Polymer Chemistry

CHM 605

CONTENTS
1. History & Basics
2. Nomenclature
3. Physical Properties
4. Molecular Weight
5. Mechanisms & Methods of
Polymerization
6.
7.

Structure & Strength of Polymers

Commercially Important Polymers

8.
9.
10.
11.

Processing of Plastics
Appendix
Laboratory Experiments
Test Questions

108

CHM 605
Part 8
PROCESSING
OF
PLASTICS

109

PROCESSING POLYMERS
Plastics can be molded into many different shapes.
Plastics are often shaped in molds. A mold is a reusable cavity into which plastic material is
deposited. Molds are usually made of 2 halves so that the mold can be opened when the plastic
has hardened (cured) and the part can be ejected.
Diagram of a Closed Mold Used With Injection Molding Machines
parting line of mold

flash = excess plastic squeezed

through the parting line
mold cavities

rear
platen
(movable)

front
platen
(fixed)

sprue = feed opening

to mold from
machine
front
platen
(fixed)

runner = circular channel

connecting sprue
to gates
flash
rear half of mold
(movable)

front half of mold

gate = opening to mold cavity

Some of the more common methods of converting plastic granules, powders and liquids into
final products are listed below:
a. Compression Molding and Transfer Molding: A measured quantity of a thermosetting
resin is placed in a mold, heated, and compressed to fill the mold
b. Injection Molding: Intricately-shaped parts are produced as liquid plastic is squeezed into
a closed mold (like plaster of Paris or like a cookie cutter). See diagram of closed mold,
above.
c. Extrusion: Long continuous shapes, such as pipe and rod, are squeezed (extruded)
through an open mold, called a die, like toothpaste that is squeezed out of a tube.
d. Blow Molding: The ends of a heated tube of plastic (called a parison) are pinched off in the
jaws of a mold. Compressed air forces the plastic to open and set in the shape the mold.
Plastic bottles are blow molded in this fashion.
e. Calendering: Softened thermoplastic material is squeezed between counter-rotating
rollers to produce plastic sheet and film.
110

Compression Molding
A measured quantity of thermosetting
resin is placed in a mold. The mold is
heated, pressure is applied and the molten
material completely fills the mold cavity.
The resin crosslinks and hardens. This
may take from 3 to 20 minutes. Once
cured, the part is ejected from the mold
and the process is repeated.
The resin that is placed in the mold may be
a powder, a liquid, a putty (bulk molding
compound) or a solid (preform).

Compression Molding

Transfer Molding

Transfer molding is very similar to compression molding, except that the resin is not fed
directly into the mold cavity, but into a separate chamber where it is heated under pressure
until molten. Then a plunger pushes the melted resin through runners and gates into the mold
cavity. Automobile distributor caps are commonly made by compression molding or transfer
molding phenolics.
Transfer Molding
PLUNGER

A: A preform is placed in the mold and heated

B: The plunger forces the melted resin through the runners into the mold cavity
C: After curing, the hardened thermoset is ejected from the mold.

111

Injection Molding
Injection molding is by far the most widely used process of forming plastics. It is primarily
used for thermoplastics. The basic process involves six steps:
1. The hopper is loaded with granular plastic
2. Granules are pushed through a heated barrel and the plastic is heated until it becomes
soft enough to flow. The resin is forced forward by a ram or heated screw
3. The softened material is squeezed through a nozzle into a mold cavity.
4. When cool, the halves of the mold are separated.
5. The solid part is ejected from the mold.
6. Gates connecting the product to the runner system are removed.

mold

heated
barrel
nozzle

scre
w

granules
in
hopper

Injection Molding Machine

Injection molded parts can be intricate

or simple. Plastic cups, knives, forks,
electrical plate covers are just a few of
the thousands of a thermoplastic
products manufactured by injection
molding.

Injection Molded Parts

112

Extrusion

An extrusion machine is essentially the same as an

injection molding machine, with the exception that
the closed mold of an injection molding machine is
replaced with an open mold, called a die. Long and
continuous profiles, such as rod, tube and pipe are
made by extrusion molding.
In the diagram above, the extruded plastic is
squeezed into a film as it is compressed between
rollers. Sheets of plastic are formed when molten
plastic is extruded through a long narrow die. The
extruded film is then squeezed between water
cooled rollers (drums) that smooth and solidify the
plastic into sheets.
This extrusion die is 72 inches wide.
When attached to an extruder, the
molten plastic is formed as a thin sheet.

Extrusion coating (laminating) is a

process in which paper or other
substrates are pressed together with an
extruded film, as shown. Rain coats are
made by laminating PVC on nylon fabric
Extrusion coating (laminating) process. The
substrate and molten plastic are squeezed
between rollers, bonding the plastic film to the
substrate.

113

In the diagram on the right, copper wire is pulled

through a plastic extruder and becomes plastic
coated in the process.

Calendering

Extruder die for wire

coating

Another process used to produce film and

sheets of thermoplastic is calendering.
Thermoplastic granules are melted in a
long trough-like hopper and squeezed
through a series of rollers. Vinyl wall
coverings, linoleum floor coverings and
shower curtains are examples of products
made by calendaring.

114

Blow Molding

This extruder is fitted with a die that forms hollow tubes

(parisons).

Bottles are made by blowing air into a thin tube of

extruded plastic. The extruded tube of film to be
blown is called a parison. The parison is placed in
a mold that has the shape of the bottle. The mold
pinches off one end and air is blown into the open
end. The air forces the soft plastic tube to inflate
until it fills the mold cavity.

The parisons original shape

is shown inside its final shape
(a bottle)

A parison

A:
B:
C:
D:

C
B

A parison is placed in a mold.

the mold is closed pinching off the bottom of the parison
Air is blown into the parison to inflate it until it takes the shape of the mold.
The mold is opened and the blow molded bottle is ejected.

115

CHM 605
Part 9
Appendix

116

Review of n-Alkane Nomenclature

1
2
3
4
5
6
7
8
9

methane
ethane
propane
butane
pentane
hexane
heptane
octane
nonane

#C
s
10
11
12
13
14
15
16
17
18
19

30
31
32
33
34
35
36
37
38
39

triacontane
hentriacontane
dotriacontane
tritriacontane
tetratriacontane
pentatriacontane
hexatriacontane
heptatriacontane
octatriacontane
nonatriacontane

40
41
42
43
44
45
46
47
48
49

tetracontane
hentetracontane
dotetracontane
tritetracontane
tetratetracontane
pentatetracontane
hexatetracontane
heptatetracontane
octatetracontane
nonatetracontane

50
51
52
53
54
55
56
57
58
59

pentacontane
henpentacontane
dopentacontane
tripentacontane
tetrapentacontane
pentapentacontane
hexapentacontane
heptapentacontane
octapentacontane
nonapentacontane

60
61
62
63
64
65
66
67
68
69
#Cs

hexacontane
henhexacontane
dohexacontane
trihexacontane
tetrahexacontane
pentahexacontane
hexahexacontane
heptahexacontane
octahexacontane
nonahexacontane

heptacontane
henheptacontane
doheptacontane
triheptacontane
tetraheptacontane
pentaheptacontane
hexaheptacontane
heptaheptacontane
octaheptacontane
nonaheptacontane

80
81
82
83
84
85
86
87
88
89
#C
s

octacontane
henoctacontane
dooctacontane
trioctacontane
tetraoctacontane
pentaoctacontane
hexaoctacontane
heptaoctacontane
octaoctacontane
nonaoctacontane

90
91
92
93
94
95
96
97
98
99

nonacontane
hennonacontane
dononacontane
trinonacontane
tetranonacontane
pentanonacontane
hexanonacontane
heptanonacontane
octanonacontane
nonanonacontane

70
71
72
73
74
75
76
77
78
79
#C
s
100

#Cs

decane
undecane
dodecane
tridecane
tetradecane
pentadecane
hexadecane
heptadecane
octadecane
nonadecane

