Polymer

Appearance of real linear polymer chains as recorded using an atomic force microscope on surface under liquid medium. Chain contour length for this polymer is ~204 nm; thickness is ~0.4 nm. A polymer is a large molecule (macromolecule) composed of repeating structural units. hese su!units are typically connected !y co"alent chemical !onds. Although the term polymer is sometimes taken to refer to plastics# it actually encompasses a large class of natural and synthetic materials $ith a $ide "ariety of properties. %ecause of the e&traordinary range of properties of polymeric materials# they play an essential and u!iquitous role in e"eryday life. his role ranges from familiar synthetic plastics and elastomers to natural !iopolymers such as nucleic acids and proteins that are essential for life. 'atural polymeric materials such as shellac# am!er# and natural ru!!er ha"e !een used for centuries. A "ariety of other natural polymers e&ist# such as cellulose# $hich is the main constituent of $ood and paper. he list of synthetic polymers includes synthetic ru!!er# %akelite# neoprene# nylon# ()C# polystyrene# polyethylene# polypropylene# polyacrylonitrile# ()%# silicone# and many more. *ost commonly# the continuously linked !ack!one of a polymer used for the preparation of plastics consists mainly of car!on atoms. A simple e&ample is polyethylene# $hose repeating unit is !ased on ethylene monomer. +o$e"er# other structures do e&ist; for e&ample# elements such as silicon form familiar materials such as silicones# e&amples !eing silly putty and $aterproof plum!ing sealant. ,&ygen is also commonly present in polymer !ack!ones# such as those of polyethylene glycol# polysaccharides (in glycosidic !onds)# and -'A (in phosphodiester !onds). (olymers are studied in the fields of polymer chemistry# polymer physics# and polymer science.

Overview
.hile the term polymer in popular usage suggests /plastic/# polymers comprise a large class of natural and synthetic materials $ith a "ariety of properties and purposes. 'atural polymer materials such as shellac and am!er ha"e !een in use for centuries. (aper is manufactured from cellulose# a naturally occurring polysaccharide found in plants. %iopolymers such as proteins and nucleic acids play important roles in !iological processes.

+enri %raconnot0s pioneering $ork in deri"ati"e cellulose compounds is perhaps the earliest important $ork in modern polymer science. he de"elopment of "ulcani1ation later in the nineteenth century impro"ed the dura!ility of the natural polymer ru!!er# signifying the first populari1ed semi2synthetic polymer. he first $holly synthetic polymer# %akelite# $as disco"ered in 3405. 6ntil the 3420s# most scientists !elie"ed that polymers $ere clusters of small molecules (called colloids)# $ithout definite molecular $eights# held together !y an unkno$n force# a concept kno$n as association theory. 7n 3422# 8erman chemist +ermann 9taudinger proposed that polymers $ere comprised of /macromolecules/ consisted of long chains of atoms held together !y co"alent !onds. hough poorly recei"ed at first# e&perimental $ork !y .allace Carothers# +erman *ark# and others pro"ided further e"idence for 9taudinger0s theory. %y the mid234:0s# the macromolecular theory of polymer structure $as $idely accepted. ;or this and other $ork in the field# 9taudinger $as ultimately a$arded the 'o!el (ri1e. 7n the inter"ening century# synthetic polymer materials such as 'ylon# polyethylene# eflon# and silicone ha"e formed the !asis for a !urgeoning polymer industry. 9ynthetic polymers today find application in nearly e"ery industry and area of life. (olymers are used in the fa!rication of microprocessors# the de"elopment of ne$ pharmaceuticals# and impro"ing yield in petroleum e&traction. (olymers are used as adhesi"es and lu!ricants# as $ell as structural components for products ranging from childrens0 toys to aircraft. ;uture applications include polymeric transistors and su!strates for fle&i!le components and displays# enhanced drug deli"ery methods# and the de"elopment of smart materials.

Polymer science
*ost polymer research may !e categori1ed as polymer science# a su!2discipline of materials science $hich includes researchers in chemistry (especially organic chemistry)# physics# and engineering. he field of polymer science includes !oth e&perimental and theoretical research. he 76(AC recommends that polymer science !e roughly di"ided into t$o su!disciplines< polymer chemistry (or macromolecular chemistry) and polymer physics. 7n practice the distinction !et$een the t$o is rarely clearcut. he study of !iological polymers# their structure# function# and method of synthesis is generally the pur"ie$ of !iology# !iochemistry# and !iophysics. hese disciplines share some of the terminology familiar to polymer science# especially $hen descri!ing the synthesis of !iopolymers such as -'A or polysaccharides. +o$e"er# usage differences persist# such as the practice of using

the term macromolecule to descri!e large non2polymer molecules and comple&es of multiple molecular components# such as hemoglo!in. 9u!stances $ith distinct !iological function are rarely descri!ed in the terminology of polymer science. ;or e&ample# a protein is rarely referred to as a copolymer.

Etymology
he $ord polymer is deri"ed from the 8reek $ords - - polymeaning /many/; and - meros meaning /part/. he term $as coined in 3=:: !y >?ns >aco! %er1elius# although his definition of a polymer $as quite different from the modern definition. (see 'e$ chemical terms)

Historical development
9tarting in 3=33# +enri %raconnot did pioneering $ork in deri"ati"e cellulose compounds# perhaps the earliest important $ork in polymer science. he de"elopment of "ulcani1ation later in the nineteenth century impro"ed the dura!ility of the natural polymer ru!!er# signifying the first populari1ed semi2synthetic polymer. 7n 3405# @eo %aekeland created the first completely synthetic polymer# %akelite# !y reacting phenol and formaldehyde at precisely controlled temperature and pressure. %akelite $as then pu!licly introduced in 3404. -espite significant ad"ances in synthesis and characteri1ation of polymers# a correct understanding of polymer molecular structure did not emerge until the 3420s. %efore then# scientists !elie"ed that polymers $ere clusters of small molecules (called colloids)# $ithout definite molecular $eights# held together !y an unkno$n force# a concept kno$n as association theory. 7n 3422# +ermann 9taudinger proposed that polymers consisted of long chains of atoms held together !y co"alent !onds# an idea $hich did not gain $ide acceptance for o"er a decade and for $hich 9taudinger $as ultimately a$arded the 'o!el (ri1e. .ork !y .allace Carothers in the 3420s also demonstrated that polymers could !e synthesi1ed rationally from their constituent monomers. An important contri!ution to synthetic polymer science $as made !y the 7talian chemist 8iulio 'atta and the 8erman chemist Aarl Biegler# $ho $on the 'o!el (ri1e in Chemistry in 34C: for the de"elopment of the Biegler2'atta catalyst. ;urther recognition of the importance of polymers came $ith the a$ard of the 'o!el (ri1e in Chemistry in 3454 to (aul ;lory# $hose e&tensi"e $ork on polymers included the kinetics of step2gro$th polymeri1ation and of addition polymeri1ation# chain transfer# e&cluded "olume# the ;lory2+uggins solution theory# and the ;lory con"ention.

