MSE 355 POLYMER PROCESSING

• Reference Books
• The Elements of Polymer Science and Engineering by
Alfred Rudin.
• Principles of Polymer Processing by Z. Tadmor & C.G.
Gogos
• Materials Science & Engineering, An introduction by
Callister.
• Introduction to Materials Science & Engineering by J.F.
Shackelford.
• Plastics Engineering by R.J. Crawford; Pergamon Press

1
 Polymers
• Pure polymeric materials are the polymers,
additives turn them into plastics
• Two important classes of plastics;
– Thermoplastics materials
– Thermosetting plastics

2
 Polymers
• Advantages of plastics:
– Lightness
– Resilience
– Resistance to corrosion
– Colour fastness
– Transparency
– Ease of processing, etc

3
 Polymers
• Natural polymers
– Silk
– Shellac Bitumen
– Rubber
– Cellulose
• Have long chain-like molecules
• 2 classes of plastics
• Thermoplastics and Thermosets
4
 Thermoplastics
• Examples
• Polyethylene(PE)
• Polyvinyl chloride (PVC)
• Polystyrene (PS)
• Nylon
• Cellulose acetate
• Acetal
• Polycarbonate
• Polymethyl methacrylate (PMMA)
• Polypropylene (PP) 5
 Thermoplastics
• 2 classes of Thermoplastics
• Crystalline (ordered), e.g polyethylene, nylon.
• Amorphous (random), e.g acrylic, polystyrene
• Degree of crystallinity is dependent on the
thermal history
• Characteristics of crystalline plastics
– Always opaque and
– Exhibit a relatively large shrinkage during
moulding
6
 Thermoplastics
• Some advantages of high crystallinity
– High rigidity, especially at elevated temperatures.
– Low friction, hard wearing.
– High hardness.
– Increased resistance to environmental stress
cracking.
– Can be effectively reinforced.
– Ability to be stretched.
– Greater creep resistance

7
 Thermosetting plastics
• Plastic is produced by a chemical reaction and
involves two stages
• Stage 1
• Formation of long chain-like molecules
• Stage 2
• Crosslinking of chains under application of
heat and pressure.
– Bonds formed cannot be softened

8
 Thermosetting plastics
• Characteristics
– Rigid
– Mechanical properties are not heat sensitive

• Examples
– Phenol formaldehyde
– Melamine formaldehyde
– Urea formaldehyde
– Epoxies
– Some polyesters
9
 Polymer Science
• Polymer Technology always precedes Polymer
Science
• Mastication of rubber in 1820
• Patents on vulcanization 20 years later
• Structure of natural rubber determined 100
years later

10
 Definitions in Polymer Science
• Polymer: The word means ‘‘many parts’’.
• Designates a large molecule made up of small
repeating units
• Structure of polystyrene

11
 Definitions
• Macromolecule is a synonym for polymer

• Monomer: a molecule which combines with

other molecules of the same or different type
to form a polymer
• Acrylonitrile, CH2=CHCN is the monomer for
polyacrylonitrile

12
 Definitions
• Polyacrylonitrile

13
 Definitions
• Polyacrylonitrile: basic constituent of ‘‘acrylic’’
fibres
• Uses
– Sweaters
– Hats
– Hand-knitting yarns
– Rugs
– Upholstery
– First produced by Dupont Corporation (1941)

14
 Definitions
• Oligomer: oligomer is a low-molecular-weight
polymer.
• Will contain at least two monomer units.
• Hexatriacontone (n-CH3-(CH2)29-CH3) –
oligomer of polyethylene
• ~CH2-CH2- CH2- CH2~
• Oligomeric articles do not have practically
useful strength
15
 Definitions
• Greek roots of these terms
• Meros ⇒ part;
• Oligo ⇒ few
• Poly ⇒ many
• Mono ⇒ one

16
 Repeating Unit
• Repeating Units: portion of the
macromolecule such that the complete
polymer except for the ends might be
produced by linking together a sufficiently
large number of these units

17
 Repeating Unit
• comprise a single identifiable precursor e.g.
polystyrene

18
 Repeating Unit
• Or composed of the residues of several
smaller molecules e.g. poly(hexamethylene
adipamide)

19
 Repeating Unit
• The repeating unit may not be necessarily
generated from molecules whose structures
are essentially those being repeated e.g
polyvinyl alcohol

20
 Repeating Unit
• Expected starting material is

• Starting material is vinyl acetate

21
 Degree of Polymerization
• End Groups
• The exact nature of the end group is
frequently unknown

• Degree of Polymerization
• The number of repeating units in the polymer
molecule

