Moore group researchers develop new technique to synthesize ring polymers

Date

11/12/19

The Moore group recently published a paper in the Journal of the American Chemical Society that describes a new way of synthesizing ring polymers. These polymers are usually difficult to prepare, and the group hopes that their technique will have the potential to advance both science and technology as it relates to molecular architecture.

Although ring polymers are usually difficult to prepare, a recent paper published by the Moore group shows a new method to easily make large molecular loops.

A polymer is a large molecule that has repeating groups called monomers. These monomers join together like beads on a string, like polyethylene or Teflon. These linear polymer types are easier to make compared to ring polymers.

“Ring polymers are not fully studied because they are difficult to make,” said Qiong Wu, a postdoctoral researcher at the Beckman Institute and an author on the paper.

The most recent paper by the Moore group, “Architecture-Controlled Ring-Opening Polymerization for Dynamic Covalent Poly(disulfide)s,” was published in the Journal of the American Chemical Society and describes a new technique to make ring polymers more easily.

Moore Group members Yuan Jia (left), an undergraduate in chemistry, and Yun Liu, a postdoctoral researcher
Moore group members Yuan Jia (left), an undergraduate in chemistry, and Yun Liu, a postdoctoral researcher, are interested in developing new techniques to synthesize ring polymers.

Usually, rings are made by connecting the two ends of a linear polymer. “This is a very challenging process because the chance of finding two ends among many repeating units is very little,” said Yun Liu, a postdoctoral researcher at Beckman and an author on the paper.

To deal with this challenge, the researchers used disulfide bonds, which contain two sulfur atoms, to make their ring polymers. These bonds are widely present in biology, chemistry, and material sciences. “These bonds are responsive to a lot of stimuli,” Liu said. “We were therefore hoping to control the polymer properties using this bond.”

The researchers use a small ring, which contains a disulfide bond, as the repeating monomer. They then use aryl thiol initiators to crack open the small ring, which further cracks open others to form polymers. The aryl thiols are found to be very special; they allow the chains to rapidly close up before the polymers become too big. And these ring polymers continue to grow by repeating the ring-opening and closing process. “If you use alkyl thiols, the ring cannot close up and you get linear polymers,” Liu said. “The resulting architectures of the polymers are simply controlled by choosing the right initiators.”

Many of the experiments were carried out by Yuan Jia, a chemistry undergraduate in the Moore group.  “It is an easy setup that involves mixing the ingredients at room temperature,” Liu said. “It is also a rapid reaction that can be finished within 10 minutes.”

Qiong Wu is a postdoctoral researcher in the Moore Group
Qiong Wu is a postdoctoral researcher in the Moore group and specializes in the chemistry of ring polymers.

Ring polymers are important wherever it is important to reduce viscosity, such as redox flow batteries. The new polymers offer the additional advantage that the polymer can revert back to monomer in a controlled way. This may be important for longer lasting devices. “Flow batteries often have a loss in performance because the polymer gets degraded,” Liu said. “Since disulfide bonds respond to the redox process, we would like to control the life cycle of the batteries by breaking and reforming the disulfide bonds.”

The Moore group is interested in expanding this class of sulfur-containing polymers. “We make these polymers by opening the small rings (i.e., the monomers), a driving force for the polymerization,” Liu said. “It’s not a lot of driving force and therefore we have to use really high concentration of the monomers. We want to use monomers that are more efficient.”

“Chemists have always worried about how to synthesize polymers from raw materials,” said Jeff Moore, the director of the Beckman Institute, an Ikenberry endowed chair and a professor of chemistry at Illinois. “We are interested in whether we can revert [the polymer] back to raw materials and have a new cycle being again.”

The research was financially supported by the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

“Architecture-Controlled Ring-Opening Polymerization for Dynamic Covalent Poly(disulfide)s,” published in the Journal of the American Chemical Society, is online: DOI: 10.1021/jacs.9b08957


