100608 Final Exam Introduction to Polymers (each part, a,b,c,…, is worth 2.

2 points)

1) Polymers are different than low-molecular weight oligomers. For example an oligomeric
polyethylene is wax, oligomeric polystyrene is similar to naphthalene (moth balls),
oligomeric rubber is oil or grease. One way to quantify the difference between an
oligomer and a polymer is through rheology.
a) Give Newton’s law for viscosity.
b) Define the shear stress.
c) Define the rate of strain.
d) Define the velocity gradient.
e) The tensile (or extensional) viscosity is used to describe the ability of a fluid to form a
fiber. Explain how the tensile (or extensional) viscosity is defined.
f) Sketch the behavior of viscosity as a function of velocity gradient showing how the
zero-shear-rate viscosity or Newtonian-plateau viscosity are obtained.
g) Sketch the dependence of the zero-shear-rate viscosity on molecular weight.
h) How can your plot of part “b” be used to define a polymer?

2) GPC is a common technique to determine the molecular weight of a polymer.

a) What does GPC stand for? Give two other names for this instrument and explain what
each of these names has to do with the functioning of this instrument.
b) How is the polydispersity index, PDI, obtained from a GPC curve? (Explain how
moments are calculated from the GPC curve in your answer.)
c) How is the PDI related to the standard deviation for the distribution curve?

3) Molecular weight can be obtained by a number of methods.

a) What molecular weight average is obtained with light scattering? Relate this
molecular weight average to the moments of the distribution curve, M1, M2, M3.
b) Explain the function of a membrane osmometer in determining the molecular weight
of a polymer by comparing with the ideal gas law. What molecular weight average is
obtained from a membrane osmometer?
c) Explain how molecular weight can be obtained using a capillary viscometer.
d) What moment of molecular weight is obtained in a capillary viscometer? Define this
molecular weight using the Mark-Houwink equation, η = kMa.

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4)  Draw  the  structure  or  give  the  name  of  the  following  polymers  and  indicate  which  of  the  
two  types  of  polymerization  could  be  responsible  for  this  polymer.    Indicate,  where  
appropriate,  the  polyester,  polyamide  or  polyurethane  linkages.    
a)  polyethylene  terephthalate  
b)    
 
 
 
 
c)    
 
 
 
d)    
 
 
 
 
 
e)  Poly  vinyl  alcohol  
f)  List  the  4  types  of  polyethylene  that  are  commonly  used  in  industry  and  indicate  
the  difference  in  chain  structure  between  these  types.  
g)  Describe  the  difference  between  atactic  and  isotactic  polymers.  

5) The synthesis of glyptal involves a trifunctional and a difunctional reactant in a condensation

reaction.
a) Give the monomers involved in glyptal synthesis in a stoichiometrically balanced
chemical reaction equation.
b) What solvent is used to make glyptal?
c) Draw the structure of sodium acetate and explain why it was used in this reaction.
d) Give the structure of glyptal and the structure of PET (PETE) and comment on the
difference in properties between these two similar polyesters based on the difference in
chemical structure.

6) a) What are the three main stages of chain growth polymerization?

b) Write an expression for the rate of propagation for chain growth polymerization in
terms of the monomer concentration and the initiator concentration.
c) Obtain an exponential expression for the monomer concentration from part c and
show that this is linear for early stages of the reaction.
d) Obtain an expression for the kinetic chain length for chain growth polymerization in
terms of the monomer concentration and the initiator concentration.

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7) Suspension polymerization is similar to emulsion polymerization.
a) Describe the importance of water to emulsion and suspension polymerization. Does
water play an identical role in these two polymerizations? Is water a solvent?
b) Describe the initiator that we used in suspension polymerization. What condition is
needed to initiate this reaction? Why was a different initiator used in the emulsion
polymerization?
c) What is divinyl benzene and why is it included in this reaction?
d) What controls the size of the polymer beads (droplet size) that result from suspension
polymerization?
e) What was the advantage of emulsion polymerization (over suspension polymerization)
that lead to its development by Goodyear Tire and Rubber in the 1920’s?

8) a) Give the Flory-Huggins equation for polymer blends and explain which part
corresponds to entropy and which to enthalpy of mixing.
b) Sketch this function for χ below the critical point, at the critical point and above the
critical point.
c) Show where the binodal and spinodal points are determined in the plot of b.
d) Show how the plot of part c can be used to construct a phase diagram.
e) Explain what an LCST and UCST phase diagram is and how they can be obtained
from an interaction parameter of the form A + B/T. Why does PVME/water display an
LCST phase diagram?

