Richard F. Daley and Sally J.

Daley
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Organic
Chemistry
Chapter 22

Polymer Chemistry
22.1 Structural Characteristics of Polymers 1138 22.2 Polymer Nomenclature 1141 22.3 Types of Polymerization Reactions 1144 22.4 Chain-Growth Polymerization 1146 Synthesis of Poly(vinyl acetate) 1155 Sidebar - Natural Rubber 1155 22.5 Controlling Stereochemistry in Vinyl Polymers 22.6 Nonvinyl Chain-Growth Polymerization 22.7 Step-Growth Polymerization 1163 Synthesis of Poly(ethylene terephthalate) Sidebar - Plastic Recycling 1167 22.8 Copolymers 1169 Sidebar - Plasticizers 1172 22.9 Cross-Linked Polymers 1173 Key Ideas from Chapter 22 1178

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Copyright 1996-2001 by Richard F. Daley & Sally J. Daley All Rights Reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior written permission of the copyright holder.

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Chapter 22

Polymer Chemistry
Chapter Outline
22.1 22.2 22.3 22.4 22.5 22.6 22.7 22.8 22.9 Structural Characteristics of Polymers
A look at the various types of polymers

Polymer Nomenclature
An introduction to naming polymers

Types of Polymerization Reactions

Categories of polymer forming reactions

Chain-Growth Polymerization
The mechanism for the formation of vinyl chain-growth polymers

Controlling Stereochemistry in Vinyl Polymers

The Ziegler-Natta polymerization catalyst for vinyl polymers

Nonvinyl Chain-Growth Polymerization

Mechanisms for chain-growth polymer formation for nonvinyl polymers

Step-Growth Polymerization
The mechanisms for the formation of some representative stepgrowth polymers

Copolymers
An examination of the various types of copolymers

Cross-Linked Polymers
Types of cross-linking that occur in polymers

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Objectives
Recognize the various types of polymer structures Know how to name both source-based and nonvinyl polymers Recognize the monomers that produce polymers Write the mechanisms for cationic, anionic, and radical polymerization of vinyl monomers Know the stereochemical types of vinyl polymers Write the mechanism for representative non-vinyl chain-growth polymerizations Recognize the similarity of the step-growth polymerization reactions to those studied in earlier chapters Know the types of copolymers Recognize how cross-linking occurs in epoxy polymers

Observation is a passive science, experimentation an active science. Claude Bernard

A polymer is a molecule made up of many smaller units called monomers.

A reaction forming a polymer is a polymerization reaction.

polymer is a large molecule that consists of a number of smaller repeating units made from molecules called monomers. Polymers are formed by some repetitive reaction that adds these monomer units one-by-one to the growing chain of the polymer. The process of converting the monomer units to a polymer is called polymerization. Polymers, sometimes called macromolecules, affect your life in many ways. For example, plastics are synthetic polymers, and they are all around you. Industry makes plastics into such things as fibers, structural materials, and protective films. Except for fuels, more plastics are manufactured in the world than any other organic material. One-third of all industrial chemists work in the polymer industry. Another way that polymers affect your life is in the natural chemistry of the life processes. Proteins and enzymes are polyamide polymers. Proteins are an important part of the structure of all animals, and enzymes catalyze the chemical processes that make

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those bodies function. Cellulose and starches are polymers of individual sugar molecules. Cellulose is the structural material of plants, and starches are the energy storage medium for plants. Both RNA and DNA are polymers of individual nucleic acids. These two classes of molecules control the genetic make-up of your body. This chapter focuses primarily on synthetic polymers. Chapters 24 and 25 cover some types of natural macromolecules. Generally, the size and stereochemistry of the polymer molecule determine the properties of that molecule. This chapter examines how those features determine a polymer's physical properties. This chapter also discusses polymer synthesis.

22.1 Structural Characteristics of Polymers

The composition of polymers is a sequence of repeating monomer units that are covalently bonded together. The reactions that connect these repeating units can involve any of the functional groups discussed previously. The functional group on the repeating unit provides the reactive site for the connecting reaction. The repeating units of polymers have a variety of possible structures. When all the repeating units in a particular polymer have the same structure, that polymer is called a homopolymer.
nA A A A A A A A A or An

In a homopolymer, all the repeating units are identical.

An example of a homopolymer is polyvinyl chloride.

CH2 CH Cl CH2CHCH2CHCH2CHCH2CHCH2CH Cl Cl Cl Cl Cl or CH2CH n Cl

Polyvinyl chloride

A copolymer contains more than one type of monomer unit.

When different repeating units make up the polymer chain, the polymer is called a copolymer. There are three types of copolymers: 1) alternating copolymers, 2) block copolymers, and 3) random copolymers. If you designate the repeating units as A and B, the following illustration shows representations of these three types of copolymers.
Alternating copolymer nA + nB A B A B A B A B

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Block copolymer mA + nB Random copolymer mA + nB A B B B A A B B A A A A A B B B

An example of the alternating copolymer is Nylon 66.

O O O O n

n H2N(CH2)6NH2 + n ClC(CH2)4CCl

NH(CH2)6NHC(CH2)4C Nylon 66

A linear polymer is a molecule with a series of connected repeating units with no branching. A branched polymer has bonds branching from the backbone of a linear polymer. Cross-linked polymers are linear polymer molecules joined by a branching connection.

All the above examples are linear polymers. Some polymers contain additional covalent links to repeating units at various locations on the backbone. Such polymers are called branched polymers. Linear or branched polymer chains can be connected by some additional covalent links. These polymers are called crosslinked polymers.
Polymer End Groups
The structural drawings of all the polymers discussed in this chapter show a bond extending out of the brackets that enclose the repeating unit. The functional groups on the ends of the polymer chains are left unspecified because the end groups are an insignificant portion of the total chain. These groups have very little effect on the physical properties of the polymer. In a given sample of polymer, a variety of end groups may be present depending on how the polymer was synthesized.

Compressive, flexural, and tensile strength, as well as impact resistance are measures of the mechanical strength of a polymer.

The physical properties of a specific polymer are the result of two molecular characteristics: 1) the length of the molecule and 2) the functional group associated with the repeating units. To determine the length of a polymer chain, chemists use the molecular weight of the polymer. Different polymers of the same chain length have similar physical properties regardless of the functional group present unless the functional group can hydrogen bond or disrupt the intermolecular van der Waals forces. These two interactions are more important in determining the physical properties of the polymer than is the molecular weight. The physical properties of interest to a consumer are those that show how well the polymer performs in response to various stresses. These responses include compressive, flexural, and tensile strength, as well as impact resistance. Compressive strength is a measure of how much compression a sample can tolerate before it

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The molecules of a crystalline polymer line up in a regular way similar to the smaller molecules in a crystal.

fails. Flexural strength is a measure of resistance to breaking or snapping when the sample is bent. Tensile strength is a measure of resistance to stretching. Impact resistance is a measure of how well a sample resists damage from a sudden impact. Some polymers have the characteristics of a crystalline solid. Crystalline polymers have chains that tend to orient themselves in a regular way, similar to the way the molecules in a crystalline solid orient themselves. The chains are held together in this regular orientation by hydrogen bonds or dipole alignments. These polymers generally have characteristic melting points, are strong, and nonelastic. Linear polyethylene is an example of such a crystalline polymer.

