Contributed by:
The highlights are:
1. Basic principles
2. Molecular weight and polymer solutions
3. Chemical structure and polymer morphology
4. Chemical structure and polymer properties
5. Evaluation, characterization, and analysis of polymers
6. Vinyl polymers
7. Non-vinyl polymers
1.
POLYMER
SCIENCE AND TECHNOLOGY
KINETICS AND THERMODYNAMICS
DR. MOHAMMED ISSA – ASSOCIATE PROFESSOR
DEPT. OF CHEM. ENG. – UNIV. OF TECHNOLOGY
11
SEPT. 2013
1
2.
PART Ⅰ POLYMER STRUCTURE AND PROPERTIES
1. Basic principles
2. Molecular weight and polymer solutions
3. Chemical structure and polymer morphology
4. Chemical structure and polymer properties
5. Evaluation, characterization, and analysis of polymers
POLYMER CHEMISTRY
2
3.
PART Ⅱ VINYL POLYMERS
6. Free radical polymerization
7. Ionic polymerization
8. Vinyl polymerization with complex coordination catalysts
9. Reactions of vinyl polymers
POLYMER CHEMISTRY
3
4.
PART Ⅲ NONVINYL POLYMERS
10. Step-reaction and ring-opening polymerization
11. Polyethers, polysulfides, and related polymers
12. Polyesters
13. Polyamides and related polymers
14. Phenol-, urea-, and melamine-formaldehyde polymers
15. Heterocyclic polymers
16. Inorganic and partially inorganic polymers
17. Miscellaneous organic polymers
18. Natural polymers
POLYMER CHEMISTRY
4
5.
Chapter 1. Basic principles
1.1 Introduction and Historical Development
1.2 Definitions
1.3 Polymerization Processes
1.4 Step-reaction Polymerization
1.5 Chain-reaction Polymerization
1.6 Step-reaction Addition and Chain-reaction Condensation
1.7 Nomenclature
1.8 Industrial Polymers
1.9 Polymer Recycling
POLYMER CHEMISTRY
5
6.
1.1 Introduction and Historical Development
A. Development of civilization
Stone age → Bronze age → Iron age → Polymer age
B. Application of polymeric materials
ｏ PE milk bottles
ｏ Polyamide bulletproof vests
ｏ Polyurethane artificial heart
ｏ Fluorinated phosphazene elastomer for arctic
environments
POLYMER CHEMISTRY
6
7.
C. The purpose of this book
1. Property difference between polymer and
low molecular weight compound
2. Chemistry of polymer synthesis
3. Chemistry of polymer modification
POLYMER CHEMISTRY
7
8.
D. Development of polymer chemistry
1833 년 : Berzelius, the first use of terminology, polymer
1839 년 : Synthesis of polystyrene
1860s : Poly(ethylene glycol), Poly(ethylene succinate)
1900s : Leo Baekeland, synthesis of phenol formaldehyde
1920s : Hermann staudinger
Structure of polymer(long-chain molecules), Novel
Prize(1953 년 )
1939 년 : W.H. Carothers, Nylon synthesis (Du Pont)
1963 년 : Ziegler-Natta, stereoregular polymerization
1974 년 : Paul Flory, polymer solution property
1984 년 : Bruce Merrifield, solid-phase protein process POLYMER CHEMISTRY
8
9.
E. Examples of monomers and polymers
Monomer Polymer
CH2 CH2
CH2CH2
CH2 CHCl CH2CH2
Cl
O
H2C CH2 CH2CH2O
HOCH2CH2OH CH2CH2O
O
HO CO2H O C
POLYMER CHEMISTRY
9
10.
1.2 Definitions
A. Acoording to the amount of repeating units
monomer : one unit
oligomer : few
polymer : many (poly – many, mer – part)
telechelic polymer : polymer containing reactive end group
(tele = far, chele = claw)
telechelic oligomer : oligomer containing reactive end group
macromer(=macro monomer) : monomer containing long
POLYMER CHEMISTRY
10
11.
1.2 Definitions
B. DP : Degree of polymerization
The total number of repeating units
contained terminal group
C. The kinds of applied monomers
One kind : Homopolymer
Two kinds : Copolymer
Three kinds : Terpolymer
POLYMER CHEMISTRY
11
12.
D. Types of copolymer
Homopolymer : -A-A-A-A-A-A-A-A-
Random copolymer : -A-B-B-A-B-A-A-B-
Alternating copolymer : -A-B-A-B-A-B-A-B-
Block copolymer : -A-A-A-A-B-B-B-B-
Graft copolymer : -A-A-A-A-A-A-A-A-
B-B-B-B-B- POLYMER CHEMISTRY
12
13.
E. Representation of polymer types
(a) linear (b) branch
(c) network
POLYMER CHEMISTRY
13
14.
F. Representation of polymer architectures
(a) star polymer (b) comb polymer
(c)ladder polymer (d) semi- ladder
(or stepladder) polymer
14
POLYMER CHEMISTRY
15.
F. Representation of polymer architectures
(e) polyrotaxane (f) polycatenane
(g) dendrimer
POLYMER CHEMISTRY
15
16.
