Atom transfer radical polymerization and copolymerization of vinyl acetate catalyzed by copper halide/terpyridine
Copper-mediated atom transfer radical polymerization (ATRP) is versatile for living polymerizations of a wide range of monomers, but ATRP of vinyl acetate (VAc) remains challenging due to the low homolytic cleavage activity of the carbon-halide bond of the dormant poly(vinyl acetate) (PVAc) chains a...
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| Veröffentlicht in: | AIChE journal 2009-03, Vol.55 (3), p.737-746 |
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| creator | Tang, Huadong Radosz, Maciej Shen, Youqing |
| description | Copper-mediated atom transfer radical polymerization (ATRP) is versatile for living polymerizations of a wide range of monomers, but ATRP of vinyl acetate (VAc) remains challenging due to the low homolytic cleavage activity of the carbon-halide bond of the dormant poly(vinyl acetate) (PVAc) chains and the high reactivity of growing PVAc radicals. Therefore, all the reported highly active copper-based catalysts are inactive in ATRP of VAc. Herein, we report the first copper-catalyst mediated ATRP of VAc using CuBr/2,2':6',2"-terpyridine (tPy) or CuCl/tPy as catalysts. The polymerization was a first order reaction with respect to the monomer concentration. The molecular weights of the resulting PVAc linearly increased with the VAc conversion. The living character was further proven by self-chain extension of PVAc. Using polystyrene (PS) as a macroinitiator, a well-defined diblock copolymer PS-b-PVAc was prepared. Hydrolysis of the PS-b-PVAc produced a PS-b-poly(vinyl alcohol) amphiphilic diblock copolymer. © 2009 American Institute of Chemical Engineers AIChE J, 2009 |
| doi_str_mv | 10.1002/aic.11706 |
| format | Article |
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Therefore, all the reported highly active copper-based catalysts are inactive in ATRP of VAc. Herein, we report the first copper-catalyst mediated ATRP of VAc using CuBr/2,2':6',2"-terpyridine (tPy) or CuCl/tPy as catalysts. The polymerization was a first order reaction with respect to the monomer concentration. The molecular weights of the resulting PVAc linearly increased with the VAc conversion. The living character was further proven by self-chain extension of PVAc. Using polystyrene (PS) as a macroinitiator, a well-defined diblock copolymer PS-b-PVAc was prepared. 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Nomenclature, chemical documentation, computer chemistry</subject><ispartof>AIChE journal, 2009-03, Vol.55 (3), p.737-746</ispartof><rights>Copyright © 2009 American Institute of Chemical Engineers (AIChE)</rights><rights>2009 INIST-CNRS</rights><rights>Copyright American Institute of Chemical Engineers Mar 2009</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4886-50ae5b8bb0d0f6ec61cfa98f161a454e4e6e8e7b89e5cf6017fe38056768a3ef3</citedby><cites>FETCH-LOGICAL-c4886-50ae5b8bb0d0f6ec61cfa98f161a454e4e6e8e7b89e5cf6017fe38056768a3ef3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Faic.11706$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Faic.11706$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=21200089$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Tang, Huadong</creatorcontrib><creatorcontrib>Radosz, Maciej</creatorcontrib><creatorcontrib>Shen, Youqing</creatorcontrib><title>Atom transfer radical polymerization and copolymerization of vinyl acetate catalyzed by copper halide/terpyridine</title><title>AIChE journal</title><addtitle>AIChE J</addtitle><description>Copper-mediated atom transfer radical polymerization (ATRP) is versatile for living polymerizations of a wide range of monomers, but ATRP of vinyl acetate (VAc) remains challenging due to the low homolytic cleavage activity of the carbon-halide bond of the dormant poly(vinyl acetate) (PVAc) chains and the high reactivity of growing PVAc radicals. Therefore, all the reported highly active copper-based catalysts are inactive in ATRP of VAc. Herein, we report the first copper-catalyst mediated ATRP of VAc using CuBr/2,2':6',2"-terpyridine (tPy) or CuCl/tPy as catalysts. The polymerization was a first order reaction with respect to the monomer concentration. The molecular weights of the resulting PVAc linearly increased with the VAc conversion. The living character was further proven by self-chain extension of PVAc. Using polystyrene (PS) as a macroinitiator, a well-defined diblock copolymer PS-b-PVAc was prepared. Hydrolysis of the PS-b-PVAc produced a PS-b-poly(vinyl alcohol) amphiphilic diblock copolymer. © 2009 American Institute of Chemical Engineers AIChE J, 2009</description><subject>Applied sciences</subject><subject>atom transfer radical</subject><subject>Catalysis</subject><subject>Catalysts</subject><subject>Catalytic reactions</subject><subject>Chemical engineering</subject><subject>Chemistry</subject><subject>Copolymerization</subject><subject>Copper</subject><subject>Exact sciences and technology</subject><subject>General and physical chemistry</subject><subject>Ions</subject><subject>living radical polymerization</subject><subject>Molecular weight</subject><subject>Organic polymers</subject><subject>Physicochemistry of polymers</subject><subject>Polymerization</subject><subject>Preparation, kinetics, thermodynamics, mechanism