Scientists are developing greener plastics – the bigger challenge is moving

them from lab to market

(Article)

Synthetic plastics have made many aspect of modern life cheaper, safer and more
convenient. However, we have failed to figure out how to get rid of them after we use
them.

Unlike other forms of trash, such as food and paper, most synthetic plastics
cannot be easily degraded by live microorganisms or through chemical processes. As a
result, a growing plastic waste crisis threatens the health of our planet. It is embodied by
the Great Pacific Garbage Patch – a massive zone of floating plastic trash, three times
the size of France, stretching between California and Hawaii. Scientists have estimated
that if current trends continue, the mass of plastics in the ocean will equal the mass of
fish by 2050. Making plastics from petroleum also increases carbon dioxide levels in the
atmosphere, contributing to climate change.

Much of my work has been dedicated to finding sustainable ways to make and

break down plastics. My lab and others are making progress on both fronts. But these
new alternatives have to compete with synthetic plastics that have established
infrastructures and optimized processes. Without supportive government policies,
innovative plastic alternatives will have trouble crossing the so-called “valley of death”
from the lab to the market.
 Reflection
(Scientists are developing greener plastics – the bigger challenge is moving them from lab to market)

Plastic problems is very hard to deal with. Since they were introduced in the
1970s, plastic bag have infiltrated our lives. According to Caroline Williams in New
Scientist, globally, we carry home between 500 billion and a trillion every year – about
150 bags for every person on earth, or, to put it another way, a million every minute and
rising. This alarms people in the world as plastics are used only once. Other single-use
plastics include straws, coffee stirrers, soda and water bottles and most food packaging
materials. The country’s so-called “sachet economy” has also contributed to the
proliferation of plastics. Products sold in single-use sachets include instant coffee,
shampoo, cooking oil, food seasoning and toothpaste. Once they’re used, they are just
thrown away. This is kinda sad because all of us contributes to this problem. Along with
reducing unnecessary plastic consumption, Worldwatch says that finding more
environmentally friendly packaging alternatives, and improving product and packaging
design to use less plastic, many challenges associated with plastics could be addressed
by improving management of the material across its life cycle. However, government is
not supporting this idea and scientists having a hard time to introduce it to the people.
 Living polymerization takes 3D printing into fourth dimension
(Journal)

Repairing and reusing plastics and delivering cancer drugs more effectively are
only two of many potential applications of a new 3D/4D printing technology developed
by researchers at the University of New South Wales (UNSW) Sydney in Australia and
the University of Auckland in New Zealand. In a paper in Angewandte Chemie
International Edition, the researchers report the successful merging of 3D printing and
photo-controlled/living polymerization – a chemical process for creating polymers. In
4D printing, a subset of 3D printing, the printed object can transform its shape in
response to certain conditions. The new controlled polymerization method, in which the
researchers use visible light to create an environmentally friendly ‘living’ plastic or
polymer, opens a new world of possibilities for the manufacture of advanced solid
materials.
The research built upon PET-RAFT (photoinduced electron/energy transfer-
reversible addition fragmentation chain transfer) polymerization, a new way to make
controlled polymers using visible light. These polymers can be reactivated for further
growth, unlike traditional polymers which are ‘dead’ after being made. Since this
development, the technology has expanded and proven useful for making well-
controlled molecules for many applications, including drug delivery. Lead author Cyrille
Boyer at UNSW Sydney said that his team's latest breakthrough involved the
development of a new 3D printing system that takes advantage of PET-RAFT
polymerization to allow 3D printed materials to be easily modified after printing.
"4D printing is a subset of 3D printing. But with 4D printing, the 3D-printed
object can change its shape and chemical or physical properties and adapt to its
environment," Corrigan said. "In our work, the 3D-printed material could reversibly
change its shape when it was exposed to water and then dried. For example, the 3D
object starts as a flat plane and when exposed to certain conditions it will start to fold –
that's a 4D material. So, the fourth dimension is time."
The researchers are hopeful that their new 3D/4D printing process will lead to
the production of functional materials able to solve many of the problems facing society
today. According to Boyer, the new method has a multitude of applications for everyday
items – particularly if a deformed or broken object needs to be repaired or modified.
"The main application is of course recycling, because instead of using a plastic object
once, it can be repaired and reused," he said. "For ordinary recycling you take the
materials away and have to reconstruct them, but for the new 'living' material it will be
able to repair itself. For example, if you want to put the UNSW logo on a mug, you can
modify the surface of the object and grow the polymers to show UNSW because the
object is not dead; it's a living object and can continue to grow and expand."
 "Current 3D printing approaches are typically limited by the harsh conditions
required, such as strong UV light and toxic chemicals, which limits their use in making
biomaterials," he said. "But with the application of PET-RAFT polymerization to 3D
printing, we can produce long polymer molecules using visible light rather than heat,
which is the typical polymerization method. Using heat above 40°C kills cells, but for
visible light polymerization we can use room temperature, so the viability of the cells is
much higher."
Boyer added that their new technique would allow commercial and non-expert
operators to produce materials with seemingly endless properties and applications. "We
want to explore our system to find and address any limitations to allow for better uptake
and implementation of this technology," he said. "There is so much we can do by
combining 3D and 4D printing with controlled polymerization to make advanced and
functional materials for many applications to benefit society."
 Reflection
(Living polymerization takes 3D printing into fourth dimension)