9ynthetic polymer materials such as nylon# polyethylene# eflon# and silicone ha"e formed the !asis for a !urgeoning polymer industry. hese years ha"e also sho$n significant de"elopments in rational polymer synthesis. *ost commercially important polymers today are entirely synthetic and produced in high "olume on appropriately scaled organic synthetic techniques. 9ynthetic polymers today find application in nearly e"ery industry and area of life. (olymers are $idely used as adhesi"es and lu!ricants# as $ell as structural components for products ranging from children0s toys to aircraft. hey ha"e !een employed in a "ariety of !iomedical applications ranging from implanta!le de"ices to controlled drug deli"ery. (olymers such as poly(methyl methacrylate) find application as photoresist materials used in semiconductor manufacturing and lo$2k dielectrics for use in high2performance microprocessors. Decently# polymers ha"e also !een employed as fle&i!le su!strates in the de"elopment of organic light2emitting diodes for electronic display.

Describing polymers
Molecular description
7n many instances a polymer molecule may !e descri!ed using the same terminology used to descri!e any molecule. *olecular structure may !e descri!ed in terms of !ond lengths and angles; mass may !e descri!ed in terms of molecular $eight. +o$e"er# the si1e and comple&itiy of polymer molecules often require the use of speciali1ed terminology to precisely descri!e the nature of the monomer(s) and ho$ those monomers are connected or arranged. he mass of a polymer molecule may !e descri!ed using standard con"entional for molecular or molar mass. his molecular $eight# e&pressed in -altons# is used frequently to descri!e comple& !iopolymers# such as proteins. An altnerate e&pression for molecular mass is the degree of polymeri1ation (-()# essentially the num!er of monomer units $hich comprise the polymer or !lock. -( is especially con"enient for homopolymers or !lock copolymers# and is used frequency $hen descri!ing the e&tent of a polymeri1ation reaction. @a!oratory syntheses tend to produce polymer samples comprised of molecules $ith a "ariety of different molecular $eights. hus# the molecular $eight of a synthetic polymer is generally e&pressed in terms of a summary statistic# such as the num!er2a"eraged molecular $eight (*n) or $eight2a"eraged molecular $eight(*$). he ratio of these t$o "alues is kno$n as the polydispersity inde&# $hich is an indicator of the distri!ution of molecular $eights $ithin a polymer sample. ;or commercial polymer samples it is common to see all three "alues reported.

he si1e and comple&ity of polymer molecules also requires speciali1ed descriptions of molecular dimensions and ordering. 8lo!ular macromolecules# such as proteins# may ha"e a $ell2defined semi2rigid structure $here con"entional descriptions of atomic positions# !ond lengths# and angles are adequate and appropriate. ,n the other hand# structurally simple polymers# such as linear polymers# possess hundreds or thousands of degrees of rotational freedom# allo$ing the polymer chain to adopt multiple conformations. he si1e and positions of such molecules are descri!ed statistically# $ith molecular "olume e&pressed as a function of the radius of gyration or mean end2to2end distance. *olecular simulations or light scattering may also !e used to determine an energetically fa"ora!le /a"erage conformation/ for a collection of polymer molecules. -escri!ing the crystallinity of a polymer presents some degree of am!iguity. 7n some cases# the term crystalline finds identical usage to that used in con"entional crystallography. ;or e&ample# the structure of a crystalline protein or polynucleotide# such as a sample prepared for &2ray crystallography# may !e defined in terms of a con"entional unit cell comprised of one or more polymer molecules $ith cell dimensions of hundreds of angstroms or more. .hen applied to a synthetic polymer# ho$e"er# the term crystalline implies regions of three2dimensional ordering on atomic (rather than macromolecular) length scales# usually arising from intramolecular folding andEor stacking of adFacent chains. 9ynthetic polymers may consist of !oth crystalline and amorphous regions; the degree of crystallinity may !e e&pressed in terms of a $eight fraction or "olume fraction of crystalline material. ;e$ synthetic polymers are entirely crystalline. A stereochemical description of a polymer molecule also requires speciali1ed terminology. here are some polymers in $hich chirality in the monomer is retained follo$ing polymeri1ation. 7n other polymers a chiral center may !e created !y the polymeri1ation process. here is also a large "oca!ulary used to descri!e the nature of the monomers and the precise arrangement of these monomers relati"e to one another. A polymer consisting of e&actly one type of monomer# such as poly(styrene)# is classifed as a homopolymer. (olymers $ith more than one "ariety of monomer are called copolymers# such as ethylene2"inyl acetate. 9ome !iological polymers are composed of a "ariety of different !ut structurally related monomers# such as polynucleotides composed of nucleotide su!units.

A polyelectrolyte molecule is a polymer molecule comprised of primarily ioni1a!le repeating su!units. An ionomer molecule is also ioni1a!le# !ut to a lesser degree. he 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 $ith one or more su!stituent side chains or !ranches. 9pecial types of !ranched polymers include star polymers# com! polymers# and !rush polymers. 7f 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 !ranch point from $hich four or more distinct chains emanate. A polymer molecule $ith a high degree of crosslinking is referred to as a polymer network.

