Lecture 9

Polymers: Free Radical and Condensation Polymerization

Extracellular Matrix
Lab Section
 Basic mammalian cell culture

 Hydrogel fabrication, collagen type I

 Chemical routes to modulate hydrogel stiffness

 Mechanical measurements

 2D versus 3D cell seeding/encapsulation

 Staining, imaging and quantification

Step-Growth/Condensation Polymerization

 Difference between polyester, polyamides

 How does polymer property change as a

function of polymer linkage

 Predict the polymer product from a given

monomer(s) and identify the monomer(s)
given the polymer product.

 Reaction time versus molecular weight

Commonly used synthetic polymers in medical applications

Acronym Full name and uses O Chemical

O Structure
+ OH heat
PE Polyethylene – acetabular cup HO
HO OH
1,4-Benzenedicarboxylic acid 1,2-Ethanediol
(Terephthalic acid) (Ethylene glycol)

PET Polyethylene terephthalate

O O
(PET) or Dacron – vascular graft O + 2 nH2 O
O
n
Poly(ethylene terephthalate)
PMMA polymethyl methacrylate – dental (Dacron, Mylar)
bases, bone cements, contact
lens and intraocular lens, bone
fixate
Nylon Stockings, sutures
Commonly used synthetic polymers in medical applications
Acronym Full name and uses Chemical Structure
PEG Poly(ethylene glycol) – coating
surface to improve hydrophilicity

PLA, PGA Poly(lactic acid) (PLA) poly

(glycolic acid) (PGA)-
bioresorbable stents, tissue
scaffold

PCL Poly(caprolactone) – resorbable

tissue scaffold

Example: Draw the repeating unit of PLGA?

Chain-Growth Polymerization: addition of
the monomer unit to the chain involves an
attack by a radical on the unsaturated
monomer

Involves 3 distinctly different steps:

 Radical Initiation

 Chain Propagation

 Termination (via coupling)

 Chain Transfer
 Characteristics of Chain-Growth Polymerization

 Repeating unit in the polymer and the monomer has the same composition.

 Kinetic category of chain reactions, with either free radicals or ionic groups responsible
for propagating the chain length.

 All-carbon chain backbone (mostly), with pendant substituent groups.

What are the features of step-wise polymerization in comparison then?

Rate of polymerization ~ rate of propagation, slowest step
Radical coupling

Disproportionation
Initiators
 Peroxides and hydroperoxides are the most widely used
 Decompose into radicals at a rate dependent on Temp and Chemical Structure
 Initiators
 Azo initiators
a,a’-azobis(isobutyronitrile) or AIBN

T½ 1.30 hours at 80 oC
Initiators
Redox Initiators
 Rates are controlled by [metal ion] or [peroxide].

 Useful for low temperature polymerization in emulsion conditions.

Initiators
Irgacure 2959
Photo-initiators

LAP
 Molecular Weight Control
 Temperature
increased temperature leads to increased rate of RXN; may increase or decrease Mw
 Solvent
If polymer loses solubility at a certain Mw, PDI may decrease b/c all polymers crash out of solution
 [initiator]
Increase [initiator] affords smaller fragments
 [monomer]
 Initiator type
 Polymerization Mechanism
 Initiator - highly reactive transient molecules or active centers
 Propagation - addition of monomer units to active chain end

 Termination - active centers are destroyed (rxn stops)

