Polymer

A polymer is a substance composed of molecules with large molecular mass consisting of repeating structural units, or monomers, connected by covalent chemical bonds. The individual molecules which comprise a polymer are referred to as polymer molecules, where the word "polymer" functions as an adjective.

Overview

While the term polymer in popular usage suggests "plastic", polymers comprise a large class of natural and synthetic materials with a variety of properties and purposes. Natural polymer materials such as shellac and amber have been in use for centuries. Paper is manufactured from cellulose, a naturally occurring polysaccharide found in plants. Biopolymers such as proteins and nucleic acids play important roles in biological processes.

Henri Braconnot's pioneering work in derivative cellulose compounds is perhaps the earliest important work in modern polymer science. The development of vulcanization later in the nineteenth century improved the durability of the natural polymer rubber, signifying the first popularized semi-synthetic polymer. The first wholly synthetic polymer, Bakelite, was introduced in 1909.

Until the 1920s, most scientists believed that polymers were clusters of small molecules (called colloids), without definite molecular weights, held together by an unknown force, a concept known as association theory. In 1922, German chemist Hermann Staudinger proposed that polymers were comprised of "macromolecules" consisted of long chains of atoms held together by covalent bonds. Though poorly received at first, experimental work by Wallace Carothers, Herman Mark, and others provided further evidence for Staudinger's theory. By the mid-1930s, the macromolecular theory of polymer structure was widely accepted. For this and other work in the field, Staudinger was ultimately awarded the Nobel Prize. In the intervening century, synthetic polymer materials such as Nylon, polyethylene, Teflon, and silicone have formed the basis for a burgeoning polymer industry.

Synthetic polymers today find application in nearly every industry and area of life. Polymers are used in the fabrication of microprocessors, the development of new pharmaceuticals, and improving yield in petroleum extraction. Polymers are used as adhesives and lubricants, as well as structural components for products ranging from childrens' toys to aircraft. Future applications include polymeric transistors and substrates for flexible components and displays, enhanced drug delivery methods, and the development of smart materials.

Polymer science

See Also: Polymer science

Most polymer research may be categorized as polymer science, a sub-discipline of materials science which includes researchers in chemistry (especially organic chemistry), physics, and engineering. The field of polymer science includes both experimental and theoretical research. The IUPAC recommends that polymer science be roughly divided into two subdisciplines:

• Polymer chemistry or macromolecular chemistry, concerned with the chemical synthesis and chemical properties of polymers.
• Polymer physics, concerned with the bulk properties of polymer materials and engineering applications.

The study of biological polymers, their structure, function, and method of synthesis is generally the purview of biology, biochemistry, and biophysics. These disciplines share some of the terminology familiar to polymer science, especially when describing the synthesis of biopolymers such as DNA or polysaccharides. However, usage differences persist, such as the practice of using the term macromolecule to describe large non-polymer molecules and complexes of multiple molecular components, such as hemoglobin. Substances with distinct biological function are rarely described in the terminology of polymer science. For example, a protein is rarely referred to as a copolymer.

Polymer synthesis

Polymers are synthesized by three primary methods: organic synthesis in a laboratory or factory, biological synthesis in living cells and organisms, or by chemical modification of naturally occurring polymers.

Organic synthesis

In 1907, Leo Baekeland created the first completely synthetic polymer, Bakelite, by reacting phenol and formaldehyde at precisely controlled temperature and pressure. Subsequent work by Wallace Carothers in the 1920s demonstrated that polymers could be synthesized rationally from their constituent monomers. The intervening years have shown significant developments in rational polymer synthesis. Most commercially important polymers today are entirely synthetic, produced in high volume on appropriately scaled organic synthetic techniques.

Laboratory synthetic methods are generally divided into two categories, chain-growth polymerization and addition polymerization though some newer methods, such as plasma polymerization do not neatly fit into either category. Synthetic polymerization reactions may be carried out with or without a catalyst. Efforts towards rational synthesis of biopolymers via laboratory synthetic methods, especially artificial synthesis of proteins, is an area of intense research.

Biological synthesis

Natural polymers and biopolymers formed in living cells may be synthesized by enzyme-mediated processes, such as the formation of DNA catalyzed by DNA polymerase. The synthesis of proteins involves multiple enzyme-mediated processes to transcribe genetic information from the DNA and subsequently translate that information to synthesize the specified protein. The protein may be modified further following translation in order to provide appropriate structure and function.

Modification of natural polymers

Many commercially important polymers are synthesized by chemical modification of naturally occurring polymers. Prominent examples include the reaction of nitric acid and cellulose to form nitrocellulose and the formation of vulcanized rubber by heating natural rubber in the presence of sulfur.

