Living Cationic Cyclopolymerization of Divinyl Ether with Bulky Substituents: Synthesis of High-Molecular-Weight Cyclopolymers and Star-Shaped Cyclopolymers
Living cationic cyclopolymerization of 1,2-bis(2-vinyloxyethoxy)-3,5-di-tert-butylbenzene (1) was investigated with the CH3CH(OiBu)OCOCH3/Et1.5AlCl1.5/CH3COOEt initiating system in toluene at 0°C. All the reactions proceeded quantitatively to give gel-free polymers, soluble in organic solvents. The...
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| Veröffentlicht in: | KOBUNSHI RONBUNSHU 2019/05/25, Vol.76(3), pp.216-225 |
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| creator | NIWA, Takahiro YAMAMOTO, Takafumi HASHIMOTO, Tamotsu URUSHISAKI, Michio SAKAGUCHI, Toshikazu |
| description | Living cationic cyclopolymerization of 1,2-bis(2-vinyloxyethoxy)-3,5-di-tert-butylbenzene (1) was investigated with the CH3CH(OiBu)OCOCH3/Et1.5AlCl1.5/CH3COOEt initiating system in toluene at 0°C. All the reactions proceeded quantitatively to give gel-free polymers, soluble in organic solvents. The number-average molecular weight (Mn) of the polymers increased in direct proportion to monomer conversion and further increased on addition of a fresh monomer feed to the almost completely polymerized reaction mixture, indicating that living cyclopolymerization of 1 occurred. The content of unreacted vinyl groups in the produced soluble polymers was less than ~2 mol%, and therefore, the degree of cyclization of the polymers was determined to be over ~98%. Preparation of high-molecular-weight cyclopoly(1) was achieved by sequential monomer addition to the living polymerization system and polymer linking reaction of living cyclopoly(1) leading to star-shaped polymers. Glass transition temperature (Tg) of linear cyclopoly(1) (Mn = 18,500) was 134°C and Tg of star-shaped cyclopoly(1) (Mn = 95,900) was 132°C, and thermal decomposition temperatures (Tds) of these cyclopoly(1) were over 350°C, indicating their high thermal stability. |
| doi_str_mv | 10.1295/koron.2019-0002 |
| format | Article |
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All the reactions proceeded quantitatively to give gel-free polymers, soluble in organic solvents. The number-average molecular weight (Mn) of the polymers increased in direct proportion to monomer conversion and further increased on addition of a fresh monomer feed to the almost completely polymerized reaction mixture, indicating that living cyclopolymerization of 1 occurred. The content of unreacted vinyl groups in the produced soluble polymers was less than ~2 mol%, and therefore, the degree of cyclization of the polymers was determined to be over ~98%. Preparation of high-molecular-weight cyclopoly(1) was achieved by sequential monomer addition to the living polymerization system and polymer linking reaction of living cyclopoly(1) leading to star-shaped polymers. Glass transition temperature (Tg) of linear cyclopoly(1) (Mn = 18,500) was 134°C and Tg of star-shaped cyclopoly(1) (Mn = 95,900) was 132°C, and thermal decomposition temperatures (Tds) of these cyclopoly(1) were over 350°C, indicating their high thermal stability.</description><identifier>ISSN: 0386-2186</identifier><identifier>EISSN: 1881-5685</identifier><identifier>DOI: 10.1295/koron.2019-0002</identifier><language>jpn</language><publisher>Tokyo: The Society of Polymer Science, Japan</publisher><subject>Addition polymerization ; Bulky Substituent ; Cationic Polymerization ; Cations ; Chemical synthesis ; Cyclopolymer ; Cyclopolymerization ; Divinyl Ether ; Divinyl ethers ; Glass transition temperature ; Living Polymerization ; Molecular weight ; Monomers ; Polymerization ; Polymers ; Star-Shaped Polymer ; Thermal decomposition ; Thermal stability ; Toluene</subject><ispartof>KOBUNSHI RONBUNSHU, 2019/05/25, Vol.76(3), pp.216-225</ispartof><rights>2019 The Society of Polymer