G. Thermoplastic and thermoset (reaction to temperature)
Thermoplastic : Linear or branched polymer
Thermoset : Network polymer
POLYMER CHEMISTRY
16
17.
1.3 Polymerization Processes
A. Classification of polymers to be suggested by Carothers
Addition polymers : repeating units and monomers are same
Condensation polymers : repeating units and monomers
are not equal, to be split out small molecule
POLYMER CHEMISTRY
17
18.
Other examples
1. Polyester from lactone (1.7) &
from ω-hydroxycarboxylic acid (1.8)
O O
(1.7)
O C O R C
R
O (1.8)
OH R CO2H O R C + H2O
POLYMER CHEMISTRY
18
19.
Other examples
2. Polyamide from lactam (1.9), and
from ω-aminocarboxylic acid (1.10)
O O
(1.9)
NH C NH R C
R
O
+ H2O (1.10)
H2N R CO2H NH R C
POLYMER CHEMISTRY
19
20.
Other examples
3. Polyurethane from diisocyanate and dialcohol(1.11)
and from diamine and bischloroformate(1.12):
OCN R NCO + HO R' OH
O O
(1.11)
CNH R NHCO R' O
O O
H 2N R NH2 + ClCO R' OCCl
O O
(1.12)
CNH R NHCO R' O + 2HCl
POLYMER CHEMISTRY
20
21.
Other examples
4. Hydrocarbon polymer from ethylene (1.13), and from α,ω-
dibromide (1.14)
initiator
CH2 CH2 CH2CH2 (1.13)
2Na
BrCH2(CH2)8CH2Br CH2CH2 + 2NaBr (1.14)
5
FUNCTIONAL POLYMERS LAB
POLYMER CHEMISTRY
21
22.
1.3 Polymerization Processes
B. Modern classification of polymerization according to
polymerization mechanism
Step growth polymerization : Polymers build up stepwise
Chain growth polymerization : Addition polymerization
molecular weights increase successively,
one by one monomer
Ring-opening polymerization may be either step
or chain reaction
POLYMER CHEMISTRY
22
23.
1.4 Step-reaction Polymerization
A. Monomer to have difunctional group
1. One having both reactive functional groups in one molecule
A R B R X
O
HO R CO2H O R C + H2O (1.8)
O
+ H2 O (1.10)
H2N R CO2H NH R C
POLYMER CHEMISTRY
23
24.
2. Other having two difunctional monomers
A R A + B R' B R X R' X
OCN R NCO + HO R' OH
O O
(1.11)
CNH R NHCO R' O
O O
H2N R NH2 + ClCO R' OCCl
(1.12)
O O
CNH R NHCO R' O + 2HCl
POLYMER CHEMISTRY
24
25.
B. Reaction : Condensation reaction using functional group
Example - Polyesterification
O
n HO CO2H O C + nH2O (1.3)
n
CO2H + nHOCH2CH2OH
nHO2C (1.4)
O O
C COCH2CH2O n
+ 2nH2O
25
26.
C. Carothers equation
( NO : number of molecules
N : total molecules after a given reaction period.
NO – N : The amount reacted
P : The reaction conversion )
NO
P= Or N = NO(1 P)
N NO
( DP is the average number of repeating units of all molecules present)
DP = NO/N
1
DP =
1-P
For example 1
DP =
At 98% conversion 1- 0.98 POLYMER CHEMISTRY
26
27.
(A) Unreacted monomer
A A A A A A A A A A A A
B B B B B B B B B B B B
(B) 50% reacted, DP = 1.3
A A A A A A A A A A A A
B B B B B B B B B B B B
(C) 75% reacted, DP = 1.7
A A A A A A A A A A A A
(c)
B B B B B B B B B B B B
(D) 100% reacted, DP = 3
A A A A A A A A A A A A
(d)
B B B B B B B B B B B B
27
28.
1.5 Chain-reaction Polymerization
A. Monomer : vinyl monomer
χ
CH2=CH2
B. Reaction : Addition reaction initiated by active species
C. Mechanism :
Initiation
.
R + CH2=CH2 → RCH2CH2 .
Propagation.
RCH2CH2 + CH2=CH2 → RCH2CH2CH2CH2
.
POLYMER CHEMISTRY
28
29.
TABLE 1.1 Comparison of Step-Reaction and
Chain-Reaction Polymerization
Step Reaction Chain Reaction
Growth occurs throughout matrix by Growth occurs by successive addition of
monomer units to limited number of
reaction between monomers, oligomers,
growing chains
and polymers
DP can be very high
DP low to moderate
a
Monomer consumed relatively slowly, but
Monomer consumed rapidly while
molecular weight increases rapidly
molecular weight increases slowly
Initiation and propagation mechanisms different
No initiator needed; same reaction Usually chain-terminating step involved
mechanism throughout Polymerizaion rate increases initially as
No termination step; end groups still reactive
initiator units generated; remains relatively
Polymerization rate decreases steadily as constant until monomer depleted
functional groups consumed
DP, average degree of polymerization. 29
30.
1.6 Step-reaction Addition and
Chain-reaction Condensation
A. Step-reaction Addition.
O
(CH2)6 +
O
O
(CH2)6 (1.15)
O
POLYMER CHEMISTRY
30
31.
