Polymers

CONCEPT

Formed from hydrocarbons, hydrocarbon derivatives, or sometimes from silicon, polymers are the basis not only for numerous natural materials, but also for most of the synthetic plastics that one encounters every day. Polymers consist of extremely large, chain-like molecules that are, in turn, made up of numerous smaller, repeating units called monomers. Chains of polymers can be compared to paper clips linked together in long strands, and sometimes cross-linked to form even more durable chains. Polymers can be composed of more than one type of monomer, and they can be altered in other ways. Likewise they are created by two different chemical processes, and thus are divided into addition and condensation polymers. Among the natural polymers are wool, hair, silk, rubber, and sand, while the many synthetic polymers include nylon, synthetic rubber, Teflon, Formica, Dacron, and so forth. It is very difficult to spend a day without encountering a natural polymer—even if hair is removed from the list—but in the twenty-first century, it is probably even harder to avoid synthetic polymers, which have collectively revolutionized human existence.

HOW IT WORKS

Polymers of Silicon and Carbon

Polymers can be defined as large, typically chainlike molecules composed of numerous smaller, repeating units known as monomers. There are numerous varieties of monomers, and since these can be combined in different ways to form polymers, there are even more of the latter.
The name “polymer” does not, in itself, define the materials that polymers contain. A handful of polymers, such as natural sand or synthetic silicone oils and rubbers, are built around silicon. However, the vast majority of polymers center around an element that occupies a position just above silicon on the periodic table: carbon.
The similarities between these two are so great, in fact, that some chemists speak of Group 4 (Group 14 in the IUPAC system) on the periodic table as the “carbon family.” Both carbon and silicon have the ability to form long chains of atoms that include bonds with other elements. The heavier elements of this “family,” however (most notably lead), are made of atoms too big to form the vast array of chains and compounds for which silicon and carbon are noted.
Indeed, not even silicon—though it is at the center of an enormous range of inorganic compounds—can compete with carbon in its ability to form arrangements of atoms in various shapes and sizes, and hence to participate in an almost limitless array of compounds. The reason, in large part, is that carbon atoms are much smaller than those of silicon, and thus can bond to one another and still leave room for other bonds.
Carbon is such an important element that an entire essay in this topic is devoted to it, while a second essay discusses organic chemistry, the study of compounds containing carbon. In the present context, there will be occasional references to non-carbon (that is, silicon) polymers, but the majority of our attention will be devoted to hydrocarbon and hydrocarbon-derivative polymers, which most of us know simply as “plastics.”
Cotton is an example of a natural polymer.
Cotton is an example of a natural polymer.

Organic Chemistry

As explained in the essay on Organic Chemistry, chemists once defined the term “organic” as relating only to living organisms; the materials that make them up; materials derived from them; and substances that come from formerly living organisms. This definition, which more or less represents the everyday meaning of “organic,” includes a huge array of life forms and materials: humans, all other animals, insects, plants, microorganisms, and viruses; all substances that make up their structures (for example, blood, DNA, and proteins); all products that come from them (a list diverse enough to encompass everything from urine to honey); and all materials derived from the bodies of organisms that were once alive (paper, for instance, or fossil fuels).
As broad as this definition is, it is not broad enough to represent all the substances addressed by organic chemistry—the study of carbon, its compounds, and their properties. All living or once-living things do contain carbon; however, organic chemistry is also concerned with carbon-containing materials—for instance, the synthetic plastics we will discuss in this essay—that have never been part of a living organism.
It should be noted that while organic chemistry involves only materials that contain carbon,carbon itself is found in other compounds not considered organic: oxides such as carbon dioxide and monoxide, as well as carbonates, most notably calcium carbonate or limestone. In other words, as broad as the meaning of”organic” is, it still does not encompass all substances containing carbon.

