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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.
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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.

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Granules are pushed through a heated barrel and the plastic is heated until it becomes soft enough to flow. Gates connecting the product to the runner system are removed. forks. The hopper is loaded with granular plastic 2. The resin is forced forward by a ram or heated screw 3. Injection Molded Parts 112 . When cool.Injection Molding Injection molding is by far the most widely used process of forming plastics. 4. Plastic cups. The solid part is ejected from the mold. the halves of the mold are separated. electrical plate covers are just a few of the thousands of a thermoplastic products manufactured by injection molding. The softened material is squeezed through a nozzle into a mold cavity. 5. mold heated barrel nozzle scre w granules in hopper Injection Molding Machine Injection molded parts can be intricate or simple. It is primarily used for thermoplastics. knives. The basic process involves six steps: 1. 6.

When attached to an extruder. Rain coats are made by laminating PVC on nylon fabric Extrusion coating (‘laminating’) process. The substrate and molten plastic are squeezed between rollers. Long and continuous profiles. bonding the plastic film to the substrate. 113 . Extrusion coating (‘laminating’) is a process in which paper or other substrates are pressed together with an extruded film. In the diagram above. the extruded plastic is squeezed into a film as it is compressed between rollers.Extrusion An extrusion machine is essentially the same as an injection molding machine. This extrusion die is 72 inches wide. the molten plastic is formed as a thin sheet. tube and pipe are made by extrusion molding. called a ‘die’. Sheets of plastic are formed when molten plastic is extruded through a long narrow die. with the exception that the closed mold of an injection molding machine is replaced with an open mold. as shown. such as rod. The extruded film is then squeezed between water cooled rollers (drums) that smooth and solidify the plastic into sheets.

114 . linoleum floor coverings and shower curtains are examples of products made by calendaring. Calendering Extruder die for wire coating Another process used to produce film and sheets of thermoplastic is calendering.In the diagram on the right. Vinyl wall coverings. copper wire is pulled through a plastic extruder and becomes plastic coated in the process. Thermoplastic granules are melted in a long trough-like hopper and squeezed through a series of rollers.

Blow Molding This extruder is fitted with a die that forms hollow tubes (parisons). The parison is placed in a mold that has the shape of the bottle. The parison’s original shape is shown inside its final shape (a bottle) A parison A A: B: C: D: C B D A parison is placed in a mold. The mold is opened and the blow molded bottle is ejected. The mold pinches off one end and air is blown into the open end. The extruded tube of film to be blown is called a parison. The air forces the soft plastic tube to inflate until it fills the mold cavity. Bottles are made by blowing air into a thin tube of extruded plastic. 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. 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 #C’s 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 #C’s 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 .

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 . Lactams are formed from amino acids when the amino group and the carboxyl group react to eliminate HOH and form an amide.Lactams: Cyclic amides are called lactams. O O C CH2 CH2 _ OH O C H2O CH2 D 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’.

The common names of lactones.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. 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. are formed by changing the ‘-ic acid’ ending of the hydroxy acid to ‘-olactone’. O O C C CH2 H+ OH _HO 2 OH CH2 O CH2 O O 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. used more often than IUPAC names. O O O O O O CH3 CH3 (c) -butyrolactone -butyrolactone (I) 3-hydroxybutanoic acid lactone 4-hydroxybutanoic acid lactone -valerolactone 4-hydroxypentanoic acid lactone 120 .

Despite their differences in physical state.. If double bonds are present.  or triglycerides. C36H74 Animal Fats and Vegetable Oils: Animal fats are solids. It is not an ester but rather a long chain HC.. olive oil.. e.  Aqueous NaOH will break down (‘hydrolyze’) triglycerides into glycerol and 3 fatty acids. Bees produce beeswax to form a honeycomb. but rather a mixture of high molecular weight alkanes.Waxes.g.e. e. 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.e.. triacontanol and the C16 acid. triesters of glycerol and Note: This hydrolysis is essentially the reverse of CH2-OH HO-C-R CH2-O-C-R Fischer Esterification. Loss of the alkoxide yields the fat or oil glycerol fatty acids carboxylate. corn oil and peanut oil. an even The fatty acids obtained by hydrolysis of triglycerides are most commonly unbranched andthe contain number of C atoms from 12  20. is not a true wax.e. Paraffin wax.. Acidification yields acid. O  (TAG’s) O Draw the mechanism of base hydrolysis of a TAG.g. OH adds to HO-C-R' CH-O-C-R' 2.  Both fats and oils are triacylglycerols 3 long-chain carboxylic acids. i. Carnauba wax is a mixture of very high molecular weight waxes.g.. OH + CH-OH substitution. 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. i. they are usually of Z (cis) geometry. 121 . fats and oils are chemically similar. sunflower oil. i. Beeswax is mostly triacontyl hexadecanoate. hexadecanoic acid.g.  The carboxylic acid usually has an even number of C’s (16  36)  The alcohol also has an even number of C’s ( 24  36) e..g. Base O O hydrolysis is nucleophilic acyl 1. used to make candle and seal preserves.g. e.. Fats and Oils: Waxes: are esters of long-chain carboxylic acids and long-chain alcohols. the ester of the C30 alcohol. 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 TAG’s. butter and lard whereas vegetable oils are liquids. H3 O+ an ester’s carbonyl group O O producing a tetrahedral CH2-OH HO-C-R" CH2-O-C-R" intermediate.