9) a) Write an expression for p for a system with an average functionality favg and show that
when Mn goes to infinity, p goes to pc = 2/favg.
b) Give the structure of TEOS
c) Show the reaction scheme (including stoichiometry) for hydrolysis of TEOS.
d) Show the reaction stoichiometry for the condensation of tetra hydroxy silicate or
titanate to silica (SiO2) or titania (TiO2).
e) Explain how water can act as both a catalyst and a reactant in the
hydrolysis/condensation reaction of TEOS.

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 Answers: 100406 Quiz 1. Introduction to Polymers
1)
a) Give Newton’s law for viscosity.
Shear stress is proportional to the shear strain rate with the viscosity as the scaling coefficient
τ = ηγ˙ .
b) Define the shear stress.
c) Define the rate of strain.
d) Define the velocity gradient.
A force is applied to a surface whose normal is perpendicular to the direction of the force. The
ratio of the stress to the area is the shear stress, τ. The length changes in the direction of the
force with a gradient normal to the force. The ratio of the length change with respect to the gap
or gradient distance is the shear strain, γ. We usually consider a dynamic shear process where
the gradient of the x-velocity in the y-direction is the rate of shear strain. The rate of strain is the
same as the velocity gradient.

e) The tensile (or extensional) viscosity is used to describe the ability of a fluid to form a
fiber. Explain how the tensile (or extensional) viscosity might be defined.
A force is applied to the surface normal to the force. The length changes in the same direction as
the force. σ = Fx/Ax and εxx = ΔLx/Lx, the elongational rate of strain is the velocity of the vertical
strain so you need to pull the fluid like pulling taffy except with a continuous rate of strain.

The extensional viscosity is defined as η† = σ xx / ε xx . A special experimental design is necessary

to measure the extensional viscosity.
2) a) Sketch the behavior of viscosity as a function of velocity gradient showing how the
zero-shear-rate viscosity or Newtonian-plateau viscosity are obtained.

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 b) Sketch the dependence of the zero-shear-rate viscosity on molecular weight.

c) How can your plot of part “b” be used to define a polymer?

Above the entanglement molecular weight the material behaves like a polymer since it displays
melt strength, shear thinning and other features normally associated with polymers.

1) a) Gel permeation chromatography, Size Exclusion Chromatography (SEC) and High

Pressure Liquid Chromatography (HPLC).
b) The instrument involves pumping a dilute liquid solution of a polymer under high pressure
through a gel and observing the concentration of polymer in the effluent stream. The polymer
permeates the gel following pathways that are large enough through the gel molecular structure
to allow for passage. The molecular weights of the polymer are separated by the process of size
exclusion. That is, large polymers are excluded from small pores in the gel so that these large
molecules pass through the large pores quickly and elute first. Small polymers are not excluded
from the gel pores and have a higher residence time in the gel structure, eluting at a later time.
c) PDI is the ratio of the weight average molecular weight, Mw, to the number average molecular
weight, Mn. Mw is obtained from the ratio of the second to the first moments, M2/M1 = Mw. The

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moments are obtained by integration of the GPC curve, P(M) times the power of the molecular
∞

∫M
P
P(M )dM
weight of interest, M P = 0
∞
. Mn = M1 .
∫ P(M )dM
0
d)
∞ ∞ ∞ ∞

∫ ( M − M1) P(M)dM ∫ M 2 P(M)dM − 2 ∫ MM1P(M)dM + M12 ∫ P(M)dM

2

σ= 0
∞ = 0 0
∞
0

∫ P(M)dM ∫ P(M)dM
0 0

⎛M ⎞
= M 2 − M12 = M12 ⎜ 22 −1⎟ = M12 ( PDI −1)
⎝ M1 ⎠
⎛ M2⎞ ⎛ 1 ⎞
= M 2 ⎜1− 1 ⎟ = M 2 ⎜1− ⎟
⎝ M2 ⎠ ⎝ PDI ⎠

2) a) Light scattering yields the weight average molecular weight. M2/M1 = Mw.
b)

c) M1 = Mn is obtained.
d), e) The intrinsic viscosity is obtained from the flow time for the solvent, tsolv, and the flow
time of the solution tsolution using the Poiseuille equation.
t solution
= 1 + φ [η ]
t solv
[η ] = kM va
where the second equation is the Mark-Houwink equation and the molecular weight Mv is the
viscosity average which is between the weight and the z average in magnitude.

3) a) Step growth, polyurethane. Chain growth, polystyrene.

