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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

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CHM 605
Part 4
MOLECULAR
WEIGHT
OF
POLYMERS
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Molecular Weight:
Because of their large molecular size, polymers possess unique chemical and
physical properties. These properties begin to appear when the polymer chain
is of sufficient length, i.e., when the molecular weight exceeds a threshold
value, and becomes more prominent as the size of the molecule increases.

Note the increase in melting points with increasing molecular weight in the
paraffin series: C20H42 (35 C), C30H62 (65 C), C40H82 (81 C), C50H102 (92
C), C60H122 (99 C), and C70H142 (105 C). Highly linear polyethylene of
molecular weight greater than three million exhibits a melting point of 132
C. The melting point of 100% crystalline, completely unbranched
polyethylenes of infinitely high molecular weight (density at 25 C of 1.002
g/cm3) is reported as 143 C.
The dependence of the melting point of polyethylene on the degree of
polymerization (DP) is shown in Figure 2.
140
120
100
mp
(° C)

80
60
40
20
0
0

500

1000

1500

DP of PE

Figure 2. Melting point of PE versus degree of polymerization.

The dimer of ethylene (butylene) is a gas, but oligomers with a DP of 3 or
more (that is, C6 or higher paraffins) are liquids, with the liquid viscosity
increasing with the chain length. Polyethylenes with DP of about 30 are
grease-like, and those with DP around 50 are waxes.

As the DP value exceeds 400, or the molecular weight exceeds about
10,000, polyethylenes become hard resins with melting points above 100 °C.
The increase in melting point with chain length in the higher molecular
weight range is small. Here crystallinity has a greater influence on the
melting point.

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e. Increased molecular entanglement hinders crystalline packing and thereby lowers density..Figure 3: Variation of Physical Properties with Molecular Weight commercial range of PE's P r o p e r t y tensile strength impact strength melt viscosity Molecular Weight Variation in molecular weight will also lead to differences in mechanical properties. but the melt viscosity continues to increase rapidly.e. all of these increasing with higher molecular weight. i. Note in Figure 3 that the strength properties increase rapidly at first as the chain length increases and then level off.  Molecular weight also influences properties related to large solid deformations. the higher the molecular weight the greater the number of points of attraction and entanglement between molecules.. tensile strength. 40 . and melt viscosity. elongation at break. The range of molecular weights chosen for commercial polymers represents a compromise between maximum properties and processability. i. impact strength.  Polymers with very high molecular weights have superior mechanical properties but are difficult to process and fabricate due to their high melt viscosities.

Recall that each of these effects are proportional to the number of moles of solute (polymer) present in a solvent. viscosity: Ostwalt viscometers are used to measure relative viscosity of dilute solutions of polymers. A suitable detector (e. a concentration gradient is established with larger particles in the lower layers of the solution. average molecular weight is determined by a variety of techniques. virtually all synthetic polymers and some natural polymers are polydisperse. The molecular weight of a polymer is reported as an average.g. ultracentrifuge: After centrifuging a solution of the polymer at high speeds for several weeks. Such compounds are said to be monodisperse. each giving slightly differing values. A crosslinked porous polystyrene packing ('gel') separates polymer molecules based on their size. e.   The extent of variation of molecular weight and size in a polymer sample is known as its molecular weight distribution. and osmotic pressure. conductance. i. vapor pressure lowering.g. titration of reactive end groups such as carboxylic acid groups or amine groups 2. The concentration of polymer at various depths is then determined by optical methods. Methods of determining molecular weight include the following 1. etc. The flow of smaller polymer molecules is slowed down as they diffuse into the pores of the gel while larger molecules move through the column more quickly. all molecules are the same size and therefore have identical molecular weights (M). The viscosity is directly proportional to the polymer chain length. 5.e. In contrast. gel permeation chromatography: (size exclusion chromatography). freezing point depression. Thus most polymers do not contain molecules of the same size and therefore do not have a single molecular weight.. end group analysis.Molecular Weight Distribution of Polymers: In ordinary chemical compounds such as sucrose. count and weigh all the molecules of a sample. Since it is not generally possible to physically segregate.. (MWD) and the MWD has considerable influence upon the physical properties of the polymer. 6. 41 .) indicates the relative concentrations. 3. light scattering: The intensity of light scattered is proportional to the square of the mass of the particle in solution 4. colligative properties. boiling point elevation. photometer.

The tests may be grouped into three types. a polyamide made by reacting a diacyl chloride with excess diamine produces a polymer with amine end groups on all chains. A sample of a polymer contains chains of different lengths. number average MW tests. weight average MW tests and viscosity average MW tests. They can be titrated with standard HCl titrant. This only works for polymers that have reactive end groups. Number Average MW Tests: These tests measure the number of molecules present in a sample. In order to determine the average MW of a polymer sample we conduct chemical and/or physical tests. This is physically impossible to do. all glucose molecules (C6H12O6) have the same molecular weight (180. Thus a polymer does not have an exact and absolute molecular weight.00 g sample requires 50.000 g/mol) 3 roses cost $4 2 tires cost $90 9 roses )  $12 9 roses cost $x = $4 x ( 3 roses 4 tires cost $x = $90 x ( 4 tires )  $180 2 tires 42 . 1. polyesters (made by reacting a diol with excess diacid) will have carboxylic acid end groups on all chains. (ans.15 g/mol). Calculate the number average MW of a polyester given that titration of a 10. 40. If we could separate all polymer chains in a sample and count the number of chains of each weight. End Group Analysis involves titrating reactive end groups with a standard acid or base titrant. Similarly. For example.Molecular Weight Determination of Polymers A non polymeric substance has a fixed molecular weight.00 mL of 0. Titration of a weighed portion of the polymer with standard NaOH yields the number average MW of the polymer.0100 M NaOH titrant. For example. we could then calculate an average molecular weight for a given sample. Different tests may give different values for the molecular weight of the same sample.

43 .

Calculate the number average MW of a water soluble polymer given the following data. pure H2O boils at 17.03 g H2O. the number average MW can be calculated. boiling point elevation. Colligative Properties include vapor pressure lowering.46 mmHg. These properties vary in proportion to the number of moles (mole fraction) of a substance and hold for both polymeric and non polymeric substances. = 1247 g/mol) 44 . At the same temperature.000g polymer are dissolved in 36. freezing point depression and osmotic pressure. Psoln = (P0solvent)(xsolvent) where P = vapor pressure and x = mole fraction A solution of the polymer can be boiled at room temperature by evacuating the vapor space above the solution.53 mmHg. Since a liquid boils when its vapor pressure equals the pressure of atmosphere above it. the polymer solution will boil when the applied pressure becomes equal to the vapor pressure of the solution. 10. (ans. By accurately measuring this pressure and the pressure at which pure solvent boils (at the same temperature).2. a) Vapor Pressure Lowering: Recall from Raoult’s law that the vapor pressure above a solution is inversely proportional to the mole fraction of non volatile solute dissolved in a solution. At 20°C this solution boils at 17.

b) Boiling Point Elevation: The boiling point of a liquid is elevated if a non volatile solute is dissolved in it (because its vapor pressure is lowered as explained above). m = molality of solute. the solution boils at 76. Tb = kbm where Tb = bpelevation.84 °C. The normal bp of CCl4 is 76.00 g CCl4.95 Kelvinskgsolventmolesolute-1. (ans. = 4950 g/mol) Boiling Point Elevation of Calcium Chloride Solutions 45 . The molal bp elevation constant for CCl4 is 4. kb is constant for a solvent Calculate the number average MW of a polymer given that when 10.74 °C.000g polymer are dissolved in 100.

46 .

Freezing Point Depression of Calcium Chloride Solutions

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c) Freezing Point Depression: The freezing point of a liquid is depressed
when a non volatile solute is dissolved in it. (Recall that NaCl and/or CaCl2
are applied to roads to melt ice, by lowering the freezing point of water).
Tf = kfm where Tf = fpdepression, m = molality of solute, kf is constant for
a solvent
Calculate the number average MW of water soluble polymer given that the
freezing point of an aqueous solution of the polymer is –0.14 °C. The
solution is prepared by dissolving 72.00 g polymer in 500.00 g H2O. The
molal fp depression constant for water is 1.86 Kelvinskgsolventmolesolute-1.
(ans. = 1910 g/mol)

d) Osmotic Pressure: Osmotic pressure is that pressure, which must be
applied to a solution to prevent osmosis, i.e., to prevent the passage of
pure solvent through a semi permeable membrane into a solution.
 = MRT where  = osmotic pressure. M = molarity, R = gas constant, T
= Kelvins.
Unlike the other colligative properties, osmotic pressure displays a large
response for even dilute solutions. For example, calculate the osmotic
pressure (atm and m H2O) of a solution of 6.00 g urea (MW = 60.0 g/mol)
dissolved in 2.00 L H2O at 20°C. The gas constant (R) is 0.08206
Latmmol-1K-1. (ans. = 1.20 atm and 12.4 m H2O!)
Calculate the number average MW of a water soluble polymer given that
when 15.00 g polymer is dissolved and diluted to 200.00 mL, its osmotic
pressure at 20°C measures 0.00605 atm (ans. = 298,000 g/mol)

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Weight Average Molecular Weight Tests:
These tests measure the average size of polymer molecules. Size is
proportional to weight.
Intensity

1. Light Scattering: Solutions of non polymeric
solutes, like aqueous NaCl, are transparent
to light because the solute and solvent
molecules are much smaller than the
wavelength of light. The light bends around
small molecules and ions and such particles
are therefore invisible. Polymer molecules,
however, are larger than the wavelength of
UV and, in some cases, visible light.

weight avg. MW

When light passes through a solution of
polymeric solutes, the light is scattered.
The intensity of light scattered is
proportional to the square of the mass of
the particle in solution.
To use light scattering to measure MW, one needs a series of standards of
equal concentration but varying and known MW. A calibration curve of
intensity of scattered light vs. weight average MW is plotted. The intensity
of light scattered by a solution of the same type of polymer at equal
concentration is measured and its weight average MW is read from a graph.

2. Ultracentrifuge: After centrifuging a solution of the polymer at high
speeds for several weeks, a concentration gradient is established with
larger particles in the lower layers of the solution. The concentration of
polymer at various depths is then determined by optical methods.
3. Gel Permeation Chromatography: (size exclusion chromatography). A
crosslinked porous, polystyrene packing ('gel') separates polymer
molecules based on their size. The flow of smaller polymer molecules is
slowed down as they diffuse into the pores of the gel while larger
molecules move through the column more quickly. A suitable detector
(e.g. photometer, conductance, etc.) indicates the relative
concentrations.

Ostwalt viscometers are used to measure relative
viscosity of dilute solutions of polymers. The
viscosity is directly proportional to the polymer
chain length. To determine the viscosity average
MW of a polymer, one must first prepare a series
of standards of equal concentration (w/v) but

Viscosity

Viscosity Average Molecular Weight:

49
viscosity avg.
MW

varying and known MW. The viscosity of a solution of the same type of polymer at equal concentration is measured and its viscosity average MW is read from a graph. 50 .

= Mi wi = weight fraction of polymer with molec. = Mi Example: A polyethylene sample contains 50 mol % of a species with molecular weight of 10.000 g/mol and 50 mol % of species of molecular weight 20.000 g/mol. Mw. is the common arithmetic mean calculated by counting the number of molecules (or moles) of each particular size. Similarly. just as the average score in a series of organic tests is calculated by adding all scores and dividing by the number of tests. wt. of polymer with molecular wt. Note that DP = ( M/weight of a mer) Ans: Mn = 15. the molecular weight of each species is multiplied by the weight fraction of that species.000. Mw . wt. = Mi ni = mole fraction polymer with molec. DPn = 540. the molecular weight of each species was multiplied by the mole fraction of that species.Number-Average Molecular Weight: The number-average molecular weight. DPw = 610 51 . in the calculation of weight-average molecular weight. and DPw. Calculate Mn.000. Mw = 17. summing these. Mn. 2 Wi M i   N i M i  M i Ni M i   M w   wi M i    W i  Ni M i  Ni M i where … Wi = wt. = Mi Weight-Average Molecular Weight: In the calculation of Mn . DPn. Mn  N 1M1  N 2 M 2  N1  N 2 N M N i i i   ni M i where … Ni = # moles polymer with molecular wt. and then dividing this sum by the total number of molecules (or moles).

7 1.1 . Polydispersity Index: For all polydisperse polymers Mw is always greater than Mn . the presence of short chains acts as a plasticizer by reducing entanglement of the larger polymer chains.200 2-4 epoxy resins 0.  Mn is obtained by end-group analysis and by colligative properties. Polymer  Mn ( 10-3) Mw ( 10-3) Mw / Mn alkyd resins 25 . Values of Mv always lie between Mw and Mn and are usually 10 to 20% below Mw .1. Mv . 52 .2.  The ratio Mw / Mn . called the polydispersity index. These methods measure the number of molecules in a sample. increased toughness) and of lower melt viscosity than a sample of the same polymer with a lower index. the wider the MWD of a sample.50 50 . The example serves to illustrate the concepts. Only in the case of a monodisperse. Light scattering is dependent upon the size (weight) of particles. where all molecules are the same size.35 .0 .. Some typical data is given in the following table .52 1.1.8 polybutadiene 2 . Viscosity-Average Molecular Weight: Because viscosity measurement of a polymer solution is comparatively simple. this method is commonly performed and the molecular weight determined by this method is called viscosity-average molecular weight.50 2.1 .5 acrylic polymer 25 . The reason for introducing different measures of average molecular weight is because the various analytic techniques described above give different values for average molecular weight.Both Mn and Mw are theoretical concepts and are not calculated in the manner of the previous example..1 A large polydispersity index indicates a polymer is more deformable (reduced stiffness. The farther the polydisperse is from 1. does Mw = Mn .600 1. is a measure of the MWD of a polymer.  Mw is obtained by light scattering techniques (photometric methods).35 .0.05 .4 0.350 40 .

