{"@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/1390282679393778944.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1246/nikkashi.1973.1636"}},{"identifier":{"@type":"URI","@value":"https://www.jstage.jst.go.jp/article/nikkashi1972/1973/9/1973_9_1636/_pdf"}},{"identifier":{"@type":"NAID","@value":"130004154735"}}],"dc:title":[{"@language":"en","@value":"Gaseous Ethylene Polymerization over Ziegler-Natta Catalyst in the Absence of Solvent"},{"@language":"ja","@value":"Ziegler-Natta系触媒によるエチレン無溶媒気相重合"}],"description":[{"type":"abstract","notation":[{"@language":"en","@value":"Using catalyst systems, TiC13-A1Et3 and TiC13-AIEt2Cl, polymerizations of ethylene were carried out in gas phase. The effects of hydrogen on the polymerization rate and on the average molecular weight of produced polymers have been investigated in connection with the kinetic behaviors of polymerization. The kinetic behaviors of polymerization are similar to those of the propylene polymerizations with the same catalyst systems. The effects of hydrogen on the rate of polymerization with these catalysts were different; a small but clear enhancement of the rate in the region of small amounts of hydrogen added was observed in the case with TiCl3-AIEt2Cl, while a monotonic depression of the rate with increasing amount of hydrogen added was observed with TiC13-AIEt3. The stationary polymerization rate in the latter case is expressed by, <BR>R0<BR>RH=------<BR>1+ PnH2<BR>and the average molecular weight is expressed by<BR>MOV<BR>MHV=------<BR>1+ PmH2<BR>with a=a6exp(-11 kca1/RT), b=b0exp(-5kcal/RT), n=O.6 and m=0.6. In these equations, superscripts H and O designate the values in the presence and absence of hydrogen, respectively. The latter expression can be also applied to the polymerization with TiCl3-AIEt2Cl, providing that m=O.5.<BR>The above results have been understood on the basis of supposition that dissociative hydrogen atoms on the catalyst surface are participating in the transfer of growing chains."},{"@language":"ja","@value":"Ziegler-Natta系触媒(TiCls-AIEtsおよびTiCls-AIEt2Cl)によるエチレン気相重合を速度論ならびに生成ポリマーの平均分子量の両面から検討した。また画素の分子量:制御作用杢調べた。重合の速度論的挙動は,本触媒系によるプロピレン気相重合の結果と一致した。水素共存下では,重合速度におよぼす水素添加の影響は両触媒系において異なった。TiCls-AIEt3系では,少量の水素添加(2 cmHg)により重合速度の増大が見られた。一方,TiCI3-AIEt2C1系では,重合速度は添加水素圧の増加にともない単調に低下し,そのようすは永素非存在下での定常速度を鵡とすれば次式で表わし傳た。<BR>R<BR>また生成ポリマーの平均分子量の水素圧依存性は,<BR>M<BR>となり,=oexp(11 kca R T),=, 6 exp(5kca1/R T), n=O. 6およびm O.6であった。生成ポリマ, tの平均分子量の水素圧依存性に関する上式は,TiCI, AIEt2CI系においても適用可能であり,m O,5であった。<BR>上記の結果から,三塩化チタン表面の解離吸着水素原子が生成ポリマー分子量の低下に関与しているものと推定した。"}],"abstractLicenseFlag":"disallow"}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1030285133292124928","@type":"Researcher","personIdentifier":[{"@type":"KAKEN_RESEARCHERS","@value":"40016639"},{"@type":"NRID","@value":"1000040016639"},{"@type":"NRID","@value":"9000000602386"},{"@type":"NRID","@value":"9000002476123"},{"@type":"NRID","@value":"9000004419654"},{"@type":"NRID","@value":"9000006304145"},{"@type":"NRID","@value":"9000004841948"},{"@type":"NRID","@value":"9000347104644"},{"@type":"NRID","@value":"9000001061085"},{"@type":"NRID","@value":"9000413770620"},{"@type":"NRID","@value":"9000000973315"},{"@type":"NRID","@value":"9000002921076"},{"@type":"NRID","@value":"9000253182714"},{"@type":"NRID","@value":"9000283198258"},{"@type":"NRID","@value":"9000017938518"},{"@type":"NRID","@value":"9000007750735"},{"@type":"NRID","@value":"9000000513496"},{"@type":"NRID","@value":"9000021265314"},{"@type":"NRID","@value":"9000283144488"},{"@type":"NRID","@value":"9000256014979"},{"@type":"NRID","@value":"9000256034241"},{"@type":"NRID","@value":"9000254933320"},{"@type":"NRID","@value":"9000256197661"},{"@type":"NRID","@value":"9000021299269"},{"@type":"NRID","@value":"9000252917124"},{"@type":"NRID","@value":"9000256045516"},{"@type":"NRID","@value":"9000000471689"},{"@type":"NRID","@value":"9000255706937"},{"@type":"NRID","@value":"9000254932889"},{"@type":"NRID","@value":"9000008619435"},{"@type":"NRID","@value":"9000018364348"},{"@type":"NRID","@value":"9000000400761"},{"@type":"NRID","@value":"9000004185451"},{"@type":"NRID","@value":"9000021283060"},{"@type":"NRID","@value":"9