Orientation of the chains of a crystalline polymer

The molecules in an amorphous polymer do not have any preferred alignment. A glassy solid is a solid that is often hard and brittle.

Amorphous polymers are similar to glassy solids. Amorphous polymers do not have a characteristic melting point. Instead, they often make an indistinct transition from the glassy solid to a viscous liquid called the glass transition temperature. These polymers do not have a regular orientation in the solid state. Amorphous polymers are generally not particularly strong and tend to be quite elastic. Rubber is an example of an amorphous polymer.

The glass transition temperature is the temperature at which a polymer transforms from a glass to a viscous liquid

Orientation of the chains of an amorphous polymer

Ordered regions among the amorphous regions in a semicrystalline polymer are called crystallites.

Many polymers are neither completely crystalline nor completely amorphous. Segments of the chains lie parallel to each other in regions called crystallites. Other segments of the chains are not ordered. Such polymers are called semicrystalline polymers. These polymers have much of the strength of a crystalline polymer along with much of the flexibility of an amorphous polymer. Nylon is an example of a semicrystalline polymer.

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Semicrystalline polymers are polymers with regions of disorder and crystallites.

Crystalline regions (Crystallites) Amorphous region

Orientation of the chains of a semicrystalline polymer

Crystalline polymers generally are opaque, but amorphous polymers generally are transparent. Thus, increasing the number of crystallites in a polymer normally reduces the transparency of the polymer. An example is polystyrene. Amorphous polystyrene is found in a number of transparent, brittle "plastic" items, such as drinking cups.

22.2 Polymer Nomenclature

The IUPAC has proposed some logical rules for naming polymers, but polymer chemists seldom use them because many polymers are so branched and cross-linked that their names are very complex. Thus, this section is only an introduction to the fundamentals of naming polymers. Many polymer chemists use source based naming. They name the monomer then add the poly- prefix. A complication with this method is that chemists use the common names of the monomers more often than their IUPAC names. For example, the common name for ethenylbenzene is styrene, so chemists call the polymer of styrene polystyrene. In addition to using common names, chemists refer to many polymers by their trade names. They use the trade name Teflon more frequently than the IUPAC name of polytetrafluroethylene. Vinyl polymers are among the easiest polymers to name when following the common name method. Simply use the monomer's common name with the prefix poly-. If the monomer's name includes more than one word, or if a letter or number precedes the name, enclose the monomer's name in parentheses. Thus, the polymer of 1pentene is poly(1-pentene). Table 22.1 lists a few common names for vinyl polymers.

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Monomer
CH2 CH2 CH2 CHCH3

Monomer Name
Ethylene Propylene

Polymer
CH2CH2 n

Polymer Name
Polyethylene Polypropylene

CH2CH CH3

CH2 CHCN

Acrylonitrile

CH2CH CN

Polyacrylonitrile

CH3 CH2 C COOCH3

Methyl methacrylate

CH3 CH2C n COOCH3

Poly(methyl methacrylate)

CH2 CH OCCH3 O CH2 CHCl

Vinyl acetate

CH2CH

n OCCH3 O

Poly(vinyl acetate)

Vinyl chloride

CH2CH Cl

Poly(vinyl chloride)

CH2 CH

Styrene

CH2CH

Polystyrene

CF2 CF2

Tetrafluoroethylene

CF2CF2

Polytetrafluoroethylene

Table 22.1. Representative names for some vinyl polymers.

Nonvinyl polymers generally have some atom other than carbon as a part of the backbone of the polymer. As with the vinyl polymers, the nomenclature of these polymers is often source based or based on their trade names. Nylon is an example of a family of compounds that chemists call by their trade names. To name them, use the word Nylon followed by a number for the number of carbons in the monomer(s) for that Nylon. Nylon 6 is a polymer made from monomers that consist of a single cyclic amide with six carbons. The monomers in Nylon 68 are diamines with six carbons and dicarboxylic acids with eight carbons.

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NHCH2CH2CH2CH2CH2CH2NHCCH2CH2CH2CH2CH2CH2C n From a 6 carbon amine From an 8 carbon carboxylic acid Nylon 68

Table 22.2 lists a few representative nonvinyl polymer names. Monomer

O CH2 CH2 O
Propiolactone

Monomer Name
Ethylene oxide

Polymer
CH2CH2O

Polymer Name
Poly(ethylene oxide)

O OCH2CH2C n
O CO n

Polypropiolactone

O
HOCH2CH2OH +
O HOC O COH

Ethylene glycol + Terephthalic acid

O CH2CH2OC

Poly(ethylene terephthalate)

O O NH
Caprolactam

NH(CH2)5C

Polycaprolactam

n
O O n

Nylon 6 Poly(hexamethylene sebacate) Nylon 68

H2N(CH2)6NH2 + HOOC(CH2)6COOH

Hexamethylenediamine + Sebacic acid

NH(CH2)6NHC(CH2)6C

Table 22.2. Representative names for some nonvinyl polymers.

Exercise 22.1 Name the following polymers and draw structural formulas for the monomers that form each of the polymers. a)
CH2CH n CH2CH3

b)
O OCH2CH2CH2C
n

c)
CH2CH n OH

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d)
n

e)
CH3 CHCH n CH2CH3

f)
O O n NH(CH2)6NHC(CH2)4C

Sample solution b) Polybutyrolactone

O O

22.3 Types of Polymerization Reactions

Chemists classify polymerization reactions in terms of their reaction mechanisms. There are two types of polymerization reaction mechanisms: 1) chain-growth polymerizations and 2) stepgrowth polymerizations. A chain-growth polymerization begins when an initiator reacts with a monomer molecule to create a reactive site. This reactive site then reacts with another monomer molecule joining the two, as well as creating a new reactive site. Monomer molecules continue adding to the reactive site and forming a new reactive site as long as monomer molecules are available or until some termination reaction occurs. A polymer that forms via a chain-growth polymerization usually forms from one monomer or group of monomers with the same reactive functional group. The formation of polyethylene from ethylene in the presence of an initiator is an example of a chain-growth polymerization.
CH2 CH2 Initiator CH2CH2 n

Chain-growth polymerization adds monomer units with the same functional group to the chain. In step-growth polymerization, one functional group at the end of the chain requires a different functional group to react and lengthen the chain.