 Transfer - active chain terminates and a new chain is started

 Polymerization Techniques
M e th o d
B u lk
S u s p e n s io n ( d is p e r s e
m o n o m e r in w a t e r ,
m o water
n o m e r s o lu b le
in it ia t o r
S o lu tio n
E m u ls io n ( d is p e r s e
m o n o m e r in w a t e r
p h a s e , s u r fa c ta n ts ,
in itia tin g in w a te r
phase
A d v a n ta g e s
S im p le
H e a t o f r x n is
d is p e r s e d , lo w
v is c o s it y g r a n u la r
fo r m o f p o ly m e r , e a s y
p u r ific a tio n
H e a t o f rxn
d is p e r s e d , lo w
v is c o s ity
H e a t o r r e a c t io n is
d is p e r s e d , lo w
v is c o s ity , la r g e M w
D is a d v a n ta g e s
E x o t h e r m ic , d if f ic u lt
to c o n t r o l, h ig h
v is c o s ity
W a s h in g o r d r y in g
r e q u ir e d ,
a g g lo m e r a tio n m a y
occur
S o lv e n t, lim it e d M W ,
c h a in tr a n s f e r
r e a c tio n s
E m u ls ifie r a n d o t h e r
a g e n ts u s e d , w a s h in g
s te p s , d r y in g s t e p s
 HDPE catheter tubing

Polyethylene (PE)
• 1930 – Low MW PE used in WW1 as an insulator for radar
cables.
• Free radical polymerization PE gloves
• Tm ~ 110°C
• Packaging film, trash and grocery bags, wire
• Implants, catheter tubing
• low strength, hardness and rigidity, but has a high
ductility and impact strength as well as low friction.  

H H
C=C -(-CH2-CH2-)n-
H H
Polyethylene
Ethylene
H H
CH2 . + C=C CH2-CH2-CH2 .
H H 31
 HDPE catheter tubing

Polyethylene (PE)
• 1933 – High MW PE used in
• Ziegler-Natta catalysts or activated chromium
oxide (known as a Phillips catalyst) PE gloves
• Tm ~130°C

LLDPE (0.860-0.926 g/cm3) HDPE (0.940-0.965 g/cm3)

LDPE (0.915-0.930 g/cm )
3
“Linear Low Density” “High Density”
“Low Density”

Why linear structure has higher density?

32
Polymethylmethacrylate (PMMA)
• Hard
• Rigid
• Transparent
• Softening point 125 0C
• (molded etc)
• Tougher than polystyrene
• Good electrical insulator
• Good outdoor weather resistance (outdoor furniture)
• Radical polymerization affords amorphous polymer
Poly(acrylonitrile) (PAN)
• Textile
• Upon burning - HCN gas
• Very soluble in THF, DCM, DMSO, solvents
Poly(acrylamide) (PAM)
 Water soluble
 Can prepare gels
Poly(N-isopropylacrylamide) (PNIPAM)
• “Smart” polymer
• Responds in a predictable way to external stimuli
• Shrinks with increasing temperature
• Used in drug delivery – drugs are expelled as
polymer contracts at body temperature 37 oC
Poly(tetrafluoroethylene)
(TEFLON) (PTFE)
• Self lubricating
• Cold flow (at RT, teflon changes shape with pressure)
• True for other polymers, but the time scales are not relevant
• Suspension polymerization
• Extrusion and molding
• White opaque solid
• Waxy
• Tough
• Low coefficient of friction (non-stick)
• High chemical resistance
• High crystallinity
Teflon, polytetrafluoroethylene (PTFE)
• High strength and Chemical resistance
• High modulus and tensile properties with negligible elongation VascuGraft PTFE
• Used for orthopedic and dental devices
• Mechanical heart valve and implants
• Excellent wear and fatigue resistance
• Vascular grafts patch injured and diseased areas of arteries
• Must be flexible to allow for the difficulties of implantation and to avoid
adjacent tissue irritation

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 Chain-growth Polymerization
 Chain initiation: or
orhh 
InIn-In
-In 22InIn

InIn ++ InIn
RR RR

 Chain propagation:
InIn ++ InIn
RR RR RR RR

InIn ++ InIn
nn nn
RR RR RR RR RR
etc.
etc.
 Chain-growth Polymerization
 Chain termination:

radical
coupling
In In
n n
R R R R
2 In
n
R R

dispropor-
tionation In H
n
+ In n
R R R R
Glass Transition Temperature versus Melting Temperature
 Glass Transition (Tg) : the glass–liquid transition, is the gradual and
reversible transition in amorphous materials (or in amorphous regions within 
semicrystalline materials) from a hard and relatively brittle "glassy" state into a
viscous or rubbery state as the temperature is increased.
 An amorphous solid that exhibits a glass transition is called a glass.
 The glass-transition temperature Tg of a material characterizes the range of
temperatures over which this glass transition occurs. It is always lower than
the melting temperature, Tm, of the crystalline state of the material.
 Melting temperature: solid to liquid transition.
 Most polymers are semi-crystalline

 Polymers tend to crystallize as they precipitate or are cooled from a melt.