1.6 Step-reaction Addition and
Chain-reaction Condensation
B. Chain-reaction Condensation
BF3
CH2N2 CH2 + N2 (1.1
6)
POLYMER CHEMISTRY
31
32.
1.7 Nomenclature
A. Types of Nomenclature
a. Source name : to be based on names of corresponding
Polyethylene, Poly(vinyl chloride), Poly(ethylene oxide)
b. IUPAC name : to be based on CRU, systematic name
Poly(methylene), Poly(1-chloroethylene),
c. Functional group name :
Acoording to name of functional group in the polymer
POLYMER CHEMISTRY
Polyamide, Polyester 32
33.
1.7 Nomenclature
d. Trade name : The commercial names by manufacturer Teflon, Nylon
e. Abbreviation name : PVC, PET
f. Complex and Network polymer : Phenol-formaldehyde polymer
g. Vinyl polymer : Polyolefin
POLYMER CHEMISTRY
33
34.
1.7.1 Vinyl polymers
A. Vinyl polymers
a. Source name : Polystyrene, Poly(acrylic acid),
Poly(α-methyl styrene), Poly(1-pentene)
b. IUPAC name : Poly(1-phenylethylene), Poly(1-carboxylatoethylene)
Poly(1-methyl-1-phenylethylene), Poly(1-propylethylene)
Polystyrene Poly(acrylic acid)
CH2CH CH2CH
CO2H
Poly(α-methylstyrene) Poly(1-pentene)
CH3
CH2C
CH2CH
CH2CH2CH3
POLYMER CHEMISTRY
34
35.
1.7.1 Vinyl polymers
B. Diene monomers
CH2CH CH2CH CHCH2
HC CH2
1,2-addition 1,4-addition
Source name : 1,2-Poly(1,3-butadiene) 1,4-Poly(1,3-butadiene)
IUPAC name : Poly(1-vinylethylene) Poly(1-butene-1,4-diyl)
cf) Table 1.2
POLYMER CHEMISTRY
35
36.
1.7.2 Vinyl copolymer
Systematic
Poly[styrene-co-(methyl methacrylate)]
Poly[styrene-alt-(methyl methacrylate)]
Polystyrene-block-poly(methyl methacrylate)
Polystyrene-graft-poly(methyl methacrylate)
Concise
Copoly(styrene/methyl methacrylate)
Alt-copoly(styrene/methyl methacrylate)
Block-copoly(styrene/methyl methacrylate)
Graft-copoly(styrene/methyl methacrylate)
POLYMER CHEMISTRY
36
37.
1.7.3 Nonvinyl Polymers
O
O CCH2CH2
oxy 1-oxopropane-1,3-diyl
O CH2CH2 O C C
oxy ethylene oxy terephthaloyl
POLYMER CHEMISTRY
37
38.
* Representative Nomenclature of Nonvinyl Polymers
Monomer Polymer Source or IUPAC name
structure repeating unit Common Name
O
CH2CH2O Poly(ethylene oxide)
H2C CH2 Poly(oxyethylene)
HOCH2CH2OH CH2CH2O Poly(ethylene glycol)
Poly(oxyethylene)
O O
H2N(CH2)6NH2 NH(CH2)6NHC(CH2)8C
HO2C(CH2)8CO2H Poly(hexamethylene Poly(iminohexane-
sebacamide) or Nylon6,10 1,6-
diyliminosebacoyl)
cf) Table 1.3
POLYMER CHEMISTRY
38
39.
1.7.4 Nonvinyl copolymers
a. Poly(ethylene terephthalate-co-ethylene isophthalate)
O O O
OCH2CH2O C C OCH2CH2OC
C
O
b. Poly[(6-aminohexanoic acid)-co-(11-aminoundecanoic acid)]
O O
NH CH2 C NH CH2 C
5 10
POLYMER CHEMISTRY
39
40.
1.7.5 End Group
H OCH2CH2 OH
α-Hydro-ω-hydroxypoly(oxyethylene)
POLYMER CHEMISTRY
40
41.
1.7.6 Abbreviations
PVC Poly(vinyl chloride)
HDPE High-density polyethylene
LDPE Low-density polyethylene
PET Poly(ethylene terephthalate)
POLYMER CHEMISTRY
41
42.
1.8 Industrial Polymers
a. The world consumption of synthetic polymers
: 150 million metric tons per year.
1) Plastics : 56%
2) Fibers : 18%
3) Synthetic rubber : 11%
4) Coating and Adhesives : 15%
b.Styrene-butadiene copolymer
Synthetic rubber, PET Fiber (polyester)
Latex paint Plastic (bottle)
POLYMER CHEMISTRY
42
43.
1.8.1
Plastics
1) Commodity plastics
LDPE, HDPE, PP, PVC, PS cf) Table 1.4
2) Engineering plastics
Acetal, Polyamide, Polyamideimide, Polyarylate,
Polybenzimidazole, etc. cf) Table 1.5
3) Thermosetting plastics
Phenol-formaldehyde, Urea-formaldehyde,
Unsaturated polyester, Epoxy,
cf) Table 1.6
4) Functional plastics
Optics, Biomaterial, etc.
POLYMER CHEMISTRY
43
44.
