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</style><table class="sidebar sidebar-collapse nomobile nowraplinks hlist"><tbody><tr><th class="sidebar-title">Polymer science</th></tr><tr><td class="sidebar-image"></td></tr><tr><td class="sidebar-content">
<div class="sidebar-list mw-collapsible mw-collapsed"><div class="sidebar-list-title" style="color: var(--color-base)">Properties</div><div class="sidebar-list-content mw-collapsible-content">
<ul><li><a href="Polymer_architecture" title="Polymer architecture">Architecture</a></li>
<li><a href="Polymer#Polymer_morphology" title="Polymer">Morphology</a></li>
<li><a href="Polymer_degradation" title="Polymer degradation">Degradation</a></li>
<li><a href="Polymer#Phase_behavior" title="Polymer">Phase behavior</a>
<ul><li><a href="Mark%E2%80%93Houwink_equation" title="Mark–Houwink equation">Mark–Houwink theory</a></li>
<li><a href="Upper_critical_solution_temperature" title="Upper critical solution temperature">UCST</a></li>
<li><a href="Lower_critical_solution_temperature" title="Lower critical solution temperature">LCST</a></li>
<li><a href="Flory%E2%80%93Huggins_solution_theory" title="Flory–Huggins solution theory">Flory–Huggins solution theory</a></li>
<li><a href="Coil%E2%80%93globule_transition" title="Coil–globule transition">Coil–globule transition</a></li></ul></li></ul></div></div></td>
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<div class="sidebar-list mw-collapsible mw-collapsed"><div class="sidebar-list-title" style="color: var(--color-base)"><a href="Polymerization" title="Polymerization">Synthesis</a></div><div class="sidebar-list-content mw-collapsible-content">
<dl><dt>Chain polymerization</dt>
<dd><a href="Radical_polymerization" title="Radical polymerization">Radical polymerization</a></dd>
<dd><a href="Reversible_deactivation_radical_polymerization" class="mw-redirect" title="Reversible deactivation radical polymerization">RDRP</a>]
<dl><dd><a href="ATRP_(chemistry)" class="mw-redirect" title="ATRP (chemistry)">ATRP</a></dd>
<dd><a href="RAFT" class="mw-redirect" title="RAFT">RAFT</a></dd>
<dd><a href="Nitroxide-mediated_radical_polymerization" title="Nitroxide-mediated radical polymerization">Nitroxide-mediated radical polymerization</a></dd></dl></dd></dl>
<dl><dt><a href="Step_polymerization" class="mw-redirect" title="Step polymerization">Step polymerization</a></dt>
<dd><a href="Condensation_polymer" title="Condensation polymer">Condensation polymerization</a></dd>
<dd><a href="Addition_polymerization" class="mw-redirect" title="Addition polymerization">Addition polymerization</a></dd></dl></div></div></td>
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<div class="sidebar-list mw-collapsible mw-collapsed"><div class="sidebar-list-title" style="color: var(--color-base)"><a href="Polymer_classes_(disambiguation)" class="mw-redirect mw-disambig" title="Polymer classes (disambiguation)">Classification</a></div><div class="sidebar-list-content mw-collapsible-content">
<dl><dt>Functional type</dt>
<dd><a href="Polyolefin" title="Polyolefin">Polyolefin</a>
<dl><dd><a href="Polyethylene" title="Polyethylene">Polyethylene</a></dd>
<dd><a href="Polypropylene" title="Polypropylene">Polypropylene</a></dd>
<dd><a href="Polyisobutylene" class="mw-redirect" title="Polyisobutylene">Polyisobutylene</a></dd></dl></dd>
<dd><a href="Polyurethane" title="Polyurethane">Polyurethane</a></dd>
<dd><a href="Polyester" title="Polyester">Polyester</a></dd>
<dd><a href="Polycarbonate" title="Polycarbonate">Polycarbonate</a></dd>
<dd><a href="Vinyl_polymer" title="Vinyl polymer">Vinyl polymers</a>
<dl><dd><a href="Polyvinyl_chloride" title="Polyvinyl chloride">PVC</a></dd>
<dd><a href="Polyvinyl_alcohol" title="Polyvinyl alcohol">PVA</a></dd>
<dd><a href="Polyvinyl_acetate" title="Polyvinyl acetate">PVAc</a></dd>
<dd><a href="Polystyrene" title="Polystyrene">Polystyrene</a></dd></dl></dd></dl>
<dl><dt>Structure</dt>
<dd><a href="Homopolymer" class="mw-redirect" title="Homopolymer">Homopolymer</a></dd>
<dd><a href="Copolymer" title="Copolymer">Copolymer</a></dd>
<dd><a href="Gels" class="mw-redirect" title="Gels">Gels</a>
<dl><dd><a href="Hydrogels" class="mw-redirect" title="Hydrogels">Hydrogels</a>
<dl><dd><a href="Self-healing_hydrogels" title="Self-healing hydrogels">Self-healing hydrogels</a></dd></dl></dd></dl></dd></dl></div></div></td>
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<div class="sidebar-list mw-collapsible mw-collapsed"><div class="sidebar-list-title" style="color: var(--color-base)"><a href="Polymer_characterization" title="Polymer characterization">Characterization</a></div><div class="sidebar-list-content mw-collapsible-content">
<ul><li><a href="Gel_permeation_chromatography" title="Gel permeation chromatography">GPC</a></li>
<li><a href="Infrared_spectroscopy" title="Infrared spectroscopy">FTIR</a></li>