22
 Degree of Polymerization
• Relation between degree of polymerization
and molecular weight M is given by
• M = (DP) Mo
• Mo= formula weight of the repeating unit

• Polymerization: a chemical reaction in which

the product molecules are able to grow
indefinitely in size so long as reactants are
supplied
23
 Functionality
• Functionality
• The functionality of a molecule is the number
of sites available for bonding to other
molecules under the specific conditions of the
polymerization reaction
– Bifunctional monomer

24
 Functionality
• Polyfunctional monomer can react with more
than two other molecule e.g. Divinyl benzene

25
 Functionality
• a-functional monomer reacts with a b-
functional monomer in a nonchain reaction to
yield product molecule wit functionality of
a+b-2
• bi – or polyfunctionality is a necessary, but not
sufficient condition for polymerization to
occur

26
 Functionality
• E.g. propylene has a functionality of 2 in
reactions involving the double-bond
• Free radical reactions do not produce
macromolecules
• polymerization in heptane at 70˚C with
Al(CH2CH3)2Cl/ TiCl3 catalyst yields high
polymers

27
 Latent Functionality
• Latent Functionality: functional groups that
react under different conditions e.g
vulcanization
• Latent functionality allows chemical reactions
on polymers after they have been shaped into
desired forms

28
 Latent Functionality
• E.g of Latent functionality
• Isoprene can be polymerized at about 50˚C in
n – pentane with either
– butyl lithium or
– titanium tetrachloride/ triisobutyl aluminum
catalysts

29
 Latent Functionality
• Product is cis form of 1,4 – polyisoprene

• Double bond reacts with sulfur during

vulcanization

30
 Latent Functionality
• Vulcanized rubber

31
 Epoxy
• Epoxies
• Epoxy polymers are used mainly as
– adhesives,
– surface coatings and
– in combination with glass fibres or cloth, as light
weight, rigid structural material

32
 Epoxy
• The conversion of an epoxy polymer to an
interconnected network structure is formally
similar to the vulcanization of rubber
• Termed “curing”
• more polar and more highly hydrogen-bonded
molecules form stronger articles at lower
degrees of polymerization as shown

33
 Epoxy
• Polymeric articles and molecular weight,
– A – Polyamides B – Epoxy and phenoxy
polymers C – Olefin polymers

34
 QUIZZ 1 24/10/13
1) What is functionality?
2) What is an oligomer?
3) What is the major difference between a
thermoplast and a thermoset?

35
 Copolymers
• Homopolymer is a macromolecule derived
from a single monomer
• Copolymer contains structural units of two or
more different precursors
• Random Copolymer one in which the
monomer residues are located randomly in
the polymer molecule. ---ABAABABBAAABA---

36
 Copolymers
• Alternating Copolymer
• each monomer of one type is joined to
monomers of a second kind e.g. polymer
made from styrene and maleic anhydride
(SAN). ---ABABABABABAB---

37
 Copolymers
• Graft Copolymer: Formed by growing one
polymer as branches on another preformed
macromolecule.
• E.g. graft copolymer is impact – resistant
polystyrenes

38
 Classification of Polymers
• Many possible ways to classify polymers
• (a) According to the source of the product such
as
– Naturally occuring polymers.
– Entirely synthetic macromolecules.
– Those derived by chemical modification of naturally
occuring polymers.
• (b) Chemical structure
– Polyolific – alkenes
– Polyamide

39
 Classification of Polymers
• (c) Polymer texture during use
– Rubbery
– Glassy
– Partially crystalline
• (d) Area of application
– Adhesive
– Fiber etc.
• (e) Method of production
– Addition
– Condensation polymers

40
 Classification of Polymers
• Method of production classification originated
by W.H. Carothers

41
Condensation and Addition Polymers
• Condensation polymer is one in which the
repeating units lacks certain atoms which
were present in the monomer(s) from which
the polymer was formed
• Formed from bi – or polyfunctional monomers
• E.g Polyesters and Polyamides

42
Condensation and Addition Polymers
• Addition polymers, the recurring (repeating)
units have the same structures as the
monomer(s) from which the polymer was
formed
• E.g - polystyrene, polyethylene
• Problem: cyclic and linear monomers can
produce the same polymer.

