Array ( [0] => {{short description|Substance composed of macromolecules with repeating structural units}} [1] => {{Other uses}} [2] => {{pp-semi-indef}} [3] => {{use dmy dates|date=September 2023}} [4] => {{TopicTOC-Polymer}} [5] => [[File:Single Polymer Chains AFM.jpg|thumb|upright=0.8|Appearance of real linear polymer chains as recorded using an [[atomic force microscope]] on a surface, under liquid medium. Chain [[contour length]] for this polymer is ~204 nm; thickness is ~0.4 nm.{{cite journal|first1=Y.|last1=Roiter |first2=S.|last2=Minko|doi=10.1021/ja0558239|title= AFM Single Molecule Experiments at the Solid-Liquid Interface: In Situ Conformation of Adsorbed Flexible Polyelectrolyte Chains|journal=Journal of the American Chemical Society|volume=127|issue=45|pages=15688–15689|year=2005|pmid=16277495}}]] [6] => [7] => [15] => [[File:IUPAC definition for polymer.png|thumb|right|550px|link=https://doi.org/10.1351/goldbook.P04735|IUPAC definition for polymer]] [16] => [17] => [20] => A '''polymer''' ({{IPAc-en|ˈ|p|ɒ|l|ᵻ|m|ər}}{{cite web|title=Polymer – Definition of polymer|url=https://www.thefreedictionary.com/polymer|publisher=[[TheFreeDictionary.com|The Free Dictionary]]|access-date=23 July 2013}}{{cite encyclopedia|title=Define polymer|url=https://www.dictionary.com/browse/polymer|dictionary=[[Dictionary.com|Dictionary Reference]]|access-date=23 July 2013}}) [21] => is a [[Chemical substance|substance]] or [[material]] consisting of very large [[molecule]]s called [[macromolecule]]s, composed of many [[Repeat unit|repeating subunits]].{{cite web|url=https://www.britannica.com/science/polymer|title=Polymer on Britannica|date=25 December 2023 }} Due to their broad spectrum of properties,{{cite book |last1= Painter |first1= Paul C. |last2= Coleman |first2= Michael M. |title= Fundamentals of polymer science: an introductory text |year= 1997 |publisher= Technomic Pub. Co. |location= Lancaster, Pa. |isbn= 978-1-56676-559-6 |page= 1}} both synthetic and natural polymers play essential and ubiquitous roles in everyday life.{{cite book |last1= McCrum |first1= N. G. |last2= Buckley |first2= C. P. |last3= Bucknall |first3= C. B. |title= Principles of polymer engineering |year= 1997 |publisher= Oxford University Press |location= Oxford; New York |isbn= 978-0-19-856526-0 |page= 1}} Polymers range from familiar [[synthetic plastic]]s such as [[polystyrene]] to natural [[biopolymer]]sSaberi, A.; Bakhsheshi-Rad, H.R.; Abazari, S.; Ismail, A.F.; Sharif, S.; Ramakrishna, S.; Daroonparvar, M.; Berto, F. A Comprehensive Review on Surface Modifications of Biodegradable Magnesium-Based Implant Alloy: Polymer Coatings Opportunities and Challenges. Coatings 2021, 11, 747. https://doi.org/10.3390/coatings11070747 such as [[DNA]] and [[protein]]s that are fundamental to biological structure and function. Polymers, both natural and synthetic, are created via [[polymerization]] of many small molecules, known as [[monomer]]s. Their consequently large [[molecular mass]], relative to [[small molecule]] [[compound (chemistry)|compound]]s, produces unique [[physical property|physical properties]] including [[toughness]], high [[rubber elasticity|elasticity]], [[viscoelasticity]], and a tendency to form [[Amorphous solid|amorphous]] and [[crystallization of polymers|semicrystalline]] structures rather than [[crystal]]s. [22] => [23] => [24] => [25] => Polymers are studied in the fields of [[polymer science]] (which includes [[polymer chemistry]] and [[polymer physics]]), [[biophysics]] and [[materials science|materials science and engineering]]. Historically, products arising from the linkage of repeating units by [[covalent]] [[chemical bond]]s have been the primary focus of polymer science. An emerging important area now focuses on [[supramolecular polymer]]s formed by non-covalent links. [[Polyisoprene]] of [[latex]] [[rubber]] is an example of a natural polymer, and the [[polystyrene]] of [[expanded polystyrene|styrofoam]] is an example of a synthetic polymer. In biological contexts, essentially all biological [[macromolecule]]s—i.e., proteins (polyamides), [[nucleic acid]]s (polynucleotides), and [[polysaccharide]]s—are purely polymeric, or are composed in large part of polymeric components. [26] => [29] => [30] => [[File:Polymer chain SPT.png|thumb|Cartoon schematic of polymer molecules]] [31] => [32] => == Etymology == [33] => The term "polymer" derives {{ety|el|''πολύς'' (polus)|many, much||''μέρος'' (meros)|part}}. The term was coined in 1833 by [[Jöns Jacob Berzelius]], though [[Jöns Jacob Berzelius#New chemical terms|with a definition]] distinct from the modern [[IUPAC]] definition.If two substances had molecular formulae such that one was an integer multiple of the other – e.g., acetylene ({{chem2|C2H2}}) and benzene ({{chem2|C6H6}}) – Berzelius called the multiple formula "polymeric". See: Jöns Jakob Berzelius (1833) "''Isomerie'', Unterscheidung von damit analogen Verhältnissen" (''Isomeric'', distinction from relations analogous to it), ''Jahres-Bericht über die Fortschitte der physischen Wissenschaften …'', '''12''': 63–67. [https://books.google.com/books?id=1vs4AAAAMAAJ&pg=RA1-PA64 From page 64]: "Um diese Art von Gleichheit in der Zusammensetzung, bei Ungleichheit in den Eigenschaften, bezeichnen zu können, möchte ich für diese Körper die Benennung ''polymerische'' (von ''πολυς'' mehrere) vorschlagen." (In order to be able to denote this type of similarity in composition [which is accompanied] by differences in properties, I would like to propose the designation "polymeric" (from ''πολυς'', several) for these substances.)
Originally published in 1832 in Swedish as: Jöns Jacob Berzelius (1832) "Isomeri, dess distinktion från dermed analoga förhållanden," ''Årsberättelse om Framstegen i Fysik och Kemi'', pages 65–70; the word "polymeriska" appears on [https://books.google.com/books?id=PZUHAAAAcAAJ&pg=PA66 page 66].{{cite journal |author=Jensen, William B. |author1-link=William B. Jensen |year=2008 |title=Ask the Historian: The origin of the polymer concept |url=http://www.che.uc.edu/jensen/W.%20B.%20Jensen/Reprints/141.%20Polymer.pdf |url-status=dead |journal=Journal of Chemical Education |volume=85 |issue=5 |pages=624–625 |bibcode=2008JChEd..85..624J |doi=10.1021/ed085p624 |archive-url=https://web.archive.org/web/20180618125718/http://www.che.uc.edu/jensen/W.%20B.%20Jensen/Reprints/141.%20Polymer.pdf |archive-date=18 June 2018 |access-date=4 March 2013}} The modern concept of polymers as covalently bonded macromolecular structures was proposed in 1920 by [[Hermann Staudinger]],{{cite journal |last1=Staudinger |first1=H |year=1920 |title=Über Polymerisation |trans-title=On polymerization |url=https://babel.hathitrust.org/cgi/pt?id=uc1.b3481298;view=1up;seq=1283 |journal=Berichte der Deutschen Chemischen Gesellschaft |language=de |volume=53 |issue=6 |pages=1073–1085 |doi=10.1002/cber.19200530627}} who spent the next decade finding experimental evidence for this hypothesis.{{cite book |last1=Allcock |first1=Harry R. |title=Contemporary Polymer Chemistry |last2=Lampe |first2=Frederick W. |last3=Mark |first3=James E. |publisher=Pearson Education |year=2003 |isbn=978-0-13-065056-6 |edition=3 |page=21}} [34] => [35] => ==Common examples== [36] => {{See also|Polymer classes (disambiguation){{!}}Polymer classes}} [37] => [38] => [[File:Styrene-butadiene chain2.png|thumb|left|Structure of a [[styrene-butadiene]] chain, from a molecular simulation]] [39] => [40] => Polymers are of two types: naturally occurring and synthetic or ''man made''. [41] => [42] => ===Natural=== [43] => [[Natural polymer|Natural polymeric materials]] such as [[hemp]], [[shellac]], [[amber]], [[wool]], [[silk]], and natural [[rubber]] have been used for centuries. A variety of other natural polymers exist, such as [[cellulose]], which is the main constituent of wood and paper. [44] => [45] => ====Space polymer==== [46] => [[Hemoglycin]] (previously termed [[hemolithin]]) is a space polymer that is the first polymer of [[amino acid]]s found in [[meteorite]]s.{{cite journal|last1=McGeoch|first1=J.E.M.|last2=McGeoch|first2=M.W.|date=2015|title=Polymer amide in the Allende and Murchison meteorites.|journal=[[Meteoritics & Planetary Science]]|volume=50|pages=1971–1983|bibcode=2015M&PS...50.1971M|doi=10.1111/maps.12558|number=12|s2cid=97089690|doi-access=free}}{{cite journal |last1=McGeogh |first1=Julie E. M. |last2=McGeogh |first2=Malcolm W. |title=Chiral 480nm absorption in the hemoglycin space polymer: a possible link to replication |date=28 September 2022 |journal=[[Scientific Reports]] |volume=12 |issue=1 |page=16198 |doi=10.1038/s41598-022-21043-4 |pmid=36171277 |pmc=9519966 }}{{cite news |author=Staff |title=Polymers in meteorites provide clues to early solar system |url=https://www.sciencedaily.com/releases/2021/06/210629120835.htm |date=29 June 2021 |work=[[Science Digest]] |access-date=9 January 2023 }} [47] => [48] => ===Synthetic=== [49] => The [[list of synthetic polymers]], roughly in order of worldwide demand, includes [[polyethylene]], [[polypropylene]], [[polystyrene]], [[polyvinyl chloride]], [[synthetic rubber]], [[phenol formaldehyde resin]] (or [[Bakelite]]), [[neoprene]], [[nylon]], [[polyacrylonitrile]], [[polyvinyl butyral|PVB]], [[silicone]], and many more. More than 330 million tons of these polymers are made every year (2015).