TABLE 1.4 Commodity Plastic
Type Abbreviation Major Uses
Low-density polyethylene LDPE Packaging film, wire and cable insulation,
toys, flexible bottles housewares, coatings
High-density HDPE Bottles, drums, pipe, conduit, sheet, film,
Polyethylene wire and cable insulation
PP Automobile and appliance parts, furniture,
cordage, webbing, carpeting, film packagin
Poly(vinyl chloride) PVC Construction, rigid pipe, flooring, wire
and cable insulation, film and sheet
Polystyrene PS Packaging (foam and film), foam
insulation appliances, housewares, toys
POLYMER CHEMISTRY
44
45.
TABLE 1.5 Principal Engineering Plastics
Type Abbreviation Chapter
C Where Discussed
Acetala POM 11
Polyamideb 13
Polyamideimide PAI 13
Polyarylate 12
Polybenzimidazole PBI 17
Poltcarbonate PC 12
Polyeseterc 12
Polyetheretherketone PEEK 11
Polyetherimide PEI 11
Polyimide PI 13
Poly(phenylene oxide) PPO 11
Poly(phenylene sulfide) PPS 11
Polysulfoned 11
POLYMER CHEMISTRY
45
46.
TABLE 1.6 Principal Thermosetting Plastics
Type Abbreviation Typical Uses Chapter Where
Discussed
Phenol-formaldehyde PF Electrical and electronic equipment, 1
automobile parts, utensil handles, 4
plywood adhesives, particle board
binder
Urea-formaldehyde UF Similar to PF polymer; also 1
treatment of textiles, coatings 4
Unsaturated polyester UP Construction, automobile parts, boat 12
hulls, marine accessories,
corrosion-resistant ducting, pipe,
tanks, etc., business equipment
Epoxy - Protective coatings, adhesives, 11
electrical and electronics
applications, industrial flooring
highway paving materials,
composites
Melamine-formaldehyde MF Similar to UF polymers; decorative 14
panels, counter and table tops,
46
dinnerware
47.
1.8.2 Fibers
1) Cellulosic :
Acetate rayon, Viscose rayon
2) Noncellulosic :
Polyester, Nylon(Nylon6,6, Nylon6, etc)
Olefin
(PP, Copolymer(PVC 85%+PAN and others 15%; vinyon))
3) Acrylic :
Contain at least 80% acrylonitrile
(PAN 80% + PVC and others 20%)
POLYMER CHEMISTRY
47
48.
1.8.3 Rubber (Elastomers)
1) Natural rubber :
cis-polyisoprene
2) Synthetic rubber :
Styrene-butadiene, Polybutadiene,
Ethylene-propylene(EPDM), Polychloroprene, Polyisoprene,
Nitrile, Butyl, Silicone, Urethane
3) Thermoplastic elastomer :
Styrene-butadiene block copolymer
(SB or SBS)
POLYMER CHEMISTRY
48
49.
TABLE 1.7 Principal Synthetic
Fibers
Type Description
Acetate rayon Cellulose acetate
Viscose rayon Regenerated cellulose
Polyester Principally poly(ethylene terephthalate)
Nylon Includes nylon 66, nylon 6, and a variety of other aliphatic
and
Olefin aromatic polyamides
Includes polypropylene and copolymers of vinyl chloride,
with
lesser amounts of acrylonitrile, vinyl acetate, or vinylidene
chloride (copolymers consisting of more than 85% vinyl
chloride are called vinyon fibers)
Contain at least 80% acrylonitrile; included are modacrylic
49
fibers
50.
1.8.4 Coating and Adhesives
1) Coating :
Lacquer, Vanishes, Paint (Oil or Latex), Latex
2) Adhesives :
Solvent based, Hot melt, Pressure sensitive, etc.
Acrylate, Epoxy, Urethane, Cyanoacrylate
POLYMER CHEMISTRY
50
51.
TABLE 1.8 Principal Types of Synthetic Rubber
Type Description
Copolymer of the two monomers in various proportions depending on
properties desired; called SBR for styrene-butadiene rubber
Polybutadiene Consists almost entirely of the cis-1,4 polymer
Ethylene- Often abbreviated EPDM for ethylene-propylene-diene monomer;
propylene made up principally of ethylene and propylene units with small amoun
of a diene to provide unsaturation
PolychloroprenePrincipally the trans-1,4polymer, but also some cis-1,4 and 1,2 polymer
also known as neoprene rubber
Polyisoprene Mainly the cis-1,4 polymer; sometimes called “synthetic natural rubber”
Nitrile Copolymer of acrylonitrile and butadiene, mainly the latter
Butyl Copolyner of isobutylene and isoprene, with only small amounts of the
Latter
Silicone Contains inorganic backbone of alternating oxygen and methylated silic
atoms; also called polysiloxane (Chap. 15)
Urethane Elastomers prepared by linking polyethers through urethane groups
(Chap. 13)
51
52.
1.9 Polymer Recycling
a. Durability of polymer property
1) Advantage : Good materials for use
2) Disadvantage : Environmental problem
b. Treatment of waste polymer : Incinerate,
Landfill, Recycling
ex) Waste Tire : Paving materials
Waste PET : To make monomer ( hydrolysis )
To make polyol ( glycolysis )
POLYMER CHEMISTRY
52
53.