000021317700"},{"@type":"NRID","@value":"9000253114125"},{"@type":"NRID","@value":"9000253182372"},{"@type":"NRID","@value":"9000256380110"},{"@type":"NRID","@value":"9000257749504"},{"@type":"NRID","@value":"9000007894094"},{"@type":"NRID","@value":"9000000802108"},{"@type":"NRID","@value":"9000005065137"},{"@type":"NRID","@value":"9000347106540"},{"@type":"NRID","@value":"9000254398532"},{"@type":"NRID","@value":"9000256017539"},{"@type":"NRID","@value":"9000256419010"},{"@type":"NRID","@value":"9000017777944"},{"@type":"NRID","@value":"9000000102589"},{"@type":"NRID","@value":"9000000083171"},{"@type":"NRID","@value":"9000021192480"},{"@type":"NRID","@value":"9000021306696"},{"@type":"NRID","@value":"9000257764251"},{"@type":"NRID","@value":"9000257763626"},{"@type":"NRID","@value":"9000256035490"},{"@type":"NRID","@value":"9000021160224"},{"@type":"NRID","@value":"9000020232160"},{"@type":"NRID","@value":"9000254398975"},{"@type":"NRID","@value":"9000258695191"},{"@type":"NRID","@value":"9000256016260"},{"@type":"NRID","@value":"9000007595146"},{"@type":"NRID","@value":"9000347106494"},{"@type":"NRID","@value":"9000257700235"},{"@type":"NRID","@value":"9000256044171"},{"@type":"NRID","@value":"9000256032664"},{"@type":"NRID","@value":"9000256034412"},{"@type":"NRID","@value":"9000256198312"},{"@type":"NRID","@value":"9000283199184"},{"@type":"NRID","@value":"9000256050506"},{"@type":"NRID","@value":"9000257714820"},{"@type":"NRID","@value":"9000000797389"},{"@type":"NRID","@value":"9000021288230"},{"@type":"NRID","@value":"9000255825810"},{"@type":"NRID","@value":"9000256034106"},{"@type":"NRID","@value":"9000021245748"},{"@type":"NRID","@value":"9000254893174"},{"@type":"NRID","@value":"9000009853642"},{"@type":"NRID","@value":"9000015234664"},{"@type":"NRID","@value":"9000254799723"},{"@type":"RESEARCHMAP","@value":"https://researchmap.jp/read0069701"}],"foaf:name":[{"@language":"en","@value":"Doi Yoshiharu"},{"@language":"ja","@value":"土肥 義治"}],"jpcoar:affiliationName":[{"@language":"ja","@value":"東京工業大学工学部化学工学科"},{"@language":"en","@value":"Department of Chemical Engineering, Faculty of Engineering, Tokyo Institute of Technology"}]},{"@id":"https://cir.nii.ac.jp/crid/1410006850498360961","@type":"Researcher","personIdentifier":[{"@type":"NRID","@value":"9000256034413"}],"foaf:name":[{"@language":"en","@value":"Hsttori Yoshitaka"},{"@language":"ja","@value":"服部 兆隆"}],"jpcoar:affiliationName":[{"@language":"ja","@value":"東邦チタニウム株式会社"},{"@language":"en","@value":"Department of Chemical Engineering, Faculty of Engineering, Tokyo Institute of Technology"}]},{"@id":"https://cir.nii.ac.jp/crid/1410006850498360960","@type":"Researcher","personIdentifier":[{"@type":"NRID","@value":"9000021485088"},{"@type":"NRID","@value":"9000017630174"},{"@type":"NRID","@value":"9000254926673"}],"foaf:name":[{"@language":"en","@value":"Keii Tominaga"},{"@language":"ja","@value":"慶伊 富長"}],"jpcoar:affiliationName":[{"@language":"ja","@value":"東京工業大学工学部化学工学科"},{"@language":"en","@value":"Department of Chemical Engineering, Faculty of Engineering, Tokyo Institute of Technology"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"03694577"},{"@type":"EISSN","@value":"21850925"}],"prism:publicationName":[{"@language":"en","@value":"NIPPON KAGAKU KAISHI"},{"@language":"ja","@value":"日本化学会誌（化学と工業化学）"},{"@language":"en","@value":"Nippon Kagaku Kaishi"},{"@language":"ja","@value":"日化"},{"@language":"en","@value":"NIPPON KAGAKU KAISHI"},{"@language":"ja","@value":"日本化学会誌"}],"dc:publisher":[{"@language":"en","@value":"The Chemical Society of Japan"},{"@language":"ja","@value":"公益社団法人 日本化学会"}],"prism:publicationDate":"1973-09-10","prism:volume":"1973","prism:number":"9","prism:startingPage":"1636","prism:endingPage":"1640"},"reviewed":"false","url":[{"@id":"https://www.jstage.jst.go.jp/article/nikkashi1972/1973/9/1973_9_1636/_pdf"}],"availableAt":"1973-09-10","foaf:topic":[{"@id":"https://cir.nii.ac.jp/all?q=General%20Chemistry","dc:title":"General Chemistry"}],"dataSourceIdentifier":[{"@type":"JALC","@value":"oai:japanlinkcenter.org:0037406817"},{"@type":"CROSSREF","@value":"10.1246/nikkashi.1973.1636"},{"@type":"CIA","@value":"130004154735"}]}