Hydrocarbons

As for hydrocarbons, these are chemical compounds whose molecules are made up of nothing but carbon and hydrogen atoms. Every molecule in a hydrocarbon is built upon a “skeleton” of carbon atoms, either in closed rings or in long chains, which are sometimes straight and sometimes branched.
Theoretically, there is no limit to the number of possible hydrocarbons: not only does carbon form itself into seemingly limitless molecular shapes, but hydrogen is a particularly good partner. It is the smallest atom of any element on the periodic table, and therefore it can bond to one of carbon’s four valence electrons without getting in the way of the other three.
There are many, many varieties of hydrocarbon, classified generally as aliphatic hydrocarbons (alkanes, alkenes, and alkynes) and aromatic hydrocarbons, the latter being those that con-
Modern appliances contain numerous examples of synthetic polymers, from the flooring to the countertops to virtually all appliances.
Modern appliances contain numerous examples of synthetic polymers, from the flooring to the countertops to virtually all appliances.
tain a benzene ring. By means of a basic alteration in the shape or structure of a hydrocarbon, it is possible to create new varieties. Thus, as noted above, the number of possible hydrocarbons is essentially unlimited.
Certain hydrocarbons are particularly useful, one example being petroleum, a term that refers to a wide array of hydrocarbons. Among these is an alkane that goes by the name ofoctane (C8H18), a preferred ingredient in gasoline. Hydrocarbons can be combined with various functional groups (an atom or group of atoms whose presence identifies a specific family of compounds) to form hydrocarbon derivatives such as alcohols and esters.

REAL-LIFE APPLICATIONS

Types of Polymers and Polymerization

Many polymers exist in nature. Among these are silk, cotton, starch, sand, and asbestos, as well as the incredibly complex polymers known as RNA (ribonucleic acid) and DNA (deoxyribonucleic acid), which hold genetic codes. The polymers discussed in this essay, however, are primarily of the synthetic kind. Artificial polymers include such plastics (defined below) as polyethylene, styrofoam, and Saran wrap; fibers such as nylon, Dacron (polyester), and rayon; and other materials such as Formica, Teflon, and PVC pipe.
As noted earlier, most polymers are formed from monomers either of hydrocarbon or hydrocarbon derivatives. The most basic synthetic monomer is ethylene (C2H4), a name whose -ene ending identifies it as an alkene, a hydrocarbon formed by double bonds between carbon atoms. Another alkene hydrocarbon monomer is butadiene, whose formula is C4H6. This is an example of the fact that the formula of a compound does not tell the whole story: on paper, the difference between these two appears to be merely a matter of two extra atoms each of carbon and hydrogen. In fact, butadiene’s structure is much more complex.
Still more complex is styrene, which includes a benzene ring. Several other monomers involve other elements: chloride, in vinyl chloride; nitrogen, in acrylonitrile; and fluorine, in tetrafluo-roethylene. It is not necessary, in the present context, to keep track of all of these substances, which in any case represent just some of the more prominent among a wide variety of synthetic monomers. A good high-school or college chemistry text topic (either general chemistry or organic chemistry) should provide structural representations of these common monomers. Such representations will show, for instance, the vast differences between purely hydrocarbon monomers such as ethylene, propylene, styrene, and butadiene.
When combined into polymers, the monomers above form the basis for a variety of useful and familiar products. Once the carbon double bonds in tetrafluoroethylene (C2F4) are broken, they form the polymer known as Teflon, used in the coatings of cooking utensils, as well as in electrical insulation and bearings. Vinyl chloride breaks its double bonds to form polyvinyl chloride, better known as PVC, a material used for everything from plumbing pipe to toys to Saran wrap. Styrene, after breaking its double bonds, forms polystyrene, used in containers and thermal insulation.

