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Polymers: Introduction
• Polymer: High molecular weight molecule made
up of a small repeat unit (monomer).
– A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A
• Monomer: Low molecular weight compound that
can be connected together to give a poymer
• Oligomer: Short polymer chain
"I just want to say one word to • Copolymer: polymer made up of 2 or more
you -- just one word -- 'plastics.'" monomers
Advice to Dustin Hoffman's – Random copolymer: A-B-B-A-A-B-A-B-A-B-B-B-A-A-B
character in The Graduate – Alternating copolymer: A-B-A-B-A-B-A-B-A-B-A-B-A-B
– Block copolymer: A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B
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Types of Polymers Common Polyolefins

Monomer Polymer
• Polymer Classifications CH3
H3C
– Thermoset: cross-linked polymer that cannot be Ethylene
Polyethylene n
Repeat unit
melted (tires, rubber bands)
CH3
– Thermoplastic: Meltable plastic CH3 n
Polypropylene CH3 CH3 CH3 CH3 CH3 CH3 CH3
– Elastomers: Polymers that stretch and then return to Propylene
their original form: often thermoset polymers CH3
Ph n
– Thermoplastic elastomers: Elastic polymers that can Polystyrene Ph Ph Ph Ph Ph Ph Ph
Styrene
be melted (soles of tennis shoes)
CH3
• Polymer Families Cl n
Poly(vinyl chloride) Cl Cl Cl Cl Cl Cl Cl
– Polyolefins: made from olefin (alkene) monomers Vinyl Chloride
F2 F2 F2 F2 F2 F2
– Polyesters, Amides, Urethanes, etc.: monomers linked F2C CF2 F3 C
C
C
C
C
C
C
C
C
C
C
C
C
CF3
F2 F2 F2 nF F2 F2
by ester, amide, urethane or other functional groups Tetrafluoroethylene Poly(tetrafluoroethylene): Teflon 2

– Natural Polymers: Polysaccharides, DNA, proteins 3 4

Polyesters, Amides, and Urethanes Natural Polymers

Monomer Polymer Monomer Polymer
O O
H2 H2
HO2C CO2H OH HO O C C O H
HO
Poly(ethylene terephthalate n Isoprene Polyisoprene:
Terephthalic Ethylene Natural rubber n
acid glycol Ester
H OH H OH
O O HO H HO
O O HO O
H HO OH HO OH
HO OH H2N NH2 HO N N H OH Poly(ß-D-glycoside): H OH
4 4 4 4
Adipic Acid 1,6-Diaminohexane Nylon 6,6 H H n H H cellulose H H n
Amide ß-D-glucose
O O O O O O
H H H H
HO2C CO2H H2N NH2 HO N N H H3N H3N N N OH
O Polyamino acid:
Kevlar n R1 Rn+1 n Rn+2
Terephthalic 1,4-Diamino R protein
acid benzene Amino Acid
O O
H2 DNA
OCN C NCO OH O P O O P O
HO Base Base
O O O
Ethylene Spandex O
4,4-diisocyantophenylmethane
glycol oligonucleic acid
O O OH DNA
H H2 H H2 H2 O
HO N C N O C C O H Urethane linkage Nucleotide DNA
5 Base = C, G, T, A 6
n

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What Makes Polymers Unique? Physical Properties

Linear Polymer
• Really big molecules (macromolecules) like
polymers have very different properties than
small molecules Stretch

– Chain entanglement: Long

polymer chains get entangled with
The chains can be stretched, which causes
each other. them to flow past each other. When released,
• When the polymer is melted, the the polymer will not return to its original form.
Cross-Linked Polymer
chains can flow past each other.
• Below the melting point, the chains
can move, but only slowly. Thus the
plastic is flexible, but cannot be Stretch
easily stretched.
• Below the glass transition point, the Relax
chains become locked and the The cross-links hold the chains together.
polymer is rigid When released, the polymer will return to it's
7 original form. 8

Polymer Synthesis Addition Polymerization

• There are two major classes of polymer formation A
In* In A*
mechanisms Initiation
A

– Addition polymerization: The polymer grows by

sequential addition of monomers to a reactive site
• Chain growth is linear
• Maximum molecular weight is obtained early in the reaction
– Step-Growth polymerization: Monomers react together
to make small oligomers. Small oligomers make
bigger ones, and big oligomers react to give polymers.
• Chain growth is exponential
• Maximum molecular weight is obtained late in the reaction

9 10

Addition Polymerization Addition Polymerization

Propagation Propagation

A A
In* In A A* A In* In A A A* A
Initiation Initiation

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Addition Polymerization Types of Addition Polymerizations