Polyethylene

The mechanism for a chain-growth polymerization is often a radical reaction. As you read through the description of the chaingrowth polymerization above, you may have recognized the initiation, propagation, and termination steps from the radical reaction that you studied in Chapter 21. However, not all initiators generate radicals in the initiation and propagation steps; instead, many generate cationic or anionic intermediates. The important consideration is not whether the reaction proceeds as a radical reaction or generates a cationic or

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anionic intermediate, but that the initiator makes the chain reaction possible. A step-growth polymerization begins with a mixture of monomers that contain different functional groups. Although the mixture can contain numerous different functional groups, for simplicity look at how the reaction proceeds with a mixture of monomers that contains only two different functional groups. Each functional group type can react with the other type in the mixture but not with itself. The chain begins when one monomer joins with another monomer containing the other functional group type. The first monomer then reacts with the end of this two unit chain. Unlike the chain-growth polymerization, a step-growth polymerization usually does not have a radical, cation, or anion at the end of the growing chain. Instead, the chain grows by the reaction of the functional group. The formation of Nylon 66 is an example of a step-growth polymerization.
O O

H2NCH2CH2CH2CH2CH2CH2NH2 + HOCCH2CH2CH2CH2COH O O NHCH2CH2CH2CH2CH2CH2NHCCH2CH2CH2CH2C n Nylon 66

The formation of Nylon 66 has two steps in the step-growth mechanism. A monomer containing the diamine and another monomer containing the dicarboxylic acid react joining the two. Either of the following two reactions then occurs. The diamine reacts with the carboxylic end of the two unit polymer, or the dicarboxylic acid reacts with the amine end. Subsequent reactions occur with the proper reagent reacting with the appropriate end of the growing chain. Step 1
O O H2NCH2CH2CH2CH2CH2CH2NH2 + HOCCH2CH2CH2CH2COH O O H2NCH2CH2CH2CH2CH2CH2NHCCH2CH2CH2CH2COH

Step 2

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H2NCH2CH2CH2CH2CH2CH2NH2

H2NCH2CH2CH2CH2CH2CH2NHCCH2CH2CH2CH2COH O O

H2NCH2CH2CH2CH2CH2CH2NHCCH2CH2CH2CH2CNHCH2CH2CH2CH2CH2CHNH2

OR
O O O H2NCH2CH2CH2CH2CH2CH2NHCCH2CH2CH2CH2COH O O O

HOCCH2CH2CH2CH2COH O O

HOCCH2CH2CH2CH2CNHCH2CH2CH2CH2CH2CH2NHCCH2CH2CH2CH2COH

Another possible second step that the step-growth mechanism can follow is the reaction of the amine end of one chain with the carboxylic acid end of another chain. When this occurs, instead of all the polymer molecules growing steadily at the same rate, some grow much more rapidly. This way of joining results in a wide variety of possible molecular weights, making it more difficult to predict the characteristics of the polymer in comparison to a reaction mixture in which each chain grows at a similar pace.

22.4 Chain-Growth Polymerization

Chain-growth polymers form from radicals, cations, or anions. Because a wide variety of monomers lend themselves so readily to the formation of radicals, most chain-growth polymerization reactions proceed via radical intermediates. Some monomers do polymerize with ionic initiators, but that number is far fewer than those that polymerize with a radical initiator. Chain-growth polymerization reactions usually form vinyl polymers. One such vinyl polymer is polystyrene. Polystyrene polymerizes under radical, cationic, and anionic initiation. This section examines all three. The radical polymerization of styrene uses benzoyl peroxide as the initiator. As with the radical reactions you studied in Chapter 21, a radical polymerization follows three steps: 1) the initiation step, 2) the propagation step, and 3) the termination step. In the first reaction of the initiation step, the benzoyl peroxide undergoes a homolytic cleavage to form two benzoyloxy radicals. In the second reaction of the initiation step, each benzoyloxy radical reacts with a molecule of styrene to form a benzylic radical.

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Initiation step

In the propagation step, the chain begins to grow as the benzylic radical reacts with a molecule of styrene to add the styrene and to form a new benzylic radical. This new benzylic radical then reacts with another molecule of styrene adding the styrene and forming another new radical. This process continues many times as the polymer chain lengthens. Once started, the rate of reaction is relatively high for a chain formation. Approximately 1500-1600 styrene monomer units add to the growing chain each second. Propagation step

The propagation reaction continues until it reacts in a termination reaction or until it uses up all the monomer molecules in the reaction mixture. The most common termination reaction combines two radicals from two growing chains to form a longer chain. This reaction terminates both chain reactions because the reaction forms no new radical. Termination step

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In a chain-transfer reaction, one growing polymer chain abstracts a hydrogen atom from another polymer chain.

Another reaction that occurs in radical chain-growth polymerization is a chain-transfer reaction. In a chain-transfer reaction, the end of a growing chain abstracts a hydrogen from the benzylic position of another chain. This abstraction creates a new radical in the middle of the chain.

H x y

H n + x

This new radical site serves as a reaction site for additional monomer molecules to branch off the main polymer chain.

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Exercise 22.2 A polymerization reaction involving 1,3-butadiene and a radical initiator forms two different repeating polymer units. Account for the formation of these two units.
CH2 CH CH CH2 CH2 CH CH CH2

Cationic polymerization is similar to radical polymerization in that both react with the initiator to form a reactive site on the same carbon of the styrene. To run cationic polymerization reactions, chemists use strong Brnsted-Lowry acids, as well as Lewis acids. When they use a Lewis acid, they must also use some hydrogen halide and water. The requirement for the hydrogen halide and water suggests an involvement of a proton acid in the reaction. Again using the polymerization of styrene as an example, look at the mechanism of a cationic polymerization. The initiation step in a cationic polymerization of styrene adds a proton to the double bond of the styrene to form a carbocation. Initiation step
H H

In the propagation step, the carbocation reacts with a molecule of styrene to form a new carbocation. This step repeats itself until the

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reaction either runs out of reactants or until the polymers react in a termination step. Propagation step

H H

Repeat

The reaction can terminate by losing a proton, by reacting with a nucleophile, or by the carbocation removing a hydride from another polymer molecule. All three of these steps are typical carbocation termination reactions. Termination step

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-H

Nu Nu

H n

The removal of the hydride from another polymer chain can lead to branching of the polymer chain similar to the branching in the radical reaction. Exercise 22.3 What product would you expect in a cationic polymerization reaction of styrene if you added 1% 1,4-divinylbenzene to the reaction mixture? What difference would you expect this small amount of added material to make in the properties of the polymer? The third type of chain-growth polymerization reaction presented in this section is an anionic initiation. Alkali metals or organometallic compounds catalyze some polymerization reactions. The reactive species in these reactions is a carbanion. Thus, the reaction is called an anionic polymerization reaction. Styrene is one of those compounds that polymerizes with an anionic initiator. To run an anionic polymerization with styrene, the chemist usually prepares the initiator before adding the styrene to the reaction mixture. A common initiator in an anionic polymerization is sodium naphthalidethe radical anion of naphthalene. Chemists prepare sodium naphthalide by reacting sodium with naphthalene in THF solvent.

Anionic initiation requires a strong base to initiate the polymer chain growth.

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Na THF

Na

After preparing the sodium naphthalide, they add the styrene. The two rapidly react, transferring the radical electron in the sodium naphthalide to the styrene to form a radical anion of styrene.