TABLE 1.9 Plastics Recycling Codea
Number Letters Plastic
1 PETEb Poly(ethylene terephthalate)
2 HDPE High-density polyethylene
3 V or PVC Poly(vinyl chloride)
4 LDPE Low-density polyethylene
5 PP Polypropylene
6 PS Polystyrene
7 OTHER Others or mixed plastics
Adopted by the Society of the Plastics lndustry (SPI).
PET is the more widely accepted abbreviation.
POLYMER CHEMISTRY
53
54.
Polymers
What is a polymer?
Very Large molecules structures chain-like in nature.
Poly mer
many repeat unit
repeat repeat repeat
unit unit unit
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)
Adapted from Fig. 14.2, Callister 7e.
54
55.
Ancient Polymer History
• Originally natural polymers were used
– Wood – Rubber
– Cotton – Wool
– Leather – Silk
55
56.
Polymer Composition
Most polymers are hydrocarbons
– i.e. made up of H and C
• Saturated hydrocarbons
– Each carbon bonded to four other atoms
H H
H
C C
H
CnH2n+2
H H 56
58.
Unsaturated Hydrocarbons
• Double & triple bonds relatively reactive – can form new bonds
– Double bond – ethylene or ethene - CnH2n
H H
C C
H H
• 4-bonds, but only 3 atoms bound to C’s
58
59.
Unsaturated Hydrocarbons
– Triple bond – acetylene or ethyne - CnH2n-2
H C C H
59
60.
Unsaturated Hydrocarbons
• An aromatic hydrocarbon (abbreviated as AH)
or arene is a hydrocarbon, of which the
molecular structure incorporates one or more
planar sets of six carbon atoms that are
connected by delocalised electrons numbering
the same as if they consisted of alternating
single and double covalent bonds
60
61.
Unsaturated Hydrocarbons
• Benzene, C6H6, is the simplest and first
recognized aromatic hydrocarbon
61
62.
Unsaturated Hydrocarbons
• What is actually found is that all of the bond
lengths in the benzene rings are 1.397
angstroms
• This is roughly intermediate between the
typical lengths of single bonds (~1.5
angstroms) and double bonds (~1.3
angstroms)
62
63.
Isomerism
• Isomerism
– two compounds with same chemical formula can have
quite different structures/atomic arrangement
Ex: C8H18
• n-octane
H H H H H H H H
H C C C C C C C C H = H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3
H H H H H H H H
H3C ( CH2 ) CH3
6
• 2-methyl-4-ethyl pentane (isooctane)
CH3
H3C CH CH2 CH CH3
CH2
63
CH3
64.
Chemistry of Polymers
• Free radical polymerization
H H H H
R + C C R C C initiation
H H H H
free radical monomer
(ethylene)
H H H H H H H H
R C C + C C R C C C C propagation
H H H H H H H H
dimer
• Initiator: example - benzoyl peroxide
H H H
C O O C 2 C O =2R
H H H
64
65.
Chemistry of Polymers
Adapted from Fig.
14.1, Callister 7e.
Note: polyethylene is just a long HC
- paraffin is short polyethylene
65
66.
Bulk or Commodity Polymers
66
70.
Range of Polymers
• Traditionally, the industry has produced two
main types of synthetic polymer – plastics and
rubbers.
• Plastics are (generally) rigid materials at
service temperatures
• Rubbers are flexible, low modulus materials
which exhibit long-range elasticity.
70
71.
Range of Polymers
• Plastics are further subdivided into
thermoplastics and thermosets
71
74.
Range of Polymers
• Another way of classifying polymers is in
terms of their form or function
74
75.
Synthesis of
Polymers
1
75
76.
Synthesis of Polymers
• There are a number different methods of
preparing polymers from suitable monomers,
these are
– step-growth (or condensation) polymerisation
– addition polymerisation
– insertion polymerisation.
76
77.
Types of Polymerization
• Chain-growth polymers, also known as
addition polymers, are made by chain
reactions
77
78.
Types of Polymerization
• Step-growth polymers, also called
condensation polymers, are made by
combining two molecules by removing a small
molecule
78
79.
Addition Vs. Condensation Polymerization
• Polymerisation reactions can generally be
written as
x-mer + y-mer (x +y)-mer
• In a reaction that leads to condensation
polymers, x and y may assume any value
• i.e. chains of any size may react together as
long as they are capped with the correct
functional group
79
80.
Addition Vs. Condensation Polymerization
• In addition polymerization although x may
assume any value, y is confined to unity
• i.e. the growing chain can react only with a
monomer molecule and continue its growth
80
81.
Thermodynamics
• Thermodynamics of polymerization
determines the position of the equilibrium
between polymer and monomer(s).
• The well known thermodynamic expression:
G = H - TS
yields the basis for understanding
polymerization/depolymerization behavior.
81
82.
Thermodynamics
• For polymerization to occur (i.e., to be
thermodynamically feasible), the Gibbs free
energy of polymerization Gp < 0.
• If Gp > 0, then depolymerization will be
favored.
82
83.
Thermodynamics
• Standard enthalpy and entropy changes, Hop
and Sop are reported for reactants and
products in their appropriate standard states.