..e. It is now generally accepted that polyunsaturated vegetable oils are more easily digested and healthier than saturated fats and oils. peanut. i. Oleic and linoleic acid are the most abundant unsaturated fatty acids. have 2 or more double bonds and thus are referred to as polyunsaturated fatty acids (PUFA’s). 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. Unsaturated fats cannot pack as tightly because cis double bonds introduce kinks and bends in the HC chain disrupting packing and crystallization. Infants grow poorly and develop skin lesions if fed on a diet of nonfat milk. the lower the mp. a liquid unsaturated fatty acid is converted to a saturated solid or semisolid fat. or cottonseed oil until the desired consistency is obtained.g.. 122 . which are 9 cis and 11 & 13 trans. This is also true for TAG’s... Oleic is monounsaturated (1 double bond). Margarine and cooking fats such as Crisco vegetable shortening are produced by hydrogenating soybean.Structures and Names of Common Fatty Acids saturated # C’s 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 # C’s 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 5 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. that of lard (animal fat).  Saturated fats have a uniform (long zigzag) shape that allows them to pack tightly. Palmitic and stearic are the most abundant saturated fatty acids.  Approximately 40 different fatty acids occur naturally.  Linoleic and linolenic acids occur in cream and are essential to the human diet.  The tabulated data shows that unsaturated fatty acids generally have lower melting points than saturated fatty acids with the same # of C’s. linoleic acid (mp = -5C) + H2/Pt  stearic acid (mp = +75C) The elimination of double bonds allows for tighter packing and higher mp. etc. e. The more unsaturation. Margarine may be flavored with butyraldehyde to give it a taste like that of butter. i. linolenic. linoleic.e.

washed.  Soap is a mixture of Na+ or K+ salts of long chain fatty acids produced by hydrolysis (‘saponification’) of animal fat with an alkali..  Na+ carboxylate soaps are solid but K+ carboxylate soaps are liquid (e. 123 .(P)UFA’s Approx. antiseptics are added for medicated soaps.g. glycerol. OH CH-OH CH-O-C-R' + 2. O CH2-OH CH2-O-C-R Na + Na + O O-C-R' Na + O O-C-R" - O 1. H2 O O CH2-O-C-R" CH2-OH fat or oil glycerol O O-C-R soap R = C11 . Soap: Soap has been used for cleansing since the middle ages (1500 . dried. % Composition of Some Fats and Oils C12 C14 C16 C18 C18 C18 C18 Fats lauric myristic palmitic stearic oleic linoleic linolenic lard - 1 25 15 50 6 - butter 2 10 25 10 25 5 - human fat 1 3 25 8 46 10 - whale - 8 12 3 35 10 - beef fat - 6 27 14 49 2 - Oils lauric myristic palmitic stearic oleic linoleic linolenic coconut 50 18 8 2 6 1 - corn - 1 10 4 35 45 - olive - 1 5 5 80 7 - peanut - - 7 5 60 20 - linseed - - 5 3 20 20 - soybean - - 10 2 29 51 7 herring - 5 14 3 - 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. hand soaps).1700 AD). Our grandparents made soap by mixing animal fat with wood ashes (which contains KOH). The precipitated soap is filtered. Dyes are added to make colored soaps. It is purified by boiling with water and adding NaCl to precipitate the pure Na carboxylate salts. perfumed and pressed into bars.C19 aliphatic chains  The product of the foregoing reaction is a mixture of crude soap curds. excess alkali and water. pumice is added for scouring soaps and air is blown in for soaps that float.

These nonionic molecules are hydrophobic and float to the top as a greasy ‘acid scum’ precipitate. soap molecules are protonated to fatty acids. 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.g. which contains metal ions (Ca++..  When soap is dissolved in 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. e. The Na+ carboxylate end is ionic and thus hydrophilic (water loving) . Thus soap is soluble in both grease and water and is useful as a cleanser. soap is precipitated. Ca+2(-OOCR)2 and appears as scum (‘hard water scum’) around bathtubs and a gray tinge on white clothes. i.it dissolves in grease.  In hard water. Mg++.it dissolves in water. Fe+++). O ionic head hydrophililc head lipophobic head micelle A cluster of surfactant molecules dissolve in grease O O C O C O O O C O C O O C O O C O O C O O C O C O O O O C O C O O C O O C O C O O 124 . O C non polar HC tail hydrophobic tail lipophilic tail Soaps are “surfactants”.Soap as a Cleanser: The 2 ends of a soap molecule are different.. They reduce the surface tension of water. The long HC portion of the molecule is nonpolar and hydrophobic (water fearing) .  In acidic water (such as acid rain). surface active agents.e.

They are chemically similar to soaps.g.e. and Fe+3 salts of sulfonic acids are soluble in water. e. O H3C (CH2)11 O S O Na+ O 125 .Synthetic Detergents (‘syndets’): Synthetic detergents were developed as clothes detergents.. nonoxynol . In addition.. they have both hydrophilic and hydrophobic ends. Ca+2. R4-N+ Cl- Shampoos The active ingredient (cleanser) in many shampoos is an alkyl sulfate.. Mg+2.. O pKa  -1 R O NaOH R S OH S O - Na + pKb  15 O O alkyl substituted benzenesulfonic acid syndet R = mixture of C12 aliphatic chains  Sulfonic acids are more acidic than carboxylic acids.. but they do not form scums. CH3  (CH2 )8 (OCH2 CH2 )9 OH Some syndets are produced with cationic hydrophilic groups due to the presence of quaternary amine groups.g. i. sulfonate salts can be used in hard water without forming a scum. so their salts are not protonated in acidic water. sodium lauryl sulfate. Na salts of sulfonic acids are the most widely used class of syndets.  Some syndets are produced with nonionic hydrophilic groups containing several O-atoms or other H-bonding atoms.. e.

CHM 605 Part 10 POLYMER LABORATORY EXPERIMENTS 126 .