The radical anion is a very reactive species, so it immediately combines with another radical anion to form a dianion. Initiation step

This dianion, usually called distyryl sodium, is the starting point for the polymer formation. As the polymer forms, the anion reacts with additional molecules of styrene at each end of the distyryl sodium to form a polymeric dianion. Propagation step

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Repeat

Each polymer chain grows at a remarkably similar rate. Thus, the process produces the polymeric dianions within a narrow range of molecular weights. Their actual molecular weight depends on the ratio of the amount of initiator and of styrene present in the reaction mixture, as the amount of initiator determines the actual number of polymers that form. The reaction has no important termination reactions. The dianion is relatively stable until a source of protons is added to the solution.

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HCl CH3OH

H x H x

Exercise 22.4 Predict the order of reactivity of styrene, p-chlorostyrene, and pmethoxystyrene in radical, cationic, and anionic polymerization reactions. Polystyrene has a number of properties that make it a valuable industrial material. It is an amorphous polymer. When made in a radical polymerization reaction, polystyrene can form with molecular weights in excess of two million, although most commercial polystyrene has molecular weights under a million. The glass transition temperature for polystyrenes is above room temperature. Polystyrene is also a good thermoplastic material. It can be melted and remolded repeatedly, allowing ready recycling of the waste materials from a molding or from a discarded molded object. A thermoplastic material is different from a thermosetting material. A thermosetting material cannot be melted and remolded.

A thermoplastic material readily melts to allow remolding into desired shapes.

A thermosetting material reacts when heated, thus, it forms a new polymer that does not melt and remold again.

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Uses of Polystyrene
Polystyrene is a plastic that has a number of different industrial and consumer uses. One use involves molding it into cases for televisions and radios. In another process, manufacturers mix a low boiling material with the polystyrene, then heat the mixture. When the polymer softens, the low boiling compound vaporizes and produces a foam. Because the foams do not conduct heat well, they work well when molded into disposable cups for hot drinks and ice chests. Since the foam is quite rigid, it also makes excellent insulation for construction.

Synthesis of Poly(vinyl acetate)

O CH3COCH CH2 O (PhCO)2 n CH3CO O (92%)
Fit a 500 mL reaction kettle with a reflux condenser, mechanical stirrer, thermometer, and addition funnel. Place 80 mL of freshly distilled water in the kettle. Dissolve 80 mg of poly(styrene-co-maleic anhydride) (m.w. about 2000 with 67% styrene content) in the minimum quantity of water and exactly neutralize with 1M sodium hydroxide solution. Add this solution to the water. Prepare a solution of 86g of vinyl acetate and 150 mg of benzoyl peroxide. Add 10 mL of the vinyl acetate solution to the water and warm to 80oC. Once the exothermic polymerization reaction has begun, maintain the reaction at 80oC by either heating or cooling as required. Add the remaining vinyl acetate solution during a two hour period. Continue heating the reaction mixture for an additional 2 hours. While continuing to use the mechanical stirrer, steam distill the reaction mixture until the distillate contains no more vinyl acetate monomer. Cool, with agitation, to 4oC. Filter the polymer beads from the solution and wash repeatedly with water. Dry the beads at 30oC under reduced pressure. The final product has a molecular weight of about 1,000,000. Yield of dry polymer is 79.1 g. Discussion Questions 1. Write a mechanism for the formation of poly(vinyl acetate). 2. This process is called suspension polymerization. What is the purpose of the sodium salt of the poly(styrene-co-maleic anhydride) polymer in the reaction mixture?

[Sidebar] Natural Rubber

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Rubber is the most important and widely used natural polymer. A variety of plants in the tropical regions of the world produce rubber, but the major source of commercial rubber is the Hevea brasiliensis tree originally found in Brazil. The Hevea brasiliensis tree is now mostly grown in Southeast Asia. The Mayans also obtained rubber from this tree. They called it caoutchouc, or the weeping tree. Joseph Priestly, the noted 18th century chemist, coined the name rubber when he found that caoutchouc rubbed out pencil marks. Hevea rubber is obtained by tapping the rubber tree and collecting the viscous liquid, called latex, that flows out. Quantities of latex are obtained by tapping each tree every other day. Raw latex contains about 32 - 35% rubber and 5% other organic compounds such as sugars, fats, and steroids. Rubber is a polymer made up of 2-methyl-1,3-butadiene (isoprene) repeating units.

2-Methyl-1,3-butadiene (Isoprene)

The polymer contains cis repeating units and has a molecular weight ranging from 100,000 up to 1,000,000.

n Rubber

A related polymer, called gutta percha, is found in trees of the genus Dichopsis, which is native to Southeast Asia. Gutta percha has a structure with trans double bonds and a much lower molecular weight. A typical sample of gutta percha has a molecular weight of about 7,000. Gutta percha is not widely used today, but has been used in a variety of applications from golf ball covers to electrical insulation.

n Gutta percha

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The cis arrangement of the double bonds in rubber prevents the rubber molecules from fitting into an ordered structure. Thus, rubber is an amorphous polymer. Because of the random coiling of its polymer chains, rubber stretches easily. When stretched, the rubber molecules are forced into a higher energy state. When the tension is released, rubber snaps back to its original random coiled state. On the other hand, molecules of gutta percha pack close together so it is more crystalline than rubber. In general, gutta percha is harder and less flexible than rubber. Raw rubber is affected by environmental factors such as light, temperature, and oxygen. These factors make rubber unsuitable for a number of applications. In 1839, Charles Goodyear devised a method of reacting rubber with sulfur to form a more durable material. This process, which he called vulcanization, forms sulfur bonds in the molecule. Vulcanization forms both the cyclic structure shown on the left and the more desirable cross-linked structure shown on the right.

S S

Vulcanized rubber

Increasing the amount of sulfur makes the vulcanized polymer harder and more durable. Adding 3 - 5% sulfur makes a product good for rubber bands and inner tubes. Adding 20 - 30% sulfur makes a hard rubber that was once widely used in ways that a hard synthetic plastic is used today. The vulcanization process made early automobile tires possible.

22.5 Controlling Stereochemistry in Vinyl Polymers

The substituents on a vinyl polymer arrange themselves in one of three possible ways. Two of these possible arrangements are stereoregular; the third arrangement is random. Which arrangement the substituents take depends on the stereochemical relationship of the substituents present on the polymer backbone. The arrangement of the substituents on the backbone of the polymer is called the tacticity of that polymer. The three possible arrangements of substituents can be shown using polypropylene.

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CH3

CH3

CH3

CH3

CH3

Isotactic polypropylene

CH3

CH3 CH3

CH3 CH3

Syndiotactic polypropylene

CH3

CH3 CH3

H CH3

CH3

Atactic polypropylene In the isotactic arrangement, the substituents are on the same side of the carbon backbone of the polymer. In the syndiotactic arrangement, the substituents are on alternating sides. In the atactic arrangement, they are on random sides of the backbone.