#C
s
20
21
22
23
24
25
26
27
28
29

icosane
henicosane
docosane
tricosane
tetracosane
pentacosane
hexacosane
heptacosane
octacosane
nonacosane

hectane

117

Review of IUPAC and Common Names of Carboxylic Acids

Structure

IUPAC

name

Common name

Acyl group

IUPAC

Common

HCO2H

methanoic acid

formic acid

HCO-

methanoyl-

formyl-

CH3CO2H

ethanoic acid

acetic acid

CH3CO-

ethanoyl-

acetyl-

CH3CH2CO2H

propanoic acid

propionic acid

CH3CH2CO-

propanoyl-

propionyl-

CH3(CH2)2CO2H

butanoic acid

butyric acid

CH3(CH2)2CO-

butanoyl-

butyryl

CH3(CH2)3CO2H

pentanoic acid

valeric acid

CH3(CH2)3CO-

pentanoyl-

valeryl-

CH3(CH2)4CO2H

hexanoic acid

caproic acid

CH3(CH2)4CO-

hexanoyl-

---

CH3(CH2)5CO2H

heptanoic acid

enanthic acid

CH3(CH2)5CO-

heptanoyl-

---

CH3(CH2)6CO2H

octanoic acid

caprylic acid

CH3(CH2)6CO-

octanoyl-

---

CH3(CH2)7CO2H

nonanoic acid

pelargonic acid

CH3(CH2)7CO-

nonanoyl-

---

CH3(CH2)8CO2H

decanoic acid

capric acid

CH3(CH2)8CO-

decanoyl-

---

CH3(CH2)10CO2H

dodecanoic acid

lauric acid

CH3(CH2)10CO-

dodecanoyl-

lauryl-

CH3(CH2)12CO2H

tetradecanoic acid

myristic acid

CH3(CH2)12CO-

tetradecanoyl-

myristyl-

CH3(CH2)14CO2H

hexadecanoic acid

palmitic acid

CH3(CH2)14CO-

hexadecanoyl-

palmityl-

CH3(CH2)16CO2H

octadecanoic acid

stearic acid

CH3(CH2)16CO-

octadecanoyl-

stearyl-

CH3(CH2)18CO2H

eicosanic acid

arachidic acid

CH3(CH2)18CO-

eicosanoyl-

arachidyl-

CH3(CH2)20CO2H

docosanic acid

behenic acid

CH3(CH2)20CO-

docosanoyl-

behenyl-

HOOC-COOH

ethanedioic acid

oxalic

-OC-CO-

ethandioyl-

oxalyl-

HOOCCH2COOH

propanedioic acid

malonic acid

-OCCH2CO-

propanedioyl-

malonyl-

HOOC(CH2)2COOH

butanedioic acid

succinic acid

-OC(CH2)2CO-

butanedioyl-

succinyl-

HOOC(CH2)3COOH

pentanedioic acid

glutaric acid

-OC(CH2)3CO-

pentanedioyl-

glutaryl-

HOOC(CH2)4COOH

hexanedioic acid

adipic acid

-OC(CH2)4CO-

hexanedioyl-

adipoyl-

CH2=CHCO2H

propenoic acid

acrylic acid

CH2=CHCO-

propenoyl-

acryloyl-

CH2=C(CH3)CO2H

methyl

methacrylic acid

CH2=C(CH3)CO-

methyl

methacryloyl-

CH3CH=CHCO2H

2-butenoic acid

crotonic acid

CH3CH=CHCO-

2-butenoyl-

crotonoyl-

HO2CCH=CHCO2H

cis-2-butenedioic

maleic acid

-OCCH=CHCO-

cis-2-butenoyl-

maleoyl-

HO2CCH=CHCO2H

trans-2-butenedioic

fumaric acid

-OCCH=CHCO-

trans-2-

fumaroyl-

(CH3)2CHCO2H

2-methylpropanoic
acid

isobutyric acid

(CH3)2CHCO-

---

isobutyryl-

(CH3)2CHCH2CO2H

3-methylbutanoic acid

isovaleric acid

(CH3)2CHCH2CO-

---

isovaleryl-

118

Lactams: Cyclic amides are called lactams.

Lactams are formed from amino acids when the amino group and the carboxyl group react to
eliminate HOH and form an amide.
O

O
C
CH2
CH2

_
OH

H2O

CH2

NH
N H

CH2

NH2

CH2
4-aminobutanoic acid lactam
-butyrolactam

CH2
4-aminobutanoic acid
-aminobutyric acid

Naming lactams is the same as naming lactones except that the suffix -lactam replaces lactone.
O
O

NH

H3C

O
NH

NH

CH3
(I) 3-aminopropanoic acid lactam 4-amino-2-methylpentanoic acid lactam

6-aminohexanoic acid
lactam

(c)

-propiolactam

-methyl--valerolactam

-caprolactam

119

Lactones: Cyclic esters are called lactones.

Lactones are formed from an open chain hydroxy acid in which the hydroxyl group has reacted
with the acid group to condense out HOH and form an ester.
O

CH2

H+

OH

_HO
2

OH

CH2

CH2

CH2
CH2

CH2
4-hydroxybutanoic acid
-hydroxybutyric acid

4-hydroxybutanoic acid lactone

-butyrolactone

The IUPAC names of lactones are derived by adding the term lactone at the end of the name of
the parent acid. The common names of lactones, used more often than IUPAC names, are
formed by changing the -ic acid ending of the hydroxy acid to -olactone. A Greek letter
designates the carbon atom that bears the ester group to close the ring and substituents are
named as in the parent acid.
O

O
O

CH3

CH3

(c) -butyrolactone

-butyrolactone

(I) 3-hydroxybutanoic acid lactone 4-hydroxybutanoic acid lactone

-valerolactone
4-hydroxypentanoic acid lactone

120

Waxes, Fats and Oils:

Waxes: are esters of long-chain carboxylic acids and long-chain alcohols.

The carboxylic acid usually has an even number of Cs (16 36)

The alcohol also has an even number of Cs ( 24 36)

e.g. Bees produce beeswax to form a honeycomb. Beeswax is mostly triacontyl hexadecanoate, i.e., the ester of the C30
alcohol, triacontanol and the C16 acid, hexadecanoic acid.
O
O
+

CH3(CH2)14C OH

hexadecanoic acid

H catalyst

HO (CH2)29CH3
1-triacontanol

Fischer
Esterification

CH3(CH2)14C O (CH2)29CH3

H2O

1-triacontyl hexadecanoate

e.g. Carnauba wax is a mixture of very high molecular weight waxes. It is secreted by the Carnauba plant to coat its
leaves and prevent excess water loss by evaporation

O
CH3 (CH2 )2 6 C O (CH2 )3 3 CH3
e.g. Paraffin wax, used to make candle and seal preserves, is not a true wax, but rather a mixture of high molecular
weight alkanes. It is not an ester but rather a long chain HC, e.g., C36H74
Animal Fats and Vegetable Oils: Animal fats are solids, e.g., butter and lard whereas vegetable oils are liquids, e.g.,
sunflower oil, olive oil, corn oil and peanut oil. Despite their differences in physical state, fats and oils are chemically
similar.

Both fats and oils are triacylglycerols

3 long-chain carboxylic acids.

Aqueous NaOH will break down (hydrolyze) triglycerides into glycerol and 3 fatty acids...

or

triglycerides,

i.e.,

triesters

of

glycerol

and

Note: This hydrolysis is

essentially the reverse of
CH2-OH
HO-C-R
CH2-O-C-R
Fischer Esterification.
Base
O
O
hydrolysis
is
nucleophilic
acyl
1. OH
+
CH-OH
substitution,
i.e.,
OH
adds
to
HO-C-R'
CH-O-C-R'
2. H3 O+
an esters carbonyl group
O
O
producing
a
tetrahedral
CH2-OH
HO-C-R"
CH2-O-C-R"
intermediate.
Loss of the
alkoxide
yields
the
fat or oil
glycerol
fatty acids
carboxylate.
Acidification
yields
acid. an even
The fatty acids obtained by hydrolysis of triglycerides are most commonly
unbranched
andthe
contain
number of C atoms from 12 20. If double bonds are present, they are usually of Z (cis) geometry. The 3 fatty
acids of a specific triglyceride molecule can be different and a fat or oil from a given animal or plant is usually a
complex mixture of different TAGs.

(TAGs)

Draw the mechanism of base hydrolysis of a TAG.