Polymerization

Note that several times in the preceding paragraph, there was a reference to the breaking of carbon double bonds. This is often part of one variety of polymerization, the process whereby monomers join to form polymers. If monomers of a single type join, the resulting polymer is called a homopolymer, but if the polymer consists of more than one type of monomer, it is known as a copolymer. This joining may take place by one of two
A synthetic polymer known as kevlar is used in the construction of bulletproof vests for law-enforcement officers.
A synthetic polymer known as kevlar is used in the construction of bulletproof vests for law-enforcement officers.
processes. The first of these, addition polymerization, is fairly simple: monomers add themselves to one another, usually breaking double bonds in the process. This results in the creation of a polymer and no other products.
Much more complex is the process known as condensation polymerization, in which a small molecule called a dimer is formed as monomers join. The specifics are too complicated to discuss in any detail, but a few things can be said here about condensation polymerization. The monomers in condensation polymerization must be bifunctional, meaning that they have a functional group at each end. When characteristic structures at the ends of the monomers react to one another by forming a bond, they create a dimer, which splits off from the polymer. The products of condensation polymerization are thus not only the polymer itself, but also a dimer, which may be water, hydrochloric acid (HCl), or some other substance.

A Plastic World

a d ay in the life. Though “plastic” has a number of meanings in everyday life,
and in society at large (as we shall see), the scientific definition is much more specific. Plastics are materials, usually organic, that can be caused to flow under certain conditions of heat and pressure, and thus to assume a desired shape when the pressure and temperature conditions are withdrawn. Most plastics are made of polymers.
Every day, a person comes into contact with dozens, if not hundreds, of plastics and polymers. Consider a day in the life of a hypothetical teenage girl. She gets up in the morning, brushes her teeth with a toothbrush made of nylon, then opens a shower door—which is likely to be plastic rather than glass—and steps into a molded plastic shower or bathtub. When she gets out of the shower, she dries off with a towel containing a polymer such as rayon, perhaps while standing on tile that contains plastics, or polymers.
She puts on makeup (containing polymers) that comes in plastic containers, and later blow-dries her hair with a handheld hair dryer made of insulated plastic. Her clothes, too, are likely to contain synthetic materials made of polymers. When she goes to the kitchen for breakfast, she will almost certainly walk on flooring with a plastic coating. The countertops may be of formica, a condensation polymer, while it is likely that virtually every appliance in the room will contain plastic. If she opens the refrigerator to get out a milk container, it too will be made of plastic, or of paper with a thin plastic coating. Much of the packaging on the food she eats, as well as sandwich bags and containers for storing food, is also made of plastic.
And so it goes throughout the day. The phone she uses to call a friend, the computer she sits at to check her e-mail, and the stereo in her room all contain electrical components housed in plastic. If she goes to the gym, she may work out in Gore-tex, a fabric containing a very thin layer of plastic with billions of tiny pores, so that it lets through water vapor (that is, perspiration) without allowing the passage of liquid water. On the way to the health club, she will ride in a car that contains numerous plastic molds in the steering wheel and dashboard. If she plays a compact disc—itself a thin wafer of plastic coated with metal—she will pull it out of a plastic jewel case. Finally, at night, chances are she will sleep in sheets, and with a pillow, containing synthetic polymers.

A silent revolution

The scenario described above—a world surrounded by polymers, plastics, and synthetic materials— represents a very recent phenomenon. “Before the 1930s,” wrote John Steele Gordon in an article about plastics for American Heritage, “almost everything people saw or handled was made of materials that had been around since ancient times: wood, stone, metal, and animal and plant fibers.” All of that changed in the era just before World War II, thanks in large part to a brilliant young American chemist named Wallace Carothers (1896-1937).
By developing nylon for E. I. du Pont de Nemours and Company (known simply as “DuPont” or “du Pont”), Carothers and his colleagues virtually laid the foundation for modern polymer chemistry—a field that employs more chemists than any other. These men created what Gordon called a “materials revolution” by introducing the world to polymers and plastics, which are typically made of polymers.
Yet as Gordon went on to note, “It has been a curiously silent revolution…. When we think of the scientific triumphs of [the twentieth century], we think of nuclear physics, medicine, space exploration, and the computer. But all these developments would have been much impeded, in some cases impossible, without… plastics. And yet ‘plastic’ remains, as often as not, a term of opprobrium.”

Ambivalence toward plastics.