<li><a href="X-ray_crystallography" title="X-ray crystallography">X-ray crystallography</a></li>
<li><a href="Differential_scanning_calorimetry" title="Differential scanning calorimetry">DSC</a></li>
<li><a href="NMR_spectroscopy" class="mw-redirect" title="NMR spectroscopy">NMR</a></li>
<li><a href="Thermogravimetric_analysis" title="Thermogravimetric analysis">TGA</a></li>
<li><a href="Dynamic_mechanical_analysis" title="Dynamic mechanical analysis">DMA</a></li>
<li><a href="Rheology" title="Rheology">Rheology</a>
<ul><li><a href="Rheometer" title="Rheometer">Rheometry</a></li>
<li><a href="Viscometer" title="Viscometer">Viscometry</a></li></ul></li></ul></div></div></td>
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<div class="sidebar-list mw-collapsible mw-collapsed"><div class="sidebar-list-title" style="color: var(--color-base)">Scientists</div><div class="sidebar-list-content mw-collapsible-content">
<ul><li><a href="Paul_Flory" title="Paul Flory">Flory</a></li>
<li><a href="Alan_J._Heeger" title="Alan J. Heeger">Heeger</a></li>
<li><a href="Alan_MacDiarmid" title="Alan MacDiarmid">MacDiarmid</a></li>
<li><a href="Hideki_Shirakawa" title="Hideki Shirakawa">Shirakawa</a></li>
<li><a href="Giulio_Natta" title="Giulio Natta">Natta</a></li>
<li><a href="Sam_Edwards_(physicist)" title="Sam Edwards (physicist)"> Edwards</a></li>
<li><a href="Pierre-Gilles_de_Gennes" title="Pierre-Gilles de Gennes">de Gennes</a></li>
<li><a href="Karl_Ziegler" title="Karl Ziegler">Ziegler</a></li>
<li><a href="Hermann_Staudinger" title="Hermann Staudinger">Staudinger</a></li>
<li><a href="Charles_Goodyear" title="Charles Goodyear">Goodyear</a></li>
<li><a href="Leo_Baekeland" title="Leo Baekeland">Baekeland</a></li>
<li><a href="Nathaniel_Hayward" title="Nathaniel Hayward">Hayward</a></li>
<li><a href="Henri_Braconnot" title="Henri Braconnot">Braconnot</a></li></ul></div></div></td>
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<div class="sidebar-list mw-collapsible mw-collapsed"><div class="sidebar-list-title" style="color: var(--color-base)">Applications</div><div class="sidebar-list-content mw-collapsible-content">
<dl><dt>Industrial production</dt>
<dd><a href="Plastics_extrusion" class="mw-redirect" title="Plastics extrusion">Extrusion</a>
<dl><dd><a href="Blow_molding" title="Blow molding">Blow molding</a></dd>
<dd><a href="Extrusion_coating" title="Extrusion coating">Applied coatings</a></dd></dl></dd>
<dd><a href="Industrial_coating" class="mw-redirect" title="Industrial coating">Protective Coatings</a></dd>
<dd><a href="3D_printing" title="3D printing">3D printing</a></dd>
<dt><a href="Plastics" class="mw-redirect" title="Plastics">Consumer products</a></dt>
<dd><a href="Tire" title="Tire">Tires</a>
<dl><dd><a href="Whitewall_tires" class="mw-redirect" title="Whitewall tires">Whitewalls</a></dd></dl></dd>
<dd><a href="Cookware_and_bakeware" title="Cookware and bakeware">Cookware and bakeware</a>
<dl><dd><a href="Bakelite" title="Bakelite">Bakelite</a></dd>
<dd><a href="Foam_food_container" title="Foam food container">Food Container</a></dd></dl></dd>
<dd><a href="Vinyl_record" class="mw-redirect" title="Vinyl record">Vinyl record</a></dd>
<dd><a href="Kevlar" title="Kevlar">Kevlar</a></dd>
<dd><a href="Plastic_bottle" title="Plastic bottle">Plastic bottle</a></dd>
<dd><a href="Plastic_bag" title="Plastic bag">Plastic bag</a></dd></dl></div></div></td>
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<p><b>Tacticity</b> (from <a href="Greek_language" title="Greek language">Greek</a>: <span lang="el">τακτικός</span>, <small><a href="Romanization_of_Greek" title="Romanization of Greek">romanized</a>: </small><span title="Greek-language romanization"><i lang="el-Latn">taktikos</i></span>, "relating to arrangement or order") is the relative <a href="Stereochemistry" title="Stereochemistry">stereochemistry</a> of adjacent <a href="Chirality_(chemistry)" title="Chirality (chemistry)">chiral</a> centers within a <a href="Macromolecule" title="Macromolecule">macromolecule</a>.<sup id="cite_ref-1" class="reference"><a href="#cite_note-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup> The practical significance of tacticity rests on the effects on the physical properties of the <a href="Polymer" title="Polymer">polymer</a>. The regularity of the macromolecular structure influences the degree to which it has rigid, <a href="Crystallinity" title="Crystallinity">crystalline</a> long range order or flexible, <a href="Amorphous" class="mw-redirect" title="Amorphous">amorphous</a> long range disorder. Precise knowledge of tacticity of a polymer also helps understanding at what temperature a polymer <a href="Melting" title="Melting">melts</a>, how <a href="Soluble" class="mw-redirect" title="Soluble">soluble</a> it is in a <a href="Solvent" title="Solvent">solvent</a>, as well as its mechanical properties.
