myr + dbi) in an aqueous peroxide. During the heating period, the bulk polymerization
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mixture will increase significantly in viscosity to the point that thermodynamics of polymer solvation, and types of inter-
the mixture no longer stirs, producing a sticky, flowing molecular interactions (e.g., fluid−fiber matrix). Selected
copolymer (Figure 4). During the second lab period, students applications of organogels to oil spill cleanup37 and drug
use a small aliquot of their bulk polymerization polymer for 1H delivery38 were also discussed. The second-year organic
NMR analysis. laboratory experiment version (B) focused on an introduction
to polymer structure, terminology, and synthesis. Both versions
of lecture content included discussions of the ubiquitous
presence of plastics in society, their accumulation in the
environment, and strategies for designing more sustainable
polymers.
The two polymer syntheses offer an opportunity to explore
contrasting green reaction media and their associated learning
outcomes (Table 1). The emulsion polymerization illustrates

Table 1. Comparison of Learning Objectives for Emulsion

vs Bulk Copolymerization of β-Myrcene and Dibutyl
Itaconate

Figure 4. Linear/branched poly(myr-co-dbi) from the bulk polymer- Emulsion Copolymerization Bulk Copolymerization
ization reaction. Aqueous emulsion reaction medium Solvent-less reaction
Cross-linked polymers Linear/branched polymers

■
1
Polymer isolation by pH change H NMR composition analysis
Gel formation by swelling Monomer ratio incorporation
HAZARDS study
β-Myrcene is flammable, has a detectable odor, and should be Opaque, stretchy, elastomeric, tacky Clear, viscous, sticky material
handled in the hood with gloves. Dibutyl itaconate is not material
classified as a hazardous substance but may be a skin or eye
irritant. The 190 proof ethanol (acidified with 3% v/v 37% how the application of micelles enables use of water as the
aqueous solution of HCl) for precipitation of the polymer solvent through its hydrophilic exterior with the majority of the
should be stored in a closed container until just prior to use to organic monomers reacting in the hydrophobic, nonpolar
avoid loss of HCl gas over time. This solution is corrosive and interior. Alternatively, no solvent, or reaction in the bulk, yields
should be neutralized before disposal. The precipitated a different copolymerization product. Both reactions model
polymer must also be rinsed with water, and gloves should Green Chemistry Principle 5 in avoiding auxiliaries if possible
be worn when kneading out excess liquid. Ethanol, methanol, and/or use of safer solvents, and Green Chemistry Principle 7,
tetrahydrofuran, hexanes, ethyl acetate, t-butyl methyl ether, which is the use of renewable feedstocks.39
isopropyl alcohol, and acetone are all flammable solvents and Emulsion Polymerization Typical Student Results
potential irritants. Dimethyl sulfoxide can be an irritant upon
ingestion or exposure to skin. Chloroform, chloroform-d, and Typical student yields for the cross-linked network range from
methylene chloride are inhalation hazards and suspected 40% to 65%, which, when applied to a 20 mmol reaction,
carcinogens. Heating of the sealed vials in a reaction block results in approximately 1.5 g of material. Shortening the
should be performed in a hood with the sash closed to serve as heating period to only one hour caused the yield to suffer
a safety shield. considerably (below 20%, 0.5 g). The isolated and dried cross-

■
linked networks readily swell in relatively nonpolar organic
RESULTS AND DISCUSSION solvents, to a lesser degree in moderately polar solvents, and
unnoticeably in water. The dielectric constant (ε) is a measure
Classroom Implementation of a solvent’s ability to insulate charges from one another and
This experiment was successfully implemented in three is a useful metric for predicting polymer−solvent interactions.
different laboratory courses with students working in pairs: Students used this concept to explain the nature of a particular
two second-year undergraduate organic chemistry courses solvent’s interaction with the polymer network and compare
[small university (Augsburg University, spring 2019) and large the predictions to swelling test experiments.
university (University of Minnesota (U of MN) summer In one class implementation, the solvent polarity gradient
2019)] and an advanced polymer elective laboratory (spring was modeled by using chloroform, tetrahydrofuran, acetone,
2019, spring 2020). The second-year undergraduate laboratory dimethyl sulfoxide, and water. In a second course, ethyl
classes were composed of students from a variety of majors and acetate, methyl tert-butyl ether, acetone, methanol, and water
skill sets, only a small percentage of whom were chemistry or were the solvents explored. In yet another iteration, students
chemical engineering majors. The polymer laboratory course were required to design a gradient solvent study from a list of
consisted of exclusively upper division chemistry, chemical 11 solvents. In Figure 5, solvents are shown in ascending
engineering, and materials science majors. As such, laboratory dielectric constants from left to right with each containing a
materials and assignments were tailored to these different piece of cross-linked polymer after 60 min. Substantial swelling
levels of sophistication. occurs in nonpolar solvents, such as hexane (ε = 1.89) and
For the upper division polymer science course (version A), chloroform (ε = 4.81); minimal swelling occurs in moderately
two 50 min lectures introduced subclasses of polymer polar solvents like acetone (ε = 20.7), and no observable
networks, such as elastomers and thermosets, polymer network swelling is detected in water (ε = 80.1).40 The swelled polymer
architecture, the theory of sol fraction and gel fraction, network was less dense than chlorinated solvents like
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Figure 5. Swelling tests of 20−30 mg of cross-linked poly(myr-co-dbi) after ∼60 min in a variety of solvents lined up from left to right with
ascending dielectric constants.

