"I just want to say one word to you -- just one word -- 'plastics.

'" Advice to Dustin Hoffman's character in The Graduate

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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 Copolymer: polymer made up of 2 or more monomers
Random copolymer: A-B-B-A-A-B-A-B-A-B-B-B-A-A-B 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
Polymer Classifications
Thermoset: cross-linked polymer that cannot be melted (tires, rubber bands) Thermoplastic: Meltable plastic Elastomers: Polymers that stretch and then return to their original form: often thermoset polymers Thermoplastic elastomers: Elastic polymers that can be melted (soles of tennis shoes)

Polymer Families
Polyolefins: made from olefin (alkene) monomers Polyesters, Amides, Urethanes, etc.: monomers linked by ester, amide, urethane or other functional groups Natural Polymers: Polysaccharides, DNA, proteins 3

Common Polyolefins
Monomer
Ethylene Polyethylene H3C

Polymer
CH3
n

Repeat unit

CH3 Polypropylene Propylene Ph Polystyrene Styrene

Cl Poly(vinyl chloride) Vinyl Chloride F2C CF2 Tetrafluoroethylene F3C Poly(tetrafluoroethylene): Teflon F2 C C F2 F2 C C F2 F2 C C F2 Cl Cl Cl Cl

CH3
n

CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3

n

Ph

Ph

Ph

Ph

Ph

Ph

Ph
CH3

Cl F2 C F2 C

Cl F2 C

Cl CF3

C nF 2

C F2

C F2

Polyesters, Amides, and Urethanes

Monomer
O HO2C Terephthalic acid O O NH2 OH H2N 4 1,6-Diaminohexane Nylon 6,6 HO CO2H HO Ethylene glycol OH Poly(ethylene terephthalate Ester O O
4

Polymer
O HO H2 H2 O C C O H
n

HO 4 Adipic Acid

N H O

N 4 H Amide H N

H
n

O HO2C Terephthalic acid OCN H2 C CO2H H2N 1,4-Diamino benzene NCO NH2 Kevlar HO

H N H
n

4,4-diisocyantophenylmethane O HO H N H2 C

OH HO Spandex Ethylene glycol O H2 H2 H N O C C O H

n

Urethane linkage 5

Natural Polymers
Monomer Polymer

Isoprene H OH HO HO HO OH H H -D-glucose O H3N O H OH

Polyisoprene: Natural rubber H OH H Poly(-D-glycoside): cellulose O HO H O Polyamino acid: protein H3N R1 DNA O O P O O oligonucleic acid DNA O O Base HO H OH H O Rn+1
n

OH
n

H N

H N

O OH Rn+2

O O

R Amino Acid Base

O P O O

OH Nucleotide Base = C, G, T, A

DNA 6

What Makes Polymers Unique?

Really big molecules (macromolecules) like polymers have very different properties than small molecules
Chain entanglement: Long polymer chains get entangled with each other.
When the polymer is melted, the 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 easily stretched. Below the glass transition point, the chains become locked and the polymer is rigid
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Physical Properties
Linear Polymer

Stretch

Cross-Linked Polymer

The chains can be stretched, which causes them to flow past each other. When released, the polymer will not return to its original form.

Stretch

Relax

The cross-links hold the chains together. When released, the polymer will return to it's original form. 8

Polymer Synthesis
There are two major classes of polymer formation mechanisms
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

Addition Polymerization
A In* Initiation In A* A

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Addition Polymerization
Propagation A In* Initiation In A A* A

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Addition Polymerization
Propagation

A In* Initiation

In

A A A*

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Addition Polymerization
A In* Initiation
nA

In

A A A A*

Propagation

In

A A A A A*
n

*A *A A A A A
m

A A A A
m

In

A A A A A
n

In

A A A A A
n

In

A A A A A
n

A A A A A
m

A* Chain Transfer New reactive site is produced

B A A A A Disproportionation
m

Combination

MW

Termination Reactive site is consumed

MW
0 % conversion 100

k propagation k ter mination

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Types of Addition Polymerizations