</p><p>A <b>tactic macromolecule</b> in the <a href="IUPAC" class="mw-redirect" title="IUPAC">IUPAC</a> definition is a macromolecule in which essentially all the configurational (repeating) units are identical. In a hydrocarbon macromolecule with all carbon atoms making up the backbone in a <a href="Tetrahedral_molecular_geometry" title="Tetrahedral molecular geometry">tetrahedral molecular geometry</a>, the zigzag backbone is in the paper plane with the substituents either sticking out of the paper or retreating into the paper;, this projection is called the <a href="Natta_projection" title="Natta projection">Natta projection after Giulio</a> <a href="Giulio_Natta" title="Giulio Natta">Natta</a>. Tacticity is particularly significant in <a href="Vinyl_polymer" title="Vinyl polymer">vinyl polymers</a> of the type -<span class="chemf nowrap">H<span class="nowrap"><span style="display:inline-block;margin-bottom:-0.3em;vertical-align:-0.4em;line-height:1em;font-size:80%;text-align:left"><sup style="font-size:inherit;line-height:inherit;vertical-align:baseline"></sup><br><sub style="font-size:inherit;line-height:inherit;vertical-align:baseline">2</sub></span></span>C-CH(R)-</span>, where each <a href="Repeating_unit" class="mw-redirect" title="Repeating unit">repeating unit</a> contains a <a href="Substituent" title="Substituent">substituent</a> R attached to one side of the polymer <a href="Backbone_chain" class="mw-redirect" title="Backbone chain">backbone</a>. The arrangement of these substituents can follow a regular pattern- appearing on the same side as the previous one, on the opposite side, or in a random configuration relative to the preceding unit. <b>Monotactic</b> macromolecules have one <a href="Stereoisomerism" title="Stereoisomerism">stereoisomeric</a> atom per repeat unit, <b>ditactic</b> to <b>n-tactic</b> macromolecules have more than one stereoisomeric atom per unit.
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<div class="quotebox-title" style=""><a href="International_Union_of_Pure_and_Applied_Chemistry" title="International Union of Pure and Applied Chemistry">IUPAC</a> definition</div>
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<p>The orderliness of the succession of configurational repeating units in<br>the main chain of a regular <a href="Macromolecule" title="Macromolecule">macromolecule</a>, a regular oligomer molecule,<br>a regular block, or a regular chain.<sup id="cite_ref-2" class="reference"><a href="#cite_note-2"><span class="cite-bracket">[</span>2<span class="cite-bracket">]</span></a></sup>
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<div class="mw-heading mw-heading2"><h2 id="Definition">Definition</h2></div>
<div class="mw-heading mw-heading3"><h3 id="Diads">Diads</h3></div>
<p>Two adjacent structural units in a polymer molecule constitute a <b>diad</b>. Diads overlap: each structural unit is considered part of two diads, one diad with each neighbor. If a diad consists of two identically oriented units, the diad is called an <b><span class="nowrap">m diad</span></b> (formerly <i>meso diad</i>, as in a <a href="Meso_compound" title="Meso compound">meso compound</a>, now proscribed<sup id="cite_ref-danrotp_3-0" class="reference"><a href="#cite_note-danrotp-3"><span class="cite-bracket">[</span>3<span class="cite-bracket">]</span></a></sup>). If a diad consists of units oriented in opposition, the diad is called an <b><span class="nowrap">r diad</span></b> (formerly <i>racemo diad</i>, as in a racemic compound, now proscribed<sup id="cite_ref-danrotp_3-1" class="reference"><a href="#cite_note-danrotp-3"><span class="cite-bracket">[</span>3<span class="cite-bracket">]</span></a></sup>). In the case of vinyl polymer molecules, an <span class="nowrap">m diad</span> is one in which the substituents are oriented on the same side of the polymer backbone; in the Natta projection, they both point into the plane or both point out of the plane.
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<div class="mw-heading mw-heading3"><h3 id="Triads">Triads</h3></div>
<p>The stereochemistry of macromolecules can be defined even more precisely with the introduction of triads. An <b>isotactic triad</b> (<i>mm</i>) is made up of two overlapping m diads, a <b>syndiotactic triad</b> (also spelled <b>syndyotactic</b><sup id="cite_ref-4" class="reference"><a href="#cite_note-4"><span class="cite-bracket">[</span>4<span class="cite-bracket">]</span></a></sup>) (<i>rr</i>) consists of two overlapping <span class="nowrap">r diads</span>, and a <b>heterotactic triad</b> (<i>rm</i>) is composed of an <span class="nowrap">r diad</span> overlapping an <span class="nowrap">m diad</span>. The mass fraction of isotactic (<i>mm</i>) triads is a common quantitative measure of tacticity.
