ADVANCED POLYMERS AND COMPOSITES FOR THE MILLENNIUM

C. K. S. PILLAI
Regional Research Laboratory
Thiruvananthapuram – 695 019

Introduction

When asked about the biggest contribution of Chemistry to mankind, Lord

Alexander Todd, Nobel laureate in Chemistry in 1957 commented “I am inclined to think

that the development of polymerisation is, perhaps the biggest thing chemistry has done,

where it has had the biggest effect on life” 1. Certainly, natural or synthetic, the

transformation from simple molecules to macromolecules was a giant negentropic

quantum jump. A large number of novel materials such as plastics, fibres, elastomers,

adhesives etc. with properties that cater to the many needs of human society and industry

emerged making vast changes in all spheres of human activity. In fact, human

civilisations have been and continue to be heavily dependent on polymers, natural or

synthetic for their survival, food, shelter and clothing 2. Though polymers were used in

one form or other, they were not recognised as chemical entities until the beginning of

20th century. A series of discoveries and the large availability of petrochemicals as a

viable source for their production ensured great strides in their development into modern

materials which now have reached such a stage that human survival can not be ensured

without their use. The penetration and acceptance of plastics into the social fabric have

reached such a situation that it is now difficult to conceive a world without plastics.

Ranging from day - to - day home utensils and appliances to varied societal uses, to
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industrial products and the motor car, the telephone, the television, the air plane, the

space vehicle and finally the artificial organs, there is no area plastics has left untouched.

With a production ~ 200 million tons, the influence of polymer materials on the world

economy is enormous. As the world population doubles sometimes in the future, the

polymer production is expected to triple or quadruple in size. Polymers have affected in a

positive way modern living in all its economical, social and cultural aspects.

Polymers today occupy a unique position among materials mainly due to a

combination of attractive properties such as low density, low strength to weight ratio

excellent barrier and surface properties, transparency low corrosion rake, good thermal

insulation, slow mechanical damping, good electrical resistance, wide range of

colourability, the ease of processability into a variety of products of intricate shapes and

sizes and above all, their low cost make them highly competitive and give them an

enviable position in comparison to metals and ceramics. One of the most significant

developments that has revolutionised polymer science and technology is the generation of

knowledge to control the size, shape and structure of polymers to suit a set of properties

and functions for a particular application. The story of these developments in the

expanding horizon of polymers with examples of some of the emerging concepts and

products form the theme of the article.

The changing scenarios: looking back

The spectacular developments that the world of polymers has witnessed during

the last century can not be summarized in a short article. However, a few breakthrough
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inventions and discoveries that have revolutionized the world of materials need to be

mentioned prior to scanning the modern era.

Early man used a variety of natural polymers for food, shelter, clothing and

amenities. A variety of mechanical modifications were practiced in prehistoric times and

later it led to the production of clothing and paper. Chemical modifications were also

practiced without proper understanding of their chemistry. The tanning of leather (one of

the oldest industries in continuous production) and the embalming of corpses involved

the concepts of cross-linking of proteins using gallic and formaldehyde respectively.

Natural polymers literally dominated all spheres of life up

to the advent of synthetic polymers. During the early

period of growth prior to 1850, slow developments in the

usage of natural polymers and their composition

elucidation were recorded. In the 17th century, John

Osborne made mouldings from the natural polymer, horn.

Gums from tropical trees were exploited, especially rubber

and gutta percha for which Bewley invented the plastics

extruder in 1847. Hancocks’ rubber masticator (1820) was

Charles Goodyear (1800-1860)

one of the earliest developments. Good Years’s discovery of the vulcanization process

(1839) can be considered a break through in the utilisation of natural rubber that paved

the way for the growth of rubber industry and indirectly that of plastics industry. "There

is probably no other inert substance," Goodyear said once, "which so excites the mind." 3
 4

Gutta percha was used to protect and insulate the first submarine telegraph cables in

1850. In America in the 1850’s, shellac was used (compounded with wood flour) to

mould cases to display early photographs. It was used until the 1940’s to mould

gramophone records.

During the period between the 1850 and 1930, one can note the introduction of a

few products and processing equipments and some emphasis on structure property

determination of natural and synthetic polymers4. Thus, the introduction of the ram

extruder (1851), the screw extruder, (1860s), injection moulding (1870), the Bombury

mixture (1916) and the multiple and intermeshing screws (1916) took place during this

period. Some of the product achievements are the introduction of ebonite (Hyatt-1951),

cellulose nitrate (Hyatt 1865) – first plastic invention), phenol-formaldehyde (Bakeland

1909) and bakelite (1916), casein (1919), alkyd (1926), cellulose acetate (1927) and poly

vinyl chloride (1927) (the first synthetic thermoplastic introduced into the market) and

urea formaldehyde (1929).

It is interesting to note that nearly 10% of all British patents issued in 1855

referred to moulding materials but the major breakthrough was in

the modification of cellulose with nitric acid to give the first semi-

synthetic plastics material, cellulose nitrate. The adventure of the

plastics era seems to take its source in 1862 when the British

chemist Alexander Parkes who made this hard and brittle product

Alexander Parkes.
 5

into pliable ivory like material by mixing with camphor (the first use of a plasticizer) and

displayed it ( under the name Parkasine) at the Great International Exhibition in London,

1862. In 1869, another scientist in America, John Wesley Hyatt made the same discovery

and called it celluloid. The celluloid was used soon to manufacture combs, toys, billiard

balls, photographic films and adhesives. Taking into account its inflammability, it is used

today only to manufacture table tennis balls.

The isolation of casein, a protein, from milk in 1897 by German chemists was

another landmark. Mixed with other substances and hardened in a formaldehyde solution,

it gives a hard matter called galalithe that can be shaped into buttons and knitting needles.

It is said that four great discoveries sustained the technological transformation of a few

natural polymers for their ultimate utilization. They are: vulcanization of rubber,

mercerisation of cotton, tanning of leather and the loading of silk. These discoveries

sustain these industries even today although many of the natural polymer based industries

had to be abandoned due to competition from the emerging synthetics.

The historical turning point in the of development plastics goes back to 1907

when Leo Hendrick Bakeland (1863-1944) by seeking a substitute of the natural lac,

discovers the first heat and pressure process for processing phenol-formaldehyde resins

(first synthesized by German chemist von Baeyer in 1872)

into useful products. The British chemist James Swinburne

worked in the same direction and he deposited a patent on

the same product, one day after that of Bakeland.

Leo Bakeland (1683-1944)

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Establishment of the macromolecular concepts.

With the establishment of the “macromlecular concepts” by Herman Staudinger,

polymer science and technology underwent spectacular developments during the last

eight decades5-7. Prior to 1927, large molecules such as rubber latex of molecular weight

between 6500-105 were considered to be aggregates of smaller units. He proposed that

the elasticity of rubbers was related to the existence of long chains. It shows that the

materials manufactured by thermal processing of styrene are similar to rubber. Within a

few decades, this “greasy chemistry” image of polymers got transformed into one of the

most brilliant era of endless innovations and discoveries in the history of science. The

polymerization process is understood as a gain in properties; the polymers get a new set

of properties which were not there in the monomer. The characteristics that defines it are

high molecular weight, molecular weight distribution, micro, segmental and macro scale

motions with a glass transition temperature Tg which are other wise not there in other

materials, bulk behaviour with microstructure indicating materials property such as

mechanical properties, coexistence of amorphous and crystalline structures, versatility in

design for tailor making, solution behaviour- random coil-rod-helix, short and long range

interactions and possibility of post polymer modification, rubber elasticity and above all

information storage, sequential arrangement. The meeting of the Deutsche

Naturforschergesellschft in Deuusseldorf in 1926 was a turning point in the history of

polymer science. ‘The theory of small units’ began losing ground and the

macromolecular concept became an accepted fact. In 1936, at the faraday Society

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meeting on “Phenomenon of polymerization and polycondensation” in Cambridge, a

galaxy of scientists gave excellent presentations that established that polymer chemistry

has grown into a full scale science. The first polymer conference of the International

Union of Pure and Applied Chemistry in Liege in 1947 paved the way for establishing

polymer science as an accepted member of chemical disciplines.