Macroscopic description
he macroscopic physical properties of polymers in many cases reflect that of any other molecular su!stance. (olymer materials may !e transparent# translucent# or opaque# and may !e insulators# conductors# or semiconductors. ,ther properties# ho$e"er# especially those go"erning phase transitions# may ha"e distinct meanings (or no meaning at all) $hen applied to polymers. he /melting point/ of a polymer# for e&ample# refers not a solid2 liquid phase transition !ut a transition from a crystalline or semi2 crystalline phase to a solid amorphous phase. hough a!!re"iated as simply / m/# the property in question is more properly called the /crystalline melting temperature/. Among synthetic polymers# crystalline melting is only discussed $ith regards to thermoplastics# as thermosetting polymers $ill decompose at high temperatures rather than melt. he !oiling point of a polymer su!stance is ne"er defined# in that polymers $ill decompose !efore reaching assumed !oiling temperatures. A parameter of particular interest in synthetic polymer manufacturing is the glass transition temperature ( g)# $hich descri!es the temperature at $hich amorphous polymers undergo a second order phase transition from a ru!!ery# "iscous amorphous solid to a !rittle# glassy amorphous solid. he glass transition temperature may !e engineered !y altering the degree of !ranching or cross2linking in the polymer or !y the addition of plastici1er.

Polymer synthesis

he repeating unit of the polymer polypropylene (olymeri1ation is the process of com!ining many small molecules kno$n as monomers into a co"alently !onded chain. -uring the polymeri1ation process# some chemical groups may !e lost from each monomer. his is the case# for e&ample# in the polymeri1ation of (G polyester. he monomers are terephthalic acid (+,,C2CC+42 C,,+) and ethylene glycol (+,2C+22C+22,+) !ut the repeating unit is 2,C2CC+42C,,2C+22C+22,2# $hich corresponds to the com!ination of the t$o monomers $ith the loss of t$o $ater molecules. he distinct piece of each monomer that is incorporated into the polymer is kno$n as a repeat unit or monomer residue.

Laboratory synthesis
@a!oratory synthetic methods are generally di"ided into t$o categories# step2gro$th polymeri1ation and chain2gro$th polymeri1ation. he essential difference !et$een the t$o is that in chain gro$th polymeri1ation# monomers are added to the chain one at a time only# $hereas in step2gro$th polymeri1ation chains of monomers may com!ine $ith one another directly. +o$e"er# some ne$er methods such as plasma polymeri1ation do not fit neatly into either category. 9ynthetic polymeri1ation reactions may !e carried out $ith or $ithout a catalyst. @a!oratory synthesis of !iopolymers# especially of proteins# is an area of intensi"e research.

iological synthesis

*icrostructure of part of a -'A dou!le heli& biopolymer *ain article< %iopolymer here are three main classes of !iopolymers< polysaccharides# polypeptides# and polynucleotides. 7n li"ing cells# they may !e synthesi1ed !y en1yme2mediated processes# such as the formation of -'A cataly1ed !y -'A polymerase. he synthesis of proteins in"ol"es multiple en1yme2mediated processes to transcri!e genetic information from the -'A to D'A and su!sequently translate that information to synthesi1e the specified protein from amino acids. he protein may !e modified further follo$ing translation in order to pro"ide appropriate structure and functioning.

Modification of natural polymers

*any commercially important polymers are synthesi1ed !y chemical modification of naturally occurring polymers. (rominent e&amples include the reaction of nitric acid and cellulose to form nitrocellulose and the formation of "ulcani1ed ru!!er !y heating natural ru!!er in the presence of sulfur.

Polymer properties
(olymer properties are !roadly di"ided into se"eral classes !ased on the scale at $hich the property is defined as $ell as upon its physical !asis. he most !asic property of a polymer is the identity of its constituent monomers. A second set of properties# kno$n as microstructure# essentially descri!e the arrangement of these monomers $ithin the polymer at the scale of a single chain. hese !asic structural properties play a maFor role in determining !ulk physical properties of the polymer# $hich descri!e ho$ the polymer

!eha"es as a continuous macroscopic material. Chemical properties# at the nano2scale# descri!e ho$ the chains interact through "arious physical forces. At the macro2scale# they descri!e ho$ the !ulk polymer interacts $ith other chemicals and sol"ents.

Monomers and repeat units

he identity of the monomer residues (repeat units) comprising a polymer is its first and most important attri!ute. (olymer nomenclature is generally !ased upon the type of monomer residues comprising the polymer. (olymers that contain only a single type of repeat unit are kno$n as homopolymers# $hile polymers containing a mi&ture of repeat units are kno$n as copolymers. (oly(styrene)# for e&ample# is composed only of styrene monomer residues# and is therefore classified as a homopolymer. Gthylene2"inyl acetate# on the other hand# contains more than one "ariety of repeat unit and is thus a copolymer. 9ome !iological polymers are composed of a "ariety of different !ut structurally related monomer residues; for e&ample# polynucleotides such as -'A are composed of a "ariety of nucleotide su!units. A polymer molecule containing ioni1a!le su!units is kno$n as a polyelectrolyte or ionomer.

Microstructure
he microstructure of a polymer (sometimes called configuration) relates to the physical arrangement of monomer residues along the !ack!one of the chain. hese are the elements of polymer structure that require the !reaking of a co"alent !ond in order to change. 9tructure has a strong influence on the other properties of a polymer. ;or e&ample# t$o samples of natural ru!!er may e&hi!it different dura!ility# e"en though their molecules comprise the same monomers. Polymer architecture

ranch point in a polymer An important microstructural feature determining polymer properties is the polymer architecture. he simplest polymer architecture is a linear chain< a single !ack!one $ith no !ranches. A related un!ranching architecture is a ring polymer. A !ranched polymer molecule is composed of a main chain $ith one or more su!stituent side chains or !ranches. 9pecial types of !ranched

polymers include star polymers# com! polymers# !rush polymers# dendroni1ed polymers# ladders# and dendrimers. %ranching of polymer chains affects the a!ility of chains to slide past one another !y altering intermolecular forces# in turn affecting !ulk physical polymer properties. @ong chain !ranches may increase polymer strength# toughness# and the glass transition temperature ( g) due to an increase in the num!er of entanglements per chain. he effect of such long2chain !ranches on the si1e of the polymer in solution is characteri1ed !y the !ranching inde&. Dandom length and atactic short chains# on the other hand# may reduce polymer strength due to disruption of organi1ation and may like$ise reduce the crystallinity of the polymer. A good e&ample of this effect is related to the range of physical attri!utes of polyethylene. +igh2density polyethylene (+-(G) has a "ery lo$ degree of !ranching# is quite stiff# and is used in applications such as milk Fugs. @o$2density polyethylene (@-(G)# on the other hand# has significant num!ers of !oth long and short !ranches# is quite fle&i!le# and is used in applications such as plastic films.