121

Structures and Names of Common Fatty Acids

saturated

# Cs

Structure

mp (C)

lauric

12

CH3(CH2)10COOH

44

myristic

14

CH3(CH2)12COOH

58

palmitic

16

CH3(CH2)14COOH

63

stearic

18

CH3(CH2)16COOH

70

arachidic

20

CH3(CH2)18COOH

75

unsaturated

# Cs

Structure

mp (C)

palmitoleic

16

CH3(CH2)5CH=CH(CH2)7COOH

32

oleic

18

CH3(CH2)7CH=CH(CH2)7COOH

16

ricinoleic

18

CH3 (CH2)5CH(OH)CH2CH=CH(CH2)7COOH

linoleic

18

CH3 (CH2)4CH=CHCH2CH=CH(CH2)7COOH

-5

linolenic

18

CH3 CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH

-11

eleostearic

18

CH3 (CH2)3CH=CHCH=CHCH=CH(CH2)7COOH

+49

arachidonic

20

CH3 (CH2)4 (CH=CHCH2)4 CH2CH2COOH

-50

All double bonds are cis except in eleostearic acid, which are 9 cis and 11 & 13 trans.

The tabulated data shows that unsaturated fatty acids generally have lower melting points than saturated fatty
acids with the same # of Cs. This is also true for TAGs.

Saturated fats have a uniform (long zigzag) shape that allows them to pack tightly. Unsaturated fats cannot pack
as tightly because cis double bonds introduce kinks and bends in the HC chain disrupting packing and
crystallization. The more unsaturation, the lower the mp. The geometry of a trans double bond is similar to the
zigzag conformation of a saturated acid and it does not kink the chain as much as a cis double bond

The C=C double bonds can be reduced to C-C single bonds by catalytic hydrogenation...
e.g.,

linoleic acid (mp = -5C) + H2/Pt stearic acid (mp = +75C)

The elimination of double bonds allows for tighter packing and higher mp, i.e., a liquid unsaturated fatty acid is
converted to a saturated solid or semisolid fat.
Margarine and cooking fats such as Crisco vegetable shortening are produced by hydrogenating soybean, peanut,
or cottonseed oil until the desired consistency is obtained, i.e., that of lard (animal fat). Margarine may be flavored
with butyraldehyde to give it a taste like that of butter. It is now generally accepted that polyunsaturated
vegetable oils are more easily digested and healthier than saturated fats and oils.

Approximately 40 different fatty acids occur naturally. Palmitic and stearic are the most abundant saturated fatty
acids. Oleic and linoleic acid are the most abundant unsaturated fatty acids. Oleic is monounsaturated (1 double
bond); linoleic, linolenic, etc. have 2 or more double bonds and thus are referred to as polyunsaturated fatty acids
(PUFAs).

Linoleic and linolenic acids occur in cream and are essential to the human diet. Infants grow poorly and develop
skin lesions if fed on a diet of nonfat milk.

122

(P)UFAs

Approx. % Composition of Some Fats and Oils

C12

C14

C16

C18

C18

C18

C18

Fats

lauric

myristic

palmitic

stearic

oleic

linoleic

linolenic

lard

25

15

50

butter

10

25

10

25

human fat

25

46

10

whale

12

35

10

beef fat

27

14

49

Oils

lauric

myristic

palmitic

stearic

oleic

linoleic

linolenic

coconut

50

18

corn

10

35

45

olive

80

peanut

60

20

linseed

20

20

soybean

10

29

51

herring

14

30 *

* and other unsaturated fatty acids

Note that vegetable oils generally have a higher proportion of unsaturated fatty acids than animal fats and thus
have relatively lower melting points.

Soap:
Soap has been used for cleansing since the middle ages (1500 - 1700 AD). Our grandparents made soap by mixing
animal fat with wood ashes (which contains KOH).

Soap is a mixture of Na+ or K+ salts of long chain fatty acids produced by hydrolysis (saponification) of animal fat
with an alkali.
O
CH2-OH

CH2-O-C-R

Na

Na +

O
O-C-R'

Na +

O
O-C-R"

1. OH

CH-OH

CH-O-C-R'

2. H2 O

O
CH2-O-C-R"

CH2-OH

fat or oil

glycerol

O
O-C-R

soap

R = C11 - C19 aliphatic chains

The product of the foregoing reaction is a mixture of crude soap curds, glycerol, excess alkali and water. It is
purified by boiling with water and adding NaCl to precipitate the pure Na carboxylate salts. The precipitated soap is
filtered, washed, dried, perfumed and pressed into bars. Dyes are added to make colored soaps, antiseptics are added
for medicated soaps, pumice is added for scouring soaps and air is blown in for soaps that float.

Na+ carboxylate soaps are solid but K+ carboxylate soaps are liquid (e.g., hand soaps).

123

Soap as a Cleanser:
The 2 ends of a soap molecule are different. The Na+ carboxylate end is ionic and thus hydrophilic (water loving) - it
dissolves in water. The long HC portion of the molecule is nonpolar and hydrophobic (water fearing) - it dissolves in
grease. Thus soap is soluble in both grease and water and is useful as a cleanser.

When soap is dissolved in water, groups of 100-200 soap molecules form spherical clusters (micelles) with the
long HC tails in the center and the ionic ends outward toward the water. Particles of grease and oil are dissolved in
the micelles nonpolar centers and release the garment to which they are adhering and are rinsed away.

In acidic water (such as acid rain), soap molecules are protonated to fatty acids. These nonionic molecules are
hydrophobic and float to the top as a greasy acid scum precipitate.

In hard water, which contains metal ions (Ca++, Mg++, Fe+++), soap is precipitated,
Ca+2(-OOCR)2 and appears as scum (hard water scum) around bathtubs and a gray tinge on white clothes.

e.g.,

O
C

non polar HC tail

hydrophobic tail
lipophilic tail

Soaps are surfactants, i.e.,

surface active agents. They reduce
the surface tension of water.

ionic head
hydrophililc head
lipophobic head

micelle
A cluster of surfactant molecules
dissolve in grease

O
O

C
O C O

O
C
O

C O

O
C
O

O
C

O
C O

C
O

O C
O

C
O

O C O

O
C
O

124

Synthetic Detergents (syndets):

Synthetic detergents were developed as clothes detergents. They are chemically similar to soaps; they have both
hydrophilic and hydrophobic ends, but they do not form scums. Na salts of sulfonic acids are the most widely used
class of syndets.

pKa -1

NaOH
R

S OH

S O

Na

pKb 15

O
alkyl substituted
benzenesulfonic acid

syndet

R = mixture of C12 aliphatic chains

Sulfonic acids are more acidic than carboxylic acids, so their salts are not protonated in acidic water. In addition,
Ca+2, Mg+2, and Fe+3 salts of sulfonic acids are soluble in water; sulfonate salts can be used in hard water without
forming a scum.

Some syndets are produced with nonionic hydrophilic groups containing several O-atoms or other H-bonding
atoms, e.g., nonoxynol ....
CH3

(CH2 )8

(OCH2 CH2 )9

OH

Some syndets are produced with cationic hydrophilic groups due to the presence of quaternary amine groups, i.e.,
R4-N+ Cl-

Shampoos
The active ingredient (cleanser) in many shampoos is an alkyl sulfate, e.g., sodium lauryl sulfate.

O
H3C (CH2)11 O S O

Na+

125

CHM 605
Part 10
POLYMER
LABORATORY
EXPERIMENTS

126

EXP 1: PREPARATION OF POLYMER SLIME

THEORY:

The Polymer Slime is made by crosslinking linear poly(vinyl alcohol), PVAL, with an aqueous
solution of sodium tetraborate (Twenty Mule Team borax laundry detergent).
In aqueous solution, sodium tetraborate, Na2B4O710 H2O, forms B(OH)4- ions, which establish
tetrafunctional interactions (hydrogen bonds) with PVAL forming a loosely crosslinked gel.
Stressing the gel (pulling, distorting, squashing, etc.) breaks the crosslinks however the physical
links quickly reform.
OH
CH2

CH

CH2

- O

CH2

OH

polyvinyl alcohol
CH

HO
HO

OH
CH

aqueous B(OH)4- ions

H +

O
-

CH2

CH

+
H

CH2

H +

O
-

CH

O -

CH2

CH

CH2

CH
OH

physically crosslinked polymer

hydrogen bonds form between polar O and H atoms

The crystalline structure of solid sodium tetraborate is shown below.

O
B

O
B

O
O

Na+
O

O
B

Na+

O
O

- Na
B

+
- Na
B O

+
- Na
B O

B
O

O
B

Na+
O

O
O

B
O

O
B

Na+
O

O
O

- Na
B O

O
O

Na+

Na+

Na+
O

- Na
B

Note the Na2B4O7 repeating units in crystalline sodium tetraborate.