In recent years, 3D printer devices became cheaper, better, more useful and important
with each day that passed. Their growing importance and the features offered have
made them to become increasingly widespread. In this paper, we have presented and
analysed the impact of 3D printing technology on the society and economy. After
presenting, in the introduction, a brief history of 3D printing, in the second section we
have depicted the additive technology and the materials used in rapid prototyping. In
the third section, we have highlighted the main advantages and limitations of the 3D
printing technology, while in the fourth section we have made a survey of the most
significant existing 3D printing solutions. We have compared these 3D printing
solutions, taking into account their technical specifications and prices. One can conclude
that the 3-D printing technology’s importance and social impact increase gradually day
after day and significantly influence the human’s life, the economy and modern society.
The article is also a reflection on a specific set of digital data practices and the meaning
of such data to individuals. In analysing these new forms of human bodies, I draw on
sociomaterialist perspectives as well as the recent work of scholars who have sought to
theorise selfhood, embodiment, place and space in digital society and the nature of
people’s interactions with digital data. I argue that these objects incite intriguing ways of
thinking about the ways in digital data on embodiment, health and illnesses are
interpreted and used across a range of contexts. The article ends with some speculations
about where these technologies may be headed and outlining future research directions.
Orange is the new black gold: how peel could replace crude oil in plastics
(Article News via Science Direct)

Orange juice, both delicious and nutritious, is enjoyed by millions of people

across the world every day. However, new research indicates that it could have potential
far beyond the breakfast table. The chemicals in orange peel could be used as new
building blocks in products ranging from plastics to paracetamol – helping to break our
reliance on crude oil.

Today’s society is totally reliant on the chemicals and materials that are obtained
from our diminishing supply of fossil fuels. As such, there is an increasing global focus
on the development of renewable chemical feedstocks from a variety of sustainable
sources such as sugarcane and fatty acids in the production of biofuels. And the
chemically rich essential oils contained within waste citrus peels are another such
source that is being investigated with real zest.

This is promising, as the orange juice industry uses highly inefficient and
wasteful juicing processes, with almost 50% of the fruit thrown away. This gives a real
opportunity, then, to develop a sustainable supply of chemicals from the diverse and
plentiful molecules locked within the peels.

Limonene certainly has the potential to become an important component of a

bio-based chemical industry. The field however is still in its infancy with no commercial
limonene-based plastics on the marketplace. Issues that need to be addressed include a
finding a reliable supply and greener processing – many of the above processes for
manufacturing polymers using limonene still require petrochemicals as additives.
 Reflection
(Orange is the new black gold: how peel could replace crude oil in plastics)

According to another journal I read before, a sustainable polymer derived from

corn starch has been commercially available for the past decade primarily as disposable
packaging. Other plastic building blocks have being sourced from plant materials such
as Coca Cola’s Plant Bottle technology. These alternative renewable sources can contain
large amounts of oxygen atoms giving the resulting polymers different but
complementary properties to limonene-based plastics.

The availability of limonene is also dictated by the weather in Florida and Brazil
and by our desire to drink orange juice. Even if all of the currently available limonene
from citrus waste was made into polymers it wouldn’t make a dent in global levels of
plastic production.

However, if we could make the most of all the citrus that gets wasted, the amount
of available limonene would increase. More efficient extraction methods will also boost
availability as will advances in biotechnology. My team is also investigating how to
modify bacteria to feed off municipal waste and excrete limonene as its only product.
These sort of advances may be a way off but they are important first steps to breaking
our dependence on crude oil – molecules such as limonene will no doubt be a bright
part of our future.
 Biomimetic radical polymerization via cooperative assembly of
segregating templates
(News Article)

Segregation and templating approaches have been honed by billions of years of evolution
to direct many complex biological processes. Nature uses segregation to improve biochemical
control by organizing reactants into defined, well-regulated environments, and the transfer of
genetic information is a primary function of templating. The ribosome, wherein messenger RNA
is translated into polypeptides, combines both techniques to allow for ideal biopolymer
syntheses. Herein is presented a biomimetic segregation/templating approach to synthetic
radical polymerization. Polymerization of a nucleobase-containing vinyl monomer in the
presence of a complementary block copolymer template of low molecular weight yields high
molecular weight (Mw up to ~400,000 g mol−1), extremely low polydispersity (≤1.08) daughter
polymers. Control is attained by segregation of propagating radicals in discrete micelle cores
(via cooperative assembly of dynamic template polymers). Significantly reduced bimolecular
termination, combined with controlled propagation along a defined number of templates,
ensures unprecedented control to afford well-defined high molecular weight polymers.