</p><p>When the stereochemistry of a macromolecule is considered to be a <a href="Bernoulli_process" title="Bernoulli process">Bernoulli process</a>, the triad composition can be calculated from the probability <i>P</i><sub>m</sub> of a diad being <span class="nowrap">m type</span>. For example, when this probability is 0.25 then the probability of finding:
</p>
<ul><li>an isotactic triad is <i>P</i><sub>m</sub><sup>2</sup>, or 0.0625</li>
<li>an heterotactic triad is 2<i>P</i><sub>m</sub>(1–<i>P</i><sub>m</sub>), or 0.375</li>
<li>a syndiotactic triad is (1–<i>P</i><sub>m</sub>)<sup>2</sup>, or 0.5625</li></ul>
<p>with a total probability of 1. Similar relationships with diads exist for tetrads.<sup id="cite_ref-5" class="reference"><a href="#cite_note-5"><span class="cite-bracket">[</span>5<span class="cite-bracket">]</span></a></sup><sup class="reference nowrap"><span title="Page / location: 357">: 357 </span></sup>
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<div class="mw-heading mw-heading3"><h3 id="Tetrads,_pentads,_etc.">Tetrads, pentads, etc.</h3></div>
<p>The definition of tetrads and pentads introduce further sophistication and precision to defining tacticity, especially when information on long-range ordering is desirable. Tacticity measurements obtained by <a href="Carbon-13_NMR" class="mw-redirect" title="Carbon-13 NMR">carbon-13 NMR</a> are typically expressed in terms of the relative abundance of various pentads within the polymer molecule, e.g. <i>mmmm</i>, <i>mrrm</i>.
</p>
<div class="mw-heading mw-heading3"><h3 id="Other_conventions_for_quantifying_tacticity">Other conventions for quantifying tacticity</h3></div>
<p>The primary convention for expressing tacticity is in terms of the relative weight fraction of triad or higher-order components, as described above. An alternative expression for tacticity is the average length of <i>m</i> and <i>r</i> sequences within the polymer molecule. The average m-sequence length may be approximated from the relative abundance of pentads as follows:<sup id="cite_ref-6" class="reference"><a href="#cite_note-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup>
</p><p><span class="mwe-math-element mwe-math-element-inline"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle MSL={\frac {mmmm+{\tfrac {3}{2}}mrrr+2rmmr+{\tfrac {1}{2}}rmrm+{\tfrac {1}{2}}rmrr}{{\tfrac {1}{2}}mmmr+rmmr+{\tfrac {1}{2}}rmrm+{\tfrac {1}{2}}rmrr}}}">
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<annotation encoding="application/x-tex">{\displaystyle MSL={\frac {mmmm+{\tfrac {3}{2}}mrrr+2rmmr+{\tfrac {1}{2}}rmrm+{\tfrac {1}{2}}rmrr}{{\tfrac {1}{2}}mmmr+rmmr+{\tfrac {1}{2}}rmrm+{\tfrac {1}{2}}rmrr}}}</annotation>
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</math></span><img src="./558dd4b3fbbebd1b4fad0a7288dab92fc33539c2.svg" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -3.338ex; width:57.848ex; height:8.009ex;" alt="{\displaystyle MSL={\frac {mmmm+{\tfrac {3}{2}}mrrr+2rmmr+{\tfrac {1}{2}}rmrm+{\tfrac {1}{2}}rmrr}{{\tfrac {1}{2}}mmmr+rmmr+{\tfrac {1}{2}}rmrm+{\tfrac {1}{2}}rmrr}}}" loading="lazy"></span>
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<div class="mw-heading mw-heading2"><h2 id="Polymers">Polymers</h2></div>
<div class="mw-heading mw-heading3"><h3 id="Isotactic_polymers">Isotactic polymers</h3></div>
<p>Isotactic polymers are composed of isotactic macromolecules (IUPAC definition).<sup id="cite_ref-7" class="reference"><a href="#cite_note-7"><span class="cite-bracket">[</span>7<span class="cite-bracket">]</span></a></sup> In isotactic macromolecules, all the substituents are located on the same side of the macromolecular backbone. An isotactic macromolecule consists of 100% <span class="nowrap">m diads</span>, though IUPAC also allows the term for macromolecules with at least 95% <span class="nowrap">m diads</span> if that looser usage is explained.<sup id="cite_ref-danrotp_3-2" class="reference"><a href="#cite_note-danrotp-3"><span class="cite-bracket">[</span>3<span class="cite-bracket">]</span></a></sup> <a href="Polypropylene" title="Polypropylene">Polypropylene</a> formed by <a href="Ziegler%E2%80%93Natta_catalyst" title="Ziegler–Natta catalyst">Ziegler–Natta catalysis</a> is an example of an isotactic polymer.<sup id="cite_ref-8" class="reference"><a href="#cite_note-8"><span class="cite-bracket">[</span>8<span class="cite-bracket">]</span></a></sup> Isotactic polymers are usually <a href="Semicrystalline" class="mw-redirect" title="Semicrystalline">semicrystalline</a><sup id="cite_ref-:0_9-0" class="reference"><a href="#cite_note-:0-9"><span class="cite-bracket">[</span>9<span class="cite-bracket">]</span></a></sup> and generally (but not exclusively) crystallize in a helical configuration.<sup id="cite_ref-10" class="reference"><a href="#cite_note-10"><span class="cite-bracket">[</span>10<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-11" class="reference"><a href="#cite_note-11"><span class="cite-bracket">[</span>11<span class="cite-bracket">]</span></a></sup>
