CHM 4272 The Organic Chemistry of Polymers
S. A. Miller
Textbook: Polymer Chemistry: An Introduction, Malcolm. P. Stevens
Part I Polymer Structure and Properties (Chapters 1-5)
Part II Vinyl Polymers (Chapters 6-9)
Part III Nonvinyl Polymers (Chapters 10-18)
Chapter 1 Basic Principles
Chapter 2 Molecular Weight and Polymer Solutions
Chapter 3 Chemical Structure and Polymer Morphology
Chapter 4 Chemical Structure and Polymer Properties
Chapter 5 Evaluation, Characterization, and Analysis of Polymers
Chapter 6 Free Radical Polymerization
Chapter 7 Ionic Polymerization
Chapter 8 Vinyl Polymerization
Chapter 9 Reactions of Vinyl Polymers
Chapter 10 Step-Reaction and Ring-Opening Polymerization
Chapter 11 Polyethers, Polysulfides, and Related Polymers
Chapter 12 Polyesters
Chapter 13 Polyamides and Related Polymers
Chapter 14 Phenol-, Urea-, and Melamine-Formaldehyde Polymers
Chapter 15 Heterocyclic Polymers
Chapter 16 Inorganic and Partially Inorganic Polymers
Chapter 17 Miscellaneous Organic Polymers
Chapter 18 Natural Polymers
monomers
organic
chemistry
Spring 2012
Supplemental Textbook:
Principles of Polymerization,
Fourth Edition, George Odian
Introduction - Importance of the Polymer Field
S. A. Miller
"Polymer chemistry has become such an important part of chemical technology, and polymers
have come to play such a role in everyday living, that no chemist can consider himself
adequately trained in his science without some introduction to this field." - Carl Shipp
"Speed" Marvel
Indeed, most chemists and chemical engineers are concerned with some aspect of polymer
science and technology. A 1985 U.S. Department of Labor study reported that almost 60% of
the chemical industry workforce was involved with synthetic polymers.
The late polymer chemist Raymond B. Seymour (19121991), often referred to our time as
the polymer age.
"I am inclined to think that the development of polymerization is perhaps the biggest
thing chemistry has done, where it has had the biggest impact on everyday life."-Lord Todd
(b. 1907), president of the Royal Society of London
Introduction - Relationship to Organic Chemistry
S. A. Miller
Jns Jakob Berzelius
(1779 - 1848)
Berzelius (1833) first used the term "polymeric" to describe the
relationship of ethylene (called olefiant gas, C
2
H
4
) to butene (called
oil of wine, C
4
H
8
) and higher homologues of empirical formula CH
2
.
polymerization
Most polymerization chemistry can be simplified and
understood in terms of small-molecule organic chemistry
monomer polymer
Historical Development
Organic Chemistry Polymerization Chemistry
A + B A-B A-B + A-B -(A-B-A-B)-
polymer
poly = many
mer = part
1.1 Introduction and Historical Development
S. A. Miller
1833 J. J. Berzelius introduces the term polymer
1839 Polymerization of styrene reported (E. Simon)
1860 & 1863 Syntheses and correct structures of poly(ethylene glycol) and poly(ethylene succinate) were
published (A.-V. Loureno)
1913 Report by L. Baekeland of the synthetic polymer that later (1920s) would be
the first commercial scale polymer: Bakelite, a phenol-formaldehyde resin
1927 Heinrich Wieland, 1927 Nobel laureate in chemistry, wrote to Staudinger, "Dear colleague, drop the idea of large
molecules; organic molecules with a molecular weight higher than 5000 do not exist. Purify your products, such as
rubber, then they will crystallize and prove to be low molecular compounds!"