An isotactic polymer arranges all its substituents on the same side of the polymer chain when you view the chain as a zig-zag structure. A syndiotactic polymer has its substituents on alternating sides of the zig-zag structure. The atactic polymer has its substituents arranged randomly on the chain. The tacticity of a polymer strongly affects that polymers properties. For example, syndiotactic and isotactic polypropylene are more crystalline than atactic polypropylene. Before the 1950s, chemists produced polymers that were largely atactic because they could not control the tacticity of the polymer. In the early 1950s, chemists developed new catalyst systems that selectively produced stereoregular polymers. Having control over the stereochemistry during polymerization had important consequences in the polymer industry. For example, atactic polypropylene is a soft, low-melting amorphous solid, but isotactic polypropylene is highly crystalline and melts at 170oC. Karl Zeigler of Germany developed a series of catalysts that polymerize ethylene at low temperatures and low pressures to give a polyethylene with a high molecular weight and very little branching. This polyethylene is denser, tougher, and has a higher melting point than the polyethylene produced by the earlier high temperature, high pressure methods. Recognizing that Zeigler's catalysts were capable of polymerizing 1-alkenes (called olefins in the polymer industry) to yield stereoregular polymers, Guilio Natta of Italy developed the methodology to do it. In 1963, Zeigler and Natta jointly received the Nobel Prize for the discovery and development of these catalyst systems.

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A Zeigler-Natta catalyst is not one simple system but a mixture of a transition metal compound from groups IVA to VIIIA and an organometallic compound from groups I to III.

Et3Al. Although chemists have extensively studied the mechanism for the Zeigler-Natta catalysis, they are not clear as to what happens. The evidence indicates that the mechanism begins with the formation of a complex between titanium and aluminum.
CH3CH2 CH3 Al TiCl4 Al(CH2CH3)3 Cl Cl CH2 Ti Cl Cl CH2CH3

A typical Zeigler-Natta catalyst is a mixture of TiCl4 and

A complex is a structure that contains a bond between an empty orbital in one molecule and a pair of electrons from another.

In this complex, titanium has an empty orbital available for interaction with the electrons in the monomer, thus allowing for the formation of a complex. The complex orients the methyl group away from the titanium and towards the aluminum. The complex then rapidly rearranges to form a bond between the CH2 group of propylene and the titanium and giving C2 of the propylene a positive charge.
CH3CH2 CH3 Al Cl Cl CH2 Ti Cl CH2 Cl CH3CH2 CH3 Al Cl CH3 Cl CH2 Ti Cl Cl CH2 CH2CH3 H C CH3

CH2CH3 H C

Complex of Ti and alkene

The alkyl group of the aluminum transfers to the carbocation. This transfer happens so rapidly that the carbocation formed in the previous step does not have time to rearrange. Thus, the titanium stereospecifically inserts the propylene group between itself and the ethyl group.
CH3CH2 CH3 Al Cl Cl CH2 Ti Cl Cl CH2 CH2CH3 H C CH3 CH3 H CH3CH2 Al CH3CH2 CH2 Cl Cl Ti Cl Cl

CH2CH3

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The titanium complex continues to stereospecifically insert additional propylene monomers between itself and the last ethyl group added to the chain. This repeating reaction forms the isotactic polymer.
CH3 H CH3CH2 Al CH3CH2 CH2 Cl Cl Ti Cl Cl

CH2CH3 n CH2 CHCH3 CH3 H CH3CH2 CH3 H CH3CH2 Al CH2 CH2 n Cl Cl Ti Cl Cl

CH2CH3

To end the reaction, chemists destroy the complex by treating it with methanol.
CH3 H CH3CH2 CH3 H CH3CH2 Al CH2 CH2 n Cl Cl Ti Cl Cl

CH2CH3

CH3OH CH3CH2

CH3 H CH2

CH3 H n CH2 H

Exercise 22.5 Draw the structure for the product of the polymerization of styrene with TiCl4 and AlEt3.

22.6 Non-Vinyl Chain-Growth Polymerization

Although many of the most common commercial polymers are vinyl polymers, industry does make some important non-vinyl polymers. Several of these polymers form from cyclic compounds that undergo ring-opening reactions via chain-growth polymerization. The cyclic monomers used to make these polymers include lactams, lactones, and ethers. For example, the preparation of polyethylene oxide is a non-vinyl chain-growth polymerization. Polyethylene oxide is a water-soluble polyether that forms in a cationic polymerization reaction. The reaction proceeds by using either a Brnsted-Lowry or a Lewis acid initiator, but the reaction produces a much higher molecular weight polymer with a Lewis acid initiator. Chemists are unclear about the details of the Lewis acid mechanism. However, they

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do know the mechanism for the reaction with a Brnsted-Lowry acid. The initiation step for a Brnsted-Lowry acid involves the protonation of the ether oxygen. Initiation step

H CH2

CH2

CH2

CH2

Protonation of the oxygen gives the two carbons an enhanced reactivity that allows the protonated ether to react with a nucleophile in an SN2 reaction. The nucleophile, which is the oxygen of another molecule of ethylene oxide, opens the ring, and bonds to the carbon of the protonated ethylene oxide. This reaction starts a chain and produces a new cyclic intermediate. The new cyclic intermediate is then ready for another ring opening reaction, thus propagating the growth of the polymer. Propagation step

H CH2

CH2

CH2

CH2

CH2 HOCH2CH2

O CH2 CH2

CH2 HOCH2CH2

O CH2

n CH2

CH2

OCH2CH2

O CH2

After the reaction has used all the ethylene oxide, water is added to terminate the reaction. The water opens the final ring and produces the final monomer of the polymer. This process typically produces a polymer with a molecular weight of approximately 5,000.
CH2 H OCH2CH2 n

O CH2

H2O H

OCH2CH2

OCH2CH2OH

The synthesis of Nylon 6 follows a similar synthetic pathway a nucleophile opens a ring to produce the polymer. The substrate for the synthesis of Nylon 6 is the seven-membered cyclic compound caprolactam. -Caprolactam polymerizes rapidly under anionic

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reaction conditions. The initiation step removes the proton from the amide nitrogen to form a resonance-stabilized anion. Initiation step
O O O

NH2

-Caprolactam

In the propagation step, the anion reacts with the carbonyl carbon of another -caprolactam molecule. This reaction opens the ring and produces another resonance-stabilized anion. Propagation step
O O

O
N

HN

O n O O N NH n O

NH

After the reaction has used all the monomer present in the reaction mixture water is added to protonate the amide ion, thus completing the polymer synthesis.

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Exercise 22.6 One of the difficulties associated with the anionic lactam polymerization that forms Nylon 6 is that a proton transfer sometimes occurs within the polymer chain. This proton transfer leads to polymer chain branching. Show this reaction. Exercise 22.7 Tetrahydrofuran polymerizes in the presence of aluminum chloride and acetyl chloride to produce a polymer used as an artificial leather in shoes. Write the reaction for the initiation step. What is the structure of the polymer?
Poly(lactic acid)
A particularly interesting polyester is poly(lactic acid). The synthesis of poly(lactic acid) is a chain-growth polymerization of lactic acid.