43
Condensation and Addition Polymers

• Polyamide made from caprolactam is

technically an addition polymer (Commercial
synthesis)
• Polyamide from the amino acid a
condensation polymer
44
Condensation and Addition Polymers
• Polyethylene can be made from ethylene
(Commercial), dihaloalkanes or diazomethane
as follows

45
Condensation and Addition Polymers
• By convention
• Addition polymers - polymers whose main
chains consist entirely of C – C bonds
• Condensation polymers - those in which
heteroatoms (O, N, S, Si) exist
• Exception – polyformaldehyde
• Step – Growth and Chain – Growth
Polymerization more useful distinction of
classification
46
 Characteristics of Step-Growth
• (1) Growth of polymer molecules by stepwise
inter-molecular reaction.
– Only one reaction type is involved in the
polymerization.
• (2) Monomer units can react with each other
or with polymers of any size.
• (3) Functional group on the end of a molecule
usually assumed to have the same reactivity
as that on a polymer of any size.

47
 Characteristics of Step-Growth
• (4) High conversion of functional groups
required to produce high-molecular-weight
products.
– Average polymer molecular weight rises steadily
during the course of the polymerization.
• (5) Step-growth polymerizations involve
equilibrium between reactants on one hand
and macromolecular products and eliminated
small molecules on the other.
– High polymer cannot coexist with much monomer in
equilibrium systems

48
 Characteristics of Chain-Growth
Polymerization
• (1) Each polymer molecule increases in size at
a rapid rate once its growth has been started.
– When the macromolecule stops growing, it can
generally not react with more monomers (barring
side reactions).
• (2) Growth of polymer molecules is caused by
a kinetic chain of reactions.

49
 Characteristics of Chain-Growth
Polymerization
• (3) Chain-growth polymerization involves the
reaction of monomers with active centers that
may be free radicals, ions, or polymer-catalyst
bonds
• (4) The mechanisms and rates of the
reactions that initiate, continue and terminate
polymer growth are different

50
 Characteristics of Chain-Growth
Polymerization
• (5) Chain-growth polymerization is usually
initiated by some external source
– Energy,
– Highly reactive compound or
– Catalyst
• Reaction proceeds between monomers and an
active center

51
 Characteristics of Chain-Growth
Polymerization
• (6) Polymers made by chain-growth reactions
are often addition polymers by Carother’s
definition. The most common polymers made
by these processes have only carbon-carbon
links in their backbones.

52
 Characteristics of Chain-Growth
Polymerization
• Exception - poly( tetramethylene oxide)
• (1) Self-condensation of tetramethylene
glycol
• (2) Acid catalyzed ring opening
polymerization of tetrahydrofuran

Tetramethylene glycol Poly-Tetramethylene oxide

53
 Characteristics of Chain-Growth
Polymerization
• Self-condensation a series of etherifications
• Dimers to trimers to tetramers etc

54
 Characteristics of Chain-Growth
Polymerization
• Chain-growth polymerization - monomer
reactions initiated by a small concentration of
a strong acid

• kinetic chain reaction is propagated by

successive additions of monomer to the active
site

55
 Characteristics of Chain-Growth
Polymerization
• Kinetic chain reaction is propagated by
successive additions of monomer to the active
site

• Reactive site regenerated on the oxygen atom

• Cation is terminated by reaction with
adventitious impurities

56
 Characteristics of Chain-Growth
Polymerization
• Reaction rate of monomers with each other is
negligible compared to the rate of addition of
monomer to the cationic chain

57
 Requirements for Step-Growth
Polymerization
• Expense: theoretically many step-growth
reactions may exist to produce a given
polymer but cost of production makes one
most suitable

58
 Requirements for Step-Growth
Polymerization
• Efficiency: low efficiency and poor yield with
the desired molecular weight
• Satisfactory step-growth polymerization
reaction must satisfy the following
requirements.
– (i) The reaction must proceed at a reasonably fast
rate.
– (ii) The polymerization must be free of side
reactions which produce cyclic or otherwise
undesirable products
59
 Requirements for Step-Growth
Polymerization
• (Continued)
– (iii) The monomers which are employed must be
free of deleterious impurities.
– (iv) It must be possible to drive the process
almost to complete reaction of the functional
groups.
– (v) It must be possible to control the reaction to
produce target average molecular weights and
molecular weight distributions

60
 Speed of Step-Growth
Polymerizations
• Macromolecular structure can be produced by
alternative step-growth polymerizations of
different monomers
• Rate of a polymerization reaction depends on
the reactivity of the particular monomers
under the prevailing conditions
• Most of least expensive monomers slow at
room temperature ( instead of expensive
monomers)