-endrimer and dendron -endrimers are a special case of polymer $here e"ery monomer unit is !ranched. his tends to reduce intermolecular chain entanglement and crystalli1ation. Alternati"ely# dendritic polymers are not perfectly !ranched !ut share similar properties to dendrimers due to their high degree of !ranching. he architecture of the polymer is often physically determined !y the functionality of the monomers from $hich it is formed. his property of a monomer is defined as the num!er of reaction sites at $hich may form chemical co"alent !onds. he !asic functionality required for forming e"en a linear chain is t$o !onding sites. +igher functionality yields !ranched or e"en crosslinked or net$orked polymer chains. An effect related to !ranching is chemical crosslinking 2 the formation of co"alent !onds !et$een chains. Crosslinking tends to

increase g and increase strength and toughness. Among other applications# this process is used to strengthen ru!!ers in a process kno$n as "ulcani1ation# $hich is !ased on crosslinking !y sulfur. Car tires# for e&ample# are highly crosslinked in order to reduce the leaking of air out of the tire and to toughen their dura!ility. Graser ru!!er# on the other hand# is not crosslinked to allo$ flaking of the ru!!er and pre"ent damage to the paper. A cross2link suggests a !ranch point from $hich four or more distinct chains emanate. A polymer molecule $ith a high degree of crosslinking is referred to as a polymer net$ork. 9ufficiently high crosslink concentrations may lead to the formation of an infinite net$ork# also kno$n as a gel# in $hich net$orks of chains are of unlimited e&tentHessentially all chains ha"e linked into one molecule. !hain length he physical properties of a polymer are strongly dependent on the si1e or length of the polymer chain. ;or e&ample# as chain length is increased# melting and !oiling temperatures increase quickly. 7mpact resistance also tends to increase $ith chain length# as does the "iscosity# or resistance to flo$# of the polymer in its melt state. Chain length is related to melt "iscosity roughly as 3<30:.2# so that a tenfold increase in polymer chain length results in a "iscosity increase of o"er 3000 times. 7ncreasing chain length furthermore tends to decrease chain mo!ility# increase strength and toughness# and increase the glass transition temperature ( g). his is a result of the increase in chain interactions such as )an der .aals attractions and entanglements that come $ith increased chain length. hese interactions tend to fi& the indi"idual chains more strongly in position and resist deformations and matri& !reakup# !oth at higher stresses and higher temperatures. A common means of e&pressing the length of a chain is the degree of polymeri1ation# $hich quantifies the num!er of monomers incorporated into the chain. As $ith other molecules# a polymer0s si1e may also !e e&pressed in terms of molecular $eight. 9ince synthetic polymeri1ation techniques typically yield a polymer product including a range of molecular $eights# the $eight is often e&pressed statistically to descri!e the distri!ution of chain lengths present in the same. Common e&amples are the num!er a"erage molecular $eight and $eight a"erage molecular $eight. he ratio of these t$o "alues is the polydispersity inde&# commonly used to e&press the /$idth/ of the molecular $eight distri!ution. A final measurement is contour length# $hich can !e understood as the length of the chain !ack!one in its fully e&tended state.

he fle&i!ility of an un!ranched chain polymer is characteri1ed !y its persistence length. Monomer arrangement in copolymers

*onomers $ithin a copolymer may !e organi1ed along the !ack!one in a "ariety of $ays.

"lternating copolymers possess regularly alternating monomer residues< IA%...Jn (2). Periodic copolymers ha"e monomer residue types arranged in a repeating sequence< IAn%m...J m !eing different from n . #tatistical copolymers ha"e monomer residues arranged according to a kno$n statistical rule. A statistical copolymer in $hich the pro!a!ility of finding a particular type of monomer residue at an particular point in the chain is independent of the types of surrounding monomer residue may !e referred to as a truly random copolymer (:). lock copolymers ha"e t$o or more homopolymer su!units linked !y co"alent !onds (4). (olymers $ith t$o or three !locks of t$o distinct chemical species (e.g.# A and %) are called di!lock copolymers and tri!lock copolymers# respecti"ely. (olymers $ith three !locks# each of a different chemical species (e.g.# A# %# and C) are termed tri!lock terpolymers. $raft or grafted copolymers contain side chains that ha"e a different composition or configuration than the main chain. (K)

%acticity acticity descri!es the relati"e stereochemistry of chiral centers in neigh!oring structural units $ithin a macromolecule. here are three types< isotactic (all su!stituents on the same side)# atactic (random placement of su!stituents)# and syndiotactic (alternating placement of su!stituents).

Polymer morphology
(olymer morphology generally descri!es the arrangement and microscale ordering of polymer chains in space. !rystallinity .hen applied to polymers# the term crystalline has a some$hat am!iguous usage. 7n some cases# the term crystalline finds identical usage to that used in con"entional crystallography. ;or e&ample# the structure of a crystalline protein or polynucleotide# such as a sample prepared for &2ray crystallography# may !e defined in terms of a con"entional unit cell composed of one or more polymer molecules $ith cell dimensions of hundreds of angstroms or more. A synthetic polymer may !e lightly descri!ed as crystalline if it contains regions of three2dimensional ordering on atomic (rather than macromolecular) length scales# usually arising from intramolecular folding andEor stacking of adFacent chains. 9ynthetic polymers may consist of !oth crystalline and amorphous regions; the degree of crystallinity may !e e&pressed in terms of a $eight fraction or "olume fraction of crystalline material. ;e$ synthetic polymers are entirely crystalline. he crystallinity of polymers is characteri1ed !y their degree of crystallinity# ranging from 1ero for a completely non2crystalline polymer to one for a theoretical completely crystalline polymer. (olymers $ith microcrystalline regions are generally tougher (can !e !ent more $ithout !reaking) and more impact2resistant than totally amorphous polymers. (olymers $ith a degree of crystallinity approaching 1ero or one $ill tend to !e transparent# $hile polymers $ith intermediate degrees of crystallinity $ill tend to !e opaque due to light scattering !y crystalline or glassy regions. hus for many polymers# reduced crystallinity may also !e associated $ith increased transparency. !hain conformation he space occupied !y a polymer molecule is generally e&pressed in terms of radius of gyration# $hich is an a"erage distance from the center of mass of the chain to the chain itself. Alternati"ely# it may !e e&pressed in terms of per"aded "olume# $hich is the "olume of solution spanned !y the polymer chain and scales $ith the cu!e of the radius of gyration.

