1

Polymers
Chaptertitle

Related topics Principles more difficult to break down. This often requires de-
55 Process
Topic technologies Polymers are macromolecular compounds with more stroying the macromolecules completely.
55 Polymer electronics than 1,000 atoms. They consist of a large number of Polymers consist mainly of carbon-based organic
55 Composite materials small, self-repeating molecular units (monomers). The compounds, sometimes in combination with groups
55 Renewable materials
55 Industrial monomers can be used in different aggregate forms, as containing oxygen, nitrogen or sulphur. However, they
biotechnology solids, liquids or gases, to produce a virtually infinite can also be inorganic in nature. Inorganic macromole-
55 Food technology number of possible variants of polymers. This flexibil- cules that have industrial significance include silicons
ity, which is unique for engineering materials, makes it or polyphosphates. The organic molecules include nat-
possible to customise polymers for everyday applica- ural polymers (biopolymers), chemically modified bi-
tions. opolymers or fully synthetic polymers. Biopolymers
The number of monomers combined to make a form the basis of all living organisms and no living
polymer is known as the degree of polymerisation and creature can exist without natural macromolecular
is typically 1,000 to 100,000. The properties of these substances. Biopolymers include polypeptides (en-
macromolecules hardly change when some of these zymes, hormones, silk, collagen), polysaccharides (cel-
monomers are removed or added. Most polymers con- lulose, lignin, glycogen, chitin), polynucleotides (DNA,
sist of only one or two types of monomer, which al- RNA) and polydienes (caoutchouc: natural rubber).
ready creates different structural variants. Chemically modified biopolymers, also known as semi­
In their simplest form, monomers are strung to- synthetic plastics, are obtained by chemical conversion
gether like threads or chains. The image of a chain apt- of natural macromolecular substances, e. g. the cellu-
ly describes the structure of the macromolecule be- lose derivative celluloid (nitrocellulose) and vulcanised
cause it implies a strong but flexible combination of fibre (parchment cellulose), artificial horn (casein plas-
elements. A chain-shaped macromolecule has a natu- tic) or rubber (vulcanised caoutchouc).
ral tendency to assume a haphazardly rolled-up shape The fully synthetic polymers are based on raw ma-
like a ball of string – unless prevented from doing so terials such as crude oil, natural gas and coal and, to a
by, for instance, other macromolecules. While chemi- lesser extent, but with a slightly rising trend, on renew-
cal binding forces make the individual monomers join able resources.
together to a polymer, physical binding forces create Polymers can basically be divided into two classes:
these “balls of string”. Physical binding is easily re- structural materials and functional polymers, also
leased by application of heat, solvents or mechanical known as special effect and active substances. The
force. Chemical binding forces, however, are much structural materials include thermoplastics, thermo-
sets, elastomers and foams. Functional polymers cre-
ate special effects as active substances in their applica-
tions, such as colour transfer inhibitors in detergents,
superabsorbers in diapers and additives for concrete.
Among the structural materials, a distinction is
made between thermoplastics, duroplastics and elas-
tomers.
77 Thermoplastics. When heated, thermoplastics re-
versibly assume a plastic, i. e. deformable, state and re-
tain their new shape after cooling. They consist of
thread-shaped or only slightly branched chains of mol-
ecules.
 Structural variants of
polymers: The circles and 55 Standard plastics (mass plastics) comprise the
squares represent different thermoplasts polyvinyl chloride (PVC), polyethy-
monomers. lene (PE), polypropylene (PP) and styrenic poly-
 19