{{cite web| url = https://committee.iso.org/files/live/sites/tc61/files/The%20Plastic%20Industry%20Berlin%20Aug%202016%20-%20Copy.pdf| title = World Plastics Production}} [50] => [51] => Most commonly, the continuously linked backbone of a polymer used for the preparation of plastics consists mainly of [[carbon]] atoms. A simple example is polyethylene ('polythene' in British English), whose repeat unit or monomer is [[ethylene]]. Many other structures do exist; for example, elements such as silicon form familiar materials such as silicones, examples being [[Silly Putty]] and waterproof plumbing sealant. [[Oxygen]] is also commonly present in polymer backbones, such as those of [[polyethylene glycol]], [[polysaccharide]]s (in [[glycosidic bond]]s), and [[DNA]] (in [[phosphodiester bond]]s). [52] => [53] => ==Synthesis== [54] => {{Main|Polymerization}} [55] => [56] => [[File:Polymerization classification ENmod.png|thumb|A classification of the polymerization reactions|alt=|440x440px]] [57] => Polymerization is the process of combining many [[small molecule]]s known as monomers into a covalently bonded chain or network. During the polymerization process, some chemical groups may be lost from each monomer. This happens in the polymerization of [[polyethylene terephthalate|PET polyester]]. The monomers are [[terephthalic acid]] (HOOC{{--}}C6H4{{--}}COOH) and [[ethylene glycol]] (HO{{--}}CH2{{--}}CH2{{--}}OH) but the repeating unit is {{--}}OC{{--}}C6H4{{--}}COO{{--}}CH2{{--}}CH2{{--}}O{{--}}, which corresponds to the combination of the two monomers with the loss of two water molecules. The distinct piece of each monomer that is incorporated into the polymer is known as a [[repeat unit]] or monomer residue. [58] => [59] => Synthetic methods are generally divided into two categories, [[step-growth polymerization]] and [[addition polymerization|chain polymerization]].{{cite book |last1= Sperling |first1= L. H. (Leslie Howard) |title= Introduction to physical polymer science |year= 2006 |publisher= Wiley |location= Hoboken, N.J. |isbn= 978-0-471-70606-9 |page= 10}} The essential difference between the two is that in chain polymerization, monomers are added to the chain one at a time only,Sperling, p. 11 such as in [[polystyrene]], whereas in step-growth polymerization chains of monomers may combine with one another directly,Sperling, p. 15 such as in [[polyester]]. Step-growth polymerization can be divided into [[polycondensation]], in which low-molar-mass by-product is formed in every reaction step, and [[polyaddition]]. [60] => [[File:Styrene radical chain polymerization.jpg|Example of chain polymerization: Radical polymerization of styrene, R. is initiating radical, P. is another polymer chain radical terminating the formed chain by radical recombination.|alt=|left|frame]] [61] => [62] => Newer methods, such as [[plasma polymerization]] do not fit neatly into either category. Synthetic polymerization reactions may be carried out with or without a [[catalysis|catalyst]]. Laboratory synthesis of biopolymers, especially of [[peptide synthesis|proteins]], is an area of intensive research. [63] => [64] => ===Biological synthesis=== [65] => {{Main|Biopolymer}} [66] => [67] => [[File:DNA animation.gif|thumb|right|Microstructure of part of a DNA [[double helix]] biopolymer]] [68] => [69] => There are three main classes of biopolymers: [[polysaccharide]]s, [[polypeptide]]s, and [[polynucleotide]]s. [70] => In living cells, they may be synthesized by enzyme-mediated processes, such as the formation of DNA catalyzed by [[DNA polymerase]]. The [[protein biosynthesis|synthesis of proteins]] involves multiple enzyme-mediated processes to [[transcription (genetics)|transcribe]] genetic information from the DNA to [[ribonucleic acid|RNA]] and subsequently [[translation (biology)|translate]] that information to synthesize the specified protein from [[amino acid]]s. The protein may be [[posttranslational modification|modified further]] following translation in order to provide appropriate structure and functioning. There are other biopolymers such as [[rubber]], [[suberin]], [[melanin]], and [[lignin]]. [71] => [72] => ===Modification of natural polymers=== [73] => Naturally occurring polymers such as [[cotton]], [[starch]], and rubber were familiar materials for years before synthetic polymers such as [[polyethene]] and [[perspex]] appeared on the market. 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]]. Ways in which polymers can be modified include [[oxidation]], [[cross-link]]ing, and [[endcapping|end-capping]]. [74] => [75] => [79] => [80] => ==Structure== [81] => [82] => The structure of a polymeric material can be described at different length scales, from the sub-nm length scale up to the macroscopic one. There is in fact a hierarchy of structures, in which each stage provides the foundations for the next one.Sperling, p. 29 [83] => The starting point for the description of the structure of a polymer is the identity of its constituent monomers. Next, the [[microstructure]] essentially describes the arrangement of these monomers within the polymer at the scale of a single chain. The microstructure determines the possibility for the polymer to form phases with different arrangements, for example through [[Crystallization of polymers|crystallization]], the [[glass transition]] or [[Copolymer#Microphase separation|microphase separation]].{{cite book |last1=Bower |first1=David I. |title=An introduction to polymer physics |date=2002 |publisher=Cambridge University Press |isbn=9780511801280}} [84] => These features play a major role in determining the physical and chemical properties of a polymer. [85] => [86] => ===Monomers and repeat units=== [87] => The identity of the repeat units (monomer residues, also known as "mers") comprising a polymer is its first and most important attribute. Polymer nomenclature is generally based upon the type of monomer residues comprising the polymer. A polymer which contains only a single type of [[repeat unit]] is known as a '''homopolymer''', while a polymer containing two or more types of repeat units is known as a '''[[copolymer]]'''.Rudin, p. 17 A '''terpolymer''' is a copolymer which contains three types of repeat units.Cowie, p. 4 [88] => [89] => [[Polystyrene]] is composed only of [[styrene]]-based repeat units, and is classified as a homopolymer. [[Polyethylene terephthalate]], even though produced from two different [[monomer]]s ([[ethylene glycol]] and [[terephthalic acid]]), is usually regarded as a homopolymer because only one type of repeat unit is formed. [[Ethylene-vinyl acetate]] contains more than one variety of repeat unit and is a copolymer. Some biological polymers are composed of a variety of different but structurally related monomer residues; for example, [[polynucleotide]]s such as DNA are composed of four types of [[nucleotide]] subunits. [90] => [91] => :{| class="wikitable" style="text-align:left; font-size:90%;" width="80%" [92] => |- [93] => | class="hintergrundfarbe6" align="center" colspan="4" |'''Homopolymers and copolymers (examples)''' [94] => |- style="vertical-align:top" class="hintergrundfarbe2" [95] => | [[File:Polystyrene skeletal.svg|80px|center]] [96] => | [[File:Poly(dimethylsiloxan).svg|100px|center]] [97] => | [[File:PET.svg|200px|center]] [98] => | [[File:Styrol-Butadien-Kautschuk.svg|180px|center]] [99] => |- style="vertical-align:top" [100] => | Homopolymer [[polystyrene]] [101] => | Homopolymer [[polydimethylsiloxane]], a [[silicone]]. The main chain is formed of silicon and oxygen atoms. [102] => | The homopolymer [[polyethylene terephthalate]] has only one [[repeat unit]]. [103] => | Copolymer [[styrene-butadiene rubber]]: The repeat units based on [[styrene]] and [[1,3-Butadiene|1,3-butadiene]] form two repeating units, which can alternate in any order in the macromolecule, making the polymer thus a random copolymer. [104] => |} [105] => [106] => A polymer containing ionizable subunits (e.g., pendant [[carboxylic acid|carboxylic groups]]) is known as a [[polyelectrolyte]] or [[ionomer]], when the fraction of ionizable units is large or small respectively. [107] => [108] => ===Microstructure=== [109] => {{Main|Microstructure}} [110] => The microstructure of a polymer (sometimes called configuration) relates to the physical arrangement of monomer residues along the backbone of the chain.Sperling, p. 30 These are the elements of polymer structure that require the breaking of a covalent bond in order to change. Various polymer structures can be produced depending on the monomers and reaction conditions: A polymer may consist of linear macromolecules containing each only one unbranched chain. In the case of unbranched polyethylene, this chain is a long-chain ''n''-alkane. There are also branched macromolecules with a main chain and side chains, in the case of polyethylene the side chains would be [[alkyl groups]]. In particular unbranched macromolecules can be in the solid state semi-crystalline, crystalline chain sections highlighted red in the figure below. [111] => [112] => While branched and unbranched polymers are usually thermoplastics, many [[elastomer]]s have a wide-meshed cross-linking between the "main chains". Close-meshed crosslinking, on the other hand, leads to [[thermosets]]. Cross-links and branches are shown as red dots in the figures. Highly branched polymers are amorphous and the molecules in the solid interact randomly. [113] => [114] => :{| class="wikitable" style="text-align:center; font-size:90%;" width="60%" [115] => |- class="hintergrundfarbe2" [116] => |[[File:Polymerstruktur-linear.svg|130px]]