Generally:
– Temperature = 25oC = 298K
– Monomer – pure, bulk monomer or 1 M
solution
– Polymer – solid amorphous or slightly
crystalline
83
84.
Thermodynamics
• Polymerization is an association reaction such
that many monomers associate to form the
polymer
• Thus: Sp < 0 for nearly all polymerization
processes
84
85.
Thermodynamics
• Since depolymerization is almost always
entropically favored, the Hp must then be
sufficiently negative to compensate for the
unfavorable entropic term.
• Only then will polymerization be
thermodynamically favored by the resulting
negative Gp.
85
86.
Thermodynamics
In practice:
– Polymerization is favored at low
temperatures: TSp is small
– Depolymerization is favored at high
temperatures: TSp is large
86
87.
Thermodynamics
• Therefore, thermal instability of polymers
results when TSp overrides Hp and thus Gp
> O; this causes the system to spontaneously
depolymerize (if kinetic pathway exists).
87
88.
Thermodynamics
• the activation energy for the depropagation
reaction is higher,
• Compared to the propagation reaction its rate
increases more with increasing temperature
• As shown below, this results in a ceiling
temperature.
88
89.
Thermodynamics
• ceiling temperature
– the temperature at which the propagation and
depropagation reaction rates are exactly equal at
a given monomer concentration
6
5
kdp
4
k, sec
-1
3
kp[M]
2
kp[M] - kdp
1
Tc
0
300 350 400 450 500 550 600
o
Temperature, K 89
90.
Thermodynamics
• At long chain lengths, the chain propagation
reaction
kp
Pn* + M *
Pn+1
kdp
• is characterized by the following equilibrium
expression:
kp [ Pn*1 ] 1
*
k dp [ Pn ][M] [ M ]c
90
91.
Thermodynamics
• The standard-state enthalpy and entropy of
polymerization are related to the standard-
state monomer concentration, [M]o (usually
neat liquid or 1 M solution) as follows:
o o [ M ]o
G H TS RT ln
[M]
91
92.
Thermodynamics
• At equilibrium, G = 0, and T = Tc (assuming
that Hpo and Spo are independent of
temperature).
o o [M]o
H Tc S RTc ln
[M]c
• Or:
H o
Tc
o [M]c
S Rln
[M]o
92
93.
Thermodynamics
• Or:
[M]c H o So
ln
[M]o RTc R
93
94.
Thermodynamics
• At [M]c = [M]o, Tc = Hpo/Spo
Specific Examples of Monomer - Polymer Equilibrium
kcal/mol cal/mol-deg (H/S)
Monomer Hp Sp Tc(oC)
Ethylene -21.2 -24 610
Isobutylene -12.9 -28 175
Styrene -16.7 -25.0 395
-methyl styrene -8.4 -24 66
2,4,6-trimethyl styrene -16.7 --- ---
TFE -37 -26.8 1100
94
95.
Thermodynamics
• Notice the large variation in the -H values.
• ethylene > isobutylene - attributed to steric hinderance
along the polymer chain, which decreases the
exothermicity of the polymerization reaction.
• ethylene > styrene > -metylstyrene - also due to
increasing steric hinderance along the polymer chain.
• Note, however, that 2,4,6-trimethylstyrene has the same -
H value as styrene. Clearly, the major effect occurs for
substituents directly attached to the polymer backbone.
95
96.
Types of Addition
Polymerization
• Free Radical
• Cationic
• Anionic
96
97.
Free Radical Polymerization
• Usually, many low molecular weight alkenes
undergo rapid polymerization reactions when
treated with small amounts of a radical
initiator.
• For example, the polymerization of ethylene
97
98.
Free Radical Polymerization
98
99.
Free Radical Polymerization
99
100.
Free Radical Polymerization
100
101.
Thermodynamic considerations for the
free radical polymerization
101
102.
Thermodynamic considerations for the
free radical polymerization
Chain growth
• Activation energy for chain growth much
lower than for initiation.
• i.e. Growth velocity less temperature
dependent than initiation
102
103.
Thermodynamic considerations for the
free radical polymerization
103
104.
Thermodynamic considerations for the
free radical polymerization
104
105.
Macromonomer/Comonomer Copolymerization
Kinetics : free radical
In such copolymerizations, owing to the large differences in
molar mass between Macromonomer M and Comonomer A, the
monomer concentration is always very small : consequently the
classical instantaneous copolymerization equation
d[ A] [ A](ra [ A] [ M ]
d[ M ] [ M ]rM ([M ] [ A]
Reduces to
d[ A] ra [ A]
d[ M ] [ M ]
As in an « ideal » copolymerization the reciprocal of the radical reactivity
of the comonomer is a measure of the macromonomer to take part in the
process
Controlled Free Radical Copolymerization
105
106.
Ionic Polymerization
• Ionic polymerization is more complex than
free-radical polymerization
106
107.
Ionic Polymerization
• Whereas free radical polymerization is non-
specific, the type of ionic polymerization
procedure and catalysts depend on the nature
of the substituent (R) on the vinyl (ethenyl)
monomer.
107
108.
Ionic Polymerization
• Cationic initiation is therefore usually limited
to the polymerization of monomers where the
R group is electron-donating
• This helps stabilise the delocation of the
positive charge through the p orbitals of the
double bond
108
109.