Na2B4O710 H2O. PVAL. Stressing the gel (pulling. In aqueous solution. squashing.Na B O B B O O B Na+ O O B O O B O O B Na+ O O B O O + . sodium tetraborate. distorting.Na B O O + . OH CH2 CH CH2 .Na B O O O O O Na+ B O O Na+ B + O O Na+ O . forms B(OH)4.O CH2 + OH polyvinyl alcohol CH + n O HO HO OH CH aqueous B(OH)4. etc. with an aqueous solution of sodium tetraborate (“Twenty Mule Team” borax laundry detergent).) breaks the crosslinks however the physical links quickly reform.Na B O + . which establish tetrafunctional interactions (hydrogen bonds) with PVAL forming a loosely crosslinked gel.EXP 1: PREPARATION OF POLYMER SLIME THEORY: The Polymer Slime is made by crosslinking linear poly(vinyl alcohol). O - O B B O - O B B O B O B O O O B O Na+ O O B Na+ O B O O O .ions H H + H O H O - B O H - + - + CH2 B CH O - O + H CH2 H +  O - CH O - H + H 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. 127 .Na B B + O O O Note the Na2B4O7 repeating units in crystalline sodium tetraborate.ions.

small plastic cup with lid 5. Identify the end use of the polymer as one of the following: rubber. adhesive. liquid food coloring or Tempra paint 4. The gel is not toxic but it should not be eaten as it will cause gastrointestinal distress.MATERIALS: 1. Examine the physical properties of the gel. plastic. 5. aqueous solution (70 gpL) of PVAL linear polymer 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. concentrated. The mixture will start to thicken within 30 seconds. 3. 1. 4. and (ionomer or neutral polymer) 2. sag?. 7. 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. Measure 20 mL of the PVAL solution into the 25 mL graduated cylinder and transfer this to the small plastic cup. 25 mL graduated cylinder 7. Does it stretch?. 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. drip?. it should be discarded if it begins to grow mould. QUESTIONS: 1. disposable stirring stick 6. cellular or biopolymer. Roll the gel between your hands to complete the mixing and the crosslinking. Identify the polymer type as (thermoplastic or thermoset). 128 . film. 10 mL graduated cylinder PROCEDURE: Work over a folded piece of paper towel. (homopolymer or copolymer). If any liquid remains it can be absorbed by blotting with the paper towel. The gel can be kept for months. saturated solution of sodium tetraborate 3. Continue mixing for this period or until it becomes too thick to mix any more. composite. bounce? 6. however. fiber. Remove the gel/slime from the cup. coating. elastoplastic. Wash your hands if gloves were not worn. elastomer. 2.

Na B O O O O O Na+ B O O Na+ B + O O Na+ O .Na B B + O O O Note the Na2B4O7 repeating units in crystalline sodium tetraborate.Na B O + . forms B(OH)4. which establish tetrafunctional interactions (hydrogen bonds) with PVAL forming a crosslinked mass. sodium tetraborate.Na B O O + . PVAL. Na2B4O710 H2O. the polymer ball is much firmer than polymer slime.ions. 129 .O CH2 + OH polyvinyl alcohol CH + n O HO HO OH CH aqueous B(OH)4.EXP 2: PREPARATION OF A “Mad Science” POLYMERIC BALL THEORY: The Polymeric Ball is made by crosslinking linear poly(vinyl alcohol).Na B O B B O O B Na+ O O B O O B O O B Na+ O O B O O + . OH CH2 CH CH2 . so the crosslink density is much higher. with sodium tetraborate (“Twenty Mule Team” borax laundry detergent). The two substances are supplied as a dry premix.ions H H + H O H O - B O H - + - + CH2 B CH O - O + H CH2 H +  O - CH O - H + H 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. The concentration of tetraborate is much greater in the polymer ball than in the polymer slime. As a result. In aqueous solution. O - O B B O - O B B O B O B O O O B O Na+ O O B Na+ O B O O O .

Sodium tetraborate is a mildly alkaline detergent. 14. the ball is ready to be tested. Roll the ball between the palms of your hands to force contact between more polymer chains and to create more crosslinks. Add the dry polymer mixture to fill the mold. elastoplastic. 10. 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. Fill the beaker with tap water to the ½ or ¾ mark 9. to keep it moist while the crosslinking reaction continues. After 30 minutes. fiber. occasionally pausing to tap the mold gently to fill any voids. adhesive. After the prescribed time. 130 . 1 minute and reshaped by rolling between the hands. plastic. Identify the end use of the polymer as one of the following: rubber. film. Rinse and return molds to the instructor. * Procedure complements of Mad Science of Windsor. cellular or biopolymer. Do not allow the mold to separate during this time. 30 min. It will dry out if left in the air but can be rehydrated by again immersing it in water for ca. 11. 12. (homopolymer or copolymer). Water will seep in through the holes in the mold and initiate the cross linking reaction. remove the mold from the water. 13. composite. and (ionomer or neutral polymer) 4. QUESTIONS: 3. mold* 10. dry PVAL polymer/sodium tetraborate mixture* 9. Gloves are optional. Place the ball in a plastic bag for ca. plastic bag * Mold and polymer mixture available from Mad Science of Windsor *PROCEDURE: 8. Each package contains sufficient reagent for one mold. PVAL is not corrosive. The ball should be stored in a plastic bag. 250 mL beaker 11. Carefully open the mold and remove the polymer ball. coating. 15. Hold the filled mold submerged in the water in the beaker for 1½ minutes. A small void space at the top will fill when the polymers swells while immersed in water.MATERIALS: 8. Identify the polymer type as (thermoplastic or thermoset). elastomer. Avoid eye contact. Wash your hands if gloves were not worn.

adipoyl chloride (hexanedioyl chloride) Nylon rope pulled from the interface. Alternately. Nylon 6.6) 131 . HMDA + NaOH in water O Cl C hexamethylenediamine (HMDA) O CH2 4 C H2N + CH2 Cl - 6 NH2 HCl Nylon 6. N : O: R' R C H acid chloride . : Cl . The reaction can be carried out in a single phase (bulk polymerization) or as in this experiment. 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.. so two moles of amine reagent must be used per mole of acid chloride.EXP 3: NYLON ROPE BY INTERFACIAL CONDENSATION THEORY: Amides are produced when an acid chloride reacts with an amine. : O: R C H . The student should be able to draw the mechanism for this reaction. while the acid chloride remains dissolved in an organic phase. + .6 [Dupont’s trade name for poly(hexamethylene adipamide)] is produced when hexamethylenediamine (HMDA) reacts with adipoyl chloride.6 at interface O O Adipoyl chloride in CH2Cl2 Cl C CH2 4 C HN CH2 6 NH2 poly(hexamethylene adipamide) (Nylon 6... at the interface between two separate phases. N + R' HCl H amine amide The byproduct HCl acid will consume half of the basic amine reagent. NaOH can be added to an aqueous amine phase to consume the byproduct HCl. 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.