Template polymerization refers to how monomer units are essentially “lined up” in well-
defined “slots” along a pre-formed polymer (e.g. via H-bonding), and subsequently polymerized
along this template. Compartmentalization (the nanoreactor concept) refers to how the
progression of a radical polymerization can change if it is carried out in a confined nanospace,
such as within a micelle or polymer nanoparticle. When conducted within nanoreactors, a
radical polymerization may be influenced by the segregation effect and/or the confined space
effect. Under appropriate circumstances, the kinetics within nanoreactors can be exploited to
essentially exert some control over the polymerization. More specifically, the extent of
bimolecular termination can be reduced if radicals are segregated in separate nanoreactors.
 Reflection
(Biomimetic radical polymerization via cooperative assembly of segregating templates)

The idea of this project is thus to create micelles, where template polymerization occurs
within the micelles, thereby combining the concepts of template polymerization and
compartmentalization. One of the long-standing challenges in polymer chemistry is to prepare
polymer of tailor-made well-controlled microstructure. Nature synthesizes proteins and nucleic
acids via polymerization methods using well-regulated, segregated templates. This project is
concerned with a new polymerization methodology that mimics this approach by conducting a
radical polymerization based on template polymerization within so called nanoreactors. Block
copolymer templates are designed to assemble in a biomimetic fashion to segregate the radical
polymerization of complementary nucleobase containing vinyl monomers, to yield high
molecular weight, low polydispersity polymer chains with unprecedented control over structure
(without relying on controlled/living radical polymerization such as RAFT etc).
 Advancement in polymer synthesis
(News Article: Headline)

Researchers have developed a new method of polymer synthesis based on

two processes: “segregation” and “templating”. These processes have evolved naturally
billions of years ago.Segregation is a process that assists with biochemical regulation
and templating involves the transfer of genetic information.Polymers vary in their
functions and have different properties. The ability to accurately synthesise polymers
will have major applications for nano-medicine.
 Reflection
(Advancement in polymer synthesis)

The news article’s report on advances in polymeric waveguide technologies

developed worldwide for the telecom and datacom markets, and we describe in detail
one such technology developed at AlliedSignal. Optical polymers are versatile materials
that can be readily formed into planar single-mode, multimode, and microoptical
waveguide structures ranging in dimensions from under a micrometer to several
hundred micrometers. These materials can be thermoplastics, thermosets, or
photopolymers, and the starting formulations are typically either polymers or oligomers
in solution or liquid monomers.
 Polymers: the bridge between textiles and DDS
(News Article)

Polymer science has been the backbone of pharmaceuticals for decades. The
amalgamation of polymer science with pharmaceutical science led to a quantum leap in terms of
‘novelty’ (flexibility in physical state, shape, size and surface) in DDS design and development.
The market for controlled-release polymer systems, which extends beyond drug delivery, is now
estimated at $60 billion annually worldwide and its systems are used by over 100 million people
each year.15 Growth of world consumption of technical textiles is expected to come primarily
from nonwoven materials, especially spunlaid products, which are made from polymers rather
than fibers or filament yarns.

Polymers for use in biotextiles should possess three specific properties. The first is
their ability to be spun. This is the most important characteristic for the production of fibers.
The second property is their elasticity. This is fundamental when a variation of the shape and/or
the dimension of the DDS is required during its application. The final property is their
biocompatibility. This is vitally important for the preparation of oral DDSs, implantable DDSs,
etc. Fibers for TDDSs are derived from all types of filament-forming polymers and natural
fibers, and because of this they are used ex vivo.16 A number of other factors must be taken into
account, including how polymers influence a drug’s properties, drug delivery routes and desired
drug release profiles.
 Reflection
(Polymers: the bridge between textiles and DDS)

Textile fibers have been used to make cloth for several thousand years. First
manufactured fiber was produced commercially on 1885 and was produced from fibers of plants
and animals. Wool, flax, cotton and silk were commonly used textile fibers. Textile fibers are
characterized by the flexibility, fineness and large length in relation to the maximum transverse
dimension. DDS or doctor dental surgery,
when we classify dental restorative materials we see three major groups. These are metals,
ceramics and polymers. Polymers have a major role in most areas of restorative dentistry. The
most widely used impression materials are elastomeric polymers. Another major type of
polymeric dental material is the composite filling material for anterior teeth. Removable
dentures are made from acrylic resin and other polymers. Additional applications as polymers
include soft liners, cements, pit and fissures sealant. Both textile and in dentistry polymer has a
big role and importance to them.
 Process makes polymers truly plastic
(Journal)

Just as a chameleon changes its color to blend in with its environment, Duke University
engineers have demonstrated for the first time that they can alter the texture of plastics on
demand, for example, switching back and forth between a rough surface and a smooth one.

By applying specific voltages, the team has also shown that it can achieve this control over large
and curved surface areas.

Scientists have long been able to create different patterns or textures on plastics through a
process known as electrostatic lithography, in which patterns are "etched" onto a surface from
an electrode located above the polymer. However, once the patterns have been created by this
method, they are set permanently.

The findings follow Zhao's earlier studies, which for the first time captured on videotape how
polymers react to changing voltages. Those experiments showed that as the voltage increases,
polymers tend to start creasing, finally leading to large craters. This explained in physical terms,
for example, why polymers used to insulate electric wires tend to fail over time. The new
lithography strategy takes useful insights from this failure mechanism.

On a more fanciful note, Zhao described the possibility of creating rubber gloves whose
fingerprints could be changed on demand.

"The changeable patterns we have created in the laboratory include circles and straight and
curved lines, which are basic elements of fingerprints," Zhao said. "These elements can be
dynamically patterned and changed on a glove surface that covers fingertips.