Linear, unbranched macromolecule [117] => |[[File:Polymerstruktur-verzweigt.svg|130px]]
Branched macromolecule [118] => |[[File:Polymerstruktur-teilkristallin.svg|150px]]
Semi-crystalline structure of an unbranched polymer [119] => |[[File:Polymerstruktur-weitmaschig vernetzt.svg|130px]]
Slightly [[cross-link]]ed polymer ([[elastomer]]) [120] => |[[File:Polymerstruktur-engmaschig vernetzt.svg|130px]]
Highly cross-linked polymer ([[Thermosetting polymer|thermoset]]) [121] => |} [122] => [123] => ====Polymer architecture{{Anchor|Intermolecular forces}}==== [124] => {{Main|Polymer architecture}} [125] => [[File:Polymer Branch.svg|thumb|right|upright=0.9|Branch point in a polymer]] [126] => [127] => An important microstructural feature of a polymer is its architecture and shape, which relates to the way branch points lead to a deviation from a simple linear chain.{{cite book |last1= Rubinstein |first1= Michael |last2= Colby |first2= Ralph H. |title= Polymer physics |url= https://archive.org/details/polymerphysics00rubi_825 |url-access= limited |year= 2003 |publisher= Oxford University Press |location= Oxford; New York |isbn= 978-0-19-852059-7 |page= [https://archive.org/details/polymerphysics00rubi_825/page/n14 6]}} A [[branching (polymer chemistry)|branched polymer]] molecule is composed of a main chain with one or more substituent side chains or branches. Types of branched polymers include [[star polymer]]s, [[comb polymers]], [[polymer brush]]es, [[dendronized polymer]]s, [[ladder polymer]]s, and [[dendrimer]]s. There exist also [[two-dimensional polymer]]s (2DP) which are composed of topologically planar repeat units. A polymer's architecture affects many of its physical properties including solution viscosity, melt viscosity, solubility in various solvents, [[glass transition|glass-transition]] temperature and the size of individual polymer coils in solution. A variety of techniques may be employed for the synthesis of a polymeric material with a range of architectures, for example [[living polymerization]]. [128] => [129] => ====Chain length==== [130] => A common means of expressing the length of a chain is the [[degree of polymerization]], which quantifies the number of monomers incorporated into the chain.McCrum, p. 30Rubinstein, p. 3 As with other molecules, a polymer's size may also be expressed in terms of [[molecular weight]]. Since synthetic polymerization techniques typically yield a statistical distribution of chain lengths, the molecular weight is expressed in terms of weighted averages. The [[number-average molecular weight]] (''M''n) and [[weight-average molecular weight]] (''M''w) are most commonly reported.McCrum, p. 33Rubinstein, pp. 23–24 The ratio of these two values (''M''w / ''M''n) is the [[dispersity]] (''Đ''), which is commonly used to express the width of the molecular weight distribution.Painter, p. 22 [131] => [132] => The physical properties{{cite book |last1= De Gennes |first1= Pierre Gilles |title= Scaling concepts in polymer physics |year= 1979 |publisher= Cornell University Press |location= Ithaca, N.Y. |isbn= 978-0-8014-1203-5}} of polymer strongly depend on the length (or equivalently, the molecular weight) of the polymer chain.Rubinstein, p. 5 One important example of the physical consequences of the molecular weight is the scaling of the [[viscosity]] (resistance to flow) in the melt.McCrum, p. 37 The influence of the weight-average molecular weight (M_w) on the melt viscosity (\eta) depends on whether the polymer is above or below the onset of [[reptation|entanglements]]. Below the entanglement molecular weight{{clarify|date=December 2018}}, \eta \sim {M_w}^{1}, whereas above the entanglement molecular weight, \eta \sim {M_w}^{3.4}. In the latter case, increasing the polymer chain length 10-fold would increase the viscosity over 1000 times.Introduction to Polymer Science and Chemistry: A Problem-Solving Approach By Manas Chanda{{page needed|date=December 2018}} Increasing chain length furthermore tends to decrease chain mobility, increase strength and toughness, and increase the glass-transition temperature (Tg).{{cite journal |last1=O'Driscoll |first1=K. |last2=Amin Sanayei |first2=R. |date=July 1991 |title=Chain-length dependence of the glass transition temperature |journal=Macromolecules |volume=24 |issue=15 |pages=4479–4480 |doi= 10.1021/ma00015a038|bibcode=1991MaMol..24.4479O}} This is a result of the increase in chain interactions such as [[Van der Waals force|van der Waals attractions]] and [[reptation|entanglements]] that come with increased chain length.{{cite book|last1=Pokrovskii|first1=V. N.|year=2010|title=The Mesoscopic Theory of Polymer Dynamics|series=Springer Series in Chemical Physics|volume=95|doi=10.1007/978-90-481-2231-8|isbn=978-90-481-2230-1|bibcode=2010mtpd.book.....P|url=https://cds.cern.ch/record/1315698}}{{cite journal|last1=Edwards|first1=S. F.|year=1967|title=The statistical mechanics of polymerized material|journal=Proceedings of the Physical Society|volume=92|issue=1|pages=9–16|bibcode=1967PPS....92....9E|doi=10.1088/0370-1328/92/1/303}} These interactions tend to fix the individual chains more strongly in position and resist deformations and matrix breakup, both at higher stresses and higher temperatures. [133] => [134] => ====Monomer arrangement in copolymers==== [135] => {{Main|Copolymer}} [136] => [137] => Copolymers are classified either as statistical copolymers, alternating copolymers, block copolymers, graft copolymers or gradient copolymers. In the schematic figure below, Ⓐ and Ⓑ symbolize the two [[repeat unit]]s. [138] => [139] => :{| class="wikitable" style="text-align:center; font-size:90%;" [140] => |- class="hintergrundfarbe2" [141] => | [[File:Statistical copolymer 3D.svg|270px|Statistisches Copolymer]]
Random copolymer [142] => | [[File:Gradient copolymer 3D.svg|270px|Gradientcopolymer]]
Gradient copolymer [143] => | rowspan="2" | [[File:Graft copolymer 3D.svg|270px|Pfropfcopolymer]]
[[Graft copolymer]] [144] => |- class="hintergrundfarbe2" [145] => | [[File:Alternating copolymer 3D.svg|270px|Alternierendes Copolymer]]
Alternating copolymer [146] => | [[File:Block copolymer 3D.svg|250px|Blockcopolymer]]
[[Block copolymer]] [147] => |} [148] => [149] => *'''Alternating copolymers''' possess two regularly alternating monomer residues:Painter, p. 14 {{chem|(AB)|n}}. An example is the equimolar copolymer of [[styrene]] and [[maleic anhydride]] formed by free-radical chain-growth polymerization.Rudin, p. 18–20 A step-growth copolymer such as [[Nylon 66]] can also be considered a strictly alternating copolymer of diamine and diacid residues, but is often described as a homopolymer with the dimeric residue of one amine and one acid as a repeat unit.Cowie, p. 104 [150] => *'''Periodic copolymers''' have more than two species of monomer units in a regular sequence.{{cite journal |title=Periodic copolymer |url=https://goldbook.iupac.org/terms/view/P04494 |website=IUPAC Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). |year=2014 |publisher=International Union of Pure and Applied Chemistry |doi=10.1351/goldbook.P04494 |access-date=9 April 2020|doi-access=free }} [151] => *'''Statistical copolymers''' have monomer residues arranged according to a statistical rule. A statistical copolymer in which the probability of finding a particular type of monomer residue at a particular point in the chain is independent of the types of surrounding monomer residue may be referred to as a truly '''random copolymer'''.Painter, p. 15Sperling, p. 47 For example, the chain-growth copolymer of [[vinyl chloride]] and [[vinyl acetate]] is random. [152] => *'''Block copolymers''' have long sequences of different monomer units. Polymers with two or three blocks of two distinct chemical species (e.g., A and B) are called diblock copolymers and triblock copolymers, respectively. Polymers with three blocks, each of a different chemical species (e.g., A, B, and C) are termed triblock terpolymers. [153] => *'''Graft or grafted copolymers''' contain side chains or branches whose repeat units have a different composition or configuration than the main chain. The branches are added on to a preformed main chain macromolecule. [154] => [155] => Monomers within a copolymer may be organized along the backbone in a variety of ways. A copolymer containing a controlled arrangement of monomers is called a [[sequence-controlled polymer]].{{cite journal|last1=Lutz|first1=Jean-François|last2=Ouchi|first2=Makoto|last3=Liu|first3=David R.|last4=Sawamoto|first4=Mitsuo|date=9 August 2013|title=Sequence-Controlled Polymers|journal=Science|language=en|volume=341|issue=6146|pages=1238149|doi=10.1126/science.1238149|issn=0036-8075|pmid=23929982|s2cid=206549042}} Alternating, periodic and block copolymers are simple examples of [[sequence-controlled polymer]]s. [156] => [157] => ====Tacticity==== [158] => {{Main|Tacticity}} [159] => Tacticity describes the relative [[stereochemistry]] of [[chirality (chemistry)|chiral]] centers in neighboring structural units within a macromolecule. There are three types of tacticity: [[isotactic]] (all substituents on the same side), [[atactic]] (random placement of substituents), and [[syndiotactic]] (alternating placement of substituents). [160] => [161] => :{| class="wikitable" style="text-align:center; font-size:90%;" width="60%" [162] => |- class="hintergrundfarbe2" [163] => |[[File:Isotactic-A-2D-skeletal.png|240px]]