mers (PS, SB) which are manufactured in large Depending on the type of primary reaction, a distinc-
quantities. Typical products: shopping bags, drin- tion is made between ionic and radical polymerisa-
king cups tion. The former is characterised by repeated linking of
55 Engineering plastics have improved the mechani- the monomers via positively charged ions (cationic po-
cal, thermal and electrical properties of standard lymerisation) or negatively charged ions (anionic po-
plastics. They can be exposed to complex stresses lymerisation), and in the latter case by linking atoms
and can be used in many structurally demanding and molecules by means of free, unpaired electrons
applications. They include the polyamides (PA), po- (radicals).
lycarbonate (PC), polyethylene terephthalate (PET), In a polycondensation reaction, a low-molecular-
polybutylene terephthalate (PBT) and blends such weight compound is displaced from the monomers
as PBT/PC. Typical products: casings for computer when they join together to form a macromolecule. The
monitors, vacuum cleaners, CDs, wheel caps condensed compound is often water or an alcohol.
55 High performance plastics are engineering plastics In polyaddition, no low-molecular-weight com-
with outstanding properties, especially with pounds are cleaved off and the monomers can join to-  Schematic process chain of
plastic production
regards to heat, although their processing is often gether directly. Polyadditions are behind many every-
more demanding. They include aramides, various day applications. E. g. duroplastic epoxy resins are
polysulfones (PSU, PPSU, PAR, etc.), polyether ke- created through polyaddition of epoxy with hardening
tones (PEK, PEEK), liquid crystal polymers (LCP) agents such as amines and acid hydrides. In the cross-
and fluoropolymers (PTFE). Typical product: mi- link­ing reaction (“curing”), the epoxy ring is split
crowave crockery open.

77 Thermosets. Once moulded, these materials are

no longer plastically deformable even when exposed to Applications
heat. They consist of macromolecules that are With an annual global production of more than
crosslinked in three dimensions. At normal tempera- 100 mio. t, structural materials play an important role
tures they are hard or even brittle. Thermosets include in all areas of our daily life. The functional versatility
phenol resins, polyester resins or epoxy resins. Typical and low weight of polymers make them ideal for pro-
product: electrical plugs. ducing many household goods.
77 Elastomers. These (rubber-like) compounds are 77 Multilayer films. Foods can be kept fresh for long
characterised by high elasticity over a wide range of periods when packaged in transparent, mechanically
temperatures. The molecular chains are cross-linked robust films with special barrier properties against ox-
with each other. Typical examples are natural rubbers, ygen, moisture and oils. The many different barrier
polyurethanes and polyisobutylene. Typical product: properties are achieved by combining different plastics
tyres. that are manufactured and processed in the form of
Most functional polymers contain structures with thin (< 100 µm) and transparent multilayer films.
heteroatoms such as oxygen and nitrogen. As a result, The market requirements of the film determine its
they can carry positive and/or negative charges. This chemical composition. In many cases, polyethylene
means they are often soluble in water. (PE) or polypropylene (PP) are the basis of a multilay-
77 Manufacture of polymers. The chemical reac- er film because of their high degree of flexibility, their
tions leading from monomers to polymers are polym-
erisation, polycondensation and polyaddition. In the
case of polymerisation, monomers that contain dou-
ble bonds are converted by a chain reaction to long
polymer chains. No re-arrangement or cleavage of mo-
lecular components takes place during this process,
which proceeds in four phases:
55 primary reaction: reaction that starts the chain re-
action
55 growth reaction: build-up of molecule chains
55 chain transfer: branching of molecule chains  The commonest classes of
55 chain termination: reactions that lead to the end of polymers and their types of
the chain reaction cross-linking
1 Polymers

barrier effect against water vapour and their sealability able film cover consists of a combination of polyethyl-
(i. e. bonding with other polymers by temperature and ene and BOPA – a biaxially oriented polyamide – in
pressure). Thanks to these properties, the use of PE which the molecular chains of the polymer are aligned
films as household cling film is a long-term success in a highly organised manner, providing high tear re-
story. If the requirements are more exacting, however, sistance.
a combination with polyamides is often chosen. PA has 77 Manufacture. Various methods allow to orient
properties that PE and PP lack: it is tough and flexible polymer molecules in a film. The orientation and
at the same time, retains oxygen and carbon dioxide stretch process can take place simultaneously or con-
and keeps its shape well even at high temperatures. secutively. All methods use an extruder to melt and
Depending on the application, barrier substances such transport the polyamide. The underlying principle is
as ethylene vinyl alcohol (EVOH), bonding agents, and similar to that of a meat grinder. The extruder ends in
adhesives that hold the different layers together, are a heated nozzle, whose specifications depend on the
also added. method used and the form of the film that is to be
One typical application for these composite mate- manufactured. A horizontally arranged nozzle pro-
rials is seen in the now highly popular dish-style packs duces a flat sheet, so-called cast film. A circular nozzle
used to present sausage and cheese slices in an attrac- with a vertical haul-off unit “blows” a film directly into
tive manner. The tough, thermoformed dish is made of the form of a tube.
a layer of polypropylene and polyamide joined by a 77 Superabsorbers. These are crosslinked polymers
bonding agent. The flexible, peelable and often re-seal- made from acrylic acid that can absorb many times