127

MATERIALS:
1. concentrated, aqueous solution (70 gpL) of PVAL linear polymer
2. saturated solution of sodium tetraborate
3. liquid food coloring or Tempra paint
4. small plastic cup with lid
5. disposable stirring stick
6. 25 mL graduated cylinder
7. 10 mL graduated cylinder
PROCEDURE:
Work over a folded piece of paper towel.
1. Measure 20 mL of the PVAL solution into the 25 mL graduated cylinder and transfer this to the
small plastic cup.
2. Add one drop of food coloring (or a tiny amount of Tempra paint) to the PVAL solution and mix
with the stirring stick to distribute the color.
3. Measure 4 to 5 mL of borate solution into the 10 mL graduated cylinder and pour this into the
colored PVAL solution and mix thoroughly with the stirring stick. The mixture will start to
thicken within 30 seconds. Continue mixing for this period or until it becomes too thick to mix
any more.
4. Remove the gel/slime from the cup. If any liquid remains it can be absorbed by blotting with
the paper towel. Roll the gel between your hands to complete the mixing and the crosslinking.
5. Examine the physical properties of the gel. Does it stretch?, sag?, drip?, bounce?
6. The ball should be stored in the sealed cup. It will dry out and harden if left in the air but can
be rehydrated by wetting it with a few mL of water and reshaping it by rolling between the
hands. The gel can be kept for months, however, it should be discarded if it begins to grow
mould.
7. Wash your hands if gloves were not worn. The gel is not toxic but it should not be eaten as it
will cause gastrointestinal distress.
QUESTIONS:
1. Identify the polymer type as (thermoplastic or thermoset), (homopolymer or copolymer), and
(ionomer or neutral polymer)
2. Identify the end use of the polymer as one of the following: rubber, elastomer, elastoplastic,
plastic, fiber, coating, adhesive, film, composite, cellular or biopolymer.

128

EXP 2: PREPARATION OF A Mad Science POLYMERIC BALL

THEORY:
The Polymeric Ball is made by crosslinking linear poly(vinyl alcohol), PVAL, with sodium
tetraborate (Twenty Mule Team borax laundry detergent).
The two substances are supplied as a dry premix. In aqueous solution, sodium tetraborate,
Na2B4O710 H2O, forms B(OH)4- ions, which establish tetrafunctional interactions (hydrogen bonds)
with PVAL forming a crosslinked mass. The concentration of tetraborate is much greater in the
polymer ball than in the polymer slime, so the crosslink density is much higher. As a result, the
polymer ball is much firmer than polymer slime.
OH
CH2

CH

CH2

- O

CH2

OH

polyvinyl alcohol
CH

HO
HO

OH
CH

aqueous B(OH)4- ions

H +

O
-

CH2

CH

+
H

CH2

H +

O
-

CH

O -

CH2

CH

CH2

CH
OH

physically crosslinked polymer

hydrogen bonds form between polar O and H atoms

The crystalline structure of sodium tetraborate ion is shown below.

O
B

O
B

O
O

Na+
O

O
B

Na+

O
O

- Na
B

+
- Na
B O

+
- Na
B O

B
O

O
B

Na+
O

O
O

B
O

O
B

Na+
O

O
O

- Na
B O

O
O

Na+

Na+

Na+
O

- Na
B

Note the Na2B4O7 repeating units in crystalline sodium tetraborate.

129

MATERIALS:
8. dry PVAL polymer/sodium tetraborate mixture*
9. mold*
10. 250 mL beaker
11. plastic bag
* Mold and polymer mixture available from Mad Science of Windsor
*PROCEDURE:
8. Fill the beaker with tap water to the or mark
9. Connect the two halves of the mold and hold it between your index finger and thumb so that
the open end (spout) is facing up. Gloves are optional. Sodium tetraborate is a mildly alkaline
detergent. PVAL is not corrosive. Avoid eye contact.
10. Add the dry polymer mixture to fill the mold, occasionally pausing to tap the mold gently to fill
any voids. Each package contains sufficient reagent for one mold. A small void space at the top
will fill when the polymers swells while immersed in water.
11. Hold the filled mold submerged in the water in the beaker for 1 minutes. Do not allow the
mold to separate during this time. Water will seep in through the holes in the mold and initiate
the cross linking reaction.
12. After the prescribed time, remove the mold from the water. Carefully open the mold and
remove the polymer ball. Roll the ball between the palms of your hands to force contact
between more polymer chains and to create more crosslinks.
13. Place the ball in a plastic bag for ca. 30 min. to keep it moist while the crosslinking reaction
continues. After 30 minutes, the ball is ready to be tested.
14. The ball should be stored in a plastic bag. It will dry out if left in the air but can be rehydrated
by again immersing it in water for ca. 1 minute and reshaped by rolling between the hands.
15. Rinse and return molds to the instructor. Wash your hands if gloves were not worn.

* Procedure complements of Mad Science of Windsor.

QUESTIONS:
3. Identify the polymer type as (thermoplastic or thermoset), (homopolymer or copolymer), and
(ionomer or neutral polymer)
4. Identify the end use of the polymer as one of the following: rubber, elastomer, elastoplastic,
plastic, fiber, coating, adhesive, film, composite, cellular or biopolymer.

130

EXP 3: NYLON ROPE BY INTERFACIAL CONDENSATION

THEORY:
Amides are produced when an acid chloride reacts with an amine. The student should be able to
draw the mechanism for this reaction.
: O:
R

H
..
:
Cl
..

..
N

: O:
R'

acid chloride

..
N

R'

HCl

H
amine

amide

The byproduct HCl acid will consume half of the basic amine reagent, so two moles of amine
reagent must be used per mole of acid chloride. Alternately, NaOH can be added to an aqueous
amine phase to consume the byproduct HCl, while the acid chloride remains dissolved in an
organic phase. The amine migrates into the organic phase to react with the acid chloride and the
HCl produced in the organic phase, migrates to the aqueous phase where it is neutralized. NaOH is
a good nucleophile and would preferentially react with the acid chloride (producing a carboxylate
salt) if it were soluble in the organic phase but NaOH is insoluble in the organic phase.
Nylon 6,6 [Duponts trade name for poly(hexamethylene adipamide)] is produced when
hexamethylenediamine (HMDA) reacts with adipoyl chloride. The reaction can be carried out in a
single phase (bulk polymerization) or as in this experiment, at the interface between two separate
phases.

adipoyl chloride
(hexanedioyl chloride)

Nylon rope pulled

from the interface.
HMDA + NaOH in water

O
Cl

hexamethylenediamine
(HMDA)

O
CH2

H2N

CH2

Cl

NH2

HCl

Nylon 6,6 at interface

O

Adipoyl chloride in CH2Cl2

Cl

CH2

HN

CH2

NH2

poly(hexamethylene adipamide)
(Nylon 6,6)

131

PROCEDURE:
16. Prepare reagent a) and b) in separate flasks:
a) Prepare 5% adipoyl chloride in CH2Cl2. [Caution: Adipoyl chloride is corrosive. Use in a fume
hood]
b) Prepare an aqueous solution that is 5% HMDA and 2%w NaOH.
17. Pour the denser organic solution into a small beaker first.
18. Slowly and carefully pour an equal volume of the aqueous solution on top of the organic layer.
Do not allow the solutions to mix when combining them. You should obtain two separate
layers. A thin white layer will appear at the interface when the two solutions are brought into
contact. This is Nylon 6,6 formed by interfacial condensation.
19. Use a wire or tweezers to slowly pull the white solid layer up out of the solution and a long fiber
is drawn.
20. Rinse the fibers under running water and study their feel and strength.
QUESTIONS:
1. Show the mechanism of amide formation during reaction of an acid chloride and an amine.
2. Identify the polymerization type as one of the following: chain growth, step growth
(condensation or rearrangement) or ring scission.
3. Identify the polymerization technique as one of the following: bulk, solution, suspension or
emulsion.
4. Identify the polymer type as either thermoplastic or thermoset.
5. Identify the end use of the polymer as one of the following: rubber (elastomer), plastic (resin),
fiber, coating, adhesive (sealant), film, composite, cellular or biopolymer.