"A spy's glove may be cool, but probably not for everyone," Zhao said. "However, the same
technology can produce gloves with on-demand textures and smoothness tuned for various
applications, such as climbing and gripping. Furthermore, surfaces capable of dynamically
changing patterns are also useful for many technologies, such as microfluidics and camouflage."
 Reflection
(Process makes polymers truly plastic)

On a more fanciful note, Zhao described the possibility of creating rubber gloves
whose fingerprints could be changed on demand. Other potential usages of the new
method include creating surfaces that are self-cleaning and water-repellent, or even as
platforms for controlled-release drug-eluting devices. Polymer materials show great
potential for easily fabricated display devices, Development of these materials requires
control of both electronic and optical properties. They discuss an idea in which
semiconducting polymer mirrors that also transport charge are used to control the
optical emission from light emitting diodes. This work opens the way for new polymer
optoelectronic devices.
Plastics, the environment and human health: current consensus
and future trends
(Journal)

Plastics have transformed everyday life; usage is increasing and annual production is
likely to exceed 300 million tonnes by 2010. In this concluding paper to the Theme Issue on
Plastics, the Environment and Human Health, we synthesize current understanding of the
benefits and concerns surrounding the use of plastics and look to future priorities, challenges
and opportunities. It is evident that plastics bring many societal benefits and offer future
technological and medical advances. However, concerns about usage and disposal are diverse
and include accumulation of waste in landfills and in natural habitats, physical problems for
wildlife resulting from ingestion or entanglement in plastic, the leaching of chemicals from
plastic products and the potential for plastics to transfer chemicals to wildlife and humans.
However, perhaps the most important overriding concern, which is implicit throughout this
volume, is that our current usage is not sustainable. Around 4 per cent of world oil production is
used as a feedstock to make plastics and a similar amount is used as energy in the process. Yet
over a third of current production is used to make items of packaging, which are then rapidly
discarded. Given our declining reserves of fossil fuels, and finite capacity for disposal of waste to
landfill, this linear use of hydrocarbons, via packaging and other short-lived applications of
plastic, is simply not sustainable. There are solutions, including material reduction, design for
end-of-life recyclability, increased recycling capacity, development of bio-based feedstocks,
strategies to reduce littering, the application of green chemistry life-cycle analyses and revised
risk assessment approaches. Such measures will be most effective through the combined actions
of the public, industry, scientists and policymakers. There is some urgency, as the quantity of
plastics produced in the first 10 years of the current century is likely to approach the quantity
produced in the entire century that preceded.
 Reflection
(Plastics, the environment and human health: current consensus and future trends)

The durability of plastics and their potential for diverse applications, including
widespread use as disposable items, were anticipated, but the problems associated with waste
management and plastic debris were not. This paper synthesizes current understanding of the
benefits and concerns surrounding the use of plastics and looks to challenges, opportunities and
priorities for the future. The content draws upon papers submitted to this Theme Issue on
Plastics, the Environment and Human Health together with other sources. While selected
citations are given to original sources of information, we primarily refer the reader to the
discussion of a particular topic, and the associated references, in the Theme Issue papers. Here,
we consider the subject from seven perspectives: plastics as materials; accumulation of plastic
waste in the natural environment; effects of plastic debris in the environment and on wildlife;
effects on humans; production, usage, disposal and waste management solutions; biopolymers,
degradable and biodegradable polymer solutions; and policy measures.
 New polymer coating helps reduce the need for toilet flushing
(News Article)

Every day, more than 141 billion liters of water are used just to flush toilets. With millions of
global citizens experiencing water scarcity, what if that amount could be reduced by 50%? This
possibility could now arise from research conducted at Penn State and reported in a paper in
Nature Sustainability.
"Our team has developed a robust bio-inspired, liquid, sludge- and bacteria-repellent coating
that can essentially make a toilet self-cleaning," said Tak-Sing Wong, professor of engineering
and associate professor of mechanical engineering and biomedical engineering at Penn State.
In the Wong Laboratory for Nature Inspired Engineering, housed within the Department of
Mechanical Engineering and the Materials Research Institute, researchers have shown that this
coating can dramatically reduce the amount of water needed to flush a conventional toilet,
which usually requires 6 liters.
Co-developed by Jing Wang, a doctoral graduate from Wong's lab, the liquid-entrenched smooth
surface (LESS) coating is a two-step spray that, among other applications, can be applied to a
ceramic toilet bowl. The first spray, created from molecularly grafted polymers, is the initial step
in building an extremely smooth and liquid-repellent foundation.
"When it dries, the first spray grows molecules that look like little hairs, with a diameter of about
1,000,000 times thinner than a human's," Wang explained. While this first application creates
an extremely smooth surface, the second spray infuses a thin layer of lubricant around those
nanoscopic ‘hairs’ to create a super-slippery surface.
"When we put that coating on a toilet in the lab and dump synthetic fecal matter on it, it (the
synthetic fecal matter) just completely slides down and nothing sticks to it (the toilet)," Wang
said.
"Poop sticking to the toilet is not only unpleasant to users, but it also presents serious health
concerns," Wong said. However, if a waterless toilet or urinal used the LESS coating, the team
predicts these types of fixtures would be more appealing and safer for widespread use.
"Our goal is to bring impactful technology to the market so everyone can benefit," Wong said.
"To maximize the impact of our coating technology, we need to get it out of the lab." Looking
forward, the team hopes spotLESS Materials will play a role in sustaining the world's water
resources and continue expanding the reach of their technology. "As a researcher in an academic
setting, my goal is to invent things that everyone can benefit from," Wong said. "As a Penn
Stater, I see this culture being amplified through entrepreneurship, and I'm excited to
contribute."
 Reflection
(New polymer coating helps reduce the need for toilet flushing)