PROCEDURE: 16. Identify the polymer type as either thermoplastic or thermoset. solution.6 formed by interfacial condensation. Identify the polymerization technique as one of the following: bulk. 4. adhesive (sealant). Identify the polymerization type as one of the following: chain growth. 17. fiber. Prepare reagent a) and b) in separate flasks: a) Prepare 5% adipoyl chloride in CH2Cl2. A thin white layer will appear at the interface when the two solutions are brought into contact. 18. Pour the denser organic solution into a small beaker first. Show the mechanism of amide formation during reaction of an acid chloride and an amine. Do not allow the solutions to mix when combining them. 19. step growth (condensation or rearrangement) or ring scission. This is Nylon 6. 132 . Use in a fume hood] b) Prepare an aqueous solution that is 5% HMDA and 2%w NaOH. cellular or biopolymer. You should obtain two separate layers. film. QUESTIONS: 1. 5. suspension or emulsion. [Caution: Adipoyl chloride is corrosive. Slowly and carefully pour an equal volume of the aqueous solution on top of the organic layer. composite. Use a wire or tweezers to slowly pull the white solid layer up out of the solution and a long fiber is drawn. 2. 3. Identify the end use of the polymer as one of the following: rubber (elastomer). plastic (resin). Rinse the fibers under running water and study their feel and strength. 20. coating.

a sensitizer.. mix and reheat. N C C ... NH C n Nylon 6 poly(caprolactam) initiated monomer PROCEDURE: Do the heating in a fume hood. the second caprolactam molecule undergoes ring scission. . 21. which propagates the chain. :O: + Na H: :O: C . corrosive. Angle the test tube toward the back of the fume hood. i. therefore. is used extensively in automobile tire cords and for gears and bearings in small mechanical devices. 24. Wear safety glasses and avoid contact with the reagents. The anionic N subsequently bonds to the weakly electrophilic carbonyl-C on another monomer molecule. The catalyst used in this reaction is sodium hydride. Clamp a test tube above a Bunsen burner in a fume hood. and is explosive in water.EXP 4: Ring Opening Polymerization And the Formation of Nylon 6 THEORY: The ring-opening polymerization of caprolactam is a commercial process.. N: :O: .NH propagation . In the test tube place 4 g of caprolactam and 0. 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.. Its carbonyl-C to N bond breaks heterolytically producing an NH anion. Ordinarily anionic polymerizations must be run in the absence of oxygen. this is referred to as an anionic polymerization. In order to accommodate the electron pair donated by the N anion. Sodium hydride is strongly basic. N H :O: C O .e.. When the solution is so viscous that it will barely flow. 25. 22. an irritant and a neurologic hazard.25 g polyethylene glycol Heat the mixture with a small.. as indicated by an increase in viscosity. N H - C :O: C . If polymerization has not occurred within 5 minutes remove the tube from the heat. The sodium hydride initiates the reaction by removing the weakly acidic lactam proton from caprolactam to form a N anion (a good nucleophile). cool it somewhat. Nylon 6. Polymerization takes place rapidly.. 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 230°C) over a 2 minute period. add another 50 mg of sodium hydride. 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. 23. insert a wood stick or Pasteur pipet and draw fibers from the melt 133 . Caprolactam is toxic. The nylon produced. N H O (CH2)5 etc.

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

a coin. The most important property of PMMA is its optical clarity. Draw the structure of the peroxide initiator from its name. It is not an Acrylic. film. you may stir in a small curiosa (e. Although it contains repeating ester linkages. 31. This plastic exhibits up to 92% light transmittance. Identify the polymerization type as one of the following: chain growth. composite. inhalation and skin contact. sparkles. cellular or biopolymer.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. which is used to make acrylic fabrics. Show the mechanism of initiation and propagation of the PMMA chain. Heat the mixture in a water bath or heating block at ca. Identify the end use of the polymer as one of the following: rubber (elastomer).g. 29. Acrylics refer to a different polymer. etc. 2. add 2 drops of tert-butyl peroxybenzoate and thoroughly mix the liquids. step growth (condensation or rearrangement) or ring scission. Place 2 ml of methyl methacrylate into a test tube. automobile taillights. QUESTIONS: 26. PROCEDURE: 1.. and good overall weather resistance which together result in a high retention of clarity and light transmittance even after very long periods of time. and plastic lenses for eyewear including hard contact lenses. the highest of any plastic material. compact discs (CD’s). insects. Identify the polymerization technique as one of the following: bulk. poly(acrylonitrile) abbreviated PAN. Identify the polymer type as either thermoplastic or thermoset. It also has very low sensitivity to UV light. If desired. coating. 28. PMMA is not strictly classed as a polyester.. 1½). 135 . Caution: t-butyl peroxybenzoate is a strong oxidizer and is harmful by ingestion. 27. You may simply write the initiator as I . i. 30. 3. Leave a thermometer in one cell of the heating block to check the temperature. These excellent properties have led to applications such as windshields (for planes and helicopters). plastic (resin). 80 C for 1 hour. PMMA resin is sold under the Trade names Plexiglass and Lucite. adhesive (sealant). Do not heat above 85°C.e. suspension or emulsion. methyl 2methylpropenoate). fiber.) which will be encapsulated in the resin after curing. very low oxidation sensitivity. (Heating block on high heat with a setting of ca. display cases. solution.