 Multilayer films for food packaging: A multilayer film structure  Extruder for processing polymers: The starting material (mainly

makes it possible to combine many different barrier properties. polyethylene, polypropylene, polyvinyl chloride and polystyrene),
Top: Tear and perforation resistant thin biaxially oriented polya­ usually available in the form of powder or granules, is poured into
mide (BOPA) films with their longitudinally and transversely a feed hopper. The material is then heated and blended to pro­
stretched, parallel oriented molecular chains. Bottom: Combining duce a homogeneous mass. By means of a worm conveyer, the
the good barrier properties of polyamides (PA) against oxygen mass is pressed at the end of the extruder through a shaping
with the good barrier properties of polyethylene (PE) or polypro­ nozzle head. Different products are obtained depending on the
pylene (PP) against water vapour and moisture produces effective shape of the nozzle head.
packaging systems even with low film thicknesses. Source: BASF

crosswise stretching
lengthwise stretching (70-90 °C)
(50-57 °C)

 Manufacture of a step-by-step oriented cast film: In cast film

extrusion, the melt exits through a broad slit nozzle. The film
broad slit nozzle sheet obtained is then stretched lengthwise and crosswise to in­
thermofixing edge
crease its strength. The improved mechanical properties allow
(180-207 °C) trimming roller the use of thinner films. The structure is then fixed by heating.
Source: BASF
 21

their own weight in liquid. The granules, measuring

only 0.1–0.8 mm in diameter, resemble crystals of ta-
ble salt. The polymer granules do not dissolve in water, H2O
but rather absorb the liquid and swell. Superabsorbers H2O H2O H2O H2O
can absorb 1,000 times their own weight in distilled Na
Na

Na
water, 300 times their own weight in tap water or 50 H2O H2O H2O

times their own weight in body fluids such as urine. Na

H2O

And this is how superabsorbers work: the individual H2O H2O

H2O

acrylic acid molecules (monomers) are linked together Na

by polymerisation to form a long chain. A downstream equilibrium

Equilibrium
reaction with sodium hydroxide then produces nega-
tive charges on the chains that are neutralised by the H2O

positively charged sodium ions from the sodium hy-

droxide. On contact with water, the sodium ions dis-
solve in the water and the negatively charged strands
of the polymer chain repel each other electrostatically.  Superabsorbers: On contact with an aqueous liquid, they ab­

sorb up to 1000 times their own weight and convert it into a solid
The polymer network swells and capillary forces draw
gel. Source: BASF
up the water into the resulting cavities created between
the molecules. In addition, an osmotic pressure devel-
ops that draws the water into the superabsorber.
Mass products of the hygiene industry account for distributes it over the entire layer to allow as many ab-
98% of the consumption of superabsorbers. The other, sorber granules as possible to come into contact with
special applications are packaging, cable sheathing or the liquid and absorb it. The absorbent forces are so
auxiliary materials for agriculture in the form of geo- high that no liquid is released even if the baby slides
humus used to increase the water storage capacity of along the floor with the diaper. The diaper’s final layer
soil. In industrialised countries, about 44 billion dia- is a water-impermeable polyethylene film.
pers are used annually. They consist of three layers. 77 Additives for concrete. Concrete is probably the
The first is a porous plastic film of polypropylene, single most important engineering material. About
which is in direct contact with the skin. Polypropylene 7 billion m3 of concrete are used annually worldwide.
is water repellent and does not store any moisture. Be- A broad spectrum of characteristics and properties are
ing porous, this film allows the urine to pass through required to cover the extensive range of applications
it. Underneath this film we find a fabric made of cellu- for this material, e. g. in the transport sector (bridges)
lose incorporating the granular superabsorber. The or as prefabricated concrete parts. These are achieved
cellulose, also known as fluff, absorbs the liquid and by adding small amounts of flow promoters such as

side chain density backbone charge density

a) c)

b) d)

