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26 C&EN ​| ​CEN.ACS.ORG ​| JUNE 18, 2018

POLLUTION​ Chemical ​a

chemical
solutions

problem ​ for ​ Researchers

explore ways to convert plastics into valuable products and to develop

intrinsically recyclable polymers
SAM LEMONICK, ​

T​ C&EN WEST ​he trash solve dimensions: ​COAST

world’s crisis because mounting is social, hard it has to

technical,
many
plastic
and economic. But because chemistry brought the problem into the world, it doesn’t
seem unreasonable to look to chemistry for a solution.
Such a solution will require that today’s chemists figure out how to undo the hard work of their prede- cessors. The
polymers we use as plastics were de- signed to be durable and stable. They’re difficult to break down on purpose.
Now, as the need for finding better ways to han- dle plastic waste grows, some researchers are finding ways to
take plastics apart. Several companies have started up in the past decade to capitalize on these processes. Some
methods return plastics to their monomeric form in the hope that the re- claimed building blocks might replace
fossil fuels as the feedstock for new materials. Other processes yield fuels or additives for other products.
Developing new recycling meth- ods is especially important as the kinds of polymers we use have started to
change. A growing number of prod- ucts and applications, such as cars and wind tur- bines, are relying on the
strength of composite materials made with fiberglass and carbon fiber. These mate- rials use polymer resins that
cannot simply be melted and re-formed like other plastics, and chemists are just starting to develop

U.S. ​methods for recycling them in re-

recycling status ​temperature, and pressure of the search labs.
While existing methods can recycle some pyrolysis
​ process. But other researchers are think-

polymers, like poly(ethylene terephthalate), at Pyrolysis

​ can address the poly- ing about recycling as they
develop

relatively high rates, new technology is needed for styrene

​ contaminant problem. new materials that might not
be

other types.
Faulkner says that because the as difficult to deal with as today’s
desired products vaporize as the plastics. These projects could yield resins and plastics that are intrin-
Key: ​Mass-produced ​Percentage recycled
polymer breaks down, the valuable compounds can be separated from sically easy to recycle.
With such developments, it’s conceivable that, one day, chem-
Poly(ethylene terephthalate)
 4.5 billion kg ​19.5% ​Note: T​ hese data, from EPA, are for the U.S. in 2012 and were ​published in 2014.
some of the dyes, processing aids, pesticides, and food contaminants during the reaction. Later separa- ists might deliver a
plastic bottle that can be reincarnated infinitely.
O​O ​
tion steps are still needed, though,
he says.
Trash to treasure
O ​O​n
Agilyx started out with a more generalized process for turn- ing plastic waste into valuable All plastics are not equal when it
comes to recycling. Polyethylene polymers are the easy-to-handle
High-density polyethylene
5.5 billion kg
10.3% ​products. In 2004, then called
Plas2Fuel, the company built reac- tors to convert mixed plastic waste favorites. Poly(ethylene tere-
into a mixed hydrocarbon product phthalate) (PET) and high-density
called Agilyx Synthetic Crude Oil. polyethylene are the most com-
This mixture can be refined like monly recycled plastics in the U.S.
natural crude oil. Agilyx had built Products made with these plastics are stamped with a recycling sym- bol encircling the
numbers “1” and
Poly(vinyl chloride)
0.9 billion kg
0.0% ​and sold several of these systems to waste management companies across the country before the price “2,”
respectively. When embla-
of oil dropped in 2015, making the zoned with these numbers, called
crude alternative less competi- resin identification codes (RICs),
tive with what comes out of the plastics can be shredded, cleaned,
ground. That’s when the company and remade into new bottles or

started getting its polystyrene re- lower-quality materials like carpet fiber.​On the other end of the scale,
Low-density polyethylene
7.4 billion kg
5.3% ​cycling plant on-line. But Faulkner says with oil prices climbing again and China limiting how much many curbside
recycling programs
plastic waste it will accept from don’t even accept polystyrene (RIC
the U.S. and other countries, Agi- 6), used in food packaging, packing
lyx is seeing renewed interest in peanuts, and disposable cutlery.
its oil production process. Like polyethylene plastics, polysty- rene waste can be processed and
Polypropylene
Other companies are hoping to turn waste plastics into valuable reused to make new products. It
7.2 billion kg
0.6% ​chemical products or feedstocks. A just doesn’t happen often.
lot of the attention has focused on “Plastic foam is troublesome for
polyethylene. most material recovery facilities in
GreenMantra Technologies the country,” says Chris Faulkner,
in Brantford, Ontario, employs a vice president of technology and
thermocatalytic process to turn project management at Agilyx, which has developed a chemical process to recycle
polystyrene.
1​PET​2
HDPE
n​3​Cl