132

EXP 4: Ring Opening Polymerization And the Formation of Nylon 6

THEORY:

The ring-opening polymerization of caprolactam is a commercial process. The nylon produced,

Nylon 6, is used extensively in automobile tire cords and for gears and bearings in small
mechanical devices.
The catalyst used in this reaction is sodium hydride; therefore, this is referred to as an anionic
polymerization. The sodium hydride initiates the reaction by removing the weakly acidic lactam
proton from caprolactam to form a N anion (a good nucleophile). The anionic N subsequently
bonds to the weakly electrophilic carbonyl-C on another monomer molecule. In order to
accommodate the electron pair donated by the N anion, the second caprolactam molecule
undergoes ring scission. Its carbonyl-C to N bond breaks heterolytically producing an NH anion,
which propagates the chain.
Ordinarily anionic polymerizations must be run in the absence of oxygen, but the addition of
polyethylene glycol serves to complex with the sodium ion (just as 18-crown-6 ether does) and
enhances the catalytic activity of sodium hydride.
:O:
+

Na H:

:O:
C

..
N

:O:
C

..

N:

:O:

..
N

:O:
C

..
N

..
..NH
propagation

..
N

H
O
(CH2)5

etc.

NH

n
Nylon 6
poly(caprolactam)

initiated
monomer

PROCEDURE:
Do the heating in a fume hood. Wear safety glasses and avoid contact with the reagents.
Caprolactam is toxic, a sensitizer, an irritant and a neurologic hazard.
Sodium hydride is strongly basic, i.e., corrosive, and is explosive in water.
21. Clamp a test tube above a Bunsen burner in a fume hood. Angle the test tube toward the back
of the fume hood.
22. In the test tube place 4 g of caprolactam and 0.25 g polyethylene glycol Heat the mixture with
a small, cool flame and as soon as it has melted remove the flame and add 50 mg of gray (not
white) sodium hydride (50% dispersion in mineral oil).
Close the container of NaH immediately after dispensing since it is moisture sensitive.
23. Mix the catalyst with the reactants by stirring with a Pasteur pipette (or swirling the test tube)
and heat the mixture rapidly to boiling (200 to 230C) over a 2 minute period. Polymerization
takes place rapidly, as indicated by an increase in viscosity.
24. If polymerization has not occurred within 5 minutes remove the tube from the heat, cool it
somewhat, add another 50 mg of sodium hydride, mix and reheat.

25. When the solution is so viscous that it will barely flow, insert a wood stick or Pasteur pipet and
draw fibers from the melt
133

QUESTIONS:
5. Identify the polymerization type as one of the following: chain growth, step growth
(condensation or rearrangement) or ring scission.
6. Identify the polymerization technique as one of the following: bulk, solution, suspension or
emulsion.
7. Identify the polymer type as either thermoplastic or thermoset.
8. Identify the end use of the polymer as one of the following: rubber (elastomer), plastic (resin),
fiber, coating, adhesive (sealant), film, composite, cellular or biopolymer.

134

EXP 5: PREPARATION OF PMMA

THEORY:
Poly(methyl methacrylate) is a transparent (amorphous) plastic made by free radical
polymerization of methyl methacrylate (the methyl ester of 2-methylpropenoic acid, i.e., methyl 2methylpropenoate). PMMA resin is sold under the Trade names Plexiglass and Lucite. It is not an
Acrylic. Acrylics refer to a different polymer; poly(acrylonitrile) abbreviated PAN, which is used to
make acrylic fabrics.
The most important property of PMMA is its optical clarity. This plastic exhibits up to 92% light
transmittance, the highest of any plastic material. It also has very low sensitivity to UV light, very
low oxidation sensitivity, and good overall weather resistance which together result in a high
retention of clarity and light transmittance even after very long periods of time. These excellent
properties have led to applications such as windshields (for planes and helicopters), automobile
taillights, compact discs (CDs), display cases, and plastic lenses for eyewear including hard contact
lenses.
Although it contains repeating ester linkages, PMMA is not strictly classed as a polyester.
PROCEDURE:
1. Place 2 ml of methyl methacrylate into a test tube, add 2 drops of tert-butyl peroxybenzoate
and thoroughly mix the liquids.
Caution: t-butyl peroxybenzoate is a strong oxidizer and is harmful by ingestion, inhalation and
skin contact.
2. If desired, you may stir in a small curiosa (e.g., sparkles, insects, a coin, etc.) which will be
encapsulated in the resin after curing.
3. Heat the mixture in a water bath or heating block at ca. 80 C for 1 hour. (Heating block on high
heat with a setting of ca. 1). Leave a thermometer in one cell of the heating block to check the
temperature. Do not heat above 85C.
QUESTIONS:
26. Draw the structure of the peroxide initiator from its name.
27. Show the mechanism of initiation and propagation of the PMMA chain. You may simply write
the initiator as I .
28. Identify the polymerization type as one of the following: chain growth, step growth
(condensation or rearrangement) or ring scission.
29. Identify the polymerization technique as one of the following: bulk, solution, suspension or
emulsion.
30. Identify the polymer type as either thermoplastic or thermoset.
31. Identify the end use of the polymer as one of the following: rubber (elastomer), plastic (resin),
fiber, coating, adhesive (sealant), film, composite, cellular or biopolymer.

135

EXP 6: PREPARATION OF A RIGID, CLOSED-CELL POLYURETHANE FOAM

THEORY:
The familiar flexible foam material used in sofa cushions and automobile seats is a polyurethane
(PU) foam. Rigid PU foam is used as a building insulation (as well as polystyrene foamStyrofoam). Foams are described as open cell (the openings are interconnected) or closed cell
(gas bubbles are isolated).
A urethane (also called a carbamate) is a functional group that looks like an amide on one side and
an ester on the other. It is made by reacting an isocyanate with an alcohol. The student should be
able to draw the mechanism.

..
N

..
O
..

..
O
..

R'

an alcohol

an isocyanate

..
N

:O :
C

..
O
..

R'

an isocyanate

In this experiment, toluenediisocyanate (TDI) reacts with 1,2,3-propanetriol (glycerol) to form a

polyurethane.
CH3
CH3
O

2,4-toluenediisocyanate
( a difunctional monomer)

CH2

CH

CH2

OH

OH

OH

1,2,3-propanetriol
(a trifunctional monomer)

CH

CH2

CH2

OH

OH
n

a polyurethane

Isocyanates react with water to form an amine and carbon dioxide gas.

..
N

..
O
..

..
O
..

R
H

..
N

: O:
C

..
OH
..

decomposes
R

..
N

CO2

a carbamic acid
(unstable)

For this reason, a small amount of water is added during the polymerization. The evolution of CO2
gas forms bubbles in the polymer creating the foam.

136

PROCEDURE:
4. Support a paper cup in a suitably sized beaker. Into the cup add the following ingredients:
a) 5.5 mL castor oil
b) 1 mL glycerol
c) 2 drops each of water, triethylamine, and Dow Corning 200 silicone oil
5. Mix the liquids with a glass stirring rod until smooth
6. In a fume hood, add 4 mL of TDI [Caution: very toxic; do not breathe the vapors]
7. Stir thoroughly for ca. 30 to 60 seconds until a creamy emulsion is obtained and bubbles begin
to evolve.
8. Allow the mixture to stand while polymerization continues. The product may take up to 24
hours to harden but the foam is produced within 5 to 10 minutes.
QUESTIONS:
32. Show the mechanism of urethane formation from an isocyanate and an alcohol
33. Identify the polymerization type as one of the following: chain growth, step growth
(condensation or rearrangement) or ring scission.
34. Identify the polymerization technique as one of the following: bulk, solution, suspension or
emulsion.
35. Identify the polymer type as either thermoplastic or thermoset.
36. Identify the end use of the polymer as one of the following: rubber (elastomer), plastic (resin),
fiber, coating, adhesive (sealant), film, composite, cellular or biopolymer.