Mechanical properties

A polyethylene sample necking under tension. he !ulk properties of a polymer are those most often of end2use interest. hese are the properties that dictate ho$ the polymer actually !eha"es on a macroscopic scale. %ensile strength he tensile strength of a material quantifies ho$ much stress the material $ill endure !efore suffering permanent deformation. his is "ery important in applications that rely upon a polymer0s physical strength or dura!ility. ;or e&ample# a ru!!er !and $ith a higher tensile strength $ill hold a greater $eight !efore snapping. 7n general# tensile strength increases $ith polymer chain length and crosslinking of polymer chains. &oung's modulus of elasticity Loung0s *odulus quantifies the elasticity of the polymer. 7t is defined# for small strains# as the ratio of rate of change of stress to strain. @ike tensile strength# this is highly rele"ant in polymer applications in"ol"ing the physical properties of polymers# such as ru!!er !ands. he modulus is strongly dependent on temperature.

%ransport properties
ransport properties such as diffusi"ity relate to ho$ rapidly molecules mo"e through the polymer matri&. hese are "ery important in many applications of polymers for films and mem!ranes.

Phase behavior
Melting point he term melting point# $hen applied to polymers# suggests not a solid2liquid phase transition !ut a transition from a crystalline or semi2crystalline phase to a solid amorphous phase. hough

a!!re"iated as simply Tm# the property in question is more properly called the crystalline melting temperature. Among synthetic polymers# crystalline melting is only discussed $ith regards to thermoplastics# as thermosetting polymers $ill decompose at high temperatures rather than melt. $lass transition temperature A parameter of particular interest in synthetic polymer manufacturing is the glass transition temperature ( g)# $hich descri!es the temperature at $hich amorphous polymers undergo a transition from a ru!!ery# "iscous amorphous solid# to a !rittle# glassy amorphous solid. he glass transition temperature may !e engineered !y altering the degree of !ranching or crosslinking in the polymer or !y the addition of plastici1er. Mi(ing behavior

(hase diagram of the typical mi&ing !eha"ior of $eakly interacting polymer solutions. 7n general# polymeric mi&tures are far less misci!le than mi&tures of small molecule materials. his effect results from the fact that the dri"ing force for mi&ing is usually entropy# not interaction energy. 7n other $ords# misci!le materials usually form a solution not !ecause their interaction $ith each other is more fa"ora!le than their self2 interaction# !ut !ecause of an increase in entropy and hence free energy associated $ith increasing the amount of "olume a"aila!le to each component. his increase in entropy scales $ith the num!er of particles (or moles) !eing mi&ed. 9ince polymeric molecules are

much larger and hence generally ha"e much higher specific "olumes than small molecules# the num!er of molecules in"ol"ed in a polymeric mi&ture is far smaller than the num!er in a small molecule mi&ture of equal "olume. he energetics of mi&ing# on the other hand# is compara!le on a per "olume !asis for polymeric and small molecule mi&tures. his tends to increase the free energy of mi&ing for polymer solutions and thus make sol"ation less fa"ora!le. hus# concentrated solutions of polymers are far rarer than those of small molecules. ;urthermore# the phase !eha"ior of polymer solutions and mi&tures is more comple& than that of small molecule mi&tures. .hereas most small molecule solutions e&hi!it only an upper critical solution temperature phase transition# at $hich phase separation occurs $ith cooling# polymer mi&tures commonly e&hi!it a lo$er critical solution temperature phase transition# at $hich phase separation occurs $ith heating. 7n dilute solution# the properties of the polymer are characteri1ed !y the interaction !et$een the sol"ent and the polymer. 7n a good sol"ent# the polymer appears s$ollen and occupies a large "olume. 7n this scenario# intermolecular forces !et$een the sol"ent and monomer su!units dominate o"er intramolecular interactions. 7n a !ad sol"ent or poor sol"ent# intramolecular forces dominate and the chain contracts. 7n the theta sol"ent# or the state of the polymer solution $here the "alue of the second "irial coefficient !ecomes 0# the intermolecular polymer2sol"ent repulsion !alances e&actly the intramolecular monomer2monomer attraction. 6nder the theta condition (also called the ;lory condition)# the polymer !eha"es like an ideal random coil. he transition !et$een the states is kno$n as a coil2glo!ule transition. )nclusion of plastici*ers 7nclusion of plastici1ers tends to lo$er g and increase polymer fle&i!ility. (lastici1ers are generally small molecules that are chemically similar to the polymer and create gaps !et$een polymer chains for greater mo!ility and reduced interchain interactions. A good e&ample of the action of plastici1ers is related to poly"inylchlorides or ()Cs. A u()C# or unplastici1ed poly"inylchloride# is used for things such as pipes. A pipe has no plastici1ers in it# !ecause it needs to remain strong and heat2 resistant. (lastici1ed ()C is used for clothing for a fle&i!le quality. (lastici1ers are also put in some types of cling film to make the polymer more fle&i!le.