Hermann Staudinger: The Father of Polymer

Chemistry (1881-1965). Nobel prize-1953

The period since 1930 could well be called the age of

polymer materials with a phenomenal growth taking

place leading to the production of a series of synthetic

fibers (nylons, polyesters, polyolefins, acrylics,

aramide, carbon etc.) a variety of plastics (thermoplastics that soften and become

reprocessable under heat and pressure and thermosets that sets to hard infusible resins

and are not reprocessable) and elastomers (chloroprene, nitrile, styrene-butadiene, butyl,

isobutene-isoprene rubbers etc.) and coatings and adhesives. While the early 50’s

witnessed the growth of commodity plastics (high volume-low value, capital intensive

polymers sold by specifications rather than by performance-polyethylenes,

polypropylenes, polystyrenes and polyvinyl chloride), the 1960’s saw the emergence of

engineering polymers (medium volume-medium priced having predominantly

engineering applications.) Here what was sold was not only a commodity but also a

material with a property that gives specific performance. And the 1970’s saw the

specialities (high value low volume products(, tailor made to meet the high performance
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situations. The emergency of the engineering and speciality polymers made more

emphasis on property and performance, which gave rise to specialization of industries by

technological domain and exploitation of both horizontal on vertical synergies. Blends

and alloys were designed to balance the strengths and weaknesses of individual polymers

and similarly the advanced composites that reinforces a high strength organic or

inorganic fibre in an engineering or commodity polymer to get light weight high strength,

durable, tough, corrosion resistant structural materials to replace metals. These

developments required a thorough knowledge of end use markets as they are tailored to

specific end use for which a greater technical source was needed. As the scale of

production is low, the industry is characterized by low capital costs, but cost of

knowledge generation and R&D investments are extremely high. A complexity in design

and production with high capital input go up, sharing of knowledge and globalization of

industries becomes trends of the day. Companies form joint ventures or expand into other

regions. So continued innovative efforts to open up new grades and to find out new

applications are the strengths of successful industries.

The exponential growth of polymeric materials during this period was due to

generation of information on (a) sciences of the polymerization and polymer, (b)

structure-property correlations, (c) new techniques of production, and (d) newer design

criteria in their applications. During this period a host of polymers with unprecedented

properties were made and commercialised. Flory’ masterpiece treatment of

polymerization kinetics and thermodynemics and solution properties paved the

foundation of polymer chemistry.

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The discovery of a variety of polymerisation processes

coupled with significant advances in theory helped to launch

and sustain a materials revolution that is still very much under

way today7. Novel methods of characterization and data

obtained by structure-property correlations generated enough

information of tailor making of polymers with specific

property profiles and end use applications. Starting with the

Paul J. Flory, 1910-1985, Nobel prize 1974

heat and pressure process for the production of phenol-

formaldehyde resins by Leo Bakeland in 1907, the science and

technology of polymers have matured significantly over the last

hundred years. The pioneering work of Wallace H. Carothers at

DuPont on polyesters and polyamides paved way for the chemistry

of condensation polymers. With the invention of nylon, he has set

in motion the materials revolution that continues even today in the

Fig.1.Nylon parachute

development of products with specific characteristics such as light weight and high

strength. When Du Pont decided to develop nylon into a commercial fiber, the

company specifically intended to use it to compete with silk in the women’s hosiery

market. In addition to women stockings, nylon was then tested for the suspensions of

parachute. Years of research devoted to targeting this particular market proved

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enormously successful. Nylon was one the few polymers which had a remarkably short

development time from lab to market.

W. H. Carothers, April 27, 1896 – April 29, 1937

Aramids are a family of nylons, including Nomex® and

Kevlar®. Kevlar® is used to make things like bullet

proof vests and puncture resistant bicycle tires.

Taking cue from the work of Carothers, the

English chemists, Whinfield and Dickson developed in

1941 the first synthetic polyester fibre by polycondensation of terephthalic acid and

ethylene glycol. In over four thousand years, textiles have seen only three basic

developments aside from mechanical mass production: mercerized cotton, synthetic dyes

and rayon. Nylon is a fourth. Unlike nylons, the polyesters have better mechanical

properties which allied to its properties of surface allow it to use in composite materials

with glass fibres with very high added value. It was Nathaniel Wyeth who first

discovered how to make bottles from PET.

The story of polytetrafluoroethylene (PTFE, Teflon®) is interesting in the sense

that it was discovered accidentally in April 1938 by DuPont chemist, Dr. Roy J. Plunkett

who found while working with gases related to Freon® refrigerants that a frozen,

compressed sample of tetrafluoroethylene had polymerized spontaneously into a white,

waxy solid9. Taking into account its extraordinary chemical resistance, it was very largely

useful during the chemical processing of uranium necessary to manufacture the first

atomic bomb. The TEFLON was made available to public only in the 1960's. This is a
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highly inert and the most slippery material in existence. These properties have made it

one of the most valuable and versatile technologies ever invented, contributing to

significant advancements in areas such as aerospace, communications, electronics,

industrial processes and architecture.

Although it had been noted since 1880 that the acrylic acid solidified at high

temperature under pressure, it took another 50 years to develop poly(methylmethacrylate)

commonly known as the Plexiglass. The transparent character of the polymer for

replacing glass in certain applications requiring "glasses" resistant to shocks was noted

only later. In 1930 started the industrial production of plexiglass.

Another interesting story is that of polyethylene with out which much of devices

of transport of information and generation of energy would be unrealizable. The

discovery of this material goes back to 1933 when ICI researchers working on the

reaction of ethylene with benza ldehyde under very high pressure (1400 atmospheres) at

170 °C noted the polymermisation of ethylene by analyzing the white solid found on

walls of the reaction vessel9. Credit also should go to Prof. Carl S. Marvel whose student

M.E.P.Friedrich noted in 1930 the unexpected formation of polyethylene in a reaction

involving ethylene in the presence of lithium alkyl compound at ordinary pressure. At

that time he thought polyethylene was good for nothing. It took two years for the

researchers from ICI controlling the reaction (which is dangerous because of its explosive

nature) but the industrial production started only in 1939 with the approach of the war.

The soldiers needed excellent dielectric insulators.

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It is in 1942 that Standley Kipping makes a success of the first synthesis of

silicones which served the war enormously with its high thermal stability for various

applications. The industrial expansion of poly(vinylchloride) (PVC), discovered by

French Henri Regnault in 1835 which remained unused due to its hardness and difficulty

in processing took place with the discovery of new plasticizers in 1943.

The discovery of plycarbonate in 1953 by Daniel Fox at GE was also an accident.

He searched for bis-guaiacol, but instead got bisphenol- A which he used for in his

experiment to finally end with the discovery of polycarbonate.

The story has been built and sustained by a galaxy of eminent scientists and

engineers such as Staudinger, Carothers, Meyer, Ridel, Mark, Melvile, Schulz, Houwink,

Astbury, Bawn, Bernal, Evans, Melville, Rideal, Thoamson, Nasini, Natta, Champetier,

Chapiro, Magat, Sadron, Hermans, Houwink, Staverman, Errera, Smets, Claesson,

Ranby, Ant-Wuorinen, W. Kuhn, K. H. Meyer, Siegner, to mention a few whose

contributions can not be highlighted in a short article. Hence a summary of the

contributions of the period is given in Table 14.

TABLE – 1
SIGNIFICANT DEVELOPMENTS IN POLYMERS AFFTER 1930

Milestones Year Milestones Year

Plastization of PVC 1930 Fluorocarbon 1943

Nylon 1930 Cellulose propionate 1945
Condensation of polymers 1930 Tetrafluoroethlyene, commercially 1945
Neoprene 1931 Organosols, plasticizers, commercially 1946
Organo silicon polymers 1931 Polyurethane elastomer 1946
Patent on screw plastization Epoxy, commercially 1947
Of injection moulding 1932 ABS 1948
PMMA, commercial synthesis 1933 Automatic screw transfer press 1949
Unsaturated polyester resin 1933 Allylic 1949
Ehthyl cellulose, commercially 1933 First large scale production of PTFF 1950
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Polyethylene, high pressure