CHM 605 Part 5 METHODS & MECHANISMS OF POLYMERIZATIO N 53 .

but with rearrangement rather than elimination of a small molecule. high crystallinity PE. e. B.g. U. Thermal methods use heat to cause polymerization.g. Co-ordination catalysts are stereo specific. etc. 3. Gamma radiation from Co60 has been used to avoid contamination from other ingredients. 54 . ethylene glycol condenses with terephthalic acid to eliminate water and produce poly(ethylene terephthalate). trade name Teflon). II. which can react together in a sequence of ring-opening and polyaddition. Free radicals act as catalysts (loosely) in chain polymerization mechanisms B. Polyurethanes area also produced by stepwise growth. Ring opening also called ‘ring scission’ occurs with cyclic monomers having functional groups on the same molecule. light causes photochemical polymerization C. Ions (cations or anions) act as catalysts in polymerizations C. Chain reaction polymerization or ‘addition’ polymerization may occur via any of a free radical mechanism. (PET) by esterification. Most famous are the Ziegler-Natta supported metal salts which allow the formation of high density.V. Similarly.e. i.. a cationic or anionic mechanism. The common examples are vinyl polymerizations. I. diamines react with dicarboxylic acids in an acid-base reaction eliminating water and forming polyamides (nylon).Methods of Polymerization: Two basic methods of polymerization are catalytic or non-catalytic and both of these are subdivided .. or a coordination catalyst mechanism. Poly(ethylene oxide) and nylon 6 are representative of this polymerization type. Non-catalytic methods: (initiate without adding chemicals) A. Types of Polymerization: 1. e. PP.. For example. Catalytic methods: (initiate with the addition of chemicals) A. water. 2. polyethylene and polybutadiene in which double bonds are opened. D. Stepwise or Step-Growth polymerization often occurs with the elimination of a small molecule. Electrolytic polymerization occurs at the anode or cathode of an electrochemical cell as a result of electric current. polystyrene and poly(tetrafluoroethylene) (PTFE...

A free radical is an organic molecule containing atoms with unpaired electrons... These acyloxy radicals then decompose to form two aryl (or alky) radicals and CO2 . homolytic cleavage of the weak O-O peroxide bond yields two acyloxy radicals.Free Radical Chain-Growth Polymerizations: Free radical polymerization proceeds by the following three-part process . on heating or other stimulation decomposes into free radicals. I . It may be brought about by heat or light (e... B) Propagation: The newly initiated monomer radical adds further monomer molecules in rapid succession (propagates) to form a polymer chain. which is then capable of starting the polymerization of the otherwise unreactive monomer. (AIBN).. which decompose on heating or by the absorption of UV light to produce two organic radicals and N2 ... The second part of initiation is the addition of the initiator radical to the monomer to give an initiated monomer radical . Acyl peroxides such as benzoyl peroxide typically decompose upon heating in a two-step process.. UV) but is most commonly achieved by addition of an initiator. b) propagation. In the first step. The foregoing reactions can be summarized as . a material which....I  2 I where I = initiator. 55 .. The active center is continually relocated to the end of the chain. c) termination and chain transfer A) Initiation: is the formation of an active species.   The free radical initiators are usually either peroxides or azo compounds with weak covalent bonds capable of undergoing homolytic cleavage.. Another common class of initiators used in radical polymerizations are azo compounds such as azobisisobutyronitrile. a) initiation.g.

56 .

free-radical polymerized vinyl polymers contain  98% 'head-to-tail linkages'. long-chain radical becomes Termination: Polymerization stops when the growing. Mercaptans such as dodecyl mercaptan.Radical additions to double bonds occur in such a way as to always give the more stable (more substituted) radical. and chlorinated solvents. AB may be monomer. [Relatively few chains are activated].   Combination (or coupling) occurs when 2 long chain radicals react to form an inert final polymer. one terminated in an alkane and the other in an alkene. Disproportionation involves the abstraction of an H atom in the beta position to the propagating radical of one chain by the radical end group of another chain. Thus there is no net change in the radical concentration. (C 12H25SH). B. solvent. the new radical. Depending upon its reactivity. In order to suppress this unwanted reaction. c) Propagation continues until the growing. As a result. These terminate one chain but at the same time. Chain transfer agents are sometimes added to lower molecular weight. The results of chain transfer are formation of side chains in polymer molecules. 57 . a solvent molecule. may or may not initiate the growth of another polymer. or added modifier (chain transfer agent). deactivated by termination or chain transfer. Combination is a rapid. are common chain transfer agents. such as CCl4. the concentration of initiator is kept low (~ 10 -9 to 10-7 M). Chain Transfer: occurs when H is abstracted by the radical end group from the side of another polymer chain. begin another chain. This process results in two dead chains. diffusion-controlled process that occurs without an activation barrier. polymer. or another monomer. long-chain radical becomes completely deactivated by either combination (also called coupling) or by disproportionation.

e. the dissociation of peroxide or persulfate initiators is greatly accelerated by the presence of a reducing agent such as HSO3. even below 0 C.. K2S2O8 initiator plus NaHSO3 reducing agent - S2O8-2 + HSO3.g.g.- S2O8-2 SO4. When polymerization is to be carried out extra initiator must be added. These inhibitors stabilize free radicals by resonance and thus suppress polymerization. a small amount of inhibitor such as hydroquinone or butylated hydroxytoluene (BHT) is added to prevent premature polymerization. hydroperoxide initiator plus FeSO47H2O complexed in EDTA ROOH + Fe+2  RO + OH..g.or Fe+2  e.- + O O O O SO4.- - O S OH O S O + O - O O O HSO3. Inhibitors for Free Radical Polymerization: Oxygen reacts with free radicals forming peroxides or hydroperoxides stopping polymerization and causing chain transfer.- + - O K+ - O S O O O S O S - K+ O O S + + O S O O O - SO4.. SO4-2 + SO4  + HSO3 SO4.+ Fe+3 Fe+2 R O O H R O + O H R O + - O H + Fe+3 The use of redox initiators allows attainment of high rates of free radical formation at low temperatures. Thus many free radical polymerizations are carried out in oxygen-free conditions. In some cases. 58 . as with styrene.Redox Initiation: In aqueous medium free radical polymerization. + S O O - + O S OH O e. nitrogen atmosphere. The result is short oligomeric chains.- SO4-2 + O - - + S O O - O O HSO3- + - O O O O  - SO4.

59 .

Free radical. there is the possibility that either double bond may participate independently in polymerization .. unless the temperature is controlled by cooling.Autoacceleration: Chain polymerizations of vinyl monomers polymerization proceeds. termination rate slows down as the growing chains become less mobile.units. + R 60 . therefore. which contain various isomeric structural units.giving rise to 1. However.2.. especially in 'mass' ('bulk') polymerizations where solvent is not used. Free Radical Polymerization of Dienes: Conjugated dienes. + R R.4-addition 1. As The propagation rate is relatively constant as monomers move freely to the reactive chain ends of the growing polymer.and a 3. Industrially important dienes are butadiene.. Cl 1. viscosity increases.. and isoprene . High molecular weight results for the same reasons. respectively .double bond. called a 'Tromsdorff-Norish Effect'. Each of the above structures contains a 1.4.2-addition R. as well as ionic and coordination process (described later) are used. are very exothermic. chloroprene. like vinyl monomers. undergo polymerization through their multiple bonds. can cause violent explosions. 1.units and 3.2. This behavior. As a result.3-butadiene isoprene chloroprene Dienes can give rise to polymers.4. the rate of polymerization increases (autoaccelerates) along with the growing exotherm.

experimental conditions.4-mer cis-1.4-mer cis-1.3-butadiene) trans-1.4-poly(1.or trans. Anionic polymerizations involve carbanions (C-).4-poly(1.. the polymer obtained from a conjugated diene contains more than one of the above structural units. Indicate which of the following monomers would be suitable for anionic or cationic polymerization .. The relative frequency of each type depends upon the nature of the initiator. are used in anionic polymerizations.4-poly(1.3-butadiene) In general. which stabilize carbanions.isomer .unit may occur as either the cis. producing 1. Cationic polymerizations involve carbocations (C+). Vinyl monomers with electron withdrawing groups. A further possibility is that both bonds are involved in polymerization through conjugate reactions.units.With symmetrical dienes such as butadiene.3-butadiene) R CH2 CH CH CH2 CH2 CH CH CH2 trans-1. CN CO2R alkyl methacrylate CN CO2R alkyl acrylate acrylonitrile CO2R cyanoacrylate OR isobutylene vinyl ether vinyl benzene 61 .4. A 1.. Ionic Chain-Growth Polymerizations: Ionic polymerizations are those in which the chain carriers are organic ions. The choice of ionic procedure depends greatly upon the electronic nature of the monomer to be polymerized. and the structure of the diene. whereas vinyl monomers with electron donating groups are used for cationic polymerizations.4. these two units become identical. 1..

Alkyl groups donate e. inductive effect or resonance effect Inductive Effect refers to movement of electron density through  bonds due to EN between the aromatic C and the atom bonded to it.density from the ring. halogens. lone-pair electrons and that are bonded directly to an aromatic or allylic system are able to transfer electron density in this manner.density into the ring through the  system via overlap of the oxygen 2p orbital with the ring carbon’s 2p orbital.Recognizing Electron Donating and Electron Withdrawing Groups Recall: Substituents on aromatic rings affect both reactivity and orientation (location) of electrophilic aromatic substitution (EAS). OS-orbitals are closer to the nucleus and hold their O electrons tighter. e..and destabilize the C+ and thus deactivate the ring toward EAS Substituents donate or withdraw electron density by either or both of the following two mechanisms. moving lone-pair e. Also the sp 2 C in the ring is more electronegative (1/3 s-character) than the sp 3 alkyl group carbon (1/4 s-character). note the relative rates of nitration of the following aromatic compounds .g..  Substituents which donate electron density make the ring a better Nu: . For example.. i. cyano & nitro groups withdraw e . the sp3 oxygen in phenol hybridizes to sp2. Atoms that have non bonded. carbonyl..and stabilize the C+ intermediate and thus activate the ring toward EAS  Substituents which withdraw electron density make the ring a poorer Nu: . -OH 1000 -H 1 -Cl 0.e.density because they are relatively large & polarizable. + CH3 C C N Cl N O Resonance Effect refers to movement of electron density through  bonds via overlapping p-orbitals especially in conjugated systems.033 -NO2 6  10-8 Substituents affect EAS when they either donate or withdraw electron density to or from the ring.. C C 2p C O . For example. 3px 2p C C C . : H sp2 C C C 3py C C C 3pz Cl 3pz 3s 62 .

-NR3+ groups o. and -R groups 2. ring activating and o-. The net effect depends upon which one is greater. -Y=Z. ring deactivating and m. e. e. where Y has  1 lone-pair of electrons Aromatic substituents are of 3 types . -NO2.and pdirecting NH2 OCH3 o.. the -OH group is ring activating so its resonance effect must be greater than its inductive effect. -NH2. CN.. Electron withdrawing groups have the general form.directing. 63 .g.. 1. the -OH is electron donating by resonance but electron withdrawing inductively. p. -OR. p..directing.Note that the same atom can withdraw electron density inductively and donate electron density by resonance at the same time. . -X groups (the halogens) 3.and pdirecting F CH3 m-directing Br O O CH C OH O NH C CH3 H Cl I deactivators activators Electron Donor Groups NO2 Reactivity Reactivity OH SO3H O O COCH3 C CH3 C N N+R3 deactivators Weak electron withdrawing groups Strong electron withdrawing groups Increasing ability to donate electrons to sp2 hybridized carbon atoms. -Y: . -NR2.g.g. -SO3H. COOH. -OH. ring deactivating and o-. however. For example. where Z is more EN than Y Electron donating groups have the general form.directing.. e. -NHR.

64 .  Draw resonance structures to show how styrene can stabilize either a benzylic cation or anion through resonance..g. Both water and oxygen can react with and deactivate ionic end groups and so both must be carefully excluded from these reactions. Both anionic and cationic polymerizations are run at very low temperatures (e. -78 C) to reduce the frequency of unwanted terminations and transfer reactions.

 In the electron transfer process. The radical anion then can either be further reduced to a dianion…  1. The newly formed carbanion then acts as a nucleophile and adds to another monomer and the propagation continues .. a single initiator can now propagate chains from both ends because it has two active end group carbanions. Alternately. again yielding a dianion .Anionic Polymerizations: Anionic polymerizations can be initiated by a) addition of a Nu:.to the alkene monomer or b) an electron-transfer process The nucleophilic addition uses metal alkyls such as methyl. - + Na Na+ - sodium naphthalide radical anion styryl radical anion 65 . an active metal such as Li or Na donates 1 electron to the monomer converting it to a radical anion. Sodium naphthalide reacts with alkene monomers such as styrene producing a radical anion monomer. a homogeneous initiation is performed by first reducing naphthalene with Na to produce sodium naphthalide radical anion... - Li+ radical anion - - - + Li+ Li+ Li+ dianion radical anion In either case.  Initiation is heterogeneous using a metal reducing agent.3-butadiene Li Li - + Li+ radical anion - Li+ Li+ dianion or can dimerize.or secbutyllithium. which is soluble..