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<div class="mw-heading mw-heading3"><h3 id="Syndiotactic_polymers">Syndiotactic polymers</h3></div>
<p>In syndiotactic or <b>syntactic</b> macromolecules the substituents have alternate positions along the chain. The macromolecule comprises 100% <span class="nowrap">r diads</span>, though IUPAC also allows the term for macromolecules with at least 95% <span class="nowrap">r diads</span> if that looser usage is explained. Syndiotactic <a href="Polystyrene" title="Polystyrene">polystyrene</a>, made by <a href="Metallocene_catalysis_polymerization" class="mw-redirect" title="Metallocene catalysis polymerization">metallocene catalysis polymerization</a>, is crystalline with a <a href="Melting_point" title="Melting point">melting point</a> of 161 °C. <a href="Gutta_percha" class="mw-redirect" title="Gutta percha">Gutta percha</a> is also an example syndiotactic polymer.<sup id="cite_ref-12" class="reference"><a href="#cite_note-12"><span class="cite-bracket">[</span>12<span class="cite-bracket">]</span></a></sup>
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<div class="mw-heading mw-heading3"><h3 id="Atactic_polymers">Atactic polymers</h3></div>
<p>In atactic macromolecules the substituents are placed randomly along the chain. The percentage of <span class="nowrap">m diads</span> is understood to be between 45 and 55% unless otherwise specified, but it could be any value other than 0 or 100% if that usage is clarified.<sup id="cite_ref-danrotp_3-3" class="reference"><a href="#cite_note-danrotp-3"><span class="cite-bracket">[</span>3<span class="cite-bracket">]</span></a></sup> With the aid of spectroscopic techniques such as <a href="Nuclear_magnetic_resonance" title="Nuclear magnetic resonance">NMR</a>, it is possible to pinpoint the composition of a polymer in terms of the percentages for each triad.<sup id="cite_ref-13" class="reference"><a href="#cite_note-13"><span class="cite-bracket">[</span>13<span class="cite-bracket">]</span></a></sup>
</p>
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<p>Polymers that are formed by <a href="Free-radical_polymerization" class="mw-redirect" title="Free-radical polymerization">free-radical mechanisms</a>, such as <a href="Polyvinyl_chloride" title="Polyvinyl chloride">polyvinyl chloride</a> are usually atactic. Due to their random nature atactic polymers are usually <a href="Amorphous" class="mw-redirect" title="Amorphous">amorphous</a>. In <i>hemi-isotactic macromolecules</i> every other repeat unit has a random substituent.
</p><p>Atactic polymers such as <a href="Polystyrene" title="Polystyrene">polystyrene</a> (<a href="Polystyrene" title="Polystyrene">PS</a>) are technologically very important. It is possible to obtain syndiotactic polystyrene using a <a href="Kaminsky_catalyst" title="Kaminsky catalyst">Kaminsky catalyst</a>,<sup id="cite_ref-14" class="reference"><a href="#cite_note-14"><span class="cite-bracket">[</span>14<span class="cite-bracket">]</span></a></sup> but most industrial polystyrene produced is atactic. The two materials have very different properties because the irregular structure of the atactic version makes it impossible for the polymer chains to stack in a regular fashion: whereas syndiotactic PS is a semicrystalline material, the more common atactic version cannot crystallize and forms a <i>glass</i> instead. This example is quite general in that many polymers of economic importance are atactic glass formers.
</p>
<div class="mw-heading mw-heading3"><h3 id="Eutactic_polymers">Eutactic polymers</h3></div>
<p>In eutactic macromolecules, substituents may occupy any specific (but potentially complex) sequence of positions along the chain. Isotactic and syndiotactic polymers are instances of the more general class of eutactic polymers, which also includes heterogeneous macromolecules in which the sequence consists of substituents of different kinds (for example, the side-chains in proteins and the bases in nucleic acids).
