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</ul> </div> </div> </div> </div> </nav> </div> </header> </div> <div class="mw-page-container"> <div class="mw-page-container-inner"> <div class="vector-sitenotice-container"> <div id="siteNotice"></div> </div> <div class="vector-column-start"> <div class="vector-main-menu-container"> <div id="mw-navigation"> <nav id="mw-panel" class="vector-main-menu-landmark" aria-label="站点"> <div id="vector-main-menu-pinned-container" class="vector-pinned-container"> </div> </nav> </div> </div> <div class="vector-sticky-pinned-container"> <nav id="mw-panel-toc" aria-label="目录" data-event-name="ui.sidebar-toc" class="mw-table-of-contents-container vector-toc-landmark"> <div id="vector-toc-pinned-container" class="vector-pinned-container"> <div id="vector-toc" class="vector-toc vector-pinnable-element"> <div class="vector-pinnable-header vector-toc-pinnable-header vector-pinnable-header-pinned" data-feature-name="toc-pinned" data-pinnable-element-id="vector-toc" > <h2 class="vector-pinnable-header-label">目录</h2> <button class="vector-pinnable-header-toggle-button vector-pinnable-header-pin-button" data-event-name="pinnable-header.vector-toc.pin">移至侧栏</button> <button class="vector-pinnable-header-toggle-button vector-pinnable-header-unpin-button" data-event-name="pinnable-header.vector-toc.unpin">隐藏</button> </div> <ul class="vector-toc-contents" id="mw-panel-toc-list"> <li id="toc-mw-content-text" class="vector-toc-list-item vector-toc-level-1"> <a href="#" class="vector-toc-link"> <div class="vector-toc-text">序言</div> </a> </li> <li id="toc-單體" class="vector-toc-list-item vector-toc-level-1 vector-toc-list-item-expanded"> <a class="vector-toc-link" href="#單體"> <div class="vector-toc-text"> <span class="vector-toc-numb">1</span> <span>單體</span> </div> </a> <button aria-controls="toc-單體-sublist" class="cdx-button cdx-button--weight-quiet cdx-button--icon-only vector-toc-toggle"> <span class="vector-icon mw-ui-icon-wikimedia-expand"></span> <span>开关單體子章节</span> </button> <ul id="toc-單體-sublist" class="vector-toc-list"> <li id="toc-烯烴" class="vector-toc-list-item vector-toc-level-2"> <a class="vector-toc-link" href="#烯烴"> <div class="vector-toc-text"> <span class="vector-toc-numb">1.1</span> <span>烯烴</span> </div> </a> <ul id="toc-烯烴-sublist" class="vector-toc-list"> </ul> </li> <li id="toc-具雜環單體" class="vector-toc-list-item vector-toc-level-2"> <a class="vector-toc-link" href="#具雜環單體"> <div class="vector-toc-text"> <span class="vector-toc-numb">1.2</span> <span>具雜環單體</span> </div> </a> <ul id="toc-具雜環單體-sublist" class="vector-toc-list"> </ul> </li> </ul> </li> <li id="toc-合成" class="vector-toc-list-item vector-toc-level-1 vector-toc-list-item-expanded"> <a class="vector-toc-link" href="#合成"> <div class="vector-toc-text"> <span class="vector-toc-numb">2</span> <span>合成</span> </div> </a> <button aria-controls="toc-合成-sublist" class="cdx-button cdx-button--weight-quiet cdx-button--icon-only vector-toc-toggle"> <span class="vector-icon mw-ui-icon-wikimedia-expand"></span> <span>开关合成子章节</span> </button> <ul id="toc-合成-sublist" class="vector-toc-list"> <li id="toc-链引发" class="vector-toc-list-item vector-toc-level-2"> <a class="vector-toc-link" href="#链引发"> <div class="vector-toc-text"> <span class="vector-toc-numb">2.1</span> <span>链引发</span> </div> </a> <ul id="toc-链引发-sublist" class="vector-toc-list"> <li id="toc-典型的質子酸" class="vector-toc-list-item vector-toc-level-3"> <a class="vector-toc-link" href="#典型的質子酸"> <div class="vector-toc-text"> <span class="vector-toc-numb">2.1.1</span> <span>典型的質子酸</span> </div> </a> <ul id="toc-典型的質子酸-sublist" class="vector-toc-list"> </ul> </li> <li id="toc-路易斯酸/傅-克反應催化劑" class="vector-toc-list-item vector-toc-level-3"> <a class="vector-toc-link" href="#路易斯酸/傅-克反應催化劑"> <div class="vector-toc-text"> <span class="vector-toc-numb">2.1.2</span> <span>路易斯酸/傅-克反應催化劑</span> </div> </a> <ul id="toc-路易斯酸/傅-克反應催化劑-sublist" class="vector-toc-list"> </ul> </li> <li id="toc-碳烯陽離子鹽" class="vector-toc-list-item vector-toc-level-3"> <a class="vector-toc-link" href="#碳烯陽離子鹽"> <div class="vector-toc-text"> <span class="vector-toc-numb">2.1.3</span> <span>碳烯陽離子鹽</span> </div> </a> <ul id="toc-碳烯陽離子鹽-sublist" class="vector-toc-list"> </ul> </li> <li id="toc-游離輻射" class="vector-toc-list-item vector-toc-level-3"> <a class="vector-toc-link" href="#游離輻射"> <div class="vector-toc-text"> <span class="vector-toc-numb">2.1.4</span> <span>游離輻射</span> </div> </a> <ul id="toc-游離輻射-sublist" class="vector-toc-list"> </ul> </li> </ul> </li> <li id="toc-链增长" class="vector-toc-list-item vector-toc-level-2"> <a class="vector-toc-link" href="#链增长"> <div class="vector-toc-text"> <span class="vector-toc-numb">2.2</span> <span>链增长</span> </div> </a> <ul id="toc-链增长-sublist" class="vector-toc-list"> <li id="toc-溫度的影響" class="vector-toc-list-item vector-toc-level-3"> <a class="vector-toc-link" href="#溫度的影響"> <div class="vector-toc-text"> <span class="vector-toc-numb">2.2.1</span> <span>溫度的影響</span> </div> </a> <ul id="toc-溫度的影響-sublist" class="vector-toc-list"> </ul> </li> <li id="toc-溶劑與抗衡離子的影響" class="vector-toc-list-item vector-toc-level-3"> <a class="vector-toc-link" href="#溶劑與抗衡離子的影響"> <div class="vector-toc-text"> <span class="vector-toc-numb">2.2.2</span> <span>溶劑與抗衡離子的影響</span> </div> </a> <ul id="toc-溶劑與抗衡離子的影響-sublist" class="vector-toc-list"> </ul> </li> </ul> </li> <li id="toc-链终止" class="vector-toc-list-item vector-toc-level-2"> <a class="vector-toc-link" href="#链终止"> <div class="vector-toc-text"> <span class="vector-toc-numb">2.3</span> <span>链终止</span> </div> </a> <ul id="toc-链终止-sublist" class="vector-toc-list"> </ul> </li> <li id="toc-鏈的轉移" class="vector-toc-list-item vector-toc-level-2"> <a class="vector-toc-link" href="#鏈的轉移"> <div class="vector-toc-text"> <span class="vector-toc-numb">2.4</span> <span>鏈的轉移</span> </div> </a> <ul id="toc-鏈的轉移-sublist" class="vector-toc-list"> </ul> </li> <li id="toc-陽離子開環聚合反應" class="vector-toc-list-item vector-toc-level-2"> <a class="vector-toc-link" href="#陽離子開環聚合反應"> <div class="vector-toc-text"> <span class="vector-toc-numb">2.5</span> <span>陽離子開環聚合反應</span> </div> </a> <ul id="toc-陽離子開環聚合反應-sublist" class="vector-toc-list"> </ul> </li> </ul> </li> <li id="toc-動力學" class="vector-toc-list-item vector-toc-level-1 vector-toc-list-item-expanded"> <a class="vector-toc-link" href="#動力學"> <div class="vector-toc-text"> <span class="vector-toc-numb">3</span> <span>動力學</span> </div> </a> <ul id="toc-動力學-sublist" class="vector-toc-list"> </ul> </li> <li id="toc-活性聚合反應" class="vector-toc-list-item vector-toc-level-1 vector-toc-list-item-expanded"> <a class="vector-toc-link" href="#活性聚合反應"> <div class="vector-toc-text"> <span class="vector-toc-numb">4</span> <span>活性聚合反應</span> </div> </a> <ul id="toc-活性聚合反應-sublist" class="vector-toc-list"> </ul> </li> <li id="toc-商業應用" class="vector-toc-list-item vector-toc-level-1 vector-toc-list-item-expanded"> <a class="vector-toc-link" href="#商業應用"> <div class="vector-toc-text"> <span class="vector-toc-numb">5</span> <span>商業應用</span> </div> </a> <ul id="toc-商業應用-sublist" class="vector-toc-list"> </ul> </li> <li id="toc-參考" class="vector-toc-list-item vector-toc-level-1 vector-toc-list-item-expanded"> <a class="vector-toc-link" href="#參考"> <div class="vector-toc-text"> <span class="vector-toc-numb">6</span> <span>參考</span> </div> </a> <ul id="toc-參考-sublist" class="vector-toc-list"> </ul> </li> </ul> </div> </div> </nav> </div> </div> <div class="mw-content-container"> <main id="content" class="mw-body"> <header class="mw-body-header vector-page-titlebar"> <nav aria-label="目录" class="vector-toc-landmark"> <div id="vector-page-titlebar-toc" class="vector-dropdown vector-page-titlebar-toc vector-button-flush-left" title="目录" > <input type="checkbox" id="vector-page-titlebar-toc-checkbox" role="button" aria-haspopup="true" data-event-name="ui.dropdown-vector-page-titlebar-toc" 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title=""><a href="https://de.wikipedia.org/wiki/Kationische_Kettenpolymerisation" title="Kationische Kettenpolymerisation – 德语" lang="de" hreflang="de" data-title="Kationische Kettenpolymerisation" data-language-autonym="Deutsch" data-language-local-name="德语" class="interlanguage-link-target"><span>Deutsch</span></a></li><li class="interlanguage-link interwiki-en mw-list-item"><a href="https://en.wikipedia.org/wiki/Cationic_polymerization" title="Cationic polymerization – 英语" lang="en" hreflang="en" data-title="Cationic polymerization" data-language-autonym="English" data-language-local-name="英语" class="interlanguage-link-target"><span>English</span></a></li><li class="interlanguage-link interwiki-es mw-list-item"><a href="https://es.wikipedia.org/wiki/Polimerizaci%C3%B3n_cati%C3%B3nica" title="Polimerización catiónica – 西班牙语" lang="es" hreflang="es" data-title="Polimerización catiónica" data-language-autonym="Español" data-language-local-name="西班牙语" class="interlanguage-link-target"><span>Español</span></a></li><li class="interlanguage-link interwiki-et mw-list-item"><a href="https://et.wikipedia.org/wiki/Katioonne_pol%C3%BCmerisatsioon" title="Katioonne polümerisatsioon – 爱沙尼亚语" lang="et" hreflang="et" data-title="Katioonne polümerisatsioon" data-language-autonym="Eesti" data-language-local-name="爱沙尼亚语" class="interlanguage-link-target"><span>Eesti</span></a></li><li class="interlanguage-link interwiki-eu mw-list-item"><a href="https://eu.wikipedia.org/wiki/Katioi-polimerizazio" title="Katioi-polimerizazio – 巴斯克语" lang="eu" hreflang="eu" data-title="Katioi-polimerizazio" data-language-autonym="Euskara" data-language-local-name="巴斯克语" class="interlanguage-link-target"><span>Euskara</span></a></li><li class="interlanguage-link interwiki-fr mw-list-item"><a href="https://fr.wikipedia.org/wiki/Polym%C3%A9risation_cationique" title="Polymérisation cationique – 法语" lang="fr" hreflang="fr" data-title="Polymérisation cationique" data-language-autonym="Français" data-language-local-name="法语" class="interlanguage-link-target"><span>Français</span></a></li><li class="interlanguage-link interwiki-hr mw-list-item"><a href="https://hr.wikipedia.org/wiki/Kationska_polimerizacija" title="Kationska polimerizacija – 克罗地亚语" lang="hr" hreflang="hr" data-title="Kationska polimerizacija" data-language-autonym="Hrvatski" data-language-local-name="克罗地亚语" class="interlanguage-link-target"><span>Hrvatski</span></a></li><li class="interlanguage-link interwiki-it mw-list-item"><a href="https://it.wikipedia.org/wiki/Polimerizzazione_cationica" title="Polimerizzazione cationica – 意大利语" lang="it" hreflang="it" data-title="Polimerizzazione cationica" data-language-autonym="Italiano" data-language-local-name="意大利语" class="interlanguage-link-target"><span>Italiano</span></a></li><li class="interlanguage-link interwiki-pt mw-list-item"><a href="https://pt.wikipedia.org/wiki/Polimeriza%C3%A7%C3%A3o_cati%C3%B4nica" title="Polimerização catiônica – 葡萄牙语" lang="pt" hreflang="pt" data-title="Polimerização catiônica" data-language-autonym="Português" data-language-local-name="葡萄牙语" class="interlanguage-link-target"><span>Português</span></a></li> </ul> <div