This is called 'living polymerization'.1 or less (chains grow to similar lengths). bimolecular coupling and disproportionation reactions are unlikely. respectively. In absence of chain transfer reactions. With careful attention to these conditions and clean reagents and equipment. growing chains in both directions. the polymer chains remain alive (active).e. 66 . ionic polymerizations produce polymers with narrow molecular weight distributions. negative charge. The dianion then propagates at both ends. under ideal conditions.The styryl radical anion couples to form the dianion as previously described. i.e. Another way to terminate the chains is to add electrophilic terminating agents that will functionalize the end groups. CO 2 or ethylene oxide will terminate the chains and produce carboxylic acid and alcohol groups. with polydispersity indices of 1.. since propagating chain ends carry the same. e. Molecular weight can now be controlled. For example. - - styryl radical anion     styryl radical anion - - styryl dianion - - styryl dianion growing at both ends The propagation of anionic polymerizations is similar to free radical polymerizations with the important distinction that many of the chaintransfer and termination reactions that plague radical processes are absent. i. propagation will continue until all monomer is consumed yet the polymer ends remain active. Note that since carbanions are strong bases that will abstract protons... i.g.e. alcohol or water. More monomer can be added to increase the molecular weight or the polymer chains can be terminated (killed) at this point by adding a monomer with an acidic proton. anionic polymerizations require solvents and monomers that do not have acidic protons otherwise termination may occur.. Compare this with chain-growth polymers that typically have polydispersity indices of 2 or higher.

3-butadiene butadiene dianion - H2C CH CH CH2 + butadiene C Li+ radical anion - HC - Li+ Li+ CH2 CH CH CH2 butadiene many times CH2 - - + CH2 CH CH CH2 CH2 CH CH CH2 + H2C CH N N C many times acrylonitile - HC N - CH2 C HC N C H2C CH2 CH CH CH2 CH2 CH CH CH2 n CH2 n CH C n CH2 N CH C N many times styrene HC CH2 HC n N C H2C CH2 n CH CH CH2 CH2 CH CH CH2 CH2 n CH C n CH2 CH n N Acrylonitrile Butadiene Styrene (ABS) tri-block copolymer 67 . when formed as a 'tri-block' copolymer (styrene1. Acrylonitrile Butadiene Styrene (ABS) terpolymer. behaves like a cross-linked elastomer. If a different monomer is added.4-poly(1. For example.3butadiene) (Tg = -102 C).4-cis-polybutadiene-styrene). Unlike true network elastomers. brittle polystyrene (Tg = 100 C) and rubbery cis-1. can be made as a tri-block copolymer by anionic polymerization… Li + - Li - 1. (used in black Drain Waste Vent (DWV) piping). this tri-block can be melted and reprocessed. block copolymers are produced. stiff.

propagation. 68 . and termination.Problem: Write a complete mechanism for the polymerization of PS initiated with naphthalene and sodium and terminated with water. Label the steps as initiation.

3 C+ and thus terminating the polymerization or causing branching. ether. aryl. Only alkenes with electron donating groups (alkyl.g. cationic polymerizations are carried out at low temperatures and with pure. hydride abstraction can occur from a polymer chain.  Alternately... AsF6-.. 2-chloro-2-phenylpropane) co-initiator will form the initial carbocation.Cationic Polymerization: Like anionic polymerizations. Chain transfer. The protic acid must have a non-nucleophilic counterion in order to avoid 1. ZnCl2) combined with an alkyl halide (e.. SnCl4.e.  Cationic polymerization is unsuited for monomers like propylene.. the more stable (more substituted) carbocation is formed. The 3 C+ is 12-15 kcal/mol more stable than the 2 C+. Suitable counter ions include HSO 4-. which forms 2 C+'s. forming a more stable. Polymerization then proceeds by electrophilic attack of the carbocation on the double bond. As per Markovnikov's rule. and BF4. i. a Lewis acid (BF3. clean reagents and equipment. CH3 CH3 CH3 CH3 H2C H3C CH CH3 CH3 CH3 CH3 CH3 branching on side of a chain CH2 CH CH3 69 .  CH3 H hydride abstraction CH3 CH3 CH3 CH3 existing PP chain 3°C+ H CH2 2°C+ CH CH2 CH3 CH terminated CH3 chain end of a growing chain + CHAIN TRANSFER side of chain is initiated CH3 CH2 CH3 CH3 CH3 CH3 CH CH3 H2C H3C CH3 CH3 CH3 CH3 CH etc. etc.2addition across the double bond. AlCl3. Initiation is with a strong protic acid or with a Lewis acid.) are polymerized cationically. amino groups.

Problem: Write a complete mechanism for the polymerization of isobutylene initiated by 2-chloro-2-phenylpropane and SnCl4. 70 .

surface TiCl3 molecules are activated by alkyl exchange with Al Et3.e. free radical processes which required severe and dangerous reaction conditions.. anionic.e. The ethyl group is attached by a  bond to the titanium and the sixth position is a vacant d-orbital. TiCl3.200 C! A major improvement began in 1954 when Karl Ziegler and Guilio Natta disclosed a low-pressure coordination polymerization process for the production of high density polyethylene. The  cloud of the alkene overlaps the empty d-orbital of the metal forming a  complex.Chain-Growth by Coordination Catalysts and the Ziegler-Natta Process: The first polymerization processes for polyethylene were high pressure. mainly patents. Since that time an avalanche of literature. sometimes as high as three million. i. Initiation: In the generally accepted monometallic. the most common Ziegler catalyst. The fifth chloride ion is replaced by an ethyl group. The coordination catalysts are generally formed by the interaction of the alkyls of group  to  metals with halides and other derivatives of transition metals in groups IV-VIII of the periodic table. describing catalyst systems for the production of crystalline polyolefins has continued unabated. coordination mechanism of Ziegler polymerization. These pentacoordinate. i. The titanium-alkyl bond is weakened in a transition state. The resulting active catalyst is an incomplete octahedral structure with four chloride ions anchored in the interior of the solid lattice. Ethylene bubbled into this suspension at room temperature and 1-4 atm. pressure yielded a linear polyethylene of high molecular weight. 71 . Ziegler reacted titanium tetrachloride liquid with diethylaluminum chloride in xylene (or diesel oil). an alkene (ethylene) attaches itself to titanium by a  bond.. Et Et Cl2 Ti Cl4 Cl Cl1 Al Et 3 5-coordinated Ti ion Et Et Cl2 Ti Cl4 Cl1 Cl3 Al Cl 2 Cl Cl4 Ti + Cl Al Et2 Cl1 Cl3 Cl3 active catalyst In the preceding diagram the ions Cl1 and Cl4 are also held by a second Ti atom in the crystal lattice of TiCl3 and are thus considered nonexchangeable. is octahedrally coordinated except at the solid surfaces where electroneutrality requires that chlorine vacancies exist. 200 MPa (2000 atm) pressure and 180 . HDPE.

Termination by -elimination: CH3 CH2 CH2 Cl2 Cl4 Ti Cl1 CH2 H R C H CH2 Cl2 Cl4 Ti + CH2 CHR Cl1 Cl3 -elimination Cl3 Termination by hydrogenation: (Cat = catalyst) CH2=CHR + H2  CH3-CH2R Most efforts in catalyst research and development have concentrated on catalyst efficiency. Ziegler catalysis can be applied to varied systems to produce HDPE grades for all modern requirements. Chain termination is controlled either by increased polymerization temperature. resulting in so-called second. which gives -elimination. which saturates the alkene monomers.thus facilitating insertion of the alkene between the alkyl group and the titanium atom via newly formed  bonds. 10. 10 to more than 1000 kg HDPE/g Ti.and third-generation Ziegler processes. or by addition of hydrogen. This was accomplished by supporting the Ti catalyst on magnesiumbased substrates such as Mg(OH)Cl which affords a greater surface area of activated titanium. Et Et Cl2 Cl4 Cl2 C2H4 Ti Ti Cl4 Cl1 Cl1 Cl3 active catalyst Et Et CH2 CH2 Cl2 CH2 Ti Cl4 CH2 Cl1 Cl3 .complex Cl3 transition state CH2 Cl2 Ti Cl4 CH2 Cl1 Cl3 new active centre Like the foregoing initiation reaction.000 to ultrahigh molecular weight HDPE (UHMW-HDPE) with molecular weight of 72 . At low reaction temperatures (below 50 C) the polymer attains high molecular weight. propagation involves repeated insertion of ethylene monomer between the titanium-carbon bond. including waxes of molecular weight of ca. This propagation from the root is analogous to hair growth but is opposite to free radical polymerization in which the polymer chain grows at the tip. Catalyst efficiency was raised from ca.

Over 60  109 pounds/year of PE are produced world wide using Ziegler-Natta catalyst processes. Due to this versatility. Ziegler polyethylene has acquired a leading commercial position throughout the industrialized world.several millions. Ziegler-Natta catalysts are also responsible for the development of isotactic and syndiotactic vinyl polymers. 73 .

. C + . i. is produced by self-condensation of 6-aminohexanoic acid. For example Nylon 6. C : O+ ..  Stepwise polymerizations are performed by reacting two different monomers. + H2O + H2 SO4 +OH H proton transfer Monomers of only one kind with the structure A-R-B will also polymerize by stepwise growth. Important step-growth polymers include nylons... A-R-A + B-R-B.. H N + H amine R CONDENSATION REACTION acid/base O H reaction  R C O carboxylate anion + H N R H -H2O O R C N R amide H quaternary aminium cation In stepwise polymerization.. the most abundant species (monomers) tend to react first.. [poly(6-aminohexanoic acid)]. is a polyester produced by reacting a diol (ethylene glycol) with a diacid (terephthalic acid). R . Thus only high-yielding 74 . This is because. OH . OH . poly(ethylene terephthalate). Difunctional monomers react with compatible functional groups combine in stepwise fashion to form dimers.. OH . then octamers. cationic. and tire cords.e. anionic.  R C R' ..OH R C + R' . past 99% conversion. then tetramers. all monomer reacts producing all oligomeric (short) chains.. i. etc... polyesters. (PET). in the early stages of polymerization. according to simple probability.Stepwise (Step-Growth) Polymerization: The second type of polymerization. H : O: H H HSO4 + H . when there is finally a probability of larger chains reacting with each other. and coordination) is stepwise polymerization. . where A and B are functional end groups which react with each other but not with themselves.. .e.. epoxies and phenolics. O: H . For example. polyurethanes.. The formation of high molecular weight chains does not occur until late in the reaction.. O R C H O carboxylic acid  . O R' OH ' . rope.. R C O . used in brush bristles. The mechanism of Fischer Esterification is reviewed below : O: H HSO4 : O: R C OR' : : : O: R . after chain-reaction polymerizations (free radical..

Furthermore.reactants can be used if high molecular weight product is desired. monomer purity is very important because any impurities such as monofunctional molecules. deactivate the chain ends and stop further growth. 75 . added to the chain ends.

2-diaminoethane (ethylenediamine) 2HNCH2CH2NH2 1. 1.2-diaminoethane. halohydric acids. H R + N O C N R R H amine H O N C N R R O N C N R H H isocyanate H urea proton transfer in the intermediate Problem: Draw the product of polymerization of 1.. a molecular rearrangement occurs during the reaction . Rearrangement reactions. alcohol. are those which eliminate (condense out) small molecules such as water.   Condensation reactions. proceed without byproduct formation. 76 .. For example.. etc.Stepwise polymerization can be subdivided into two types .. as in the examples above.4-diisocyanatobenzene + 1.4-diisocyanatobenzene + O C N N C O + 2HNCH2CH2NH2 Problem: Draw the product of polymerization of hexamethylenediamine (HMDA) and hexamethylenediisocyanate (HMDI). diamines react with diisocyanates to produce polyureas without a byproduct.

.. N C C . ethylene oxide polymerizes to poly(ethylene oxide) . :O: . propagation 2. Usually. N 2.....Ring-Opening (Ring-Scission) Polymerization: Many cyclic compounds undergo ring opening reactions which lead to polymer formation. the ring-opening and subsequent polyaddition produces linear polymers... 1. (CH2)5 etc. 1.. N: 1. the structural units (mers) of such polymers have the same composition as the monomer. 2. N H :O: C O .. N H C :O: C :O: .. NH.  2. however. -Caprolactam polymerizes to Nylon 6 . NH C n Nylon 6 poly(-caprolactam) -caprolactam initiated 6-aminohexanoic acid lactam monomer  For example. Ionic initiation is usually effective in this polymerization type.. Na+ H:- :O: C . H O 1. 77 .