</p>
<div class="mw-heading mw-heading2"><h2 id="Effect_on_polymer_properties">Effect on polymer properties</h2></div>
<p>Tacticity has a significant effect on <a href="Crystallization_of_polymers" title="Crystallization of polymers">polymer crystallinity</a>, and thus affects other properties that depend on crystallinity such as strength, melting point, and solubility. Isotactic and syndiotactic polymers have a more ordered structure and can form semicrystalline materials, while atactic polymers are generally amorphous (i.e. not crystalline) because their lack of order prevents them from packing into a crystal lattice.<sup id="cite_ref-:0_9-1" class="reference"><a href="#cite_note-:0-9"><span class="cite-bracket">[</span>9<span class="cite-bracket">]</span></a></sup> Crystallinity generally leads to better mechanical strength, solvent resistance, and barrier properties, but amorphous polymers do not necessarily have poor mechanical properties and can have other advantages such as optical clarity.<sup id="cite_ref-:0_9-2" class="reference"><a href="#cite_note-:0-9"><span class="cite-bracket">[</span>9<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-15" class="reference"><a href="#cite_note-15"><span class="cite-bracket">[</span>15<span class="cite-bracket">]</span></a></sup> As an example, atactic polypropylene is an amorphous polymer with a <a href="Glass_transition" title="Glass transition">glass-transition temperature</a>, <i>T</i><sub>g</sub>, of -27 °C, while isotactic polypropylene is crystalline with a <i>T</i><sub>g</sub> of -26 °C and a melting temperature, <i>T</i><sub>m</sub>, of 160 °C and syndiotactic polypropylene is also crystalline with a higher <i>T</i><sub>g</sub> of -4.3 °C and a lower <i>T</i><sub>m</sub> of 126 °C.<sup id="cite_ref-16" class="reference"><a href="#cite_note-16"><span class="cite-bracket">[</span>16<span class="cite-bracket">]</span></a></sup> Isotactic polypropylene is strong and high-melting and so is widely used in a range of applications, while atactic polypropylene is soft and waxy and sees only limited use in adhesives and as an asphalt additive.<sup id="cite_ref-:0_9-3" class="reference"><a href="#cite_note-:0-9"><span class="cite-bracket">[</span>9<span class="cite-bracket">]</span></a></sup>
</p>
<div class="mw-heading mw-heading2"><h2 id="Stereocontrolled_polymerization">Stereocontrolled polymerization</h2></div>
<p>Polymers with controlled tacticity (i.e. not atactic) must be produced via some type of stereocontrolled polymerization. Stereocontrolled polymerizations have been demonstrated with a variety of chain-growth polymerization mechanisms, although stereocontrolled <a href="Radical_polymerization" title="Radical polymerization">radical</a> and <a href="Cationic_polymerization" title="Cationic polymerization">cationic polymerizations</a> are less common than stereocontrolled <a href="Coordination_polymerization" title="Coordination polymerization">coordination</a> and <a href="Anionic_addition_polymerization" title="Anionic addition polymerization">anionic polymerizations</a> due to a lack of stereochemical definition at the propagating chain end.<sup id="cite_ref-17" class="reference"><a href="#cite_note-17"><span class="cite-bracket">[</span>17<span class="cite-bracket">]</span></a></sup> Stereocontrolled polymerization of chiral monomers can also be enantioselective, meaning that one <a href="Enantiomer" title="Enantiomer">enantiomer</a> of the monomer is selectively polymerized to give an isotactic polymer.<sup id="cite_ref-18" class="reference"><a href="#cite_note-18"><span class="cite-bracket">[</span>18<span class="cite-bracket">]</span></a></sup> Depending on the origin of stereoselectivity, stereocontrolled polymerizations can be classified as polymer chain-end control or enantiomorphic site control.
</p>
<div class="mw-heading mw-heading3"><h3 id="Polymer_chain-end_control">Polymer chain-end control</h3></div>
<p>In polymer chain-end control, the stereochemistry of the most recent monomer added to the polymer chain determines the stereochemistry of the next monomer added. In an isoselective polymerization, the next monomer to be inserted will have the same stereochemistry as the previous monomer, while in a syndioselective polymerization it will be the opposite. The stereoselectivity of a polymerization with polymer chain-end control is quantified by <i>P</i><sub>m</sub> and <i>P</i><sub>r</sub>, the probabilities of forming an m and r diad, respectively. An isoselective polymerization has a <i>P</i><sub>m</sub> approaching 1, while a syndioselective polymerization has a <i>P</i><sub>r</sub> approaching 1. When a stereoerror occurs (i.e. a monomer is added in the less favored orientation, such as the formation of a r diad in an isoselective polymerization), it is propagated, meaning that in an isoselective polymerization the substituents would switch from all being on one side of the polymer chain to all being on the other side.<sup id="cite_ref-:1_19-0" class="reference"><a href="#cite_note-:1-19"><span class="cite-bracket">[</span>19<span class="cite-bracket">]</span></a></sup>