class="after-portlet after-portlet-lang"><span class="wb-langlinks-edit wb-langlinks-link"><a href="https://www.wikidata.org/wiki/Special:EntityPage/Q3046749#sitelinks-wikipedia" title="编辑跨语言链接" class="wbc-editpage">编辑链接</a></span></div> </div> </div> </div> </header> <div class="vector-page-toolbar"> <div class="vector-page-toolbar-container"> <div id="left-navigation"> <nav aria-label="命名空间"> <div id="p-associated-pages" class="vector-menu vector-menu-tabs mw-portlet mw-portlet-associated-pages" > <div class="vector-menu-content"> <ul class="vector-menu-content-list"> <li id="ca-nstab-main" class="selected vector-tab-noicon mw-list-item"><a href="/wiki/%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89" title="浏览条目正文[c]" 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aria-label="页面工具"> <div id="vector-page-tools-pinned-container" class="vector-pinned-container"> </div> </nav> <nav class="vector-appearance-landmark" aria-label="外观"> <div id="vector-appearance-pinned-container" class="vector-pinned-container"> <div id="vector-appearance" class="vector-appearance vector-pinnable-element"> <div class="vector-pinnable-header vector-appearance-pinnable-header vector-pinnable-header-pinned" data-feature-name="appearance-pinned" data-pinnable-element-id="vector-appearance" data-pinned-container-id="vector-appearance-pinned-container" data-unpinned-container-id="vector-appearance-unpinned-container" > <div class="vector-pinnable-header-label">外观</div> <button class="vector-pinnable-header-toggle-button vector-pinnable-header-pin-button" data-event-name="pinnable-header.vector-appearance.pin">移至侧栏</button> <button class="vector-pinnable-header-toggle-button vector-pinnable-header-unpin-button" 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(prefers-color-scheme:dark){html.skin-theme-clientpref-os .mw-parser-output .ambox{border-left-color:#36c!important}html.skin-theme-clientpref-os .mw-parser-output .ambox-speedy,html.skin-theme-clientpref-os .mw-parser-output .ambox-delete{border-left-color:#b32424!important}html.skin-theme-clientpref-os .mw-parser-output .ambox-speedy{background-color:#300!important}html.skin-theme-clientpref-os .mw-parser-output .ambox-content{border-left-color:#f28500!important}html.skin-theme-clientpref-os .mw-parser-output .ambox-style{border-left-color:#fc3!important}html.skin-theme-clientpref-os .mw-parser-output .ambox-move{border-left-color:#9932cc!important}html.skin-theme-clientpref-os .mw-parser-output .ambox-protection{border-left-color:#a2a9b1!important}}</style><table class="box-Expert_needed plainlinks metadata ambox ambox-content" role="presentation"><tbody><tr><td class="mbox-image"><div style="width:52px"><span typeof="mw:File"><span><img alt="" src="//upload.wikimedia.org/wikipedia/commons/thumb/b/b4/Ambox_important.svg/40px-Ambox_important.svg.png" decoding="async" width="40" height="40" class="mw-file-element" srcset="//upload.wikimedia.org/wikipedia/commons/thumb/b/b4/Ambox_important.svg/60px-Ambox_important.svg.png 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/b/b4/Ambox_important.svg/80px-Ambox_important.svg.png 2x" data-file-width="40" data-file-height="40" /></span></span></div></td><td class="mbox-text"><div class="mbox-text-span">此條目需要<b>精通或熟悉相关主题的编者</b>参与及协助编辑。<span class="hide-when-compact"></span> <small class="date-container"><i>(<span class="date">2014年6月25日</span>)</i></small><span class="hide-when-compact"><br /><small>請<a href="/wiki/Wikipedia:%E5%B0%88%E5%AE%B6%E9%82%80%E8%AB%8B%E5%B7%A5%E4%BD%9C%E5%B0%8F%E7%B5%84" title="Wikipedia:專家邀請工作小組">邀請</a>適合的人士<a class="external text" href="https://zh.wikipedia.org/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit">改善本条目</a>。更多的細節與詳情請參见<a href="/wiki/Talk:%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89" title="Talk:陽離子聚合反應">討論頁</a>。</small></span><span class="hide-when-compact"></span></div></td></tr></tbody></table> <p><b>陽離子聚合反應</b>為一種鏈增長<a href="/wiki/%E8%81%9A%E5%90%88%E5%8F%8D%E5%BA%94" class="mw-redirect" title="聚合反应">聚合反應</a>，反應中陽離子引發劑(cationic initiator)會將電荷轉移單體，使單體變得有反應性。而這個具反應性單體會與其他單體進行相似的反應，最後形成聚合物。.<sup id="cite_ref-Odian_1-0" class="reference"><a href="#cite_note-Odian-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-EPSE_2-0" class="reference"><a href="#cite_note-EPSE-2"><span class="cite-bracket">[</span>2<span class="cite-bracket">]</span></a></sup> 陽離子聚合反應中的這種單體，必須受具有提供電子取代基(electron-donating substituent)的<a href="/wiki/%E7%83%AF%E7%83%B4" class="mw-redirect" title="烯烴">烯烴</a>(olefins)和雜環(heterocycles)限制。相似於陰離子聚合反應，陽離子聚合反應對反應中所使用的<a href="/wiki/%E6%BA%B6%E5%8A%91" class="mw-redirect" title="溶劑">溶劑</a>(solvent)非常敏感，特別是溶劑可形成游離離子(free ions)的能力，此能力決定了增長的陽離子鏈的反應性。陽離子聚合反應用於聚<a href="/wiki/%E5%BC%82%E4%B8%81%E7%83%AF" title="异丁烯">異丁烯</a>(polyisobutylene)的產生(如：<a href="/wiki/%E4%B8%81%E5%9F%BA%E6%A9%A1%E8%83%B6" title="丁基橡胶">丁基橡膠</a>用於輪胎的內胎)和聚N-乙烯基咔唑(N-vinylcarbazole，PVK)<sup id="cite_ref-CH_421_3-0" class="reference"><a href="#cite_note-CH_421-3"><span class="cite-bracket">[</span>3<span class="cite-bracket">]</span></a></sup> </p><p><br /> </p> <style data-mw-deduplicate="TemplateStyles:r64637320">.mw-parser-output .quotebox{background-color:#F9F9F9;border:1px solid #aaa;box-sizing:border-box;padding:.25em .5em;font-size:88%;max-width:100%}.mw-parser-output .quotebox.floatleft{margin:.5em 1.4em .8em 0}.mw-parser-output .quotebox.floatright{margin:.5em 0 .8em 1.4em}.mw-parser-output .quotebox.centered{margin:.5em auto .8em auto}.mw-parser-output .quotebox p{font-style:inherit;margin-bottom:0}.mw-parser-output .quotebox-title{background-color:#F9F9F9;text-align:center;font-size:larger;font-weight:bold;margin-bottom:0}.mw-parser-output .quotebox-quote.quoted:before{font-family:"Times New Roman",serif;font-weight:bold;font-size:large;color:gray;content:" “ ";vertical-align:-45%;line-height:0}.mw-parser-output .quotebox-quote.quoted:after{font-family:"Times New Roman",serif;font-weight:bold;font-size:large;color:gray;content:" ” ";line-height:0}.mw-parser-output .quotebox .left-aligned{text-align:left}.mw-parser-output .quotebox .right-aligned{text-align:right}.mw-parser-output .quotebox .center-aligned{text-align:center}.mw-parser-output .quotebox cite{display:block;font-style:normal}@media all and (max-width:720px){.mw-parser-output .quotebox{width:100%!important;margin:0 0 .8em!important;float:none!important}}</style><div class="quotebox" style="float: right; clear: right; margin: 0.5em 0 0.8em 1.4em; padding: 6px; border: 1px solid #aaa; font-size: 88%; background-color: #F9F9F9;"><div class="" style="background-color: inherit;color: inherit; text-align: center; font-size: larger; font-weight: bold;">IUPAC definition</div><div class="" style="position: relative; text-align: left;">離子<a href="/wiki/%E8%81%9A%E5%90%88%E5%8F%8D%E5%BA%94" class="mw-redirect" title="聚合反应">聚合反應</a>中的動力鏈攜帶者( kinetic-chain carriers)為陽離子。<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></div></div> <p><br /> </p> <meta property="mw:PageProp/toc" /> <div class="mw-heading mw-heading2"><h2 id="單體"><span id=".E5.96.AE.E9.AB.94"></span>單體</h2><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=1" title="编辑章节：單體"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p>陽離子聚合反應的單體規模受限於兩個主要種類：<a href="/wiki/%E7%83%AF%E7%83%B4" class="mw-redirect" title="烯烴">烯烴</a>(Olefins)和具雜環單體(Heterocyclic monmers)。若要兩種單體同時發生陽離子聚合反應，只有在利於熱(thermally favorable)的反應中才會發生。以烯烴單體為例，是因為此單體中的雙鍵之<a href="/wiki/%E5%BC%82%E6%9E%84%E5%8C%96%E5%8F%8D%E5%BA%94" title="异构化反应">異構化反應</a>(isomerization)；而對雜環單體來說，是因為單體之環張力(ring strain)的釋放和在有些例子中，重複的單元的異構化反應。陽離子聚合反應中的單體具親核性(nucleophilic)，且在聚合反應中可形成穩定的陽離子。<sup id="cite_ref-KM_book_5-0" class="reference"><a href="#cite_note-KM_book-5"><span class="cite-bracket">[</span>5<span class="cite-bracket">]</span></a></sup> </p><p><br /> </p> <div class="mw-heading mw-heading3"><h3 id="烯烴"><span id=".E7.83.AF.E7.83.B4"></span><a href="/wiki/%E7%83%AF%E7%83%B4" class="mw-redirect" title="烯烴">烯烴</a></h3><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=2" title="编辑章节：烯烴"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div><p> 具有提供電子的取代基的烯烴單體會發生陽離子聚合反應，這些提供電子的取代基使烯烴具有親核性，足以攻擊親電子性引發劑(electrophilic initiators)或使聚合鏈增長。同時，這些接上單體之提供電子的取代基能穩定對接下來聚合反應所產生的陽離子電荷。有些具有反應性的烯烴，具有<a href="/wiki/%E6%9D%82%E5%8E%9F%E5%AD%90" title="杂原子">雜原子</a>基(heteroatom groups)的反應性會好於烷基(alkyl)或芳香基(aryl groups)，在下圖從左至右反應性越差為排序，表現烯烴的反應性。無論如何，碳烯陽離子(carbenium ion)形成的反應性與單體的反應性相反。<sup id="cite_ref-KM_book_5-1" class="reference"><a href="#cite_note-KM_book-5"><span class="cite-bracket">[</span>5<span class="cite-bracket">]</span></a></sup> </p><figure class="mw-halign-center" typeof="mw:File/Thumb"><a href="/wiki/File:Olefin_Reactivity.png" class="mw-file-description"><img src="//upload.wikimedia.org/wikipedia/commons/thumb/6/6e/Olefin_Reactivity.png/450px-Olefin_Reactivity.png" decoding="async" width="450" height="102" class="mw-file-element" srcset="//upload.wikimedia.org/wikipedia/commons/thumb/6/6e/Olefin_Reactivity.png/675px-Olefin_Reactivity.png 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/6/6e/Olefin_Reactivity.png/900px-Olefin_Reactivity.png 2x" data-file-width="1633" data-file-height="371" /></a><figcaption>由左至右為反應性越差</figcaption></figure> <div class="mw-heading mw-heading3"><h3 id="具雜環單體"><span id=".E5.85.B7.E9.9B.9C.E7.92.B0.E5.96.AE.E9.AB.94"></span>具雜環單體</h3><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=3" title="编辑章节：具雜環單體"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <figure class="mw-default-size" typeof="mw:File/Thumb"><a href="/wiki/File:Heterocyclic_monomers.png" class="mw-file-description"><img src="//upload.wikimedia.org/wikipedia/commons/thumb/f/f3/Heterocyclic_monomers.png/220px-Heterocyclic_monomers.png" decoding="async" width="220" height="148" class="mw-file-element" srcset="//upload.wikimedia.org/wikipedia/commons/thumb/f/f3/Heterocyclic_monomers.png/330px-Heterocyclic_monomers.png 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/f/f3/Heterocyclic_monomers.png/440px-Heterocyclic_monomers.png 2x" data-file-width="812" data-file-height="547" /></a><figcaption>具雜環單體的例子</figcaption></figure> <p>具雜環單體會陽離子聚合成<a href="/wiki/%E5%86%85%E9%85%AF" title="内酯">內酯</a>(lactone)、<a href="/wiki/%E5%86%85%E9%85%B0%E8%83%BA" title="内酰胺">內醯胺</a>(lactam)和環胺類(cyclic amine)，當加入引發劑(initiator)時，環狀單體會產生線性聚合物(linear polymers)。具雜環單體的反應性取決於，其自身的環張力，具有大環張力的單體，如<a href="/wiki/%E7%8E%AF%E6%B0%A7%E4%B9%99%E7%83%B7" title="环氧乙烷">環氧乙烷</a>(oxirane)，環氧乙烷相較於1，3-二氧環庚烷(1,3-dioxepane)具有較大的反應性，因為1，3-二氧環庚烷的環張力較小。六個(或以上)碳形成的環不傾向發生聚合反應，因為環張力較低。<sup id="cite_ref-Cowie_Textbook_6-0" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup> </p> <div class="mw-heading mw-heading2"><h2 id="合成"><span id=".E5.90.88.E6.88.90"></span>合成</h2><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=4" title="编辑章节：合成"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <div class="mw-heading mw-heading3"><h3 id="链引发"><span id=".E9.93.BE.E5.BC.95.E5.8F.91"></span>链引发</h3><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=5" title="编辑章节：链引发"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p>链引发為陽離子聚合反應的第一步驟，在链引发步驟中會從已做好的聚合鏈中產生碳烯陽離子(carbenium ion)。