Polymerized 1934 Nobel prize of Staudinger 1953
PVC, commercially 1934 PE by org. metallic catalyst 1953
Melamine formaldehyde resin 1934 Cis polyisoprene 1954
Plasticised PVC commercially
In US 1935 High mol. Wt. Sterio regular PE 1954
PS commercially 1936 Polyurethane, commercially USA 1954
Acrylic and PVAC 1936 PE without pressure 1954
Automatic compression,
Moulding commercially 1937 PP commercially 1955
High pressure polyethylene ICI
Patent 1937 Acetal 1956
Polyamide, commercially 1937 Polycarbonate developed 1957
Polyurethane first produced 1937 PP, commercially introduced in US 1957
CAB introduced 1938 HDPE 1957
Melamine, commercially 1938 Polyether urethane introduced in USA 1957
Nylon 1938 Chlorinated polyether commercially 1957
Commercial blow moulding
Of acetate and styrene 1938 PC, commercially 1959
Polymerization of caprolactum Acetals, commercially 1959
(Nylon 6) 1938 Isotactic polymer dev. 1960
Polystyrene 1938 Vinyldene fluride, commercially 1961
First patent on epoxy 1939 Phenoxy, commercially 1962
Styrene plastics became 1939 Polyallomers, commercially 1962
commercial PVLC 1939 Ethylene-propylene rubber commercially 1962
MF 1939 Ethylene vinyl acetate 1964
PE commercially
(internationally) 1940 Ionomers, commercially 1964
Synthetic rubber industry
Initiated (USA) 1941 Polyimide, introduced as a fabricated
Polyester urethane (Germany) 1941 product 1964
PETP 1941 PPO, commercially 1964
Silicone, industrially 1942 Methylpentene, commercially 1965
Polyester, commercially 1942 Parylene, commercially 1965
PE production 1942 Polysulphone,commercially 1965
Urea fornmaldehyde 1942 Thermoplastic elastomers (polyester) 1970
LDPE 1942 Injection moldable, polyesters 1972
Patent on epoxy 1942 Aromatic polyamides 1974
Nitrile barrier resins 1975

This was followed by a series of developments such as polyaramides, polyester

carbonate, polyether ether ketone, poly (ether imide), poly-(aryl ether sulphone),

polycarbosilane, bismaleimides, ultra high molecular weight polyethylene, polycarbonate

polyurethane, water curable silane modified thrermoplastic polymers, poly (alkoxy

phenylenes), i-butene propylene random copolymer, acetylene terminated monomers and

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resins, doped-stretched-oriented polyacetylenes, highly aromatic condensed ring

polymers etc.

A new paradigm shift

Polymer science and technology in the new millennium are facing new challenges

and opportunities. A couple of exciting developments including the new design

paradigms such as shift from the macroscopic design philosophy to molecular level

design philosophy, the promises of the design of “structure controlled macromolecules”

visualize phenomenal developments in the new millennium11,12. Polymers began

emerging from mere chemical entities to modern materials that required a synergy or

synthesis of many disciplines such as Chemistry, Physics, Engineering, Materials Science

and Molecular Biology. The transition from concept of idea through laboratory and pilot

plant to practical application has been highly accelerated recently. Additionally,

cooperation between several fields of scientific and

engineering skills requiring high levels of interdisciplinary

interactions has made possible imaginative and unprecedented

developments to take place. This has made Prof. Heman F.

Mark to remark that “the potential of polymer chemistry will

be limited only by the imagination and ingenuity of

scientists”.

H. F. Mark, 1895 -- 1992

Criteria regarding development of Materials for the future

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Possible scenarios for the millennium polymers that are already in and that are yet

to come one should consider as number factors such as: (i) issues such as performance vs

cost, eco-friendliness and sustainable growth vs large scale production and resource

conservation. Polymers that are coming and that on stage will be governed by

performance and cost. Of course issues such as eco-friendliness and resource

conservation will have to considered, (ii) Parameters such as energy efficiency in

production and safety in manufacturing will have a greater role, (iii) Should go for zero

waste generation, (iv) Should be based on knowledge of past directions and

developments, recent trends and personal experience.

One should also consider (a) the speed with which technological change occurs (b)

the purity obtainable in manufacturing systems and (c) the changing models of materials

development.

Molecular design and process design

One of the most significant contributions of the developments in polymer science

& technology during the last century is the generation of information for tailor making of

polymers through molecular design and process and product design13. A “golden period”

of polymers thus emerged during 1950 to 1975 gave rise to an explosive growth from 1 to

43 mega tons of production. During this period, the concept of macromolecules came to

be accepted. New techniques and polymerisation and novel methods of charcaterisation

and analytical tools were developed. Most of the commodity polymers and a few
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engineering plastics were developed and commercialised during this period as described

in elsewhere.

(a) Chemistry: Molecular design

Structure-property correlation studies revealed a few key parameters that control

properties of polymers: chain length, chain sequence, chain isomerism and chain

topology. Control over these parameters are the key to development of polymers with

specific property profiles. The polymers with absolutely defined chain length and

stereochemistry were made and characterised through the use of rational design of

catalysts. Copolymers were synthesized and characterised with precise sequences. A set

of design principles was developed based on these parameters. They involved control of

structural regularity and packing, intermolecular forces, crystallization, cross linking,

chain stiffening, fictionalization, self –assembly, advanced structures etc. a short

discussion on few of these parameters is presented.

Apart from a variety of polymerization techniques, two tools that are frequently

used to control some of these factors are crystallization and cross linking. It is well

known that a certain amount of molecular weight is required to achieve stable property.

Similarly, molecular weight distribution has significant effects on the property profile of

polymers. For example, in the development of Kevlar fibre, a high performance

polyaramide, a problem of variation in fibre property was encountered when

polymerization solvent was changed from hexamethylphosphoramide (HMPA to N-

methyl pyrrolidone (NMP) and calcium chloride system, the viscosity of both solutions

showing no difference. However, the gel permeation chromatograph showed a difference

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in molecular weight distribution, the difference being attributed to the participation of

low molecular species in the latter solvent. The problem was resolved, when a new

reactor design prevented, early nucleation. In applications such as biomaterials, a narrow

molecular weight distribution is preferred for a stable, durable and biocompatible product

whereas a wide molecular weight distribution may not create any problems in surface

coating where low molecular weight species get polymerized and crosslinked to a durable

protective film.

Structural regularity

Regularity in the arrangement of the repeating unit and the side groups enable

chains to pack closely to form complex ordered structures that give rise to crystalline

arrays interspersed in a matrix of amorphous material. Crystalline behaviour increases

density, melting point, stiffness resistance to solvents and resistance to heat. For

example, a significant property improvement was observed in polyethylene and

polypropylene when stereoregular polymerization was adopted. As the polymer chains

are packed more densely in the crystalline regions, the isotactic forms of PP are stiffer

and more resistant to heat than the atatic forms of polypropylene. Conventional chain

reaction polymerization involves creation of an active center to which monomers are

added randomly in propagation stage and terminated to get a polymer whose order of

regularity and branching are difficult to control. Table 2 shows the improvement in

property on using Ziegler-Natta catalyst for polymerizing PE and PP.

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Table 2. Effect of stereoregular polymersiation on the properties of PE and PP

Polymer Property Conventional Stereoregular

polymerization polymerisation

PE Density, g/cc 0.92 0.95-97

Tm, °C 111 124-134

Crystallinity, % 60 90

PP Density, g/cc == 0.95

Tm, °C Viscous liquid 165

Tacticity, Atactic Tactic

To improve cohesion between molecules and to increase the strength of forces

between chains, the introduction of polar monomers or groups of hydrogen bonding is

used. The vulnerability of polystyrene to solvents and heat could be controlled by

copolymerization with acrylonitrile, a polar monomer. Similarly, the brittleness of

polystyrene was reduced significantly when copolymerized with butadiene in high impact

polystyrene or styrene-butadiene rubber. The tiny rubber particles in continuous matrix

of polystyrene toughen the system while retaining the stiffness of polystyrene. The high
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rigidity and resistance to solvents exhibited by PVC in comparison to other commodity

plastics are due to the polar chlorine atom, which increases the lateral cohesive energy

density. The exceptionally high strength of cellulose in comparison to starch (both are

polymers of glucose) originates from the difference in the arrangements of the glucose

units. The 1,6 β- glycosidic linkage in cellulose favours hydrogen bonding, an example

from nature which man could imitate.

Recent structural studies of the high strength high modulus aramide fibre showed

extensive hydrogen bonding which allows formation of sheet like structures stacked

radially resulting in perfect radial as well as longitudinal order as shown in Fig. 2.

hydrogen bonding in

aramide.

Fig. 2 hydrogen bonding

in aramide

Cross-linking

The principle of cross linking have been extensively used to achieve the

maximum level of inter-molecular interactions to get three-dimensional network

structures giving rise to hard, stiff and strong materials. One of the earliest examples is

that of phenolics. The classical example of the vulcanization of rubber involves cross
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linking through sulphur. Innumerable other ways of cross-linking have been reported in

many hydroxy, amino, epoxy and urethane systems. The transition from flexible to hard

rigid material can be achieved by controlling cross link density and the topology of the

network. For example, if two segments with glass transition temperature (Tg) of 100o C.

(segmented linear) and Tg-50o C. (branched) are cross linked, then the material will be

extrudable and mouldable plastic above 100o C., but between 100 and 50o C.