With this novel slippery surface, the toilets can effectively clean residue from inside the
bowl and dispose of the waste with only a fraction of the water previously needed. The
researchers also predict the coating could last for about 500 flushes in a conventional toilet
before a reapplication of the lubricant layer is needed. To address these issues in both the US
and around the world, Wong and his collaborators Wang, Birgitt Boschitsch and Nan Sun, all
mechanical engineering alumni, began a start-up venture. With support from various funding
bodies, their company, spotLESS Materials, is already bringing the LESS coating to market.
While other liquid-infused slippery surfaces can take hours to cure, the LESS two-step coating
takes less than five minutes. In their experiments, the researchers also found that the surface
effectively repelled bacteria, particularly ones that spread infectious diseases and unpleasant
odors. If it were widely adopted in the US, this coating could help direct critical resources
toward other important activities, such as to drought-stricken areas or to regions experiencing
chronic water scarcity, said the researchers. Driven by these humanitarian solutions, the
researchers also hope their work can make an impact in the developing world. The technology
could be used within waterless toilets, which are used extensively around the world.
 Storing renewable energy even when there is no sun or wind
(News Article)

A team from the US Department of Energy’s Berkeley Lab, along with international
collaborators, have developed a new type of versatile and affordable grid battery membrane for
flow batteries that can store renewable energy. Flow batteries store electricity in tanks of liquid
electrolyte, and could help enhance how an electrical grid can be powered by renewable energy.

A simple empirical model that compared battery performance to that of various

membranes and the effect that a range of battery membranes can have on the lifetime of a flow
battery was also developed. It helps show the need for a membrane for different battery
chemistries, with the technology and model for the battery’s performance and lifetime
improving the assessment of each battery component. The membrane screen significantly
reduces the time taken to identify how long a battery will last once the entire cell has been
assembled.

In addition, the AquaPIM technology does not use fluorinated polymer membranes, an
expensive part of the battery, making them more affordable. As study leader Brett Helms points
out, “Our AquaPIM membrane technology is well-positioned to accelerate the path to market for
flow batteries that use scalable, low-cost, water-based chemistries”.

The researchers now hope to apply AquaPIM membranes across a wider range of
aqueous flow battery chemistries, such as metals and inorganics and organics and polymers, and
to assess if the membranes are compatible with other aqueous alkaline zinc batteries.
 Reflection
(Storing renewable energy even when there is no sun or wind)

Although the majority of grid battery chemistries comprising highly alkaline electrodes,
with a positively charged cathode and a negatively charged anode, current membranes are
developed for acidic chemistries, such as the fluorinated membranes used in fuel cells and not
for alkaline flow batteries. The team found that the grid battery membranes modified with an
“amidoxime” permitted ions to quickly travel between the anode and cathode. AquaPIM
membranes lead to stable alkaline cells, with prototypes retaining the integrity of the charge-
storing materials in the cathode as well as the anode. When the membranes were characterized,
it was found that such characteristics were universal across AquaPIM variants, and that the
structure of the polymers in the membrane were very resistant to pore collapse under highly
basic conditions in alkaline electrolytes.
 Catalyst switching creates one material out of four polymers
(News Article)

By juggling four different chemical reactions in a single flask, researchers at King

Abdullah University of Science and Technology (KAUST) in Saudi Arabia have combined four
polymers to form a single multicrystalline substance. Materials that seamlessly combine
multiple polymers in this way potentially merge the best aspects of each material.

“Double-crystalline block copolymers have myriad applications, such as for energy

storage, tissue engineering and drug delivery,” says Viko Ladelta, a member of Hadjichristidis’s
team.

“But the synthetic procedures are very demanding,” Ladelta explains. “It was difficult to
perform even the synthesis of double-crystalline block copolymers, due to the incompatibility of
the monomers and catalysts.” Making materials that incorporate four different monomers in
four chemically different blocks – tetra-crystalline tetrablock quarterpolymers – leads to even
greater incompatibility.

“This strategy saves time and also avoids the risk of any contamination of the polymer,”
Ladelta says.

Hadjichristidis’s group have previously used catalyst switching between organic catalysts
to create double-crystalline and triple-crystalline polymers. Now, for the first time, the team has
shown that it is possible to adjust the pH and switch from an organic catalyst to a metal catalyst
to make a tetracrystalline tetrablock quarterpolymer.