Summary of Polymerization Types: In addition to the 3 types of polymerization. several miscellaneous types are found such as oxidative coupling. However.. The following table summarizes the main types of polymerization used for some important polymers .. Monomer ED or EW Radical Cationic   Anionic Coordination group ethylene --- propylene ED  isobutylene dienes   ---  styrene  vinyl chloride  vinylidene chloride  vinyl fluoride  tetrafluoroethyl ene  vinyl ethers           vinyl esters  acrylic esters    acrylonitrile    78 . these can generally be grouped into one of the three main types. Various special cases will be detailed as they are encountered in our study of specific polymers later in this course. Oxidative coupling has an unusual redox initiation but then proceeds by a free radical mechanism. described above.

commercial scale polymerizations are almost always conducted in the liquid phase. The liquid monomer is cast directly in the form (mold) and polymerized by addition of a suitable catalyst. the final polymer solution is usually used directly in further coatings operations. All of these variations find widespread use in industry. e. contact of monomer and initiator. This is most commonly applied to stepwise polymerization reactions. The monomers are injected in molds for auto bumpers and react quickly after mixing and injection. Most polymers shrink up to 20% during polymerization and this must be taken into account when building the mold. Bulk polymerizations are subject to the Tromsdorff-Norish effect as cooling is difficult. One limitation is the possibility of chain transfer to the solvent with consequent formation of low MW polymer. It is difficult to remove residual unreacted monomer since it is trapped in the polymer matrix. The system is kept as a fluid by maintaining a sufficiently high temperature. Polyurethanes and polyureas are also bulk polymerized by Reaction Injection Molding (RIM). There is a progressive increase in MW and high viscosity of the resultant polymer. This is common for addition with vinyl monomers as well as many condensation polymers. The low viscosity facilitates mixing. alkyd resins for paints. (PMMA). In practice. Another limitation is the need to remove the solvent in order to isolate a pure polymer. Solution Polymerization: In this method. Plexiglas. and cooling. which can lead to handling difficulties. For example. often with a small amount of catalyst to increase reaction rate. 79 . fillers are added to some polymers to reduce shrinkage. The method merely involves heating the monomer(s). However. the monomer is dissolved in a solvent prior to polymerization. Bulk (Mass) Polymerization: Here the system is composed of only monomer and polymer (and possibly initiator but no solvent). Sheets up to one inch thick are produced in this fashion. the liquid phase. 2.g. 1. methyl methacrylate is bulk polymerized to poly(methyl methacrylate) sheets.Polymerization Methods (Techniques/Media): In principle. in the coatings industry. Polyester or epoxy resins are bulk polymerized with glass fiber to produce FRP. or the gas phase. the polymer is still considered to be of relatively high purity since no solvent is added. a polymerization reaction can be carried out in the solid phase. however.. Alternately. It is also used for ionic polymerization of gaseous vinyl monomers. Liquid phase polymerizations may be subdivided into four groups according to the nature of the physical system employed.

e. washed and dried. SO3. PS. A diamine is dissolved in water and an acid halide is dissolved in an organic solvent. Polymerization of a solid occurs at the interface of the two solutions and the polymer is wound up and pulled away exposing fresh monomers. Nylon fiber is produced by this technique. PMMA. Dispersion stabilizers [poly(vinyl alcohol) or starch] are added to coat the droplets and prevent their coagulation. and PVA are polymerized in this fashion. PS beads for ion exchange resins are produced by suspension polymerization. This is suitable for free radical polymerization. The polymer forms small beads (100 .1 to 1 mm in diameter). A continuous strand of polymer is produced. i. which will terminate the chains by proton transfer.Na+ SO3. PVC. 80 . is critically dependent upon stir speed and droplet size. 3.Na+ CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH SO3.1000 m) that sink to the bottom and are easily recovered.Na+ SO3. Suspension (Dispersion) Polymerization: The monomer is dispersed in water. Benzoyl peroxide initiator is used.. decomposing at 80 C or lauryl peroxide which decomposes at 50 C. Vigorous stirring produces small droplets (about 0.Na+ Temperature regulation is not a problem and product is of high purity but MW distribution is difficult to control. The two immiscible solvents are carefully placed in contact without mixing (two layers form).Another special case of Solution polymerization is interfacial condensation. but not ionic since water has acidic protons.

polymerization occurs within the micelle and termination occurs when chains grow beyond the micelle. accelerated by redox systems.4. is used. Most rubbers are manufactured by this process as well as latex coatings and adhesives for textiles and paper. ingredient formulations are complicated and must be precise. At the end of the process. When initiator enters a micelle. High MW's are obtained ( 106) and temperature control is excellent. Surfactants (like soaps) have hydrophilic (ionic) heads and hydrophobic (nonpolar) tails. Rather 3-6% surfactant is added to form a stable emulsion. then washed and dried before further processing. In addition. The micelles form stable dispersions (emulsions) without stirring. Some 50100 surfactant molecules surround monomer droplets forming a tiny sphere (micelle). the polymer is forced to coagulate (0. 81 . Free radical polymerization. However. it is difficult to wash out all residue to obtain a pure polymer.5 m) and precipitate by salting out.5 . monomer is dispersed in water but not by stirring. Emulsion Polymerization: Similar to the suspension method. As a result the polymer has poor electrical insulation properties.

CHM 605 Part 6 STRUCTURE & STRENGTH OF POLYMERS 82 .

H H H H H H H H H H The C-C-C bond angles are 112 and the ‘contour length’ is 2.55 Angstroms per ethylene monomer unit polymerized (1. See instructions on the next page.275 Angstroms per methylene group). Its fully extended (‘straight’) chain conformation is a planar zigzag conformation. Calculate the average length (in m) of a chain of UHMWPE from a sample with MW = 107 g/mol With the aid of a micrometer. determine your lower limit of visibility.POLYMER MORPHOLOGY RELATED TO STRENGTH Chain Conformations of PE: HDPE is a linear (unbranched) chain-like molecule. o 1.55 A      Calculate the average length (in m) of a chain of UHMWPE from a sample with MW = 106 g/mol.54 A  o o 2. which can adopt many conformations. 83 . How does this compare to the length of a chain of UHMWPE with MW = 10 7 mol/L? Postulate what force(s) hold these UHMWPE chains together.

each equal to 1 mm.01 mm DIVISION 15 20 25 0. Every 5th division is numbered from 0 to 25. One revolution of the thimble moves 0.5 mm DIVISION (distance moved by 1 revolution of thimble) Zero Corrections:  Close the spindle onto the anvil and check the micrometer reading. If the micrometer reading is not zero.01 mm METRIC MICROMETER: BARREL SCALE MEASUREMENT OPENING 0 55 THIMBLE SCALE 5 0 10 15 RATCHET 20 25 45 SPINDLE ANVIL BARREL 0.5 mm)  The thimble scale has 50 divisions. It should read exactly 0. add or subtract a correction factor to all readings.01 mm THIMBLE FRAME  The upper barrel scale is divided into 25 divisions. and 25). 15.THE 0. Determine the correction factor as per the following example… 84 .5 mm = 0. 10. 5.5 mm (500 m) on the barrel scale.01 mm (10 m) THIMBLE SCALE HORIZONTAL READING LINE BARREL SCALE 0 55 10 0. 20. (0.000 mm when correctly calibrated.  One division on the thimble equals 1/50  0.  On the lower part of the barrel scale. each mm is divided in half (0.

To correct. subtract 0.01 mm from all micrometer readings.e..g. this means it reads 0.01 mm (when completely closed – at zero).01 mm too high (above the true measurement). 85 . if the micrometer reads 0.

e. b AXIS b c a b AXIS spherulite 86 .1% in hexane) quiescently (undisturbed) it forms thin lozenge-shaped crystals. These spherulites are approx. solution crystallized PE is very brittle because the layers separate easily. the polymer chain folds back and forth on itself many times. i.1 . Many separate crystals grow stacked one on top to the other with relatively few molecules anchored in more than one crystal. few ‘tie molecules’. Crystallization from the Melt: When crystallized quiescently from the melt. spherical crystals (‘spherulites’) form.Crystallization from Solution: When PE is crystallized from dilute solution (0.. As a result of this morphology. 100 m in diameter and are easily visible under a low powered polarizing microscope. The few tie molecules that form do so because of tears in crystals caused by motion with the solvent. 20 µm ca 100 Å 100 carbon atoms polymer chain a) side view orientation b) top view ( c AXIS) Within the crystal.

the spherulites are pulled apart. Fibrils ca 10 m diameter Engineers and chemists have worked to change the morphology of polymers before.The spherulites appear in the shape of a Maltese cross. 87 . The only resistance is due to a few inter-spherulitic tie molecules. When the polymer is subjected to tensile (stretching) forces. This optical effect is due to birefringence. Spherulites grow outward in spiraling (twisting) branches from independent nuclei until they meet other growing spherulites. during. Birefringence is measured as the difference in the refractive indices of the 2 beams. The optical effect is due to the crystallization pattern of the spherulites. Birefringence is the splitting of incoming light into 2 diverging beams of plane polarized light each with a different refractive index. and after crystallization to improve its strength properties.

the extrusion of filaments after conversion of solid PE melt polymer to a fluid state by dissolving in a suitable solvent or. The second roller is operated 3 to 8 times faster than the first one. however. in the form of thin threads. is fed from a hopper into the inert atmosphere of an electrically heated extruder cylinder and forced forward by a heated melting extruded filaments screw differential speed rollers bobbin Figure 16.. At this stage of the process.e. PE is extruded at 225-300 C.7-6. Melt spinning of PE The disordered polymer. in the form of powder spinneret or pellets. in the liquid state. A spinneret may contain a few or a few hundred holes ranging in size from 0. well above its melting point. melting. into a current of air where it is cooled to a temperature well below its melting point.5 mm in diameter. as in the case of polyolefins. This arrangement yields a net tensile force that stretches the fiber to a draw ratio of 3 to 8 times (300-800% elongation). pump (Figure 16). this can be carried out at room temperature. depending on the filament size required. where T g < -100 C. the crystalline threads. is then pumped through a spinneret (a flat plate with a large number of small holes drilled through it). the crystallite orientation is very poorly developed. In order to draw at commercially acceptable rates of 1. i. or drawing. The 88 .7 m/s PE is heated during drawing. PE polymer chips The primary fabrication process in the commercial hopper production of synthetic fibers is spinning. in order to sufficiently reduce the melt viscosity of the high molecular weight (200.000) polymer used in PE fibers. a fiber has much higher strength and stiffness than the same polymer when it is bulk polymerized. The liquid polymer emerges from the spinneret.3-2. Cold drawing requires that the fiber be kept above the T g but in the case of PE. Bulk polymer. The necessary high orientation for fiber properties is achieved by stretching. This is accomplished by passing the fibers through two pairs of rollers rotating at different speeds. Crystallization naturally ensues.Melt Spinning: As a rule.

drawn PE fibers display a significant decrease in extensibility (% elongation at break) and an increase in tensile strength and tensile modulus (stiffness) compared to undrawn PE.e. The fiber is held taut during the heating and subsequent cooling to prevent relaxation.filament is finally wound up on a bobbin (spool). annealing. is conducted to stabilize the final fiber structure and properties by stress relief. As a result of the applied stress.. i. 89 . Further heating below the softening point. (Table IV).

amorphous layer and intramicrofibrillar tie molecules interfibrillar tie molecules 90 . As a result the polymer gains considerable stiffness and strength. the folded chains within the spherulites or crystallites are unfolded and realigned into parallel bundles of straight. Mechanical properties of PE fibers versus draw ratio. Controlled application of stress during or after crystallization is seen to produce dramatic improvements in strength and stretch resistance of polymers. section of fibril bundle amorphous layer & tie molecules microcrystallites microfibril fibril (bundle of microfibrils) microcrystallite necking intermicrofibrillar tie molecules stack of parallel lamellae 15A. chain-extended molecules.Table IV. we need to look at the molecular rearrangement caused by this process. X-ray diffraction shows that during the ‘drawing’ (stretching) operation. 15B. The taught. Stress Induced Crystallization: Melt spinning is an example of stress-induced crystallization. To understand why. is the direct result of the formation of a greater number of interlamellar. Draw Ratio undrawn LDPE undrawn HDPE drawn HDPE drawn HDPE drawn HDPE drawn HDPE 7:1 8:1 9:1 10:1 Tensile Strength MPa 10 30 430 500 590 660 % Elongation at Break 800 1000 40 30 22 15 Tensile Modulus MPa 200 1000 5000 8000 10000 12000 * Tensile modulus is a unit of ‘stiffness’. The greatest improvement of mechanical properties. extended-chain tie molecules. aligned chains are essentially prestretched and now many polymer chains interlink crystalline regions so that an applied load is spread over a large area of the polymer. which occurs at the highest draw ratios.

which is in its solid state above T g.01-0.g. As the stretching is continued.32 1 120 11-17 110 cotton (cellulose) 1.54 4 550 7-9 130 silk (protein) 1. Linear PE. in a phenomenon called "necking down" (Figure 14).5 200 polyester (PET) 1.4-0. 1 dener = 1g/9000m Fibres of ≤ 1 denier are microfibers. highly localized reduction in cross-sectional area. is called cold drawing.denier: a unit of density of fibres = mass (g) per 9000m (9km) fibre.2-4.25 4 440 - - Necking and Cold Drawing of Bulk Samples: To elongate and thin out a polymer. Physical properties of important commercial fibers.90 5 400 0. pantyhose.6 1. 2 (C) LDPE 0. Specific Fiber Gravity Tenacity Tensile (g/denier Strength ) (MPa) %H O Max.17 3 310 1.8 200 acrylic (PAN) 1. tenacity: rupture strength (ultimate strength) in weight (g) ÷ linear density Table V. the thin. The draw ratio. when cold drawn. polyesters. The diameters of the drawn and undrawn portions remain about the same throughout the process. drawn section increases in length at the expense of the undrawn portion. or ratio of the length of the drawn fiber to that of the undrawn.95 5 420 nil 110 isotactic PP 0. 91 .14 7 710 4. but can be much higher (10 to 1 or more) in linear polyethylene. like many other crystalline polymers. and polyamides.5 230 wool (protein) 1. does not gradually become thinner but undergoes an abrupt.1 130 Nylon-6. is about 4 or 5 to 1 for a number of polymers including branched polyethylene. e.38 5 610 0.92 2 160 nil 90 HDPE 0. Use Absorbe d Temp..