Isotactic [164] => |[[File:Syndiotactic-2D-skeletal.png|280px]]
Syndiotactic [165] => |[[File:Atactic-2D-skeletal.png|240px]]
Atactic (i. e. random) [166] => |} [167] => [168] => ===Morphology=== [169] => Polymer morphology generally describes the arrangement and microscale ordering of polymer chains in space. The macroscopic physical properties of a polymer are related to the interactions between the polymer chains. [170] => [171] => {| class="wikitable floatright" style="text-align:center; font-size:90%;" width="30%" [172] => |- class="hintergrundfarbe2" [173] => | [[File:Statistischer Kneul.svg|100px]]
Randomly oriented polymer [174] => | [[File:Verhakungen.svg|200px]]
Interlocking of several polymers [175] => |} [176] => [177] => * '''Disordered polymers:''' In the solid state, atactic polymers, polymers with a high degree of [[Branching (polymer chemistry)|branching]] and random copolymers form [[Amorphous solid|amorphous]] (i.e. glassy structures).Bernd Tieke: ''Makromolekulare Chemie.'' 3. Auflage, Wiley-VCH, Weinheim 2014, S. 295f (in German). In melt and solution, polymers tend to form a constantly changing "statistical cluster", see [[Freely Jointed Chain|freely-jointed-chain model]]. In the [[Solid|solid state]], the respective [[Protein conformation|conformations]] of the molecules are frozen. Hooking and entanglement of chain molecules lead to a "mechanical bond" between the chains. [[Intermolecular force|Intermolecular]] and intramolecular attractive forces only occur at sites where molecule segments are close enough to each other. The irregular structures of the molecules prevent a narrower arrangement. [178] => [179] => {| class="wikitable floatright" style="text-align:center; font-size:90%;" width="30%" [180] => |- class="hintergrundfarbe2" [181] => | [[File:Polyethylene-xtal-view-down-axis-3D-balls-perspective.png|180px]]
Polyethylene: zigzag conformation of molecules in close packed chains [182] => | [[File:Lamellen.svg|180px]]
Lamella with tie molecules [183] => | [[File:Spherulite2de.svg|180px]]
[[Spherulite (polymer physics)|Spherulite]] [184] => |} [185] => {| class="wikitable floatright" style="text-align:center; font-size:90%;" width="30%" [186] => |- class="hintergrundfarbe2" [187] => | [[File:Helix-Polypropylen.svg|100px]]
[[polypropylene]] [[helix]] [188] => | [[File:P-Aramid H-Brücken.svg|200px]]
[[Aramide|''p''-Aramid]], red dotted: hydrogen bonds [189] => |} [190] => [191] => * '''Linear polymers''' with periodic structure, low branching and stereoregularity (e. g. not atactic) have a [[semi-crystalline]] structure in the solid state. In simple polymers (such as polyethylene), the chains are present in the crystal in zigzag conformation. Several zigzag conformations form dense chain packs, called crystallites or lamellae. The lamellae are much thinner than the polymers are long (often about 10 nm).[[Wolfgang Kaiser (physicist)|Wolfgang Kaiser]]: ''Kunststoffchemie für Ingenieure.'' 3. Auflage, Carl Hanser, München 2011, S. 84. They are formed by more or less regular folding of one or more molecular chains. Amorphous structures exist between the lamellae. Individual molecules can lead to entanglements between the lamellae and can also be involved in the formation of two (or more) lamellae (chains than called tie molecules). Several lamellae form a superstructure, a [[Spherulite (polymer physics)|spherulite]], often with a diameter in the range of 0.05 to 1 mm. [192] => :The type and arrangement of (functional) residues of the repeat units effects or determines the crystallinity and strength of the secondary valence bonds. In isotactic polypropylene, the molecules form a helix. Like the zigzag conformation, such helices allow a dense chain packing. Particularly strong intermolecular interactions occur when the residues of the repeating units allow the formation of [[hydrogen bond]]s, as in the case of [[Aramid|''p''-aramid]]. The formation of strong intramolecular associations may produce diverse folded states of single linear chains with distinct [[circuit topology]]. Crystallinity and superstructure are always dependent on the conditions of their formation, see also: [[crystallization of polymers]]. Compared to amorphous structures, semi-crystalline structures lead to a higher stiffness, density, melting temperature and higher resistance of a polymer. [193] => [194] => * '''Cross-linked polymers:''' Wide-meshed cross-linked polymers are [[elastomer]]s and cannot be molten (unlike [[thermoplastic]]s); heating cross-linked polymers only leads to [[Thermal decomposition|decomposition]]. [[Thermoplastic elastomer]]s, on the other hand, are reversibly "physically crosslinked" and can be molten. Block copolymers in which a hard segment of the polymer has a tendency to crystallize and a soft segment has an amorphous structure are one type of thermoplastic elastomers: the hard segments ensure wide-meshed, physical crosslinking. [195] => [196] => {| class="wikitable centered" style="text-align:center; font-size:90%;" width="80%" [197] => |- class="hintergrundfarbe2" valign="top" [198] => | [[File:Polymerstruktur-weitmaschig vernetzt.svg|130px]]
Wide-meshed cross-linked polymer (elastomer) [199] => | [[File:Polymerstruktur-weitmaschig vernetzt-gestreckt.svg|270px]]

Wide-meshed cross-linked polymer (elastomer) under [[tensile stress]] [200] => | [[File:Polymerstruktur-TPE-teilkristallin.svg|140px]]
[[Crystallite]]s as "crosslinking sites": one type of [[thermoplastic elastomer]] [201] => | [[File:Polymerstruktur-TPE-teilkristallin gestreckt.svg|250px]]

Semi-crystalline thermoplastic elastomer under tensile stress [202] => |} [203] => [204] => ====Crystallinity==== [205] => 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 composed of one or more polymer molecules with cell dimensions of hundreds of [[angstrom]]s or more. A synthetic polymer may be loosely described as crystalline if it contains regions of three-dimensional ordering on atomic (rather than macromolecular) length scales, usually arising from intramolecular folding 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.{{cite journal |date=August 2014 |title=Types of polymer: Requirements of fibre forming polymer |url=https://textileapex.blogspot.com/2014/08/polymer.html|website= Textile Apex|last= Sayed|first= Abu}} The crystallinity of polymers is characterized by their degree of crystallinity, ranging from zero for a completely non-crystalline polymer to one for a theoretical completely crystalline polymer. Polymers with microcrystalline regions are generally tougher (can be bent more without breaking) and more impact-resistant than totally amorphous polymers.{{cite book|last1=Allcock|first1=Harry R.|last2=Lampe|first2=Frederick W.|last3=Mark|first3=James E.|title=Contemporary Polymer Chemistry|publisher=Pearson Education|edition=3|year=2003|page=546|isbn=978-0-13-065056-6}} Polymers with a degree of crystallinity approaching zero or one will tend to be transparent, while polymers with intermediate degrees of crystallinity will tend to be opaque due to light scattering by crystalline or glassy regions. For many polymers, crystallinity may also be associated with decreased transparency. [206] => [207] => ====Chain conformation==== [208] => The space occupied by a polymer molecule is generally expressed in terms of [[radius of gyration]], which is an average distance from the center of mass of the chain to the chain itself. Alternatively, it may be expressed in terms of [[pervaded volume]], which is the volume spanned by the polymer chain and scales with the cube of the radius of gyration.Rubinstein, p. 13 [209] => The simplest theoretical models for polymers in the molten, amorphous state are [[ideal chain]]s. [210] => [211] => ==Properties== [212] => [213] => Polymer properties depend of their structure and they are divided into classes according to their physical bases. Many physical and chemical properties describe how a polymer behaves as a continuous macroscopic material. They are classified as bulk properties, or [[Intensive and extensive properties#Intensive properties|intensive properties]] according to [[thermodynamics]]. [214] => [215] => ===Mechanical properties=== [216] => [[File:Stable neck MDPE.jpg|upright=0.5|thumb|right|A polyethylene sample that has [[necking (engineering)|necked]] under tension]] [217] => The bulk properties of a polymer are those most often of end-use interest. These are the properties that dictate how the polymer actually behaves on a macroscopic scale. [218] => [219] => ====Tensile strength==== [220] => The [[tensile strength]] of a material quantifies how much elongating stress the material will endure before failure.