抗衡離子(counterion)應為非親核性的(non-nucleophilic)，否則反應會瞬間終止。對陽離子聚合反應有許多引發劑(initiators)，有些引發劑需要共引發劑(coinitiator)來產生所需種類的陽離子。<sup id="cite_ref-Kennedy_7-0" class="reference"><a href="#cite_note-Kennedy-7"><span class="cite-bracket">[</span>7<span class="cite-bracket">]</span></a></sup> </p> <div class="mw-heading mw-heading4"><h4 id="典型的質子酸"><span id=".E5.85.B8.E5.9E.8B.E7.9A.84.E8.B3.AA.E5.AD.90.E9.85.B8"></span>典型的質子酸</h4><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=6" title="编辑章节：典型的質子酸"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p>強質子酸可使用於形成陽離子引發種類，若要產生足夠量的不同種陽離子，需要高濃度的質子酸。產生的抗衡離子(A<sup>–</sup>)具有較弱的親核性，因為要避免其與帶質子的烯烴結合，而使反應提早終止。<sup id="cite_ref-KM_book_5-2" class="reference"><a href="#cite_note-KM_book-5"><span class="cite-bracket">[</span>5<span class="cite-bracket">]</span></a></sup> 常見的質子酸有<a href="/wiki/%E7%A3%B7%E9%85%B8" title="磷酸">磷酸</a>、<a href="/wiki/%E7%A1%AB%E9%85%B8" title="硫酸">硫酸</a>和<a href="/wiki/%E4%B8%89%E6%B0%9F%E7%94%B2%E7%A3%BA%E9%85%B8" title="三氟甲磺酸">三氟甲磺酸</a>只有分子量小的聚合物可形成這些引發劑。<sup id="cite_ref-Odian_1-1" class="reference"><a href="#cite_note-Odian-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup> </p> <figure class="mw-halign-center" typeof="mw:File/Thumb"><a href="/wiki/File:Protic_acid_initiation.png" class="mw-file-description"><img src="//upload.wikimedia.org/wikipedia/commons/thumb/9/9f/Protic_acid_initiation.png/375px-Protic_acid_initiation.png" decoding="async" width="375" height="49" class="mw-file-element" srcset="//upload.wikimedia.org/wikipedia/commons/thumb/9/9f/Protic_acid_initiation.png/563px-Protic_acid_initiation.png 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/9/9f/Protic_acid_initiation.png/750px-Protic_acid_initiation.png 2x" data-file-width="1067" data-file-height="138" /></a><figcaption>質子酸的起始反應</figcaption></figure> <div class="mw-heading mw-heading4"><h4 id="路易斯酸/傅-克反應催化劑"><span id=".E8.B7.AF.E6.98.93.E6.96.AF.E9.85.B8.2F.E5.82.85-.E5.85.8B.E5.8F.8D.E6.87.89.E5.82.AC.E5.8C.96.E5.8A.91"></span>路易斯酸/<a href="/wiki/%E5%82%85-%E5%85%8B%E5%8F%8D%E5%BA%94" class="mw-redirect" title="傅-克反应">傅-克反應</a>催化劑</h4><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=7" title="编辑章节：路易斯酸/傅-克反應催化劑"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p><a href="/wiki/%E8%B7%AF%E6%98%93%E6%96%AF%E9%85%B8" class="mw-redirect" title="路易斯酸">路易斯酸</a>(Lewis acids)為最常使用於陽離子聚合反應的起始步驟的化合物，其中常使用的路易斯酸為SnCl<sub>4</sub>、AlCl<sub>3</sub>、 BF<sub>3</sub>和TiCl<sub>4</sub>，雖然單獨使用這些路易斯酸可引起聚合反應，且此反應會與合適的陽離子來源快速發生。陽離子來源可為<a href="/wiki/%E6%B0%B4" title="水">水</a>、<a href="/wiki/%E9%85%92%E7%B2%BE" class="mw-redirect" title="酒精">酒精</a>，甚至或碳陽離子提供者(carbocation donor)，如<a href="/wiki/%E9%85%AF" title="酯">酯</a>或<a href="/wiki/%E9%85%B8%E9%85%90" title="酸酐">酸酐</a>。在此系統中，當碳源為引發劑時，路易斯酸作為共引發劑。當引發劑與共引發劑反應，反應中的中間複合物(intermediate complex)可與單體進行反應。由引發劑-共引發劑複合物產生的抗衡離子較路易斯酸A<sup>–</sup>親核性低。當加入反應性較好的路易斯酸時，鹵素(Halogens)，如<a href="/wiki/%E6%B0%AF" title="氯">氯</a>、<a href="/wiki/%E6%BA%B4" title="溴">溴</a>也可引發陽離子聚合反應。<sup id="cite_ref-Odian_1-2" class="reference"><a href="#cite_note-Odian-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup> </p> <figure class="mw-halign-center" typeof="mw:File/Thumb"><a href="/wiki/File:Lewis_acid_initiation.png" class="mw-file-description"><img src="//upload.wikimedia.org/wikipedia/commons/thumb/3/3f/Lewis_acid_initiation.png/325px-Lewis_acid_initiation.png" decoding="async" width="325" height="93" class="mw-file-element" srcset="//upload.wikimedia.org/wikipedia/commons/thumb/3/3f/Lewis_acid_initiation.png/488px-Lewis_acid_initiation.png 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/3/3f/Lewis_acid_initiation.png/650px-Lewis_acid_initiation.png 2x" data-file-width="1082" data-file-height="308" /></a><figcaption><a href="/wiki/%E4%B8%89%E6%B0%9F%E5%8C%96%E7%A1%BC" title="三氟化硼">三氟化硼</a>(共引發劑)和水(引發劑)的起始反應</figcaption></figure> <p><br /> </p> <div class="mw-heading mw-heading4"><h4 id="碳烯陽離子鹽"><span id=".E7.A2.B3.E7.83.AF.E9.99.BD.E9.9B.A2.E5.AD.90.E9.B9.BD"></span>碳烯陽離子鹽</h4><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=8" title="编辑章节：碳烯陽離子鹽"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p>只有具最好反應性的烯烴，可用穩定的碳烯陽離子來誘導烯烴鏈的增長，以得到明確的結構。在動力學中最常研究起始反應，因為測量<a href="/wiki/%E7%A2%B3%E6%AD%A3%E9%9B%A2%E5%AD%90" class="mw-redirect" title="碳正離子">碳正離子</a>吸收值的消失是比較容易的。常見的碳烯陽離子有三苯基氯甲烷和鎓陽離子。<sup id="cite_ref-KM_book_5-3" class="reference"><a href="#cite_note-KM_book-5"><span class="cite-bracket">[</span>5<span class="cite-bracket">]</span></a></sup> </p> <figure class="mw-halign-center" typeof="mw:File/Thumb"><a href="/wiki/File:Carbenium_ion_initiation.png" class="mw-file-description"><img src="//upload.wikimedia.org/wikipedia/commons/thumb/c/c4/Carbenium_ion_initiation.png/325px-Carbenium_ion_initiation.png" decoding="async" width="325" height="96" class="mw-file-element" srcset="//upload.wikimedia.org/wikipedia/commons/thumb/c/c4/Carbenium_ion_initiation.png/488px-Carbenium_ion_initiation.png 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/c/c4/Carbenium_ion_initiation.png/650px-Carbenium_ion_initiation.png 2x" data-file-width="1009" data-file-height="297" /></a><figcaption>三苯甲基自由基碳烯陽離子的起始反應</figcaption></figure> <div class="mw-heading mw-heading4"><h4 id="游離輻射"><span id=".E6.B8.B8.E9.9B.A2.E8.BC.BB.E5.B0.84"></span>游離輻射</h4><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=9" title="编辑章节：游離輻射"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p><a href="/wiki/%E6%B8%B8%E9%9B%A2%E8%BC%BB%E5%B0%84" title="游離輻射">游離輻射</a>(Ionizing radiation)可形成自由基陽離子對，並與單體反應而開始了陽離子聚合反應。要控制自由基陽離子很困難，且受單體和反應環境影響。自由基的形成和陰離子的種類也常常是研究目標。<sup id="cite_ref-KM_book_5-4" class="reference"><a href="#cite_note-KM_book-5"><span class="cite-bracket">[</span>5<span class="cite-bracket">]</span></a></sup> </p> <figure class="mw-halign-center" typeof="mw:File/Thumb"><a href="/wiki/File:Ionizing_radiation_initiation.png" class="mw-file-description"><img src="//upload.wikimedia.org/wikipedia/commons/thumb/8/83/Ionizing_radiation_initiation.png/375px-Ionizing_radiation_initiation.png" decoding="async" width="375" height="46" class="mw-file-element" srcset="//upload.wikimedia.org/wikipedia/commons/thumb/8/83/Ionizing_radiation_initiation.png/563px-Ionizing_radiation_initiation.png 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/8/83/Ionizing_radiation_initiation.png/750px-Ionizing_radiation_initiation.png 2x" data-file-width="1120" data-file-height="136" /></a><figcaption>使用游離輻射的起始反應</figcaption></figure> <div class="mw-heading mw-heading3"><h3 id="链增长"><span id=".E9.93.BE.E5.A2.9E.E9.95.BF"></span>链增长</h3><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=10" title="编辑章节：链增长"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p>链增长(Propagation)的進行是透過加入單體給活化的種類(即碳烯離子)。單體是以從頭到尾(head-to-tail)形式加入至增長的鏈中；在這個過程，會產生陽離子的尾端，而下一個循環的單體則由此加入。<sup id="cite_ref-Cowie_Textbook_6-1" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup> </p> <figure class="mw-halign-center" typeof="mw:File/Thumb"><a href="/wiki/File:Propagation_pathway2.png" class="mw-file-description"><img src="//upload.wikimedia.org/wikipedia/commons/thumb/d/de/Propagation_pathway2.png/375px-Propagation_pathway2.png" decoding="async" width="375" height="53" class="mw-file-element" srcset="//upload.wikimedia.org/wikipedia/commons/thumb/d/de/Propagation_pathway2.png/563px-Propagation_pathway2.png 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/d/de/Propagation_pathway2.png/750px-Propagation_pathway2.png 2x" data-file-width="1119" data-file-height="158" /></a><figcaption>常見的增生反應途徑</figcaption></figure> <div class="mw-heading mw-heading4"><h4 id="溫度的影響"><span id=".E6.BA.AB.E5.BA.A6.E7.9A.84.E5.BD.B1.E9.9F.BF"></span>溫度的影響</h4><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=11" title="编辑章节：溫度的影響"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p>反應時的溫度會影響增生速率，整個陽離子聚合反應的<a href="/wiki/%E6%B4%BB%E5%8C%96%E8%83%BD" title="活化能">活化能</a>(<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\mathit {E}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mrow class="MJX-TeXAtom-ORD"> <mrow class="MJX-TeXAtom-ORD"> <mi class="MJX-tex-mathit" mathvariant="italic">E</mi> </mrow> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\mathit {E}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/af04a4c2023b2f3459b8d3f965b97c9d353ebda8" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.338ex; margin-right: -0.151ex; width:1.727ex; height:2.176ex;" alt="{\displaystyle {\mathit {E}}}" /></span>)取決於起始反應(<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\mathit {E_{i}}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mrow class="MJX-TeXAtom-ORD"> <mrow class="MJX-TeXAtom-ORD"> <msub> <mi class="MJX-tex-mathit" mathvariant="italic">E</mi> <mrow class="MJX-TeXAtom-ORD"> <mi class="MJX-tex-mathit" mathvariant="italic">i</mi> </mrow> </msub> </mrow> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\mathit {E_{i}}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/0951e537faae56f58ba0ea3087bd0df6e81c0975" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.671ex; width:2.313ex; height:2.509ex;" alt="{\displaystyle {\mathit {E_{i}}}}" /></span>)、增生反應(<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\mathit {E_{p}}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mrow class="MJX-TeXAtom-ORD"> <mrow class="MJX-TeXAtom-ORD"> <msub> <mi class="MJX-tex-mathit" mathvariant="italic">E</mi> <mrow class="MJX-TeXAtom-ORD"> <mi class="MJX-tex-mathit" mathvariant="italic">p</mi> </mrow> </msub> </mrow> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\mathit {E_{p}}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/fd4a4d08c40cbd07559ce57c8a2cf68fc8f6fdbd" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -1.005ex; width:2.648ex; height:2.843ex;" alt="{\displaystyle {\mathit {E_{p}}}}" /></span>)和終止反應(<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\mathit {E_{t}}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mrow class="MJX-TeXAtom-ORD"> <mrow class="MJX-TeXAtom-ORD"> <msub> <mi class="MJX-tex-mathit" mathvariant="italic">E</mi> <mrow class="MJX-TeXAtom-ORD"> <mi class="MJX-tex-mathit" mathvariant="italic">t</mi> </mrow> </msub> </mrow> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\mathit {E_{t}}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/9c9a8a64b65ac63c7977c2a6c0134a6ca49f80b5" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.671ex; width:2.354ex; height:2.509ex;" alt="{\displaystyle {\mathit {E_{t}}}}" /></span>)的活化能。 </p> <dl><dd><span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle \textstyle E=E_{i}+E_{p}-E_{t}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mstyle displaystyle="false" scriptlevel="0"> <mi>E</mi> <mo>=</mo> <msub> <mi>E</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>i</mi> </mrow> </msub> <mo>+</mo> <msub> <mi>E</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>p</mi> </mrow> </msub> <mo>−</mo> <msub> <mi>E</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>t</mi> </mrow> </msub> </mstyle> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle \textstyle E=E_{i}+E_{p}-E_{t}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/d39bfac50ebe5f596876c729a304c791ae69b24a" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -1.005ex; width:18.385ex; height:2.843ex;" alt="{\displaystyle \textstyle E=E_{i}+E_{p}-E_{t}}" /></span></dd></dl> <p>常理來說，<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\mathit {E_{p}}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mrow class="MJX-TeXAtom-ORD"> <mrow class="MJX-TeXAtom-ORD"> <msub> <mi class="MJX-tex-mathit" mathvariant="italic">E</mi> <mrow class="MJX-TeXAtom-ORD"> <mi class="MJX-tex-mathit" mathvariant="italic">p</mi> </mrow> </msub> </mrow> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\mathit {E_{p}}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/fd4a4d08c40cbd07559ce57c8a2cf68fc8f6fdbd" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -1.005ex; width:2.648ex; height:2.843ex;" alt="{\displaystyle {\mathit {E_{p}}}}" /></span>值小於<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\mathit {E_{i}}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mrow class="MJX-TeXAtom-ORD"> <mrow class="MJX-TeXAtom-ORD"> <msub> <mi class="MJX-tex-mathit" mathvariant="italic">E</mi> <mrow class="MJX-TeXAtom-ORD"> <mi class="MJX-tex-mathit" mathvariant="italic">i</mi> </mrow> </msub> </mrow> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\mathit {E_{i}}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/0951e537faae56f58ba0ea3087bd0df6e81c0975" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.671ex; width:2.313ex; height:2.509ex;" alt="{\displaystyle {\mathit {E_{i}}}}" /></span>和<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\mathit {E_{t}}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mrow class="MJX-TeXAtom-ORD"> <mrow class="MJX-TeXAtom-ORD"> <msub> <mi class="MJX-tex-mathit" mathvariant="italic">E</mi> <mrow class="MJX-TeXAtom-ORD"> <mi class="MJX-tex-mathit" mathvariant="italic">t</mi> </mrow> </msub> </mrow> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\mathit {E_{t}}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/9c9a8a64b65ac63c7977c2a6c0134a6ca49f80b5" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.671ex; width:2.354ex; height:2.509ex;" alt="{\displaystyle {\mathit {E_{t}}}}" /></span>，這意味著整個反應的<a href="/wiki/%E6%B4%BB%E5%8C%96%E8%83%BD" title="活化能">活化能</a>為負值。但在這情況下，當反應溫度下降，使增生速率增加，相反地，這個反應的活動能為正值。<sup id="cite_ref-Cowie_Textbook_6-2" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup> </p><p>反應溫度也影響了鏈的長度，低反應溫度(170-190 K)可聚合成最長鏈，<sup id="cite_ref-Cowie_Textbook_6-3" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup>得終止反應和其他副反應(side reactions)的活化能較增長反應還要大。<sup id="cite_ref-KM_book_5-5" class="reference"><a href="#cite_note-KM_book-5"><span class="cite-bracket">[</span>5<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-Cowie_Textbook_6-4" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup>當反應溫度增加時，終止反應的能量障礙被克服，而使聚合反應過程中產生較短鏈。<sup id="cite_ref-Cowie_Textbook_6-5" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup> </p> <div class="mw-heading mw-heading4"><h4 id="溶劑與抗衡離子的影響"><span id=".E6.BA.B6.E5.8A.91.E8.88.87.E6.8A.97.E8.A1.A1.E9.9B.A2.E5.AD.90.E7.9A.84.E5.BD.B1.E9.9F.BF"></span>溶劑與抗衡離子的影響</h4><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=12" title="编辑章节：溶劑與抗衡離子的影響"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p>溶劑(solvent)與抗衡離子(又稱為反離子，gegen ion)對增生反應速率有重要的影響，抗衡離子與碳烯離子有不一樣的結合距離，範圍從<a href="/wiki/%E5%85%B1%E5%83%B9%E9%8D%B5" class="mw-redirect" title="共價鍵">共價鍵</a>的形成、離子對的緊密結合<b>(不分開)</b>、溶劑分離離子對(solvent-separated ion pair)<b>(部分分開)</b>和游離離子<b>(完全分離)</b>。<sup id="cite_ref-Odian_1-3" class="reference"><a href="#cite_note-Odian-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-Cowie_Textbook_6-6" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup> </p> <figure class="mw-halign-center" typeof="mw:File/Thumb"><a href="/wiki/File:Gegen_Ion_Pairs.png" class="mw-file-description"><img src="//upload.wikimedia.org/wikipedia/commons/thumb/b/b3/Gegen_Ion_Pairs.png/450px-Gegen_Ion_Pairs.png" decoding="async" width="450" height="61" class="mw-file-element" srcset="//upload.wikimedia.org/wikipedia/commons/thumb/b/b3/Gegen_Ion_Pairs.png/675px-Gegen_Ion_Pairs.png 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/b/b3/Gegen_Ion_Pairs.png/900px-Gegen_Ion_Pairs.png 2x" data-file-width="1575" data-file-height="215" /></a><figcaption>碳烯離子(R<sup>+</sup>)和抗衡離子(X<sup>–</sup>)間的結合距離</figcaption></figure> <p>最強的交互作用為共價鍵的結合；最弱則是離子對中出現自由離子。<sup id="cite_ref-Cowie_Textbook_6-7" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup>在陽離子聚合反應中，離子在離子對與自由離子間會傾向平衡(不論是緊密接合或溶劑分離時)。.<sup id="cite_ref-Odian_1-4" class="reference"><a href="#cite_note-Odian-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup>反應中使用的溶劑越具極性(polar)，<a href="/wiki/%E6%BA%B6%E5%8A%91%E5%8C%96" title="溶劑化">溶劑化</a>(solvation)和離子的分離越好，因為自由離子的反應性較離子對高，其增生速率在極性溶劑中會比較快。<sup id="cite_ref-Cowie_Textbook_6-8" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-Raave_8-0" class="reference"><a href="#cite_note-Raave-8"><span class="cite-bracket">[</span>8<span class="cite-bracket">]</span></a></sup> </p><p>抗衡離子的大小也是一個決定因素，較小的抗衡離子，具有較高的電子密度，與碳烯離子反應時也具有較強的靜電交互作用；較大的抗衡離子則電子密度較低。<sup id="cite_ref-Odian_1-5" class="reference"><a href="#cite_note-Odian-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup>近一步來說，一個較小抗衡離子與極性溶劑作用時，相較電子密度較低的抗衡離子來說，會比較容易溶劑化。這個結果表示，當增加溶劑的溶劑化能力時，可提高的增生速率。<sup id="cite_ref-Cowie_Textbook_6-9" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup> </p> <div class="mw-heading mw-heading3"><h3 id="链终止"><span id=".E9.93.BE.E7.BB.88.E6.AD.A2"></span>链终止</h3><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=13" title="编辑章节：链终止"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p>終止反應的發生是透過抗衡離子與單一分子的轉移，在這個過程中抗衡離子的陰離子部分會與增生鏈的末端結合。若減少引發劑-共引發劑複合物的濃度，這不只會讓增生鏈失去活性，也會使動力鏈(kinetic chain)被終止。<sup id="cite_ref-Odian_1-6" class="reference"><a href="#cite_note-Odian-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-Cowie_Textbook_6-10" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup> </p> <figure class="mw-halign-center" typeof="mw:File/Thumb"><a href="/wiki/File:Termination.png" class="mw-file-description"><img src="//upload.wikimedia.org/wikipedia/commons/thumb/c/c9/Termination.png/375px-Termination.png" decoding="async" width="375" height="55" class="mw-file-element" srcset="//upload.wikimedia.org/wikipedia/commons/thumb/c/c9/Termination.png/563px-Termination.png 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/c/c9/Termination.png/750px-Termination.png 2x" data-file-width="1061" data-file-height="157" /></a><figcaption>結合抗衡離子的陰離子部分的終止反應</figcaption></figure> <div class="mw-heading mw-heading3"><h3 id="鏈的轉移"><span id=".E9.8F.88.E7.9A.84.E8.BD.89.E7.A7.BB"></span>鏈的轉移</h3><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=14" title="编辑章节：鏈的轉移"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p>有兩種方式能發生鏈的轉移： </p><p>1、從活性鏈(active chain)的末端分離氫(hydrogen abstraction)，並轉移至<b>抗衡離子</b>上。<sup id="cite_ref-Cowie_Textbook_6-11" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-Raave_8-1" class="reference"><a href="#cite_note-Raave-8"><span class="cite-bracket">[</span>8<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-Fahlman_9-0" class="reference"><a href="#cite_note-Fahlman-9"><span class="cite-bracket">[</span>9<span class="cite-bracket">]</span></a></sup>在此過程中，鏈的增長會終止，但是引發劑-共引發劑複合物(initiator-coinitiator complex)會產生，誘導更多鏈的產生。<sup id="cite_ref-KM_book_5-6" class="reference"><a href="#cite_note-KM_book-5"><span class="cite-bracket">[</span>5<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-Cowie_Textbook_6-12" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup> </p> <figure class="mw-halign-center" typeof="mw:File/Thumb"><a href="/wiki/File:Change_transfer_with_counter_ion.png" class="mw-file-description"><img src="//upload.wikimedia.org/wikipedia/commons/thumb/c/c1/Change_transfer_with_counter_ion.png/375px-Change_transfer_with_counter_ion.png" decoding="async" width="375" height="54" class="mw-file-element" srcset="//upload.wikimedia.org/wikipedia/commons/thumb/c/c1/Change_transfer_with_counter_ion.png/563px-Change_transfer_with_counter_ion.png 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/c/c1/Change_transfer_with_counter_ion.png/750px-Change_transfer_with_counter_ion.png 2x" data-file-width="1267" data-file-height="181" /></a><figcaption>分離氫至<b>抗衡離子</b>之鏈的轉移</figcaption></figure> <p>2、從活性鏈(active chain)的末端分離氫(hydrogen abstraction)，並轉移至<b>單體</b>上。這個步驟會增長鏈終止，但也會形成新的碳烯陽離子-抗衡離子複合物(carbenium ion-counterion complex)，此複合物會讓增長反應繼續，讓動力鏈(kinetic chain)維持不變。<sup id="cite_ref-Cowie_Textbook_6-13" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup> </p> <figure class="mw-halign-center" typeof="mw:File/Thumb"><a href="/wiki/File:Charge_transfer_with_monomer.png" class="mw-file-description"><img src="//upload.wikimedia.org/wikipedia/commons/thumb/f/fd/Charge_transfer_with_monomer.png/375px-Charge_transfer_with_monomer.png" decoding="async" width="375" height="55" class="mw-file-element" srcset="//upload.wikimedia.org/wikipedia/commons/thumb/f/fd/Charge_transfer_with_monomer.png/563px-Charge_transfer_with_monomer.png 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/f/fd/Charge_transfer_with_monomer.png/750px-Charge_transfer_with_monomer.png 2x" data-file-width="1270" data-file-height="186" /></a><figcaption>分離氫至<b>單體</b>之鏈的轉移</figcaption></figure> <div class="mw-heading mw-heading3"><h3 id="陽離子開環聚合反應"><span id=".E9.99.BD.E9.9B.A2.E5.AD.90.E9.96.8B.E7.92.B0.E8.81.9A.E5.90.88.E5.8F.8D.E6.87.89"></span>陽離子開環聚合反應</h3><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=15" title="编辑章节：陽離子開環聚合反應"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p>陽離子開環聚合反應(Cationic ring-opening polymerization)與起始、增生、終止反應所以走的反應機制相同。然而，在這個<b>陽離子開環聚合反應</b>中，單體單元需相較產物線狀聚合鏈成<b>環狀</b>。這個產物線狀聚合鏈可以降低上限溫度(ceiling temperature)，因此聚合鏈的封端(end-capping)，必須避免解劇作用(depolymerization)。