Anionic
Li+ Ph Ph C3H7 Li

n Ph C4H9 Ph
n

Li+ Ph

C4H9

Radical
n
PhCO2 Ph

Ph PhCO2

Ph

PhCO2 Ph

Cationic

Ph

Ph Cl3Al OH2

n
H Ph HOAlCl3

Ph

H Ph

HOAlCl3
n

Ph

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Step-Growth Polymerization
Stage 1 n n Consumption of monomer

Stage 2 Combination of small fragments

Stage 3 Reaction of oligomers to give high molecular weight polymer 15

Step-Growth Polymerization
Because high polymer does not form until the end of the reaction, high molecular weight polymer is not obtained unless high conversion of monomer is achieved.
1000

Xn =
100

1 1- p

10 Degree of Polymerization

Xn = Degree of polymerization p = mole fraction monomer conversion

1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Mole Fraction Conversion (p)

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Nylon-6,6
O Cl O NaOH
4

O Cl

O
4

Cl

H2N

NH2

Adipoyl chloride

1,6-Diaminohexane

N H

N H

O Adipoyl chloride in hexane Nylon 6,6 Diamine, NaOH, in H2O HO

O
4

N H

N H

H
n

6 carbon diacid

6 carbon diamine

Nylon-6,6

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Nylon-6,6
Since the reactants are in different phases, they can only react at the phase boundary. Once a layer of polymer forms, no more reaction occurs. Removing the polymer allows more reaction to occur.

Adipoyl chloride in hexane Nylon 6,6 Diamine, NaOH, in H2O

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Molecular Weight of Polymers

Unlike small molecules, polymers are typically a mixture of differently sized molecules. Only an average molecular weight can be defined. Measuring molecular weight Size exclusion chromatography Viscosity Measurements of average molecular weight (M.W.) Number average M.W. (Mn): Total weight of all chains divided by # of chains Weight average M.W. (Mw): Weighted average. Always larger than Mn Viscosity average M.W. (Mv): Average determined by viscosity measurements. Closer to Mw than M

Mv Mn Mw

# of molecules increasing molecular weight

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What the Weights Mean

Mn: This gives you the true average weight Let's say you had the following polymer sample: 2 chains: 1,000,000 Dalton 2,000,000 5 chains: 700,000 Dalton 3,500,000 10 chains: 400,000 Dalton 4,000,000 4 chains: 100,000 Dalton 400,000 2 chains: 50,000 Dalton 100,000 10,000,000 10,000,000/23 = 435,000 Dalton 1 Dalton = 1 g/mole

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Weight Average Molecular Weight

Mw: Since most of the polymer mass is in the heavier fractions, this gives the average molecular weight of the most abundant polymer fraction by mass. 2,000,000 = 0.20 1,000,000 = 200,000 10,000,000 3,500,000 = 0.35 700,000 = 245,000 10,000,000 4,000,000 = 0.40 400,000 = 160,000 10,000,000 400,000 = 0.04 100,000 = 4,000 10,000,000 100,000 = 0.01 50,000 = 500 10,000,000 Total = 609,500
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Polymer Microstructure
Polyolefins with side chains have stereocenters on every other carbon
CH3
n

CH3 CH3 CH3 CH3 CH3 CH3 CH3

With so many stereocenters, the stereochemistry can be complex. There are three main stereochemical classifications for polymers. Atactic: random orientation

Isotactic: All stereocenters have same orientation

Syndiotactic: Alternating stereochemistry

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How to Determine Microstructure?

C NMR is a very powerful way to determine the microstructure of a polymer.
13

2 13C

NMR shift is sensitive to the two stereocenters on either side on sptectrometers > 300 MHz. This is called pentad resolution.

mmrm pentad m = meso (same orientation) r = racemic (opposite orientation)

C NMR spectrum of CH3 region of atactic polypropylene

13

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Why is this important?

Tacticity affects the physical properties
Atactic polymers will generally be amorphous, soft, flexible materials Isotactic and syndiotactic polymers will be more crystalline, thus harder and less flexible

Polypropylene (PP) is a good example

Atactic PP is a low melting, gooey material Isoatactic PP is high melting (176), crystalline, tough material that is industrially useful Syndiotactic PP has similar properties, but is very clear. It is harder to synthesize

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