 Structural variants of flow promoters for concrete: The comb-like architecture of flow promoters for

concrete is tailor-made for the target application. Left: Increasing the number of side chains (a–b)
 Structure of a baby‘s diaper with superabsorbers: It is both leads to a bulky molecular structure that can stabilise the concrete for a longer time. Right: The same
thinner and more absorbent than a conventional diaper. Even at stabilisation effect is achieved when the charge density of the flow promoter is reduced (c–d). A stabi­
elevated pressure, the absorbed liquid is not released. Source: lised concrete is used for ready-mix concrete. Flow promoters sketched in Figure a) or c) are used for
BASF precast concrete.
1 Polymers

scatters and absorbs most of the IR radiation (i. e. heat

radiation) that conventional EPS allows to pass
through. The particle size, shape and distribution of
the graphite in the foam are key factors producing this
effect. The insulating effect of a foam can even be in-
creased still further if the diameter of the cavities is re-
duced to less than 100 nm. These tiny cavities now
only have sufficient space for a single gas molecule and
heat transport via groups of molecules is interrupted.
Thus, the energy flux is further reduced, the insulation
performance enhanced.
Polymers of one and the same type are subject to
the same law: high flowability means reduced mechan-
ical properties. Conversely, very tough types have
much lower flowability. This long-established para-
 Product by process: Radical and anionic polymerisation lead to digm has recently been overthrown. Using a nanopar-
different supramolecular structures. The manufacturing process ticulate additive, a polybutylene terephthalate has been
of the polymer made from styrene and butadiene determines
whether the product is opaque or transparent. Source: BASF created with unchanged mechanical properties but
greatly improved flowability. This “high speed effect”
hastens processing operations and reduces energy
costs by 30–50 %. It also enables the manufacture of
highly intricate components.
those based on polycarboxylate ether. The desired Another approach to design new properties is the
properties of the concrete can be achieved by modify- combination of different well-known materials. One
ing the number of charges in the main chain and the example of the functional polymers is a novel binder
number, length and distribution of the side chains. (COL. 9) for facade coatings. It consists of a dispersion
of organic plastic polymer particles in which nanoscale
particles of silica, the basic constituent of glass and
Trends quartz, are embedded and evenly distributed. Thanks
Polymer development no longer involves the unspecif- to this unique combination of elastic soft organic ma-
ic search for new polymers. Instead, polymers are tai- terial and hard mineral, COL.9-based coatings com-
lor-made for specific applications. The control of bine the different advantages of conventional coating
structural hierarchies of nano- and microscale supra­ types. In contrast to brittle, mineral-based coatings,
molecular structures are expected to generate new so- for example, the widely used synthetic resin-based dis-
lutions. persion paints are highly crack-resistant. But in sum-
77 Tailor-made property design. Processing two mer, when dark house walls reach temperatures of
defined components under different conditions can 80 °C and more in the sun, these coatings betray their
lead to completely new product properties. Styrolux weakness: when exposed to heat the synthetic resin
and Styroflex, for example, are two styrene-butadiene begins to soften, and particles of soot and other con-
block copolymers produced by anionic polymerisa- taminants stick to their surface. Because of its high sil-
tion. Styrolux is transparent and tough, while Styroflex ica content, however, the nanocomposite of the binder
is flexible. Both products are impermeable to oxygen lacks this thermoplastic tackiness. At the same time,
and water vapour. Radical polymerisation produces a the mineral particles provide the coating with a hy-
third polymer, an opaque, impact resistant polystyrene drophilic, i. e. water-attracting, surface upon which
(HIPS) of the type found in the interior components of raindrops are immediately dispersed. As for cleanli-
refrigerators. The considerable differences in the prop- ness, COL.9-based coatings offer a dual benefit: in
erties are due to the slightly differing micro- and nano- heavy rain, particles of dirt are simply washed away. At
scale morphologies. the same time, the thin film of water remaining when
77 Nanoeffects. Polymer foams such as expanded the rain has stopped dries extremely quickly. This pre-
®
polystyrene (EPS, e. g. Styropor ) are widely used as vents mould formation.
insulating materials in construction. The insulating 77 Phase change materials. Phase change materials
performance of the foam can be increased significant- are used in building materials to effectively absorb
ly by incorporating graphite in the sheets. Graphite day-time temperatures. These properties are brought
 23