Advanced structures

The newly emerging liquid crystal polymers are said to hold the market, because

of their use in electrical and electronics applications. Their high temperatures

applications make them ideal for chip carriers. Liquid crystallinity develops out of the

rod like character of the components, which make them aligned under certain conditions.

This spontaneous orientation from melt or solution has been used for drawing fibres of

aramide with liquid crystalline order when the polymer chains are oriented along the axis

of the fibre. In the development of such materials, a tetrahedral model was adopted as

against the simple triad model whose three corners represent molecular design, process

design and property. Now, the fourth corner of the tetrahedron represents the advanced

structure which creatively integrates the other three corners using systems engineering

that combines the talents of professionals in many disciplines.

Unlike liquid crystal polymers another rigid rod polymer that showed unusual

pseudoplastic behaviour with metallurgical properties is polybenzimidazolne whose Tg

is above 427o C . It can withstand oxidation temperatures of 288o C for 1000 h

continuously without oxidative degradation and is processed through a sintering

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technology. The fibre is used for clothing in fire fighting, race can drivers and industrial

workers. It is aimed for use as exotic metal, ceramic and carbon replacement. The parts

will not crack, they are as hard as granite, do not corrode and embrittle. Apart from

military and aerospace applications, they have promising potential in biomedical field.

The advanced design techniques have been useful in developing polymers for

applications such as photo resists, electron beam resists, conducting polymers,

piezoelectric and pyroelectric polymers, optical fibres, electrects, phase change polymers,

target specific pesticides and drug carriers, separators and solid electrolytes for batteries,

biocompatible artificial organs, high molecular weight soluble polymers, ceramic

precursor polymers, etc.

When polyvinylidine fluoride (CH2 CF2) was brought into a trans trans

configuration, a permanently depolarized material resulted which functioned as a

sensitive transducer converting electric pulses into sound and vice versa (loud speakers,

hearing aids, etc.). Polymers having polyconjugated structures which can have orbital

overlap along the chain energy state, exhibit electrical conductivity. For example, doped

stretched polyacetylenes have conductivities as high as 2000 ohms-1 cm-1. Doped poly (p-

phenylene) are other examples in this series which could turn out to be candidates for all

plastic light weight thin film battery. The discovery of extremely high optical non-

linearity in polydiacetylene and polybenzimidazole makes them suitable for optical

computers or communication systems.

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Two of the advances in polymer systems that emerged recently are advanced

composites and the so called combined materials known as alloys and blends14. In the

event of increasing cost of devising entirely new monomers for specialty polymers, alloys

and blends and composites have a promising future. Blends combine the promising

properties of the individual polymers where as composites exhibit synergy in properties

through reinforcing a fibre in a resin matrix that helps to transfer the load through

an`interphase. A unique example of a blend is that of polycarbonate with polyethylene

terephthalate. Because neither polymer is a dominant component, the two phases co-exist

in an intricate interpenetrating network poly(pheneylene oxide)-high impact polystyrene

blend, an amorphous brittle system is transformed into a ductile material. Toughening

nylon through incorporating of rubber particles provides usage in high performance

engineering. It has been suggested that multiphase polymer systems with controllable

nanostructures can be designed by manipulating specific molecular interactions14. These

may find applications in molecular switch or multi-stable memory elements.

Advanced composites made from reinforcing fibres such as carbon or aramide in

thermoset matrices such as epoxy and polyimides and thermoplastic matrixes such as

poly(ether ether ketone) have properties that make them suitable for applications where a

balance of heat resistance, mechanical properties and damage tolerance is required.

Much more intricately structured material systems with supramolecular structures may

emerge based on synthesis of information from studies on both natural and synthetic

polymers. New approaches to molecular recognition directed self-assembly of polymers

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with supramolecular structures by mechanisms resembling natural systems such as

tobacco co mosaic virus have come into vogue.

Processing and product design.

Recent chemical approaches adopted to the design of polymers for achieving

desired property profiles have been described. Improvements in property could be

achieved through the control of their bulk behaviour and microstructure by process

engineering and product design (conventional methods are well as known and so are not

discussed here). Two recent developments in polymer processing are blending and

orientation stretching. While blending combines the good properties of several polymers,

orientation enhances the strength of single polymers by extending the ordinarily folded

chains along the fibre axis.

Orientation gives rise to alignment of polymer chains that lend tensile strength

and modulus to a fibre drawn from a semi crystalline polymer. Recently super drawn

polyethylene (PE) of modulus 117-172 GPa and tensile strength 2.5-3 GPa with specific

strength greater than that of steel was prepared by a special technique of orientation

called gel stretching. This achievement was made possible through changes brought

down in the microstructure of polyethylene. Like most semicrystalline polymers, PE has

spherulitic structure made of lamellae or plates radiating from a common center. Within

each lamellae, the polymer chains fold back and forth between two planes with the region

between them being amorphous. When the polymer is drawn into a fibre, the spherulities
 24

pull apart and the crystalline lamellae break up into smaller blocks of folded chains.

More extensive drawing partially unfolds the blocks and the mircrofibrils merge. In an

ideal morphology, all the polymer chains would lie along the axis of the chain.

Extensive slow drawing near the melting point is another method. Polypropylene

sheets prepared by solid state extrusion had three times the tensile strength and nine times

the toughness than that of oriented PP.

Synergy in properties could be achieved through alternating layers of two

different polymers. Microporous membranes were made by repeatedly stretching PP film

at high and low temperatures. The process created micro tears of several Angstrom units

of diameter that could be used to separate gases. More processing techniques of recent

origin include reaction injection moulding (RIM), sheet moulding compound (SMC),

radiation curing of polymer, the push-pull LCP moulding process. One could expect

emergence of future technologies to unfold the polymer chains and realign and orient

them so that the ultimate materials of the future could be obtained. New synthetic

methods where sequence of the comonomer(s) can be controlled may open further

avenues of polymers for structural and functional applications in the future.

Hierarchically structured and intricately designed combinations and composites with

specialty metals and ceramics engineered to exacting specifications will emerge to solve

future materials problems. Convergence of various materials disciplines will be required

to solve the complex problems of materials systems of future human society.

 25

These developments are illustrated specifically by discussing certain salient

features of processes and products of immense importance in the millennium.

New Polymerization Processes

New polymerization techniques were developed to meet the challenge to make

polymers with absolutely uniform length with control on polymer stereochemistry and

copolymers with precisely determined sequences and to provide control of both topology

and molecular geometry. The goal was to synthesize macromolecules with great

precision, providing absolute control at molecular level over properties such as

composition, composition distribution, molecular weight, molecular weight distribution,

stereospecificity, regiospecificity, branching, distribution, topology, functionality and

chirality.

One of the most exciting developments for controlling polymer properties through the

control of polymerization processes is that of living polymers

developed by Prof. Michael Swarc in 196515. Szwarc

discovered living polymerization, a reaction that allows the

resultant polymers to maintain chain-end reactivity even after

completion of the reaction. This advance allows the synthesis

of polymers with controlled molecular weights, and with

Prof. Michael Szwarc, 1900-2000

functional groups placed at particular positions in the polymer chain. An example of an

"end-functionalized polymer"--created by a living

 26

polymerization reaction--is the liquid rubbers used in some industrial applications. Before

Szwarc's discovery, this precise control of polymer synthesis was impossible, creating a

serious obstacle to the development of advanced polymeric materials.

Professor Szwarc also made fundamental contributions to the development of "block

polymers," in which two or more different polymer chains are connected to each other

through chemical bonds by the sequential addition of monomers to living polymers. This

has led to the manufacture of a variety of

unique polymeric materials, such as

thermoplastic elastomers.

Fig.3 shows a comparison of molecular

weight distribution achieved by free

radical polymersation vs living polymer

technique. It can seen that one gets a

beautiful narrow distribution for living

polymers.

Fig.3 A comparison of molecular weight distribution achieved by free radical

polymersation vs living polymer technique

The significance of living polymers is that it does not have a termination step and

there is an active carbanion able to react further where by one can build the molecular

weight by will by adding fresh monomer.

 27

Novel design principles and polymerization techniques are emerging in recent

times16,17, Control of cationic polymersation and more recently free radical

polymersiation has been achived16. In all these cases the concept is the concept is the

same namely control of reactivity through the control of active centres to prevent side or

termination reactions. Cationic polymerization methods can be sued to prepare

functionalized polymers using the Inferter technique developed by Prof. J. P. Kennedy.