{{cite book|author-link=M. F. Ashby|last1=Ashby|first1=Michael|last2=Jones|first2=David|title=Engineering Materials|url=https://archive.org/details/engineeringmater01jone|url-access=limited|pages=[https://archive.org/details/engineeringmater01jone/page/n199 191]–195|publisher=Butterworth-Heinermann|year=1996|edition=2|isbn=978-0-7506-2766-5}}{{cite book|first1=M. A.|last1=Meyers|first2=K. K.|last2=Chawla|title=Mechanical Behavior of Materials|publisher=Cambridge University Press|year=1999|page=41|url=http://www.toodoc.com/Mechanical-Behavior-of-Materials-ebook.html|isbn=978-0-521-86675-0|access-date=31 December 2018|archive-url=https://web.archive.org/web/20131102010325/http://www.toodoc.com/Mechanical-Behavior-of-Materials-ebook.html|archive-date=2 November 2013|url-status=dead}} This is very important in applications that rely upon a polymer's physical strength or durability. For example, a rubber band with a higher tensile strength will hold a greater weight before snapping. In general, tensile strength increases with polymer chain length and [[cross-link|crosslinking]] of polymer chains. [221] => [222] => ====Young's modulus of elasticity==== [223] => [[Young's modulus]] quantifies the [[elasticity (physics)|elasticity]] of the polymer. It is defined, for small [[deformation (mechanics)#Strain|strain]]s, as the ratio of rate of change of stress to strain. Like tensile strength, this is highly relevant in polymer applications involving the physical properties of polymers, such as rubber bands. The modulus is strongly dependent on temperature. [[Viscoelasticity]] describes a complex time-dependent elastic response, which will exhibit [[hysteresis]] in the stress-strain curve when the load is removed. [[Dynamic mechanical analysis]] or DMA measures this complex modulus by oscillating the load and measuring the resulting strain as a function of time. [224] => [225] => ===Transport properties=== [226] => [[Transport phenomena|Transport properties]] such as [[mass diffusivity|diffusivity]] describe how rapidly molecules move through the polymer matrix. These are very important in many applications of polymers for films and membranes. [227] => [228] => The movement of individual macromolecules occurs by a process called [[reptation]] in which each chain molecule is constrained by entanglements with neighboring chains to move within a virtual tube. The theory of reptation can explain polymer molecule dynamics and [[viscoelasticity]].{{cite book |last1=Fried |first1=Joel R. |title=Polymer Science & Technology |publisher=Prentice Hall |isbn=0-13-018168-4 |pages=155–6 |edition=2nd|year=2003}} [229] => [230] => ===Phase behavior=== [231] => [232] => ====Crystallization and melting==== [233] => [[File:Thermal transitions in amorphous and semicrystalline polymers.tif|thumb|300x300px|Thermal transitions in '''(A)''' amorphous and '''(B)''' semicrystalline polymers, represented as traces from [[differential scanning calorimetry]]. As the temperature increases, both amorphous and semicrystalline polymers go through the [[glass transition]] (''T''g). Amorphous polymers '''(A)''' do not exhibit other phase transitions, though semicrystalline polymers '''(B)''' undergo crystallization and melting (at temperatures ''T''c and ''T''m, respectively).]] [234] => Depending on their chemical structures, polymers may be either semi-crystalline or amorphous. Semi-crystalline polymers can undergo [[crystallization of polymers|crystallization and melting transitions]], whereas amorphous polymers do not. In polymers, crystallization and melting do not suggest solid-liquid phase transitions, as in the case of water or other molecular fluids. Instead, crystallization and melting refer to the phase transitions between two solid states (''i.e.'', semi-crystalline and amorphous). Crystallization occurs above the glass-transition temperature (''T''g) and below the melting temperature (''T''m). [235] => [236] => ====Glass transition==== [237] => All polymers (amorphous or semi-crystalline) go through [[glass transition]]s. The glass-transition temperature (''T''g) is a crucial physical parameter for polymer manufacturing, processing, and use. Below ''T''g, molecular motions are frozen and polymers are brittle and glassy. Above ''T''g, molecular motions are activated and polymers are rubbery and viscous. The glass-transition temperature may be engineered by altering the degree of branching or crosslinking in the polymer or by the addition of [[plasticizer]]s.{{cite book|title=Polymer Handbook|last1=Brandrup|first1=J.|last2=Immergut|first2=E.H.|last3=Grulke|first3=E.A.|publisher=Wiley-Interscience|year=1999|isbn=978-0-471-47936-9|edition=4}} [238] => [239] => Whereas crystallization and melting are first-order [[phase transition]]s, the glass transition is not.{{cite journal|url=https://www.degruyter.com/downloadpdf/j/pac.2011.83.issue-10/pac-rec-10-11-13/pac-rec-10-11-13.pdf|title=Definitions of terms relating to crystalline polymers (IUPAC Recommendations 2011)|journal=Pure and Applied Chemistry|volume=83|issue=10|pages=1831–1871|last1=Meille|first1=S.|last2=Allegra|first2=G.|doi=10.1351/PAC-REC-10-11-13|access-date=31 December 2018|last3=Geil|first3=P.|last4=He|first4=J.|display-authors=3|year=2011|s2cid=98823962}} The glass transition shares features of second-order phase transitions (such as discontinuity in the heat capacity, as shown in the figure), but it is generally not considered a thermodynamic transition between equilibrium states. [240] => [241] => ====Mixing behavior==== [242] => [[File:LCST-UCST plot.svg|thumb|upright=1.4|Phase diagram of the typical mixing behavior of weakly interacting polymer solutions, showing [[spinodal]] curves and [[binodal]] coexistence curves]] [243] => In general, polymeric mixtures are far less [[miscible]] than mixtures of [[small molecule]] materials. This effect results from the fact that the driving force for mixing is usually [[entropy]], not interaction energy. In other words, miscible materials usually form a solution not because their interaction with each other is more favorable than their self-interaction, but because of an increase in entropy and hence free energy associated with increasing the amount of volume available to each component. This increase in entropy scales with the number of particles (or moles) being mixed. Since polymeric molecules are much larger and hence generally have much higher specific volumes than small molecules, the number of molecules involved in a polymeric mixture is far smaller than the number in a small molecule mixture of equal volume. The energetics of mixing, on the other hand, is comparable on a per volume basis for polymeric and small molecule mixtures. This tends to increase the free energy of mixing for polymer solutions and thereby making solvation less favorable, and thereby making the availability of concentrated solutions of polymers far rarer than those of small molecules. [244] => [245] => Furthermore, the phase behavior of polymer solutions and mixtures is more complex than that of small molecule mixtures. Whereas most small molecule solutions exhibit only an [[upper critical solution temperature]] phase transition (UCST), at which phase separation occurs with cooling, polymer mixtures commonly exhibit a [[lower critical solution temperature]] phase transition (LCST), at which phase separation occurs with heating. [246] => [247] => In dilute solutions, the properties of the polymer are characterized by the interaction between the solvent and the polymer. In a good solvent, the polymer appears swollen and occupies a large volume. In this scenario, intermolecular forces between the solvent and monomer subunits dominate over intramolecular interactions. In a bad solvent or poor solvent, intramolecular forces dominate and the chain contracts. In the [[theta solvent]], or the state of the polymer solution where the value of the second virial coefficient becomes 0, the intermolecular polymer-solvent repulsion balances exactly the intramolecular monomer-monomer attraction. Under the theta condition (also called the [[Paul J. Flory|Flory]] condition), the polymer behaves like an ideal [[random coil]]. The transition between the states is known as a [[coil–globule transition]]. [248] => [249] => ====Inclusion of plasticizers==== [250] => Inclusion of plasticizers tends to lower Tg and increase polymer flexibility. Addition of the plasticizer will also modify dependence of the glass-transition temperature Tg on the cooling rate.