Standard foam Nanofoam

e
ibl
ns

temperature
se

200µm 500nm
phase transition
temperature
pore size > 100 µm pore size > 0.5 µm
therm. conduct. > 30 mW/Km therm. conduct. < 15 mW/Km
5µ
m
latent le
ib
ns
se

e latent heat
ibl
ns
se
0.1 µm

100 µm heat flow

 Functional principle of nanoporous foams: Standard foams  Latent heat is the amount of energy required by a substance

have a pore size of 100 μm, which corresponds to 10 cells per when passing from one phase to the other – for example from ice
millimetre. Nanofoams have a drastically reduced pore size of less to water or from water to steam. It is called latent, because it is not
than 0.5 μm, which corresponds to 2000 cells per millimetre. In apparent in the form of temperature differences. This is why a
nanofoams, the number molecules per cell is so low that the melting ice cube removes large amounts of heat from the sur­
molecules do not “see” or transfer energy to each other. As a con­ rounding liquid and keeps a long drink cool for a prolonged period
sequence, insulation efficiency is greatly improved. Source: BASF even in summer. Because melting 1 kg of ice at 0 °C requires a
whopping 330 kJ – the same amount of energy could heat the
cold water to about 80 °C. Right: The sun heats the room. At a
temperature of 26 °C, the wax begins to melt and absorbs the ex­
cess heat. The wax is microencapsulated in a high-strength acrylic
polymer shell and these capsules are embedded in a matrix of
about by microencapsulated heat storers that use par- gypsum. Source: BASF
affin wax. This material acts as a thermal buffer: dur-
ing the day, the wax heats up and liquefies, absorbing
large amounts of energy. During the night, when the
outside temperatures fall, the wax solidifies, releasing
the energy. The amount of energy stored and the tem- new properties (e. g. conductivity) are successfully
perature at which the phase transitions occur depend introduced. Strong growth is particularly foreseen
greatly on the material. The length of the hydrocarbon in medical and electronics applications, especially
molecule is the determining factor in paraffin waxes: in connection with nanosized structures.
paraffin with a chain length of 16 carbon atoms melts 55 Manufacturing plastics as bulk material will give
at about 20 °C, while chains with 18 atoms need 28 °C. way to custom designing of plastics for specific ap-
Melting points between 6–60 °C can therefore be se- plications.
lected by choosing a different chain length. The chal- 55 A growing understanding of the effects of the su-
lenge is to integrate the melting wax safely into build- pramolecular structures – and combining physical
ing materials like wall plaster, mortar or gypsum findings and phenomena with chemistry and bio-
boards. The process is called microencapsulation: tiny logy – will open up a new range of applications for
droplets of wax are enclosed in a virtually indestructi- polymers in the years ahead.
ble polymer capsule that can withstand even drilling 55 The combination of polymers and specific na-
and sawing. noscale structures will produce materials that play Internet
a key role in solving problems that must be faced in 55 www.e-polymers.org
the years ahead, including resource conservation, 55 http://plc.cwru.edu/tutorial/
Prospects reduction of energy consumption and generating enhanced/files/polymers/
apps/apps.htm
55 Polymers will continue to stimulate future deve- power.
55 www.cem.msu.edu/~reusch/
lopment trends in a number of industries, inclu- VirtualText/polymers.htm
ding automotive, packaging, construction and Prof. Dr. Franz Brandstetter 55 http://openlearn.open.
electrical sectors. They will increasingly supplant Dr. Jens Assmann ac.uk/mod/resource/view.
classical engineering materials, such as metals, as BASF AG, Ludwigshafen php?id=196651&direct=1