and catalysts</subject><subject>Reaction kinetics</subject><subject>Reactors</subject><subject>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</subject><issn>0001-1541</issn><issn>1547-5905</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2009</creationdate><recordtype>article</recordtype><recordid>eNp90c1u1DAUBeAIgcRQWPAEREiAWKRjx79ZTke0VBSQgAqpG-uOcw0umTi1M5T06XFJ6aISrCxb3z2yfYriKSX7lJB6Cd7uU6qIvFcsqOCqEg0R94sFIYRW-YA-LB6ldJ53tdL1orhYjWFbjhH65DCWEVpvoSuH0E1bjP4KRh_6Evq2tOHOYXDlT99PXQkWRxixtDBCN11hW26maz7kwO_Q-RaXI8Zhir71PT4uHjjoEj65WfeK08M3X9Zvq5OPR8fr1UlludayEgRQbPRmQ1riJFpJrYNGOyopcMGRo0SNaqMbFNZJQpVDpomQSmpg6Nhe8WrOHWK42GEazdYni10HPYZdMoozooRkOsuX_5WMCU245hk-vwPPwy72-RWGNg1TkmuS0esZ2RhSiujMEP0W4mQoMdcdmdyR-dNRti9uAiHlb3e5BuvT7UBN69ybbrJbzu7Sdzj9O9Csjtd_k6t5wqcRf91OQPxhpGJKmK8fjkwt3h0078_OzKfsn83eQTDwLeZbnH6uCWWEikYqTthvgWG56A</recordid><startdate>200903</startdate><enddate>200903</enddate><creator>Tang, Huadong</creator><creator>Radosz, Maciej</creator><creator>Shen, Youqing</creator><general>Wiley Subscription Services, Inc., A Wiley Company</general><general>Wiley</general><general>American Institute of Chemical Engineers</general><scope>FBQ</scope><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7ST</scope><scope>7U5</scope><scope>8FD</scope><scope>C1K</scope><scope>L7M</scope><scope>SOI</scope></search><sort><creationdate>200903</creationdate><title>Atom transfer radical polymerization and copolymerization of vinyl acetate catalyzed by copper halide/terpyridine</title><author>Tang, Huadong ; Radosz, Maciej ; Shen, Youqing</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4886-50ae5b8bb0d0f6ec61cfa98f161a454e4e6e8e7b89e5cf6017fe38056768a3ef3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2009</creationdate><topic>Applied sciences</topic><topic>atom transfer radical</topic><topic>Catalysis</topic><topic>Catalysts</topic><topic>Catalytic reactions</topic><topic>Chemical engineering</topic><topic>Chemistry</topic><topic>Copolymerization</topic><topic>Copper</topic><topic>Exact sciences and technology</topic><topic>General and physical chemistry</topic><topic>Ions</topic><topic>living radical polymerization</topic><topic>Molecular weight</topic><topic>Organic polymers</topic><topic>Physicochemistry of polymers</topic><topic>Polymerization</topic><topic>Preparation, kinetics, thermodynamics, mechanism and catalysts</topic><topic>Reaction kinetics</topic><topic>Reactors</topic><topic>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Tang, Huadong</creatorcontrib><creatorcontrib>Radosz, Maciej</creatorcontrib><creatorcontrib>Shen, Youqing</creatorcontrib><collection>AGRIS</collection><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>Environment Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>Environment Abstracts</collection><jtitle>AIChE journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Tang, Huadong</au><au>Radosz, Maciej</au><au>Shen, Youqing</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Atom transfer radical polymerization and copolymerization of vinyl acetate catalyzed by copper halide/terpyridine</atitle><jtitle>AIChE journal</jtitle><addtitle>AIChE J</addtitle><date>2009-03</date><risdate>2009</risdate><volume>55</volume><issue>3</issue><spage>737</spage><epage>746</epage><pages>737-746</pages><issn>0001-1541</issn><eissn>1547-5905</eissn><coden>AICEAC</coden><abstract>Copper-mediated atom transfer radical polymerization (ATRP) is versatile for living polymerizations of a wide range of monomers, but ATRP of vinyl acetate (VAc) remains challenging due to the low homolytic cleavage activity of the carbon-halide bond of the dormant poly(vinyl acetate) (PVAc) chains and the high reactivity of growing PVAc radicals. Therefore, all the reported highly active copper-based catalysts are inactive in ATRP of VAc. Herein, we report the first copper-catalyst mediated ATRP of VAc using CuBr/2,2':6',2"-terpyridine (tPy) or CuCl/tPy as catalysts. The polymerization was a first order reaction with respect to the monomer concentration. The molecular weights of the resulting PVAc linearly increased with the VAc conversion. The living character was further proven by self-chain extension of PVAc. Using polystyrene (PS) as a macroinitiator, a well-defined diblock copolymer PS-b-PVAc was prepared. Hydrolysis of the PS-b-PVAc produced a PS-b-poly(vinyl alcohol) amphiphilic diblock copolymer. © 2009 American Institute of Chemical Engineers AIChE J, 2009</abstract><cop>Hoboken</cop><pub>Wiley Subscription Services, Inc., A Wiley Company</pub><doi>10.1002/aic.11706</doi><tpages>10</tpages></addata></record> |
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| subjects | Applied sciences atom transfer radical Catalysis Catalysts Catalytic reactions Chemical engineering Chemistry Copolymerization Copper Exact sciences and technology General and physical chemistry Ions living radical polymerization Molecular weight Organic polymers Physicochemistry of polymers Polymerization Preparation, kinetics, thermodynamics, mechanism and catalysts Reaction kinetics Reactors Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry |
| title | Atom transfer radical polymerization and copolymerization of vinyl acetate catalyzed by copper halide/terpyridine |
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