137

EXP 7: IDENTIFICATION OF A POLYMER

Techniques used to identify a polymer include the following:
1. Preliminary examination
2. Elemental analysis (Lassaigne's Test)
3. Solubility test
4. IR analysis (KBr disc)
5. Flame Test/Melting Test
6. Specific gravity determination
Preliminary Examination:
Based on a preliminary examination, a polymer can sometimes be classified as belonging to one of the following groups:
a. rubber
b. flexible thermoplastic
c. rigid thermoplastic
d. thermoset
Manufacturer's Labeling Code: The composition of an increasing number of plastic products is identified using the SPI
(Society for Plastics Industry) recycling code, which is usually stamped on the bottom of the product. The number is
often enclosed in the triangular arrows recycling symbol. The code is as follows:
1.
PETE - Polyethylene Terephthalate
2.
HDPE - High Density Polyethylene
3.
V - Vinyl / Polyvinyl Chloride (PVC)
4.
LDPE - Low Density Polyethylene
5.
PP - Polypropylene
6.
PS - Polystyrene
7.
Other
End Use: In the case of a finished article, the intended use can very often indicate the nature of the polymer. For
example:
Elastic bands and tires are rubbers (elastomers).
Elastic bands are usually natural rubber
(cis-1,4-polyisoprene). Automobile tires are usually a blend of styrene butadiene rubber (SBR) and
natural rubber.
Pot handles and cutlery handles are usually thermosets (e.g., phenolics). Dishes are likely to be melamineformaldehyde thermosets.
Garden hoses, shower curtains and raincoats are usually PVC.
Tents and screens are usually nylon.
Floating rope is usually polypropylene.
Foam upholstery cushions are usually polyurethanes.
Bulletproof glass, sunglasses and reading glasses with plastic lenses are polycarbonate.
Feel: Teflon and polyethylene feel waxy. Thermosets feel hard and sound brittle when dropped or struck with a
metallic object. Rubbers are flexible and sometimes stretchy.
Color: Most polymers are available in a wide color range resulting from the addition of various pigments. Phenolformaldehyde thermosets (Bakelite) are inherently dark colored. If a polymer is light in color, it is not a phenolformaldehyde thermoset.
In the absence of additives, pure amorphous polymers have high optical clarity (transparent) whereas
crystalline polymers are translucent to opaque. The following are examples of transparent polymers: PET (pop bottles),
PMMA (Plexiglas), PC (bulletproof glass), PVAc (blister packaging).

138

Elemental Analysis (Lassaigne's Test):

The presence of N (e.g., polyamides), halogens [e.g., PVC or poly(vinylidene chloride) - Saran wrap] and
S (vulcanized rubber and polysulfide caulkings) can be identified by inorganic qualitative analysis after sodium fusion.
Additives may interfere; e.g., some flame-retardants contain Cl or Br.
Solubility:
Thermoplastics are soluble in appropriate solvents whereas thermosets may swell but are insoluble. Plastics may
require long exposure to a solvent to dissolve. Agitation significantly reduces dissolving time. The following table
illustrates polymer solubility behavior. The general rule of like-dissolves-like applies, i.e.; hydrocarbon solvents tend to
dissolve non-polar polymers, whereas polar solvents tend to dissolve polymers containing polar functional groups.
Plastic
ABS
LDPE, HDPE
PA (polyamides)
PET
PMMA
PP
PPO
PS
PVC
I = insoluble

Gasoline
SW
I
I
I
I
I
I
S
I

SW = swells

Toluene
S
I
I
I
SW
I
SW
S
SW

Acetone
S
I
I
I
S
I
S
S
SW

Cyclohexanone
S
I
I
I
S
I
S
S
S

S = soluble

Solubility behavior is shown at room temperature. Heating can solubilize thermoplastics such as
PE and PP.
IR Analysis:
The infrared spectrum of a polymer sample that has been ground into a KBr disc will identify major functional groups
such as carbonyl stretches (polyesters), N-H stretches (polyamides), aromatic bends (polystyrene), alkene stretches
(cis-1,4-polyisoprene), O-H stretches [poly(vinyl alcohol)], CN stretches (polyacrylonitrile), and C-H stretches
(polyethylene).
Flame Tests/ Melt Tests:
The melting range of a thermoplastic can be determined after melting a few chips of the plastic in a test tube. A
thermometer or thermocouple lead immersed in the melt can be used to measure the temperature at which
solidification occurs. During freezing, the rate of cooling levels out as the latent heat of fusion is released. The melting
point range can be compared to tables available from the literature.
Flame tests identify the ease of ignition, rate of burning, color of flame and soot, as well as odors of combustion
products. A detailed procedure is attached.
Specific Gravity:
The relative density of a polymer is very helpful in determining its identity. Polyethylenes, polypropylenes and
polyallomers (block copolymers of ethylene and propylene) float in water (s.g. < 1.0) whereas virtually all other (noncellular) polymers sink. Although the addition of fillers can change the relative density of polymers, even so, the
method narrows down the number of possible choices. A detailed procedure is attached.

139

SIMPLE TESTS FOR IDENTIFYING POLYMERS

Flame Tests:

Test the flammability of each kind of polymer listed below by holding it in a flame for 5 to
10 seconds and then remove it from the flame. Hold the sample over an asbestos pad to
catch any drips. Work in or near a fume hood and try to direct as many of the fumes as
possible into to the fume hood.
Observe and record the characteristics identified in the table of results below. Discuss the
characteristics with your partners and fill in as much of the table as possible.
Perform the Beilstein test on PVC and any other samples you wish. A copper wire heated in
a flame with melting polymer burns bright green if a halogen is present. Halogenated
polymers can be identified in this way.
Many polymers have characteristic odors when burned or melted. It is not advisable to
inhale these odors since most are unhealthy. Odors of melted polymers (e.g., in test tubes)
are more characteristic than the odors of burning polymers. It is not uncommon for people
working in polymer businesses, e.g., polymer recycling, to ignite a small piece of plastic with
a cigarette lighter and identify the polymer based on flame test and odor.
Based on the flame tests, identify which polymers are thermoplastic (T. Plastic) and which
are thermoset (T. Set). Thermoplastics melt (Touch the hot polymer to the asbestos pad
and see if the polymer is liquid). Thermosets are decomposed at high temperature, but do
not melt. They char and smoke but do not melt.
Compare your results with the handouts "ID your plastics by flame tests".

Specific Gravity:

Polyolefins, i.e., polyethylene, polypropylene and polyallomers (block copolymers of

ethylene and propylene) float in water (s.g. < 1.0). Most other polymers sink in water (s.g. >
1.0). Test the specific gravity on any samples for which you can readily obtain a small piece.
Drop a small piece in a beaker of water. Be sure that the sample is wetted i.e., overcome
surface tension by pushing the plastic under the surface. Specific gravity tests do not apply
to plastics that are produced as expanded foams. Enclosed gas cells within the plastic will
cause even dense polymers to float. For simplicity, polymer s.g. is determined vs. H2O @
23C.
Specific gravity can be accurately measured by weighing a polymer sample in air and in a
fluid, e.g., water. The s.g. can be calculated as follows
BA
s. g.
B A D C

s. g.

B = wt. of sample + wire in air

A = wt. of wire in air
C = wt of wire in water
D = wt. of sample + wire in water

For C, immerse only as

much of the wire as was
immersed when weighing
the sample.

densityof object
wt. of sple.(in air)
(wt. of sple. wirein air) - (wt. of wirein air)
BA

densityof water wt. of H 2O (displacedby sple.)

(wt. of sple.in air) - (wt. of sple.in H 2O)
( B A) ( D C )

[Archimedes principle: An object immersed in water is buoyed up with a force equal to the weight of water it displaces. For

plastics that are less dense than water (olefins), secure the wire so that the sample is held
under water or hang a lead weight on the sample and incorporate this into the calculation.
140

Specific Gravity of Some Common Polymers

POLYMERS
(Alphabetized)
acetal
acrylic
ABS
aluminum
cellulose acetate
cellulose nitrate
diallyl phthalate
epoxy (cast)
FEP
glass
ionomer
melamine formaldehyde
Nylon
oak
phenoxy
phenol formaldehyde
PMMA
poly(vinylidene chloride)
polyallomer
polycarbonate
polyester
polyethylene, L. D.
polyethylene, H. D.
poly(phenylene oxide)
polypropylene
polystyrene
polysulfone
polyurethane
poly(vinyl chloride)
silicone
steel
tetrafluoroethylene

S.G.
1.42
1.18
1.04
2.50
1.30
1.25
1.50
1.11
2.14
2.50
0.94
1.48
1.15
0.86
1.17
1.27
1.18
1.70
0.89
1.20
1.10
0.91
0.95
1.06
0.89
1.06
1.24
1.18
1.25
1.75
7.70
2.16