 Acting to inhibit crystallization are that polymers are large molecules. Complicated and irregular
shapes prevent efficient packing into ordered structures.

 As a result, polymers in the solid state tend to be composed of

 ordered crystalline domains

 disordered amorphous domains

 More crystalline domain – stronger and less flexible

 Temperature Effects
Tg Tm

log(Modulus)
semicrystalline
Semi-crystalline

crosslinked
Cross-linked
T linear amorphous

Temperature
Summary
• Molecules, monomers, polymers
• Mw and Mn and PDI
• Effect of intermolecular chain-chain interactions on polymer properties such as Tg and Tm
• Amorphous vs crystalline
• Effect of crosslinking

• Recommended readings:
• Basic Organic Chemistry for the Life Sciences
• ISBN: 978-3-319-07605-8
• Free access on BU online library!

44
Summary
• Recommended online lectures
• Intro to Organic Chemistry
• https://ocw.mit.edu/courses/materials-science-and-engineering/3-091sc-introduction-
to-solid-state-chemistry-fall-2010/organic-materials/27-introduction-to-organic-
chemistry/
• Polymer nomenclature and structures
• https://ocw.mit.edu/courses/materials-science-and-engineering/3-091sc-introduction-
to-solid-state-chemistry-fall-2010/organic-materials/28-polymers-structure-composition/
• Polymerization
• https://ocw.mit.edu/courses/materials-science-and-engineering/3-091sc-introduction-
to-solid-state-chemistry-fall-2010/organic-materials/29-polymers-synthesis-properties-
applications/

45
 Specific Applications
Application Properties and design requirement Polymers used
Dental • Stability and corrosion resistance, plasticity • PMMA-based resins for
• Strength and fatigue resistance, coating fillings/prosthesis
activity • Polyamides
• Good adhesion; integration with tissue

Ophthalmic •Gel or film forming ability; hydrophilicity •Polyacrylamide gels

•Oxygen permeability •PHEMA & copolymers
Orthopedic •Strength and resistance to mechanical PE, PMMA, PL, PG, PLG
restraints and fatigue
•Good integration with bones and muscles
Cardiovascular •Fatigue resistance, lubricity, sterilizability Silicones, teflon, poly(urethanes),
•Lack of thrombus, emboli formation PEO
•Lack of chronic inflammatory response
Drug Delivery •Appropriate drug release profile PLG, EVA, silicones, HEMA,
•Compatibility with drug, biocompatibility PCPP-SA
Sutures •Good tensile strength, strength retention Silk, catgut, PLG, PTMC, nylon
•Flexibility, knot retention, low tissue drag
Melting Temperatures (Tm)
• Factors contributing to high melting temperatures
• High interchain forces promote microcrystallinity
• Restricted motion (-CH=CH- vs. –H2C-CH2- )
• Secondary bonding ( H-bonds, Ionic bonds)
• Symmetry
• Linear chains (packing density)
Amorphous polymer: Glass Transition
Temperature (Tg)
Effect of side chain (R) of a representative vinyl polymer
R Tg (°C)

48
Amorphous polymer: Glass Transition
Temperature (Tg)
• Increase inter-chain interaction such as H-bond, π- π stacking (aromatic ring) will increase Tg

Polymer Tg (°C)
Polyethylene (LDPE) -125
Polypropylene (atactic) -20 **
Poly(vinyl acetate) (PVAc) 28
Poly(ethyleneterephthalate) (PET) 69
Poly(vinyl alcohol) (PVA) 85
Poly(vinyl chloride) (PVC) 81
Polypropylene (isotactic) 100
Polystyrene (PS) 100 **
Poly(methylmethacrylate) (atactic) 105