For example . flex endurance.g.  They are even more costly than Engineering Resins. the degree of crystallinity in the specimen does not change greatly during drawing if crystallinity was previously high but may increase if crystallinity was low.  Most are 2-4 times the price of large volume olefin polymers. High Performance Plastics: are those with exceptionally high strength and/or dimensional stability at high temperature. silicone rubbers.neck formation in drawn polyethylene Figure 14. e. compressive strength. Al and Mg in plumbing parts. tear resistance.  This category includes thermosets as well as thermoplastics. Failure Tests Determine Ultimate Properties: Most industrial tests of polymers are carried to failure with some attempt to simulate the end use.. etc. 92 . stiffness. impact resistance. In general. ULTIMATE PROPERTIES OF POLYMERS The maximum punishment a polymer can endure before failure provides a measure of its “ultimate properties”. PC. e.  Examples include Nylon 66. poly(butylene terephthalate). hardware and automotive parts. and polyimides. and styrene polymers. Kevlar). Necking down of PE during cold drawing.. aromatic polyamides (e. PTFE. aromatic polyesters. creep resistance. vinyl chloride.  fast impact is used to simulate dropping a PS drinking glass. acetals. phenolics. epoxies. PPO-PS blends. and polysulfone. Engineering Resins: designate a group of heterochain thermoplastics that can compete with die cast metals such as Zn.g.. tensile strength.  Boron.. glass. or graphite fibers may be added..  They can be used without reinforcing fillers but glass or mineral reinforcement improve dimensional stability at high temperatures.g.

.com/watch?v=I28m4FZzqro&NR=1 93 . wear tests measure abrasion resistance of tires  tensile (pulling) tests measure load capacity and stretch for ropes and cables  flexure tests determine life span of plastic hinges One of the most important failure tests is obtained by stretching a dumbbellshaped specimen of the test material until it breaks. The amount of deformation (extension) is measured by an extensometer.) is applied by a ‘tensile testing machine’. The following definitions apply . The data is plotted on a ‘stress-strain curve’ and evaluated..youtube. A gradually-increasing tensile force (in N or lb.  Stress () = Force applied per unit area of a specimen  Strain (e) = proportional (or %) elongation HDPE Tensile test http://www.

The specimen is firmly clamped in the grips of a tensile testing machine. During the test. 1/8 " thick ½ " wide 6 – 8 ½” long Specimen for Tensile Testing elongation (strain) gage tensile force (stress) gage specimen clamped in grips Tensile Tensile Testing Testing Machine Machine Zwick/Roell Zwick/Roell Optical Optical Extensometer Extensometer 94 .Tensile Testing Hardware The material to be tested is molded or cut to standard dimensions. A plot of this data generates a stress strain curve. Tensile testing is conducted under the same conditions for various materials. the applied tensile force (‘stress’) and the extension (‘strain’) are simultaneously recorded. The tensile machine stretches the material at a slow constant speed until rupture occurs. This gives a direct comparison of the strength properties of different materials.

tensile force Up to the propotional limit. E. This deformation is also completely elastic (fully recovered when tension is released). (elongation) e.  (lb/in2) lb/in2 = lb/in2 = psi in/in N/m2 = N/m2 = Pa m/m strain. (in/in) h2 95 . stress. aka 'Young's Modulus' or Modulus of Elasticity. tensile force Beyond the elastic limit. This elongation is fully recovered when the tension is released. (elongation) e.h2) is a measure of the toughness of the material. (in/in) Toughness is the area under a stress strain curve Notched Izod Test for Toughness Toughness is usually measured by the Notched Izod test. tensile force Between the propotional limit and the elastic limit. The difference in height (h1 . polymer chains are pulled apart and will not fully recover when tension is released.  (lb/in2) h1 strain. A notched sample is secured in a clamp and broken by striking with a heavy pivoting weight. polymer chains are uncoiled. interatomic bonds are stretched and bent. Permanent deformation ("plastic deformation") occurs. Slope below proportional limit is 'stiffness'. elastic limit proportional limit E =  e stress.

Elastic limit of a polymer 7. Ultimate (Tensile) strength 5. Rupture strength 6.1. Rupture of a ceramic Stress-Strain Curve 1 8 4 stress 3 5 2 9 7 6 strain 2. Elastic limit 4. Rupture of a polymer 96 . Proportional limit of a low-mcarbon steel 3.

e.8.  Yield strength (9) is slightly beyond the elastic limit. 1. The strain occurring up to the proportional limit is due to bending and stretching of intramolecular bonds. i. (also the ‘tensile modulus of elasticity’ or simply the ‘modulus of elasticity’) is the ratio of stress to strain below the proportional limit. the molecular chains are pulled away from each other and will not fully recoil when the stress is removed. Rupture of an elastomer 9. the initial slope of the stress-strain curve.. Beyond the elastic limit.2%.. It is chosen as the stress at which plastic deformation reaches 0. The strain between the proportional limit and the elastic limit (3) is due to uncoiling of molecular chains. 7 & 8 above.  Young’s Modulus (E).  Elastic limit (6 & 3 above) is the maximum stress a material can endure without permanent deformation.  Proportional limit (2 above) is the maximum stress at which the stress-strain curve is linear.e. 97 . It is a measure of the ‘stiffness’ of a material. Both of these deformations are completely recoverable (perfectly elastic) when the force is removed from the specimen. 7. They are thus called ‘elastic deformations’. a point above which most structural materials are considered useless. It is usually about the same as the modulus of compressive elasticity.  Ultimate strength (tensile strength) is the maximum stress supported by the specimen during the test. Yield strength  Rupture strength is the stress at which complete breakage occurs. i. 1. i. 5.. This permanent deformation is called ‘plastic deformation’. 4. & 8 above.e.

98 .

 Polymers are often classified based on their stress-strain curves . scratching. Most polymers (and metals) show this behavior and its magnitude is directly proportional to temperature. Spectra) have extremely low tensile creep since its polymer chains are fully aligned. acetals.g.. It is a measure of the total energy absorbed per unit volume of material. PE hard and strong hard and e. Both glass and high carbon steels are hard but glass is brittle whereas steel is strong.  Creep is slow elongation resulting from long-term loading. Toughness is the area under the stress-strain curve.  Specific strength is the ratio of tensile strength to density ()..  Hardness includes resistance to indentation. soft and weak e.g. phenolics Nylon soft and tough e. The hardness of plastics is measured by determining a material’s resistance to penetration by a hard metallic ball or specially shaped diamond penetrator. Do not confuse hardness and brittleness.g. 99 . PC.. marring and penetration.g. PAN fiber e. Some of the newer UHMWPE fibers (e. The area or depth of indentation is measured after impact by the ball.g.g. PTFE hard and brittle tough e. Toughness is directly proportional to both the strength and ductility of a material but these tend to be inversely related. Hardness is related to yield strength and correlates well to these values. Ductility is the ability of a material to be drawn into a wire or thin thread..

100 . It is determined by striking a sample with a swinging pendulum or by dropping increasingly heavy weights on a sample until cracking occurs. Impact resistance is a measure of the energy necessary to break a sample per unit thickness upon impact. Linear. high MW polymers outperform crosslinks.

UV Absorbers such as carbon-black in auto tires or phenyl salicylate (Salol in sunscreens) convert UV radiation to IR radiation.  Examples include powdered clays. Colorants including dyes and pigments give color to plastic. peanut shells. wood flour.POLYMER ADDITIVES A large variety of additives are used in polymers. and talc have high specific heats and absorb large amount of heat thereby protecting the polymer against excessive temperature rise. white CaCO3 6. For example .  Glass fibers and fabrics are added to polyesters and epoxies for boat hulls and auto bodies  Boron and graphite fibers are used to stiffen golf clubs. and coconut shells) Finely divided additives often interact with polymer chains by either van der Waals’ forces or by actual covalent bond formation (C-black and glass fibers) acting as crosslinks between polymer chains. 1. and agricultural wastes (corn husks. Reinforcements are added to increase the stiffness and strength of polymers. Plasticizers decreases brittleness (lower T g) and increase impact resistance  DOP and TCP in PVC 4. sailboards and racing kayaks  Nylon and Dacron (polyesters) cords and fabrics stiffen automobile tires  Honeycombs provide the highest strength to weight ratios in sailboard hulls  Wound filaments (glass or polymer) provide maximum strength in cylindrical pressure vessels and tanks 2. Inert Fillers are added largely to reduce cost and give marginal improvement to strength and temperature resistance. Thermal stabilizers such as CaCO3. THERMAL RESISTANCE OF POLYMERS 101 . silica. Al2O3. cotton. Toughness Modifiers improve impact and abrasion resistance and toughness.  Finely ground rubber is mixed with molten plastics during injection molding 3. The basic kinds of polymer additives.. their purpose and examples are given . C-black.  Red dyes.. CaCO 3.. 5. 3 Kinds of Stabilizers are common A. Antioxidants such as BHT inhibit O2 and O3 from initiating free radical depolymerization of vinyl polymers C.. diatomaceous earth. B.

g. e. 102 . cotton. Rayon. Nylon (polyamides). are noted for high temp. PTFE.polymer chain bonds. amide or hydroxyl groups that can form strong intermolecular bonds. wool and silk all contain ester.. use (to 290 C) also due to its high polarity.High temperature resistance is achieved by polar polymers. Silicone elastomers (polysiloxanes) are useful to 300 C due to its strongly polar -Si-O-Si-O. Fluorinated polymers. Dacron (polyester).

2 1.92 0. (psi  103 ) (psi  103 ) E Impact St.g.92 0.3 . (ftlb/in) Max.20 2-5 10 20 350 70 .90 0.1 1.5 120 25 30 25 4 Ultimate Properties of Some Important Polymers Polymer ABS cellulose acetate epoxy + glass fiber PTFE Nylon 66 Nylon 66 + 30% glass phenolformaldehyde polycarbonate poly(phenylene oxide) polypropylene LDPE HDPE poly(methyl methacrylate) PS (general s. Observed mechanical properties of HDPE fibers and other materials.95 1.7 no break 1 .4 Tensile Modulus ( GPa ) 10501400 200 200 80 70 4 1.20 0.1 10 10 800 -1700 350 360 16 5.3 1.6 2.4 0.95 2 4 1 0.400 3000 60 420 1000 3 -6 1-3 0.3 65 .7 0.5 0.0 175 190 0.7.2 1.7 7.4 5-9 0.1 0. S.10 3 2 2.03 0.5 90 105 260 290 150 200 1. T. Temp.2 3-6 7 .2 5 0.7 2.50 - Specific Strength ( N / tex ) - Specific Modulus ( N / tex ) 300-400 1.80 103 .5 2-9 5 .4 0.04 0.4 175 1. Use (C) 1.6 .5 0.4 6 .Table VIII.4 130 100 120 90 1.8 2.11 200 20 200 400 0.03 0.2 0.04 1. Fiber diamond graphite hard steel glass aluminum drawn HDPE polyisopre ne Tensile Density Strength 3 ( g / cm ) ( GPa ) 3.04 5-8 400 0.

purpose) PVC (rigid) PVC (plasticized) 1.895 MPa 1 ftlb/in = 53.3 7 3 500 variable 1 .20 variable 65 .4 1.4 J/m 104 .80 Conversion Factors: 1 psi = 6.80 65 .895 kPa or 1000 psi = 6.

CHM 605 Part 7 COMMERCIALLY IMPORTANT POLYMERS 105 .

regenerating the acid chloride and amine. Amines are fair nucleophiles and will readily react via nucleophilic acyl substitution. Tertiary amines. Nylon 6. O R C Cl ammonia or 1° amine or 2° amine O R :NHR2 acid chloride C - O Cl Cl - R R C N + R H H O H C N R + HCl amide + NH2R Aminolysis of an acid chloride yields an amide and liberates HCl. 3º amines will not compete with the amine reagent as a nucleophile because in the unstable protonated amide that would form cannot deprotonate (no H’s on N).: O: C R POLYAMIDES N R n all polyamides have the amide functional group discovered ca. are sometimes used to scavenge the HCl by product and drive the reaction forward. e. acid chloride plus amine 2. Either 2 moles of the amine must be added per mole of acid chloride or a base must be added to neutralize the byproduct HCl. ring opening of a lactam (cyclic amide) Acid Chloride Plus Amine: In the laboratory. acid anhydride plus amine 3. The nucleophilic addition of the 3° amine will reverse. 1930 by Wallace Carothers at Dupont. such as an acid chloride or acid anhydride. however. the HCl byproduct neutralizes an equivalent of the amine reagent. The mechanism of the reaction of an acid chloride with an amine to produce an amide is shown. carboxylic acid plus amine 4.. N: + H Cl N+ H Cl - Pyridine (a 3° amine) neutralizes HCl byproduct 106 .g. such as pyridine. amides are usually synthesized by the reaction of an amine with a reactive carboxylic acid derivative.6 1st large market was women’s hosiery Nylon is Dupont’s trade name for aliphatic polyamides Aramid is a generic term for fully aromatic polyamides      Preparation of Polyamides: Polyamides can be synthesized by a number of reactions: 1.