These are likely to lead to a host of new performance materials. A few of the

well new techniques that have emerged during

recent times are: group transfer polymerisation,

ring opening metathesis polymerization, atom

transfer polymerization, telechelic

polymerization, photo and thermal iniferters

mediated polymerization etc. Other techniques

used in controlling polymer properties through

synthesis are living polymerization, ring opening

polymerization, group transfer polymerization,

Prof. J. P. Kennedy, Institute of Polymer Science, University of Akron.

macro-monomer synthesis’s topochemical solid stage polymerization, oxidative coupling

polymerization, electro polymerization etc.

 28

Novel Catalysts
.
The most exciting developments in catalyst took place with the invention of the

Ziegler –Natta catalyst for the preparation of stereo regular polymers. But, as shown in

Fig. in polymerizations involving Ziegler-Natta catalysts the addition of a monomer is

controller sterically to get a stereoregular polymer.

The effect of the use of new catalysts was immediately felt in the production of PP

which increased from 2 million tons to 13 million tons. Explosive developments in

catalysts for polyolefins will catapult PP to more than 25 million tons by early part of the

21st century. Scheme 1 shows the mechanism of Ziegler-Natta polymerization.

Karl Ziegler 1898

-1973
Nobel prize 1963

Giulio Natta 1903-

1979 Nobel prize 1963

Scheme 1: the mechanism of Ziegler-Natta polymerization

 29

The fast emerging catalyst front is the metallocene catalysts (Fig. 4). The

herterogeneous Ziegler –Natta catalyst gives a broad molecular weight distribution. With

group IVB transition metallocenes, the typically titanium, zirconium or hafnium, the

catalysts give a high degree of stereo regularity, narrow molecular weight distribution,

and more uniform sequences. This century is to witness spectacular developments in this

area.

Fig. 4 Structure of metallocene catalyst

 30

Structural characterization

Along with the paradigm shift in polymrisation chemistry, unique analytical tools

were developed to throw insights into polymer structure. Better methods were

developed for the determination of molecular weights and molecular weight distribution,

structural analysis by FTIR and NMR, successful application of materials evaluation

technique to polymers, novel techniques of application Raman spectroscopy to polymers,

discovery of MALDITOF etc. are miles stones in developing better analytical tools for

the elucidation of structures of polymers. This has culminated in recently awarding

Nobel prizes to John B. Fenn, Koichi Tanaka and Kurt Wüthrich for their work "for the

development of methods for identification and structure analyses of biological

macromolecules”, "for their development of soft desorption ionisation methods for mass

spectrometric analyses of biological macromolecules" and "for his development of

 31

nuclear magnetic resonance spectroscopy for determining the three-dimensional structure

of biological macromolecules in solution" respectively.

Noble prize in 2002

John B. Fenn, Koichi Tanaka and

Kurt Wüthrich

Nonlinear Polymer Architectures

Recent discoveries to fabricate macromolecules with hyper-branched dendritic

geometries have broken the existing concept of linear macromolecules. These polymers

are entirely devoid of entanglements and have low viscosities with monodisperse

structures and well defined topology possessing unusual physical properties. The are

examples of structure controlled methodology for producing nanoscopic structures with

high functional densities poised to play a critical role in many areas such as biology,

medicine, sensors, catalysis, information storage and transfer and tribology. Typical

examples are given Figs.5.

 32

Fig. 5. Examples of hyper-branched dendritic geometries

Dendrimers are typically well-defined globular macromolecules constructed

around a core unit. During

synthesis, each successive

reaction step leads to an

additional "generation" of

branching. Ideally, dendrimers

exhibit monodispersity, which

From left, dendrimer pioneers Tomalia, Vögtle, and Newkome

means that all the molecules are exactly the same in terms of their structure, composition,

and molecular weight. However, because the syntheses of higher generations require

numerous steps, the final products often contain defects18,19

Application of Polymer Design Principles to Biology using polymer

supported synthesis

The discovery of polymer supported synthesis of pectides by Merrifield has greatly

stimulated progress in biochemistry, molecular biology, pharmacology and medicine. It is
also of practical importance, both for the development of new drugs and for gene
technology. Merrifield's method involves binding the first of the many amino acid
residues of which a protein is composed to a polymer support which is a functionalized
cross linked polymer.
 33

Robert Bruce Merrifield b. 1921. Nobel prize in

Chemistry, 1984 for the "for his development of
methodology for chemical synthesis on a solid matrix"

The alpha helix of proteins and the double helix of DNA

Two great discoveries that revolutionised the world of molecular biology are the

elucidation of the structure of the alpha helix of proteins and the double helix of DNA.

Both are biomacromolecules and hence should find a place in this article. Prof. Linus

Pauling was awarded the Nobel prize in Chemistry in 1954 for

his seminal work on the nature of the

chemical bond and the structure of

molecules and crystals and also

acknowledged his application of the

resulting concepts to the elucidation of

the structure of proteins, specifically the

alpha helix (Fig. 6). Linus Pauling (1901-1994) Nobel prize

in Chemistry 1954

While a visiting lecturer at Oxford University in 1948,

Pauling had a sudden insight regarding the fundamental structure

of proteins, an insight that had eluded him for more than a decade.
 34

Fig. 6 The alpha helix: The -helix is a rod like structure stabilized by hydrogen bonds
between the CO and the NH groups of the main chain

Working with a sheet of paper that he folded over at sites where he knew from

theoretical considerations that the chain could bend, he found that the polypeptide chain,

formed from sequences of amino acids, would coil into a particular helical structure,

which he named the alpha helix. He based this theoretical configuration on chemical-

bonding considerations plus x-ray diffraction evidence from certain fibrous proteins. This

proposal, as well as a companion concept of a related "pleated sheet" structure, proved

correct. Subsequent x-ray diffraction studies have found that the alpha helix is a major

component of both globular and fibrous proteins and extensively controls their structure

and function.

The structure of DNA

On Feb. 28, 1953, Francis Crick walked into the Eagle pub in Cambridge,ngland,

and, as James Watson later recalled, announced that "we had found the secret of life."20

Actually, they had. That morning, Watson and Crick had figured out the structure of

deoxyribonucleic acid, DNA. And that structure-a "double helix" (Fig.7 a-c ) that can

"unzip" to make copies of itself -confirmed suspicions that DNA carries life's hereditary

information.

In fact, it was Rosalind Franklin (1920-1957) who produced the first usable X-ray

pictures (Fig.7d) of DNA ever taken. Watson used her pictures to determine that DNA

spirals into a double helix (See Fig.7 a-c). She was not included in the publication that

reported the structure of DNA and she died before the Nobel Prize was given to Watson
 35

and Crick. Scientists still debate whether she would have shared the prize with them had

she lived.

Fig. 7a-d.

Fig. 7a DNA model prepared by Watson and crick

Fig. 7b. ball model of DNA, Fig. 7c. Ribbon model of DNA
Fig. 7d X-ray picture of DNA produced by Rosalind Franklin

Rosalind Franklin
(right)
James Dewey Watson,
Francis H Crick and
Maurice H. F. Wilkins, The Nobel
Prize in Physiology or Medicine 1962, "for their discoveries concerning the molecular
structure of nucleic acids and its significance for information transfer in living material

Intelligent Polymer Materials

With the dawn of the new millennium, Polymers could be made to adapt to their

environment to ensure an optimization of their behaviour or that of the system to which

they are built-in. Time dependent response of a material to an externally applied stimuli
 36

or environment is often called “intelligence”. The materials which adapt their optical

properties or shape to an environmental stimulus are called smart or intelligent polymers.

Clothing that generates solar power, fabrics that beep if you risk athletic injury and bed

sheets that monitor your heartbeat and physiological health are now in the market.

In biotic systems, intelligence is characterized by heterogeneity, dynamics and co-

operativity of functions. Stimuli responsive smart polymers are the fashion now. They are

going to invade the 21st century market. These will be driven by functional performance

in areas such as biological activity, electrical conductivity, electronic properties, sensors

and optical properties. Intelligent soft hydrogels are actively being explored in areas as

diverse as controlled drug delivery systems, soft robotics, heat sensors and self-regulating

catalysts. Similarly, stimuli responsive artificial organs, molecular motors, smart surfaces

coatings etc. will hit the market soon.

Fig 8. explains how smart polymers can

separate specific proteins from a

mixture by bonding with them through

hydrogen bonding and then over a

change in pH or temperature get

precipitated and thus can be separated.

Fig. 8 Separation of proteins from a mixture by smart polymers.