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b) Step growth involves reaction of all monomers at once that combine to make
dimers/tetramers etc. All monomers are consumed immediately when the reaction begins and
the molecular weight growth is slow. You need a extent of reaction of 1 for this reaction to yield
high molecular weight polymers.
Chain growth involves initiation using an initiator and propagation of the polymer as a chain
with a propagating chain end. High molecular weight is achieved early on and polymer is
produced even at moderate extents of reaction. There is monomer present even at the end of the
reaction that must be removed from the polymer generally.
c)

 
d) n1  =  nn  =  1/(1-­‐p);    nw  =  (1+p)/(1-­‐p)  
e)    PDI  =  nw/n1  =  (1+p)  
 

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1)  
 

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h)     Isotactic   polymers   are   composed   of   all   meso   diads,   mm   triads   (all   the   same  
sterochemical   arrangement).     Atactic   are   composed   of   a   random   distribution   of   triads   so  
50%   m   and   50%   r   and   25%   mm,   25%   rr   (syndiotactic)   and   50%   mr   (heterotactic).     Atactic  
generally  refers  to  a  polymer  that  will  not  crystallize.  
 

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2) a) 3 phthalic anhydride + 2 Glycerol

b) The reaction is run neat (no solvent).

c) The overall extent of reaction relies on the functionality of the monomers and the viscosity
(kinetics) of the reacting system. If the system forms a glass too early the reaction ends since
molecular mobility is needed for the reaction to occur. Sodium Acetate is used to decrease the
functionality of the system to make the system less viscous during the reaction and yielding an
overall higher extent of reaction.

d)

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e) Glyptal PET (PETE)

Glyptal has di ortho carboxylic substutited aromatic group and PET has di para substituted
aromatic group. This makes PET more flexible than glyptal. Also, the trifunctionality of
glycerin versus the difunctionality of ethylene glycol leads to a network structure that is more
rigid compared to PET.

2) a) Initiation, propagation and termination.

b) A catalyst is not consumed in a reaction but plays a part in facilitating the reaction. Initiators
are consumed and generally lead to one end group of the chain-polymerized polymer. So an
initiator is not a catalyst even though it is used in a small amount to facilitate a reaction.
d[ M ] fk d
c) R p = − = kp [ I] [ M ] = K [ I] [ M ]
dt kt
d)
[M ]
d[M ]
t

∫ = −K [ I ] ∫0 dt
[M ] [ M ]
0

⎛ [M ] ⎞
ln ⎜ ⎟ = −K [ I ]t
⎝ [ M ]0 ⎠
[ M ] = [ M ]0 exp ( −K [ I ]t )
x x2 x3 x4
The exponential can be expanded, exp− x = 1− + − + − ...
1! 2! 3! 4!
(
For short times we can consider only the first two terms so, [ M ] ≈ [ M ] 0 1− K [ I] t )
fkd
kp [I ] [ M ]
Rp Rp kt kp [M]
e) υ = = = =
Ri Rt fkd [ I ] k t fk d [ I ]

1) a) Bulk polymerization heats up to much so the idea in both emulsion and suspension
polymerization is to disperse the bulk polymerization into small droplets where heat transfer is
fast to a water phase. In emulsion polymerization the initiator is in the water phase and the water
phase also contains reservoirs of monomer that feed the micellar reacting nano-droplets. In
suspension polymerization the initiator is in the monomer phase so multiple initiated chains exist
in each droplet. The kinetics of polymerization are the same for suspension and for bulk.
b) Benzoyl peroxide was used. It is initiated by heat at about 80C. BP goes into the monomer
phase. In emulsion polymerization potassium persulfate was used as the initiator and it was in
the water phase so it initiated the micelles only at the interface.

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c) Divinyl benzene (below) acts as a tetrafunctional crosslinking agent making a network in the
suspension particles.

d) The droplet size is controlled by the rate of mixing, the amount of polymer and the presence
of polyvinylalcohol. The size is a balance between coalescence and breakup of the
monomer/polymer droplets.
e) Emulsion polymerization allowed the production of sticky polymers such as polybutadiene
and polyisoprene rubber.

ΔG φ A φ
3) a) = ln φ A + B ln φ B + φ Aφ B χ AB
RT x A xB
xi is the degree of polymerization of component i.

b) Critical point is chi = 2

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c) Binodal is where the first derivative is equal for two points (circles), this is the miscibility
limit. Spinodal is where the second derivative is zero (squares). This defines the metastable
region between binodal and spinodal. The critical point is where the third derivative is zero
(central maximum).

d) The points of part c are plotted on a temperature versus composition plot as shown in the
notes and in class. You should sketch out how to do this in your answer to this question.

e) Gone over in class.

1)

2)

a)

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 b)

c)

d)

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