!hemical properties

he attracti"e forces !et$een polymer chains play a large part in determining a polymer0s properties. %ecause polymer chains are so long# these interchain forces are amplified far !eyond the attractions !et$een con"entional molecules. -ifferent side groups on the polymer can lend the polymer to ionic !onding or hydrogen !onding !et$een its o$n chains. hese stronger forces typically result in higher tensile strength and higher crystalline melting points. he intermolecular forces in polymers can !e affected !y dipoles in the monomer units. (olymers containing amide or car!onyl groups can form hydrogen !onds !et$een adFacent chains; the partially positi"ely charged hydrogen atoms in '2+ groups of one chain are strongly attracted to the partially negati"ely charged o&ygen atoms in CM, groups on another. hese strong hydrogen !onds# for e&ample# result in the high tensile strength and melting point of polymers containing urethane or urea linkages. (olyesters ha"e dipole2dipole !onding !et$een the o&ygen atoms in CM, groups and the hydrogen atoms in +2C groups. -ipole !onding is not as strong as hydrogen !onding# so a polyester0s melting point and strength are lo$er than Ae"lar0s ( $aron)# !ut polyesters ha"e greater fle&i!ility. Gthene# ho$e"er# has no permanent dipole. he attracti"e forces !et$een polyethylene chains arise from $eak "an der .aals forces. *olecules can !e thought of as !eing surrounded !y a cloud of negati"e electrons. As t$o polymer chains approach# their electron clouds repel one another. his has the effect of lo$ering the electron density on one side of a polymer chain# creating a slight positi"e dipole on this side. his charge is enough to attract the second polymer chain. )an der .aals forces are quite $eak# ho$e"er# so polyethylene can ha"e a lo$er melting temperature compared to other polymers.

#tandardi*ed polymer nomenclature

here are multiple con"entions for naming polymer su!stances. *any commonly used polymers# such as those found in consumer products# are referred to !y a common or tri"ial name. he tri"ial name is assigned !ased on historical precedent or popular usage rather than a standardi1ed naming con"ention. %oth the American Chemical 9ociety (AC9)I:2J and 76(ACI::J ha"e proposed standardi1ed naming con"entions; the AC9 and 76(AC con"entions are similar !ut not identical.I:4J G&amples of the differences !et$een the "arious naming con"entions are gi"en in the ta!le !elo$< !ommon "!# name name (oly(ethylene (oly(o&yethylene) )+P"! name (oly(o&yethene)

o&ide) or (G, (oly(o&y23#22 (oly(ethylene ethanediylo&ycar!ony (oly(o&yetheneo&yterephthalo terephthalate) l23#42 yl) or (G phenylenecar!onyl) (olyIamino(32o&o23#C2 (olyIamino(32o&ohe&an23#C2 'ylon C he&anediyl)J diyl)J 7n !oth standardi1ed con"entions# the polymers0 names are intended to reflect the monomer(s) from $hich they are synthesi1ed rather than the precise nature of the repeating su!unit. ;or e&ample# the polymer synthesi1ed from the simple alkene ethene is called polyethylene# retaining the -ene suffi& e"en though the dou!le !ond is remo"ed during the polymeri1ation process<

Polymer characteri*ation
he characteri1ation of a polymer requires se"eral parameters $hich need to !e specified. his is !ecause a polymer actually consists of a statistical distri!ution of chains of "arying lengths# and each chain consists of monomer residues $hich affect its properties. A "ariety of la! techniques are used to determine the properties of polymers. echniques such as $ide angle N2ray scattering# small angle N2ray scattering# and small angle neutron scattering are used to determine the crystalline structure of polymers. 8el permeation chromatography is used to determine the num!er a"erage molecular $eight# $eight a"erage molecular $eight# and polydispersity. ; 7D# Daman and '*D can !e used to determine composition. hermal properties such as the glass transition temperature and melting point can !e determined !y differential scanning calorimetry and dynamic mechanical analysis. (yrolysis follo$ed !y analysis of the fragments is one more technique for determining the possi!le structure of the polymer. hermogra"imetry is a useful technique to e"aluate the thermal sta!ility of the polymer. -etailed analyses of 8 cur"es also allo$ us

to kno$ a !it of the phase segregation in polymers. Dheological properties are also commonly used to help determine molecular architecture (molecular $eight# molecular $eight distri!ution and !ranching)as $ell as to understand ho$ the polymer $ill process# through measurements of the polymer in the melt phase. Another (olymer characteri1ation technique is Automatic Continuous ,nline *onitoring of (olymeri1ation Deactions (AC,*() $hich pro"ides real2time characteri1ation of polymeri1ation reactions. 7t can !e used as an analytical method in DO-# as a tool for reaction optimi1ation at the !ench and pilot plant le"el and# e"entually# for feed!ack control of full2scale reactors. AC,*( measures in a model2 independent fashion the e"olution of a"erage molar mass and intrinsic "iscosity# monomer con"ersion kinetics and# in the case of copolymers# also the a"erage composition drift and distri!ution. 7t is applica!le in the areas of free radical and controlled radical homo2 and copolymeri1ation# polyelectrolyte synthesis# heterogeneous phase reactions# including emulsion polymeri1ation# adaptation to !atch and continuous reactors# and modifications of polymers.

E,"MPLE# OPOL&ME.# P.EP"."%)O0 M.%HOD#

/)%H

%HE).

POL&#%&.E0E1 "n "ddition Polymer (olystyrene is used to make many types of containers such as"ideocassette cases# compact disk Fe$el !o&es#ta!le$are (forks# kni"es and spoons)# and cafeteria trays. A foamed formof polystyrene is used to make coffee cups# grocery store meat trays# and !uilding insulation. o minimi1e fumes in the la!oratory# this procedure uses a styrene casting resin. #afety Precautions .ear safety goggles at all times in the la!oratory. 9tyrene is harmful !y inhalation. 7t is an irritant to the eyes and respiratory system. .ork in a$ell "entilated area. *ethyl ethyl ketone is an irritant. .ork in a $ell "entilated area. Materials needed 9tyrene casting resin Casting resin catalyst# methyl ethyl ketone +alf of a small petri dish 9tirring rod ,ptional< A clean dry coin# such as a penny Procedure *easure 3K m@ of styrene casting resin into a paper cup. Add K drops of catalyst to the resin. 9tir $ell.

(our the resin mi&ture into a clean half of a petri dish. Allo$ the mi&ture to sit# undistur!ed# forappro&imately one hour or until hard. 7f desired# a clean# dry penny can !e added to the resin after it has set for a!out K minutes. oa"oid air !u!!les# coat the penny $ith a small amount of the mi&ed resin !efore adding it to theresin mi&ture in the petri dish.