Fig. 9 depicts the structure of molecules that can operate molecular switches as proposed

by Prof. Lean Marie Lehn (Nobel prize in Chemistry 1987) of France. This is a

reversible photo controlled molecular switching device. On and off takes place on
 37

applying UV light or red light whereby the molecule can be opened and closed to act like

a switch. When UV light is shown on the

Molecule 1a chemical bond is formed making a

central ring. When red light is shown on the closed

form of molecule 2, the

ring opens and the

molecule 1 is got back.

Thus, we have a photo

reversible photo

controlled molecular

switching device.

Fig. 9 The Molecular switch Prof. Lean Marie Lehn (Nobel

prize in Chemistry 1987)

Smart polymers provide light-activated switch to turn enzymes on and off

Researchers at the University of Washington have applied research in how proteins bind

with different molecules to create a molecular switch that enables them to turn an enzyme

on and off. The innovation holds promise for a wide range of laboratory processes,

including highly targeted drug therapies. The study describes a reversible switch for the

enzyme endoglucanase in which light is the trigger for turning the switch on and off.

Endoglucanase is an enzyme that facilitates the breakdown of cellulose. The conditions in

the earlier work that prompted the smart polymers to react were temperature and acidity.

The latest findings are even more exciting, according to Patrick Stayton, UW professor of
 38

Bioengineering, because the trigger is light. “Light is the real interesting one,” said

Stayton, who, with colleague Allan S. Hoffman, professor of bioengineering, leads the

group, which also includes researchers from Genecor International, a California biotech

firm. “It’s easily reversible – it

really is a true switch.” In the

case of endoglucanase, a

contracted polymer thread

blocks the site and an

expanded one moves away

from the site (see Fig. 10),

leaving it open. Researchers

synthesized two light-sensitive

polymers, called DMAA and

DMAAm. When exposed to

visible light, DMAA becomes

Fig. 10. Light activated polymer switch for controlling the activity of enzymes.

hydrophilic – it attracts water molecules and expands. When the visible light is replaced

by ultraviolet light, DMMA becomes hydrophobic, expelling the water molecules and

contracting into a coil. DMMAm works in reverse: under UV light it expands, and under

visible light it contracts. So the switch works by enabling endoglucanase to bind or

unbind with cellulose, depending on the type of light applied.

 39

"Smart" polymers in drug delivery

Smart polymers are emerging in a number of ways in the area of highly demanding

drug delivery systems. Dendritic Box- Cavities in dendrimer can be used for small guest

molecules. The drug is sprayed into the soft inside core of the dendrimer and a hard core

is built around it giving a molecular container of nanoscopic dimension to make a multi

functional nanodevice. This can deliver a drug, sense it that is there and report back. Prof.

Bert Meijer, Eeindhoven University is working on ideas similar to what is shown in Fig.

11.

A "smart" therapeutic nanodevice will have components which perform these

functions: diseased cell recognition diagnosis of disease state, drug delivery reporting

location, reporting outcome of therapy. Fig. 11 a-c gives an idea about the advanced drug

delivery system. This principle is adopted by Starpharma Pooled Development Ltd, Aus.

Viva Gel Dendrimer for HIV treatment. Fig. 11 c shows how a drug prevents the HIV

virus prevents the proteins of the body coming into contact with the virus.

Fig. 11 a

Fig.11 b.
 40

Fig .11 a-c. a. Doping

drug into the a dendrimer. b. the
therapeutic nanodevice having
various functions of sensing,
targeting etc. c. A drug prevents
the HIV virus prevents the
proteins of the body coming into
contact with the virus.

Fig. 11. c.

Supramolecular polymer chemistry

Supramolecular polymer chemistry emerges when manipulation of molecular

interactions (hydrogen bonding, donor-acceptor effects, etc,) recognition process to

generate main chain or side chain supramolecular polymers by the self assembly of

complementary monomeric compounds. The resulting ‘living polymer’ can be further

extended for incorporating desirable groups for property improvement. The

supramolecular associations in the case of polymers may involve intra or inter molecular

forces in the main chain or side chain leading to folding and self assembly processes.

The applications of supramolecular self-assembly polymers are vast. Of

special interest is the generation of fictional arrays on the basis of self-assembly of photo-

, electro-, lono- active components. The development of supramolecular devices using

supramolecular recognition, non-linear optical properties, molecular wires, molecular

photonics, ion and molecular sensors, switiching devices etc. might definitely bring

about a revolution in molecular electronics. The Molecular switch built by Prof. Lehn

shown earlier is an example.

 41

Fig. 12 shows

another

examples of self

self assembled

molecules built

from natural

monomers21.

The

development of

supramolecular

devices using

supramolecular

recognition,

Fig. 12. Self self assembled molecules built from natural monomers.
might definitely bring about a revolution in molecular electronics.

non-linear optical properties, molecular wires, molecular photonics, ion and molecular

sensors, switching devices etc.

Fig. 13a shows the imaging of a single molecular wire based of a self assembly

of monolayer film of phynelene- ethylene molecule with a thioacetate group using

turnable microwave alternating- current scanning tunnelling microscope (STM).

 42

Dvora Perahia, Rakchart Traiphol and H.

F. Bunz (Department of Chemistry, Clemson

University, South Carolina and the Department of

Chemistry and Biochemistry, The University of

South Carolina, Columbia, South Carolina, USA)

describe the supramolecular assembling of thin

films of poly(p-phenyleneethynylene)s (Fig. 13 b)

on the surface of oxidized single-crystal silicon

wafers.

Fig. 13 a. Imaging of a single molecular

wire based of a self assembly of monolayer film
of phynelene- ethylene molecule

Self assembly of conjugated oligomers and polymers on surfaces is at the heart of the

emerging field of molecular electronics and nanomachinery. Of particular interest are

cases where thin films of conjugated polymers on silicon or other conventional

semiconductors self-assemble into nanoscopic structures, “nanopatterns”, a necessary

prerequisite for the long-term goal of nanodevice construction.

 43

Fig. 13 b Self Assembling of Wire like Poly(p-phenyleneethynylene)s

Polymers for Electrical & Electro-optical Applications

Exiting developments are in the area of polymers having conjugated structures for

rechargeable batteries, information storage, electroluminescent display etc. This is

exemplified by the fact that the Nobel Prize for the year 2000 went to Conducting

polymers.

Alan J. Heeger Alan G. MacDiarmid Hideki Shirakawa

Nobel prize 2000

Interests in polymer for optoelectronic technologies have grown because of their

tailorable properties such as optical quality, transparency, refractive index, the ability to

make specified structures with materials such as thin films and fibers and nonlinear

susceptibility.

At the beginning of the 1970s, the Japanese chemist Shirakawa found that it was

possible to synthesize polyacetylene in a new way, in which he could control the

proportions of cis- and trans-isomers in the black polyacetylene film that appeared on the
 44

inside of the reaction vessel. Once - by mistake - a thousand-fold too much catalyst was

added. To Shirakawa's surprise, this time a beautiful silvery film appeared.

The silvery film was trans-polyacetylene, and the corresponding reaction at another

temperature gave a copper-coloured film instead. The latter film appeared to consist of

almost pure cis-polyacetylene. When MacDiarmid heard about Shirakawa's discovery of

an organic polymer that also gleamed like silver, he invited Shirakawa to the University

of Pennsylvania in Philadelphia. They set about modifying polyacetylene by oxidation

with iodine vapour. One of Heeger's students measured the conductivity of the iodine-

doped trans-polyacetylene and - eureka! The conductivity had increased ten million

times! In the summer of 1977, Heeger, MacDiarmid, Shirakawa, and co-workers,

published their discovery in the article "Synthesis of electrically conducting organic

polymers: Halogen derivatives of polyacetylene (CH)n" in The Journal of Chemical

Society, Chemical Communications22. The discovery was considered a major

breakthrough. Since then the field has grown immensely, and also given rise to many new

and exciting applications. They also worked on polyaniline another conducting polymer

which they could make conducting by doping with functionalized dopants such as

camphor sulphonic acid. (See Fig. 14)

 45

Fig. 14. Functionalisation of polyaniline using functionalized dopants.

Protonation, plasticisation . solubilisation and melt processability could be achieved by

using molecules such as the sulphonic acid derivatives of cardanol (see Fig. 15)23 .

H CH3 CH2COOH
O O O

C15H31 C15H31 C15H31

SO3H SO3H SO3H
(SPDP) (SPDA) (SPDPAA)

Fig. 15. Structures of functionalized dopants made from cardanol that enable successful
doping of polyaniline to get highly conducting free-standing films.