Science, Japan</rights><rights>Copyright Japan Science and Technology Agency 2019</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,781,785,1884,27926,27927</link.rule.ids></links><search><creatorcontrib>NIWA, Takahiro</creatorcontrib><creatorcontrib>YAMAMOTO, Takafumi</creatorcontrib><creatorcontrib>HASHIMOTO, Tamotsu</creatorcontrib><creatorcontrib>URUSHISAKI, Michio</creatorcontrib><creatorcontrib>SAKAGUCHI, Toshikazu</creatorcontrib><title>Living Cationic Cyclopolymerization of Divinyl Ether with Bulky Substituents: Synthesis of High-Molecular-Weight Cyclopolymers and Star-Shaped Cyclopolymers</title><title>KOBUNSHI RONBUNSHU</title><addtitle>KOBUNSHI RONBUNSHU</addtitle><description>Living cationic cyclopolymerization of 1,2-bis(2-vinyloxyethoxy)-3,5-di-tert-butylbenzene (1) was investigated with the CH3CH(OiBu)OCOCH3/Et1.5AlCl1.5/CH3COOEt initiating system in toluene at 0°C. All the reactions proceeded quantitatively to give gel-free polymers, soluble in organic solvents. The number-average molecular weight (Mn) of the polymers increased in direct proportion to monomer conversion and further increased on addition of a fresh monomer feed to the almost completely polymerized reaction mixture, indicating that living cyclopolymerization of 1 occurred. The content of unreacted vinyl groups in the produced soluble polymers was less than ~2 mol%, and therefore, the degree of cyclization of the polymers was determined to be over ~98%. Preparation of high-molecular-weight cyclopoly(1) was achieved by sequential monomer addition to the living polymerization system and polymer linking reaction of living cyclopoly(1) leading to star-shaped polymers. Glass transition temperature (Tg) of linear cyclopoly(1) (Mn = 18,500) was 134°C and Tg of star-shaped cyclopoly(1) (Mn = 95,900) was 132°C, and thermal decomposition temperatures (Tds) of these cyclopoly(1) were over 350°C, indicating their high thermal stability.</description><subject>Addition polymerization</subject><subject>Bulky Substituent</subject><subject>Cationic Polymerization</subject><subject>Cations</subject><subject>Chemical synthesis</subject><subject>Cyclopolymer</subject><subject>Cyclopolymerization</subject><subject>Divinyl Ether</subject><subject>Divinyl ethers</subject><subject>Glass transition temperature</subject><subject>Living Polymerization</subject><subject>Molecular weight</subject><subject>Monomers</subject><subject>Polymerization</subject><subject>Polymers</subject><subject>Star-Shaped Polymer</subject><subject>Thermal decomposition</subject><subject>Thermal stability</subject><subject>Toluene</subject><issn>0386-2186</issn><issn>1881-5685</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNpVkTFPwzAQhS0EElXpzGqJ2cVOasdhg1IoUhFDQIyWkziN2zQOtgMKv4UfS9IipC53unvfvRseAJcET0kQ0-utsaaeBpjECGMcnIAR4Zwgyjg9BSMccoYCwtk5mDinU4xp3KOYjcDPSn_qeg3n0mtT6wzOu6wyjam6nbL6e7-FpoD3A9ZVcOFLZeGX9iW8a6ttB5M2dV77VtXe3cCkq3vAaTfcLPW6RM-mUllbSYveVT_7owcOyjqHie_VpJSNyo_VC3BWyMqpyV8fg7eHxet8iVYvj0_z2xXakIh6RPM8YwyzNJopiilLOSvwjAQ8KFQezlIWyyImKaOKRAWNMp5mBZcFzVOex2GYh2NwdfBtrPlolfNiY1pb9y9FEPCo94xD2lOLA7VxXq6VaKzeSdsJab3OKiX2GYiIiXAoQxZiyOJfz0ppharDX1nliTs</recordid><startdate>20190101</startdate><enddate>20190101</enddate><creator>NIWA, Takahiro</creator><creator>YAMAMOTO, Takafumi</creator><creator>HASHIMOTO, Tamotsu</creator><creator>URUSHISAKI, Michio</creator><creator>SAKAGUCHI, Toshikazu</creator><general>The Society of Polymer Science, Japan</general><general>Japan Science and Technology Agency</general><scope>7SR</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>20190101</creationdate><title>Living Cationic Cyclopolymerization of Divinyl Ether with Bulky Substituents: Synthesis of High-Molecular-Weight Cyclopolymers and Star-Shaped Cyclopolymers</title><author>NIWA, Takahiro ; YAMAMOTO, Takafumi ; HASHIMOTO, Tamotsu ; URUSHISAKI, Michio ; SAKAGUCHI, Toshikazu</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-j175t-5ddc6606b74e5056b86f041282fed34b69af91b65e17f57c8bcf8af5db8d933d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>jpn</language><creationdate>2019</creationdate><topic>Addition polymerization</topic><topic>Bulky Substituent</topic><topic>Cationic Polymerization</topic><topic>Cations</topic><topic>Chemical synthesis</topic><topic>Cyclopolymer</topic><topic>Cyclopolymerization</topic><topic>Divinyl Ether</topic><topic>Divinyl ethers</topic><topic>Glass transition temperature</topic><topic>Living Polymerization</topic><topic>Molecular weight</topic><topic>Monomers</topic><topic>Polymerization</topic><topic>Polymers</topic><topic>Star-Shaped Polymer</topic><topic>Thermal decomposition</topic><topic>Thermal stability</topic><topic>Toluene</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>NIWA, Takahiro</creatorcontrib><creatorcontrib>YAMAMOTO, Takafumi</creatorcontrib><creatorcontrib>HASHIMOTO, Tamotsu</creatorcontrib><creatorcontrib>URUSHISAKI, Michio</creatorcontrib><creatorcontrib>SAKAGUCHI, Toshikazu</creatorcontrib><collection>Engineered Materials Abstracts</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>KOBUNSHI RONBUNSHU</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>NIWA, Takahiro</au><au>YAMAMOTO, Takafumi</au><au>HASHIMOTO, Tamotsu</au><au>URUSHISAKI, Michio</au><au>SAKAGUCHI, Toshikazu</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Living Cationic Cyclopolymerization of Divinyl Ether with Bulky Substituents: Synthesis of High-Molecular-Weight Cyclopolymers and Star-Shaped Cyclopolymers</atitle><jtitle>KOBUNSHI RONBUNSHU</jtitle><addtitle>KOBUNSHI RONBUNSHU</addtitle><date>2019-01-01</date><risdate>2019</risdate><volume>76</volume><issue>3</issue><spage>216</spage><epage>225</epage><pages>216-225</pages><issn>0386-2186</issn><eissn>1881-5685</eissn><abstract>Living cationic cyclopolymerization of 1,2-bis(2-vinyloxyethoxy)-3,5-di-tert-butylbenzene (1) was investigated with the CH3CH(OiBu)OCOCH3/Et1.5AlCl1.5/CH3COOEt initiating system in toluene at 0°C. All the reactions proceeded quantitatively to give gel-free polymers, soluble in organic solvents. The number-average molecular weight (Mn) of the polymers increased in direct proportion to monomer conversion and further increased on addition of a fresh monomer feed to the almost completely polymerized reaction mixture, indicating that living cyclopolymerization of 1 occurred. The content of unreacted vinyl groups in the produced soluble polymers was less than ~2 mol%, and therefore, the degree of cyclization of the polymers was determined to be over ~98%. Preparation of high-molecular-weight cyclopoly(1) was achieved by sequential monomer addition to the living polymerization system and polymer linking reaction of living cyclopoly(1) leading to star-shaped polymers. Glass transition temperature (Tg) of linear cyclopoly(1) (Mn = 18,500) was 134°C and Tg of star-shaped cyclopoly(1) (Mn = 95,900) was 132°C, and thermal decomposition temperatures (Tds) of these cyclopoly(1) were over 350°C, indicating their high thermal stability.</abstract><cop>Tokyo</cop><pub>The Society of Polymer Science, Japan</pub><doi>10.1295/koron.2019-0002</doi><tpages>10</tpages><oa>free_for_read</oa></addata></record> |
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| source | J-STAGE Free |
| subjects | Addition polymerization Bulky Substituent Cationic Polymerization Cations Chemical synthesis Cyclopolymer Cyclopolymerization Divinyl Ether Divinyl ethers Glass transition temperature Living Polymerization Molecular weight Monomers Polymerization Polymers Star-Shaped Polymer Thermal decomposition Thermal stability Toluene |
| title | Living Cationic Cyclopolymerization of Divinyl Ether with Bulky Substituents: Synthesis of High-Molecular-Weight Cyclopolymers and Star-Shaped Cyclopolymers |
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