PVC​n

4
LDPE
n

5​PP​nP
​ olystyrene

2.2 billion kg
0.9% ​plastic into waxes for asphalt
roads and roofs, as well as addi- tives for plastics, adhesives, and A big challenge in recycling
coatings. Domenic Di Mondo, polystyrene is contamination. Ac-
vice president of technology and tually, it’s a problem for all plastics recycling; if oily molecules, water,

6​business development, says those

products haven’t typically come and other contaminants make it into recycled materials, the sub-

PS
n​from recycled materials. “We’re
driving a circular economy and in stances can disrupt and weaken
most cases creating products with the polymers. Polystyrene clam-
even higher value than the virgin shell containers and coffee cups
starting material,” he says. are especially likely to be dirty, adding to
company can revert polystyrene back to
When the company started in 2010, its the cost of processing them for recycling.
monomeric styrene, toluene, and ethyl-
first target was polyethylene. GreenMan- Agilyx uses pyrolysis to break down
benzene, which is a precursor to styrene.
tra uses a heterogeneous thermocatalytic polystyrene at its Tigard, Ore., facility,
Faulkner wouldn’t share the exact details
process to turn the plastic into different heating it in an oxygen-deprived envi-
of Agilyx’s process but says it can select
specialty chemical products. Di Mondo says ronment so the plastics don’t burn. The
for different products by tuning the time,
the process requires lower temperatures
JUNE 18, 2018 | ​CEN.ACS.ORG ​| ​C&EN ​27
mostly than pyrolysis and gives the company a high
ty that the polymers alone don’t have.
undamaged by the process (​Green ​degree of control over what gets produced.
The makers of cars, planes, and wind
Chem. ​2017, DOI: 10.1039/c7gc01737e). Di Mondo wouldn’t specify what catalysts
turbine blades rely on these composite
Although Zhang says he has licensed GreenMantra uses, but patent documents
materials because of their high strength-
some of his technology to a Chinese com- related to the polyethylene process de-
to-weight ratio. Unlike plastic bottles,
pany and has had interest from others, scribe it as using an iron- and copper-based
these products don’t get thrown away
these methods are a long way from com- catalyst. Di Mondo says that because the
every day. But when their lifetimes do end,
mercial applications. As a result, Zhang method uses a solid catalyst and no sol-
a lot of thermoset-polymer-based compos-
and others are working on a possibly easi- vents and has a small physical footprint, the
ites get sent to landfills.
er path to recycling thermosets: designing process can be easily scaled up.
“We really have no way of dealing with
new polymers with recycling in mind. The company now processes polyeth-
those polymers,” says Megan Robertson,
Such research could save the chemists a ylene and polypropyl- ene at its Brantford facility, and it plans to open a polystyrene
pilot plant in 2019. But it hasn’t targeted all types of plastic. Chlo- rine in poly(vinyl chlo-
O​
B ​ B O B O ​+ HO
​ ​B​ride) poses too many health and environ- mental risks for most recyclers, even the ones using
mechanical recycling, and Di Mondo says GreenMantra has not focused on PET because existing recycling processes are
sufficient to keep large amounts of it out of the landfill.
a chemical engineer at the University of
lot of trouble trying to break down the ma- Houston.