</p>
<div class="mw-heading mw-heading3"><h3 id="Enantiomorphic_site_control">Enantiomorphic site control</h3></div>
<p>In enantiomorphic site control, the stereochemistry of the next monomer added is instead determined by the stereochemistry of the catalyst. The stereoselectivity of a polymerization with enantiomorphic site control is often quantified by the site control selectivity α, the probability of adding a monomer with a certain <a href="Absolute_configuration" title="Absolute configuration">absolute configuration</a>. For an isoselective polymerization, an α value of 0 or 1 indicates a fully isotactic polymer while an α value of 0.5 indicates an atactic polymer. When a stereoerror occurs, it is corrected, meaning that (in an isoselective polymerization) substituents will return to being on the same side of the polymer chain that they were on before the error.<sup id="cite_ref-:1_19-1" class="reference"><a href="#cite_note-:1-19"><span class="cite-bracket">[</span>19<span class="cite-bracket">]</span></a></sup>
</p>
<div class="mw-heading mw-heading2"><h2 id="Head/tail_configuration">Head/tail configuration</h2></div>
<p>In <a href="Vinyl_polymer" title="Vinyl polymer">vinyl polymers</a>, the complete configuration can be further described by defining polymer head/tail configuration. In a regular macromolecule, monomer units are normally linked in a head to tail configuration such that β-substituents are located on alternating carbon atoms. However, it is possible for defects to form where substituents are placed on adjacent carbon atoms, producing a head/head tail/tail configuration, such as by recombination of two growing <a href="Free_radical_polymerization" class="mw-redirect" title="Free radical polymerization">radical chains</a>, or by direct head-head addition if <a href="Steric" class="mw-redirect" title="Steric">steric</a> effects are weak enough, such as in <a href="Polyvinylidene_fluoride" title="Polyvinylidene fluoride">polyvinylidene fluoride</a>.<sup id="cite_ref-20" class="reference"><a href="#cite_note-20"><span class="cite-bracket">[</span>20<span class="cite-bracket">]</span></a></sup>
</p>
<div class="mw-heading mw-heading2"><h2 id="Techniques_for_measuring_tacticity">Techniques for measuring tacticity</h2></div>
<p>Tacticity may be measured directly using <a href="Proton" title="Proton">proton</a> or <a href="Carbon-13" title="Carbon-13">carbon-13</a> <a href="NMR" class="mw-redirect" title="NMR">NMR</a>. This technique enables quantification of the tacticity distribution by comparison of peak areas or integral ranges corresponding to known diads (r, m), triads (mm, rm+mr, rr) and/or higher order <i>n</i>-ads, depending on spectral resolution. In cases of limited resolution, stochastic methods such as <a href="Bernoulli_process" title="Bernoulli process">Bernoullian</a> or <a href="Markov_chain" title="Markov chain">Markovian analysis</a> may also be used to fit the distribution and predict higher <i>n</i>-ads and calculate the isotacticity of the polymer to the desired level.<sup id="cite_ref-21" class="reference"><a href="#cite_note-21"><span class="cite-bracket">[</span>21<span class="cite-bracket">]</span></a></sup>
</p><p>Other techniques sensitive to tacticity include <a href="X-ray_powder_diffraction" class="mw-redirect" title="X-ray powder diffraction">x-ray powder diffraction</a>, <a href="Secondary_ion_mass_spectrometry" class="mw-redirect" title="Secondary ion mass spectrometry">secondary ion mass spectrometry</a> (SIMS),<sup id="cite_ref-22" class="reference"><a href="#cite_note-22"><span class="cite-bracket">[</span>22<span class="cite-bracket">]</span></a></sup> vibrational spectroscopy (FTIR)<sup id="cite_ref-23" class="reference"><a href="#cite_note-23"><span class="cite-bracket">[</span>23<span class="cite-bracket">]</span></a></sup> and especially two-dimensional techniques.<sup id="cite_ref-24" class="reference"><a href="#cite_note-24"><span class="cite-bracket">[</span>24<span class="cite-bracket">]</span></a></sup> Tacticity may also be inferred by measuring another physical property, such as melting temperature, when the relationship between tacticity and that property is well-established.<sup id="cite_ref-25" class="reference"><a href="#cite_note-25"><span class="cite-bracket">[</span>25<span class="cite-bracket">]</span></a></sup>
</p>
<div class="mw-heading mw-heading2"><h2 id="References">References</h2></div>
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<li id="cite_note-21"><span class="mw-cite-backlink"><b><a href="#cite_ref-21">^</a></b></span> <span class="reference-text"><cite id="CITEREFWuSheer1977" class="citation journal cs1">Wu, Ting Kai; Sheer, M. Lana (1977). "Carbon-13 NMR Determination of Pentad Tacticity of Poly(vinyl alcohol)". <i>Macromolecules</i>. <b>10</b> (3): 529. <a href="Bibcode_(identifier)" class="mw-redirect" title="Bibcode (identifier)">Bibcode</a>:<a rel="nofollow" class="external text" href="https://ui.adsabs.harvard.edu/abs/1977MaMol..10..529W">1977MaMol..10..529W</a>. <a href="Doi_(identifier)" class="mw-redirect" title="Doi (identifier)">doi</a>:<a rel="nofollow" class="external text" href="https://doi.org/10.1021%2Fma60057a006">10.1021/ma60057a006</a>.</cite></span>