O HOCHCOH CH3 Lactic acid

O OCHC CH3 Poly(lactic acid) n

Surgeons use poly(lactic acid) to do temporary surgical implants because the implant allows the body's healing processes to replace the implant with normal body tissues. Over a period of time, the body hydrolyzes the polymer to lactic acid. The lactic acid then follows the normal metabolic pathway to carbon dioxide and water. Thus, all traces of the surgical implant are gone from the body.

22.7 Step-Growth Polymerization

Step-growth polymerization requires the reaction of two different difunctional monomers to form an alternating copolymer. Each monomer type cannot react with itself; each reacts only with the other. Thus, as the polymer molecule grows, the two different monomers take turns reacting to bond onto the polymer chain. Polyesters, polyamides, and polyurethanes are examples of copolymers that form following the step-growth polymerization pathway. Most of the step-growth polymers discussed in this section have much lower molecular weights than do vinyl polymers due to the increase of intermolecular interactions between the functional groups. The functional groups interact more intermolecularly because of their

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In a transesterification reaction, one ester reacts with an alcohol forming a different ester.

polarity. The advantage of this lower molecular weight is that it gives the polymer a lower melting point than similar polymers with higher molecular weight. The lower melting point makes it easier to mold useful items from the molten polymer. Poly(ethylene terephthalate) is a typical polyester that is prepared via the transesterification of dimethyl terephthalate and ethylene glycol.
O CH3OC O COCH3 HOCH2CH2OH 197oC O C O COCH2CH2O Poly(ethylene terephthalate) n + CH3OH

Transesterification
A transesterification reaction usually has an equilibrium constant near one, thus, at equilibrium the reaction mixture has similar quantities of all the possible esters. Using the methyl ester helps with the reaction because the methyl ester forms methanol, a low boiling point alcohol. The methanol can be boiled off from the reaction mixture, thus driving the reaction to completion.

Synthesis of Poly(ethylene terephthalate)

O CH3OC O COCH3 HOCH2CH2OH 197oC O C O COCH2CH2O n Poly(ethylene terephthalate) (100%)
Distill ethylene glycol from sodium metal in a nitrogen atmosphere. Place 15.5 g of dimethyl terephthalate and 11.8 g of the freshly distilled ethylene glycol in a heavy walled tube with a constricted upper portion and a vacuum attachment. Add 25 mg of calcium acetate dihydrate and 6 mg of antimony trioxide. Enclose the tube in a metal protective sleeve. Warm the reaction mixture in an oil bath to dissolve the mixture. When dissolved, place a capillary tube with a slow stream of nitrogen in the solution. Heat to 197oC and maintain the nitrogen flow. Heat 2-3 hours at 197oC, or until all

Dimethyl terephthalate

+ CH3OH

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the methanol has been removed. Heat the tube to 225oC for 20 minutes and then at 285oC for an additional 10 minutes. Cap the top of the tube, connect the side arm to a vacuum pump, and reduce the pressure to 0.3 mm of Hg. Heat at 285oC for 3.5 hours. Remove the tube from the heat and cool the tube behind a safety shield. On cooling, the polymer contracts from the walls of the tube and may cause it to shatter. The yield of polymer is 15.3 g, m.p. about 270oC. Discussion Questions 1. Why is the initial phase of the reaction run at 197oC? 2. What would be the effect on the molecular weight of the polymer if you stopped the process before all the methanol is removed?

Interfacial polymerization occurs when the monomers are dissolved in immiscible solvents. When they thoroughly mix the two solutions together, the polymer forms.

Poly(hexamethylene adipate), more commonly called Nylon 66, is a typical example of a polyamide. In one synthetic method used to prepare Nylon 66, as well as many other Nylons, chemists dissolve a diacid chloride in an organic solvent and the diamine in aqueous sodium hydroxide. Because the two solutions are not soluble in each other, the polymer forms at the interface between the two layers in a process called interfacial polymerization. With thorough mixing, the interface area of the two layers increases. After the polymer forms, the chemist filters the polymer from the reaction mixture.
O O NH2CH2CH2CH2CH2CH2CH2NH2 H2O, Cl2C CCl2 NaOH O O NHCH2CH2CH2CH2CH2CH2NHCCH2CH2CH2CH2C n Poly(hexamethylene adipate)

ClCCH2CH2CH2CH2CCl

If, instead of using an alkyl group with the diamine, the chemist uses an aromatic ring, the polymerization process inserts an aromatic ring into the polymer. The polymer that forms is much more rigid than the polymer that forms with an alkyl group because the aromatic ring increases the crystallinity of the polymer. As a consequence, polymers with aromatic rings are exceptionally strong. Kevlar , for example, has a tensile strength much higher than steel but is significantly lighter than steel.
O HN HNC O C n Poly(p-phenylene terephthalamide)
Kevlar

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Kevlarmakes an excellent reinforcing fiber in tires. Bulletproof vests contain up to 18 layers of cloth woven from Kevlar yarn. Polyurethanes are produced by a step-growth polymerization of a diisocyanate with a diol. For example, toluene-2,4-diisocyanate reacts with ethylene glycol to form the polyurethane.
CH3 HOCH2CH2OH CH3 O OCH2CH2OCNH O NHC n

OCN

NCO

The mechanism for this reaction is a nucleophilic addition to the C=N bond of the isocyanate.
H R' N C O H R' N O C

ROH

H OR H R' N

O C OR

A Urethane

Polyurethanes are widely used in making foams. Their major commercial use is in cushions for furniture and as a foam-in-place insulating material. Industrial chemists have several ways for making foams. Here is one of those ways. The chemist mixes a small amount of water with the polyurethane reaction mixture. The water reacts with some of the isocyanate groups to form an amine and carbon dioxide.
H R N C O H R N O C

HOH

H OH H R H N

O C O H

RNH2 + CO2

As the polymer forms, it traps the bubbles of carbon dioxide that are also forming. These carbon dioxide bubbles give the polyurethane a foamy texture as the polymer hardens. Generally, during the early part of the polymerization process, the manufacturers vigorously stir the polymer mixture to encourage the formation of smaller bubbles.

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Then, as the foam becomes more viscous, they inject the mixture into a mold to form the polymer into the desired object. Exercise 22.8 What monomer(s) do the following polymers require to form? a)
O n

b)
O O O O n

c)
O O NH n C(CH2)6CNH

d)
O S n

e)
O CNH CH2 O NHCOCH2CH2CH2CH2CH2CH2O n

Sample solution a)
O O n

[Sidebar] Plastic Recycling

People today are very dependent on the use of plastics because plastics are used in a wide variety of applications ranging from throwaway packaging to high-tech materials. However, the use of plastics has created a disposal problem. In the United States, 21% of the volume and 8% of the weight of garbage come from plastics. Most of this garbage is disposable packaging materials. The very durability of plastics makes the problem of plastic garbage a serious problem.