​O
terials when they’re thrown away. ​The trouble with ​thermosets O
​
HO

OH
Jinwen Zhang, a polymer scientist at
To create these new recycling-ready Washington State University, is one per-
materials, Zhang has zeroed in on the son trying to change that. He’s developed

source of thermoset stability—the cross- ​Another class of polymers called ther-

mild catalytic processes to break down es-
linkers. The materials he’s making are mosets presents a unique set of recycling
ter linkages in amine-cured epoxy resins, a
known as vitrimers, a subset of thermo- challenges. Unlike thermoplastics, such as
type of thermoset that is common in com-
sets with cross-linking bonds that form polyethylene, polystyrene, and polypropyl-
posite materials. Zhang showed he could
and break depending on temperature. In ene that can be melted and molded into
dissolve resin in carbon-fiber scraps from
a way, they act like a glass, malleable at new forms, thermoset polymers harden

a major aircraft maker using a ZnCl​2​-etha-

high temperatures and hardening when irreversibly thanks to covalent cross-linkers
nol catalyst at 250 oC. His group recovered
they cool. If manufacturers used such vit- that bridge polymer strands. These poly-
carbon fibers and un-cross-linked oligo-
rimers as resins in composite materials, mers are increasingly used as resins and
mers from the resin. A scanning electron
the resulting products could be recycled combined with carbon fiber or other mate-
microscope showed that the fibers were
through mechanical processes similar to rials to achieve tensile strength and elastici-
still smooth, indicating that they were
those used for thermoplastics.

160 ​12 atm ​°​C 190 ​1 atm ​°​C ​O ​O

O​
B ​ B ​B ​+ BOH
Boroxine rings can break and easily re-form throughout this thermoset, enabling it to be

reshaped (shown). With boiling water, the thermoset can even revert to its monomers.

O OH ​Polymers like the vitrimer ​shown could be used OH

​ O​O ​as recyclable resins in CH​
​ 3

composite materials. ​OH ​When heated at 12 atm with ethanol and zinc ​O
O
O

+ ​O

O ​O O
​
O HO

OH ​+ ​Residual zinc ​catalyst left over from the polymerization process, this particular vitrimer CH​
​ 3

breaks down at its ester linkages, making it recycling ready.

CH​3
HO
OH ​OH

O​O
O

CH​3 ​HO
OH
O ​O
O

O ​OH
O
O ​O
​
28 C&EN | CEN.ACS.ORG | JUNE 18, 2018

plastics Zhang developed a vitrimer based on

or so-called self-immolative, polymers to
on the market right now (​Science ​eugenol, a renewable phenylpropene found
develop new thermoplastics. Pioneered
2018, DOI: 10.1126/science.aar5498). in nutmeg, cinnamon, and other plants
by chemist Doron Shabat of Tel Aviv Uni-
Chen has long focused on ring-open- (​Macromolecules 2​ 017, DOI: 10.1021/acs.mac-
versity, self-immolative polymers are in-
ing reactions to synthesize polymers. romol.7b01889). When heated with ethanol
herently unstable but have an endcap that
“Ring-opening polymerization is a highly and some zinc catalyst left over from the
prevents their depolymerization. When
effective way of making high-molecu- polymerization process, the vitrimer breaks
triggered by light or a specific chemical,
lar-weight polymers in a short period of down at its ester linkages. Zhang says he’s
the endcap releases and triggers depo-
time,” he says. He recently reported po- also experimented with lignin, which can be
lymerization. “Self-immolative polymers
lymerization of a strained, two-ring mono- extracted from plants, as a vitrimer.
embody that ideal notion of how we could
mer called 3,4-T6GBL into either a linear University of Houston’s Robertson has
potentially recycle plastics,” says Eliza-
or cyclic polymer, depending on the metal also developed recyclable thermosets by
beth Gillies, a chemist at the University of finding renewable chemicals to replace
Western Ontario.

catalyst ​catalyst, used.

