Exercise 1 Exercise 1

Composite materials

Advanced materials

Transportation vehicles

Nonrenewable resources

Nonrenewable resources

Organic compound

Nuclear energy

Raw materials

Recycling technology





Exercise 2
materials processing
high-tech
engineering materials
visible light




implant
environmental quality
nonmetallic elements
impurity
clay minerals
fiberglass
visible light






Unit 3/ Lesson 1 polymer
www.polymer.cn
http://www.agpa.uakron.edu/p16/whatarepolymers/intro/player.html
Questions for discussion
What do the terms of PE,PU,PVC stand
for?
Can you list some other polymers you
know know
Can you give a definition for polymer?
What are oligomers and macromers?

Polymers are all around us. They are the

main components of food (starch/

,
protein), clothes (silk, cotton, polyester polyester,
nylon), dwellings (wood-cellulose/

,
paints) and also our bodies (nucleic acids nucleic acids,
Can you list some polymers? Can you list some polymers?
paints) and also our bodies (nucleic acids nucleic acids,
poly polysaccharides, proteins).

No distinction is made between biopolymers biopolymers

and synthetic polymers synthetic polymers.
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Can you give a definition for polymer? Can you give a definition for polymer?

The definition of a polymer is

a substance,
- -R R- -R R- -R R- -R R- -
,or in general
- -[R] [R]
n n
- -
,
where R is a bifunctional entity (or bivalent
radical /

) which is not capable not capable of a
separate existence

separate existence

where n is the degree of polymerization degree of polymerization,

DP
n n

Polymers are constructed from monomer

units, connected by covalent bonds.
#;Q #;Q #;Q #;Q
Can you give a definition for polymer? Can you give a definition for polymer?

This definition excludes excludes simple organic and

inorganic compounds, e.g. CH
4
, NaCl, and
also exclude also exclude materials like diamond diamond, silica silica
and metals metals which appear to have the
properties of polymer, but are capable of properties of polymer, but are capable of
being vaporized vaporized into monomer units.
j| j| j| j|(@]]T)
],j{0
4
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Q|(,{(TQ|@||,
]])](#]@[,
jq|p].
Oligomers and macromers Oligomers and macromers

The molecular weight (MW) molecular weight (MW) can be obtained

from the MW of the monomer multiplied by n.

When the value of n is small, say say 2~20 the

substances are called oligomers oligomers /

, often substances are called oligomers oligomers /

, often
these oligomers are capable of further
polymerizations and are then referred to as
macromers macromers.
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A polymer with a MW of 10
7
, if fully extended,
should have a length of ~1mm and a diameter of
~0.5nm.

This is equivalent in

size to uncooked
spaghetti

~2km in length. spaghetti

~2km in length.

However, in reality, in bulk polymers

the chain is never fully extended
How to determine
the movements of polymer chains?
I. Temperature
II. Chemical make-up of the backbone C-C-C- chain; whether
the chain is flexible flexible (aliphatic structure) or or rigid rigid (aromatic)
#@ #@ #@ #@
|y@ |y@ |y@ |y@
the chain is flexible flexible (aliphatic structure) or or rigid rigid (aromatic)
III. The presence or absence presence or absence of side-chains on the backbone
IV. The inter-polymer chain attraction (weak weakdipole/dipole dipole/dipole,
HH--bonding bonding or strong or strong covalent bonds, cross-linking)
I. The molecular weight molecular weight (MW) and molecular weight molecular weight
distribution distribution (MWD) of polymer
Some properties of polymers Some properties of polymers

Amorphous or partially crystalline

Nearly all of the properties of polymers can be
predicted if the above factors are known.
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Melting temperature of the crystalline phase (T

m
)

Brittle or tough

Rigidity or stiffness

dissolubility

Thermoplastic and thermosetting Thermoplastic and thermosetting

Polymers are really effect chemicals

in that they are used as
materials, with each application requiring
different polymer properties.

Plastics Plastics, fibers, films films, elastomers ,

adhesives adhesives, paints, etc.,
How many groups of polymers How many groups of polymers
are mentioned? are mentioned?

Economics, that is the cost of making and

fabricating the polymer is of prime
importance.