+ H . R' R H an alcohol an isocyanate . OH . The student should be able to draw the mechanism. O . H decomposes R . N :O : C .. It is made by reacting an isocyanate with an alcohol.3-propanetriol (glycerol) to form a polyurethane...3-propanetriol (a trifunctional monomer) C N N C H O O CH CH2 CH2 OH OH n a polyurethane Isocyanates react with water to form an amine and carbon dioxide gas. toluenediisocyanate (TDI) reacts with 1. O . R H .2. The evolution of CO2 gas forms bubbles in the polymer creating the ‘foam’. O . N C ... O . R ..... CH3 CH3 O C N N C O + 2. Foams are described as open cell (the openings are interconnected) or closed cell (gas bubbles are isolated).. R .. N : O: C . a small amount of water is added during the polymerization. N H + CO2 H a carbamic acid (unstable) For this reason. + H .. N C .. Rigid PU foam is used as a building insulation (as well as polystyrene foam‘Styrofoam’). R' an isocyanate In this experiment.4-toluenediisocyanate ( a difunctional monomer) CH2 CH CH2 OH OH OH O 1. O .. CLOSED-CELL POLYURETHANE FOAM THEORY: The familiar flexible foam material used in sofa cushions and automobile seats is a polyurethane (PU) foam.EXP 6: PREPARATION OF A RIGID... 136 .2. A urethane (also called a ‘carbamate’) is a functional group that looks like an amide on one side and an ester on the other..

36. cellular or biopolymer. fiber. 8. 35. Into the cup add the following ingredients: a) 5. The product may take up to 24 hours to harden but the foam is produced within 5 to 10 minutes. Identify the end use of the polymer as one of the following: rubber (elastomer). solution. Support a paper cup in a suitably sized beaker. add 4 mL of TDI [Caution: very toxic. film. 30 to 60 seconds until a creamy emulsion is obtained and bubbles begin to evolve. do not breathe the vapors] 7. QUESTIONS: 32. coating. 137 . composite. step growth (condensation or rearrangement) or ring scission. Mix the liquids with a glass stirring rod until smooth 6. Show the mechanism of urethane formation from an isocyanate and an alcohol 33. Identify the polymerization technique as one of the following: bulk. and Dow Corning 200 silicone oil 5. Identify the polymer type as either thermoplastic or thermoset.5 mL castor oil b) 1 mL glycerol c) 2 drops each of water. Allow the mixture to stand while polymerization continues. suspension or emulsion. Stir thoroughly for ca.PROCEDURE: 4. triethylamine. Identify the polymerization type as one of the following: chain growth. In a fume hood. adhesive (sealant). plastic (resin). 34.

g. flexible thermoplastic c.Low Density Polyethylene 5.EXP 7: IDENTIFICATION OF A POLYMER Techniques used to identify a polymer include the following: 1. Flame Test/Melting Test 6.  Foam upholstery cushions are usually polyurethanes. LDPE . 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. Rubbers are flexible and sometimes stretchy.  Bulletproof glass. Other End Use: In the case of a finished article.4-polyisoprene).High Density Polyethylene 3. shower curtains and raincoats are usually PVC.  Floating rope is usually polypropylene. Automobile tires are usually a blend of styrene butadiene rubber (SBR) and natural rubber. For example:  Elastic bands and tires are rubbers (elastomers). The code is as follows: 1. If a polymer is light in color. which is usually stamped on the bottom of the product. PP . sunglasses and reading glasses with plastic lenses are polycarbonate.  Garden hoses. PS .. phenolics). The following are examples of transparent polymers: PET (pop bottles). Dishes are likely to be melamineformaldehyde thermosets. IR analysis (KBr disc) 5. PC (bulletproof glass). it is not a phenolformaldehyde thermoset.Polyethylene Terephthalate 2. pure amorphous polymers have high optical clarity (transparent) whereas crystalline polymers are translucent to opaque. Preliminary examination 2.Polystyrene 7. PETE . rigid thermoplastic d. Specific gravity determination Preliminary Examination: Based on a preliminary examination. Thermosets feel hard and sound brittle when dropped or struck with a metallic object.  Pot handles and cutlery handles are usually thermosets (e. V . Phenolformaldehyde thermosets (Bakelite) are inherently dark colored. the intended use can very often indicate the nature of the polymer.Polypropylene 6. rubber b. a polymer can sometimes be classified as belonging to one of the following groups: a. PVAc (blister packaging). PMMA (Plexiglas). In the absence of additives. The number is often enclosed in the triangular arrows recycling symbol. Elemental analysis (Lassaigne's Test) 3. Elastic bands are usually natural rubber (cis-1. 138 .Vinyl / Polyvinyl Chloride (PVC) 4. Color: Most polymers are available in a wide color range resulting from the addition of various pigments. Feel: Teflon and polyethylene feel waxy. Solubility test 4.  Tents and screens are usually nylon. HDPE .

alkene stretches (cis-1. 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.e.g. Plastic ABS LDPE. polyamides). A detailed procedure is attached. the method narrows down the number of possible choices. N-H stretches (polyamides). PVC or poly(vinylidene chloride) . Specific Gravity: The relative density of a polymer is very helpful in determining its identity. even so.. 139 . some flame-retardants contain Cl or Br. Polyethylenes. the rate of cooling levels out as the latent heat of fusion is released. whereas polar solvents tend to dissolve polymers containing polar functional groups.Elemental Analysis (Lassaigne's Test): The presence of N (e. The following table illustrates polymer solubility behavior. Plastics may require long exposure to a solvent to dissolve.Saran wrap] and S (vulcanized rubber and polysulfide caulkings) can be identified by inorganic qualitative analysis after sodium fusion. i. Additives may interfere. 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.g. 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). < 1. Solubility: Thermoplastics are soluble in appropriate solvents whereas thermosets may swell but are insoluble.. aromatic bends (polystyrene). color of flame and soot. Heating can solubilize thermoplastics such as PE and PP.. halogens [e. O-H stretches [poly(vinyl alcohol)]. polypropylenes and polyallomers (block copolymers of ethylene and propylene) float in water (s. The melting point range can be compared to tables available from the literature. The general rule of like-dissolves-like applies. rate of burning. and C-H stretches (polyethylene). A thermometer or thermocouple lead immersed in the melt can be used to measure the temperature at which solidification occurs. Although the addition of fillers can change the relative density of polymers.0) whereas virtually all other (noncellular) polymers sink. e. Flame tests identify the ease of ignition. hydrocarbon solvents tend to dissolve non-polar polymers. CN stretches (polyacrylonitrile).g.. During freezing. Agitation significantly reduces dissolving time.4-polyisoprene). A detailed procedure is attached.g. as well as odors of combustion products.

