{"@context":{"@vocab":"https://cir.nii.ac.jp/schema/1.0/","rdfs":"http://www.w3.org/2000/01/rdf-schema#","dc":"http://purl.org/dc/elements/1.1/","dcterms":"http://purl.org/dc/terms/","foaf":"http://xmlns.com/foaf/0.1/","prism":"http://prismstandard.org/namespaces/basic/2.0/","cinii":"http://ci.nii.ac.jp/ns/1.0/","datacite":"https://schema.datacite.org/meta/kernel-4/","ndl":"http://ndl.go.jp/dcndl/terms/","jpcoar":"https://github.com/JPCOAR/schema/blob/master/2.0/"},"@id":"https://cir.nii.ac.jp/crid/1390001206520122752.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1295/koron1944.26.153"}},{"identifier":{"@type":"NAID","@value":"130004032784"}}],"dc:title":[{"@language":"en","@value":"Effect of Reaction Medium on the Copolymerization of Acrylonitrile and Sodium Methallyl Sulfonate"},{"@value":"アクリロニトリルとメタクリルスルホン酸ナトリウムの共重合性に及ぼす重合媒体の影響"}],"dc:language":"ja","description":[{"type":"abstract","notation":[{"@language":"en","@value":"The copolymerization of acrylonitrile (AN) with sodium methallyl sulfonate (SMAS) in dimethyl sulfoxide (DMSO) at pH 7, in aqueous DMSO solution (6% H<SUB>2</SUB>0) at pH 7, in DMSO at pH 1.5, in aqueous solutions at pH 7 and at pH 1.5 has been investigated. Monomer reactivity ratios at 45°C for AN and SMAS were found to be <I>r</I><SUB>1</SUB>=0.45, <I>r</I><SUB>2</SUB>=1.50 in DMSO at pH 7; <I>r</I><SUB>1</SUB>=0.55, <I>r</I><SUB>2</SUB>=1.20 in aqueous DMSO; <I>r</I><SUB>1</SUB>=0.75, <I>r</I><SUB>2</SUB> =1.30 in DMSO at pH 1.5; <I>r</I><SUB>1</SUB>=0.85, <I>r</I><SUB>2</SUB>=0.50 in aqueous solution at pH 7; <I>r</I><SUB>1</SUB>=1.10, <I>r</I><SUB>2</SUB>=0.70 in aqueous solution at pH 1.5. From these values Price's <I>Q</I> and <I>e</I> values, for SMAS were calculated, and it was found that they are 0.63 and 0.57 in DMSO at pH 7, and O.51 and O.55 in aqueous DMSO, 0.67 and 1.04 in DMSO at pH 1.5, O.23 and O.28 in aqueous solution at pH 7, and 0.27 and 0.69 in aqueous solution at pH 1.5 respectively. The large differences in reactivity of SMAS may be attributed to the different electron distributions in SMAS in each solvent which are caused by poor solvating power of dimethylsulfoxide and by the addition of protons. Homopolymerization of SMAS shows first-order dependence on the initiator concentration, and this is attributed to degradative chain transfer of SMAS. The rate of copolymerization of AN and SMAS decreases with increasing SMAS content. It has been found that there is a peculiar effect in the range of 8-12 mole % of SMAS monomer feed in aqueous solution which is in the transition state from homogeneous t heterogeneous phase."},{"@value":"酸性基を有する単量体の重合溶媒および酸性度による反応性の差を比較することを目的として, アクリロニトリル (AN) とメタリルスルホン酸ナトリウム (SMAS) の共重合をpH 7の水中, pH 1.5の水中, pH 7のジメチルスルホキシド (DMSO) 中, pH 1.5のDMSO中およびpH 7の6%含水DMSO中で検討した。単量体反応性比はpH 7の水中で<I>r</I><SUB>1</SUB> (AN) =0.85, <I>r</I><SUB>2</SUB> (SMAS) =0.50, pH 1.5の水中で<I>r</I><SUB>1</SUB>=1.10, <I>r</I><SUB>2</SUB>=0.70, pH 7のDMSO中で<I>r</I><SUB>1</SUB>=0.45, <I>r</I><SUB>2</SUB>=1.50, pH 1.5のDMSO中で<I>r</I><SUB>1</SUB>=0.75, <I>r</I><SUB>2</SUB>=1.30, pH 7の6%含水DMSO中で<I>r</I><SUB>1</SUB>=0.55, <I>r</I><SUB>2</SUB>=1.20であった。これらの値からSMASの<I>Q</I>値と<I>e</I>値はそれぞれpH 7の水中で0.23および0.28, pH 1.5の水中で0.27および0.69, pH 7のDMSO中で0.63および0.57, pH 1.5のDMSO中で0.67および1.04, さらにpH 7の6%含水DMSO中で0.51および0.55であった。このようにSMASの反応性に大きな差が生ずるのは, DMSO中では溶媒がカチオンに配位し, アニオンへの溶媒和がなく, 解離が抑制されること, 水の添加による解離の増加, プロトン添加による抑制によるものと思われる。共鳴項<I>Q</I>もDMSO中では大きくなる。SMASの単独重合速度は著しく遅く, 開始剤濃度に比例する。共重合速度はSMASの含有量が多くなるにつれて一様に著しく低下するが, 水系では均一系と不均一系の境界領域の特異な効果が見られる。"}],"abstractLicenseFlag":"disallow"}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1410572171114403072","@type":"Researcher","personIdentifier":[{"@type":"NRID","@value":"9000254927351"}],"foaf:name":[{"@language":"en","@value":"Izumi Zenzi"},{"@language":"ja","@value":"泉 善二"}],"jpcoar:affiliationName":[{"@language":"en","@value":"Ehime Research Laboratories, Toyo Rayon Co., Ltd."},{"@language":"ja","@value":"東洋レーヨン株式会社技術開発部愛媛研究室"}]},{"@id":"https://cir.nii.ac.jp/crid/1410572171114403073","@type":"Researcher","personIdentifier":[{"@type":"NRID","@value":"9000254927352"}],"foaf:name":[{"@language":"en","@value":"Kitagawa Hideji"},{"@language":"ja","@value":"北川 日出次"}],"jpcoar:affiliationName":[{"@language":"en","@value":"Ehime Research Laboratories, Toyo Rayon Co., Ltd."},{"@language":"ja","@value":"東洋レーヨン株式会社技術開発部愛媛研究室"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"00232556"},{"@type":"EISSN","@value":"18848079"}],"prism:publicationName":[{"@language":"en","@value":"Kobunshi Kagaku"},{"@language":"ja","@value":"高分子化學"},{"@language":"en","@value":"Kobunshi Kagaku"},{"@language":"ja","@value":"高分子化學"}],"dc:publisher":[{"@language":"en","@value":"The Society of Polymer Science, Japan"},{"@language":"ja","@value":"公益社団法人 高分子学会"}],"prism:publicationDate":"1969","prism:volume":"26","prism:number":"286","prism:startingPage":"153","prism:endingPage":"157"},"reviewed":"false","availableAt":"1969","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1390001206291690752","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"ESR Studies of Copolymerization of Water-Soluble Monomers with Acrylonitrile"}]}],"dataSourceIdentifier":[{"@type":"JALC","@value":"oai:japanlinkcenter.org:0037009349"},{"@type":"CROSSREF","@value":"10.1295/koron1944.26.153"},{"@type":"CIA","@value":"130004032784"},{"@type":"CROSSREF","@value":"10.1295/polymj.5.208_references_DOI_9zYvaXVQczvOExbX4tdWC4r10Z7"}]}