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Recycling plastics is the obvious answer to the problem of plastic garbage. Their durability and low reactivity make plastics ideal candidates for recycling. Then why arent more plastics being recycled? The answer has more to do with consumer habits and economics than technical obstacles. As recycling centers and curbside pickup become more common, more plastics will be recycled. The Society of the Plastics Industry developed a code that is now used on many plastic materials. This code provides information about the plastic used in the product. The code guides both consumers and recyclers in separating various plastics. Table 22.3 shows the recycling code numbers. Recycling Code 1 PET 2 HDPE 3 V Polymer Common Consumer Products Soft drink bottles and household chemical bottles Milk and water jugs, bottles, and grocery bags Shower curtains, shampoo bottles, vinyl siding, floor tiles, credit cards Sandwich bags, shrink wrap, trash and grocery bags, squeeze bottles Plastic lids, bottle caps, toys, diaper linings, clothing fibers Styrofoam materials, egg cartons, appliances, packaging. Many Typical uses for Recycled Plastic Soft drink bottles and household chemical bottles Bottles and molded containers Plastic floor mats

Poly(ethylene terephthalate) High-density polyethylene Poly(vinyl chloride), Vinyl, or PVC Low-density polyethylene

4 LDPE

Trash and grocery bags

5 PP

Polypropylene

Usually part of a mixed resin material Molded items: rulers, cafeteria trays, Frisbees, videocassettes Plastic lumber, playground equipment, road reflectors

6 PS

Polystyrene

All other plastics and mixed resins

Table 22.3. Society of the Plastic Industry recycling codes.

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Most recycling involves separation of the plastic from impurities, washing the plastic, and packaging it for sale. Only poly(ethylene terephthalate) (PET) and high-density polyethylene (HDPE) are currently being recycled in large quantities. Most other plastics are recycled only in small quantities, if at all. A typical recycling process begins with separation of the polymer from contaminants. For example, a PET soft drink bottle usually has a paper label, a HDPE base, adhesive for holding the base and label in place, and a HDPE or aluminum cap. These must be separated for effective recycling. Mixtures of materials are not very useful for further manufacturing. After sorting the various components of a soft drink bottle, the PET bottles are shredded into small chips. An air cyclone is used to remove the paper and other lightweight materials, and the chips are subjected to a detergent wash to remove any remaining labels and adhesives. The PET chips are then separated from any HDPE chips by a floatation method. PET and HDPE have different densities. Thus, choosing the correct solvent permits separation of the two materials. The chips are dried and any remaining aluminum pieces are removed electrostatically. The plastic chips are now nearly free from contaminants. Over 30% of all PET soft drink bottles are recycled by this method. The Eastman Kodak Company has developed an alternative to these physical methods of purification called chemical recycling. Kodak uses large amounts of PET in making photographic film. It recycles the scraps by a process known as methanolysis. Section 22.7 describes how PET is made by a transesterification reaction. Kodak recycles PET by a transesterification reaction that is the reverse of the one used to synthesize PET.
O C O COCH2CH2O n Poly(ethylene terephthalate) O CH3OC O COCH3 CH3OH

HOCH2CH2OH

The products, ethylene glycol and dimethyl terephthalate, are purified. They are then ready to be used in further synthesis.

22.8 Copolymers

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An alternating copolymer has two different repeating units alternating along the chain.

A polymer chain that forms in a copolymerization reaction consists of two or more different repeating units. In a step-growth copolymerization, the polymers generally form an alternating copolymer.
nA + nB A B A B A B A B

Some chain-growth polymers also form alternating copolymers. Styrene and acrylonitrile both polymerize readily under radical conditions. When they are mixed under the appropriate reaction conditions, the styrene radical prefers to react with an acrylonitrile monomer, and the acrylonitrile radical prefers to react with a styrene monomer. The preference for each radical to react with the other monomer is more than 98%. Thus, the polymer that forms is mostly an alternating copolymer.

+ Styrene

CN Acrylonitrile

CN

Styrene-Acrylonitrile copolymer
A block copolymer has two or more short homopolymer chains bonded together to form a longer chain.

A block copolymer consists of two or more short chains of repeating units bonded together to form a longer polymer chain.
mA + nB

One method for the synthesis of a block copolymer is an anionic polymerization of an alkene. For example, as discussed in Section 22.4, the anionic polymerization of styrene produces the following dianion.

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In a living polymer, the polymer chain remains reactive until the chemist deliberately adds a reagent to stop the reaction.

This kind of polymeric dianion is called a living polymer. After a living polymer reacts with all the monomer available in the reaction solution, you can add another monomer. This second monomer then reacts with the reactive site on the living polymer. For example, if you add methyl methacrylate monomer to the dianion, the methyl methacrylate polymerizes to each end of the anionic site. This reaction adds another block to the polymer. The reaction also produces a new dianion at each end of the polymer, thus keeping the polymer alive. The reagents commonly used to quench the anionic polymerization of styrene are methanol and HCl.

O H2C CCOCH3 CH3

CH3

CH3 y O x+1 x+1

CH3

CH3

COCH3 COCH3 O

y COCH3 COCH3 O O

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Random copolymers have no predictable sequence to the repeating units in the chain.

When the reaction has used all the methyl methacrylate, you can add more styrene or even a different monomer. The chain will continue growing until you add methanol and HCl to protonate the dianion. Block copolymers are useful because they have the properties of both polymers. For example, a styrene-methyl methacrylate copolymer has the crystallinity of polystyrene and the toughness of poly(methyl methacrylate). A third type of copolymer is the random copolymer. An example random copolymer is shown below.
mA + nB

Because there is no repetitive way of making the same random copolymer twice, this type of reaction has little commercial value. Exercise 22.9 If you synthesize a block copolymer from a reaction that starts with sodium naphthalide and styrene at 78oC, then you add ethylene oxide and run the reaction at +75oC, and quench it with HCl in CH3OH, what is the structure of the copolymer you have formed?

[Sidebar] Plasticizers
Plasticizers are the most widely used polymer additives in the polymer industry. Their function is to increase the flexibility of a particular polymer. A plasticizer is a nonvolatile liquid that dissolves in the polymer. Similar to the way that an impurity decreases the melting point of a small organic compound, adding a plasticizer to a polymer decreases the glass transition temperature of the polymer. The most common plasticizer is di(2-ethylhexyl) phthalate.
O CH2CH3 O O O CH2CHCH2CH2CH2CH3 CH2CHCH2CH2CH2CH3 CH2CH3

Di(2-ethylhexyl) phthalate

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Plasticizers are selected based on several criteria: cost, compatibility, and permanence. Permanence is how well the plasticizer remains in the polymer. Plasticizers evaporate from the polymer and are removed when the polymer comes in contact with solvents or lubricants. However, if the loss of plasticizer is more rapid than the expected life of the product, the plasticizer is not sufficiently permanent. The permanence of a plasticizer contributes to a problem with recycling those plastics. Most manufacturers have proprietary formulations for plasticizers, so no two are alike. Even similar plastic products may have different plasticizers. The difficulty is that different plasticizers may require different processes to remove them from the plastic. The frequently used, soft, flexible vinyl is actually poly(vinyl chloride) with significant amounts of plasticizer. Poly(vinyl chloride) is a hard, brittle polymer with a glass transition temperature about 80oC. Because poly(vinyl chloride) has so many useful properties, most samples contain plasticizer. Often as much as 50% of a poly(vinyl chloride) sample is plasticizer. Permanence is important in these products as they become hard and brittle when the plasticizer eventually evaporates. Phthalate esters are used as plasticizers in many polymers in automobile interiors. The new car smell enjoyed by many car owners is the result of the plasticizer vaporizing in the interior of the automobile. The smell actually advertises the deterioration of the polymers in the interior of the car, particularly so with the vinyl upholstery. If a new car is closed and left in the sun, it becomes very hot and enough plasticizer can evaporate and condense on the windows to leave a sticky film.