S.G.
(Range)

1.34-1.78

1.13-1.20

1.25-1.30

1.01-1.20
0.91-0.92
0.94-0.96

1.04-1.10
1.11-1.25
1.16-1.35

2.14-2.20

POLYMERS
(SG prioritized)
oak
polyallomer
polypropylene
polyethylene, L. D.
ionomer
polyethylene, H. D.
ABS
poly(phenylene oxide)
polystyrene
polyester
epoxy (cast)
Nylon
phenoxy
acrylic
PMMA
polyurethane
polycarbonate
polysulfone
cellulose nitrate
poly(vinyl chloride)
phenol formaldehyde
cellulose acetate
acetal
melamine formaldehyde
diallyl phthalate
poly(vinylidene chloride)
silicone
FEP
tetrafluoroethylene
aluminum
glass
steel

S.G.
0.86
0.89
0.89
0.91
0.94
0.95
1.04
1.06
1.06
1.10
1.11
1.15
1.17
1.18
1.18
1.18
1.20
1.24
1.25
1.25
1.27
1.30
1.42
1.48
1.50
1.70
1.75
2.14
2.16
2.50
2.50
7.70

S.G.
(Range)

0.91-0.92
0.94-0.96

1.04-1.10
1.01-1.20
1.13-1.20

1.11-1.25

1.16-1.35
1.25-1.30

1.34-1.78

2.14-2.20

The specific gravity of a given polymer may vary due to the method of polymerization and
the method by which the polymer is processed.
The method of polymerization may affect the extent of chain branching. For example,
compare highly-branched LDPE with sparsely-branched HDPE.
The method of processing may affect the extent of crystallization. Rapid cooling produces
an amorphous (less dense) polymer. Slow cooling or cooling under stress (e.g., melt
spinning or gel spinning) often induces crystallization, resulting in a more dense polymer.
The addition of a filler is another cause for variation of s.g. of a given polymer.

141

POLYMER IDENTIFICATION FLAME TEST

Polymer

SE

or
P

Speed of
Burn
(slow, med.,
fast)

Chars (C)
or
Melts (M)

Drips

Flame
Color

Smoke
Color

Sinks ()
or
Floats ()
in water

TP
or
TS

REMARKS

PVC (Tygon tubing)

Vulcanized black
rubber
PS
Melamine
(Melmac dish)
PMMA (Plexiglass)
Polycarbonate (Lexan)
FRP Epoxy
PP
ABS (drain pipe)
PE

SE = Self Extinguishing, P = Propagating; TP = Thermoplastic, TS = Thermoset

142

EXP 7: POLYMER IDENTIFICATION LAB

Procedure:
1. Perform a flame test and a float/sink test on all the types of polymers for which samples
have been provided. There is a set of small beakers containing small polymer chips for
these two tests.
For the float/sink test, do not use a piece of plastic that has been burned. Use a fresh piece
of plastic. Ensure that the surface of the plastic is completely wetted. Using tweezers,
shake the piece under water to release any air bubbles adhering to the surface of the
plastic. Adhering air bubbles may cause a dense plastic to float.
Record observations for all the characteristics listed on the Polymer Identification Flame
Test (Float/Sink Test) chart.
Do not burn any other plastics without the instructors permission and be sure to work in a
fume hood over an asbestos pad or gypsum board to catch all drips. See the Flame Test
instructions for details on performing the test.
Each student must submit his/her own copy of the results next week.
Accurately determine the specific gravity (s.g.) of 3 different polymer samples supplied by
the instructor. Compare the results with the s.g. values listed on the table of Specific
Gravities handout supplied by your instructor. Also consider other physical properties
such as sink/float, feel, stiffness, clarity, color, etc. Do not burn any of the S.G. samples.
Report the Sample Identification number (-A, -B, -C, U-1, U-2, etc.), the calculated
s.g., and the polymer identity you have determined. Calculations are not required.

BIBLIOGRAPHY

1. Baird, R; Baird, D. Industrial Plastics; Goodheart-Willcox Company: USA, 1986.

143

CHM 605
Part 11
POLYMER
TEST
QUESTIONS

144

POLYMER REVIEW
1.

2.

3.
4.
5.
6.
7.
8.
9.
10.

11.

12.
13.
14.
15.
16.

17.
18.
19.
20.
21.

Polymer history: Complete the following ...

a) ....................................... is a polymer used by the Mayan Indians of S. America
b) ....................................... was the polymer first used as an ivory replacement
c) ....................................... was the first thermal resistant polymer, i.e., pot handles
d) ....................................... is known as the Father of polymer chemistry.
State, define or explain in as few words as possible ...
a) Staudingers Macromolecular
f) mer
Hypothesis
g) mesomer
b) homopolymer
h) oligomer
c) copolymer
i) high polymer
d) terpolymer
j) degree of polymerization
e) ionomer
Using A and B for monomers, show & name 4 different arrangements of comonomers in copolymers
List the 3 most important feedstock monomers for making polymers.
List 9 groups of polymers classified according to end use and 1 chemical name of a polymer for each.
Sketch the appearance of linear, branched and crosslinked polymer chains.
Give one example each for monomers with functionality of 2, 3, and 4
State 4 characteristics each for thermoplastics and thermosets.
Name 3 thermoplastics and 3 thermosets.
Explain in as few words as possible ..
a) amorphous polymer
c) glassy state
b) crystalline polymer
d) tacticity
Sketch polymer chains in their planar zigzag conformation showing ...
a) isotactic polypropylene
b) syndiotactic polystyrene
c) atactic poly(vinyl chloride)
For each polymer in question 11, state whether it is amorphous or crystalline.
Sketch cis- and trans-1,4-polybutadiene to show their stereochemistry.
Give names or draw structures of polymers using IUPAC and common nomenclature for all examples
covered in class.
Write the 7 SPI recycle symbols and the corresponding chemical names and abbreviations..
Explain briefly ..
a) crystallite
c) 1st order transition temperature
b) glass transition temperature
d) 2nd order transition temperature
Name and draw the structures of 2 commercial plasticizers.
Explain briefly, the function of a plasticizer with respect to its physical properties.
List 2 polymers with low Tg and 2 with high Tg
State if these polymers have high or low Tg and why: PS, isotactic/atactic PP, PVC, and PE
Answer with or . Increasing the number of branches in a polymer
a) causes the crystallinity to .......
b) causes the density to .......
c) cause the melting point to .......
d) causes the tensile strength to .......

145

22.
23.
24.
25.

Give the approximate density and melting point of LDPE and HDPE.
What is the lowest DP at which the melting point of PE exceeds 100 C?
What is the DP of PE with the formula C200H402? What is the MW of PE given DP=3000?
Calculate the DP of PP with avg. molecular weight of 200,000

26. List 6 methods of determining average molecular weight of a polymer and state whether the method determines
number-average, weight-average, or viscosity-average molecular weight.
27. Calculate the average MW of a polymer using data re: any of the colligative properties as discussed in class
28. Arrange these 3 molecular weights in decreasing magnitude as determined on the same sample of polymer.
29. Using a simple graph (with labeled axes) explain the difference between a polydispersity index of 1.1 vs. 4.
30. What effect does a high polydispersity index have on a polymers physical properties?
31. List 4 non-catalytic methods and 3 catalytic methods of polymerization
32. Name the 3 main types of polymerization and name 1 example of a polymer for each.
33. By means of equations show the complete cycle of free radical polymerization of a vinyl polymer (e.g., PE, PP,
PVC, PTFE, PS) (Instructors choice on a test). Include termination by combination and disproportionation, chain
transfer with solvent (e.g., CCl4), polymer, and chain transfer agent.
34. Give the formula and name of 1 chain transfer agent.
35. State the effect avg. molecular weight on...
a) adding chain transfer agent
b) adding a very small quantity of initiator
36. Give the formulas or structures of, and state the names of 2 common free radical initiators for free radical
polymerization. Show the mechanism of their dissociation and give the formula/structure of their products.
37. List 2 initiator accelerators (i.e., redox initiators)
38. Give the name and structure of 2 free radical inhibitors. Why are they needed?
39. Use resonance structures to show and explain why one of these inhibitors is effective.
40. What are the cause, effect and mode of prevention of the Tromsdorff-Norish Effect?
41. List 3 dienes which can be free-radical polymerized and draw their structures.
42. Show the mechanism of initiation and propagation of free radical polymerization of a diene (1,4 or 1,2)
43. Draw structures of 3 monomers which can be polymerized a) cationically, b) anioinically
44. Draw resonance structures to show how styrene can stabilize either a benzylic cation, anion or free radical
(Instructors choice on test).
45. Show the mechanism by which water can deactivate a cationic (or anionic) end group.
46. Show the mechanism of initiation of anionic polymerization of vinyl chloride with methyl lithium (or with Li
metal, or Li + naphthalene). Then show one propagation step.
47. Show the mechanism by which functional end groups can be created by termination with carbon dioxide and with
ethylene oxide.
48. Write equations to show cationic polymerization of isobutylene including its initiation with H2SO4 or with a Lewis
acid catalyst (e.g., BF3, AlCl3, SnCl4, ZnCl2).
49. List the approximate conditions (temp., pressure) of the high pressure PE process and the Ziegler-Natta Coordination
Process. State the type of polymer produced by each and list 2 applications for both types of PE.
50. What is the catalyst commonly used in the Ziegler-Natta process?
51. What is meant by propagation from the root vs. propagation at the tip? Which process causes each of these
kinds of propagation?
52. List examples of 4 different types of polymers that are polymerized by the step-growth method.
53. Show the mechanism of step-growth polymerization of poly(ethylene terephthalate) (or Nylon 6).
54. Name 2 subdivisions of step-growth polymerizations and briefly state their difference.