<sup id="cite_ref-Cowie_Textbook_6-14" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup> </p> <figure class="mw-halign-center" typeof="mw:File/Thumb"><a href="/wiki/File:ROP_cationic.png" class="mw-file-description"><img src="//upload.wikimedia.org/wikipedia/commons/thumb/b/bb/ROP_cationic.png/550px-ROP_cationic.png" decoding="async" width="550" height="166" class="mw-file-element" srcset="//upload.wikimedia.org/wikipedia/commons/thumb/b/bb/ROP_cationic.png/825px-ROP_cationic.png 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/b/bb/ROP_cationic.png/1100px-ROP_cationic.png 2x" data-file-width="2119" data-file-height="640" /></a><figcaption>氧雜環丁烷與甲醇反應的陽離子開環聚合作用，包含(a、b)起始反應、(c)增生反應和(d)終止反應</figcaption></figure> <div class="mw-heading mw-heading2"><h2 id="動力學"><span id=".E5.8B.95.E5.8A.9B.E5.AD.B8"></span>動力學</h2><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=16" title="编辑章节：動力學"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p>增生反應速率和聚合化的程度可以由聚合反應的化學<a href="/wiki/%E5%8B%95%E5%8A%9B%E5%AD%B8" title="動力學">動力學</a>來分析，起始（引发）、增生（增长）、終止反應和鏈轉移反應的反應方程式，以下為常見形式： </p> <dl><dd><span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\text{I}}^{+}~+~{\text{M}}~~{\xrightarrow {k_{i}}}~~{\text{M}}^{+}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <msup> <mrow class="MJX-TeXAtom-ORD"> <mtext>I</mtext> </mrow> <mrow class="MJX-TeXAtom-ORD"> <mo>+</mo> </mrow> </msup> <mtext> </mtext> <mo>+</mo> <mtext> </mtext> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mtext> </mtext> <mtext> </mtext> <mrow class="MJX-TeXAtom-ORD"> <mover> <mo>→</mo> <mpadded width="+0.611em" lspace="0.278em" voffset=".15em"> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>i</mi> </mrow> </msub> </mpadded> </mover> </mrow> <mtext> </mtext> <mtext> </mtext> <msup> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mrow class="MJX-TeXAtom-ORD"> <mo>+</mo> </mrow> </msup> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\text{I}}^{+}~+~{\text{M}}~~{\xrightarrow {k_{i}}}~~{\text{M}}^{+}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/2985239e62372d770f6e5814d12980910a7d7455" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.505ex; margin-top: -0.351ex; width:17.252ex; height:4.009ex;" alt="{\displaystyle {\text{I}}^{+}~+~{\text{M}}~~{\xrightarrow {k_{i}}}~~{\text{M}}^{+}}" /></span></dd></dl> <dl><dd><span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\text{M}}^{+}~+~{\text{M}}~~{\xrightarrow {k_{p}}}~~{\text{M}}^{+}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <msup> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mrow class="MJX-TeXAtom-ORD"> <mo>+</mo> </mrow> </msup> <mtext> </mtext> <mo>+</mo> <mtext> </mtext> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mtext> </mtext> <mtext> </mtext> <mrow class="MJX-TeXAtom-ORD"> <mover> <mo>→</mo> <mpadded width="+0.611em" lspace="0.278em" voffset=".15em"> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>p</mi> </mrow> </msub> </mpadded> </mover> </mrow> <mtext> </mtext> <mtext> </mtext> <msup> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mrow class="MJX-TeXAtom-ORD"> <mo>+</mo> </mrow> </msup> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\text{M}}^{+}~+~{\text{M}}~~{\xrightarrow {k_{p}}}~~{\text{M}}^{+}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/4c200fe09810d19d40fa215cd86a5dd489ffeb84" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.505ex; margin-top: -0.344ex; width:18.754ex; height:4.176ex;" alt="{\displaystyle {\text{M}}^{+}~+~{\text{M}}~~{\xrightarrow {k_{p}}}~~{\text{M}}^{+}}" /></span></dd></dl> <dl><dd><span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\text{M}}^{+}~~{\xrightarrow {k_{t}}}~~{\text{M}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <msup> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mrow class="MJX-TeXAtom-ORD"> <mo>+</mo> </mrow> </msup> <mtext> </mtext> <mtext> </mtext> <mrow class="MJX-TeXAtom-ORD"> <mover> <mo>→</mo> <mpadded width="+0.611em" lspace="0.278em" voffset=".15em"> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>t</mi> </mrow> </msub> </mpadded> </mover> </mrow> <mtext> </mtext> <mtext> </mtext> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\text{M}}^{+}~~{\xrightarrow {k_{t}}}~~{\text{M}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/6257e420cedc7061707d0d6ed8d888b6929ecd2e" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.028ex; margin-top: -0.397ex; margin-bottom: -0.477ex; width:10.922ex; height:4.009ex;" alt="{\displaystyle {\text{M}}^{+}~~{\xrightarrow {k_{t}}}~~{\text{M}}}" /></span></dd></dl> <dl><dd><span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\text{M}}^{+}~+~{\text{M}}~~{\xrightarrow {k_{tr}}}~~{\text{M}}~+~{\text{M}}^{+}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <msup> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mrow class="MJX-TeXAtom-ORD"> <mo>+</mo> </mrow> </msup> <mtext> </mtext> <mo>+</mo> <mtext> </mtext> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mtext> </mtext> <mtext> </mtext> <mrow class="MJX-TeXAtom-ORD"> <mover> <mo>→</mo> <mpadded width="+0.611em" lspace="0.278em" voffset=".15em"> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>t</mi> <mi>r</mi> </mrow> </msub> </mpadded> </mover> </mrow> <mtext> </mtext> <mtext> </mtext> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mtext> </mtext> <mo>+</mo> <mtext> </mtext> <msup> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mrow class="MJX-TeXAtom-ORD"> <mo>+</mo> </mrow> </msup> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\text{M}}^{+}~+~{\text{M}}~~{\xrightarrow {k_{tr}}}~~{\text{M}}~+~{\text{M}}^{+}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/7315f394dca0c0b59587c303f6b5fa13f4609b8d" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.505ex; margin-top: -0.397ex; width:25.3ex; height:4.009ex;" alt="{\displaystyle {\text{M}}^{+}~+~{\text{M}}~~{\xrightarrow {k_{tr}}}~~{\text{M}}~+~{\text{M}}^{+}}" /></span></dd></dl> <p>其中，I<sup>+</sup>為引發劑、M為單體、M<sup>+</sup>為增生中心(propagating center)；<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\mathit {k_{i}}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mrow class="MJX-TeXAtom-ORD"> <mrow class="MJX-TeXAtom-ORD"> <msub> <mi class="MJX-tex-mathit" mathvariant="italic">k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi class="MJX-tex-mathit" mathvariant="italic">i</mi> </mrow> </msub> </mrow> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\mathit {k_{i}}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/9f5034d0b6a22aef7b097cbbe3b8a76d350c4f44" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.671ex; width:1.807ex; height:2.509ex;" alt="{\displaystyle {\mathit {k_{i}}}}" /></span>、<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\mathit {k_{p}}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mrow class="MJX-TeXAtom-ORD"> <mrow class="MJX-TeXAtom-ORD"> <msub> <mi class="MJX-tex-mathit" mathvariant="italic">k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi class="MJX-tex-mathit" mathvariant="italic">p</mi> </mrow> </msub> </mrow> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\mathit {k_{p}}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/a5e5e51624fee074ad7c643a84b9e42fec68a980" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -1.005ex; width:2.142ex; height:2.843ex;" alt="{\displaystyle {\mathit {k_{p}}}}" /></span>、<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\mathit {k_{t}}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mrow class="MJX-TeXAtom-ORD"> <mrow class="MJX-TeXAtom-ORD"> <msub> <mi class="MJX-tex-mathit" mathvariant="italic">k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi class="MJX-tex-mathit" mathvariant="italic">t</mi> </mrow> </msub> </mrow> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\mathit {k_{t}}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/878716515e71243aa8aeeb51e2c69ff97f29e10e" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.671ex; width:1.848ex; height:2.509ex;" alt="{\displaystyle {\mathit {k_{t}}}}" /></span>和<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\mathit {k_{tr}}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mrow class="MJX-TeXAtom-ORD"> <mrow class="MJX-TeXAtom-ORD"> <msub> <mi class="MJX-tex-mathit" mathvariant="italic">k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi class="MJX-tex-mathit" mathvariant="italic">t</mi> <mi class="MJX-tex-mathit" mathvariant="italic">r</mi> </mrow> </msub> </mrow> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\mathit {k_{tr}}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/57f106e2c4d2bbaaed0c1b4cb65213d438dd4c99" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.671ex; width:2.542ex; height:2.509ex;" alt="{\displaystyle {\mathit {k_{tr}}}}" /></span>分別為起始、增生、終止反應和鏈轉移反應的反應速率常數。<sup id="cite_ref-KM_book_5-7" class="reference"><a href="#cite_note-KM_book-5"><span class="cite-bracket">[</span>5<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-Cowie_Textbook_6-15" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-Ebewele_10-0" class="reference"><a href="#cite_note-Ebewele-10"><span class="cite-bracket">[</span>10<span class="cite-bracket">]</span></a></sup> 簡單來說，抗衡離子並未出現在以上反應方程式中，且只考慮鏈轉移反應的單體。以下為產生速率方程式(The resulting rate equations)，括弧表示反應濃度。 </p> <dl><dd>链引发速率 <span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle R_{i}=k_{i}[{\text{I}}^{+}][{\text{M}}]}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <msub> <mi>R</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>i</mi> </mrow> </msub> <mo>=</mo> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>i</mi> </mrow> </msub> <mo stretchy="false">[</mo> <msup> <mrow class="MJX-TeXAtom-ORD"> <mtext>I</mtext> </mrow> <mrow class="MJX-TeXAtom-ORD"> <mo>+</mo> </mrow> </msup> <mo stretchy="false">]</mo> <mo stretchy="false">[</mo> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mo stretchy="false">]</mo> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle R_{i}=k_{i}[{\text{I}}^{+}][{\text{M}}]}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/adbbea66db0c2c06f8eb7f115146d389ed359b5b" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.838ex; width:14.742ex; height:3.009ex;" alt="{\displaystyle R_{i}=k_{i}[{\text{I}}^{+}][{\text{M}}]}" /></span></dd></dl> <dl><dd>链增长速率 <span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle R_{p}=k_{p}[{\text{M}}^{+}][{\text{M}}]}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <msub> <mi>R</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>p</mi> </mrow> </msub> <mo>=</mo> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>p</mi> </mrow> </msub> <mo stretchy="false">[</mo> <msup> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mrow class="MJX-TeXAtom-ORD"> <mo>+</mo> </mrow> </msup> <mo stretchy="false">]</mo> <mo stretchy="false">[</mo> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mo stretchy="false">]</mo> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle R_{p}=k_{p}[{\text{M}}^{+}][{\text{M}}]}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/7c7511eb4097abf86610310cd278d90fb3c96f1e" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -1.005ex; width:16.552ex; height:3.176ex;" alt="{\displaystyle R_{p}=k_{p}[{\text{M}}^{+}][{\text{M}}]}" /></span></dd></dl> <dl><dd>链终止速率 <span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle R_{t}=k_{t}[{\text{M}}^{+}]}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <msub> <mi>R</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>t</mi> </mrow> </msub> <mo>=</mo> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>t</mi> </mrow> </msub> <mo stretchy="false">[</mo> <msup> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mrow class="MJX-TeXAtom-ORD"> <mo>+</mo> </mrow> </msup> <mo stretchy="false">]</mo> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle R_{t}=k_{t}[{\text{M}}^{+}]}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/429d0cddeedf41900ff92dfc59054ffc698de537" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.838ex; width:12.661ex; height:3.009ex;" alt="{\displaystyle R_{t}=k_{t}[{\text{M}}^{+}]}" /></span></dd></dl> <dl><dd>链转移速率 <span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle R_{tr}=k_{tr}[{\text{M}}^{+}][{\text{M}}]}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <msub> <mi>R</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>t</mi> <mi>r</mi> </mrow> </msub> <mo>=</mo> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>t</mi> <mi>r</mi> </mrow> </msub> <mo