49
Polymer Morphology
3. Elastomer – flexible polymer in its temperature range between Tg and the melt temperature.
4. Polymer blends – mixing two or more polymer together
• Miscible (clear single Tg)
• Immiscible (opaque – more than one Tg)
5. Plasticizer – many polymer rigid (PVC), so to soften the polymer add a low molecular weight
molecule

50
Amorphous polymer
• Amorphous state is characteristic of those polymers in the solid state
that do not crystallize
• This characteristic is present above the melting points of a polymer
(except for liquid crystals)
• If a molten polymer retains it amorphous nature upon cooling to the
solid state – the process is called vitrification (as opposed to
crystallization)
“Glass state “ – no long range order

51
Amorphous polymer: Glass Transition
Temperature (Tg)
• A polymer transition from solid (amorphous state) to rubbery elastomeric flexible plastic
• Heat == kinetic energy == motion increases = Tg rubber = Tm melt
• More segmental motion of chains

52
Amorphous polymer: Glass Transition
Temperature (Tg)
1. Transition usually accompanied by more long-range molecular motion- greater rotational freedom
- more segmental motions of polymer chains.
2. Usually not a sharp transition (2-5 oC)
3. With this change : a) volume increases; b) enthalpy changes; c) modulus decreases; d) refractive
index decreases
4. Not a separation of polymers
5. Above the Tg --- soft,
extensible elastomeric

53
Crystalline polymer
1. Highly regular structure (stereo-regular)
2. No chain branching
3. Polar groups (strong intermolecular forces)
4. Regions of the polymer, where the polymer molecules order
themselves in a thermodynamically favorable alignment
5. Fringed micelle models define crystallinity in terms of ordered
regions called crystallites
6. Crystallinity induced
a) cooling a molten polymer
b) evaporation of a polymer solution
c) heating a polymer under vacuum (annealing)
d) stretching a polymer and heating (drawing)
e) promote closer packing re-orientation of the polymer towards the
crystalline state 54
Crystalline polymer
7. Crystalline polymer are generally tougher, stiffer, more opaque, more
resistant to solvents and higher densities than the amorphous state
counterparts
• Higher cohesion strength from more effective intermolecular forces
8. Crystalline polymers melt over a narrow range Tm

Crystalline polymer Amorphous polymer Semi-crystalline polymer

55
Thermoplastics vs thermoset plastics
1. Thermoplastics - A polymer that can be melted and molded into a shape that is retained when
it is cooled.
2. Thermosetting A polymer that can be molded when it is first prepared but, once it is cooled,
hardens irreversibly and cannot be remelted.
• On heating, thermoset plastics become cross-linked and form a rigid network.

thermosetting

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 Polymer Blends
 Physical mixture of two or more different copolymers or polymers that are not linked by a
covalent bond
 Like a “metal alloy”
 Miscible blends

 Immiscible blends

 Difficult to predict miscibility, but resulting properties can be predicted

 Properties of immiscible blends much less predictable

Thermal Transitions
• Melting temperature (Tm) (crystalline sample)
• The temperature above which atomic movement is
sufficient to break the highly order structure.
• At temperatures above Tm the material is a liquid
and deforms as viscous flow.
• Below the Tm the material is ordered with grain
boundaries intact.

58
Thermal Transitions
• Factors that influence melting temperature (T m)
• % crystallinity: increased cryst = higher T m
• Degree of branching: increased DOB = lower T m
• Mw (area of contact and large Mw less number of end groups):
increased Mw = higher Tm
• Architectures
• H-bonding: increased H-bonding = higher T m
• Van der Waals: increased VdW = higher T m

59
Glass Transition Temperature, Tg
• Glass transition temperature (Tg) (amorphous,
glassy sample )
• The temperature below which the sample is a solid
(glass) - sample becomes more and more viscous and
looks like a solid at low temperature.

