History of Polymer

One hundred years ago, in 1920, the German chemist Hermann Staudinger published his classic paper
entitled "Über Polymerisation" ("On Polymerization"). In that paper, he proposed a chain structure for
rubber, each chain-like molecule consisting of many identical chemical units (isoprene monomers). He
also claimed that the unusual tensile strength and elasticity of rubber are a result of the great length of
these chains or, as polymer scientists of today would say, of their high molecular weight, and the vast
number of carbon-carbon double bonds between the subunits within each molecule.

Several years later, Staudinger termed such high molecular weight chain-like molecules "Makromolekül"
("macromolecule"). After a prolonged controversy, Staudinger's macromolecular theory was eventually
accepted by the scientific community. This led to some of the most profound scientific developments of
the 20th century, affecting many aspects of our lives.

Since the 19th century, researchers reported unusually high molecular weights for some natural
products such as rubber, cellulose, resins, and proteins. Ordinary organic substances, including alcohol,
petrol, or sugar, have a molecular weight in the range of 50 – 500. For the natural organic products in
question, the range is from 50,000 to several million.

In some respects, these organic products behaved like inorganic colloids – they could reside in solutions
as huge particles with very low diffusibility. At that time, it was challenging to imagine molecules with a
considerable size capable of stable existence. Instead, many renowned organic chemists such
as Wolfgang Ostwald, Hans Pringsheim, and Kurt Hess, suggested the concept of clusters or aggregates
of much smaller molecules held together by strong intermolecular forces of aggregation.
Staudinger strongly opposed the analogy between inorganic colloids and organic high molecular weight
substances. He argued that all physical and chemical properties of organic matter are defined by their
intrinsic molecular structure and not from physical forces outside the molecules. This gave birth to a
long-lasting colloid/macromolecule debate.

Rubber: From Small to Large Molecules

Between 1922 and 1930, Staudinger continued his experiments with chemically modified rubber and
published his findings in 19 papers, where he thoroughly investigated the properties of catalytically-
hydrogenated natural rubber. His results demonstrated that the loss of the double bond in saturated
rubber did not affect the "colloidal properties" of the material. He firmly believed that this proved the
presence of covalent bonds between the building blocks of the rubber molecules.
X-Rays Shed Light on Unusual Diffraction Patterns in Cellulose Fibers

In the early decades of the 20th century, novel physical methods, such as X-rays and electron
diffractions, were adopted to study natural fibers (cellulose), rubber, and proteins. While Staudinger was
publishing his findings on rubber modification, Reginald O. Herzog and W. Jancke studied the structure of
cellulose fibers by X-ray diffraction. They observed unusual diffraction patterns consisting of diffused
spots placed symmetrically in groups of four.

Subsequently, these diffractograms were interpreted by Michael Polanyi, who suggested that at least
part of the cellulose material was crystalline and consisted of either long chains of glucose rings or
dimers of rings. Despite that ambiguous conclusion, Polanyi's interpretation was a significant step
towards the establishment of the macromolecular theory.

Between 1925 and 1926, Polanyi's colleagues J.R. Katz, E.A. Hauser, and H. Mark observed that the X-ray
diffractogram of stretched rubber displayed a pattern that could be associated with partially crystallized
material. This result was supporting the idea that flexible macromolecular chains, when exposed to
mechanical deformation, can be ordered into thin, elongated, and well-oriented bundles with high
internal order.
Around that time, the research into high molecular weight materials was picking up pace across the
Atlantic. In 1926, O. L. Sponsler and W. H. Dore, working at the University of California, Los Angeles,
presented a comprehensive structure of the cellulose molecule - a chain of glucose rings joined by
covalent bonds.
In 1928, Wallace H. Carothers at the DuPont Company started ambitious and systematic research to
synthesize new materials with specific structures through established organic reactions. As a result, he
came up with a new class of fully synthetic polymers called polyamides, or "nylons," that could be
melted and drawn into a remarkably strong fiber. More importantly, his results helped to establish,
without further criticism, the idea of macromolecules as the building blocks of the organic matter.
The Golden Age of Polymers

The word "polymer" was introduced by Jöns Jacob Berzelius in the 1830s to describe molecules in which
the same atomic groups were arranged repeatedly. He considered benzene (C6H6) to be a polymer of
ethyne (or acetylene, C2H2). Over the years, the term covered larger and larger molecules, until
eventually it was used to denote the long flexible macromolecules formed of multiple base units known
as "monomers" (from Greek: monos - "one" and meros - "part"). The macromolecules themselves
became "polymers" (poly is the Greek word for "many").
The 1930s and 1940s marked the golden age for the development of new synthetic polymers. Scientists
in both academic and industrial laboratories were synthesizing new monomers from abundant and
inexpensive raw materials. At the same time, the processes of polymerization (a chain-growth process,
where the monomers attach sequentially to the active end of the growing polymer chain) and
polycondensation (a step-growth process that combines two or more different monomers in an
alternating structure) were refined for increased efficiency and yield.

