POLYMER STRUCTURES

Polymers

Naturally occurring

Wood, rubber, cotton, wool, leather Proteins, enzymes, starches, cellulose

Synthetic (from organic molecules)

Plastics, synthetic rubbers, Fibers

Polymer Structures
ISSUES TO ADDRESS...
What are the general structural and chemical characteristics of polymer molecules?

What are some of the common polymeric materials, and how do they differ chemically?
How is the crystalline state in polymers different from that in metals and ceramics ?

Hydrocarbon molecules

Most polymers are organic in origin Many organic materials are hydrocarbons

Covalent bonds Each C has 4 electrons that may participate in covalent bonding Single electron pair sharing single bond

Polymer Composition

Saturated hydrocarbons Each carbon singly bonded to four other atoms Example: Ethane, C2H6

H C C

Unsaturated Hydrocarbons

Double & triple bonds somewhat unstable can form new bonds

Double bond found in ethylene or ethene - C2H4

H C C H

H H

Triple bond found in acetylene or ethyne - C2H2

H C C H
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Isomerism

Isomerism two compounds with same chemical formula can have quite different structures for example: C8H18

normal-octane
= H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3

H H H H H H H H H C C C C C C C C H H H H H H H H H

H3C ( CH2 ) CH3

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2,4-dimethylhexane
CH3 H3C CH CH2 CH CH3 CH2 CH3
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Polymer Molecules

Much larger in comparison to the hydrocarbon molecules Macromolecules A chain of carbon atoms is the backbone Mer The repeating unit in a polymer chain Monomer a stable unit from which the polymer is synthesized

Polymerization and Polymer Chemistry

Free radical polymerization

H H R + C C H H monomer (ethylene) H H + C C H H H H R C C H H initiation

free radical

H H R C C H H

H H H H R C C C C H H H H

propagation

Initiator: example - benzoyl peroxide

H H H 2 H H C O H
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dimer

C O O C

=2R

Chemistry of Polymer molecules

H H

C C
H H

Monomer

Types of Polymers

Homopolymer

All repeating units along a chain are of the same type; polymer formed from a single monomer Eg. polyethylene, formed by polymerization of ethylene 2 or more different mer units involved PMMA

Copolymer

Bulk or Commodity Polymers

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Bulk or Commodity Polymers (cont)

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Bulk or Commodity Polymers (cont)

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VMSE: Polymer Repeat Unit Structures

Manipulate and rotate polymer structures in 3-dimensions

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MOLECULAR WEIGHT
Large molecular weights for polymers with very long chains Molecular weight, M: Mass of a mole of chains.
Not all chains in a polymer are of the same length i.e., there is a distribution of molecular weights

Low M

high M

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Molecular weights

Number average molecular weight Mn

Mn = xi Mi

Mi represents mean (middle) molecular weight of size range i xi is the fraction of the total number of chains within the corresponding size range

Weight average molecular weight Mw

Mw = wi Mi

wi is the weight fraction of molecules within the same size interval

Example

Find the molecular weight

Example solution
Mol. Wt. range Mean Mi (g/mol) (g/mol) 5000 10,000 7500 10,000 15,000 12500 15,000 20,000 17500 20,000 25,000 22500 25,000 30,000 27500 30,000 35,000 32500 wi 0.12 0.18 0.26 0.21 0.14 0.09 = 1.0 wiMi 900 2250 4550 4725 3850 xi 0.2 0.1 0.3 0.1 0.1 xiMi 1500 1250 5250 2250 2750

2925 0.2 6500 Mw Mw =wiMi = 1.0 =xiMi = 19,200 19500

Degree of Polymerization, DP
DP = average number of repeat units per chain
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 H H H H H H H H H H H H H

DP = 6

Mn DP = m
where m = average molecular weight of repeat unit for copolymers this is calculated as follows: m = Sfi mi
Chain fraction mol. wt of repeat unit i
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