Ionic Polymerization
• Anionic initiation, requires the R group to be
electron withdrawing in order to promote the
formation of a stable carbanion (ie, -M and -I
effects help stabilise the negative charge).
109
110.
Ionic Polymerization
110
111.
Ionic Polymerization
111
112.
Ionic Polymerization
• M is a Monomer Unit.
• As these ions are associated with a counter-
ion or gegen-ion the solvent has important
effects on the polymerization procedure.
112
113.
Ionic Polymerization
(ii) Chain Propagation depends on :
• Ion separation
• The nature of the Solvent
• Nature of the counter Ion
113
114.
Anionic Polymerization
• Involves the polymerization of monomers that
have strong electron-withdrawing groups, eg,
acrylonitrile, vinyl chloride, methyl
methacrylate, styrene etc. The reactions can
be initiated by methods (b) and (c) as shown
in the sheet on ionic polymerization
114
115.
Anionic Polymerization
• eg, for mechanism (b)
115
116.
Anionic Polymerization
• The gegen-ion may be inorganic or organic
and typical initiators include KNH2, n-BuLi,
and Grignard reagents such as alkyl
magnesium bromides
116
117.
Anionic Polymerization
• If the monomer has only a weak electron-
withdrawing group then a strong base initiator
is required, eg, butyllithium; for strong
electron-withdrawing groups only a weak
base initiator is required, eg, a Grignard
reagent.
117
118.
Anionic Polymerization
• Initiation mechanism (c) requires the direct
transfer of an electron from the donor to the
monomer in order to form a radical anion.
• This can be achieved by using an alkali metal
eg.,
118
119.
Anionic Polymerization of Styrene
119
120.
Anionic Polymerization of Styrene
120
121.
Anionic Polymerization of Styrene
121
122.
Anionic Polymerization of Styrene
122
123.
Anionic Polymerization of Styrene
The activation energy for transfer is larger than
for propagation, and so the chain length
decreases with increasing temperature.
123
124.
Anionic Kinetics
• A general description of the kinetics is
complicated however some useful
approximations may be attained.
124
125.
Anionic Kinetics — approximations
1. The rate of polymerization will be proportional to
the product of the monomer concentration of
growing chain ends.
2. Under conditions of negligible association each
initiator molecule will start a growing chain
3. In the absence of terminating impurities the
number of growing chain ends will always equal the
number of initiator molecules added
125
126.
Anionic Kinetics
1. If propagation is rate controling
• rp d M k p M I 0 (11-1)
dt
126
127.
Anionic Kinetics
2. In BuLi polymerization at high concentrations
in non polar solvents, the chain ends are
present almost exclusively as inactive
dimmers, which dissociate slightly according
to the equilibrium
BuM x
Li
2
k
2 BuM x Li
127
128.
Anionic Kinetics
• Where K= BuM x Li 2 / BuM x Li 2 1
3.The concentration of active chain ends is then
1
BuM x
Li
K BuM2
x
Li
2
1/ 2
(11-3)
• Now it takes two initiator molecules to make
one inactive chain dimmer, so
BuLi I 0 (11-4)
BuM
x Li
2
2
2 128
129.
Anionic Kinetics
• The rate of polymerisation then becomes
1/ 2
d M 1/ 2 I 0
rp k p K
dt 2 (11-5)
• The low value of K, reflecting the presence of most chain ends
in the inactive association state, gives rise to the low rates of
polymerisation in nonpolar solvents. At very high
concentrations, association may be even greater and the rate
essentially independent of [I0]
129
130.
Cationic Polymerization
130
131.
Cationic Polymerization
• (ii) PropagationChain growth takes place
through the repeated addition of a monomer
in a head-to-tail manner to the ion with
retention of the ionic character throughout
131
132.
Cationic Polymerization
132
133.
Cationic Polymerization
(iii) Termination
Termination of cationic polymerization
reactions are less well-defined than in free-
radical processes. Two possibilities exist as
follows:
133
134.
Cationic Polymerization
134
135.
Cationic Polymerization
• Hydrogen abstraction occurs from the
growing chain to regenerate the catalyst-co-
catalyst complex.
• Covalent combination of the active centre
with a catalyst-co-catalyst complex fragment
may occur giving two inactive species.
135
136.
Cationic Polymerization
• The kinetic chain is terminated and the
initiator complex is reduced - a more effective
route to reaction termination.
136
137.
Cationic Polymerization
137
138.
Cationic Polymerization
• The kinetics of these reactions is not well
understood, but they proceed very rapidly at
extremely low temperatures.
138
139.
Polymerization Processes
• TWO USEFUL DISTINCTIONS ;
– BETWEEN BATCH AND CONTINUOUS
– AND BETWEEN SINGLE - PHASE AND MULTI -
PHASE
• SINGLE - PHASE
– Bulk or Melt Polymerization
– Solution Polymerization
139
140.
Polymerization Processes
140
141.
Bulk Polymerization
• The simplest technique
• Gives the highest-purity polymer
• Only monomer, a monomer soluble initiator
and perhaps a chain transfer agent are used
• This process can be used for many free radical
polymerizations and some step-growth
(condensation) polymerisation.