New methods were developed for better characterization of the microstructure of the polymer
macromolecules. This, in turn, allowed the engineering of polymers with specific physical and chemical
properties by tailoring the structure and the arrangement of the polymer chains.
The availability of polyvinyl chloride (PVC), polyurethane (PU), nylon fibers and neoprene (the first
synthetic rubber), polytetrafluoroethylene (PTFE or "Teflon"), and polystyrene (PS) revolutionized the
manufacturing of human-made fibers, films, plastics, rubbers, coatings, and adhesives. These new
synthetic materials had no resemblance to their raw materials (usually oil or natural gas). They were
outperforming their natural counterparts, while at the same time being cheaper and more accessible.
The growing automotive industry and rubber demand during World War II stimulated the large-scale
production of artificial rubber.
The booming success of synthetic fibers, synthetic rubber, and new functional materials taught the
polymer industry a vital lesson: fundamental research can lead to products that replace natural
materials.
The Scientific Recognition of Polymer Scientists
The combination of applied and fundamental research can sometimes lead to Nobel prizes. Hermann
Staudinger received the Nobel prize in chemistry in 1953 for his life-long work in the field of
macromolecular chemistry.
In 1963, the Nobel prize in chemistry was awarded to Karl Ziegler and Giulio Natta for the development
of a catalytic process that allowed scientists to conduct well-controlled polymerization at room
temperature and atmospheric pressure. This paved the way for the mass-production of polyethylene and
polypropylene, the two most widely-used commodity polymers.

Paul J. Flory received the Nobel prize in chemistry in 1974 for his fundamental contributions to polymer
science. He was instrumental in developing the modern understanding of how polymer macromolecules
behave. His research showed that the individual molecules in a polymer differ in terms of chain length
and that the properties of synthetic polymers can be described only as "average" properties. These ideas
were further developed into the concept of "molecular weight distribution," one of the fundamental
properties of the polymer materials.
What are Bio-Polymers?

Bio-polymers are the basis of all life on our planet. Polypeptides (proteins) and polynucleotides (DNA
and RNA) dominate the functional and informational machinery of life, while polysaccharides (sugars)
are important in physical structure, energy storage, and intermolecular interactions.

In 1963, the Nobel prize in physiology and medicine was awarded to Francis H. C. Crick, James D.
Watson, and Maurice H. W. Wilkins for their work in the 1950s on the structure of the nucleic acids, the
most important of all informational bio-polymers.

Growing Interest in Organic Electronics and OLEDs

The Nobel prize in chemistry in 2000 was awarded to Alan J. Heeger, Alan G. MacDiarmid, and Hideki
Shirakawa for the discovery of the high electrical conductivity of doped polyethyne (or polyacetylene) in
the middle of the 1970s. This sparked an ever-growing interest in the field of organic conductive
polymers that can be tailored to achieve desired electronic and optical functionality. The use of organic
compounds in microelectronics led to the development of organic light-emitting diodes (OLEDs) used in
the modern display technology and high-performance lithium-polymer batteries.

Environmental Impact on Polymers

The use of polymers is still expanding and, with a global production of several hundred millions of tons
annually, synthetic polymers have become a significant factor in the economy of all industrialized
countries in the world. This has created the major environmental problem of how to deal with this non-
biodegradable waste. Although recycling has become a major industry, it is limited by the available
markets for reclaimed materials and is profitable only for limited classes of polymers.
Small-Molecule Release from Long Polymer Chains

Industrial synthesis of long polymer chains is a somewhat random process and often leaves some
unreacted monomers in the final product that can be harmful to the environment. Formaldehyde,
styrene (from polystyrene used in food containers, for example), vinyl chloride, and bisphenol-A (from
polycarbonates) are known carcinogens. Other polymers contain modifiers (plasticizers, flame
retardants, UV protectors, etc.) to alter their properties. Many of the monomers and the modifier
molecules are small enough to be able to diffuse through the polymer matrix and eventually to be
released into any liquid or air in contact with the polymer.
Micro-Plastic in the Environment and the Prospects of Biodegradation of Synthetic Polymers

A growing concern is that the non-biodegradable polymers are disposed of in landfills or are floating in
the oceans. These are subjected to weathering and partial photodecomposition, catalyzed by the
exposure to sunlight, resulting in small plastic fragments with sizes down to a few microns, which are
released in the groundwater or the marine habitats. Many of these materials are less dense than water,
and once they enter aquatic systems, they tend to remain there indefinitely. Aquatic animals can also
swallow larger fragments of plastic waste by mistake.