H C . . this method is the most common industrial method. The catalyst used in this reaction is sodium hydride.. initiated monomer poly(caprolactam) . therefore.. Although not as elegant as synthesis from an acid chloride or acid anhydride. : O: CH3 C . Na+ H:C . The sodium hydride initiates the reaction by removing the weakly acidic lactam proton from caprolactam to form a N anion (a good nucleophile). Its carbonyl-C to N bond breaks heterolytically producing an NH anion.. O . CH3NH2 : O: H3C C . this is referred to as an anionic polymerization.. NH 3.... the second caprolactam molecule undergoes ring scission. 1° & 2° amines react but not 3° amines. Either 2 moles of amine must be used or a 3° amine is needed to scavenge the RCOOH byproduct. (CH2)5 NH C N N n 107 Nylon 6 propagation etc. water is eliminated from the quaternary amine/carboxylate salt yielding an amide. RNH 2) because amines are bases which convert carboxylic acids to non electrophilic carboxylate anions and themselves are protonated to non nucleophilic quaternary amine cations (e. O C 2 O C O C - 3 CH3 R H 1 2 O 1 O N O 3 R C H + N R R O H O C O CH3 R N C a carboxlyic acid and an amide are formed CH3 Note that the amine must have atRleast one H. Aminolysis of a carboxylic acid anhydride yields an amide and a carboxylic acid..g... H C . C C ...Acid Anhydride Plus Amine: The nucleophilic acyl substitution reaction of an acid anhydride with an amine proceeds by the same mechanism.. _ : O . on heating. C : NH N . In order to accommodate the electron pair donated by the N anion. H :O: :O: :O: N O N O . Carboxylic Acid Plus Amine: Amides are difficult to prepare in the laboratory by direct reaction of carboxylic acids with amines (e. Ring Opening of Lactams: The mechanism is shown for the ring-opening polymerization caprolactam producing Nylon 6.. :O: :O: which propagates the chain. The heating is easily accomplished in large reactors and the carboxylic acid is less expensive than the corresponding acid chloride or acid anhydride. NH2 However. H + . + NH3CH3 : O:  - H2O CH3 C .g. RNH 3+). The anionic N subsequently bonds to the weakly electrophilic carbonyl-C on another monomer molecule..

Nylon 3 has three C’s in the main chain of its mer. O . : O: . etc. C n or alkyl isocyanate . Nylon 2 has two C’s in the main chain of its mer. names. proteins n R O ring scission C NH C C H CH3 n H CH3 CH3 C O CH2 C semicommercial scale NH CH3 n 3-amino-3-methylbutanoic acid lactam -methyl--butyrolactam Nylon 4: n N H O ring scission O CH2 3 C NH n very polar good H2O absorption similar to cotton 4-aminobutanoic acid lactam -butyrolactam -pyrrolidone Nylon 5: n N H O ring scission 5-aminopentanoic acid lactam -valerolactam -piperidone 108 ... N C . O .. Nylon 2: O NH2 n CH R Nylon 3: H2O C OH O NH CH -amino acids C silk.VARIOUS NYLONS AND ARAMIDS: There are many different polyamides. N . n R Nylon 1: .. The structures.. N R C n R Nylon 1 has one C in the main chain of its mer (repeating unit).. and preparations of common polyamides follow..

etc.Nylon 6: O C n ring scission NH 2nd largest production among Nylons for rope. brush bristles.HCl O CH2 4 C Cl adipoyl chloride hexanedioyl chloride Nylon 6. flexibility increases and mp decreases. 6-aminohexanoic acid lactam -caprolactam 6-aminohexanoic acid O H2N n acid O Nylon 7: n H2N CH2 6 CH2 5 C -aminocaproic OH  C OH - industrial in Soviet Union H2O 7-aminoheptanoic acid -aminoenanthic acid Nylon 11: n O H2N CH2  C OH 10 - industrial in Europe H2O 11-aminoundecanoic acid O C industrial in Europe NH Nylon 12: (CH2)11 12-aminododecanoic acid lactam -lauryllactam As distance between amide groups increases.6: is the largest production polyamide in North America (multiple uses) O n H2N CH2 6 NH2 + n HO HMDA O CH2 C O CH2 HMDA OH  - H2O adipic acid hexamethylenediamine n H2N 4 C 6 NH2 + Cl C hexanedioic acid . Nylon 6.10 # C's in amine # C's in acid 109 .

HCl 1. It has a lower mp than similar homopolymers and hence easier processing.12: O n H2N CH2 6 + NH2 C n HO HMDA O CH2 C  OH 10 - H2O extract from castor oil dodecanedioic acid Nylon 6.O Nylon 6. high mp (> 500°C) terephthaloyl chloride o-polymer mp 200 .300°C O O C C NaOH Cl . 110 .10: n H2N CH2 6 + NH2 O CH2 C n HO HMDA 8 C OH O  - HN H2O CH2 6 NH C O CH2 8 C n sebaccic acid decanedioic acid Nylon 6.4-benzenediamine p-phenylenediamine n H2N NH2 + n Cl 1.4-benzenedioic acid terephthalic acid ARAMIDS: Fully aromatic polyamides (not called Nylons) n H2N NH2 + n Cl O O C C 1.3-benzenediamine m-phenylenediamine NaOH Cl - HCl HN NH O O C C n 1.3-benzenedioyl chloride isophthaloyl chloride Nomex mp = 365 °C Copolymer Blends/Block Copolymers: Nylon 6.4-benzendioyl chloride Kevlar (fibres in bullet proof vests) rigid.6/6.10 is used in adhesives and coatings.T: n H2N CH2 6 + NH2 n HO HMDA O O C C  OH - H2O 1.

p. drapery slides.  Nylons have natural antifriction properties (low coefficient of friction) and low gas and vapor permeability. carpets. peroxide bleaches. appliances. rods. intermolecular H.g.  aliphatic nylon molded and extruded products: gears. 111 . belts and tires. oil.000 >500 2. grease).000 psi Nylon 6 Nylon 6. formic acid and UV light.  Longer HC chain nylons have greater flexibility.Properties and Uses of Nylons Properties: s. parachute fabric. housings and structural parts for business machines. cooking bags. apparel. electrical cable insulation.6 Kevlar (fiber) 1. hot formamide. (psi) Modulus (psi) Tm (C) H2O absorption (%) $/lb 1 GPa = 145.6 has the largest production volume of the nylons and nylon 6 is second largest..bonding and tight packing. electric razors.000 19. Together they comprise > 90% of all the nylon production.000 420. Applications: Aliphatic Nylons: Nylon 6.  aliphatic nylon fibers: brush bristles. ammonia.1 10. tubes. e. cams. zip fasteners. nylon 3 and nylon 4. PVC coated rainwear.000 230 1.g. This results in strong  Chemical resistance: Nylons are resistant to non polar solvents (gasoline. surgical thread.000. abrasion resistant thermoplastics (“Engineering resins”). hosiery. rollers. tents.  Nylons are translucent or pale white because they are highly crystalline thermoplastics. lower m.7 >4 ~2 ~2 ~10  Nylons are strong. Tensile St. reinforcements for hoses.000 265 1. bearings. rope. and lower H 2O absorption. and acetone but are attacked by chlorine.4 400.0 1. They are FDA approved as a food packaging material.  Nylons have relatively high H 2O absorption especially those with short HC chains. impellers. hot phenol.1 10.  Nylons are very polar because of their amide groups. tough.  They are self-extinguishing when ignited.

tennis rackets. airplane flaps and rudders. and helicopter fuselages.Aramid Fibers: (“High Performance Fibers”) The outstanding strength. crash helmets. stiffness. and thermal resistance of Aramid fibers results in their use as reinforcing agents in epoxy (and other) composites for fishing rods. skis. 112 . race car bodies. bullet proof vests. golf club shafts.

POLYESTERS:
Polyesters are among the most versatile of polymers. They are used widely in
fibers, plastics [especially Fiber glass Reinforced Plastic (FRP)) and coatings
(especially alkyd paints)
The common synthetic methods are step growth, polycondensation reactions.
RCO2H + R’OH  RCO2R’ + HOH

1. direct esterification
2. transesterification

RCO2R’’ + R’OH  RCO2R’ + R’’OH

3. diacid chloride + polyol

RCOCl + R’OH  RCO2R’ + HCl

4. diacid anhydride + polyol (RCO)2O + R’OH  RCO2R’ + RCO2H
All methods involve nucleophilic addition to the electrophilic carbonyl C.
1. Direct Esterification (Fischer Esterification):
Reaction rates with carboxylic acids and esters are slow, but are increased by
acid catalysis.
: O:
R

..

H
: O+

H+ HSO4-

..

R

OH
..

C

C

: O:

..
..OH

R

..

C
+

H

H

H

: O:

..
..OH

..
OH
..

R

C
+
R' ..
O

R'
OH
' ..

: O:
R

C

R' ..
O:

H

: O:

-

HSO4

..

R C OR'
..
+
H2O
+
H2 SO4

..

+OH
H

proton transfer

2. Transesterification (Ester Exchange):
The dicarboxylic acid (used in Direct Esterification) is replaced with a diester.
The mechanism of acid catalyzed ester exchange is the same as that of acid
catalyzed direct esterification.
O
R

O

H2SO4

C

O

+

R''

R'

ester

O

R

H

C

O

+

R'

R''

ester

alcohol

O

H

alcohol

Base catalyzed transesterification is straightforward.

R'

O

H

+

O
R

2

C
ester

O

H2

+

R'

pKb = -21

pKa = ca. 16

1

Na H

O

-

Na+

sodium alkoxide

O

2

+

R''
1

R'

O

-

Na+

R

C

O

ester

R'

+

R''

O

-

Na+

113

114

3. Diacyl Chlorides + Diols:
Because acid chlorides are good electrophiles, alcohols react directly without
catalysis even though alcohols are weak nucleophiles.

1

2

O
R

C

3

2

Cl

+

Cl

R'

O

3

O

-

R

H

C

O

O

HCl

H

+

R

C

O

R'

R'

1
acid chloride

ester

alcohol

Tertiary amines, such as pyridine, are often added to neutralize the acid
byproduct and drive the reaction to completion.
N:

+

H

N+

Cl

Cl

H

-

4. Diacid Anhydrides + Diols:
Acid anhydrides are also reactive electrophiles and they react directly with
alcohols forming esters. Tertiary amines react with the acid byproduct and drive
the reaction to completion.
1

O
R

2

C

2

O

O
C

+

R

R'

O

H

-

3

O
O

C

R

3

C

O

+

O
H
R'

1
alcohol

acid anhydride

R

O

carboxylate

O

RCOH
R
carboxylic
acid

C

O

R'

ester

Types of Polyesters:

1.

Linear Thermoplastics:
a)
from polycondensation reactions e.g., PET, poly (p-hydroxybenzoic
acid), PC
b)

2.

from rearrangement of lactones (ring opening), e.g., -caprolactone

Crosslinked Thermosets
a)
polyester resins from polyfunctional (polyhydric) alcohols, e.g., alkyd
paints
b)
unsaturated polyester resins, e.g., for Fiberglass Reinforced Plastic
(FRP)
115

O HO C OH p-hydoxybenzoic acid H2SO4 poly(p-hydroxybenzoic acid) poly(p-benzoate) Para-substitution on the aromatic ring creates high linearity and thus allows close alignment (tight packing) of chains. vacuum removes excess EG High crystallinity can be induced via drawing processes. Polymerization is bulk or solution with an excess of EG as solvent. Poly(p-hydroxybenzoic acid) is completely aromatic.. This packing.. dimethyl terephthalate.270 °C  low MW polyester 200 °C 3 hrs CH3OH 280°C. PET melts at 260 . H2SO4 H3C O O O C C excess O CH3 + HO CH2 CH2 OH ethylene glycol dimethyl terephthalate linear. Mylar film) mp. high MW PET (Dacron fiber. is the most important . The polymer is melt pressed into sheets (Mylar) or drawn into fibers (Dacron..e. they polarize light when an electrical potential (voltage) is applied to them. i. = 260 .e.Linear Thermoplastics: In theory. gives rise to a relatively high melting point.   TPA is high melting (sublimes at 300 C) and insoluble in most solvents so its dimethyl ester is used. many are possible. Poly(ethylene terephthalate). Terylene. calculators. PET. coupled with the short distance between the polar ester groups. The aromatic groups increase the polymer’s rigidity..270 C. Fortrel). etc.. i. 116 . which melts at 141 C and is soluble in CH3OH or ethylene glycol (EG). It also creates unusual optical properties. Such aromatic polyesters make up the liquid crystals of LCD watches.

O C O.  The product is a noncrystalline. PC is sold under the trade name ‘Lexan’ or ‘Merlon’.  The diol is 2. its derivatives (phosgene or diphenyl carbonate) are used. impact resistant thermoplastic with a melting point of ~230 C.Na+ sodium carbonate O O O R O C O n polycarbonate R R C O polyester R n Poly(-caprolactone): by polymerization of -caprolactone is one example of a polyester produced by ring opening (rearrangement) of cyclic esters. mp = 230 °C bisphenol A Diphenylcarbonate is much a less toxic substitute for phosgene gas. H2CO3) are famous for their impact resistance and optical clarity. NaOH.  Since carbonic acid is unstable. O HO C OH carbonic acid Na+ . polycarbonates are structurally different than polyesters. commonly called ‘bisphenol A’. it is bullet proof (‘bullet proof glass’).Polycarbonates: (polyesters of carbonic acid. When cast in sheets of 1 inch thickness. Most prescription ‘plastic’ eye glass lenses are made of polycarbonate. O CH3 HO C O H + O C O 200°C vacuum CH3 bisphenol A  3 OH Lexan + phenol diphenyl carbonate Note that even though both are produced from the reaction diols with diacid chlorides. O Cl C Cl + HO C O CH3 phosgene carbonyl dichloride  3 CH3 1 + H Cl 1 2 O 2 C Cl HCl polycarbonate (PC) Lexan. transparent. O O -caprolactone H+HSO4- poly(-caprolactone) 117 . The base (pyridine or NaOH) consumes the by-product HCl and forces the reaction.2-bis(4-hydroxyphenyl)propane. or into a suspension of bisphenol A and methylene chloride which is stirred in aq.  Phosgene gas is so reactive that is can be simply bubbled into a solution of bisphenol A in pyridine at room temperature.