NLO Polymers

Interests in polymer for optoelectronic technologies has grown because of their

tailorable properties such as optical quality,

transparency, refractive index, the ability to

make specified structures with materials such

as thin films and fibers and nonlinear

susceptibility. Major applications include,

telecommunications, optical signal

processing, computing and data storage, as

polymer-based electro-optic modulators and

switches, optical fibers for

telecommunications, computer switching

Prof. N. Bloembergen, Nobel Prize, 1981

 46

using a combination of electrical and optical signals is based on second-order effects,

electro optic (EO) wave-guides made from polymer films that switch and modulate

optical signals. NLOP films can also be used for frequency doubling. Prof. N.

Bloembergen and co-workers were awarded the Nobel Prize in 1981 for exploring the

NLO responses of material systems. Fig shows the structure of NLO polymers with high

thermal and temporal stability 24.

O
O
N O C O
C N m
n
R R'

Fig 16. The structure of NLO polymers with high thermal and temporal stability .

Light emitting polymers

Polymers can also be made to light up, but by another principle, namely

electroluminescence, which is used in photodiodes. These photodiodes are, in principal,

more energy saving and generate less heat than light bulbs.

Light-emitting polymers were first observed in 1990 at the University of Cambridge,

U.K., by the group led by Richard Friend. Friend's group, based in physics, and a group

in chemistry, led by Andrew Holmes, were collaborating to research PPV, short for

poly(1,4-phenylene vinylene). This polymer has the ability to conduct electric current, a
 47

rare property for any organic material. What made it even rarer was that as it conducted it

emitted light. The teams reported this amazing electroluminescence in Nature24.

Poly(1,4-phenylene vinylene) PPV (Fig. 17) , a conducting polymer emit light

(electroluminescence) when put between two electrodes (Jeremy Burroughes, Richard

Friend and Donal Bradley of Cambridge University). Used in LEDs to replace gallium

phosphide25.

Electroluminescence from semiconductive polymers

has been known for about ten years. Today there is

extensive commercial interest in photodiodes and in

light-emitting diodes (LEDs). A LED can consist of a

Fig. 17. Poly(1,4-phenylene vinylene)

conductive polymer as an electrode on one side, then a semiconductive polymer in the

middle and, at the other end, a thin metal foil as electrode. When a voltage is applied

between the electrodes, the semiconductive polymer will start emitting light. Heegers

LEC device consists of a solubilized form of PPV (with alkoxy groups attached) blended

with an ion-transport polymer, poly(ethylene oxide), and with aluminum electrodes that

were deposited on the surface. With a dash of lithium salt to promote conductivity,

Heeger has produced a device that emits light within seconds, uses lower voltages, and is

still operative after one year's storage with its original efficiency. (See Fig. 18)
 48

Fig. 18. Light emitting polymers

There are many applications of this brilliant plastic. In a few years, for example, flat

television screens based on LED film will become reality, as will luminous traffic signs

and information signs. Since it is relatively simple to produce large, thin layers of plastic,

one can also imagine light-emitting wallpaper in our homes, and other spectacular things.

Liquid crystalline polymers

Liquid crystalline polymers (LCPs) rose into prominence because of two

potential findings which resulted in their use in high performance and functional

applications : (a) the orientational order of the LC phase can be retained in the polymer

after processing thereby the performance properties underwent a quantum jump to values

close to those of theoretical predictions thereby obtaining extremely high modulus, high

strength, high heat resistance etc. which were not imaginable in earlier situations and

(b) that the LC phase can be trapped or stabilised in the glassy phase of the polymer so

that the electro-optical and magnetic properties can be conveniently manipulated for

applications in areas such as imaging technology, non-linear optics, telecommunications

etc25. Moreover, they have excellent dimensional stability, thermal stability, and flame
 49

resistance. Coupled with the absence of creep and shrinkage, these properties make them

ideal candidates for the high performance applications.

Poly(p-phenyleneterephtalamide) is one of the earliest LCPs discovered by

Stephane Kowelek of du Pont. The exceptional behaviour of LCPs can be understood

from Fig.19 where the tensile properties of a number of fibres are compared with that of

Kevlar. LCPs do not encounter the normal brittle or catastrophic failures which can be

seen from Fig. showing the behaviour of Kevlarâ reinforced epoxy composites. These

exceptional behaviours stem from the hydrogen bonded sheet like structure (Fig. ).

Additional property improvement occurs during processing / spinning when the

spontaneous molecular

orientation characteristic

of LCPs results. LCPs

overtake aluminium and

steel in specific strength

and specific modulus.

These data are enough to

show the importance of

LCPs. Fig. 20 explains

how structural

Fig. 19 Comparison of properties of Kevlar with other fibres.

hierarchies built into LC polyesters by spontaneous ordering gives rise to immense

enhancement of proerties. These type of structures are not seen in ordinary

 50

thermoplastics. Fig. 21. is a Schleiren texture of LCP

polyester of

structure (Fig. 22) in

which a aliphatic

carbonyl has been

introduced to impart

biodegradability26.

Fig. 20. Structural hierarchy of LC polyesters Fig. 21. Schleiren texture of LC

polyester.

O O O
O Ar O C C O (CH2)n C
y
x

n = 1, 2 ,

Ar =
, ,

Fig. 22. Structure of LC polyester wherein an aliphatic carbonyl introduces

biodegradability.
 51

Supercomputing with DNA

Computer scientist Leonard Adleman sparked international interest last year by

showing that DNA could be used as a computing medium. Adleman's method works by

taking advantage of the fact that information can be written onto individual DNA

molecules, using the alphabet of four bases that all living things use to record genetic

information. A DNA computation is done by coding a problem into this alphabet and

then creating conditions under which DNA molecules are formed that encode all possible

solutions of a problem. This process produces billions of billions of molecules encoding

wrong answers, along with perhaps a few encoding the right one.

Computer scientist Leonard Adleman and molecular biologist Myron Goodman and their
DNA computing model (Fig 23)

These billions of DNA

molecules easily fit into a

small test-tube. And with

modern molecular genetics

methods, it's possible to

perform chemical

procedures that reliably

isolate the few DNA

 52

molecules encoding the correct answer from all the

others.

The design (Fig. 23) involves two DNA

molecules bonded together to perform the

computational steps. An enzyme known as FokI acts

as the computer's hardware by cleaving a piece of

the input molecule and releasing the energy stored in

the bonds. This heat energy then powers the next

computation. A. microliter of solution could hold

three trillion computers, which together would

perform 66 billion operations a second.

Fig. 23. The Computing DNA model

According to Goodman, the fastest supercomputers now available can perform about

109 (1 billion) operations per second. By using DNA molecules, he and Adleman hope to

achieve effective speeds of as much as 1017 operations per second - enough to crack the

DES problem.

Nanomaterials: Carbon Nanotubes

Considerable attention has been paid to assembling nanoparticles into ordered two

or three dimensional superstructures in the past few years due to their wide range of

structures and properties. Novel structures have revealed that the electronic and optical

properties are distinctly different from those of individual nanoparticles or their

 53

macroscopic equivalents. The ability to synthesize ordered nanoagglomeates such as

nanocrystal superlattice structures will provide a new horizon to study the collective

properties stemming from particle interaction and develop future optical, nanoscale

electronic and information storage devices.

The discovery of carbon nanotubes in 1991 (the C60 - buckminster fullerene, a new

form of carbon) has provided scientists with a new material that has the properties and

dimensions that are amenable to nanodevices. The discovery of C60 was credited to who

Sir H. W. Kroto, R. E. Smalley and R. F. Curl Jr. who won the Nobel Prize for Chemistry

in 1996. More recently Iijima discovered long hollow tubes of carbon: highly conductive

or can behave as semiconductors depending upon structure. They have exceptional

mechanical properties: an elastic

modulus (stiffness) or around

1000 GPa (compared with steel at

200 GPa) combined with high

strength and resilience

Robert F. Curl Jr., , Sir Harold W. Kroto, Richard E. Smalley , the Nobel Prize for
Chemistry in 1996.

Carbon Nanotubes (Fig 24) which are about 10,000

times thinner than a human hair consist of rolled up

sheets of carbon hexagons. They have the potential for

use as minuscule wires or in ultrasmall electronic

Fig. 24. Carbon nanotubes.

 54

devices. IBM researchers using an atomic force microscope (AFM), an instrument whose

tip can apply accurately measured forces to atoms and molecules, have recently devised a

means of changing a nanotube's position, shape and orientation, as well as cutting it.

These attributes make nanotubes exciting new building blocks for nanodevices, but are

also extremely interesting for micro and macroscopic applications. Figs. 25 and 26

provide data on applications and growth.

Fig. 25. Applications of carbon nanotubes Fig. 26. US nanomaterials market.