{{Citation [251] => |last1= Capponi [252] => |first1= S. [253] => |last2= Alvarez [254] => |first2= F. [255] => |last3= Racko [256] => |first3= D. [257] => |title= Free Volume in a PVME Polymer–Water Solution [258] => |journal= Macromolecules [259] => |volume= XXX [260] => |pages= XXX-XXX [261] => |year= 2020 [262] => |issue= XXX [263] => |doi= 10.1021/acs.macromol.0c00472 |bibcode= 2020MaMol..53.4770C [264] => |hdl= 10261/218380 [265] => |s2cid= 219911779 [266] => |hdl-access= free [267] => }} [268] => The mobility of the chain can further change if the molecules of plasticizer give rise to hydrogen bonding formation. Plasticizers are generally small molecules that are chemically similar to the polymer and create gaps between polymer chains for greater mobility and fewer interchain interactions. A good example of the action of plasticizers is related to polyvinylchlorides or PVCs. A uPVC, or unplasticized polyvinylchloride, is used for things such as pipes. A pipe has no plasticizers in it, because it needs to remain strong and heat-resistant. Plasticized PVC is used in clothing for a flexible quality. Plasticizers are also put in some types of cling film to make the polymer more flexible. [269] => [270] => ===Chemical properties=== [271] => The attractive forces between polymer chains play a large part in determining the polymer's properties. Because polymer chains are so long, they have many such interchain interactions per molecule, amplifying the effect of these interactions on the polymer properties in comparison to attractions between conventional molecules. Different side groups on the polymer can lend the polymer to [[ionic bonding]] or [[hydrogen bonding]] between its own chains. These stronger forces typically result in higher tensile strength and higher crystalline melting points. [272] => [273] => The intermolecular forces in polymers can be affected by [[dipole]]s in the monomer units. Polymers containing [[amide]] or [[carbonyl]] groups can form [[hydrogen bond]]s between adjacent chains; the partially positively charged hydrogen atoms in N-H groups of one chain are strongly attracted to the partially negatively charged oxygen atoms in C=O groups on another. These strong hydrogen bonds, for example, result in the high tensile strength and melting point of polymers containing [[carbamate|urethane]] or [[urea]] linkages. [[Polyester]]s have [[intermolecular force#Dipole-dipole interactions|dipole-dipole bonding]] between the oxygen atoms in C=O groups and the hydrogen atoms in H-C groups. Dipole bonding is not as strong as hydrogen bonding, so a polyester's melting point and strength are lower than [[Kevlar]]'s ([[Twaron]]), but polyesters have greater flexibility. Polymers with non-polar units such as polyethylene interact only through weak [[Van der Waals force]]s. As a result, they typically have lower melting temperatures than other polymers. [274] => [275] => When a polymer is dispersed or dissolved in a liquid, such as in commercial products like paints and glues, the chemical properties and molecular interactions influence how the solution flows and can even lead to [[self-assembly]] of the polymer into complex structures. When a polymer is applied as a coating, the chemical properties will influence the adhesion of the coating and how it interacts with external materials, such as [[superhydrophobic]] polymer coatings leading to water resistance. Overall the chemical properties of a polymer are important elements for designing new polymeric material products. [276] => [277] => ===Optical properties=== [278] => Polymers such as [[poly(methyl methacrylate)|PMMA]] and HEMA:MMA are used as matrices in the gain medium of [[solid-state dye laser]]s, also known as solid-state dye-doped polymer lasers. These polymers have a high surface quality and are also highly transparent so that the laser properties are dominated by the [[laser dye]] used to dope the polymer matrix. These type of lasers, that also belong to the class of [[organic laser]]s, are known to yield very narrow [[laser linewidth|linewidths]] which is useful for spectroscopy and analytical applications.{{cite journal|doi=10.1364/AO.38.006347|pmid=18324163|title=Multiple-prism grating solid-state dye laser oscillator: optimized architecture|year=1999|last1=Duarte|first1=F. J. |journal=Applied Optics|volume=38|issue=30|pages=6347–6349|bibcode= 1999ApOpt..38.6347D}} An important optical parameter in the polymer used in laser applications is the change in refractive index with temperature [279] => also known as dn/dT. For the polymers mentioned here the (dn/dT) ~ −1.4 × 10−4 in units of K−1 in the 297 ≤ T ≤ 337 K range.{{cite book |title= Tunable Laser Optics |publisher= Elsevier Academic |location=New York |year=2003 |isbn=978-0122226960 |author= Duarte, F. J. |author-link= F. J. Duarte}} [280] => [281] => ===Electrical properties=== [282] => Most conventional polymers such as polyethylene are [[Insulator (electricity)|electrical insulators]], but the development of polymers containing [[Conjugated system|π-conjugated bonds]] has led to a wealth of polymer-based [[semiconductor]]s, such as [[polythiophene]]s. This has led to many applications in the field of [[organic electronics]]. [283] => [284] => ==Applications== [285] => Nowadays, synthetic polymers are used in almost all walks of life. Modern society would look very different without them. The spreading of polymer use is connected to their unique properties: low density, low cost, good thermal/electrical insulation properties, high resistance to corrosion, low-energy demanding polymer manufacture and facile processing into final products. For a given application, the properties of a polymer can be tuned or enhanced by combination with other materials, as in [[Polymer matrix composite|composites]]. Their application allows to save energy (lighter cars and planes, thermally insulated buildings), protect food and drinking water (packaging), save land and lower use of fertilizers (synthetic fibres), preserve other materials (coatings), protect and save lives (hygiene, medical applications). A representative, non-exhaustive list of applications is given below. [286] => [287] => * Clothing, sportswear and accessories: [[Polyester#Uses and applications|polyester]] and [[PVC clothing]], [[spandex]], [[sneakers|sport shoes]], [[wetsuit]]s, [[Ball (association football)|footballs]] and [[Billiard ball#Snooker|billiard balls]], [[ski]]s and [[snowboard]]s, [[Racket (sports equipment)|rackets]], [[parachute]]s, [[sailcloth|sail]]s, [[tent|tents and shelters]]. [288] => * Electronic and photonic technologies: organic [[Organic electronics|field effect transistors]] (OFET), [[OLED#Polymer light-emitting diodes|light emitting diodes]] (OLED) and [[organic solar cell|solar cells]], [[Television set|television components]], [[compact disc]]s (CD), [[photoresist]]s, [[holography]]. [289] => * Packaging and containers: [[Plastic film|films]], [[Plastic bottle|bottles]], [[food packaging]], [[barrel]]s. [290] => * Insulation: [[Insulator (electricity)|electrical]] and [[thermal insulation]], [[spray foam]]s. [291] => * Construction and structural applications: [[garden furniture]], [[polyvinyl chloride|PVC]] windows, flooring, [[seal (mechanical)|sealing]], [[Plastic pipework|pipes]]. [292] => * Paints, glues and lubricants: [[varnish]], [[adhesive]]s, [[dispersant]]s, [[anti-graffiti coating]]s, [[Biofouling#Non-toxic coatings|antifouling coatings]], [[non-stick surface]]s, [[lubricant]]s. [293] => * Car parts: [[tire]]s, [[Bumper (car)|bumpers]], [[windshield]]s, [[windscreen wiper]]s, [[fuel tank]]s, [[car seat]]s. [294] => * Household items: [[bucket]]s, [[kitchenware]], toys (e.g., [[construction set]]s and [[Rubik's cube]]). [295] => * Medical applications: [[Blood transfusion|blood bag]], [[syringe]]s, [[rubber glove]]s, [[surgical suture]], [[contact lens]]es, [[prosthesis]], [[Drug carrier|controlled drug delivery and release]], [[Growth medium|matrices for cell growth]]. [296] => * Personal hygiene and healthcare: [[diaper]]s using [[superabsorbent polymer]]s, [[toothbrush]]es, [[cosmetics]], [[shampoo]], [[condom]]s. [297] => * Security: [[personal protective equipment]], [[bulletproof vest]]s, [[space suit]]s, [[rope]]s. [298] => * Separation technologies: [[synthetic membrane]]s, [[Fuel cell#Proton-exchange membrane fuel cells|fuel cell membranes]], [[filtration]], [[ion-exchange resin]]s. [299] => * Money: [[polymer banknote]]s and [[payment card]]s. [300] => * [[3D printing]]. [301] => [302] => ==Standardized nomenclature== [303] => 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]] (ACS)CAS: Index Guide, Appendix IV ((c) 1998) and [[IUPAC]]{{cite journal|author=IUPAC|title=Nomenclature of Regular Single-Strand Organic Polymers|journal=Pure Appl. Chem.