stretchy="false">[</mo> <msup> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mrow class="MJX-TeXAtom-ORD"> <mo>+</mo> </mrow> </msup> <mo stretchy="false">]</mo> <mo stretchy="false">[</mo> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mo stretchy="false">]</mo> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle R_{tr}=k_{tr}[{\text{M}}^{+}][{\text{M}}]}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/cf1bd8772418608f528beb16996012745bd0270d" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.838ex; width:17.569ex; height:3.009ex;" alt="{\displaystyle R_{tr}=k_{tr}[{\text{M}}^{+}][{\text{M}}]}" /></span></dd></dl> <p>假設，在<a href="/wiki/%E7%A9%A9%E6%85%8B" class="mw-redirect" title="穩態">穩態</a>條件下，即引发反應的速度<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle R_{i}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <msub> <mi>R</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>i</mi> </mrow> </msub> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle R_{i}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/db421291be9d0103404ced7495b363437b67b6b1" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.671ex; width:2.564ex; height:2.509ex;" alt="{\displaystyle R_{i}}" /></span>=終止反應的速度<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle R_{t}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <msub> <mi>R</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>t</mi> </mrow> </msub> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle R_{t}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/d65b678ee539ac36de96b554af181ac03b7f16a8" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.671ex; width:2.59ex; height:2.509ex;" alt="{\displaystyle R_{t}}" /></span>：<sup id="cite_ref-Cowie_Textbook_6-16" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-Ebewele_10-1" class="reference"><a href="#cite_note-Ebewele-10"><span class="cite-bracket">[</span>10<span class="cite-bracket">]</span></a></sup> </p> <dl><dd><span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle [{\text{M}}^{+}]={k_{i}[{\text{I}}^{+}][{\text{M}}] \over k_{t}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mo stretchy="false">[</mo> <msup> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mrow class="MJX-TeXAtom-ORD"> <mo>+</mo> </mrow> </msup> <mo stretchy="false">]</mo> <mo>=</mo> <mrow class="MJX-TeXAtom-ORD"> <mfrac> <mrow> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>i</mi> </mrow> </msub> <mo stretchy="false">[</mo> <msup> <mrow class="MJX-TeXAtom-ORD"> <mtext>I</mtext> </mrow> <mrow class="MJX-TeXAtom-ORD"> <mo>+</mo> </mrow> </msup> <mo stretchy="false">]</mo> <mo stretchy="false">[</mo> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mo stretchy="false">]</mo> </mrow> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>t</mi> </mrow> </msub> </mfrac> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle [{\text{M}}^{+}]={k_{i}[{\text{I}}^{+}][{\text{M}}] \over k_{t}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/21d942c4774e30d37953ab621eda557e80dcdcd9" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -2.338ex; width:17.95ex; height:6.343ex;" alt="{\displaystyle [{\text{M}}^{+}]={k_{i}[{\text{I}}^{+}][{\text{M}}] \over k_{t}}}" /></span></dd></dl> <p>這個方程式中的，[M<sup>+</sup>]可用於增生反應速率的方程式中：<sup id="cite_ref-Cowie_Textbook_6-17" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-Ebewele_10-2" class="reference"><a href="#cite_note-Ebewele-10"><span class="cite-bracket">[</span>10<span class="cite-bracket">]</span></a></sup> </p> <dl><dd><span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle R_{p}={k_{p}k_{i}[{\text{M}}]^{2}[{\text{I}}^{+}] \over k_{t}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <msub> <mi>R</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>p</mi> </mrow> </msub> <mo>=</mo> <mrow class="MJX-TeXAtom-ORD"> <mfrac> <mrow> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>p</mi> </mrow> </msub> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>i</mi> </mrow> </msub> <mo stretchy="false">[</mo> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <msup> <mo stretchy="false">]</mo> <mrow class="MJX-TeXAtom-ORD"> <mn>2</mn> </mrow> </msup> <mo stretchy="false">[</mo> <msup> <mrow class="MJX-TeXAtom-ORD"> <mtext>I</mtext> </mrow> <mrow class="MJX-TeXAtom-ORD"> <mo>+</mo> </mrow> </msup> <mo stretchy="false">]</mo> </mrow> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>t</mi> </mrow> </msub> </mfrac> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle R_{p}={k_{p}k_{i}[{\text{M}}]^{2}[{\text{I}}^{+}] \over k_{t}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/3d29d6e3947ae493b61f131225373f14dd8f4ebc" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -2.338ex; width:19.162ex; height:6.343ex;" alt="{\displaystyle R_{p}={k_{p}k_{i}[{\text{M}}]^{2}[{\text{I}}^{+}] \over k_{t}}}" /></span></dd></dl> <p>從上述方程式中，可得，當增加反應單體和引發劑的濃度時，增生反應速率也會增加。 </p><p>聚合化的程度(<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\mathit {X_{n}}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mrow class="MJX-TeXAtom-ORD"> <mrow class="MJX-TeXAtom-ORD"> <msub> <mi class="MJX-tex-mathit" mathvariant="italic">X</mi> <mrow class="MJX-TeXAtom-ORD"> <mi class="MJX-tex-mathit" mathvariant="italic">n</mi> </mrow> </msub> </mrow> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\mathit {X_{n}}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/db60fdf1d7a020e5f06e65629e1d6fe64e72bb91" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.671ex; width:2.883ex; height:2.509ex;" alt="{\displaystyle {\mathit {X_{n}}}}" /></span>，动力学链长)，可從增生反應速率和終止反應速率求得：<sup id="cite_ref-Cowie_Textbook_6-18" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-Ebewele_10-3" class="reference"><a href="#cite_note-Ebewele-10"><span class="cite-bracket">[</span>10<span class="cite-bracket">]</span></a></sup> </p> <dl><dd><span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle Xn=R_{p}/R_{t}={k_{p}[{\text{M}}] \over k_{t}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mi>X</mi> <mi>n</mi> <mo>=</mo> <msub> <mi>R</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>p</mi> </mrow> </msub> <mrow class="MJX-TeXAtom-ORD"> <mo>/</mo> </mrow> <msub> <mi>R</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>t</mi> </mrow> </msub> <mo>=</mo> <mrow class="MJX-TeXAtom-ORD"> <mfrac> <mrow> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>p</mi> </mrow> </msub> <mo stretchy="false">[</mo> <mrow class="MJX-TeXAtom-ORD"> <mtext>M</mtext> </mrow> <mo stretchy="false">]</mo> </mrow> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>t</mi> </mrow> </msub> </mfrac> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle Xn=R_{p}/R_{t}={k_{p}[{\text{M}}] \over k_{t}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/d951ebe514faa0d4061c91a85f75c72fd32346e8" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -2.338ex; width:22.678ex; height:6.176ex;" alt="{\displaystyle Xn=R_{p}/R_{t}={k_{p}[{\text{M}}] \over k_{t}}}" /></span></dd></dl> <p>若終止反應不如链轉移反應明顯，则<span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle {\mathit {X_{n}}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mrow class="MJX-TeXAtom-ORD"> <mrow class="MJX-TeXAtom-ORD"> <msub> <mi class="MJX-tex-mathit" mathvariant="italic">X</mi> <mrow class="MJX-TeXAtom-ORD"> <mi class="MJX-tex-mathit" mathvariant="italic">n</mi> </mrow> </msub> </mrow> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle {\mathit {X_{n}}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/db60fdf1d7a020e5f06e65629e1d6fe64e72bb91" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -0.671ex; width:2.883ex; height:2.509ex;" alt="{\displaystyle {\mathit {X_{n}}}}" /></span>會變成<sup id="cite_ref-Cowie_Textbook_6-19" class="reference"><a href="#cite_note-Cowie_Textbook-6"><span class="cite-bracket">[</span>6<span class="cite-bracket">]</span></a></sup><sup id="cite_ref-Ebewele_10-4" class="reference"><a href="#cite_note-Ebewele-10"><span class="cite-bracket">[</span>10<span class="cite-bracket">]</span></a></sup> </p> <dl><dd><span class="mwe-math-element"><span class="mwe-math-mathml-inline mwe-math-mathml-a11y" style="display: none;"><math xmlns="http://www.w3.org/1998/Math/MathML" alttext="{\displaystyle Xn=R_{p}/R_{tr}={k_{p} \over k_{tr}}}"> <semantics> <mrow class="MJX-TeXAtom-ORD"> <mstyle displaystyle="true" scriptlevel="0"> <mi>X</mi> <mi>n</mi> <mo>=</mo> <msub> <mi>R</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>p</mi> </mrow> </msub> <mrow class="MJX-TeXAtom-ORD"> <mo>/</mo> </mrow> <msub> <mi>R</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>t</mi> <mi>r</mi> </mrow> </msub> <mo>=</mo> <mrow class="MJX-TeXAtom-ORD"> <mfrac> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>p</mi> </mrow> </msub> <msub> <mi>k</mi> <mrow class="MJX-TeXAtom-ORD"> <mi>t</mi> <mi>r</mi> </mrow> </msub> </mfrac> </mrow> </mstyle> </mrow> <annotation encoding="application/x-tex">{\displaystyle Xn=R_{p}/R_{tr}={k_{p} \over k_{tr}}}</annotation> </semantics> </math></span><img src="https://wikimedia.org/api/rest_v1/media/math/render/svg/a7b6370152439bb9f0ced2b5b043065e67cb247b" class="mwe-math-fallback-image-inline mw-invert skin-invert" aria-hidden="true" style="vertical-align: -2.338ex; width:20.504ex; height:6.009ex;" alt="{\displaystyle Xn=R_{p}/R_{tr}={k_{p} \over k_{tr}}}" /></span></dd></dl> <div class="mw-heading mw-heading2"><h2 id="活性聚合反應"><span id=".E6.B4.BB.E6.80.A7.E8.81.9A.E5.90.88.E5.8F.8D.E6.87.89"></span>活性聚合反應</h2><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=17" title="编辑章节：活性聚合反應"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p><a href="/wiki/%E6%B4%BB%E6%80%A7%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89" title="活性聚合反應">活性聚合反應</a>(Living polymerization)：在1984年，東村(Higashimura)和澤本(Sawamoto)提出對烷基乙烯基醚(alkyl vinyl ethers)的第一個活性陽離子聚合反應。這個種類的聚合反應，受明確的單體控制；在活性陽離子聚合反應中，終止反應扮演了重要的角色，因為終止反應是基本消除(essentially eliminated),故陽離子鏈會持續增長，直到單體被消耗殆盡<sup id="cite_ref-Sawamoto_11-0" class="reference"><a href="#cite_note-Sawamoto-11"><span class="cite-bracket">[</span>11<span class="cite-bracket">]</span></a></sup>。 </p> <div class="mw-heading mw-heading2"><h2 id="商業應用"><span id=".E5.95.86.E6.A5.AD.E6.87.89.E7.94.A8"></span>商業應用</h2><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=18" title="编辑章节：商業應用"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <p>陽離子聚合反應最大的商業應用是，製造聚異丁烯(polyisobutylene，PIB)產物，包含<a href="/wiki/%E8%81%9A%E4%B8%81%E7%83%AF" title="聚丁烯">聚丁烯</a>(polybutene)和<a href="/wiki/%E4%B8%81%E5%9F%BA%E6%A9%A1%E8%83%B6" title="丁基橡胶">丁基橡膠</a>(butyl rubber)。這些聚合物有各式各樣的應用，從<a href="/wiki/%E9%BB%8F%E5%90%88%E5%89%82" title="黏合剂">黏合劑</a>(adhesives)和<a href="/w/index.php?title=%E5%AF%86%E5%B0%81%E5%89%82&action=edit&redlink=1" class="new" title="密封剂（页面不存在）">密封剂</a>(sealants)到防護手套(protective gloves)和醫療瓶塞(pharmaceutical stoppers)。合成各式的異丁烯產物的反應環境，取決於產物欲產生的分子量和使用的單體種類。最常用到的反應條件為，低分子量(5–10 x 10<sup>4</sup> Da)的聚異丁烯或TiCl<sub>4</sub>處於溫度範圍為−40 to 10 °C。