chloroform and dichloromethane, causing it to float. Time Student Survey Results for Spring 2020 Polymer Course
interval photos from 5 to 60 min of Figure 5 are provided in Student experimental data and feedback were collected via a
the SI. Google Form survey and determined to be exempt of IRB
Bulk Polymerization Typical Student Results review (U of MN, IRB ID: STUDY00011272). Tables 2 and 3
The copolymer synthesized by bulk polymerization was
analyzed by 1H NMR spectroscopy in CDCl3. Students used Table 2. U of MN Polymer Laboratory Course (N = 45),
end-group analysis (EGA) to calculate an approximate Mn Spring 2020, Likert Question Results
value relative to the furthest downfield aromatic initiator
Standard
resonance (d, 8.1 ppm) and the integrations of the alkene Statement Averagea Deviation
resonances of poly(myr) (4.9−5.2 ppm) and the ester triplets
The introduction gave a clear overview of the 5.04 0.74
of poly(dbi) (3.8−4.1 ppm) as illustrated in Figure 6. experiment and learning outcomes
Emulsion Polymerization: The experimental 5.27 0.91
procedure was clearly written and easy to follow
Bulk Polymerization: The experimental procedure 5.44 0.66
was clearly written and easy to follow
Radical Polymerization Assignment: My 4.96 0.83
understanding of radical polymerization
mechanisms was enhanced by this assignment
The 1H NMR assignment instructions for the bulk 4.96 1.07
polymer were helpful in my interpretation of the
NMR spectrum
My NMR interpretation skills were enhanced through 4.67 0.98
this experiment
My understanding of cross-linked organogels and the 4.73 1.19
relationship between their swelling behavior in
terms of enthalpy and entropy was improved with
this lab
Lab 4 is a valuable addition to the 4223W curriculum 5.24 0.74
1 a
Figure 6. Key H NMR resonances of poly(myr-co-dbi) used for end- Based on the Likert scale: 1 = strongly disagree; 2 = disagree; 3 =
group analysis. slightly disagree; 4 = slightly agree; 5 = agree; 6 = strongly agree.

are results from a student survey of the U of MN polymer

Representative spectra of the starting materials and a student laboratory course during the spring of 2020. Students
product are available in the SI. Groups of students synthesized performed day 1 of the two syntheses; however, school closure
copolymers with varying ratios of myr and dbi, and their 1H from the COVID-19 pandemic made it necessary to provide
NMR interpretations and data were polled for group photos of the swelling experiment on this second trial. 1H
discussion, adding a discovery-based and cooperative learning NMR spectral data was collected for each student sample and
dimension to the experiment. provided for student workup and analysis. The experimental
Not surprisingly, students’ calculated Mn values varied from results, interpretations, and conclusions were submitted as a
ca. 10 to 30 kg/mol (theoretical Mn values 16−20 kg/mol) due full laboratory report.
to automated sample submissions, student inexperience in Two assignment sheets, one focused on 1 H NMR
performing these calculations, and the previously mentioned interpretation and one focused on the radical mechanism
inaccuracies from radical couplings containing phenyl moieties. and swelling behavior of the copolymers, guided students
It was noted that the use of PTFE-capped vials afforded more through the major learning outcomes and interpretations
consistent Mn values, most likely by minimizing the loss of the required for their reports. As depicted in Table 2, students felt
volatile myr monomer over the course of the reaction. their understanding of radical polymerization, 1H NMR
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Table 3. U of MN Polymer Laboratory Course (N = 45), Spring 2020, Experimental Results