“Our plan is to expand the scope of the catalyst switch strategy to other types of
polymerization,” Ladelta says. “We will synthesize more complex multicrystalline polymers and
collaborate with polymer physicists to understand the physical properties to guide us toward
real-world applications.”
 Reflection
(Catalyst switching creates one material out of four polymers)

Polymers are long-chain molecules made by connecting together small molecule

‘monomeric units’, like a string of identical beads on a necklace. Recently, researchers have
developed ways to make ‘double-crystalline’ copolymers, in which one part of the chain is made
from one kind of monomer and the other part is made from another monomer. Adding together
an even greater number of different polymer sections has the potential to produce materials
with even more advanced properties. To help overcome this incompatibility problem,
Hadjichristidis and his team developed a novel process they call catalyst switching. Most organic
catalysts used to promote a polymer-forming reaction known as ring-opening polymerization
are either acids or bases. By adding one type of monomer to the polymer chain under basic
conditions, then adjusting the pH and using a second catalyst to add the next monomer,
Hadjichristidis and his team were able to create multiblock polymers in a single reaction pot.
 Novel monomer produces more degradable polymers
(News Article)

Chemists at the Massachusetts Institute of Technology (MIT) have devised a way to synthesize polymers
that can break down more readily in the body and in the environment.

The MIT research team has come up with a way to make these polymers more degradable by adding a
novel type of building block to the backbone of the polymer. This new building block, or monomer, forms
chemical bonds that can be broken down by weak acids, bases, and ions such as fluoride.

"We believe that this is the first general way to produce ROMP polymers with facile degradability under
biologically relevant conditions," says Jeremiah Johnson, an associate professor of chemistry at MIT and
senior author of a paper on this work in Nature Chemistry. "The nice part is that it works using the
standard ROMP workflow; you just need to sprinkle in the new monomer, making it very convenient."

This building block could be incorporated into polymers for a wide variety of uses, including not only
medical applications but also synthesis of industrial polymers that would break down more rapidly after
use, the researchers say.

The most common building blocks of ROMP-generated polymers are molecules called norbornenes, which
contain a ring structure that can be easily opened up and strung together to form polymers. Molecules
such as drugs or imaging agents can be added to norbornenes before the polymerization occurs.

Johnson's lab has used this synthesis approach to create polymers with many different structures,
including linear polymers, bottlebrush polymers and star-shaped polymers. These novel materials could
be used for delivering many cancer drugs at once, or carrying imaging agents for magnetic resonance
imaging (MRI) and other types of imaging.

To circumvent that issue, Johnson's lab has focused on developing small polymers, on the order of about
10nm in diameter, which could be cleared from the body more easily than larger particles. Other chemists
have tried to make the polymers degradable by using building blocks other than norbornenes, but these
building blocks don't polymerize as efficiently. It's also more difficult to attach drugs or other molecules to
them, and they often require harsh conditions to degrade. The researchers came upon a possible solution
through work being done for another project by MIT postdoc Peyton Shieh. He was looking for new ways
to trigger drug release from polymers, when he synthesized a ring-containing molecule that is similar to
norbornene but contains an oxygen-silicon-oxygen bond. The researchers discovered that this kind of
ring, called a silyl ether, can also be opened up and polymerized with the ROMP reaction, leading to
polymers with oxygen-silicon-oxygen bonds that degrade more easily. Thus, instead of using this silyl
ether for drug release, the researchers decided to try incorporating it into the polymer backbone to make
it degradable. They found that by simply adding the silyl-ether monomer in a 1:1 ratio with norbornene
monomers, they could create similar polymer structures to those previously made, with the new monomer
incorporated fairly uniformly throughout the backbone. But now, when exposed to a slightly acidic pH,
around 6.5, the polymer chain begins to break apart.
 Reflection
(Novel monomer produces more degradable polymers)

A chemical reaction called ring-opening metathesis polymerization (ROMP) is handy for

building novel polymers for various uses, such as nanofabrication, high-performance resins, and
delivering drugs or imaging agents. However, one downside to this synthesis method is that the
resulting polymers do not naturally break down in natural environments, such as inside the
body. In tests in mice, the researchers found that during the first week or two, the degradable
polymers showed the same distribution through the body as the original polymers, but they
began to break down soon after that. After six weeks, the concentrations of the new polymers in
the body were between three and 10 times less than the concentrations of the original polymers,
depending on the exact chemical composition of the silyl-ether monomers that the researchers
used. The researchers have also started working on adding the new monomers to industrial
resins, such as plastics or adhesives. They believe it would be economically feasible to
incorporate these monomers into the manufacturing processes of industrial polymers to make
them more degradable, and they are now working with Millipore-Sigma to commercialize this
family of monomers and make them available for research. A new type of polymer designed by
chemists at MIT incorporates a special monomer (yellow) that helps the polymers to break down
more easily under certain conditions. The findings suggest that adding this monomer to
polymers for drug delivery or imaging could help them be cleared from the body more quickly.
WE MADE PLASTIC. WE DEPEND ON IT. NOW WE’RE DROWNING IN IT.
(Journal)

If plastic had been invented when the Pilgrims sailed from Plymouth, England, to North
America—and the Mayflower had been stocked with bottled water and plastic-wrapped snacks—
their plastic trash would likely still be around, four centuries later.

We should give thanks that the Pilgrims didn’t have plastic, I thought recently as I rode a
train to Plymouth along England’s south coast. I was on my way to see a man who would help
me make sense of the whole mess we’ve made with plastic, especially in the ocean.