Glycerol is trifunctional. R O H R O C O R O C O C O O C O H O C O O R R O H R O H R +O H C O O C O C O R O H Study the formation of a crosslinked glyptal network HO CH2 O OH CH CH2 OH O C HO CH2 CH CH2 OH OH C O O O C C O OH HO CH2 CH CH2 OH O C O C O O O C HO CH2 CH CH2 OH OH O O CH2 CH CH2 C O O C O O C HO CH2 O O OH CH CH2 OH CH2 CH CH2 O O C C O O O C O C O O O C O C O HO CH2 CH CH2 OH OH O CH2 CH CH2 O C O C O O CH2 CH CH2 O O O C O C O O CH2 CH CH2 CH2 CH CH2 O O C O C O C O C O O O 118 . thermoset called a glyptal Sketch a mechanism for the reaction of phthalic anhydride with 2 molecules of alcohol. They react to form a 3dimensional crosslinked.Saturated alkyd polyester resins for paints: (Students: read ‘Lipids for Polymers’ on blackboard) Phthalic anhydride is difunctional.

119 . but they are added to other coatings to improve adhesion and gloss.Glyptals are brittle because of their high crosslink density and are thus unsuitable to be used alone as paints.

Metal ions of cobalt. The alkene groups in the unsaturated fatty acid esters are crosslinked by oxygen yielding a thermoset coating.Unsaturated Oil Modified Alkyd Paint: Triglycerides like tung oil are triesters of unsaturated fatty acids such as linoleic and linolenic acids. zinc. O CH2 CH OH O OH CH2 OH + CH2 CH CH2 OH C O CH2 CH R C O CH CH2 R O C C R HO R OH O CH2 CH2 O CH OH CH2 C C + O O OH O R OH OH CH2 O CH2 CH O HO CH2 R OH The diols are reacted with phthalic anhydride to produce a linear polyester alkyd paint. MEK. Paint manufacturers react glycerol with triglycerides in a two to one molar ratio in an ester exchange (transesterification) reaction producing difunctional glyceryl monomers (diols). HO CH CH2 OH C O O C HO CH2 O R C O CH CH2 OH O O CH2 O C C O O C R O O R C O CH CH2 O C O C O O CH2 CH CH2 O O CH2 O C O C C O C O O C O C O O O R C O CH O CH2 CH2 O C O C O O H2C CH CH2 O O O When the thermoplastic alkyd paint is applied to a surface. the solvent evaporates and exposes the thermoplastic to air. lithium. 120 . dissolved in a solvent such as xylene. lead. accelerate the oxidative crosslinking. etc. etc.

methyl ethyl ketone peroxide) is added at the time of application to initiate free radical crosslinking.  Short oils with few double bonds give hard durable finishes but require baking to cure (baked enamels). drying oils.g. Oil Modified Alkyds (for alkyd paints) As described on the previous page.. and may yellow on aging..  A small quantity of a free radical initiator (e. The modified polyols are polymerized by reaction with phthalic anhydride. The drying oils are modified by partial ester exchange with glycerol (glycerolysis). Triglycerides are triesters of fatty acids such as linoleic and linolenic acid. The polymer contains unsaturation (double bonds) from the drying oils and these crosslink in the presence of O 2 during air drying of the paint film.  Long oils with many double bonds give faster drying finishes which are softer. COOH H C C H HOOC fumaric acid phthalic anhydride O O C C O or HO CH2 OH x + O + O O HO CH2 + OH x maleic anhydride O O CH2 x O C O CH CH C O CH2 x O O O C C CH This low MW unsaturated polyester is dissolved in styrene O CH2 O and crosslinked with methyl ethyl ketone peroxide H3C C O O CH2CH3 121 . vinyl benzene. linseed oil and tung oil. i. Promoters such as Co naphthanate are added to accelerate the crosslinking. less durable.e.Unsaturated. producing a viscous solution. are naturally occurring triglycerides. e..  Polymerization is carried out until a low MW linear unsaturated polymer liquid is obtained. Unsaturated Polyesters: (for FRP) The most common is produced from a glycol (diol) and either maleic anhydride or fumaric acid. This is dissolved in styrene. Phthalic anhydride is also copolymerized to reduce the crosslink density and hence reduce brittleness.g.

(psi) Modulus (psi) Tm (C) H2O absorption (%) $/ lb. business equipment housings.000. and high strength arise from the aromatic groups and from its polarity  polyesters are not self-extinguishing but can be made so by the addition of chlorine containing reagents or with antimony trioxide.000 500. sterilizable food packaging PC:  outstanding optical clarity (low crystallinity) and impact resistance but poor scratch resistance and UV sensitive. recyclable bottles. molded bath tub and shower inserts.Properties and Applications of Polyesters: s.000 245 . Tensile St.000 .000 thermoset 0. lamp sockets.3 . % Crystallinity PET: PET resin PC resin PE thermoset FRP 1.3 15.g.3 10.resists alcohols and dilute acids or bases but is attacked by oxidizers. electronic parts and appliance housings.p. strong acids and bases. and Fortrel  PET films include Mylar  PET resin applications include pump housings. Unsaturated (Crosslinked) Polyesters:  primary use is for FRP usually with chopped glass fibers in auto bodies (Corvette).40 1. low CO 2 permeability.6 1 1 < 50 1. insulator)  high m. light duty gears. moderate polarity and low HOH absorption. high impact resistance and strength.000 > 1.. bulletproof windows (Lexan).265 1. electrical switches and connectors. high m.  poor chemical resistance.2. and many solvents such as HC’s (especially aromatics)  PC resin applications include break resistant lenses for eyeglasses. auto ignition coils.5 low   PET is an engineering resin low crystallinity.5 0. microwaveable containers. Oil Modified Alkyds: 122 . electric hand tool housings. good optical clarity.  high temperature resistance. auto tail lamp lenses.000 270 1. moderate polarity and low moisture absorption. good electrical properties (i.30. Terylene.2 10..e.000 350.5 20 . boat and auto body repair kits.  PET is FDA approved for food service  PET fibers include Dacron.p.

 primary use is in alkyd enamel paints 123 .

The mixture is separated by fractional distillation. and Union Carbide silicone elastomers and sealants for high temperature applications. 124 . G.  The R-group is commonly methyl or phenyl Polymerization: + R2SiCl2 Bulk polymerization via hydrolysis is most common 2 H2O + 2 HCl R2Si(OH)2 a dialkylsilanediol R HO R Si OH + HO R Si OH R R H2O HO  R Si R O Si R O H a linear polysiloxane ( a silicone) n O O H3C C acetate ester end group R O Si R R R O Si R Si O R n O O C Na+ -O CH3 acetate ester end group C CH3 sodium acetate NaOH Before the polysiloxane reaches a high molecular weight.E.g. The acetate groups replace the OH end groups capping the polymer. In this condition. the polysiloxane is stable for months if protected from the atmosphere. Monomer Preparation: tetrachlorosilane SiCl4 (g) Grignard + CH3MgCl MgCl2 + CH3SiCl3 trichloromethylsilane (a trifunctional monomer) + (CH3)2SiCl2 dichlorodimethylsilane (a difunctional monomer) MgCl2 CH3SiCl3 + (CH3)2SiCl2 + CH3MgCl MgCl2 + (CH3)3SiCl chlorotrimethylsilane (monofunctional) (CH3)3SiCl + CH3MgCl MgCl2 + (CH3)4Si tetramethylsilane (unusable) CH3MgCl  A 2:1 ratio of RMgCl : SiCl4 produces mostly difunctional dichlorodimethylsilane monomer. Dow Corning. the reaction is halted by addition of sodium acetate..SILICONES (Polysiloxanes) e.

Upon exposure to moisture (in air or water).. 170 C RTV = room temperature vulcanizing (curing) includes stannous octoate catalyst which accelerates the ionic catalyzation  CH3 groups impart low surface tension and high water repellence. The odour of vinegar is distinct.e.e... i. Silicone rubber/elastomers: high MW (>50. linear dimethyl silicone polymer.e. poly(dimethylsiloxane)  C6H5 groups impart water repellence and high temperature stability. i. i.. the acetate end groups are hydrolyzed back to OH groups and the polymerization resumes until a high molecular weight is attained. methyltrichlorosilane or vinyl silicone monomer + peroxide catalyst for free radical crosslinking.e.e. O O H3C R R Si R Si O O O C CH3 O H H3C O R R R n C Si R H O Si H R O H R R H + Si O C R n Si O n O H R Acetic acid is liberated as polymerization proceeds. poly(diphenylsiloxane) CH3 CH3 Si CH3 Si O n O CH3 poly(dimethylsilicone) Si Si O O n poly(diphenylsilicone) 125 . Silicone oils: low MW. HTV = high temperature vulcanizing (curing).000) polymer incorporating variable amounts of trifunctional monomer for crosslinking. i. i.. a small amount of monofunctional units (trimethylchlorosilane monomer) is added to control MW by terminating chains.

g. e...g. i.. for high temp.e. the most flexible material known  excellent high temperature stability (Tm > 300 C)  polar. transparent to UV and high oxidative resistance  nontoxic and environmentally safe  Low Tensile strength (only a few hundred psi but with SiO 2 filler can achieve 2000 psi)  expensive ($2-$6/lb) Applications of Polysiloxanes:  hydraulic fluids (especially for aviation)  heat exchange fluids.Properties of Polysiloxanes: Silicone Oils:  low freezing point and low temperature coefficient of viscosity Silicone Rubbers and Elastomers:  excellent low temperature flexibility (Tg = -130 C).  immune to UV. chemically resistant. waxes  good dielectric.e. mp determination  glass sizing (couples glass fibers to organic C when the functional group is on the -C)  water repellent coatings.g. i. no cholesterol oils for deep frying  Surperballs and Silly Putty 126 . hydrophobic. e. e. silicone insulation on auto ignition wires  gaskets. waterproof sealers for brick  greases. seals  caulking (RTV)  mold release agents  heart valves. car polishes. nonflammable..

. 2 CHClF2  CF2=CF2 + 2 HCl 4.e.e. and suspension polymerization in water. i. PTFE production grew to commercial scale in < 10 years. and some perfluorinated solvents boiling near 300 C. exceptional ‘lubricity’ (non-stick). emulsion. 2 HF + CHCl3  CHClF2 + 2 HCl SbF3) 3.e.FLUOROCARBON POLYMERS Fluorocarbon polymers are expensive ($5-$27/lb) but have several outstanding properties.  PTFE has an unusually wide temperature service range. i.e.. The polymerizations are very exothermic and temperature must be controlled to avoid explosions.e. n CF2=CF2  -( CF2-CF2)n- (catalyst = SbCl5 + (catalyst = peroxides) Properties:  PTFE is highly polar but has no H-bonding. i. Tm = 327 C and Tg < -100 C  PTFE has the highest dielectric constant of any polymer. best electrical insulator  It is non-flammable but emits toxic and corrosive fumes when thermally decomposed. waxy) and similar tensile strength. Various organic and inorganic peroxides are used. Because of its exceptional properties. CaF2 + H2SO4  2 HF (g) + CaSO4 (s) 2. Even O 2 catalyses these polymers.. no leaks. PTFE has the lowest coefficient of friction of any solid material. It is subject to creep under load and cold flow even when not stressed.  The tight. Na in kerosene solvent.. which accounts for its use in non-stick finishes. no H’s. It naturally crystallizes to > 90% crystallinity and is thus a white opaque material (not transparent).  The tight bonding also accounts for its natural lubricity. zero HOH absorption. The polymer is produced by bulk. i. ~3000 psi. strong fluorine-carbon bonds make it the most chemically resistant thermoplastic polymer.  The commercial process is as follows. 1. and excellent thermal resistance. Investigation revealed that the gas had spontaneously polymerized to a white.. waxy solid. PTFE [poly(tetrafluoroethylene)]:  PTFE constitutes ~ 90% of all fluorocarbon polymer production  It was accidentally discovered in 1938 by a technician at Du Pont noticed that a sealed drum of tetrafluoroethylene gas decreased in pressure without a corresponding mass reduction.  The polymer has the hardness and texture of PE (i. 127 . PTFE... It is attacked by only a few chemicals such as F 2. unparalleled chemical resistance.  All fluorocarbon polymers are made by addition polymerization using free radical catalysis.

heated extrusion and screw injection. i.Processing:  The melt viscosity of PTFE is too high for it to be processed by conventional thermoplastic methods. Its melting point is very close to its decomposition temperature.. 128 .e.

Teflon  129 .Poly(tetradifluoroethylene).