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.in air) . is determined vs. A copper wire heated in a flame with melting polymer burns bright green if a halogen is present. Thermosets are decomposed at high temperature. polymer s.g. For plastics that are less dense than water (olefins)..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. H2O @ 23ºC.0).g. Thermoplastics melt (Touch the hot polymer to the asbestos pad and see if the polymer is liquid). g.g.  B  A D  C s.g.g. Most other polymers sink in water (s.g. of sple. > 1. polymer recycling. Specific gravity can be accurately measured by weighing a polymer sample in air and in a fluid. Work in or near a fume hood and try to direct as many of the fumes as possible into to the fume hood.. < 1. 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. Enclosed gas cells within the plastic will cause even dense polymers to float. of wirein air) BA    densityof water wt. immerse only as much of the wire as was immersed when weighing the sample. of sple. Plastic) and which are thermoset (T. of wire in air C = wt of wire in water D = wt.e. Drop a small piece in a beaker of water. identify which polymers are thermoplastic (T.. Odors of melted polymers (e. densityof object wt. Discuss the characteristics with your partners and fill in as much of the table as possible. e.g. Specific gravity tests do not apply to plastics that are produced as expanded foams. Be sure that the sample is wetted i. of H 2O (displacedby sple. in test tubes) are more characteristic than the odors of burning polymers. but do not melt.  B = wt.. It is not uncommon for people working in polymer businesses.. of sample + wire in air A = wt. Perform the Beilstein test on PVC and any other samples you wish. Set). i. Specific Gravity:   Polyolefins. Based on the flame tests. They char and smoke but do not melt. polyethylene. g.e. It is not advisable to inhale these odors since most are unhealthy.) (wt.(wt. e. to ignite a small piece of plastic with a cigarette lighter and identify the polymer based on flame test and odor. overcome surface tension by pushing the plastic under the surface. Test the specific gravity on any samples for which you can readily obtain a small piece.0). The s. Observe and record the characteristics identified in the table of results below. of sample + wire in water For C. water. wirein air) . can be calculated as follows… BA s. of sple. Halogenated polymers can be identified in this way. polypropylene and polyallomers (block copolymers of ethylene and propylene) float in water (s. Hold the sample over an asbestos pad to catch any drips. Many polymers have characteristic odors when burned or melted. Compare your results with the handouts "ID your plastics by flame tests". 140 . For simplicity.(in air) (wt.(wt.

D.10 1.18 1.24 1.g.18 1.15 1.24 1.89 1.16-1. H. 141 .18 1.96 1.04 2.06 0.14-2.25 1.17 1.42 1.94 0.89 0.01-1.06 1. (Range) 0. The method of processing may affect the extent of crystallization.04 1.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.34-1. Slow cooling or cooling under stress (e.25 1.25-1.14-2.11 1.17 1.30 1.89 1.15 0. ionomer polyethylene. L.89 0.95 1.11-1.70 0. D.50 2.94-0.13-1.25 1.25-1. 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.18 1. poly(phenylene oxide) polypropylene polystyrene polysulfone polyurethane poly(vinyl chloride) silicone steel tetrafluoroethylene S.20 1.70 2.06 1.01-1.G.50 7. compare highly-branched LDPE with sparsely-branched HDPE.11 2. D. (Range) 1. Rapid cooling produces an amorphous (less dense) polymer.30 1.91-0.18 1. of a given polymer.92 0.91-0.14 2. H.50 0.20 1. The addition of a filler is another cause for variation of s.16 2.G. L.g..25 1.50 1.94 1.20 0.75 2. 1.30 1. polyethylene.48 1.27 1.20 The specific gravity of a given polymer may vary due to the method of polymerization and the method by which the polymer is processed.78 1.48 1. D.20 POLYMERS (SG prioritized) oak polyallomer polypropylene polyethylene.G.86 0.91 0.13-1.16-1.91 0.96 1.75 7.94-0.18 1.70 S.42 1.16 S. The method of polymerization may affect the extent of chain branching.25 1.30 1.06 1.92 0.86 1.35 2.14 2.50 1. resulting in a more dense polymer.10 1.34-1.10 1.25 1.20 1. melt spinning or gel spinning) often induces crystallization. 0.20 1.70 1.50 1.10 0.04-1.95 1. For example.27 1.35 1.11-1.78 2.04-1.20 1.

. TP = Thermoplastic. TS = Thermoset 142 . P = Propagating.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.

the calculated s. Baird. samples. clarity. shake the piece under water to release any air bubbles adhering to the surface of the plastic. Ensure that the surface of the plastic is completely wetted.G. R. See the Flame Test instructions for details on performing the test. do not use a piece of plastic that has been burned. Calculations are not required. 1986. BIBLIOGRAPHY 1.) of 3 different polymer samples supplied by the instructor. 143 . color. There is a set of small beakers containing small polymer chips for these two tests. Perform a flame test and a float/sink test on all the types of polymers for which samples have been provided. ‘U-2’. Goodheart-Willcox Company: USA.EXP 7: POLYMER IDENTIFICATION LAB Procedure: 1. feel. Accurately determine the specific gravity (s. Do not burn any of the S. Adhering air bubbles may cause a dense plastic to float. Using tweezers. stiffness. Compare the results with the s. Do not burn any other plastics without the instructor’s permission and be sure to work in a fume hood over an asbestos pad or gypsum board to catch all drips. etc. ‘-B’.g.g. For the float/sink test. Record observations for all the characteristics listed on the Polymer Identification Flame Test (Float/Sink Test) chart. etc. ‘-C’. Also consider other physical properties such as sink/float. Baird. Industrial Plastics. D.).. ‘U-1’. Report the Sample Identification number (‘-A’.g. values listed on the table of Specific Gravities handout supplied by your instructor. and the polymer identity you have determined. Use a fresh piece of plastic. Each student must submit his/her own copy of the results next week.