22.9 Cross-Linked Polymers

Cross-linked polymers consist of smaller polymer chains that are bonded together. Each chain is bonded to multiple chains. Generally, the reaction proceeds by first synthesizing the prepolymers. The prepolymers then undergo a reaction that links them together. The most familiar cross-linked polymers are the two-part epoxy adhesives: 1) the resin and 2) the hardener. A typical resin is a prepolymer derived from epichlorohydrin and bisphenol A. When these two molecules react, they produce a prepolymer with hydroxyl groups in the chain and, because epichlorohydrin is present in excess, with epoxy groups at the ends of the chain. Typically this prepolymer has a molecular weight of approximately 1500 2000.

A prepolymer is a low molecular weight polymer that has functional groups available for reaction with a cross-linking agent.

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CH3 Cl

HO

C CH3

OH

NaOH

Epichlorohydrin O CH3 O C

Bisphenol A

CH3

OCH2CHCH2 O OH n

C CH3

CH3

The mechanism for the formation of the prepolymer begins with the formation of the phenolate anion. The phenolate anion reacts with the epichlorohydrin in a nucleophilic reaction bonding the two together and opening the epoxide ring. A new epoxide ring then forms by nucleophilic reaction of the resulting alkoxide with the carbon bearing the chloride. This sequence repeats forming a prepolymer containing 25 to 50 repeating units.

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OH

CH3 R = HO C CH3 R O O

Cl Cl

O O

Repeat

CH3 O C CH3 O O

OCH2CHCH2 O OH n

C CH3

CH3

Cross-linking takes place when the user mixes the hardener with the prepolymer. The process is very rapid. Thus, the person using the epoxy adhesive must mix the resin and hardener immediately before using it. A typical hardener is tris(2-aminoethyl)amine.
H2NCH2CH2 NCH2CH2NH2 H2NCH2CH2 Tris(2-aminoethyl)amine

Because both hardener and prepolymer have a number of polar groups that can hydrogen bond and coordinate strongly with the surfaces to be bonded together, epoxy adhesives form very strong bonds. Below is a schematic illustration of the cross-linking process.

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H2NCH2CH2 NCH2CH2NH2 H2NCH2CH2

HNCH2CH2 NCH2CH2NH2 HNCH2CH2

Exercise 22.10 Chemists synthesize bisphenol A from two moles of phenol and one mole of acetone. Propose a mechanism for this acid-catalyzed reaction.

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The first commercially available cross-linked polymer was synthesized by the reaction of phenol with formaldehyde. This process, developed by Leo Hendrik Baekeland, produced a product called Bakelite. Bakelite, patented early in the twentieth century, is a highly cross-linked three-dimensional network molecule that is very resistant to solvents, heat, and electricity. By the 1920s, Bakelite had found its way into a variety of household products from handles for cooking pots to electrical fixtures. Its wide variety of uses earned its inventor a feature on the cover of Time. The preparation of Bakelite is quite simpleheat a mixture of phenol and formaldehyde with aqueous acid. This process forms the polymer network of phenol rings connected at the ortho and para positions with methylene groups.
OH +
O

HCH

H3O

OH CH2 CH2

OH CH2

OH CH2

OH CH2 CH2 CH2

OH CH2

OH CH2 OH CH2 CH2 CH2 CH2 CH2 CH2 OH CH2 CH2 OH CH2

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Exercise 22.11 The first step in the formation of Bakelite is the formation of a mixture of o- and p-hydroxymethylphenol. Write a mechanism that explains the formation of these intermediates.
OH + O HCH H3O OH + CH2OH HOH2C OH

Key Ideas from Chapter 22

A polymer, sometimes called a macromolecule, is a very large molecule formed from smaller molecules called monomers. Monomers convert to polymers in a polymerization reaction. A homopolymer is a polymer synthesized from a single kind of monomer. The synthesis for a copolymer involves two or more different kinds of monomers. A copolymer has one of the three following structures: 1) alternating, 2) block, or 3) random copolymer. The monomer molecules alternate in the polymer chain of alternating copolymers. Blocks of homopolymers are bonded together in block copolymers. Random copolymers arrange the repeating units in a random order along the polymer chain. A polymer is either linear, branched, or cross-linked. Solid polymers are either crystalline, amorphous, or have regions of both crystalline and amorphous structure. Few polymers are completely crystalline, more are amorphous, and still more have both crystalline and amorphous domains. Homopolymers are usually named as polymonomer. If the monomer has a number or symbol prefix, enclose it in parentheses as poly(monomer). Name copolymers by combining the names of both monomers. For example, to name the polyester formed from ethylene glycol and terephthalic acid is poly(ethylene terephthalate).

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Polymers form following either the chain-growth polymerization pathway or the step-growth polymerization pathway. In a chain-growth polymerization, one monomer reacts with another monomer that contains the same functional groups. In a step-growth polymerization, one monomer reacts with a repeating unit formed from a different monomer. Two or more monomers alternately react with the growing polymer chain. Chain-growth reaction mechanisms have initiation, propagation, and termination steps. The polymerization reaction of vinyl monomers occurs under radical, cationic, or anionic conditions. Many anionic chain-growth mechanisms produce living polymers. A living polymer can react further with additional monomers that are either the same as the original vinyl monomer or a different vinyl monomer. Vinyl polymers have several different arrangements of substituents on the polymer chain. Two of these arrangements are stereoregular and the third is random. The arrangements are called the tacticity of the polymer. Isotactic polymers have the substituents on the same side when you draw the polymer in the zigzag form. Syndiotactic polymers have the substituents on opposite sides when you draw the polymer in the zigzag form. Atactic polymers have the substituents randomly arranged when you draw the polymer in the zigzag form. Ziegler-Natta catalysts control the stereochemistry of the polymer. Chain-growth polymerization occurs with non-vinyl polymers. Ring opening polymerization of cyclic lactams, ethers, lactones, etc., form polymers with heteroatoms in the polymer chain. Step-growth polymerization requires the copolymerization of two monomers forming an alternating copolymer.

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Cross-linking polymerization reactions involve forming very high molecular weight polymers by reaction of low molecular weight prepolymers with some cross-linking agent.

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