This has led to a rough grouping of

polymers into: polymers into:
Commodity polymers Commodity polymers
Engineering polymers Engineering polymers
Advanced polymeric materials Advanced polymeric materials
Commodity polymers
Polyethylene
Polypropylene (PP)
low density polyethylene (LDPE) low density polyethylene (LDPE)
High density polyethylene (HDPE) High density polyethylene (HDPE)
Linear low density polyethylene (LLDPE) Linear low density polyethylene (LLDPE)
Poly vinyl chloride (PVC)
Polystyrene (PS)
Each of these is prepared on the 10 million tonnes/year
scale. The price is <$1500/tonne.
Engineering polymers Engineering polymers

The materials have enjoyed the highest

percentages growth of any polymers in the last ten
years

and are principally principally used as replacements replacements for

metals for moderate temperature and metals for moderate temperature and
environmental conditions or they may have
outstanding chemical inertness and/or special
properties


Engineering Polymers
Low friction polytetrafluoroethylene (PTFE)
Acetal (or polyoxymethylene, POM/ )
Nylons (polyamides / )
Polyethylene or polybutylene terephthalate Polyethylene or polybutylene terephthalate
/ (PET or PBT)
Polycarbonate (of bisphenol A / A) PC
Polyphenylene oxide (PPO / )
The prices are ($3000~$15000)/tonne
Advanced polymeric materials Advanced polymeric materials

These have very good temperature stability good temperature stability and
when reinforced with fibers (e.g, glass, carbon
or Aramid fibres), i.e. composites composites, they are
stronger stronger than most metals on weight/weight basis.

They are usually only used sparingly, often in

critical parts of structure
.
Their price can be as high as $150,000/tonne. Their price can be as high as $150,000/tonne.



Making of polymers Making of polymers

What are the most important parameters in

making polymers?
The most important parameters in making
polymers are quality control quality control and reproducibility reproducibility


Why? Why?

They are different from simple organic compounds

such as acetone /

, where often a simple
distillation gives the desired purity.

There are many many different grades different grades of the

same

polymer, depending on the final application, e.g., e.g., polymer, depending on the final application, e.g., e.g.,
different MW, MWD, extent of branching, cross different MW, MWD, extent of branching, cross- -
linking, etc., linking, etc.,



How to make polymers? How to make polymers?

A Polymerization process consist of three

stages:
Monomer preparation
1
Polymerization
2
polymer recovery
3
(1) Monomer preparation (1) Monomer preparation

This is not discussed here, other than to

emphasize that the purity of the monomer
is paramount.
(2) polymerization (2) polymerization
Uniformity of polymer properties is absolutely Uniformity of polymer properties is absolutely
necessary necessary

not only includes MW, etc., but other

factors such as color,
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factors such as color,

shape of polymer particle ( if not palletized

or granulated /

)

catalyst residues /

odor

etc
(2) polymerization (2) polymerization

The polymerization operation has to cope

with the following parameters
I. I. Homo Homogeneous or hetero heterogeneous / reactions

II. In homogeneous system, control the viscosity /
III. Most polymerizations are exothermic / , heat has to be
removed since most polymerization are performed at constant
temperature, isothermal / ,heat removal
IV. Control of MW and MWD, branching and cross-linking

The polymerization process affects these

whether batch, semi-batch or continuous.

The residence time

of
polymerization, whether narrow or broad,
also determines MW and MWD
(2) polymerization (2) polymerization
also determines MW and MWD

As a general rule, once a process has been

perfected it is not altered, unless economics
dictate a change
(3) polymer recovery (3) polymer recovery

Unless the polymerization takes place in bulk bulk,

separation from the solvent has to be carried out.

The conventional methods of recovering chemicals,

7] 7] 7] 7] #; #; #; #;) )) )
The conventional methods of recovering chemicals,
e.g., crystallization, distillation, adsorption, etc. e.g., crystallization, distillation, adsorption, etc.
are not be used because polymers possess
properties such as high viscosity and low solubility
in solvents, and are sticky and non-volatile.
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|T|[ |T|[ |T|[ |T|[

Nevertheless, Precipitation Precipitation by using a non-

solvent followed by centrifuging centrifuging, or by
coagulation coagulation of an emulsion or latex emulsion or latex

and removal the solvent by steam steam--striping striping
can be used.
(3) polymer recovery (3) polymer recovery

can be used.



Polymerization techniques Polymerization techniques

Most polymerizations are performed in the liquid

phase using either a batch or a continuous process.
The continuous method is preferred

There are five general methods five general methods of polymerization:

bulk or mass bulk or mass bulk or mass bulk or mass
solution solution
slurry or precipitation slurry or precipitation
suspension or dispersion suspension or dispersion
emulsion emulsion