CHM 605 Part 11 POLYMER TEST QUESTIONS 144 .

.. is a polymer used by the Mayan Indians of S. 17.. was the polymer first used as an ivory replacement c) .... 9....and trans-1.. a) .. 3....... America b) . the function of a plasticizer with respect to its physical properties.... is known as the ‘Father of polymer chemistry’. show & name 4 different arrangements of comonomers in copolymers List the 3 most important feedstock monomers for making polymers... State. 12........ 21.. 14..... 3... i...POLYMER REVIEW 1. define or explain in as few words as possible .. Explain briefly ..... and PE Answer with  or ... branched and crosslinked polymer chains.. c) cause the melting point to .. state whether it is amorphous or crystalline.... Give one example each for monomers with functionality of 2.. 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..... a) amorphous polymer c) glassy state b) crystalline polymer d) tacticity Sketch polymer chains in their planar zigzag conformation showing .4-polybutadiene to show their stereochemistry... isotactic/atactic PP.... Explain in as few words as possible . 18....... Explain briefly......... d) causes the tensile strength to ..e. List 2 polymers with low Tg and 2 with high Tg State if these polymers have high or low Tg and why: PS......... Write the 7 SPI recycle symbols and the corresponding chemical names and abbreviations.. b) causes the density to . a) isotactic polypropylene b) syndiotactic polystyrene c) atactic poly(vinyl chloride) For each polymer in question 11.. 6........ PVC.... 13...... Name 3 thermoplastics and 3 thermosets..... 11... 2.... 4... 7................... 10..... 15.... Give names or draw structures of polymers using IUPAC and common nomenclature for all examples covered in class... and 4 State 4 characteristics each for thermoplastics and thermosets.. 145 ...... pot handles d) ............ Increasing the number of branches in a polymer a) causes the crystallinity to .... 5... Polymer history: Complete the following . a) Staudinger’s 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.. 16.... Sketch the appearance of linear........ 19.......... 20.. Sketch cis...... was the first thermal resistant polymer. List 9 groups of polymers classified according to end use and 1 chemical name of a polymer for each. 8.

g. 45. PP. By means of equations show the complete cycle of free radical polymerization of a vinyl polymer (e. AlCl3. Give the formula and name of 1 chain transfer agent. List the approximate conditions (temp.4 or 1. 23. molecular weight of 200. 34. 54. Show the mechanism by which functional end groups can be created by termination with carbon dioxide and with ethylene oxide.22.000 26. CCl4). 37. Show the mechanism of initiation of anionic polymerization of vinyl chloride with methyl lithium (or with Li metal. and state the names of 2 common free radical initiators for free radical polymerization. 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. Arrange these 3 molecular weights in decreasing magnitude as determined on the same sample of polymer. ‘propagation at the tip’? Which process causes each of these kinds of propagation? 52. 24. Give the name and structure of 2 free radical inhibitors. redox initiators) 38. State the effect avg. List examples of 4 different types of polymers that are polymerized by the step-growth method. 4. List 3 dienes which can be free-radical polymerized and draw their structures. Give the approximate density and melting point of LDPE and HDPE.2) 43. Show the mechanism by which water can deactivate a cationic (or anionic) end group. PTFE. 42. SnCl4. What are the cause. 47. molecular weight on. List 2 initiator accelerators (i. and chain transfer agent. or viscosity-average molecular weight. Then show one propagation step. Why are they needed? 39.. 49. polymer. What effect does a high polydispersity index have on a polymer’s physical properties? 31. 53. Name the 3 main types of polymerization and name 1 example of a polymer for each. What is the catalyst commonly used in the Ziegler-Natta process? 51. a) adding chain transfer agent b) adding a very small quantity of initiator 36. 29. Give the formulas or structures of. 25. BF3. or Li + naphthalene).g.. Write equations to show cationic polymerization of isobutylene including its initiation with H2SO4 or with a Lewis acid catalyst (e. Name 2 subdivisions of step-growth polymerizations and briefly state their difference. Draw structures of 3 monomers which can be polymerized a) cationically. Draw resonance structures to show how styrene can stabilize either a benzylic cation. List 6 methods of determining average molecular weight of a polymer and state whether the method determines number-average. chain transfer with solvent (e.g. pressure) of the high pressure PE process and the Ziegler-Natta Coordination Process. Show the mechanism of step-growth polymerization of poly(ethylene terephthalate) (or Nylon 6). PVC. Calculate the average MW of a polymer using data re: any of the colligative properties as discussed in class 28.. 48. Show the mechanism of their dissociation and give the formula/structure of their products. effect and mode of prevention of the Tromsdorff-Norish Effect? 41. weight-average. b) anioinically 44. What is meant by ‘propagation from the root’ vs.. Using a simple graph (with labeled axes) explain the difference between a polydispersity index of 1. ZnCl2). Show the mechanism of initiation and propagation of free radical polymerization of a diene (1. 146 . Use resonance structures to show and explain why one of these inhibitors is effective. 46. PE. 27. Include termination by combination and disproportionation. 30. PS) (Instructor’s choice on a test)... anion or free radical (Instructor’s choice on test). 40.. 35. State the type of polymer produced by each and list 2 applications for both types of PE.e. List 4 non-catalytic methods and 3 catalytic methods of polymerization 32. 33. 50.1 vs.