No one knows how much unrecycled plastic waste ends up in the ocean, Earth’s last sink.
Meanwhile, ocean plastic is estimated to kill millions of marine animals every year. Nearly 700
species, including endangered ones, are known to have been affected by it. Some are harmed
visibly—strangled by abandoned fishing nets or discarded six-pack rings. Many more are
probably harmed invisibly. Marine species of all sizes, from zooplankton to whales, now eat
microplastics, the bits smaller than one-fifth of an inch across. And yet there’s a key difference:
Ocean plastic is not as complicated as climate change. There are no ocean trash deniers, at least
so far. To do something about it, we don’t have to remake our planet’s entire energy system.

In the years since his first beach cleanup, Thompson has helped provide the beginnings
of an answer: The missing plastic is getting broken into pieces so small they’re hard to see. In a
2004 paper, Thompson coined the term “microplastics” for these small bits, predicting—
accurately, as it turned out—that they had “potential for large-scale accumulation” in the ocean.
When we met in Plymouth last fall, Thompson and two of his students had just completed a
study that indicated it’s not just waves and sunlight that break down plastic. In lab tests, they’d
watched amphipods of the species Orchestia gammarellus—tiny shrimplike crustaceans that are
common in European coastal waters—devour pieces of plastic bags and determined they could
shred a single bag into 1.75 million microscopic fragments. The little creatures chewed through
plastic especially fast, Thompson’s team found, when it was coated with the microbial slime that
is their normal food. They spat out or eventually excreted the plastic bits.

As Thompson and I talked about all this, a day boat called the Dolphin was carrying us
through a light chop in the Sound, off Plymouth. Thompson reeled out a fine-mesh net called a
manta trawl, usually used for studying plankton. We were close to the spot where, a few years
earlier, other researchers had collected 504 fish of 10 species and given them to Thompson.
Dissecting the fish, he was surprised to find microplastics in the guts of more than one-third of
them. The finding made international headlines.
 Reflection
(WE MADE PLASTIC. WE DEPEND ON IT. NOW WE’RE DROWNING IN IT.)

Microplastics have been found everywhere in the ocean that people have looked, from
sediments on the deepest seafloor to ice floating in the Arctic—which, as it melts over the next
decade, could release more than a trillion bits of plastic into the water, according to one
estimate. On some beaches on the Big Island of Hawaii, as much as 15 percent of the sand is
actually grains of microplastic. Kamilo Point Beach, the one I walked on, catches plastic from
the North Pacific gyre, the trashiest of five swirling current systems that transport garbage
around the ocean basins and concentrate it in great patches. At Kamilo Point the beach is piled
with laundry baskets, bottles, and containers with labels in Chinese, Japanese, Korean, English,
and occasionally, Russian. On Henderson Island, an uninhabited coral island in the South
Pacific, researchers have found an astonishing volume of plastic from South America, Asia, New
Zealand, Russia, and as far away as Scotland.

How did we get here? When did the dark side of the miracle of plastic first show itself?
It’s a question that can be asked about many of the marvels of our technological world. Since
helping the Allies win World War II—think of nylon parachutes or lightweight airplane parts—
plastics have transformed all our lives as few other inventions have, mostly for the better.
They’ve eased travel into space and revolutionized medicine. They lighten every car and jumbo
jet today, saving fuel—and pollution. In the form of clingy, light-as-air wraps, they extend the
life of fresh food. In airbags, incubators, helmets, or simply by delivering clean drinking water to
poor people in those now demonized disposable bottles, plastics save lives daily.
 Pasig river
(Journal)

The Pasig River once flowed majestically through downtown Manila, capital of the
Philippines, and emptied into pristine Manila Bay. It was a treasured waterway and civic point
of pride. It’s now listed among the top 10 rivers in the world that convey plastic waste to the sea.
As many as 72,000 tons flow downstream each year, mostly during the monsoon. In 1990 the
Pasig was declared biologically dead.

The Pasig River Rehabilitation Commission, established in 1999, is working to clean up

the river, with some signs of success. Jose Antonio Goitia, the commission’s executive director,
says he is optimistic that the Pasig could be restored someday, although he acknowledges he has
no easy way of doing that. “Maybe the best thing to do is ban plastic bags,” he says.

The remaining challenges are clearly visible every day. The river is fed by 51 tributaries,
some of them overflowing with plastic waste from squatter settlements that cantilever
precariously over creek banks. A tributary near Chinatown, where rickety shanties are wedged
between modern buildings, is so choked with plastic debris you can walk across it, forgoing the
footbridge. Manila Bay’s beaches, once recreational respites for greater Manila’s 13 million
residents, are littered with garbage, much of it plastic. Last fall Break Free From Plastic, a
coalition including Greenpeace and other groups, cleaned a beach on Freedom Island, which is
advertised as an ecotourism district; volunteers picked up 54,260 pieces of plastic, from shoes to
food containers. By the time I visited a few weeks later, the beach was littered again with bottles,
wrappers, and shopping bags.
The scene in Manila is typical of large, overcrowded urban centers across Asia. The Philippines
is a densely populated nation of 105 million people that is still struggling with the most basic
public health issues, including waterborne diseases such as typhoid and bacterial diarrhea. It’s
no surprise that it has trouble managing the explosion of plastic garbage. Manila has a
metropolitan garbage collection system that stretches across 17 separate local governments—a
source of chaos and inefficiency. In 2004 the region was already running out of land to safely
dump garbage. The shortage of landfill space, and thus the crisis, continues today.

