Polymers I:

Overview
Molecular Weight Determination
Polymerization

Prof. Wendy Liu

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  1    

 Polymer = many mers
mer mer mer
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)

•  Macromolecules which can adopt a wide variety of

molecular configurations

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  2    

 Hydrocarbons

•  Most polymers made up of covalently bonded H and C

•  Saturated hydrocarbon – all single bonds
–  Ex. Ethane C2H6
–  Stereochemistry results from hybridization of s and p orbitals
H H
H
C C

H H
H
•  Unsaturated hydrocarbon – double and triple bonds
–  Ethylene C2H4 H H
C C H C C H
–  Acetylene C2H2
H H
BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  3    
 Nomenclature
•  Polymerization- polymer forms from monomer building
blocks
H H Radical
H H
R R C C
transferred
C C
Free radical initiator H H H H
(unpaired electron) monomer

•  Polymer named after the monomeric building block

•  poly_________ or poly (____________)
–  Monomer is ethylene -> polyethylene or poly(ethylene)
–  Monomer is lactic acid -> poly(lactic acid)

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  4    

 Degree of polymerization

20 mers 16 mers

10 mers

•  -(CH2-CH2)n-
–  where n refers to the number of monomer subunits per molecule
•  The average degree of polymerization is:
–  M average molecular weight M
DP =
–  m is Molecular weight of the repeat unit m

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  5    

 Number Average Molecular Weight
•  In reality, there is a distribution of n or molecular weights of a
polymer sample – polymerization reactions aren’t perfect

number  average  molecular  weight   M n = ∑ xi M i

i

Ni
xi =
∑ Ni i
•  xi is the fraction of the total number of chains with the corresponding
size range
–  Ni is the number of chains with the corresponding size change

•  Mi is the mean molecular weight of size range i

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  6    

 Mn Number Average Molecular Weight Example
Molecular  
Number  of   Mean  Mi    
Weight  Range   xi   xiMi  
chains   (g/mol)  
(g/mol)  
100-­‐300   400   200   0.2   40  

300-­‐500   600   400   0.3   120  

500-­‐700   600   600   0.3   180  

700-­‐900   400   800   0.2   160  

∑N i
=  2000   M n = ∑ xi M i =  500  g/mol  
i i

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  7    

 M w Weight Average Molecular Weight
weight  average  molecular  weight  

M w = ∑ wi M i
i

Ni M i
wi =
∑ Ni M ii

•  wi  is  the  weight  fracKon  of  molecules  

within  the  same  size  interval  
•  Mi  is  the  mean  molecular  weight  of  
size  range  i  

•  Larger  molecular  weight  chains  make  a  

larger  contribuKon  to  the  value  

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  8    

 Polydispersity Index
•  Ratio between weight average and number average molecular
weights

Mw
PDI =
Mn

•  If PDI = 1, all of the polymers have the same molecular weight

•  As the molecular weight distribution increases, the PDI increases

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  9    

 Polymer molecular configuration

•  Isomers have the same chemical make up but different

configuration

Polymerize  

Stereoisomers are mirror A  

A  
images – can’t superimpose
without breaking a bond C   C  
E   E  
B   D   D   B  
mirror
plane
BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  10    
 Tacticity
•  Tacticity – stereoregulatory or spatial arrangement of R units along a
chain

Isotactic
On one side  

Syndiotactic
Alternating sides  

Atactic
Randomly placed  

•  To go from one configuration to another, bonds need to be broken

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  11    
 Common polymers used as biomaterials
•  PE: good wear properties, hip
implants
•  PEG: hydrophilic, low protein
adsorption (nonadhesive), drug
delivery, prevention of surgical
adhesions
•  PS: easy to manufacture, tissue
culture dishes
•  PMMA: good optical properties,
intraocular lens
•  PGA and PLA: ester bond is
degradable by hydrolysis, drug
delivery and sutures
•  PTFE “teflon”: “nonstick”
properties, very hydrophobic,
vascular grafts

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  12    
 Polymerization Mechanisms

Chain growth (addition) polymerization

Free radical polymerization
Ionic polymerization
Ring opening polymerization

Step growth polymerization

Condensation polymerization

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  13    
 Chain Growth Polymerization

•  Monomers added to growing chain one at a time

–  Formation of active center – reaction with ethylene

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  14    
 Chain Growth (cont’d)

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  15    
 Chain Growth (cont’d)

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  16    
 Example monomer & polymers

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  17    
 Chain growth: ring opening polymerization
Potassium  naphthalene  

BME111  Design  of  Biomaterials  Spring  2015      April  9    Lecture  4  Slide  18