1930sW.H. Carothers develops many synthetic polymerizations,
including the preparation of nylon
1953 Nobel Prize in Chemistry to H. Staudinger for his discoveries in the field of macromolecular chemistry
Introduced the term makromolekl (macromolecule)
1963 Nobel Prize in Chemistry to K. Ziegler and G. Natta for their discoveries in the field of the chemistry and
technology of high polymersspecifically polyethylene and polypropylene
1974 Nobel Prize in Chemistry to P. J. Flory for his fundamental achievements,
both theoretical and experimental, in the physical chemistry of macromolecules
1984 Nobel Prize in Chemistry to R. B. Merrifield for his development of methodology for chemical synthesis
on a solid matrix (Merrifield resin)
1991 Nobel Prize in Physics to P.-G. de Gennes for discovering that methods developed for studying order
phenomena in simple systems can be generalized to more complex forms of matter, in particular to
liquid crystals and polymers (e.g., reptation model)
2000 Nobel Prize in Chemistry to A. J. Heeger, A. G. MacDiarmid, and H. Shirakawa for the discovery and
development of conductive polymers
2002 Nobel Prize in Chemistry to J. B. Fenn, K. Tanaka, and K. Wthrich for mass spectrometric and NMR techniques
for characterizing biological macromolecules
2005 Nobel Prize in Chemistry to Y. Chauvin, R. H. Grubbs, and R. R. Schrock for olefin metathesis
1.2 Definitions
S. A. Miller
oligomer - (Greek oligos = few) macromolecule with only a few monomer units joined
together
repeating unit - (or monomeric unit) repeat section of polymer chain defined by
monomer structure
base unit - smallest possible repeating unit
end groups - structural units that terminate polymer chains
telechelic polymers - polymers containing reactive end groups
homochain polymers - polymers with a single atom type in the polymer chain
heterochain polymers - polymers with more than one atom type in the polymer chain
degree of polymerization (DP) - refers to the total number of structural units in a
polymer chainusually referred to as the average degree of polymerization
homopolymer - a polymer prepared from a single kind of monomer
copolymer - a polymer prepared from two kinds of monomer
terpolymer - a polymer prepared from three or more kinds of monomer
1.2 Definitions (continued)
S. A. Miller
linear - no branching other than the pendant groups associated with the monomer
branched - a polymer with pendant groups that contain multiple monomers
(e.g., graft copolymers)
network - linear or branched chains joined together by covalent bonds
star, comb, ladder, semiladder, polyrotaxane, polycatenane, dendrimer - more
complex polymer architectures (see below)
macromonomer - polymeric or oligomeric monomers
hyperbranched polymer - dendritic branching not emanating from a single core
crosslinking - the process of covalently linking polymers
thermoset - a polymer which cannot melt or flow and cannot be molded
theroplastic - a polymer which can melt and flow and can be molded
plastics, fibers, rubbers (elastomers), coatings, adhesives - classifications of
polymers based on physical or mechanical properties
1.3 Polymerization Processes
S. A. Miller
Two main groups:
(Wallace Carothers 1928)
Addition Polymers Condensation Polymers
The repeat unit of an addition
polymer has the same number
of atoms as the monomer
The repeat unit of a condensation
polymer has fewer atoms than the
monomer
lactone
!-hydroxycarboxylic acid
polyester
water
polyamide
lactam
!-aminocarboxylic acid
water
olefin
hydrocarbon
",!-dibromoalkane
salt
1.3 Polymerization Processes
S. A. Miller
To avoid ambiguity, polymerizations are now commonly characterized according to
the polymerization mechanism
step-growth chain-growth
AA AA
BB BB
AA
BB BB
BB
BB
AA
AA
BB
BBAABB
AA
BB
AA
AA
AA
AA
BB
BB
AABB
AABBAA
BB
AABB
AABB
AABB
AABB
AABB
AABBAA
AABBAABB
AABBAABB
AABBAABB
BBAABBAABB
AABBAABBAABBAABBAABB
AA
AABBAABBAABBAABBAABB
AABBAABBAABBAABBAABBAABBAABBAABBAABBAABB
A A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A A
A
A A
A A
A
A
A
A
A
A
A A
A
A
A
A
I
A A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A A
A
A A
A A
A
A
A
A
A
A
A A
A
A
A
A
IA
A
A
A
A
A A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
IAAAAAAAAAAAAAAA
A
A
A
A
A
A
A
A
A
A
A
A
A A
A
IAAAAAAAAAAAAAAAAAAAAAAAAA
A
A
A
A
A
A
A
A A
A
A
A
A
A
A
AAAAAAAAAAAAAAAAAAAAAAAAA
I
1.4 Step-growth Polymerization
S. A. Miller
1.
2.
Example:
reaction
conversion (p)
DP
N
0
= # molecules initially
N = # molecules (total)
after a given time
Example:
1.4 Step-growth Polymerization
S. A. Miller
0
200
400
600
800
1000
1200
0 0.2 0.4 0.6 0.8 1 1.2
The Carothers equation for step-growth
polymerization (1936) relates:
p = reaction conversion
and
DP = average degree of polymerization
reaction conversion (p)
DP
p = 0.999
p = 0.99
p = 0.9
rearranging,
and,
so,
DP = N
0
/N
N
0
= # molecules initially
N = # molecules (total) after a given time
1.5 Chain-growth Polymerization
S. A. Miller
radical initiator anionic initiator
then termination
Are they catalysts? ( , )
reaction
conversion (p)
DP
N
0
= # molecules initially
N = # molecules (total)
after a given time
1.5 Chain-growth Polymerization
S. A. Miller
Comparison of Step-growth and Chain-growth Polymerizations
chain-growth
step-growth
nonterminating
1.6 Step-growth Addition and Chain-growth Condensation
S. A. Miller
Usually: Step-growth polymerizations are condensation processes and
Chain-growth polymerizations are addition processes. But, there are exceptions.
