Answers to Problem set #1

1. 1. (18)
Each polymer name (1 pt) and the chemical structures (2pts), 2x3x3=18
Please refere chemical structures in the class notes or textbook
Electronics:
Electrical cables are insulated with polymers like polyethylene (PE) and polyisoprene
(PI). For wires that get really hot, we use insulation made from a fireproof polymer
called poly(vinylidene fluoride) (PVDF).
The cases of CD players are made of polystyrene (PS).
CDs themselves are made of polycarbonate (PC).
The printed circuit boards are made of epoxy.
The outside housing of a telephone set is made from a special kind of polystyrene, highimpact polystyrene. It's a graft copolymer of polystyrene with a rubbery polymer,
polybutadiene (PB). It's much less brittle than regular polystyrene.
Auto parts store
Auto body parts can be made out of polymer like acrylonitrile butadiene styrene (ABS).
The tread of a tire is made from a special rubber called poly(styrene-butadiene-styrene)
(SBS). The sidewalls are made of another rubber called polyisoprene. And the inner
liner is made of another kind of rubber called polyisobutylene (PIB).
Also, the tires are reinforced with cords made from Kevlar, a polyamide, which is also
used to make bullet-proof vests.
A windshield wiper and its blade is made from a rubber called polyisoprene.
Headlight lenses are made from polycarbonate.
A hose is made from a rubber polybutadiene (PB).
Carpeted floormats are made from nylon.
Pharmacy
Polymers are widely used in drug encapsulation/coating and delivery.
Poly(methacrylic acid) (PMA), an anionic polymer that is resistant to gastric acid, has
been used as coatings of pills.
Poly(acrylic acid) (PAA), which is pH responsive, has been used as a viscosity modifier
in creams, gels for application to topical sites (e.g. skin, eye).
It is also used in copolymers to control the drug release rate.

Poly(glycolide) (PGA) and poly(-caprolactone) (PCL) are commonly used as drug

carriers.
The bristles on a toothbrush were the first things ever made from nylon. Its handle is
made of polyethylene.
Silicones are highly flexible elastomers. They have been used in conditioners, implants,
cardiac valves, intraocular lenses.
Flexible elastic bandage contains natural rubber, polyisoprene.
2. (15)
correct chemical structure(s) of the monomer(s), 2pts, correct identification of the
polymerization mechanism, 1pt
incorrect C, H on each monomer, -0.5 pt
H
N

H
N

(CH2)6

(CH2)8

Nylon 6,10
H2N

(CH2)6

NH2

HO

(CH2)8

C
O

H2 CH3
C
C
O

OH

Step polymerization

CH3
C

OCH3

poly(methylmethacrylate) (PMMA)

CH2
OCH3

(CH2)2

Chain polymerization

n
poly(ethyleneterephthalate (PET)

HO

OH

HO

(CH2)2

OH

Step polymerization

H2C

CH

polystyrene, PS

:
H2
C

H
C
C
H2

Chain polymerization

C
H

poly(1,4-butadiene), PB

CH2

CH

H2C

C
H

Chain polymerization

3. (8)
write down the chemical structure of the monomer and polymer first.
HO(CH2)14COOH H ( O(CH2)14CO )n OH

(2)

M
1
= n
1 p Mo

(1)

Mn=M0/(1-p) = 24,000

(1)

M0 = 240

(1)

Xn = 24,000/240 = 100

(1)

p = 0.990,
the conversion is 99%

(2)

4. (38)
H2N-(CH2)6-NH2, MW= 116.21,
# of moles=9.30/116.21=0.08 moles

(2)

HOOC(CH2)4COOH, MW= 146.14

# of moles=11.68/146.14=0.08 moles

(2)

Thus, stoichiometric amounts of the two reactants are used, r =1.

Initial carboxylic groups: N0 = 2x0.08 mols
Remaining carboxylic groups, N= 2.6x10-3 mol.
Each polymer contains 2.6x10-3 mol of chains.

(2)
(1)
(1)
(1)

Repeating unit: -HN-(CH2)6-NH OC(CH2)4COMolecular weight of repeating unit = 226

(2)

Xn =

Mo = 226/2 = 113

(2)

p =(# of functional groups that have reacted)/(# of functional groups present initially)
=(2x0.08-2.6x10-3)/(2x0.08) =0.984
(2)
Xn =

M
1
= n =62.5
1 p Mo

(2)

Mn=M0/(1-p)=113/(1-0.984)= 7062

(2)

Mw
= 1 + p =1.984
Mn

(1)

M w =14012 g/mol

(1)

(b)
HOOC(CH2)4COOH is still 0.08 moles
H2N-(CH2)6-NH2, # of moles=9.413/116.21=0.081 moles

(2)

Thus, the reactant ratio is, r =0.08/0.081=0.987.

(2)

Since amine is in excess, the polymer should be terminated by amine groups, but be
careful about writing the final polymer structure, which should be
H [-HN-(CH2)6-NH OC(CH2)4CO-]NH(CH2)6-NH2
(2)
The extent of reaction can be calculated from NH2 groups
pCOOH =(# of amine groups that have reacted)/(# of amine groups present initially)
=(2x0.081-5.6x10-3)/(2x0.081) =0.965
(2)
p is typically defined as the extent of reaction of the minority functional groups, here the
carboxylic acid groups
So pCOOH = pNH2/r =0.965/0.987 = 0.9777
(2)
Xn = (1 + r)/(1 + r - 2rp)=34.85

(2)

Mn=M0 Xn=113 * Xn=3,938

(2)

Mw
= 1 + p = 1.9777
Mn

(1)

M w = 7,786 g/mol

(1)

Its clear that slightly off stoichiometric ratio will lead to dramatic decrease of molecular
weight of the final polymer.
(1)
5. (22)
Mn =

Mw

Wi

n i Mi
n

Mi

Wi

WM = wM
=
W
i

1
w
Mi
i

(3)

PDI =

Mw
Mn

(a) ni =Wi/ Mi
ni=1:1:1, assuming each polymer is 1 mole.

(2)

Wi=ni*Mi

M n =(10,000+30,000+100,000)/3=46,667 g/mol
2

M w = (10,000 +30,000 +100,000 )/ (10,000+30,000+100,000)=78,571 g/mol

PDI=1.68
(b)
Wi=1:1:1, assuming each polymer is 1g.
ni =Wi/ Mi
M n =(1+1+1)/(1/10,000+1/30,000+1/100,000)=20,930 g/mol

(2)
(2)
(1)
(2)
(2)

M w =(10,000+30,000+100,000)/3=46,667 g/mol
PDI=2.23

(2)
(1)

(c)
wi=0.145:0.855,
M n =1/(0.145/10,000+0.855/100,000)=43,383 g/mol

(2)

M w =(0.145*10,000+0.855*100,000)=86,950 g/mol
PDI=2.00

(2)
(1)