Every day Siena rides a rickety bicycle beyond Aroma’s boundaries, scanning the streets
for recyclable rubbish that he can stuff into his sidecar. Plastic soup containers are high-value
finds, paying 20 pesos (38 cents) a kilogram. Siena sorts and sells his load to a junk shop owned
by his uncle, who trucks the waste to recycling plants on the outskirts of Manila.
Waste pickers like Siena are part of the solution, some activists argue; they just need a living
wage. In the Baseco waterfront slum in Manila, a tiny recycling shop operated by the Plastic
Bank of Vancouver, British Columbia, pays a premium for bottles and hard plastic collected by
waste pickers. It then sells that plastic at a higher price to multinationals, which market their
recycled products as socially responsible.
 Siegler, the Vermont economist, has worked in enough countries and run enough
numbers to be skeptical of such schemes. “There is not enough value in plastics to make that
work,” he says. “It’s cheaper to fund a solid waste management system than to subsidize
collecting plastic.”

Refletion
(Pasig river)

The waste that clogs Manila’s beaches and waterways reinforces. Much of it
consists of sachets—tear-off packets that once held a single serving of shampoo,
toothpaste, coffee, condiments, or other products. They are sold by the millions to poor
people like Siena and his family, who can’t afford to buy more than one serving at a
time. Sachets blow around Manila like leaves falling from trees. They’re not recyclable,
so no waste picker will retrieve them. When Greenpeace cleaned the Freedom Island
beach, it posted a tally of the brand names of the sachets its volunteers had collected.
Nestlé ranked first, Unilever second. Litterbugs aren’t the only ones at fault, says
Greenpeace’s Abigail Aguilar: “We believe that the ones producing and promoting the
use of single-use plastics have a major role in the whole problem.” A Unilever
spokeswoman in Manila told me the company is developing a recyclable sachet.
 THE CHALLENGE OF RECYCLING
(Journal)

Globally, 18 percent of plastic is recycled, up from nearly zero in 1980. Plastic bottles are
one of the most widely recycled products. But other items, such as drinking straws, are harder to
recycle and often discarded. All of these measures help at some level—even beach cleanups,
futile as they sometimes seem. A beach cleanup hooked Richard Thompson on the plastic
problem a quarter century ago. But the real solution, he now thinks, is to stop plastic from
entering the ocean in the first place—and then to rethink our whole approach to the amazing
stuff. “We’ve done a lot of work making sure plastic does its job, but very little amount of work
on what happens to that product at the end of its lifetime,” he says. “I’m not saying plastics are
the enemy, but there is a lot the industry can do to help solve the problem.”

There are two fundamental ways industry can help, if it wants or is forced to. First, along
with academic scientists such as Jambeck, it can design new plastics and new plastic products
that are either biodegradable or more recyclable (see You Can Help Turn the Tide on Plastic.
Here’s How.). New materials and more recycling, along with simply avoiding unnecessary uses
of the stuff, are the long-term solutions to the plastic waste problem. But the fastest way to make
a big difference, Siegler says, is low tech. It’s more garbage trucks and landfills.

“Everyone wants a sexy answer,” he says. “The reality is, we need to just collect the trash.
Most countries that I work in, you can’t even get it off the street. We need garbage trucks and
help institutionalizing the fact that this waste needs to be collected on a regular basis and
landfilled, recycled, or burned so that it doesn’t end up going all over the place.”

That’s the second way industry could help: It could pony up. Siegler has proposed a
worldwide tax of a penny on every pound of plastic resin manufactured. The tax would raise
roughly six billion dollars a year that could be used to finance garbage collection systems in
developing nations. The idea never caught on. In the fall of 2017, though, a group of scientists
revived the concept of a global fund. The group called for an international agreement patterned
after the Paris climate accord.

At the Nairobi meeting in December, 193 nations, including the U.S., actually passed
one. The United Nations Clean Seas agreement doesn’t impose a tax on plastic. It’s nonbinding
and toothless. It’s really just a declaration of a good intention—the intention to end ocean plastic
pollution. In that way it’s less like the Paris Agreement and more like the Rio de Janeiro treaty,
in which the world pledged to combat dangerous climate change—back in 1992. Norway’s
environment minister, Vidar Helgesen, called this new agreement a strong first step.
 Reflection
(THE CHALLENGE OF RECYCLING)

This report is concerned with the complex question of dealing with plastic waste. There
are dozens of different plastics in common use, and many products are made from a mixture of
these. However , people don’t really care about throwing plastics away as they are not expensive.

The Previous pages introduced and discussed ideas such as source reduction of waste,
degradability of plastic, and the impact on environment and human ,which all inter-relate with
the central issue of plastic pollution. In addition, the report provided overview of the facts and
issues involved, together with examples from around the world which demonstrate how
progress is being made in effective waste management and production of brand new plastics is
less cost. It must be emphasized that plastic waste recycling and management are not merely the
concern of large-scale schemes and companies.

Every individual one of us can take action to deal effectively with plastic waste in our
lives, and in this small way make an essential contribution towards improving our environment
by put our own selfish needs before the needs of everything around us now and the lives of
future generations.