Anionic
A nA
In* In A A A A* In A A A A A*
Initiation Propagation n n
Ph Li+ Li+
C4H9 Ph C4H9
C3H7 Li n
*A A A A A Ph Ph Ph
A *A A A A A m
m Radical

In A A A A A In A A A A A In A A A A A A A A A A
n n m n
n Ph Ph
A* Combination PhCO2• PhCO2 PhCO2
B A A A A n
Chain Transfer
m Ph Ph Ph
Disproportionation Cationic
New reactive site
is produced
Termination
Reactive site is consumed n
MW Ph Ph
Cl3Al OH2 H H HOAlCl3
n
Ph Ph Ph
k propagation HOAlCl3
MW ∝
k ter mination

0 100 13 14
% conversion

Step-Growth Polymerization Step-Growth Polymerization

n n
Stage 1 • Because high polymer does not form until the end
Consumption
of monomer
of the reaction, high molecular weight polymer is
not obtained unless high conversion of monomer
is achieved. 1000

1
Stage 2 Xn =
1− p
Combination 100
of small fragments

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Stage 3
Xn = Degree of polymerization
Reaction of
oligomers to give p = mole fraction monomer 1
high molecular conversion 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
weight polymer Mole Fraction Conversion (p)

15 16

Nylon-6,6 Nylon-6,6
Since the reactants are in different
O O O O
NaOH phases, they can only react at the
Cl Cl H2N NH2 H phase boundary. Once a layer of
4 4 Cl 4
N 4 N
H H
Adipoyl chloride 1,6-Diaminohexane polymer forms, no more reaction
occurs. Removing the polymer allows
more reaction to occur.

O O
Adipoyl chloride H Adipoyl chloride
in hexane HO N N in hexane
4 4
H H n
Nylon 6,6 Nylon 6,6
6 carbon 6 carbon
diacid diamine
Diamine, NaOH, in H2O Diamine, NaOH, in H2O
Nylon-6,6

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Molecular Weight of Polymers What the Weights Mean

Unlike small molecules, polymers are typically a mixture of differently Mn: This gives you the true average weight
sized molecules. Only an average molecular weight can be defined.
Let's say you had the following polymer sample:
• Measuring molecular weight 2 chains: 1,000,000 Dalton 2,000,000
• Size exclusion chromatography 5 chains: 700,000 Dalton 3,500,000
• Viscosity 10 chains: 400,000 Dalton 4,000,000
4 chains: 100,000 Dalton 400,000
• Measurements of average molecular Mv Mn
weight (M.W.) 2 chains: 50,000 Dalton 100,000
• Number average M.W. (Mn): Total Mw 10,000,000
weight of all chains divided by # of 10,000,000/23 = 435,000 Dalton
chains
• Weight average M.W. (Mw): m 1 Dalton = 1 g/mole
Weighted average. Always larger
#
o
o
le
cu
le
s
f

than Mn
• Viscosity average M.W. (Mv): increasing molecular weight
Average determined by viscosity
measurements. Closer to Mw than
Mn 19 20

Weight Average Molecular Weight Polymer Microstructure

Mw: Since most of the polymer mass is in the heavier fractions, this Polyolefins with side chains have stereocenters on every other carbon
gives the average molecular weight of the most abundant polymer
fraction by mass. CH3
n

2,000,000 CH3 CH3 CH3 CH3 CH3 CH3 CH3

= 0.20 × 1,000,000 = 200,000
10,000,000 With so many stereocenters, the stereochemistry can be complex.
3,500,000 There are three main stereochemical classifications for polymers.
= 0.35 × 700,000 = 245,000
10,000,000
Atactic: random orientation
4,000,000
= 0.40 × 400,000 = 160,000
10,000,000
400,000 Isotactic: All stereocenters have same orientation
= 0.04 × 100,000 = 4,000
10,000,000
100,000
= 0.01× 50,000 = 500
10,000,000 Syndiotactic: Alternating stereochemistry
Total = 609,500

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How to Determine Microstructure? Why is this important?

13C NMR is a very powerful way to determine the microstructure of • Tacticity affects the physical properties
a polymer.
– Atactic polymers will generally be amorphous, soft,
flexible materials
2 1 1 2 – Isotactic and syndiotactic polymers will be more
13C NMR shift is sensitive to the two crystalline, thus harder and less flexible
stereocenters on either side on sptectrometers • Polypropylene (PP) is a good example
> 300 MHz. This is called pentad resolution.
– Atactic PP is a low melting, gooey material
– Isoatactic PP is high melting (176º), crystalline, tough
r m m r m r
material that is industrially useful
mmrm pentad – Syndiotactic PP has similar properties, but is very
m = meso (same orientation)
r = racemic (opposite orientation)
clear. It is harder to synthesize
13C NMR spectrum of CH3 region
of atactic polypropylene
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