|year= 1976 |volume=48|pages=373–385|doi=10.1351/pac197648030373|issue=3|doi-access=free}} have proposed standardized naming conventions; the ACS and IUPAC conventions are similar but not identical.{{cite web|url=http://www.polyacs.org/nomcl/mnn18.html|title=Macromolecular Nomenclature Note No. 18|first= E.S.|last= Wilks|url-status= dead|archive-url= https://web.archive.org/web/20030925160856/http://www.polyacs.org/nomcl/mnn18.html|archive-date= 25 September 2003}} Examples of the differences between the various naming conventions are given in the table below: [304] => [305] => {| class="wikitable" [306] => |- [307] => ! Common name [308] => ! ACS name [309] => ! IUPAC name [310] => |- [311] => | [[Poly(ethylene oxide)]] or PEO [312] => | Poly(oxyethylene) [313] => | Poly(oxyethylene) [314] => |- [315] => | [[Poly(ethylene terephthalate)]] or PET [316] => | Poly(oxy-1,2-ethanediyloxycarbonyl-1,4-phenylenecarbonyl) [317] => | Poly(oxyethyleneoxyterephthaloyl) [318] => |- [319] => | [[Nylon 6]] or Polyamide 6 [320] => | Poly[imino(1-oxo-1,6-hexanediyl)] [321] => | Poly[azanediyl(1-oxohexane-1,6-diyl)] [322] => |} [323] => [324] => In both standardized conventions, the polymers' names are intended to reflect the monomer(s) from which they are synthesized (source based nomenclature) rather than the precise nature of the repeating subunit. For example, the polymer synthesized from the simple alkene [[ethene]] is called polyethene, retaining the ''-ene'' suffix even though the double bond is removed during the polymerization process: [325] => [326] => :[[File:Ethene polymerization.png]]→[[File:Polyethylene repeat unit.svg|frameless|upright=0.45]] [327] => However, IUPAC structure based nomenclature is based on naming of the preferred [[Repeat unit|constitutional repeating unit]].{{Cite journal|last1=Hiorns|first1=R. C.|last2=Boucher|first2=R. J.|last3=Duhlev|first3=R.|last4=Hellwich|first4=Karl-Heinz|last5=Hodge|first5=Philip|last6=Jenkins|first6=Aubrey D.|last7=Jones|first7=Richard G.|last8=Kahovec|first8=Jaroslav|last9=Moad|first9=Graeme|last10=Ober|first10=C. K.|last11=Smith|first11=D. W.|date=3 October 2012|title=A brief guide to polymer nomenclature (IUPAC Technical Report)|journal=Pure and Applied Chemistry|language=en|volume=84|issue=10|pages=2167–2169|doi=10.1351/PAC-REP-12-03-05|s2cid=95629051|issn=0033-4545|doi-access=free}} [328] => [329] => ==Characterization== [330] => {{Main|Polymer characterization}} [331] => Polymer characterization spans many techniques for determining the chemical composition, molecular weight distribution, and physical properties. Select common techniques include the following: [332] => [333] => *[[Size-exclusion chromatography]] (also called [[gel permeation chromatography]]), sometimes coupled with [[static light scattering]], can used to determine the number-average molecular weight, weight-average molecular weight, and [[polydispersity|dispersity]]. [334] => *Scattering techniques, such as [[static light scattering]] and [[small-angle neutron scattering]], are used to determine the dimensions ([[radius of gyration]]) of macromolecules in solution or in the melt. These techniques are also used to characterize the three-dimensional structure of microphase-separated [[block polymer]]s, polymeric micelles, and other materials. [335] => *[[Wide-angle X-ray scattering]] (also called wide-angle X-ray diffraction) is used to determine the crystalline structure of polymers (or lack thereof). [336] => *Spectroscopy techniques, including [[FTIR|Fourier-transform infrared spectroscopy]], [[Raman spectroscopy]], and [[nuclear magnetic resonance spectroscopy]], can be used to determine the chemical composition. [337] => *[[Differential scanning calorimetry]] is used to characterize the thermal properties of polymers, such as the glass-transition temperature, crystallization temperature, and melting temperature. The glass-transition temperature can also be determined by [[dynamic mechanical analysis]]. [338] => *[[Thermogravimetry]] is a useful technique to evaluate the thermal stability of the polymer. [339] => *[[Rheology]] is used to characterize the flow and deformation behavior. It can be used to determine the [[viscosity]], [[elastic modulus|modulus]], and other rheological properties. Rheology is also often used to determine the molecular architecture (molecular weight, molecular weight distribution, branching) and to understand how the polymer can be processed. [340] => [341] => ==Degradation== [342] => {{Main|Polymer degradation}} [343] => [[File:PlasticDamage.JPG|right|thumb|A plastic item with thirty years of exposure to heat and cold, brake fluid, and sunlight. Notice the discoloration and [[crazing]] of the material (compared with replacement item in foreground).]] [344] => Polymer degradation is a change in the properties—tensile strength, [[color]], shape, or molecular weight—of a polymer or polymer-based product under the influence of one or more environmental factors, such as [[heat]], [[light]], and the presence of certain [[chemical]]s, oxygen, and [[enzymes]]. This change in properties is often the result of bond breaking in the polymer backbone ([[chain scission]]) which may occur at the chain ends or at random positions in the chain. [345] => [346] => Although such changes are frequently undesirable, in some cases, such as [[biodegradation]] and [[recycling]], they may be intended to prevent environmental [[pollution]]. Degradation can also be useful in biomedical settings. For example, a copolymer of [[polylactic acid]] and [[polyglycolic acid]] is employed in hydrolysable stitches that slowly degrade after they are applied to a wound. [347] => [348] => The susceptibility of a polymer to degradation depends on its structure. Epoxies and chains containing aromatic functionalities are especially susceptible to [[UV degradation]] while polyesters are susceptible to degradation by [[hydrolysis]]. Polymers containing an [[Saturated and unsaturated compounds|unsaturated]] backbone degrade via [[ozone cracking]]. Carbon based polymers are more susceptible to thermal degradation than [[inorganic polymer]]s such as [[polydimethylsiloxane]] and are therefore not ideal for most high-temperature applications.{{citation needed|date=February 2024}} [349] => [350] => The degradation of polyethylene occurs by random scission—a random breakage of the bonds that hold the [[atom]]s of the polymer together. When heated above 450 °C, polyethylene degrades to form a mixture of hydrocarbons. In the case of chain-end scission, monomers are released and this process is referred to as unzipping or [[depolymerization]]. Which mechanism dominates will depend on the type of polymer and temperature; in general, polymers with no or a single small substituent in the repeat unit will decompose via random-chain scission. [351] => [352] => The sorting of polymer waste for recycling purposes may be facilitated by the use of the [[resin identification code]]s developed by the [[Society of the Plastics Industry]] to identify the type of plastic. [353] => [354] => ===Product failure=== [355] => [[File:Chlorine attack1.jpg|thumb|left|Chlorine attack of acetal resin plumbing joint]] [356] => Failure of [[safety-critical]] polymer components can cause serious accidents, such as fire in the case of cracked and degraded polymer [[fuel line]]s. Chlorine-induced cracking of [[acetal resin]] plumbing joints and [[polybutylene]] pipes has caused many serious floods in domestic properties, especially in the US in the 1990s. Traces of [[chlorine]] in the water supply attacked polymers present in the plumbing, a problem which occurs faster if any of the parts have been poorly [[extruded]] or [[Injection molding|injection molded]]. Attack of the acetal joint occurred because of faulty molding, leading to cracking along the threads of the fitting where there is [[stress concentration]]. [357] => [[File:Ozone_cracks_in_tube1.jpg|thumb|Ozone-induced cracking in natural rubber tubing]] [358] => Polymer oxidation has caused accidents involving [[medical device]]s. One of the oldest known failure modes is ozone cracking caused by chain scission when [[ozone]] gas attacks susceptible [[elastomer]]s, such as [[natural rubber]] and [[nitrile rubber]]. They possess double bonds in their repeat units which are cleaved during [[ozonolysis]]. Cracks in fuel lines can penetrate the bore of the tube and cause fuel leakage. If cracking occurs in the engine compartment, electric sparks can ignite the [[gasoline]] and can cause a serious fire. In medical use degradation of polymers can lead to changes of physical and chemical characteristics of implantable devices.{{cite journal|last1=Iakovlev|first1=V.|last2=Guelcher|first2=S.|last3=Bendavid|first3=R.