• Below the Tg vibrational and rotational motion only

• Below the Tg the polymer is glassy and brittle
• Above the Tg the polymer chains are mobile and can
produce an elastic, rubbery material - molecular motion
of the polymer chains - translation motion
• Above Tg, modulus decreases, creep effects more
pronounced
• Generally Tg is below Tm 60
Glass •Transition Temperature, Tg
Related to chain mobility (Increased flexibility,
lower Tg)
• Factors that influence Tg
• flexible links in backbone
• size of pendent groups: bigger group = lower Tg ; most of
the time
• interaction between chains
• H bonds
• Van der Waals
• Plasticizers interfere with intermolecular bonding,
increase chain movement, decrease Tg
• small molecules that break-up interactions; e.g., H –
bonding; they make the sample softer
• biological plasticizer -- urea 61
Glass Transition Temperature, Tg
• Effect of Molecular weight
• Increased Mw = Increased Tg

K
• For polymer Tg  Tg,  
• Fox-Flory equation Mn
• K = constant for given polymer
• Tg∞ = Tg for infinite M
1 1 2
 
Tg Tg,1 Tg,2
• For copolymers
• Fox-Flory equation
• ω = weight fraction of monomer in copolymer

62
Effect of Temperature
Rubber
Liquid
Viscous
Liquid Tm

tough plastic
Temperature

Tg

semi-crystalline plastic Tg ≈ 2/3 Tm

crystalline solid

10 1000 100000 1000000

molecular weight (g/mol)

63
Thermal Properties
Polymer Tg (°C) Tm (°C)
Nylon 6,6 45 267
UHMWPE -125 140
Silicone -123 -29
Poly(urethane) 0-90 125-225
Poly(methyl methacrylate) 105 160
Poly(D,L-lactide) 50 Amorphous
Poly(ε-caprolactone) -60 57
Poly(glycolic acid) 35 210

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Crosslinked
•
Networks
Crosslinks
• Strengths: covalent > H-bonding > entanglements

• Crosslinking
• increased molecular weight
• swell in solvents
• Organogel - swells with organic liquids (oil spill removers)
• Hydrogel – swells with water

65
Temperature Dependence
• As temperature increases, modulus decreases
• Exception
• Elastomers - Lightly crosslinked systems
• Modulus increases with increasing temperature
• Harder to pull apart at higher temperature because the polymer chains
want to return to original conformation
• Entropy dominates

66
Time Dependence
• Rate of strain can change mechanical properties
• Increased rate of strain reduces the time for molecular rearrangements
• Rate of strain affects the modulus of viscoelastic materials
• Viscoelasticity - The response of polymeric materials to an imposed stress
may under certain conditions resemble the behavior of a solid or a liquid
• For example -- Fast strain -- material is stiffer

67
Crosslinking
• Physical - strong secondary bonding interactions between polymer chains
• Can lead to crystallinity
• Usually thermally labile

68
Chain Transfer Agent
• A chemical compound that donates a H. and then continues the
polymerization reaction
Polymerization Mechanism
• Orienticity impacted by steric and electronic effects
 Common Monomers

Monomer Common Polymer Name(s) and

Formula Name Common Uses
CH2 =CH2 Ethylene Polyethylene, Polythene;
break-resistant containers
and packaging materials
CH2 =CHCH3 Propylene Polypropylene, Herculon;
textile and carpet fibers
CH2 =CHCl Vinyl chloride Poly(vinyl chloride), PVC;
construction tubing
CH2 =CCl2 1,1-Dichloro- Poly(1,1-dichloroethylene),
ethylene Saran; food packaging
 Common Monomers
CH2 =CHCN Acrylonitrile Polyacrylonitrile, Orlon;
acrylics and acrylates
CF2 =CF2 Tetrafluoro- Poly(tetrafluoroethylene),
ethylene PTFE; nonstick coatings

CH2 =CHC6 H5 Styrene Polystyrene, Styrofoam;

insulating materials
CH2 =CHCOOEt Ethyl acrylate Poly(ethyl acrylate);
latex paints
CH2 =CCOOCH3 Methyl Poly(methyl methacrylate),
CH3 methacrylate Plexiglas; glass substitutes
Initiators