% Reporting
This
Question Expected Result Observation
Emulsion Polymerization Product: Was a trend observed for swelling behavior of “The trend observed was that less polar solvents, that is 100%
the organogel product with solvent dielectric constant/polarity? Describe. solvents with smaller dielectric constant, exhibited greater
swelling”
Bulk Polymer 1H NMR: Compare the feed ratio of monomers used to that myr:dbi 1:1 → feed ratio similara to that calculated from 1H 100%
determined by 1H NMR. NMR spectrum
myr:dbi 2:1→ feed ratio similara to that calculated from 1H 63%
NMR spectrum
myr:dbi 3:1→ feed ratio similara to that calculated from 1H 57%
NMR spectrum
a
Approximated to the nearest whole number

interpretative skills, and understanding of the thermodynamics

of organogel behavior was enhanced through these exercises.
■
*
ASSOCIATED CONTENT
sı Supporting Information
Gratifyingly, 87% of the students agreed or strongly agreed that
the experiment was a “valuable addition” to the polymer The Supporting Information is available at https://pubs.ac-
laboratory course. s.org/doi/10.1021/acs.jchemed.0c00688.
With respect to the experimental results, students uniformly Instructor information, version A for polymer laboratory
observed the expected trend in swelling behavior with polarity/ course, spectra, 7 day kinetics study, version B for
dielectric constant (Table 3). Additionally, data from the 1H organic chemistry laboratory course, and Google Form
NMR spectral analysis indicated that the majority of students survey questions (PDF, DOCX)

■
observed monomer ratios, to the whole number approxima-
tion, to the feed ratios. The 1:1 ratio of monomers was the AUTHOR INFORMATION
most consistent. Student data suggested that feed ratios of 2:1 Corresponding Author
or 3:1 myr:dbi tended to incorporate more myrcene than
expected. See the SI for further discussion on this topic. Jane E. Wissinger − Department of Chemistry, University of
Finally, when students were queried about what three aspects Minnesota, Minneapolis, Minnesota 55455, United States;
of the experiment they appreciated the most from a list of eight orcid.org/0000-0002-9240-3629; Email: jwiss@
possible statements (see SI for full survey questions), the most umn.edu
frequent responses were the following: Authors
• “learning about organogels” (56%), Ethan A. Gormong − Department of Chemistry, University of
• “performing the emulsion polymerization as a new green Minnesota, Minneapolis, Minnesota 55455, United States
medium for reaction” (51%), and Michael T. Wentzel − Department of Chemistry, Augsburg
University, Minneapolis, Minnesota 55454, United States;
• “synthesizing a polymer from potentially renewable orcid.org/0000-0002-1148-2717
feedstocks” (51%). Boen Cao − Department of Chemistry, University of

■
Minnesota, Minneapolis, Minnesota 55455, United States
CONCLUSION Laura N. Kundel − Department of Chemistry, Augsburg
University, Minneapolis, Minnesota 55454, United States
This green chemistry laboratory experiment illustrates the role Theresa M. Reineke − Department of Chemistry, University of
of the reaction medium in the radical copolymerization of Minnesota, Minneapolis, Minnesota 55455, United States;
biobased starting materials. An emulsion polymerization of two orcid.org/0000-0001-7020-3450
sustainably derived monomers uses water as the solvent and
facile precipitation of the cross-linked product by acidification Complete contact information is available at:
of the medium. The resulting organogel material demonstrates https://pubs.acs.org/10.1021/acs.jchemed.0c00688
the swelling behavior in nonpolar organic solvents. In contrast,
a bulk polymerization with varying ratios of the same two Notes
monomers results in a linear/branched copolymer with The authors declare no competing financial interest.
distinguishable sets of protons in the 1H NMR spectrum for
end-group and composition analysis.
These learning outcomes uniquely complemented other
■ ACKNOWLEDGMENTS
This work was funded by the NSF Center for Sustainable
experiments in the authors’ course curricula. However, one Polymers (CHE-1901635). The authors would like to thank
could envision expanding the scope of this chemistry to Letitia Yao for her assistance in NMR spectra acquisition. The
additional explorations in advanced courses to include authors would also like to thank Mckenna Hanson for her
reactivity ratios, kinetics, and/or quantification of gelation suggestions and assistance in the spring 2020 polymer course
capacity. All reactants are readily available with an estimated trial.
low cost of ∼$2.00 per student. According to student feedback,
implementations in introductory organic chemistry laboratory
courses and an upper division undergraduate polymer
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