"2EL)%E1 %he -irst #ynthetic Polymer %akelite# a phenol2formaldehyde polymer# $as the first completely synthetic plastic# first made !y @eo %aekeland in3405. %aekeland and an assistant started their research in 3404 looking for a synthetic su!stitute for shellac.%akelite $as commercially introduced in 3404. %akelite $as first used to make !illiard !alls# !ut# later# $as used tomake molded insulation# "al"e parts# kno!s# !uttons# knife handles# many types of molded plastic containers forradios and electronic instruments# and more. #afety Precautions .ear safety goggles at all times in the la!oratory. ;ormalin is an irritant to the skin# eyes# and mucous mem!ranes. (henol is to&ic "ia skin contact. 7t is listed as a carcinogen. 8lacial acetic acid is an irritant and can cause !urns on contact. .ork under a hood and $ear glo"es and protecti"e clothing $hen $orking $ith these materials. Materials needed (henol2formaldehyde reaction mi&ture (freshly prepared solution should !e a"aila!le. hereaction mi&ture is made !y mi&ing 2K g :C240P formaldehyde Q 20 g phenol Q KK m@ glacialacetic acid.) +ydrochloric acid# +Cl# concentrated 3K02m@ !eaker stirring rod Procedure 6nder a hood# measure 2K m@ of the phenol2formaldehyde reaction mi&ture into a 3K02m@ !eaker.(lace the !eaker on a $hite paper to$el. Add 30 m@ of concentrated hydrochloric acid# slowly# $ith stirring. Add additional hydrochloric acid# drop$ise# $ith stirring. (Lou $ill need appro&imately 2 m@ of+Cl.) As the polymeri1ation point is reached# a $hite precipitate $ill form and dissol"e. At thepoint $here polymeri1ation !egins# the $hite precipitate $ill not dissol"e. Continue to stir as the plastic forms and !ecomes pink in color. .ash the plastic $ell !efore handling.

.+ E.1 " 0atural Polymer 'atural late& is found in the inner !ark of many trees# especially thosefound in %ra1il and the ;ar Gast. he $hitesticky sap of plants such as milk$eed and dandelions is also a late&. @ate& $ill turn into a ru!!ery mass $ithin 32hours after it is e&posed to the air. he late& protects the tree or plant !y co"ering the $ound $ith a ru!!erymaterial like a !andage. C+: C+2MC2C+MC+2 22methyl23#:2!utadiene 'atural ru!!er is a polymer of isoprene (22methyl23#:2 !utadiene# see;igure 3) in the form of folded polymeric chains $hich are Foined in a net$ork structure and ha"e a high degree of fle&i!ility (9ee ;igure 2). 6pon application of a stress to a ru!!er material# such as !lo$ing up a !alloon or stretching a ru!!er !and# the polymer chain# $hich israndomly oriented# undergoes !ond rotations allo$ing the chain to !ee&tended or elongated (9ee ;igure :). he fact that the chains are Foinedin a net$ork allo$s for elastomeric reco"era!ility since the cross2linked chains cannot irre"ersi!ly slide o"er oneanother. he changes in arrangement are not constrained !y chain rigidity due to crystalli1ation or high "iscosity due to a glassy state. 9ince late& $ill solidify in air# a sta!ili1er is added to pre"entpolymeri1ation if the late& is to !e stored or shipped inliquid form. he sta!ili1er is usually 0.K to 3P ammonia. .hen the ammonia is remo"ed !y e"aporation or !yneutrali1ation# the late& $ill solidify into ru!!er.

0&LO01 " !ondensation Polymer 'ylon $as the result of research directed !y .allace +ume Carothers at du (ont. he research team $as interestedin duplicating the characteristics of silk. 'ylon gained rapid acceptance for use in stockings and in makingparachutes. Carothers# ho$e"er# $as su!Fect to !outs of depression and in 34:5# shortly !efore du (ont placednylon stockings on the market# Carothers committed suicide !y drinking cyanide. #afety Precautions .ear safety goggles at all times in the la!oratory.

he materials in this e&periment are considered to&ic. hey are irritants to the eyes and mucousmem!ranes. .ear glo"es and $ork in a $ell "entilated area.

Materials needed +e&amethylenediamine (3#C2he&anediamine)# KP aqueous solution9e!acoyl chloride (or adipyl chloride)# KP solution in cyclohe&ane9odium hydro&ide# 'a,+# 20P aqueous solution %eaker# K0 m@ ;orceps 9tirring rod. Procedure (our 30 m@ of he&amethylenediamine solution into a K0 m@ !eaker. Add 30 drops of 20P sodium hydro&ide solution. 9tir. Carefully add 30 m@ of se!acoyl chloride solution !y pouring it do$n the $all of the tilted !eaker. $o layers should !e e"ident in the !eaker and there should !e an immediate formation of apolymer film at the interface !et$een the t$o liquids. 6sing forceps# pick up the mass at the center and slo$ly dra$ out the nylon# allo$ing a RropeS to!e formed. 6se a stirring rod to $rap the rope and continue to pull it slo$ly from the mi&ture interface. .ash the nylon $ell $ith $ater !efore handling. 9tir any remaining solutions left in the !eak to form additional polymer. .ash the nylon $ell$ith $ater. Commercially# nylon is made !y mi&ing the components in !ulk. 'ylon thread# rod# and sheet aremade !y melting and forming or e&truding the polymer. #OD)+M POL&"!.&L"%E1 " !opolymer 9upera!sor!ants $ere originally de"eloped !y the 6nited 9tates -epartment of Agriculture in 34CC. his materialconsisted of a grafted copolymer of hydroly1ed starch2polyacrylonitrile (polyacrylonitrile is commonly kno$n asAcrilan# ,rion# or Creslan). he intended use $as for additi"es for drilling fluid in off2shore secondary oil reco"eryoperations and as agricultural thickeners. hese materials $ere follo$ed !y synthetic supera!sor!ants that arepolyacrylic and polyacrylonitrile !ased. 9ome of these materials are capa!le of a!sor!ing up to 2000 times their$eight of distilled $ater. .hen a starch2hydroly1ed polyacrylonitrile supera!sor!ant is mi&ed $ith glycerin or ethylene glycol# the resultingfirm gel has a ru!!ery te&ture and is "ery strong and resilient. his material can a!sor! a!out :00 to 400 times its$eight in distilled $ater and can Rgro$S many times its original si1e. his material $as formed into "arious shapesand sold under names such as /8ro$ Creatures/. he