61
 Side Reactions in Step-Growth
Polymerization
• Side reactions present a particular problem in
step-growth polymerizations (high temp)
• E.g (1) acid-catalyzed esterification of ethanol
with acetic acid is performed commercially at
about 70˚C
• (2) polyesterification of ethylene glycol and
terephthalic acid is at 275˚C for high
conversion

62
 Side Reactions in Step-Growth
Polymerization
• Particularly evident in linear polymers
• Thermosetting polymers used as adhesives
don’t experience these problems

63
 Extent of Conversion of Functional
Groups - Step-Growth Polymerization
• Basic Assumptions
• (1) Reactivity of all functional groups of the same
kind is equivalent and independent of the size of
the molecule to which the functional group is
attached.
• (2) All functional groups in an n-functional
reactant are usually assumed to be equally
reactive.
• (3) The mixture is homogeneous and occurs in a
single phase.
64
 Number Average Degree of
Polymerization in Step-Growth
Reactions
• the number average degree of polymerization
(Xn ) as a function of extent of reaction (P)
useful in designing and controlling step-
growth polymerization

65
 Number Average Degree of
Polymerization in Step-Growth
Reactions
• Assumptions
i. Each functional group need not be confined
to a single monomer e.g a mixture of acids
could be used in a polyamide reaction.
ii. The functionalities of the various monomers
may differ.
iii. The functional groups of opposite kinds need
not be present in equivalent quantities.

66
 Number Average Degree of
Polymerization in Step-Growth
Reactions
• fi = functionality of monomeric species i
• fi = the number of positions in the monomer
that is available for reaction under the
specified conditions
• average functionality, fav

• Ni = number of moles

67
 Number Average Degree of
Polymerization in Step-Growth
Reactions
• Equation (1) above holds strictly when
functional groups of opposite kinds are
present in equal concentrations
• In nonstoichiometric mixtures excess reactant
does not enter the polymerization

68
 Number Average Degree of
Polymerization in Step-Growth
Reactions
• Consider a polymerization which forms AB
links
• ni is the number of equivalents of
functional groups of type i.

69
 Number Average Degree of
Polymerization in Step-Growth
Reactions
• Initial number of monomers, No = ∑ Ni
• Nofav = total number of useful equivalents of
functional groups present at the start of the
reaction
• P = extent of reaction
• = fraction of functional groups in deficient
concentration which have reacted

70
 Number Average Degree of
Polymerization in Step-Growth
Reactions
• Note that every time a new linkage is formed
the reaction mixture will contain one less
molecule
• when the number of molecules is reduced
from No to N moles
• number of linkages formed = No – N

71
 Number Average Degree of
Polymerization in Step-Growth
Reactions
• Since it takes two functional groups to form a
linkage
• number of moles of functional groups lost in
forming No – N linkages = 2 (No – N)mols.

72
 Number Average Degree of
Polymerization in Step-Growth
Reactions
• The number average degree of polymerization
of the reaction is Xn (Carother’s Equation)

73
 Number Average Degree of
Polymerization in Step-Growth
Reactions
• Note
i. Xn is the number average degree of
polymerization of the reaction mixture and
not just of the polymer formed
ii. Xn is not necessarily equal to the degree of
polymerization DPn which is the number of
repeating units per polymer molecule

74
 Number Average Degree of
Polymerization in Step-Growth
Reactions
• a single monomer has Xn = 1, Xn = DPn = 100

• molecule with two monomers has Xn = 2, Xn =

200, DPn = 100
•

75
• If only bifunctional monomers are present and
• there are equivalent concentrations of
functional groups of opposite kinds, we have

• Carothers equation becomes

76
• When the reaction is 95% complete

• For reaction between hexamethylene diamine

and adipic acid we will have this structure
(Nylon 6,6)

• With 10 repeating units = oligomer

77
• When P = 0.98

• Nylon 6, 6 would have a molecular weight

barely high enough for fiber formation
• P = 0.995, Mn = 20,000
• Polymer melt is too viscous for fiber spinning.

78
 Step Growth Polymerization Example
• Suppose that the acid monomer for the
polymerization consisted of 0.01mol
CH3(CH2)4COOH for every 0.99mols of adipic
acid, then the number average degree of
polymerization Xn would be adversely affected
by the impurity as shown in Table 1 below

79
80
• Total amine equivalents = 2
• Total acid equivalents = 1.99

• Xn = 67 in this instance compared to 100 if the

monomers were pure

81