Describing polymers

The properties of a polymer depends both on what kinds of monomers make up the molecule, and how those monomers are arranged. For example, a linear chain polymer may be soluble or insoluble in water depending on whether it is composed of polar monomers (such as ethylene oxide) or nonpolar monomers (such as styrene). On the other hand, two samples of natural rubber may exhibit different durability even though their molecules are comprised of the same monomers. Polymer scientists have developed terminology to precisely describe both the nature of the monomers as well as their relative arrangement:

Types of monomers

The type of monomer(s) which compose a polymer molecule may generally be determined by the name of the polymer. Poly(styrene), for example, is composed of styrene monomers. Since there is no internal variety to the monomers, poly(styrene) is classifed as a homopolymer. Polymers with more than one variety of monomer are called copolymers, such as ethylene-vinyl acetate. Some biological polymers are composed of a variety of different but structurally related monomers, such as polynucleotides composed of nucleotide subunits.

A polyelectrolyte molecule is a polymer molecule comprised of primarily ionizable repeating subunits. An ionomer molecule is also ionizable, but to a lesser degree.

Arrangement of monomers

The simplest form of polymer molecule is a straight chain or linear polymer, composed of a single main chain. A branched polymer molecule is composed of a main chain with one or more substituent side chains or branches. Special types of branched polymers include star polymers, comb polymers, and brush polymers. If the polymer contains a side chain that has a different composition or configuration than the main chain the polymer is called a graft or grafted polymer. A cross-link suggests a branch point from which four or more distinct chains emanate. A polymer molecule with a high degree of crosslinking is referred to as a polymer network.

Polymer molecules may also be described in terms of how the neighboring structural units are arranged relative to each other, a property referred to as tacticity.

Physical properties of polymers

The properties of polymers vary dramatically depending on the nature, number, and arrangement of the constituent subunits. The same terminology used to describe the properties of non-polymer substances or molecules may be applied to polymers. For example, a polymer molecule may be described as polar, non-polar, or amphiphilic just as any other molecule. There are several cases, however, where a particu

Expressions of mass or size

Like any molecule, a polymer molecule may be described in terms of molecular weight or mass. In homopolymers or block copolymers, however, the molecular mass may be expressed in terms of degree of polymerization, essentially the number of monomer units which comprise the polymer or block. For synthetic polymers, the molecular weight is expressed statistically to describe the distribution of molecular weights in the sample. Examples of such statistics include the number average molecular weight and weight average molecular weight. The ratio of these two values is the polydispersity index, commonly used to express the "width" of the molecular weight.

The space occupied by a polymer molecule is generally expressed in terms of radius of gyration or excluded volume.

Expressions of crystallinity

When applied to polymers, the term crystalline has a somewhat ambiguous usage. In some cases, the term crystalline finds identical usage to that used in conventional crystallography. For example, the structure of a crystalline protein or polynucleotide, such as a sample prepared for x-ray crystallography, may be defined in terms of a conventional unit cell comprised of one or more polymer molecules with cell dimensions of hundreds of angstroms or more.

A synthetic polymer may be described as crystalline if it contains regions of three-dimensional ordering on atomic (rather than macromolecular) length scales, usually arising from intramolecular folding and/or stacking of adjacent chains. Synthetic polymers may consist of both crystalline and amorphous regions; the degree of crystallinity may be expressed in terms of a weight fraction or volume fraction of crystalline material. Few synthetic polymers are entirely crystalline.

Phase transitions

The term "melting point" when applied to polymers suggests not a solid-liquid phase transition but a transition from a crystalline or semi-crystalline phase to a solid amorphous phase. Though abbreviated as simply "T_m", the property in question is more properly called the "crystalline melting temperature". Among synthetic polymers, crystalline melting is only discussed with regards to thermoplastics, as thermosetting polymers will decompose at high temperatures rather than melt.

The boiling point of a polymer substance is never defined, in that polymers will decompose before reaching assumed boiling temperatures.

A parameter of particular interest in synthetic polymer manufacturing is the glass transition temperature (T_g), which describes the temperature at which amorphous polymers undergo a second order phase transition from a rubbery, viscous amorphous solid to a brittle, glassy amorphous solid. The glass transition temperature may be engineered by altering the degree of branching or cross-linking in the polymer or by the addition of plasticizer.

Standardized polymer nomenclature

There are multiple conventions for naming polymer substances. Many commonly used polymers, such as those found in consumer products, are referred to by a common or trivial name. The trivial name is assigned based on historical precedent or popular usage rather than a standardized naming convention. Both the American Chemical Society and IUPAC have proposed standardized naming conventions; the ACS and IUPAC conventions are similar but not identical. Examples of the difference between the various naming conventions are given in the table below:

Common Name	ACS Name	IUPAC Name
Poly(ethylene oxide) or (PEO)	poly(oxyethylene)	poly(oxyethylene)
Poly(ethylene terephthalate) or (PET)	poly(oxy-1,2-ethanediyloxycarbonyl -1,4-phenylenecarbonyl)	poly(oxyethyleneoxyterephth= aloyl)
Nylon	poly[imino(1-oxo-1,6-hexanediyl)]	poly[imino(1-oxohexane-1,6-diyl)]

In both standardized conventions the polymers names are intended to reflect the monomer(s) from which they are synthesized rather than the precise nature of the repeating subunit. For example, the polymer synthesized from the simple alkene ethene is called polyethylene, retaining the -ene suffix even though the double bond is removed during the polymerization process.