diisocyanate dialcohol
step-growth
addition
step-growth
addition
chain-growth
condensation
polyurethane
International Union of Pure and Applied Chemistry (IUPAC) (1994):
1.7 Nomenclature
S. A. Miller
1.7.1 Vinyl polymers: Generally polymers made by chain-growth
polymerization of alkenyl monomers
IUPAC:
1) The smallest structural unit (constitutional repeating unit, CRU) is identified.
2) Substituent groups on the backbone are assigned the lowest possible number.
3) The name is placed in parentheses and prefixed with poly.
Source-based terminology vs. IUPAC
1.7 Nomenclature
S. A. Miller
1,3-butadiene
1,2-addition
1,4-addition
cis-1,4-Poly(1,3-butadiene) trans-1,4-Poly(1,3-butadiene)
geometric isomerism
1.7.1 Vinyl Polymers: polymers of dienes
1.7 Nomenclature
S. A. Miller
isotactic polypropylene
syndiotactic polypropylene
atactic polypropylene
Tacticity describes the stereochemical arrangement of substituent groups
configuration
vs.
conformation
1.7 Nomenclature
S. A. Miller
IUPAC: difficult to identify repeat unit in copolymers, so source-based names are used
Systematic
Concise
1.7.2 Vinyl Copolymers
1.7 Nomenclature
S. A. Miller
1.7.3 Non-vinyl Polymers: Polyethers and Polyesters
1.7 Nomenclature
S. A. Miller
1.7.3 Non-vinyl Polymers: Polyamides
1.7 Nomenclature
S. A. Miller
ABS
EPDM
HDPE
HIPS
LLDPE
PC
PE
PEO
PET or PETE
PMMA
PP
PS
PTFE
PVA
PVC
UHMWPE
LDPE
POM
1.7.6 Abbreviations Appendix A
1.8 Industrial Polymers
S. A. Miller
Industrial polymers
Five major classifications:
1) Plastics
2) Fibers
3) Rubber
4) Adhesives
5) Coatings
Increasing modulus (stiffness)
Rubber Plastics Fibers
1976: The year plastics became the most used material in the world
1980s: Volume of consumed plastics overtook that of iron and steel
Today: Synthetic Polymers: 200+ billion kg/year
56%
11%
15%
18%
Plastics
Fibers
Rubber
Adhesives and
Coatings
1.8 Industrial Polymers
S. A. Miller
Commodity:
high volume,
low cost
Engineering:
lower volume,
higher cost
1.8.1 Plastics
1.8 Industrial Polymers
S. A. Miller
1.8.2 Fibers
World production: 30 million metric tons/year
50% synthetic (vs. natural: cotton, wool, silk)
high strength
high modulus (stiffness)
good elongation
good thermal stability
spinnability
1.8 Industrial Polymers
S. A. Miller
1.8.3 Rubber (elastomers)
n
n
cf. natural rubber
Principle
Types of
Synthetic
Rubber:
70%
Most elastomers are thermosets, but thermoplastic elastomers have recently been developed.
polyester (alkyd) synthetic varnishes, interior latex paints: styrene-butadiene copolymers
exterior latex paints: poly(vinyl acetate) and poly(acrylate ester), synthetic adhesives:
phenol-formaldehyde, urea-formaldehyde, epoxies, cyanoacrylates
e.g., Spandex
TM
1.8.4 Coatings and Adhesives
cis-1,4-Poly(isoprene) isoprene
1.9 Polymer Recycling
S. A. Miller
Plastics are probably the most versatile synthetic materials
Current U.S. production exceeds that of steel
Infamous role in trash crisis
Plastics make up 21% of the volume and 8% of the weight
of solid wastes, most of which comes from packaging
Only 2-10% of plastics are recycled on a worldwide basis
Six principle types of plastics used in packaging applications
1988, Society of the Plastics Industry created the recycling code
1.9 Polymer Recycling
S. A. Miller
SPI Resin Identification Coding System
O
O
O
O
O
O O
O
O
V
PP
PS
Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl
PETE
1
HDPE
2
3
LDPE
4
5
6
OTHER
7
LLDPE
4
or
A plastic other than 1 6 or
a combination of plastics
poly(ethylene terephthalate)
poly(vinyl chloride)
high density polyethylene
low density polyethylene or
linear low density polyethylene
polypropylene
polystyrene
variable