process is re"ersi!le and# on standing in air# the gro$ creature$ill shrink almost to its original si1e on drying. 7t can !e gro$n and dried many times. A useful application of /9uper 9lurper/ is in the liners of (ampers and other disposa!le diapers. 6nder thisapplication# the polymer gel can a!sor! up to 40 times its $eight in liquid.9uper2a!sor!ent material# sold under the name /.ater 8ra!!er/ or /.ater @ock/ is a"aila!le from garden supplystores and can !e found in the garden department of some "ariety stores.

#ome )norganic Polymers 9ome e&amples of27norganic (olymers< (Def.< #cientific "merican# 345# CC# *arch 3454)

+.

D.

Allcock#

8lass< made of rings and chains of repeating silicate units. 8lass fi!ers (fi!erglass) are used in te&tiles and in manyconstruction materials. %ricks# concrete and ceramics are three2dimensional polymers. (olyphospha1enes< general formula ('(Cl2) n . ;ormed from reacting'+4Cl $ith (ClK at 2K0TC for se"eral hours.Can !e su!stituted to alter properties. Polymeric #ulfur Materials 0eeded 9ulfur #afety Precautions 7t is recommended that a hot plate !e used in heating the sulfur in this preparation. his $ill pre"ent thesulfur from igniting and !urning to form to&ic sulfur dio&ide# a strong irritant. Aeep the !eaker of sulfurco"ered $ith a $atch glass to minimi1e sulfur "apors escaping from the !eaker. Procedure +eat ordinary sulfur to a temperature !et$een 3402350TC. he sulfur $ill turn red and !ecome "iscous a!o"e3K4TC. At 35KTC# the "iscosity of the molten sulfur !egins to decrease. (our the hot melt into $ater in a thin stream. .hen cool# it forms ru!!ery fi!ers of the (olymeric sulfur. hepolymer is not sta!le at room temperature and it $ill e"entually harden# returning to its normal yello$ color# $henthe molecules reform into eight2mem!ered rings.

Polymer degradation

A plastic item $ith thirty years of e&posure to heat and cold# !rake fluid# and sunlight. 'otice the discoloration# s$ollen dimensions# and tiny splits running through the material (olymer degradation is a change in the propertiesHtensile strength# color# shape# molecular $eight# etc.Hof a polymer or polymer2!ased product under the influence of one or more en"ironmental factors# such as heat# light# chemicals and# in some cases# gal"anic action. 7t is often due to the scission of polymer chain !onds "ia hydrolysis# leading to a decrease in the molecular mass of the polymer. Although such changes are frequently undesira!le# in some cases# such as !iodegradation and recycling# they may !e intended to pre"ent en"ironmental pollution. -egradation can also !e useful in !iomedical settings. ;or e&ample# a copolymer of (olylactic acid and polyglycolic acid is employed in hydrolysa!le stitches that slo$ly degrade after they are applied to a $ound. he suscepti!ility of a polymer to degradation depends on its structure. Gpo&ies and chains containing aromatic functionality are especially suscepti!le to 6) degradation $hile polyesters are suscepti!le to degradation !y hydrolysis# and some other polymers are especially suscepti!le to o1one cracking. Car!on !ased polymers are more suscepti!le to thermal degradation than inorganically !ound polymers such as polydimethylsilo&ane and are therefore not ideal for most high temperature applications. he degradation of polymers to form smaller molecules may proceed !y random scission or specific scission. he degradation of polyethylene occurs !y random scissionHa random !reakage of the linkages (!onds) that hold the atoms of the polymer together. .hen heated a!o"e 4K0 TC it degrades to form a mi&ture of hydrocar!ons. ,ther polymersHlike polyalphamethylstyreneHundergo specific chain scission $ith !reakage occurring only at the ends. hey literally un1ip or depolymeri1e to !ecome the constituent monomer.

he sorting of polymer $aste for recycling purposes may !e facilitated !y the use of the Desin identification codes de"eloped !y the 9ociety of the (lastics 7ndustry to identify the type of plastic.

Product failure

Chlorine attack of acetal resin plum!ing Foint 7n a finished product# such a change is to !e pre"ented or delayed. ;ailure of safety2critical polymer components can cause serious accidents# such as fire in the case of cracked and degraded polymer fuel lines. Chlorine2induced cracking of acetal resin plum!ing Foints and poly!utylene pipes has caused many serious floods in domestic properties# especially in the 69A in the 3440s. races of chlorine in the $ater supply attacked "ulnera!le polymers in the plastic plum!ing# a pro!lem $hich occurs faster if any of the parts ha"e !een poorly e&truded or inFection molded. Attack of the acetal Foint occurred !ecause of faulty molding# leading to cracking along the threads of the fitting $hich is a serious stress concentration.

,1one2induced cracking in natural ru!!er tu!ing (olymer o&idation has caused accidents in"ol"ing medical de"ices. ,ne of the oldest kno$n failure modes is o1one cracking caused !y chain scission $hen o1one gas attacks suscepti!le elastomers# such as natural ru!!er and nitrile ru!!er. hey possess dou!le !onds in their repeat units $hich are clea"ed during o1onolysis. Cracks in fuel lines can penetrate the !ore of the tu!e and cause fuel leakage. 7f cracking occurs in the engine compartment# electric sparks can ignite the gasoline and can cause a serious fire. ;uel lines can also !e attacked !y another form of degradation< hydrolysis. 'ylon C#C is suscepti!le to acid hydrolysis# and in one accident# a fractured fuel line led to a spillage of diesel into the

road. 7f diesel fuel leaks onto the road# accidents to follo$ing cars can !e caused !y the slippery nature of the deposit# $hich is like !lack ice.