<sup id="cite_ref-Odian_1-7" class="reference"><a href="#cite_note-Odian-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup>這些低分子量的聚異丁烯聚合物可用於填補縫隙，如<a href="/w/index.php?title=%E5%AF%86%E5%B0%81%E5%89%82&action=edit&redlink=1" class="new" title="密封剂（页面不存在）">密封剂</a>(sealants)；<sup id="cite_ref-Odian_1-8" class="reference"><a href="#cite_note-Odian-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup>高分子量的PIB會在較低溫度範圍(−100 to −90 °C)下、且在<a href="/wiki/%E4%BA%8C%E6%B0%AF%E7%94%B2%E7%83%B7" title="二氯甲烷">二氯甲烷</a>(methylene chloride)的極性介質內合成。<sup id="cite_ref-KM_book_5-8" class="reference"><a href="#cite_note-KM_book-5"><span class="cite-bracket">[</span>5<span class="cite-bracket">]</span></a></sup> 這些聚合物可用於,產生未相連的橡膠產物和<a href="/wiki/%E7%86%B1%E5%A1%91%E6%80%A7%E5%A1%91%E6%96%99" class="mw-redirect" title="熱塑性塑料">熱塑性塑料</a>(thermoplasts)的添加物；而其他高分子量PIB的特性為低毒性，使其可作為口香糖的基底。產生聚異丁烯之主要的化學公司，如<a href="/wiki/%E5%9F%83%E7%B4%A2" title="埃索">埃索</a>(Esso)、<a href="/wiki/%E8%89%BE%E5%85%8B%E6%A3%AE%E7%BE%8E%E5%AD%9A" class="mw-redirect" title="艾克森美孚">艾克森美孚</a>(ExxonMobil)、<a href="/wiki/%E5%B7%B4%E6%96%AF%E5%A4%AB" title="巴斯夫">巴斯夫</a>(BASF)。<sup id="cite_ref-Chanda_12-0" class="reference"><a href="#cite_note-Chanda-12"><span class="cite-bracket">[</span>12<span class="cite-bracket">]</span></a></sup> </p> <figure class="mw-halign-right" typeof="mw:File/Thumb"><a href="/wiki/File:Butyl_rubber_gloves.JPG" class="mw-file-description"><img src="//upload.wikimedia.org/wikipedia/commons/thumb/f/f7/Butyl_rubber_gloves.JPG/175px-Butyl_rubber_gloves.JPG" decoding="async" width="175" height="233" class="mw-file-element" srcset="//upload.wikimedia.org/wikipedia/commons/thumb/f/f7/Butyl_rubber_gloves.JPG/263px-Butyl_rubber_gloves.JPG 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/f/f7/Butyl_rubber_gloves.JPG/350px-Butyl_rubber_gloves.JPG 2x" data-file-width="2472" data-file-height="3296" /></a><figcaption>丁基橡膠手套</figcaption></figure> <p><a href="/wiki/%E4%B8%81%E5%9F%BA%E6%A9%A1%E8%83%B6" title="丁基橡胶">丁基橡膠</a>(Butyl rubber)與PIB相反，丁基橡膠為<a href="/wiki/%E5%85%B1%E8%81%9A%E7%89%A9" title="共聚物">共聚物</a>(copolymer)，而其單體有~98%為異丁烯(isobutylene)和2%的<a href="/wiki/%E7%95%B0%E6%88%8A%E4%BA%8C%E7%83%AF" title="異戊二烯">異戊二烯</a>(isoprene)，其具核過程相似於高分子量PIB的聚合過程。丁基橡膠聚合反應會在AlCl<sub>3</sub>作為引發劑的情況下持續產生，它的低透氣性(gas permeability)、對化學物質的抵抗力(resistance)和抵抗老化，使其可各式應用，如防護手套、電纜絕緣體(electrical cable insulation)，甚至籃球。在第二次世界大戰時期，丁基橡膠的產品越來越多，將近現今美國產生十億　磅/年產品。<sup id="cite_ref-Odian_1-9" class="reference"><a href="#cite_note-Odian-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup> </p><p>聚丁烯為另一種共聚物，包含近80%異丁烯和20%其他丁烯(通常為1-<a href="/wiki/%E4%B8%81%E7%83%AF" title="丁烯">丁烯</a>)，這些低分子量聚合物的產生(300-2500 Da)，可在較大的溫度範圍(−45 to 80 °C)中與AlCl<sub>3</sub>或BF<sub>3</sub>產生。以這些聚合物的分子量來看，它們可作為<a href="/wiki/%E9%BB%8F%E5%90%88%E5%89%82" title="黏合剂">黏合劑</a>、<a href="/w/index.php?title=%E5%AF%86%E5%B0%81%E5%89%82&action=edit&redlink=1" class="new" title="密封剂（页面不存在）">密封剂</a>、<a href="/wiki/%E5%A1%91%E5%8C%96%E5%8A%91" title="塑化劑">塑化劑</a>(plasticizers)和變速箱油(transmission fluids)的添加物，等等許多應用。這些物質為低花費且由不同的公司產生，包含<a href="/wiki/BP" title="BP">BP</a>化學、<a href="/wiki/%E5%9F%83%E7%B4%A2" title="埃索">埃索</a>(Esso)和<a href="/wiki/%E5%B7%B4%E6%96%AF%E5%A4%AB" title="巴斯夫">巴斯夫</a>(BASF)。<sup id="cite_ref-KM_book_5-9" class="reference"><a href="#cite_note-KM_book-5"><span class="cite-bracket">[</span>5<span class="cite-bracket">]</span></a></sup> </p><p>其他由陽離子聚合反應形成的聚合物為均聚物(homopolymers)和聚萜烯(polyterpenes)的共聚物(copolymers)，如植物衍生物蒎烯(pinene)，可作為增黏劑(tackifiers)。在雜環(heterocycles)領域下，1,3,5-三氧雜環己烷(1,3,5-trioxane)是與少量環氧己烷(ethylene oxide)共聚合，而成的高結晶性(highly crystalline)<a href="/wiki/%E8%81%9A%E7%94%B2%E9%86%9B" title="聚甲醛">聚甲醛</a>(polyoxymethylene)塑料；烷基乙烯基醚(alkyl vinyl ethers)的均聚合作用(homopolymerization)只能以陽離子聚合反應達到。<sup id="cite_ref-Odian_1-10" class="reference"><a href="#cite_note-Odian-1"><span class="cite-bracket">[</span>1<span class="cite-bracket">]</span></a></sup> </p> <div class="mw-heading mw-heading2"><h2 id="參考"><span id=".E5.8F.83.E8.80.83"></span>參考</h2><span class="mw-editsection"><span class="mw-editsection-bracket">[</span><a href="/w/index.php?title=%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&action=edit&section=19" title="编辑章节：參考"><span>编辑</span></a><span class="mw-editsection-bracket">]</span></span></div> <div class="reflist columns references-column-width" style="-moz-column-width: 30em; -webkit-column-width: 30em; column-width: 30em; list-style-type: decimal;"> <ol class="references"> <li id="cite_note-Odian-1"><span class="mw-cite-backlink">^ <a href="#cite_ref-Odian_1-0"><sup><b>1.00</b></sup></a> <a href="#cite_ref-Odian_1-1"><sup><b>1.01</b></sup></a> <a href="#cite_ref-Odian_1-2"><sup><b>1.02</b></sup></a> <a href="#cite_ref-Odian_1-3"><sup><b>1.03</b></sup></a> <a href="#cite_ref-Odian_1-4"><sup><b>1.04</b></sup></a> <a href="#cite_ref-Odian_1-5"><sup><b>1.05</b></sup></a> <a href="#cite_ref-Odian_1-6"><sup><b>1.06</b></sup></a> <a href="#cite_ref-Odian_1-7"><sup><b>1.07</b></sup></a> <a href="#cite_ref-Odian_1-8"><sup><b>1.08</b></sup></a> <a href="#cite_ref-Odian_1-9"><sup><b>1.09</b></sup></a> <a href="#cite_ref-Odian_1-10"><sup><b>1.10</b></sup></a></span> <span class="reference-text"><cite class="citation book">Odian, George. <a rel="nofollow" class="external text" href="http://books.google.com/?id=6cjgZbFHI4kC&lpg=PP1">Principles of Polymerization</a> 4th. Hoboken, NJ: Wiley-Interscience. 2004. <a href="/wiki/Special:%E7%BD%91%E7%BB%9C%E4%B9%A6%E6%BA%90/978-0-471-27400-1" title="Special:网络书源/978-0-471-27400-1"><span title="国际标准书号">ISBN</span> 978-0-471-27400-1</a>.</cite><span title="ctx_ver=Z39.88-2004&rfr_id=info%3Asid%2Fzh.wikipedia.org%3A%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&rft.aufirst=George&rft.aulast=Odian&rft.btitle=Principles+of+Polymerization&rft.date=2004&rft.edition=4th&rft.genre=book&rft.isbn=978-0-471-27400-1&rft.place=Hoboken%2C+NJ&rft.pub=Wiley-Interscience&rft_id=http%3A%2F%2Fbooks.google.com%2F%3Fid%3D6cjgZbFHI4kC%26lpg%3DPP1&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Abook" class="Z3988"><span style="display:none;"> </span></span></span> </li> <li id="cite_note-EPSE-2"><span class="mw-cite-backlink"><b><a href="#cite_ref-EPSE_2-0">^</a></b></span> <span class="reference-text"><cite class="citation book">Mark, Herman F.; Bikales, Norbert; <a href="/w/index.php?title=Charles_G._Overberger&action=edit&redlink=1" class="new" title="Charles G. Overberger（页面不存在）">Overberger, Charles G.</a>; Menges, Georg; Kroschwitz, Jacqueline I. Encyclopedia of Polymer Science and Engineering 2nd. Wiley-Interscience. 1990. <a href="/wiki/Special:%E7%BD%91%E7%BB%9C%E4%B9%A6%E6%BA%90/978-0-471-80950-0" title="Special:网络书源/978-0-471-80950-0"><span title="国际标准书号">ISBN</span> 978-0-471-80950-0</a>.</cite><span title="ctx_ver=Z39.88-2004&rfr_id=info%3Asid%2Fzh.wikipedia.org%3A%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&rft.aufirst=Herman+F.&rft.aulast=Mark&rft.btitle=Encyclopedia+of+Polymer+Science+and+Engineering&rft.date=1990&rft.edition=2nd&rft.genre=book&rft.isbn=978-0-471-80950-0&rft.pub=Wiley-Interscience&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Abook" class="Z3988"><span style="display:none;"> </span></span> <span style="display:none;font-size:100%" class="error citation-comment">引文使用过时参数<code style="color:inherit; border:inherit; padding:inherit;">coauthors</code> (<a href="/wiki/Help:%E5%BC%95%E6%96%87%E6%A0%BC%E5%BC%8F1%E9%94%99%E8%AF%AF#deprecated_params" title="Help:引文格式1错误">帮助</a>)</span></span> </li> <li id="cite_note-CH_421-3"><span class="mw-cite-backlink"><b><a href="#cite_ref-CH_421_3-0">^</a></b></span> <span class="reference-text"><cite class="citation web">Robello, Douglas R. <a rel="nofollow" class="external text" href="https://web.archive.org/web/20110720035424/http://chem.chem.rochester.edu/~chem421/cation.htm">Chem 421: Introduction to Polymer Chemistry – Cationic Polymerization</a>. Department of Chemistry, University of Rochester. 2002 <span class="reference-accessdate"> [<span class="nowrap">20 March</span> 2011]</span>. （<a rel="nofollow" class="external text" href="http://chem.chem.rochester.edu/~chem421/cation.htm">原始内容</a>存档于2011-07-20）.</cite><span title="ctx_ver=Z39.88-2004&rfr_id=info%3Asid%2Fzh.wikipedia.org%3A%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&rft.atitle=Chem+421%3A+Introduction+to+Polymer+Chemistry+%E2%80%93+Cationic+Polymerization&rft.aufirst=Douglas+R.&rft.aulast=Robello&rft.date=2002&rft.genre=unknown&rft.jtitle=Department+of+Chemistry%2C+University+of+Rochester&rft_id=http%3A%2F%2Fchem.chem.rochester.edu%2F~chem421%2Fcation.htm&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal" class="Z3988"><span style="display:none;"> </span></span></span> </li> <li id="cite_note-4"><span class="mw-cite-backlink"><b><a href="#cite_ref-4">^</a></b></span> <span class="reference-text"><cite class="citation journal">Jenkins, A. D.; Kratochvíl, P.; Stepto, R. F. T.; Suter, U. W. <a rel="nofollow" class="external text" href="http://pac.iupac.org/publications/pac/pdf/1996/pdf/6812x2287.pdf">Glossary of basic terms in polymer science (IUPAC Recommendations 1996)</a> <span style="font-size:85%;">(PDF)</span>. <a href="/wiki/Pure_and_Applied_Chemistry" class="mw-redirect" title="Pure and Applied Chemistry">Pure and Applied Chemistry</a>. 1996, <b>68</b> (12): 2287–2311 <span class="reference-accessdate"> [<span class="nowrap">2014-06-24</span>]</span>. <a rel="nofollow" class="external text" href="https://doi.org/10.1351%2Fpac199668122287"><span title="數位物件識別號">doi:10.1351/pac199668122287</span></a>. （原始内容<a rel="nofollow" class="external text" href="https://web.archive.org/web/20160304041907/http://pac.iupac.org/publications/pac/pdf/1996/pdf/6812x2287.pdf">存档</a> <span style="font-size:85%;">(PDF)</span>于2016-03-04）.</cite><span title="ctx_ver=Z39.88-2004&rfr_id=info%3Asid%2Fzh.wikipedia.org%3A%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&rft.atitle=Glossary+of+basic+terms+in+polymer+science+%28IUPAC+Recommendations+1996%29&rft.au=Kratochv%C3%ADl%2C+P.&rft.au=Stepto%2C+R.+F.+T.&rft.au=Suter%2C+U.+W.&rft.aufirst=A.+D.&rft.aulast=Jenkins&rft.date=1996&rft.genre=article&rft.issue=12&rft.jtitle=Pure+and+Applied+Chemistry&rft.pages=2287-2311&rft.volume=68&rft_id=http%3A%2F%2Fpac.iupac.org%2Fpublications%2Fpac%2Fpdf%2F1996%2Fpdf%2F6812x2287.pdf&rft_id=info%3Adoi%2F10.1351%2Fpac199668122287&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal" class="Z3988"><span style="display:none;"> </span></span></span> </li> <li id="cite_note-KM_book-5"><span class="mw-cite-backlink">^ <a href="#cite_ref-KM_book_5-0"><sup><b>5.00</b></sup></a> <a href="#cite_ref-KM_book_5-1"><sup><b>5.01</b></sup></a> <a href="#cite_ref-KM_book_5-2"><sup><b>5.02</b></sup></a> <a href="#cite_ref-KM_book_5-3"><sup><b>5.03</b></sup></a> <a href="#cite_ref-KM_book_5-4"><sup><b>5.04</b></sup></a> <a href="#cite_ref-KM_book_5-5"><sup><b>5.05</b></sup></a> <a href="#cite_ref-KM_book_5-6"><sup><b>5.06</b></sup></a> <a href="#cite_ref-KM_book_5-7"><sup><b>5.07</b></sup></a> <a href="#cite_ref-KM_book_5-8"><sup><b>5.08</b></sup></a> <a href="#cite_ref-KM_book_5-9"><sup><b>5.09</b></sup></a></span> <span class="reference-text"><cite class="citation book">Matyjaszewski, Krzysztof. <a rel="nofollow" class="external text" href="http://books.google.com/?id=YX9FsRYVOzcC&lpg=PP1">Cationic Polymerizations: Mechanisms, Synthesis, and Applications</a>. New York, New York: Marcel Dekker, Inc. 1996. <a href="/wiki/Special:%E7%BD%91%E7%BB%9C%E4%B9%A6%E6%BA%90/978-0-8247-9463-7" title="Special:网络书源/978-0-8247-9463-7"><span title="国际标准书号">ISBN</span> 978-0-8247-9463-7</a>.