Gordon was alluding to a cultural attitude discussed in the essay on Organic Chemistry: the association of plastics, a physical material developed by chemical processes, with the condition—spiritual, moral, and intellectual—of being “plastic” or inauthentic. This was symbolized in a famous piece of dialogue about plastics from the 1967 movie The Graduate, in which a nonplussed Ben Braddock (Dustin Hoffman) listens as one of his parents’ friends advises him to invest his future in plastics. As Gordon noted, “however intergenerationally challenged that half-drunk friend of Dustin Hoffman’s parents may have been… he was right about the importance of the materials revolution in the twentieth century.”
One aspect of society’s ambivalence over plastics relates to very genuine concerns about the environment. Most synthetic polymers are made from petroleum, a nonrenewable resource;but this is not the greatest environmental danger that plastics present. Most plastics are not biodegradable: though made of organic materials, they do not contain materials that will decompose and eventually return to the ground. Nor is there anything in plastics to attract microorganisms, which, by assisting in the decomposition of organic materials, help to facilitate the balance of decay and regeneration necessary for life on Earth.
Efforts are underway among organic chemists in the research laboratories of corporations and other institutions to develop biodegradable plastics that will speed up the decomposition of materials in the polymers—a process that normally takes decades. Until such replacement polymers are developed, however, the most environmentally friendly solution to the problem of plastics is recycling. Today only about 1% of plastics are recycled, while the rest goes into waste dumps, where they account for 30% of the volume of trash.
Long before environmental concerns came to the forefront, however, people had begun almost to fear plastics as a depersonalizing aspect of modern life. It seemed that in a given day, a person touched fewer and fewer things that came directly from the natural environment: the “wood, stone, metal, and animal and plant fibers” to which Gordon alluded. Plastics seemed to have made human life emptier; yet the truth of the matter—including the fact that plastics add more than they take away from the landscape of our world—is much more complex.

The Plastics Revolution

Though the introduction of plastics is typically associated with the twentieth century, in fact the “materials revolution” surrounding plastics began in 1865. That was the year when English chemist Alexander Parkes (1813-1890) produced the first plastic material, celluloid. Parkes could have become a rich man from his invention, but he was not a successful marketer. Instead, the man who enjoyed the first commercial success in plastics was—not surprisingly—an American, inventor John Wesley Hyatt (1837-1920).
Responding to a contest in which a billiard-ball manufacturer offered $10,000 to anyone who could create a substitute for ivory, which was extremely costly, Hyatt turned to Parkes’s celluloid. Actually, Parkes had given his creation—developed from cellulose, a substance found in the cell walls of plants—a much less appealing name, “Parkesine.” Hyatt, who used celluloid to make smooth, hard, round billiard balls (thereby winning the contest) took out a patent for the process involved in making the material he had dubbed “Celluloid,” with a capital C.
Though the Celluloid made by Hyatt’s process was flammable (as was Parkesine), it proved highly successful as a product when he introduced it in 1869. He marketed it successfully for use in items such as combs and baby rattles, and Celluloid sales received a powerful boost after photography pioneer George Eastman (1854-1932) chose the material for use in the development of film. Eventually, Celluloid would be applied in motion-picture film, and even today, the adjective “celluloid” is sometimes used in relation to the movies. Actually, Celluloid (which can be explosive in large quantities) was phased out in favor of “safety film,” or cellulose acetate, beginning in 1924.
Two important developments in the creation of synthetic polymers occurred at the turn of the century. One was the development of Galalith, an ivory-like substance made from formaldehyde and milk, by German chemist Adolf Spitteler. An even more important innovation happened in 1907, when Belgian-American chemist Leo Baekeland (1863-1944) introduced Bakelite. The latter, created in a reaction between phenol and formaldehyde, was a hard, black plastic that proved an excellent insulator. It soon found application in making telephones and household appliances, and by the 1920s, chemists had figured out how to add pigments to Bakelite, thus introducing the public to colored plastics.