83...000........ 63..002 in.... soft and tough...... final length at 9... etc..... Name one of each of the following stabilizers...... UV absorbers.... d) .. 60... Give the maximum use temperature of LDPE and HDPE 147 ........... Elongation under long-term loading is called .. a) ... Show the mechanism by which ethylene oxide is polymerized.55.. 61... an industrial method of stress induced crystallization.. Given that the planar zigzag conformation of extended chain PE has a contour length of 2.. Repeat the previous question for Solution...... List 5 inert fillers and 3 reasons for adding them................ 68.000 in............ Name 2 polymers whose maximum use temperature is close to 300 C...... Name 2 plasticizers......... Report in SI units to 3 sig figs........... Name 3 engineering resins and 3 specific applications for such resins.. ultimate strength.. 77...00165 in. original specimen width = 0..................... label the following points.... tensile strength.. and toughness for the linear initial stress strain data from a tensile test given the following data .... 57..... Give the maximum use temperature of Nylon-6... State 2 important changes that occur during stress-induced crystallization to increase stiffness and strength.. calculate DP and the contour length of chain extended molecules of PE with an average MW of 750............................................... thickness = ¼” and original length of 2.. Draw & name the reagents & product of polymerization of 1.......... and disadvantages of bulk polymerization and 3 polymers commonly produced by this technique......... 72... 84. load is 2.........00 103 lb.... 73.. the name for localized reduction of cross sectional area of a thermoplastic under tensile loading.. Suspension and Emulsion polymerization... 82............. advantages....... Draw and name the polymer produced from -caprolactam 59....... Calculate (to 3 sig figs) the proportional and % strain of a specimen with an original length of 3..... and proportional limit... crystals which form during quiescent crystallization from the melt..... Given a series of stress strain curves.......... thermal stabilizers.. List 5 reinforcing additives...... 76. 56. Name 2 colorant additives... 66... antioxidants.. elastic limit...... 65. and a final length of 3. the units which hold polymer crystals together. Name 3 high performance resins and the physical properties that set them apart..................4-diisocyanotobenzene and 1. Briefly state the meaning of a ‘failure test’ and list 6 examples... 78.. Sketch the main components of a melt spinning unit and label its parts...............5”.... rupture strength.. List the ingredients..... Calculate the modulus of compressive elasticity... 81.... 80....... stress......... b) ....... Given various stress strain curves.... proportional strain. the maximum draw ratio for polyesters and polyamides e) ......2-diaminoethane.. classify the polymer as soft and weak....20  103 lb................ 62.. 64...... Show the polymerization of HMDI and HMDA (one step) and name the type of polymer formed. Name the ultimate property that the ‘notched Izod test’ measures.......... 71. the maximum draw ratio for HDPE f) . 58.....55 Angstroms........ List 1 toughness modifier.. 69. 79. Briefly explain how polymer hardness is measured......6 and PET (see Table V on p... and name one polymer that demonstrates this... 74.. force is applied to a polymer specimen that is 1/8” thick” and ½” wide.......... Calculate the stress (in SI and British units) when 2....... State briefly why solution crystallized polymer crystals are brittle.......000 in... 61)........ Give the name of the following ............ 75. c) ....... yield strength.. 70. 67....

and PVF2 polymers. 97. (& give approx. 6-6.g. 12. value) l) highest crystallinity (& give approx. 89.. List 4 different. 88. Also show the byproduct formed.. nylon 6 resin. List 4 different.. PC resin. Draw the mechanism for the synthesis of a polyamide by reaction of: an amine + acid chloride. Kevlar and Nomex 87. Write the complete mechanism of acid catalyzed Fischer esterification. show the formation of PET by any of the four polymerization methods.. and PTFE resin and choose the 1 which best fits each of the following descriptions. 98.. Using equations. specific applications of PET 94. specific applications of aliphatic nylons and 4 specific applications of Aramid fibers. i. By means of an equation. 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. specific applications of silicones. 4. amine + acid anhydride. symbols. List 4 different. show the polymerization of nylon 6-6 from 2 different sets of starting reagents. Write the names.e. 90. and numbers of the 7 recycle groups for plastics as per the Society for Plastics Industry (SPI).. 5. direct esterification. Write the chemical formulas and names of CTFE. value) m) lowest crystallinity c) lowest Tg (& give approx.. ring opening of a lactam 86. using an acid chloride. 96. specific applications of PTFE 99. 6. Write equations to show the polymerization reaction that forms poly(dimethylsiloxane) or poly(diphenylsiloxane) (Instructor’s choice on test). or using an acid anhydride (Instructor’s choice on test). Show the byproduct (condensation product) formed. Write the formulas and names of the monomers and formulas of the polymers for the following polyamides. ester exchange. List 4 different. FEP.. value) b) highest Tm (& give approx. amine + carboxylic acid. 92. nylon 2. 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 . 91. Write the mechanism of esterification from acid chloride or acid anhydride (Instructor’s choice on test). Write equations to show the polymerization reaction that forms. 6-12.85. a) highest s. specific applications of PC 95. List 4 different. 100. Compare silicone elastomer.

compression molding. Kel F. Nomex. Kevlar. Viton. Briefly explain what is meant by the following terms: blow molding. State 4 important properties of phenolics and then 4 applications that result from these properties 104. Lexan. Name 2 polymers that float in water and 2 which sink in water. Mylar. runners. 113. 109. 107. parison. Name the type of hardener most commonly used for epoxies. Terylene. Given a diagram of an injection molding machine. Name 2 polymers that continue to burn when removed from a flame. calendering. silk. FRP. Name one type of plastic and one example of a product made by each of these processes. Dacron. extrusion. the sequence of operations in injection molding. RTV caulking. 106. Draw the mechanism of novolac formation using phenol and formaldehyde. 108. 105. Name 2 polymers that are self extinguishing. List 4 important properties of epoxies and state 4 applications. 103. Write a formula or chemical name (your choice) that corresponds to each of the following trade names: Fortrel. 110. Draw the mechanism of resole formation using sodium phenoxide and formaldehyde. 112.101. and/or transfer molding. State briefly. gate. 102. label its parts. which result from these properties. silicone. sprue. parting line and flash 111. What element(s) does the Beilstein test identify in a polymer? 149 . Draw the mechanism of epoxy prepolymer formation from bisphenol-A and epichlorohydrin.