141
142.
Polymerization Techniques
These include:
• Bulk Polymerization
• Solution Polymerization
• Suspension Polymerization
• Emulsion Polymerization
142
143.
Bulk Polymerization
• High yield per reactor volume
• Easy polymer recovery
• The option of casting the polymerisation
mixture into final product form
143
144.
Bulk Polymerization
• Difficulty in removing the last traces of
monomer
• The problem of dissipating heat produced
during the polymerization
– In practice, heat dissipated during bulk
polymerization can be improved by providing
special baffles
144
145.
Solution Polymerization
• Definition: A polymerization process in which
the monomers and the polymerization
initiators are dissolved in a nonmonomeric
liquid solvent at the beginning of the
polymerization reaction. The liquid is usually
also a solvent for the resulting polymer or
copolymer.
145
146.
Solution Polymerization
• Heat removed during polymerization can be
facilitated by conducting the polymerization in
an organic solvent or water
146
147.
Solution Polymerization
• Solvent Requirements:
• Both the initiator and the monomer be
soluble in it
• The solvent have acceptable chain transfer
characteristics and suitable melting and
boiling points for the conditions of the
polymerization and subsequent solvent-
removal step.
147
148.
Solution Polymerization
• Solvent choice may be influenced by other
factors such as flash point, cost and toxicity
• Reactors are usually stainless steel or glass
lined
148
149.
Solution Polymerization
• small yield per reactor volume
• The requirements for a separate solvent
recovery step
149
150.
Suspension Polymerization
• Definition: A polymerization process in which
the monomer, or mixture of monomers, is
dispersed by mechanical agitation in a liquid
phase, usually water, in which the monomer
droplets are polymerized while they are
dispersed by continuous agitation. Used
primarily for PVC polymerization
150
151.
Suspension Polymerization
• If the monomer is insoluble in water, bulk
polymerization can be carried out in
suspended droplets, i.e., monomer is
mechanically dispersed.
• The water phase becomes the heat transfer
medium.
151
152.
Suspension Polymerization
• So the heat transfer is very good. In this
system, the monomer must be either
– 1) insoluble in water or
– 2) only slightly soluble in water, so that when it
polymerizes it becomes insoluble in water.
152
153.
Suspension Polymerization
• The behavior inside the droplets is very much
like the behavior of bulk polymerization
• Since the droplets are only 10 to 1000 microns
in diameter, more rapid reaction rates can be
tolerated (than would be the case for bulk
polymerization) without boiling the monomer.
153
154.
Emulsion Polymerization
• Emulsion polymerization is a type of radical
polymerization that usually starts with an
emulsion incorporating water, monomer, and
surfactant.
154
155.
Emulsion Polymerization
• The most common type of emulsion
polymerization is an oil-in-water emulsion, in
which droplets of monomer (the oil) are
emulsified (with surfactants) in a continuous
phase of water.
• Water-soluble polymers, such as certain
polyvinyl alcohols or hydroxyethyl celluloses,
can also be used to act as
emulsifiers/stabilizers.
155
156.
Emulsion Polymerization – Schematic
156
157.
Emulsion Polymerization
Advantages of emulsion polymerization include:
• High molecular weight polymers can be made at fast
polymerization rates. By contrast, in bulk and
solution free radical polymerization, there is a
tradeoff between molecular weight and
polymerization rate.
• The continuous water phase is an excellent
conductor of heat and allows the heat to be removed
from the system, allowing many reaction methods to
increase their rate.
157
158.
Emulsion Polymerization
Advantages Continued:
• Since polymer molecules are contained within
the particles, viscosity remains close to that of
water and is not dependent on molecular
weight.
• The final product can be used as is and does
not generally need to be altered or processed.
158
159.
Emulsion Polymerization
Disadvantages of emulsion polymerization include:
• For dry (isolated) polymers, water removal is an
energy-intensive process
• Emulsion polymerizations are usually designed to
operate at high conversion of monomer to polymer.
This can result in significant chain transfer to
polymer.
159
160.
Fabrication
Methods
1
1 160
165.
Example
• Suggest a polymer and fabrication process
suitable to produce the following items.
Support your choice by contrasting it with
other possible alternatives.
– Car bumper
– Carry bag
– Machine gear
– Shower curtain
– Tooth brush stand
165
166.
Solution
• i) Car bumper
• Polyurethane is one of the suitable materials for car
bumpers. another suitable material is PP. Reaction injection
molding process is suitable to produce polyurethane
bumpers. Polyurethane is molded by mixing of highly reactive
liquids (isocyanateandpolyol). Because the materials are very
reactive liquids, Other molding processes such as injection
molding and compression molding can not be used for this
purpose. However, injection molding and compression
molding methods can be used to make PP bumpers.
166
167.
Solution
• ii) Carry bag
• Polyethylene (PE)is used widely for making carry
bags. Blown film extrusion methodis best suitable to
produce carry bags. Calendering method also can be
applied for the same purpose. However, considering
the production rate and thickness range that can be
produced, blown film extrusion method is ideal to
produce carry bags.
167
168.
THANK YOU
ANY QUESTIONS ?
168
+1-315-636-4485
+91 98151-74050 