Synthetic rubber

Throughout these developments, chemists had only a vague understanding of polymers, but by the 1930s, they had come to accept the model of polymers as large, flexible, chain-like molecules. One of the most promising figures in the emerging field of polymer chemistry was Carothers, who in 1926 left a teaching post at Harvard University to accept a position as director of the polymer research laboratory at DuPont.
Among the first problems Carothers tackled was the development of synthetic rubber. Natural rubber had been known for many centuries when English chemist Joseph Priestley (17331804) gave it its name because he used it to rub out pencil marks. In 1839, American inventor Charles Goodyear (1800-1860) accidentally discovered a method for making rubber more durable, after he spilled a mixture of rubber and sulfur onto a hot stove. Rather than melting, the rubber bonded with the sulfur to form a much stronger but still elastic product, and Goodyear soon patented this process under the name vulcanization.
Natural rubber, nonetheless, had many undesirable properties, and hence DuPont put Carothers to the task of developing a substitute. The result was neoprene, which he created by adding a chlorine atom to an acetylene derivative. Neoprene was stronger, more durable, and less likely to become brittle in cold weather than natural rubber. It would later prove an enormous boost to the Allied war effort, after the Japanese seized the rubber plantations of Southeast Asia in 1941.

Nylon

Had neoprene, which Carothers developed in 1931, been the extent of his achievements, he would still be remembered by science historians. However, his greatest creation still lay ahead of him. Studying the properties of silk, he became convinced that he could develop a more durable compound that could replicate the properties of silk at a much lower cost.
Carothers was not alone in his efforts, as Gordon showed in his account of events at the DuPont laboratories:
One day, an assistant, Julian Hill, noticed that when he stuck a glass stirring rod into a gooey mass at the bottom of a beaker the researchers had been investigating, he could draw out threads from it, the polymers forming spontaneously as he pulled. When Carothers was absent one day, Hill and his colleagues decided to see how far they could go with pulling threads out of goo by having one man hold the beaker while another ran down the hall with the glass rod. A very long, silk-like thread was produced.
Realizing what they had on their hands, DuPont devoted $27 million to the research efforts of Carothers and his associates at the lab, and in 1937, Carothers presented his boss with the results, saying “Here is your synthetic textile fabric.” DuPont introduced the material, nylon, to the American public the following year with one of the most famous advertising campaigns of all time: “Better Things for Better Living Through Chemistry.”
The product got an additional boost through exposure at the 1939 World’s Fair. When DuPont put 4,000 pairs of nylon stockings on the market, they sold in a matter of hours. A few months later, four million pairs sold in New York City in a single day. Women stood in line to buy stockings of nylon, a much better (and less expensive) material for that purpose than silk—but they did not have long to enjoy it. During World War II, all nylon went into making war materials such as parachutes, and nylon did not become commercially available again until 1946.
As Gordon noted, Carothers would surely have won the Nobel Prize in chemistry for his work—”but Nobel prizes go only to living recipients….” Carothers had married in 1936, and by early 1937, his wife Helen was pregnant. (Presumably, he was unaware of the fact that he was about to become a father.) Though highly enthusiastic about his work, Carothers was always shy and withdrawn, and in Gordon’s words, “he had few outlets other than work.” He was, however, a talented singer, as was his closest sibling, Isobel, a radio celebrity. Her death in January 1937 sent him into a bout of depression, and on April 29, he killed himself with a dose of cyanide. Seven months later, on November 27, Helen gave birth to a daughter, Jane.

How plastics have enhanced life

Despite his tragic end, Carothers had brought much good to the world by sparking enormous interest in polymer research and plastics. Over the years that followed, polymer chemists developed numerous products that had applications in a wide variety of areas. Some, such as polyester—a copolymer of terephthalic acid and ethylene—seemed to fit the idea of “plastics” as ugly, inauthentic, and even dehumanizing. During the 1970s, clothes of polyester became fashionable, but by the early 1980s, there was a public backlash against synthetics, and in favor of natural materials.
Yet even as the public rejected synthetic fabrics for everyday wear, Gore-tex and other synthetics became popular for outdoor and workout clothing. At the same time, the polyester that many regarded as grotesque when used in clothing was applied in making safer beverage bottles. The American Plastics Council dramatized this in a 1990s commercial that showed a few seconds in the life of a mother. Her child takes a soft-drink bottle out of the refrigerator and drops it, and the mother cringes at what she thinks she is about to see next: glass shattering around her child. But she is remembering the way things were when she was a child, when soft drinks still came in glass bottles: instead, the plastic bottle bounces harmlessly.

