Documente Academic
Documente Profesional
Documente Cultură
CHM 605
CONTENTS
1. History & Basics
2. Nomenclature
3. Physical Properties
4. Molecular Weight
5. Mechanisms & Methods of
Polymerization
6.
7.
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
rear
platen
(movable)
front
platen
(fixed)
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
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
112
Extrusion
113
Calendering
114
Blow Molding
A parison
A:
B:
C:
D:
C
B
115
CHM 605
Part 9
Appendix
116
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
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
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
CH2
H+
OH
_HO
2
OH
CH2
CH2
CH2
CH2
CH2
4-hydroxybutanoic acid
-hydroxybutyric acid
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
-valerolactone
4-hydroxypentanoic acid lactone
120
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.
Aqueous NaOH will break down (hydrolyze) triglycerides into glycerol and 3 fatty acids...
or
triglycerides,
i.e.,
triesters
of
glycerol
and
(TAGs)
121
# 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
-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.,
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
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 *
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
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
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
pKa -1
NaOH
R
S OH
S O
Na
pKb 15
O
alkyl substituted
benzenesulfonic acid
syndet
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
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
H +
O
-
CH2
CH
+
H
CH2
H +
O
-
CH
O -
CH2
CH
CH2
CH
OH
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
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
CH
CH2
- O
CH2
OH
polyvinyl alcohol
CH
HO
HO
OH
CH
H +
O
-
CH2
CH
+
H
CH2
H +
O
-
CH
O -
CH2
CH
CH2
CH
OH
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
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.
130
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)
O
Cl
hexamethylenediamine
(HMDA)
O
CH2
H2N
CH2
Cl
NH2
HCl
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
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
135
..
N
..
O
..
..
O
..
R'
an alcohol
an isocyanate
..
N
:O :
C
..
O
..
R'
an isocyanate
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
138
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
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:
s. g.
densityof object
wt. of sple.(in air)
(wt. of sple. wirein air) - (wt. of wirein air)
BA
[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
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
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
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
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.
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