|date=28 August 2015|title=Degradation of polypropylene in vivo: A microscopic analysis of meshes explanted from patients|journal=Journal of Biomedical Materials Research Part B: Applied Biomaterials|volume=105|issue=2|pages=237–248|doi=10.1002/jbm.b.33502|pmid=26315946}} [359] => [360] => [[Nylon 6,6|Nylon 66]] is susceptible to [[acid hydrolysis]], and in one accident, a fractured fuel line led to a spillage of diesel into the road. If [[diesel fuel]] leaks onto the road, accidents to following cars can be caused by the slippery nature of the deposit, which is like [[black ice]]. Furthermore, the [[asphalt concrete]] road surface will suffer damage as a result of the diesel fuel dissolving the [[asphaltene]]s from the composite material, this resulting in the degradation of the asphalt surface and structural integrity of the road. [361] => [362] => == History == [363] => {{See also|Polymer science}}Polymers have been essential components of commodities since the early days of humankind. The use of [[wool]] ([[keratin]]), [[cotton]] and [[linen]] fibres ([[cellulose]]) for garments, [[Cyperus papyrus|paper reed]] ([[cellulose]]) for [[paper]] are just a few examples of how ancient societies exploited polymer-containing raw materials to obtain artefacts. The latex sap of [[Hevea brasiliensis|"caoutchouc" trees]] ([[natural rubber]]) reached Europe in the 16th century from South America long after the [[Olmecs|Olmec]], [[Maya civilization|Maya]] and [[Aztecs|Aztec]] had started using it as a material to make balls, waterproof textiles and containers.{{Cite journal|last=Hurley|first=Paul E.|date=May 1981|title=History of Natural Rubber|journal=Journal of Macromolecular Science: Part A - Chemistry|language=en|volume=15|issue=7|pages=1279–1287|doi=10.1080/00222338108056785|issn=0022-233X}} [364] => [365] => The chemical manipulation of polymers dates back to the 19th century, although at the time the nature of these species was not understood. The behaviour of polymers was initially rationalised according to the theory proposed by [[Thomas Graham (chemist)|Thomas Graham]] which considered them as colloidal aggregates of small molecules held together by unknown forces. [366] => [367] => Notwithstanding the lack of theoretical knowledge, the potential of polymers to provide innovative, accessible and cheap materials was immediately grasped. The work carried out by [[Henri Braconnot|Braconnot]], [[Parkesine|Parkes]], Ludersdorf, [[Nathaniel Hayward|Hayward]] and many others on the modification of natural polymers determined many significant advances in the field.{{Cite journal|last=Feldman|first=Dorel|date=January 2008|title=Polymer History|journal=Designed Monomers and Polymers|language=en|volume=11|issue=1|pages=1–15|doi=10.1163/156855508X292383|s2cid=219539020|issn=1568-5551|doi-access=free}} Their contributions led to the discovery of materials such as [[celluloid]], [[galalith]], [[parkesine]], [[rayon]], [[vulcanised rubber]] and, later, [[Bakelite]]: all materials that quickly entered industrial manufacturing processes and reached households as garments components (''e.g.'', fabrics, buttons), crockery and decorative items. [368] => [369] => In 1920, [[Hermann Staudinger]] published his seminal work "Über Polymerisation",{{Cite journal|last=Staudinger|first=H.|date=12 June 1920|title=Über Polymerisation|journal=Berichte der Deutschen Chemischen Gesellschaft (A and B Series)|volume=53|issue=6|pages=1073–1085|doi=10.1002/cber.19200530627|issn=0365-9488|url=https://zenodo.org/record/1426679}} in which he proposed that polymers were in fact long chains of atoms linked by covalent bonds. His work was debated at length, but eventually it was accepted by the scientific community. Because of this work, Staudinger was awarded the Nobel Prize in 1953.{{Cite web|title=The Nobel Prize in Chemistry 1953|url=https://www.nobelprize.org/prizes/chemistry/1953/summary/|access-date=25 June 2020|website=NobelPrize.org|language=en-US}} [370] => [371] => After the 1930s polymers entered a golden age during which new types were discovered and quickly given commercial applications, replacing naturally-sourced materials. This development was fuelled by an industrial sector with a strong economic drive and it was supported by a broad academic community that contributed innovative syntheses of monomers from cheaper raw material, more efficient polymerisation processes, improved techniques for polymer characterisation and advanced, theoretical understanding of polymers. [372] => [[File:History of polymers.tif|alt=|center|frameless|922x922px|Some memorable milestones in the history of polymers{{Cite journal|last=Feldman|first=Dorel|date=1 January 2008|title=Polymer History|journal=Designed Monomers and Polymers|volume=11|issue=1|pages=1–15|doi=10.1163/156855508X292383|s2cid=219539020|doi-access=free}}]] [373] => Since 1953, [[Polymer science#Nobel prizes related to polymer science|six Nobel prizes]] have been awarded in the area of polymer science, excluding those for research on [[Biopolymer|biological macromolecules]]. This further testifies to its impact on modern science and technology. As [[Alexander R. Todd|Lord Todd]] summarised in 1980, "I am inclined to think that the development of polymerization is perhaps the biggest thing that chemistry has done, where it has had the biggest effect on everyday life".{{Cite journal|date=6 October 1980|title=Lord Todd: the state of chemistry|journal=Chemical & Engineering News Archive|volume=58|issue=40|pages=28–33|doi=10.1021/cen-v058n040.p028|issn=0009-2347}} [374] => [375] => ==See also== [376] => {{Commons category|Polymers}} [377] => {{Div col|colwidth= 20em}} [378] => *[[Ideal chain]] [379] => *[[Catenation]] [380] => *[[Inorganic polymer]] [381] => *[[List of important publications in chemistry#Polymer chemistry|Important publications in polymer chemistry]] [382] => *[[Oligomer]] [383] => *[[Polymer adsorption]] [384] => *[[Polymer classes (disambiguation)|Polymer classes]] [385] => *[[Polymer engineering]] [386] => *[[Polymery (botany)]] [387] => *[[Reactive compatibilization]] [388] => *[[Sequence-controlled polymer]] [389] => *[[Shape-memory polymer]] [390] => *[[Sol–gel process]] [391] => *[[Supramolecular polymer]] [392] => *[[Thermoplastic]] [393] => *[[Thermosetting polymer]] [394] => {{Div col end}} [395] => [396] => ==References== [397] => {{Reflist|30em}} [398] => [399] => ==Bibliography== [400] => *{{cite book |last1= Cowie |first1= J. M. G. (John McKenzie Grant) |title= Polymers: chemistry and physics of modern materials |year= 1991 |publisher= Blackie |location= Glasgow |isbn= 978-0-412-03121-2 |url-access= registration |url= https://archive.org/details/polymerschemistr0000cowi }} [401] => *{{cite book |last1= Hall |first1= Christopher |title= Polymer materials |edition= 2nd |year= 1989 |publisher= Macmillan |location= London; New York |isbn= 978-0-333-46379-6 |url= https://blogs.ed.ac.uk/christopherhall/wp-content/uploads/sites/6693/2023/03/PM2.pdf}} [402] => *{{cite book |last1= Rudin |first1= Alfred |title= The elements of polymer science and engineering |year= 1982 |publisher= Academic Press |isbn= 978-0-12-601680-2 |url-access= registration |url= https://archive.org/details/elementsofpolyme0000rudi }} [403] => *{{cite book |last1= Wright |first1= David C. |title= Environmental Stress Cracking of Plastics |year= 2001 |publisher= RAPRA |isbn= 978-1-85957-064-7}} [404] => [405] => ==External links== [406] => {{external links|date=June 2021}} [407] => {{Wiktionary}} [408] => *[https://web.archive.org/web/20180404053600/http://www.icdd.com/resources/tutorials/pdf/How%20to%20analyze%20polymers.pdf How to Analyze Polymers Using X-ray Diffraction] [409] => *[https://web.archive.org/web/20080320034241/http://www.polymerchemistryhypertext.com/ Polymer Chemistry Hypertext, Educational resource] [410] => *[https://www.pslc.ws/macrog/index.htm The Macrogalleria] [411] => *[https://www.open.edu/openlearn/ocw/mod/oucontent/view.php?id=3484&printable=1 Introduction to Polymers] [412] => *[https://web.archive.org/web/20090425134619/http://www.theotherpages.org/abbrev.html Glossary of Polymer Abbreviations] [413] => {{Condensed matter physics topics}} [414] => {{Authority control}} [415] => {{Portal bar|Science|Chemistry|Numismatics|Electronics|Algae|Money}} [416] => [417] => [[Category:Organic polymers| ]] [418] => [[Category:Polymers| ]] [419] => [[Category:Polymer chemistry]] [420] => [[Category:Soft matter]] [421] => [[Category:Materials science]] [] => )
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Polymer

Polymers are large molecules made up of repeating subunits known as monomers. They can be natural or synthetic and are widely used in various industries.

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They can be natural or synthetic and are widely used in various industries. Natural polymers include substances like cellulose, DNA, and proteins, while synthetic polymers are man-made, such as plastics and synthetic fibers. The Wikipedia page on polymers provides an overview of their characteristics, classifications, and applications. It also delves into the different types of polymerization processes and the properties of various polymers. The page offers a comprehensive understanding of polymers, their structure, and their importance in materials science and everyday life.

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