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<li id="cite_note-22"><span class="mw-cite-backlink"><b><a href="#cite_ref-22">^</a></b></span> <span class="reference-text"><cite id="CITEREFVanden_EyndeWengBertrand1997" class="citation journal cs1">Vanden Eynde, X.; Weng, L. T.; Bertrand, P. (1997). "Influence of Tacticity on Polymer Surfaces Studiedby ToF-SIMS". <i>Surface and Interface Analysis</i>. <b>25</b>: <span class="nowrap">41–</span>45. <a href="Doi_(identifier)" class="mw-redirect" title="Doi (identifier)">doi</a>:<a rel="nofollow" class="external text" href="https://doi.org/10.1002%2F%28SICI%291096-9918%28199701%2925%3A1%3C41%3A%3AAID-SIA211%3E3.0.CO%3B2-T">10.1002/(SICI)1096-9918(199701)25:1<41::AID-SIA211>3.0.CO;2-T</a>.</cite></span>
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<li id="cite_note-23"><span class="mw-cite-backlink"><b><a href="#cite_ref-23">^</a></b></span> <span class="reference-text"><cite id="CITEREFDybalKrimm1990" class="citation journal cs1">Dybal, J.; Krimm, S. (1990). "Normal-mode analysis of infrared and Raman spectra of crystalline isotactic poly(methyl methacrylate)". <i>Macromolecules</i>. <b>23</b> (5): 1301. <a href="Bibcode_(identifier)" class="mw-redirect" title="Bibcode (identifier)">Bibcode</a>:<a rel="nofollow" class="external text" href="https://ui.adsabs.harvard.edu/abs/1990MaMol..23.1301D">1990MaMol..23.1301D</a>. <a href="Doi_(identifier)" class="mw-redirect" title="Doi (identifier)">doi</a>:<a rel="nofollow" class="external text" href="https://doi.org/10.1021%2Fma00207a013">10.1021/ma00207a013</a>.</cite></span>
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<li id="cite_note-24"><span class="mw-cite-backlink"><b><a href="#cite_ref-24">^</a></b></span> <span class="reference-text"><cite id="CITEREFSchillingBoveyBruchKozlowski1985" class="citation journal cs1">Schilling, Frederic C.; Bovey, Frank A.; Bruch, Martha D.; Kozlowski, Sharon A. (1985). "Observation of the stereochemical configuration of poly(methyl methacrylate) by proton two-dimensional J-correlated and NOE-correlated NMR spectroscopy". <i>Macromolecules</i>. <b>18</b> (7): 1418. <a href="Bibcode_(identifier)" class="mw-redirect" title="Bibcode (identifier)">Bibcode</a>:<a rel="nofollow" class="external text" href="https://ui.adsabs.harvard.edu/abs/1985MaMol..18.1418S">1985MaMol..18.1418S</a>. <a href="Doi_(identifier)" class="mw-redirect" title="Doi (identifier)">doi</a>:<a rel="nofollow" class="external text" href="https://doi.org/10.1021%2Fma00149a011">10.1021/ma00149a011</a>.</cite></span>
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<li id="cite_note-25"><span class="mw-cite-backlink"><b><a href="#cite_ref-25">^</a></b></span> <span class="reference-text"><cite id="CITEREFGitsasFloudas2008" class="citation journal cs1">Gitsas, A.; Floudas, G. (2008). "Pressure Dependence of the Glass Transition in Atactic and Isotactic Polypropylene". <i>Macromolecules</i>. <b>41</b> (23): 9423. <a href="Bibcode_(identifier)" class="mw-redirect" title="Bibcode (identifier)">Bibcode</a>:<a rel="nofollow" class="external text" href="https://ui.adsabs.harvard.edu/abs/2008MaMol..41.9423G">2008MaMol..41.9423G</a>. <a href="Doi_(identifier)" class="mw-redirect" title="Doi (identifier)">doi</a>:<a rel="nofollow" class="external text" href="https://doi.org/10.1021%2Fma8014992">10.1021/ma8014992</a>.</cite></span>
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</ol></div></div>
<div class="mw-heading mw-heading2"><h2 id="Further_reading">Further reading</h2></div>
<ul><li><cite id="CITEREFWandrey,_Christine_[Prof.]2004" class="citation web cs1">Wandrey, Christine [Prof.] (2004-04-19). <a rel="nofollow" class="external text" href="https://web.archive.org/web/20040419014355/http://scgc.epfl.ch:80/load/cours_chim/cwandrey_part-2-1.pdf">"Molecular Basis of the Structure and Behavior of Polymers, Part II: Chemistry and Structure of Macromolecules—Design of Polymer Chains"</a> <span class="cs1-format">(PDF)</span>. <i>EPFL.ch</i> (polymer chemistry course materils). Lausanne, Switzerland: Laboratory of Polymers and Biomaterials, Dept. of Chemistry, Ecole Polytechnique Federale de Lausanne (EPFL). Archived from <a rel="nofollow" class="external text" href="http://scgc.epfl.ch:80/load/cours_chim/cwandrey_part-2-1.pdf">the original</a> <span class="cs1-format">(PDF)</span> on 2004-04-19.</cite></li></ul>
<div class="mw-heading mw-heading2"><h2 id="External_links">External links</h2></div>
<ul><li><a rel="nofollow" class="external text" href="https://web.archive.org/web/20040627210014/http://www.chemeng.ucla.edu/che112/Notes/polymer%20spectroscopy.pdf">Application of spectroscopy in polymer characterisation</a> @ <a href="University_of_California%2C_Los_Angeles" title="University of California, Los Angeles">University of California, Los Angeles</a></li></ul></div><!--htdig_noindex--><div><div class="zim-footer">
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