Inorganic-Organic Hybrid Nanocompoistes

Polymer nanocomposites comprise a new class of materials where nanoscale

particles such as clay or any other material are finely dispersed within the matrix. These

have been reported to exhibit markedly improved properties as compared to the pure

polymers or conventional particulate composites. These include increase of modulus and

strength, improved barrier properties, increase in solvent and heat resistance, good optical

transparency etc. which may have large potential applications in the field of optic

electrical devices, mechanics photoconductors and so on. Further these improvements

 55

are achieved by very low loadings of the inorganic component (~10 wt%) as compared to

conventional filled polymers which require a high loading of the order of 25-40 wt%.

Nanostructured organic-inorganic composites are much different from the

conventional composites with incorporation of a variety of additives in the polymer

matrices. Strong chemical bonds (covalent or ionic) or interactions such as Vander Waals

forces, hydrogen bonding or electrostatic forces, often exist between the organic and

inorganic components.

Inorganic-organic (eg.Clay-Polymer) nanocomposite materials which offer

enhanced mechanical and

thermal properties as

compared to conventional

material find application in

the electronics, automobile,

and furnishing industries. For

Fig. 27a. Diffusion of polymer through clay bodies.

example, adding such small amounts as 2% by volume of silicate nanoparticles to a

polyimide resin increases the strength by 100%.The subject of hybrids based on layered

inorganic compounds such as clays has been studied for a considerable time, but the area

is enjoying a resurgence of interest and activity as a result of the exceptional properties

which can be realised from such nanocomposites. Fig. 27 a-b depicts how polymer

molecules can be intercalated and the nano composites can be made.

 56

Fig. 27b. Polymer-clay nanocomposite.

Plastics in medicine

Polymeric materials have become essential for the upkeep and maintenance of

human health. Plastics are now inextricably linked to the well-being of millions of people

across the globe in some form or other (see Fig. 28) such as artificial hearts, heartbeat

monitors, replacement limbs, ligament

implants, sutures, safe, tamper-proof

packaging for drugs, biodegradable

coatings for medicines, medical

equipment, often disposable for hygienic

reasons - syringes, blood bags, gloves,

dressings etc.

Fig. 28 The AbioCor Implantable Replacement Heart

 57

Previous materials used in these types of medical implants and systems have

relied on one of two methods. Passive delivery systems use cyclodextrin as container or

host molecules to liberate ‘trapped’ drugs with only one variable allowed, such as time.

The second method relies on the reception of signals in abnormal conditions, such as

changes in pH, or unusual concentrations of substances such as metal ions or metabolised

drugs. These signals are then transmitted to additional electromechanical devices that are

powered by implanted batteries.

Automatic drug Delivery Systems

The big breakthrough for the automatic drug delivery was achieved when polymer

hydrogels were used for this purpose. These polymers responds to variations in pH levels

and rests upon the principle that rests upon the implementation of chemical recognition

sites into the polymer. When changes (such as alterations in pH or compound

concentration) occur in the solution surrounding the implant, the polymer can

automatically open its gates to uptake (or release) a ligand from (or into) the surrounding

aqueous solution. This has the effect of swelling or contracting the polymer. The

polymers perform in a similar way to natural vessels or muscles in that they can perform

macroscopic, reversible movements by the selective formation of supramolecular

complexes. Different receptors can be applied to the polymer to program it to respond to

alterations in different chemicals.

 58

Condensed DNA- Nanomaterials for gene therapy

One of the major developments is in gene therapy where a gene can be condesed

into a nanoparticle using cationic polymer vectors. These nanoparticles have the ability to

get transported into the cell for gene transfection and gene therapy. Fig. 29. depicts

condensation of plasmid DNA using polylysine.

Fig. 28. Condensation of Plasmid DNA by polylysine

Polylysine was used to condense DNA as early as 1969 and was initially

used merely as a model for the interaction of biopolymers such as DNA and

histone proteins. DNA is a highly negatively charge polymer due to the repeating
 59

phosphate groups along the polymer backbone. The interaction with cationic

polymers such as polylysine, spermine, and synthetic polymer

Fig. 29. Speroid structure of condense DNA

vectors etc. is therefore an electrostatic one. The

exact parameters that govern the ability of

cationic polymers to condense DNA are still

under study, although it is generally accepted

that neutralisation of the charges on the DNA

molecule, followed by hydrophobic collapse as water is displaced from the DNA

structure, may play an important role27,28.

Polymer Recycling and Disposal

The 21st century has to tackle in more energetic ways the waste problem (See Fig

30) created by the increased use of

plastic materials29. They may include (i)

Development of new technologies for

break down of the polymers by

depolymerisation of the polymer to get

monomers. The methanolysis technology

Fig 30. Plastics pollution

 60

to unzip PET and the aminolysis technology to unzip nylon, both developed by Du Pont

are examples. Biological methods will be challenges for the 21st century.

(ii) Instead of incineration, pyrolysis can be adopted to give chemicals and fuels.

(iii) Novel environmentally friendly methods to deal with plastics waste might emerge.

Biodegradable Polymers

Biodegradable polymers provide an appealing approach to material design to

replace the existing petroleum -based plastic materials. Various attempts have been

reported to synthesise biodegradable polymers. The principle behind the synthesis is to

introduce weak links within the polymer backbone which are so designed as to permit

controlled degradation of an initially high molecular weight hydrophobic polymer into

lower molecular weight oligomer which can then be utilised and consumed by micro-

organisms through degradation process. Several plastics when physically or chemically

degraded to brittleness tend to be easily degraded by microorganisms leaving CO2, water

and other harmless substances at the end of the processAn analysis of the existing

biodegradable plastics indicates inadequacies in terms of both technology and cost of

production. Novel methods are required to solve this problem. However, there are a

number excellent biodegradable plastics for use in biomedical applications. Use of

biodegradable plastics (See Fig. 31a-e) such as polylactide, polyglycollide, polyhydroxy

butyrates-valerates etc. have become world wide accepted , but their use is limited to

biomedical areas as the cost are high for applications for use in environmental problems.

Polyesteramide30 shown in Fig. 32 and chitin (Fig 33) may find applications soon.
 61

Fig. 32 a Polylacide.

Fig. 32 b: Polyhydroxybytyrate/valerate.

Fig. 32.c. Polylactide-co-glycollide.

Fig. 32.d. Poly)caprolactum)

 62

Fig. 32.d. poly-glycollide.

O O
O (CH2)n C N R1 N C (CH2)n O C R2 C
H H O O m
Fig. 33. poly(esteramide)

Fig. 34. Chitin.

Lactide is the cyclic dimer of lactic acid that exists as two optical isomers, d and l.

l-lactide is the naturally occurring isomer, and dl-lactide is the synthetic blend of d-

lactide and l-lactide. The homopolymer of l-lactide (LPLA) is a semicrystalline

polymer. These types of materials exhibit high tensile strength and low elongation,
 63

and consequently have a high modulus that makes them more suitable

for load-bearing applications such as in orthopedic fixation and sutures.

Poly(l-lactide) is about 37% crystalline, with a melting point of 175—

178°C and a glass-transition temperature of 60—65°C. The degradation

time of LPLA is much slower than that of DLPLA, requiring more than

2 years to be completely absorbed..

Fig. 35. Exhibition of clothes made from polylactide.

Poly(dl-lactide) (DLPLA) is an amorphous polymer exhibiting a random distribution of

both isomeric forms of lactic acid, and accordingly is unable to arrange into an organized

crystalline structure. This material has lower tensile strength, higher elongation, and a

much more rapid degradation time, making it more attractive as a drug delivery system

Clothes, cups, packaging and many other everyday products (see Fig.35) can be made

from polylactides.

Copolymers of l-lactide and dl-lactide have been prepared to disrupt the crystallinity of l-

lactide and accelerate the degradation process Ethicon’s Vicryl (90% glycolide and 10%

l-lactide) is an absorbable suture material.

 64

Conclusions

Polymers have established as materials with great utility in critical areas of industry

and human needs such as shelter, clothing, transportation and health. the new

millennium will find polymers, apart from meeting these established needs, emerging

into areas of demanding applications such as information storage and amplification

technologies, low energy separation technologies, molecular electronics and

photonics, sensor technologies, nanotechnology, intelligent materials and a variety of

other speciality polymers including novel biomedical technologies.In order achieve

these expectations, new design paradigms to make precision macromolecules with

rational catalyst design for control of regio- and stereo-selectivity and novel

supramolecular materials of precise length and topology are on the evolution.

Powerful methods of characterization are expected to contribute to attain such exotic

molecules.

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