KEY TERMS

Addition polymerization: A form of polymerization in which monomers having at least one double bond or triple bond simply add to one another, forming a polymer and no other products. Compare to condensation polymerization.
Alkenes: Hydrocarbons that contain double bonds.
Copolymer: A polymer composed of more than one type of monomer.
Dimer: A molecule formed by the joining of two monomers.
Double bond: A form of bonding in which two atoms share two pairs of valence electrons. Carbon is noted for its ability to form double bonds, as for instance in many hydrocarbons.
Functional groups: An atom or group of atoms whose presence identifies a specific family of compounds. When combined with hydrocarbons, various functional groups form hydrocarbon derivatives.
Homopolymer: A polymer that consists of only one type of monomer.
Hydrocarbon: Any chemical compound whose molecules are made up of nothing but carbon and hydrogen atoms.
Hydrocarbon derivatives:Families of compounds formed by the joining of hydrocarbons with various functional groups.
Monomers: Small, individual sub-units, often built of hydrocarbons, that join together to form polymers.
Organic: A term referring to any compound that contains carbon, except for oxides such as carbon dioxide, or carbonates such as calcium carbonate (i.e., limestone).
Organic chemistry: The study of carbon, its compounds, and their properties.
Plastics: Materials, usually organic, that can be caused to flow under certain conditions of heat and pressure, and thus to assume a desired shape when the pressure and temperature conditions are withdrawn. Plastics are usually made up of polymers.
Polymerization: The process whereby monomers join to form polymers.
Polymers: Large, typically chain-like molecules composed of numerous smaller, repeating units known as monomers.
Valence electrons: Electrons that occupy the highest principal energy level in an atom. These are the electrons involved in chemical bonding.
Of course, such dramatizations may seem a bit self-serving to critics of plastic, but the fact remains that plastics enhance—and in some cases even preserve—life. Kevlar, for instance, enhances life when it is used in making canoes for recreation; when used to make a bulletproof vest, it can save the life of a law-enforcement officer. Mylar, a form of polyester, enhances life when used to make a durable child’s balloon— but this highly nonreactive material also saves lives when it is applied to make replacement human blood vessels, or even replacement skin for burn victims.

Recycling

As mentioned above, plastics—for all their benefits—do pose a genuine environmental threat, due to the fact that the polymers break down much more slowly than materials from living organisms. Hence the need not only to develop biodegradable plastics, but also to work on more effective means of recycling.
One of the challenges in the recycling arena is the fact that plastics come in a variety of grades. Different catalysts are used to make polymers that possess different properties, with varying sizes of molecules, and in chains that may be linear, branched, or cross-linked. Long chains of 10,000 or more monomers can be packed closely to form a hard, tough plastic known as high-density polyethylene or HDPE, used for bottles containing milk, soft drinks, liquid soap, and other products. On the other hand, shorter, branched chains of about 500 ethylene monomers each produce a much less dense plastic, low-density polyethylene or LDPE. This is used for plastic food or garment bags, spray bottles, and so forth. There are other grades of plastic as well.
In some forms of recycling, plastics of all varieties are melted down together to yield a cheap, low-grade product known as “plastic lumber,” used in materials such as landscaping timbers, or in making park benches. In order to achieve higher-grade recycled plastics, the materials need to be separated, and to facilitate this, recycling codes have been developed. Many plastic materials sold today are stamped with a recycling code number between 1 and 6, identifying specific varieties of plastic. These can be melted or ground according to type at recycling centers, and reprocessed to make more plastics of the same grade.
To meet the environmental challenges posed by plastics, polymer chemists continue to research new methods of recycling, and of using recycled plastic. One impediment to recycling, however, is the fact that most state and local governments do not make it convenient, for instance by arranging trash pickup for items that have been separated into plastic, paper, and glass products. Though ideally private recycling centers would be preferable to government-operated recycling, few private companies have the financial resources to make recycling of plastics and other materials practical.

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