Hope for the future is that considerable efforts are devoted to finding ways for biodegradation of
synthetic organic polymers. The process of biodegradation involves microorganisms (such as bacteria,
fungi and yeasts) that can break down the organic macromolecules into small molecular weight
fragments, which can be further degraded aerobically or anaerobically, to carbon dioxide (CO2),
methane (CH4) and water.

Of particular interest is the biodegradation of synthetic oil-derived polymers such as polyethylene (PE),
polyethylene terephthalate (PET), polypropylene (PP) and polystyrene (PS). These amount for up to 60%
of the global commodity polymer production (and waste).

In 2016, Shosuke Yoshida and his colleagues at the Kyoto Institute of Technology reported a newly
isolated microorganism that can aerobically degrade PET to small molecular weight products. The
bacterium uses two separate hydrolytic enzymes to break down the PET polymer chains in a two-step
process. The bacterium uses the resulting products, ethylene glycol and terephthalic acid (one of the PET
monomers), as an energy source with CO2 and water as end products.

Non-hydrolyzable polymers (PE, PP and PP) are significantly harder to break down compared with
polymers containing hydrolyzable bonds (such as PET). However, in 2018, scientists from Stanford
University discovered that the microorganisms residing in the gut of the mealworm beetle larvae are
capable of depolymerization of PS and PE to small molecular weight intermediates that can be used as a
primary energy source for the larvae metabolism.

These remarkable discoveries offer the possibility to create genetically engineered microbial enzymes
with an enhanced aerobic or anaerobic activity towards synthetic polymers. This would allow much
faster aerobic biodegradation of organic waste. More importantly, the development of enzymatic
systems for anaerobic degradation of these materials would lead to the production of methane gas,
which can be harvested as a renewable fuel.

Define Polymer/polymerization and Polymer Terminologies

Polymer, any of a class of natural or synthetic . substances composed of very large molecules, called
macromolecules, that are multiples of simpler chemical units called monomers .. Polymers make up
many of the materials in living organisms, including, for example, proteins ., cellulose ., and nucleic
acids .. Moreover, they constitute . the basis of such minerals as diamond ., quartz ., and feldspar . and
such man-made materials as concrete ., glass ., paper ., plastics ., and rubbers ..
Organic polymers play a crucial role in living things, providing basic structural materials and participating
in vital life processes. For example, the solid . parts of all plants . are made up of polymers. These include
cellulose, lignin ., and various resins .. Cellulose is a polysaccharide ., a polymer that is composed of
sugar molecules. Lignin consists of a complicated three-dimensional network of polymers. Wood resins
are polymers of a simple hydrocarbon, isoprene .. Another familiar isoprene polymer is rubber ..

Other important natural polymers include the proteins, which are polymers of amino acids ., and
the nucleic acids ., which are polymers of nucleotides .—complex molecules composed of nitrogen-
containing bases, sugars, and phosphoric acid .. The nucleic acids carry genetic information in the
cell. Starches ., important sources of food energy derived from plants, are natural polymers composed of
glucose.

Many inorganic polymers . also are found in nature, including diamond and graphite. Both are composed
of carbon .. In diamond, carbon atoms are linked in a three-dimensional network that gives the material
its hardness. In graphite, used as a lubricant and in pencil “leads,” the carbon atoms link in planes that
can slide across one another.

Synthetic polymers are produced in different types of reactions. Many simple hydrocarbons ., such
as ethylene . and propylene ., can be transformed into polymers by adding one monomer after another
to the growing chain. Polyethylene ., composed of repeating ethylene monomers, is an addition polymer.
It may have as many as 10,000 monomers joined in long coiled chains. Polyethylene is crystalline,
translucent, and thermoplastic—i.e., it softens when heated. It is used for coatings, packaging, molded
parts, and the manufacture of bottles and containers. Polypropylene . is also crystalline and
thermoplastic but is harder than polyethylene. Its molecules may consist of from 50,000 to 200,000
monomers. This compound is used in the textile . industry . and to make molded objects.