The PTFE powder is pressed into a mold and subjected to high pressure near its melting point.  CTFE (Tm = 218 C) is second only to PTFE in chemical resistance. The process is called ‘sintering’. The edges of the powder fuse together leaving some voids.2. and fire detection devices.2-trifluoroethene via peroxide  Replacing a single F with Cl. chutes. diameter. valve and pump parts.(free radical addition hexachloroethane catalyst) 1-chloro-1. Emulsion and suspension polymerized beads of ~ 0. CCl3CCl3 + 3HF  CClF=CF2 + 3HCl + Cl2 -(CClF-CF2)n. fabric coatings. It has low crystallinity (is atactic) and thus has higher transparency. Simply contoured parts including gaskets and o-rings are produced by this process. It is widely used in microphones.  PTFE is also extruded under high pressure using a heated ram rather than a screw.5 mm diameter are applied as suspensions in oil to form nonstick coatings (the oil or solvent is removed by heating after application).  low molecular weight polymer is used as lubricating greases and oils Other Fluoropolymers: FEP: fluorinated ethylene propylene copolymer is the second largest production fluoropolymer CF2 = CF2 + CF3CF = CF2  -(A-B-A-B-A-B)TFE perfluoropropylene alternating copolymer  Its applications are much the same as PTFE PVF2: poly(vinylidene fluoride) -(CH2-CF2)n-  PVF2 is the most efficient piezoelectric (generation of electricity on deformation) polymer. Many PTFE products are produced by a powder metallurgy technique. retains many of the properties of PTFE but allows conventional processing (screw injection & extrusion). Applications:  flexible printed circuits. burglar alarms. laboratory containers. gaskets. electronic / computer terminal covers. Polymer beads or powder is used as antifriction additives in lubricants and specialty waxes. tubing. Fluoroelastomers: 130 . CTFE [poly(chlorotrifluoroethylene)]  CTFE is commonly sold under the trade name ‘Kel F’. pipe liners. This allows production of rods and hollow tubes up to 2-in. Applications:  chemical storage tank liners. electrical wire insulation as in ovens and as thermocouple leads.

leaving chain radicals to join in carbon-carbon crosslinks. which also contain some hydrogen. It is sold under the trade name ‘Viton’ and is used to manufacture a variety of thermal and chemical resistant o-rings and seals. a copolymer of perfluoropropylene (hexafluoropropylene) and PVF 2.g. e. Many fluorine-based copolymers. can be crosslinked to produce elastomers. One example is FPM rubber. Peroxides can be used to abstract hydrogen atoms. 131 . for high vacuum and cryogenic equipment..

.and tri-substitution is common. stiff.. methylolphenol difunctional monomer O + O O H C H O C H H OH dimethylolphenol trifunctional OH monomer OH HOH2C CH2OH CH2OH OH CH2OH trimethylolphenol tetrafunctional monomer CH2OH CH2OH CH2OH O O O CH2OH HOH2C CH2OH H CH2O repeat CH2O CH2OH repeat CH2OH 132 .PHENOL-FORMALDEHYDE POLYMERS Phenol-formaldehyde condensation polymers.74 O O O O Nucleophilic addition of phenoxide to the electrophilic carbon in formaldehyde results in o.and p-substituted methylolphenols.2:1). 1. + H2O pKb = -1. You will recognize phenol-formaldehyde thermoset polymers as high-temperature resistant. : OH. the initially formed product (called a resole) can be cured to a thermosetting polymer simply by heating. a weak acid. constituting a two-component system. Using an acid catalyst and an excess of phenol over formaldehyde. is deprotonated forming a resonance-stabilized phenoxide anion. the initial product (called a novolac).9 Na+ O . were the first true synthetic polymers to gain commercial importance (recall that Leo Bakeland-1907 made ‘Bakelite’). Mechanism of Resole formation: (‘One-step resin’) In the presence of a hydroxide base. often referred to as ‘phenolic resins’. Phenol-formaldehyde resins are normally prepared by two different methods. Cellulose nitrate was developed earlier [1868] but this is derived from a natural polymer. Using a base catalyst and an excess of formaldehyde over phenol (ca. O H Na+ + phenol pKa = 9. requires the addition of more formaldehyde to effect curing. 1. Since phenoxide is reactive. constituting a one-component system. phenol (pKa = 9.9). 2. in the presence of excess formaldehyde. di. cooking pot handles.

[Although the oxygen atom in phenoxide. acid catalyst O C H O H O H H + Nu:resonance form of phenol H H H O H H H H E+ protonated formaldehyde O+ H H H H O O C H H O+ CH2 OH O H CH2 OH repeat methylolphenol 133 . The heat of the press causes crosslinking and drives off the water as steam. Electrophilic aromatic substitution on the activated aromatic (phenol) occurs at the o. For example. is unstable. The mixture is spread on the surface of the wood veneers prior to placing them in a hot press. : OH OH O HOH2C . . Mechanism of Novolac Formation : (Two-step resin) In the presence of acid catalyst.. Multiple substitution is common.] The methylolphenols condense out water via S N2 on heating to give resoles. which are low MW. a hemiacetal. has greater electron density.. O HOH2C H ..and p-positions producing methylolphenols.. OH O + + OH H HOH2C H2C H H2O : OH- SN2 O HOH2C CH2 OH CH2 repeat OH OH HOCH2 CH2 CH2 CH2OH CH2OH OH CH2OH CH2 Resole low MW prepolymer CH2OH OH They are normally processed to the desired viscosity. the carbonyl oxygen is protonated producing a very electrophilic carbonyl carbon. then subsequently polymerized to a high MW network polymer (called a resite) by further heating (and thus further condensation). water-soluble prepolymers. addition does not occur at this site because the product. because of its greater electronegativity. . plywood adhesives are prepared by mixing additives such as wood flour with the basic resole solution.

The A-stage is mixed with additives (including hexamethylenetetramine in the case of novolac) and then heated to a higher MW 134 . During heat curing. soluble. and the solid product is ground to a powder. more formaldehyde must be added. then water is removed under vacuum. It is referred to as the A-stage. At this point. H O O+ H H H O H O H H O SN2 O HO methylolphenol OH CH2 O CH2 OH2 CH2 OH H H O ether H CH2 O CH2  H CH2 O H H H O+ OH CH2 CH2O OH OH H repeat CH2 H The novolac is also formed by acid catalyzed electrophilic aromatic substitution of benzylic carbocations on phenol rings.groups for crosslinking). solid hexamethylenetetramine (‘hexa’) is added.  NH3 H2O + H2O NH4+ OH- CH2O hexamethylenetetramine Commercial production of both resoles and novolacs involves 2 basic steps. crosslinked resite. Alternately.A low MW prepolymer (novolac) is formed when methylol groups interact to produce ether links via acid catalyzed S N1 and/or SN2 reaction. The monomer and catalyst are reacted in aqueous solution to a relatively low viscosity. These ether links later condense out formaldehyde when heat cured (methylene bridges remain). and fusible. the polymer is relatively low-MW. hexa releases formaldehyde and ammonia (providing alkaline OH. H O H H O+ H CH2 OH H O O H H H2O OH H O CH2 OH2 CH2 H OH H O H H CH2 + methylolphenol O+ O H OH CH2 + H O H H In order to cure the novolac to a high MW.

HDPE @ 200. 1. HDPE @ 3000-6000 psi) Applications: usually via transfer molding processes  pot and cutlery handles  electrical switches and duplexes  adhesive for laminating plywood and grinding stones  used in lacquer and varnish formulations  automotive water applications) pumps and intake manifolds (Engineering resin 135 . 180 ºC and good dimensional stability  good dielectric strength (electrical insulator)  good chemical resistance .B-stage (still thermoplastic). 60¢/lb (cf.4  tensile strength ca.6%  cost ca.000 ! (very stiff) (cf.attacked by strong bases and oxidizers  water absorption ca.000. Temp. The B-stage is applied to paper or wood before final heat curing to the crosslinked C-stage in the final molding operation. 7000 psi  tensile modulus > 1. Properties of typical phenol-formaldehyde thermoset resins:  specific gravity ca. use ca. 0.000 psi)  max.

a good nucleophile. metal. We will study the epoxy which makes up > 85% of all formulations.g.e. Na+ CH3 HO C CH3 O O Na+ + CH2 CH HO CH2 Cl C O O CH2 CH CH2 Cl CH3 CH3 3. The epoxide ring reforms (one carbon over) as an intramolecular S N2 displacement of Cl. The phenoxide anion attacks the electrophilic epoxide carbon. The weakly acidic phenol is deprotonated by NaOH producing phenoxide anion. There are a wide variety of formulations but the basic reaction is similar in most. Epoxide rings are easily opened as they have considerable ring strain... CH3 HO O C OH CH2 CH3 CH CH2 Cl 3-chloro-1..occurs when the alkoxide anion bonds with the electrophilic carbon in the terminal -CH2Cl group. e. Na+ CH3 HO C CH3 NaCl O O CH2 CH CH2 Cl CH3 HO C O O CH2 CH CH2 CH3 136 . epichlorohydrin in the presence of a base.g. . i. 60º bond angles.2-epoxypropane 'epichlorohydrin' 2. NaOH. DGEBPA (diglycidyl ether of bis-phenol A). or plastic is familiar with 2-part epoxy adhesives (glues). e.2-bis(4-hydroxyphenyl)propane 'bisphenol A' 1. The least hindered epoxide carbon is preferentially attacked and the epoxide ring opens producing an alkoxide anion. strong bonds can be obtained. notably the Chevrolet Corvette.EPOXIES Almost anyone who has tried to repair a broken household item made of glass. Formation of the thermoplastic prepolymer: An aromatic diol.. is reacted with an epoxy monomer.e. i. Epoxy adhesives have outstanding adhesion to many surfaces. bisphenol A.. Glass fiber reinforced epoxy resin (FRP) is used to construct boat hulls and some auto bodies. By mixing equal amounts from tube A (resin) and tube B (amine hardener).. CH CH 3 HO 3 C O HO H C CH3 Na+ O + H O H CH3 2. pKa = 10 Na+ : OHpKb = 4 . to produce a viscous liquid low MW prepolymer resin (Part A).

.. The newly formed terminal epoxide is opened by another phenoxide anion reforming the alkoxide. : OH- + CH3 CH3 HO C CH3 OH O CH2 CH CH2 O C CH3 O + H O H 137 . : OH- + OH CH3 Alkoxides (pKb = -2) are more reactive than phenoxides (pKb = 4) so the alkoxide is protonated by HOH producing OH.. less energetic group (phenoxide) is produced as a more reactive group (alkoxide) is destroyed (as is the case in all spontaneous reactions). CH3 HO CH3 O C CH2 O CH O CH2 C CH3 CH3 CH3 HO OH CH3 O C O CH2 CH CH2 O C CH3 OH CH3 and the alkoxide is finally protonated (converted to an alcohol) by H 2O. In effect a more stable..4. .. H CH3 HO O H CH3 O C O CH2 CH O CH2 C CH3 CH3 CH3 HO OH CH3 OH C O CH2 CH O CH2 C CH3 .which is reprotonated to HOH by reaction with more phenol. CH3 HO C CH3 OH O CH2 CH CH2 O CH3 C CH3 O H .

a polyamine hardener is used. Polymerization continues along the main chain. an anhydride is used which reacts with the -OH groups forming esters and joining chains. O 5. CH3 HO CH3 OH C O CH2 CH CH2 O O C CH3 O CH3 + CH2 repeat CH CH2 Cl epoxy polymer Since at least a 2-fold excess of epichlorohydrin is used. NH 2CH2CH2-NH-CH2CH2-NH2 (diethylenetriamine).5. In some cases..g. During the reaction. 1° amine O + CH2 CH CH2 H2N 1° amine 2° amine CH2 CH2 NH O + CH2 CH2 NH2 H2C CH CH2 diethylenetriamine H O CH2 CH N CH2 H CH2 CH2 NH H OH CH2 CH N H H2C CH CH2 H 2° amine CH2 CH2 CH2 N O CH2 CH2 NH 2° amine CH2 CH2 N OH H2C CH CH2 H 138 . Each of the amine groups can react with terminal epoxy groups of the prepolymer to form a hard 3-dimensional thermoset epoxy polymer. the prepolymer is typically only 6 to 10 units long and has epichlorohydrin units at each end. CH2 CH3 CH CH2 O C OCH2CHCH2 O CH3 OH C O CH2CH CH2 CH3 CH3 n Curing the prepolymer to thermoset with hardener: The prepolymer is crosslinked (cured) by the addition of Part B (the hardener). More commonly. NaOH is consumed and NaCl (brine) is produced. e.

Both an excess or deficiency of hardener can cause poorly developed crosslinking.0. ca.6 .. 200 ºC  water absorption ca.000 .000 psi.2. many amine hardeners cause severe skin irritation and skin discoloration.02 . Important properties of thermoset Glass Reinforced Epoxies (FRP epoxy):  specific gravity ca.20. Handle them appropriately. excellent adhesives  protective coatings. (resists strong acids and bases and solvents)  high dielectric constant (good electrical insulating ability) Applications of epoxies:  boat hulls and auto bodies (when glass fiber reinforced)  outstanding adhesion to many surfaces.e. (very stiff)  max use temp. i. 0.4 %  cost ca. 1.000 psi. In addition to their objectionable amine odour..0  tensile strength ca. > 2.  tensile modulus ca. e. epoxy paints  chemical tank liners for chemical industry  printed circuit boards for electronic components 139 .000.g.00/lb  chemical resistance is good. $1.OH OH CH2 CH CH2 N CH2 CH2 NH CH2 CH2 N H H2C O again CH2 H2C CH CH2 OH OH CH2 CH CH2 H O CH2 CH CH CH2 N CH2 CH2 NH CH2 CH2 N CH2 HO CH CH2 H2C CH CH2 CH2 3-dimensional thermoset epoxy polymer CH OH CH2 The proper ratio of epoxy to hardener must be used. Follow the manufacturer’s recommendations. 10.