Ananya Sen, Beckman Institute 

Related People

jsmoore

Directory

scheelinAlexander
Scheeline
bjmccallBenjamin
McCall
r-gennisRobert
Gennis
j-gerltJohn
Gerlt
sgranickSteve
Granick
mgruebelMartin
Gruebele
hergenroPaul
Hergenrother
huangRaven
Huang
mlkraftMary
Kraft
leckbandDeborah
Leckband
yi-luYi
Lu
martinisSusan
Martinis
snairSatish
Nair
eoldfielEric
Oldfield
rienstraChad
Rienstra
cmsCharles
Schroeder
zanZaida
Luthey-Schulten
sksScott
Silverman
s-sligarStephen
Sligar
tajkhorsEmad
Tajkhorshid
zhao5Huimin
Zhao
pbraunPaul
Braun
mdburkeMartin
Burke
jeffchanJefferson
Chan
sdenmarkScott
Denmark
dlottDana
Dlott
foutAlison
Fout
agewirthAndrew
Gewirth
ggirolamGregory
Girolami
sohirataSo
Hirata
jainPrashant
Jain
jkatzeneJohn
Katzenellenbogen
nmakriNancy
Makri
douglasmDouglas
Mitchell
jsmooreJeffrey
Moore
murphycjCatherine
Murphy
r-nuzzoRalph
Nuzzo
dimerPhilip
Phillips
rauchfuzThomas
Rauchfuss
joaquinrJoaquín
Rodríguez-López
sarlahDavid
Sarlah
kschweizKenneth
Schweizer
jsweedleJonathan
Sweedler
vddonkWilfred
van der Donk
renskeRenske
van der Veen
vuraweisJosh
Vura-Weis
mcwhite7M.
White
sczimmerSteven
Zimmerman
beakPeter
Beak
wklemperWalter
Klemperer
jdmcdonaJ.
McDonald
pogoreloTaras
Pogorelov
mshen233Mei
Shen
dewoonDavid
Woon
wboulangWilliam
Boulanger
rxbRohit
Bhargava
qchen20Qian
Chen
jianjuncJianjun
Cheng
hy66Hong
Yang
andinomaJosé
Andino Martinez
decosteDonald
DeCoste
thhuangTina
Huang
tjhummelThomas
Hummel
dkellDavid
Kell
doctorkMichael
Koerner
marvilleKelly
Marville
crrayChristian
Ray
tlbrownTheodore
Brown
rmcoatesRobert
Coates
thdjrThom
Dunning
dykstraClifford
Dykstra
j-jonasJiri
Jonas
j-lisyJames
Lisy
shapleyJohn
Shapley
pshapleyPatricia
Shapley
zumdahl2Steven
Zumdahl
ksuslickKenneth
Suslick
jcoxJenny
Cox
sqdSean
Drummond
dmillsDouglas
Mills
sheeleySarah
Sheeley
jsmaddenJoseph
Madden
cknight4Connie
Knight
schulzeHeather
Schulze
kbaumgarKeena
Finney
adkssnBeatrice
Adkisson
trabari1Katie
Trabaris
metclfKara
Metcalf
ljohnso2Lori
Johnson
lchenoweLeslie
Chenoweth
wdedoWolali
Dedo
spinnerDavid
Spinner
plblumPatricia
Simpson
stevens2Chad
Stevens
lsagekarLori
Sage-Karlson
bertholdDeborah
Berthold
kecarlsoKathryn
Carlson
sdesmondSerenity
Desmond
axelson2Jordan
Axelson
scbakerStephanie
Baker
pflotschPriscila
Falagan Lotsch
dgrayDanielle
Gray
thennes2Tom
Hennessey
holdaNancy
Holda
aibarrAlejandro
Ibarra
kimshSung Hoon
Kim
kocherg2Nikolai
Kocherginsky
philipk2Philip
Kocheril
legare2Stephanie
Legare
alewandoAgnieszka
Lewandowska
smccombiStuart
McCombie
jdm5Justin
McGlauchlen
egmooreEdwin
Moore
myerscouKathleen
Myerscough
snalla2Siva
Nalla
romanovaElena
Romanova
roubakhiStanislav
Rubakhin
shvedalxAlexander
Shved
asoudaAlexander
Soudakov
xywangXiying
Wang
kwilhelKaren
Wilhelmsen
wilkeyRandy
Wilkey
silongSilong
Zhang
schlembaMary
Schlembach
trimmellAshley
Trimmell
emccarr2Elise
McCarren
cmercierChristen
Mercier
atimpermAaron
Timperman
niesShuming
Nie
hshanHee-Sun
Han
mmgMutha
Gunasekera
kknightsKatriena
Knights
lisawLisa
Williamson
keinckKatie
Einck
kneef1Kate
Neef
park384Joyce
Park
txiang4Tiange
Xiang
e-rogersElizabeth
Rogers
j-hummelJohn
Hummel
i-paulIain
Paul
munjanjaLloyd
Munjanja
glnGayle
Nelsen
agerardAnna
Gerard
powerskaKimberly
Powers
lolshansLisa
Olshansky
miricaLiviu
Mirica
qingcao2Qing
Cao
lisa3Lisa
Johnson
tinalambTina
Lamb
baronpBaron
Peters
bransle2Sarah
Bransley
dylanmh2Dylan
Hamilton
raegansRaegan
Smith
apm8Angad
Mehta
leverittJohn
Leveritt
xingwXing
Wang
emillrEva
Miller
jmill24Jacqueline
Miller
jlbass2Julia
Bass
ramonarRamona
Rudzinski