146

55.
56.
57.
58.

Show the polymerization of HMDI and HMDA (one step) and name the type of polymer formed.
Draw & name the reagents & product of polymerization of 1,4-diisocyanotobenzene and 1,2-diaminoethane.
Show the mechanism by which ethylene oxide is polymerized.
Draw and name the polymer produced from -caprolactam

59. List the ingredients, advantages, and disadvantages of bulk polymerization and 3 polymers commonly produced
by this technique.
60. Repeat the previous question for Solution, Suspension and Emulsion polymerization.
61. Given that the planar zigzag conformation of extended chain PE has a contour length of 2.55 Angstroms, calculate
DP and the contour length of chain extended molecules of PE with an average MW of 750,000.
62. State briefly why solution crystallized polymer crystals are brittle.
63. Give the name of the following ...
a) ................................................................... crystals which form during quiescent crystallization from the melt.
b) ................................................................... the units which hold polymer crystals together.
c) ................................................................... an industrial method of stress induced crystallization.
d) ................................................................... the maximum draw ratio for polyesters and polyamides
e) ................................................................... the maximum draw ratio for HDPE
f) ................................................................... the name for localized reduction of cross sectional area of a thermoplastic
under tensile loading.
64. Sketch the main components of a melt spinning unit and label its parts.
65. State 2 important changes that occur during stress-induced crystallization to increase stiffness and strength.
66. Name 3 engineering resins and 3 specific applications for such resins.
67. Name 3 high performance resins and the physical properties that set them apart.
68. Briefly state the meaning of a failure test and list 6 examples.
69. Calculate the stress (in SI and British units) when 2.20 103 lb. force is applied to a polymer specimen that is
1/8 thick and wide.
70. Calculate (to 3 sig figs) the proportional and % strain of a specimen with an original length of 3.000 in. and a final length
of 3.002 in.
71. Given various stress strain curves, label the following points; rupture strength, tensile strength, ultimate strength,
elastic limit, yield strength, and proportional limit.
72. Calculate the modulus of compressive elasticity, stress, proportional strain, and toughness for the linear initial stress
strain data from a tensile test given the following data ... original specimen width = 0.5, thickness = and original
length of 2.000 in.; final length at 9.00 103 lb. load is 2.00165 in. Report in SI units to 3 sig figs.
73. Name the ultimate property that the notched Izod test measures.
74. Given a series of stress strain curves, classify the polymer as soft and weak, soft and tough, etc. and name one
polymer that demonstrates this.
75. Briefly explain how polymer hardness is measured.
76. Elongation under long-term loading is called ...................................................................
77. List 5 reinforcing additives.
78. List 1 toughness modifier.
79. Name 2 plasticizers.
80. Name one of each of the following stabilizers; thermal stabilizers, antioxidants, UV absorbers.
81. Name 2 colorant additives.
82. List 5 inert fillers and 3 reasons for adding them.
83. Name 2 polymers whose maximum use temperature is close to 300 C.
84. Give the maximum use temperature of Nylon-6,6 and PET (see Table V on p. 61).
Give the maximum use temperature of LDPE and HDPE

147

85. Draw the mechanism for the synthesis of a polyamide by reaction of: an amine + acid chloride, amine + acid
anhydride, amine + carboxylic acid, ring opening of a lactam
86. Write the formulas and names of the monomers and formulas of the polymers for the following polyamides...
nylon 2, 4, 5, 6, 12, 6-6, 6-12, Kevlar and Nomex
87. Using equations, show the polymerization of nylon 6-6 from 2 different sets of starting reagents.
88. List 4 different, specific applications of aliphatic nylons and 4 specific applications of Aramid fibers.
89. Write the complete mechanism of acid catalyzed Fischer esterification.
90. Write the mechanism of esterification from acid chloride or acid anhydride (Instructors choice on test).
91. By means of an equation, show the formation of PET by any of the four polymerization methods, i.e., direct
esterification, ester exchange, using an acid chloride, or using an acid anhydride (Instructors choice on test). Also
show the byproduct formed.
92. Write equations to show the polymerization reaction that forms...
a)
PC (also name the reagents) and show by products formed
b) glyptal resin (you need only show the first steps)
c) an oil modified alkyd for paints (you need only show the first steps)
d) an unsaturated alkyd for FRP (you need only show the first steps)
93. List 4 different, specific applications of PET
94. List 4 different, specific applications of PC
95. Write equations to show the polymerization reaction that forms poly(dimethylsiloxane) or
poly(diphenylsiloxane) (Instructors choice on test). Show the byproduct (condensation product) formed.
96. List 4 different, specific applications of silicones.
97. Write the names, symbols, and numbers of the 7 recycle groups for plastics as per the Society for Plastics Industry
(SPI).
98. List 4 different, specific applications of PTFE
99. Write the chemical formulas and names of CTFE, FEP, and PVF2 polymers.
100. Compare silicone elastomer, nylon 6 resin, PC resin, and PTFE resin and choose the 1 which best fits each of the
following descriptions....
a) highest s.g. (& give approx. value)
l)
highest crystallinity (& give approx. value)
b) highest Tm (& give approx. value)
m) lowest crystallinity
c) lowest Tg (& give approx. value)
n) highest optical clarity
d) lowest % HOH absorption (& give value)
o) lowest optical clarity
e) highest % HOH absorption (& give value)
p) highest H-bonding
f) highest lubricity
q) least H-bonding
g) highest chemical resistance
r) greatest flexibility
h) least chemical resistance
s) lowest Tensile strength resin
i)
highest UV resistance
t) highest impact resistance resin
j)
best electrical resistance
u) resin with greatest cold flow
k) greatest aromatic content
v) most expensive
w) most difficult to process

148

101. Write a formula or chemical name (your choice) that corresponds to each of the following trade names: Fortrel,
Dacron, Terylene, Mylar, Kevlar, Nomex, silk, Lexan, FRP, RTV caulking, silicone, Kel F, Viton.
102. Draw the mechanism of resole formation using sodium phenoxide and formaldehyde.
103. Draw the mechanism of novolac formation using phenol and formaldehyde.
State 4 important properties of phenolics and then 4 applications that result from these properties
104. Draw the mechanism of epoxy prepolymer formation from bisphenol-A and epichlorohydrin.
105. Name the type of hardener most commonly used for epoxies.
106. List 4 important properties of epoxies and state 4 applications, which result from these properties.
107. State briefly, the sequence of operations in injection molding, extrusion, and/or transfer molding.
108. Name one type of plastic and one example of a product made by each of these processes.
109. Given a diagram of an injection molding machine, label its parts.
110. Briefly explain what is meant by the following terms: blow molding, parison, compression molding, calendering,
sprue, runners, gate, parting line and flash
111. Name 2 polymers that float in water and 2 which sink in water.
112. Name 2 polymers that continue to burn when removed from a flame.
113. Name 2 polymers that are self extinguishing.
What element(s) does the Beilstein test identify in a polymer?

149