​ ​Chen Using
​ ​and his heat
​ ​team and
​ ​can a​ ZnCl​return 2​ ​some or all of bisphenol A (BPA), which is
Gillies developed an ethyl glyoxylate
the polymer to 3,4-T6GBL, a process they used as an epoxy precursor in many resins.
polymer that reverts to its monomer, ethyl
think can be repeated infinitely. The BPA alternatives she’s identified in-
glyoxylate, when the polymer’s endcap is
“The design of the monomer is the key clude epoxidized soybean oil, salicylic acid,
removed via light, hydrogen peroxide, or
for developing chemically recyclable poly- and other plant derivatives. Rob- ertson says key features she looks
O ​for in these biobased molecules are convenient functional groups
n f​ or conversion to epoxides and aromatic rings to provide strength, ​O​mimicking the chemical structure of BPA (​ACS
Sustainable Chem.
O

O
Eng. 2​ 016, DOI: 10.1021/acssusche- meng.6b01343). Because many of these molecules contain esters, Robertson says,
chemical recycling methods under development for polyesters could be applied to her thermoset polymers.
A research group at the Universi- ty of California, Irvine, led by Zhibin Guan
mild acid (​J. Am. Chem. Soc. 2​ 014, DOI:
mers with high depolymerization selectivity has turned to boroxine rings to produce re-
10.1021/ja504727u). In theory, that’s an ideal
and useful materials properties,” he says. cyclable thermosets (​J. Am. Chem. Soc. 2​ 018,
system for a recyclable polymer. In reality,
Ensuring that its core structure can be DOI: 10.1021/jacs.8b03257). These rings
she says, the current versions of these poly-
chemically recycled is the first step, accord- form through reversible reactions between
mers can’t compete with the properties or
ing to Chen. Then adding functional groups boronic acid groups on the monomers, a
cost of PET and other commercial plastics.
can achieve desirable physical properties. property that also allows the thermoset
Scott Phillips, a chemist at Boise State
One of Chen’s former postdocs, Miao to be reshaped and re-formed. In boiling
University, has designed self-immolative
Hong, now developing her own recyclable water, the polymer breaks down to its
polymers with responsive endcaps, in-
polymers at the Shanghai Institute of Or- monomers.
cluding phenoxides and alkoxides (​Green
ganic Chemistry, says chemically recyclable Researchers at IBM are also interested
Chem. 2​ 015, DOI: 10.1039/c5gc01090j).
polymers are the best solution to the prob- in chemically recyclable thermoset poly-
When these molecules get cleaved off the
lem of plastic trash. Such materials could mers because computers use the materials
polymer, they liberate two electrons that
not only make possible the infinitely recy- in many ways, including as insulators for
then cascade down the polymer, selective-
clable plastic bottle but also avoid issues electronics and in the cases that house
ly breaking off monomers.
of quality loss, seen with mechanical recy- them. Jeannette Garcia, a chemist at IBM,
But not all recyclable thermoplastics
cling, and the inability to recover valuable created poly(hexahydrotriazine), which can
need to rely on self-immolation. Eugene
products from biodegradable polymers. be converted back into its monomer with
Y.-X. Chen, a chemist at Colorado State
Still, intrinsically recyclable plastics an acid catalyst that selectively hydrolyzes
University, recently described a fully recy-
are a long way from commercial reality. the hexahydrotriazine linkers (​Science 2​ 014,
clable polymer with properties on par with
Besides technical hurdles, there are also DOI: 10.1126/science.1251484).

economic ones. For manufac- turers, it’s usually easier to ​Rethinking ​thermoplastics O
​
Lanthanum catalyst
Yttrium or zinc catalyst ​O
OO
OO
n
3,4-T6GBL
O​ZnCl​2​, heat ​
ZnCl​2​, heat
O

Eugene Y.-X. Chen of Colorado State University calls this polymer, in its linear (right) ​or cyclical

(left) form, infinitely recyclable, capable of repeatedly breaking down to its monomer (center).
OO

n ​
UV light

HO ​H​2​O​HOOH
use a tried-and-true material than a brand-new one, Garcia ​O O

Depolymerization ​O OO O​says. Although the barrier ​Thermoset polymers

to adoption is high, it isn’t aren’t the only materials
insurmountable. So she and that chemists are designing
= UV-responsive endcap
other chemists continue to to be easily recycled. Some
work on chemical solutions researchers have turned to
Two-electron reactions can degrade self-immolative polymers ​to the rapidly growing prob- the field of
self-destructive,

linearly when a trigger removes the endcap.

lem of plastic trash.
JUNE 18, 2018 | CEN.ACS.ORG | C&EN ​29