</cite><span title="ctx_ver=Z39.88-2004&rfr_id=info%3Asid%2Fzh.wikipedia.org%3A%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&rft.aufirst=Krzysztof&rft.aulast=Matyjaszewski&rft.btitle=Cationic+Polymerizations%3A+Mechanisms%2C+Synthesis%2C+and+Applications&rft.date=1996&rft.genre=book&rft.isbn=978-0-8247-9463-7&rft.place=New+York%2C+New+York&rft.pub=Marcel+Dekker%2C+Inc&rft_id=http%3A%2F%2Fbooks.google.com%2F%3Fid%3DYX9FsRYVOzcC%26lpg%3DPP1&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Abook" class="Z3988"><span style="display:none;"> </span></span></span> </li> <li id="cite_note-Cowie_Textbook-6"><span class="mw-cite-backlink">^ <a href="#cite_ref-Cowie_Textbook_6-0"><sup><b>6.00</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-1"><sup><b>6.01</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-2"><sup><b>6.02</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-3"><sup><b>6.03</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-4"><sup><b>6.04</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-5"><sup><b>6.05</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-6"><sup><b>6.06</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-7"><sup><b>6.07</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-8"><sup><b>6.08</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-9"><sup><b>6.09</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-10"><sup><b>6.10</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-11"><sup><b>6.11</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-12"><sup><b>6.12</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-13"><sup><b>6.13</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-14"><sup><b>6.14</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-15"><sup><b>6.15</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-16"><sup><b>6.16</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-17"><sup><b>6.17</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-18"><sup><b>6.18</b></sup></a> <a href="#cite_ref-Cowie_Textbook_6-19"><sup><b>6.19</b></sup></a></span> <span class="reference-text"><cite class="citation book">Cowie, John M. G.; Arrighi, Valeria. Polymers Chemistry and Physics of Modern Materials 3rd. Boca Raton: Taylor & Francis. 2008. <a href="/wiki/Special:%E7%BD%91%E7%BB%9C%E4%B9%A6%E6%BA%90/978-0-8493-9813-1" title="Special:网络书源/978-0-8493-9813-1"><span title="国际标准书号">ISBN</span> 978-0-8493-9813-1</a>.</cite><span title="ctx_ver=Z39.88-2004&rfr_id=info%3Asid%2Fzh.wikipedia.org%3A%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&rft.au=Arrighi%2C+Valeria&rft.aufirst=John+M.+G.&rft.aulast=Cowie&rft.btitle=Polymers+Chemistry+and+Physics+of+Modern+Materials&rft.date=2008&rft.edition=3rd&rft.genre=book&rft.isbn=978-0-8493-9813-1&rft.place=Boca+Raton&rft.pub=Taylor+%26+Francis&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Abook" class="Z3988"><span style="display:none;"> </span></span></span> </li> <li id="cite_note-Kennedy-7"><span class="mw-cite-backlink"><b><a href="#cite_ref-Kennedy_7-0">^</a></b></span> <span class="reference-text"><cite class="citation journal">Kennedy, J. P.; Marechal, E. Chemistry of Initiation in Carbocationic Polymerization. Journal of Polymer Science: Macromolecular Reviews. 1981, <b>16</b>: 123–198. <a rel="nofollow" class="external text" href="https://doi.org/10.1002%2Fpol.1981.230160103"><span title="數位物件識別號">doi:10.1002/pol.1981.230160103</span></a>.</cite><span title="ctx_ver=Z39.88-2004&rfr_id=info%3Asid%2Fzh.wikipedia.org%3A%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&rft.atitle=Chemistry+of+Initiation+in+Carbocationic+Polymerization&rft.au=Marechal%2C+E.&rft.aufirst=J.+P.&rft.aulast=Kennedy&rft.date=1981&rft.genre=article&rft.jtitle=Journal+of+Polymer+Science%3A+Macromolecular+Reviews&rft.pages=123-198&rft.volume=16&rft_id=info%3Adoi%2F10.1002%2Fpol.1981.230160103&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal" class="Z3988"><span style="display:none;"> </span></span></span> </li> <li id="cite_note-Raave-8"><span class="mw-cite-backlink">^ <a href="#cite_ref-Raave_8-0"><sup><b>8.0</b></sup></a> <a href="#cite_ref-Raave_8-1"><sup><b>8.1</b></sup></a></span> <span class="reference-text"><cite class="citation book">Raave, A. <a rel="nofollow" class="external text" href="http://books.google.com/books?id=b6IAVqf_LMsC&lpg=PA39">Principles of Polymer Chemistry</a> 2nd. New York, New York: Kluwer Academic/Plenum Publishers. 2000. <a href="/wiki/Special:%E7%BD%91%E7%BB%9C%E4%B9%A6%E6%BA%90/978-0-306-46368-6" title="Special:网络书源/978-0-306-46368-6"><span title="国际标准书号">ISBN</span> 978-0-306-46368-6</a>.</cite><span title="ctx_ver=Z39.88-2004&rfr_id=info%3Asid%2Fzh.wikipedia.org%3A%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&rft.aufirst=A.&rft.aulast=Raave&rft.btitle=Principles+of+Polymer+Chemistry&rft.date=2000&rft.edition=2nd&rft.genre=book&rft.isbn=978-0-306-46368-6&rft.place=New+York%2C+New+York&rft.pub=Kluwer+Academic%2FPlenum+Publishers&rft_id=http%3A%2F%2Fbooks.google.com%2Fbooks%3Fid%3Db6IAVqf_LMsC%26lpg%3DPA39&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Abook" class="Z3988"><span style="display:none;"> </span></span></span> </li> <li id="cite_note-Fahlman-9"><span class="mw-cite-backlink"><b><a href="#cite_ref-Fahlman_9-0">^</a></b></span> <span class="reference-text"><cite class="citation book">Fahlman, Bradley D. <a rel="nofollow" class="external text" href="https://web.archive.org/web/20170423082931/https://books.google.com/books?id=lByCslty2oUC&lpg=PP1">Materials Chemistry</a>. Springer. 2008 <span class="reference-accessdate"> [<span class="nowrap">2014-06-25</span>]</span>. <a href="/wiki/Special:%E7%BD%91%E7%BB%9C%E4%B9%A6%E6%BA%90/978-1-4020-6119-6" title="Special:网络书源/978-1-4020-6119-6"><span title="国际标准书号">ISBN</span> 978-1-4020-6119-6</a>. （<a rel="nofollow" class="external text" href="http://books.google.com/books?id=lByCslty2oUC&lpg=PP1">原始内容</a>存档于2017-04-23）.</cite><span title="ctx_ver=Z39.88-2004&rfr_id=info%3Asid%2Fzh.wikipedia.org%3A%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&rft.aufirst=Bradley+D.&rft.aulast=Fahlman&rft.btitle=Materials+Chemistry&rft.date=2008&rft.genre=book&rft.isbn=978-1-4020-6119-6&rft.pub=Springer&rft_id=http%3A%2F%2Fbooks.google.com%2Fbooks%3Fid%3DlByCslty2oUC%26lpg%3DPP1&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Abook" class="Z3988"><span style="display:none;"> </span></span></span> </li> <li id="cite_note-Ebewele-10"><span class="mw-cite-backlink">^ <a href="#cite_ref-Ebewele_10-0"><sup><b>10.0</b></sup></a> <a href="#cite_ref-Ebewele_10-1"><sup><b>10.1</b></sup></a> <a href="#cite_ref-Ebewele_10-2"><sup><b>10.2</b></sup></a> <a href="#cite_ref-Ebewele_10-3"><sup><b>10.3</b></sup></a> <a href="#cite_ref-Ebewele_10-4"><sup><b>10.4</b></sup></a></span> <span class="reference-text"><cite class="citation book">Ebewele, Robert Oboigbaotor. <a rel="nofollow" class="external text" href="https://web.archive.org/web/20170423113317/https://books.google.com/books?id=2Xfe3G8g1loC&lpg=PP1">Polymer Science and Technology</a>. Boca Ration, FL: Chapman & Hall/CRC Press LLC. 2000 <span class="reference-accessdate"> [<span class="nowrap">2014-06-25</span>]</span>. <a href="/wiki/Special:%E7%BD%91%E7%BB%9C%E4%B9%A6%E6%BA%90/978-0-8493-8939-9" title="Special:网络书源/978-0-8493-8939-9"><span title="国际标准书号">ISBN</span> 978-0-8493-8939-9</a>. （<a rel="nofollow" class="external text" href="http://books.google.com/books?id=2Xfe3G8g1loC&lpg=PP1">原始内容</a>存档于2017-04-23）.</cite><span title="ctx_ver=Z39.88-2004&rfr_id=info%3Asid%2Fzh.wikipedia.org%3A%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&rft.aufirst=Robert+Oboigbaotor&rft.aulast=Ebewele&rft.btitle=Polymer+Science+and+Technology&rft.date=2000&rft.genre=book&rft.isbn=978-0-8493-8939-9&rft.place=Boca+Ration%2C+FL&rft.pub=Chapman+%26+Hall%2FCRC+Press+LLC&rft_id=http%3A%2F%2Fbooks.google.com%2Fbooks%3Fid%3D2Xfe3G8g1loC%26lpg%3DPP1&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Abook" class="Z3988"><span style="display:none;"> </span></span></span> </li> <li id="cite_note-Sawamoto-11"><span class="mw-cite-backlink"><b><a href="#cite_ref-Sawamoto_11-0">^</a></b></span> <span class="reference-text"><cite class="citation journal">Sawamoto, M. <a rel="nofollow" class="external text" href="https://archive.org/details/sim_progress-in-polymer-science_1991_16_1/page/111">Modern Cationic Vinyl Polymerization</a>. Progress in Polymer Science. 1991, <b>16</b>: 111–172. <a rel="nofollow" class="external text" href="https://doi.org/10.1016%2F0079-6700%2891%2990008-9"><span title="數位物件識別號">doi:10.1016/0079-6700(91)90008-9</span></a>.</cite><span title="ctx_ver=Z39.88-2004&rfr_id=info%3Asid%2Fzh.wikipedia.org%3A%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&rft.atitle=Modern+Cationic+Vinyl+Polymerization&rft.aufirst=M.&rft.aulast=Sawamoto&rft.date=1991&rft.genre=article&rft.jtitle=Progress+in+Polymer+Science&rft.pages=111-172&rft.volume=16&rft_id=https%3A%2F%2Farchive.org%2Fdetails%2Fsim_progress-in-polymer-science_1991_16_1%2Fpage%2F111&rft_id=info%3Adoi%2F10.1016%2F0079-6700%2891%2990008-9&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal" class="Z3988"><span style="display:none;"> </span></span></span> </li> <li id="cite_note-Chanda-12"><span class="mw-cite-backlink"><b><a href="#cite_ref-Chanda_12-0">^</a></b></span> <span class="reference-text"><cite class="citation book">Chanda, Manas; Roy, Salil K. <a rel="nofollow" class="external text" href="https://web.archive.org/web/20170423021428/https://books.google.com/books?id=CF_-xp9iKHcC&lpg=SA2-PA21">Plastics Technology Handbook: Plastics Engineering Series</a> 4th. Boca Raton, FL: CSC Press. 2007 <span class="reference-accessdate"> [<span class="nowrap">2014-06-25</span>]</span>. <a href="/wiki/Special:%E7%BD%91%E7%BB%9C%E4%B9%A6%E6%BA%90/978-0-8493-7039-7" title="Special:网络书源/978-0-8493-7039-7"><span title="国际标准书号">ISBN</span> 978-0-8493-7039-7</a>. （<a rel="nofollow" class="external text" href="http://books.google.com/books?id=CF_-xp9iKHcC&lpg=SA2-PA21">原始内容</a>存档于2017-04-23）.</cite><span title="ctx_ver=Z39.88-2004&rfr_id=info%3Asid%2Fzh.wikipedia.org%3A%E9%99%BD%E9%9B%A2%E5%AD%90%E8%81%9A%E5%90%88%E5%8F%8D%E6%87%89&rft.au=Roy%2C+Salil+K.&rft.aufirst=Manas&rft.aulast=Chanda&rft.btitle=Plastics+Technology+Handbook%3A+Plastics+Engineering+Series&rft.date=2007&rft.edition=4th&rft.genre=book&rft.isbn=978-0-8493-7039-7&rft.place=Boca+Raton%2C+FL&rft.pub=CSC+Press&rft_id=http%3A%2F%2Fbooks.google.com%2Fbooks%3Fid%3DCF_-xp9iKHcC%26lpg%3DSA2-PA21&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Abook" class="Z3988"><span 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