Pub Date : 1988-09-01Epub Date: 2003-06-11DOI: 10.1016/0167-6989(88)90056-6
A.D. Pomogailo
Conditions for preparing polymer-supported metal complex catalysts by polymerization and copolymerization of metal-containing monomers (MCM), i.e., compounds with a metal-containing unit and a multiple bond capable of polymerization, were analysed. Three main types of MCM, their composition and structure, and peculiarities of their homo- and copolymerization are described. The main conversions different from polymerization of conventional monomers are highlighted. The structural arrangement of both the metal complexes and the MCM-based polymers are considered, as well as the conversion observed upon incorporation in the macrochain. The main directions of application of MCM and MCM-based polymers in catalysis are defined.
{"title":"Polymerization and copolymerization of metal-containing monomers as a means of preparing immobilized catalysts","authors":"A.D. Pomogailo","doi":"10.1016/0167-6989(88)90056-6","DOIUrl":"10.1016/0167-6989(88)90056-6","url":null,"abstract":"<div><p>Conditions for preparing polymer-supported metal complex catalysts by polymerization and copolymerization of metal-containing monomers (MCM), i.e., compounds with a metal-containing unit and a multiple bond capable of polymerization, were analysed. Three main types of MCM, their composition and structure, and peculiarities of their homo- and copolymerization are described. The main conversions different from polymerization of conventional monomers are highlighted. The structural arrangement of both the metal complexes and the MCM-based polymers are considered, as well as the conversion observed upon incorporation in the macrochain. The main directions of application of MCM and MCM-based polymers in catalysis are defined.</p></div>","PeriodicalId":101060,"journal":{"name":"Reactive Polymers, Ion Exchangers, Sorbents","volume":"9 1","pages":"Pages 109-117"},"PeriodicalIF":0.0,"publicationDate":"1988-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0167-6989(88)90056-6","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84274720","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1988-09-01Epub Date: 2003-06-11DOI: 10.1016/0167-6989(88)90052-9
Kiichi Takemoto, Koichi Kondo
Synthetic applications of polymer-bound purine and pyrimidine derivatives, based on their tautomerism, have been studied. The chloropyrimidine derivatives, which were highly reactive and could revert to the more stable lactam form, were particularly useful for dehydration and dehydrosulfanylation reactions. Alkoxypyrimidines were thermally cleaved to give olefins or esters, causing lactim to lactam transformation. Dissociation of alkylthio groups from thioalkylpurines and thioalkylpyrimidines took place under basic conditions to give olefins, indicating another example of tautomeric transformation.
{"title":"Synthetic applications of polymer-bound purine and pyrimidine bases","authors":"Kiichi Takemoto, Koichi Kondo","doi":"10.1016/0167-6989(88)90052-9","DOIUrl":"10.1016/0167-6989(88)90052-9","url":null,"abstract":"<div><p>Synthetic applications of polymer-bound purine and pyrimidine derivatives, based on their tautomerism, have been studied. The chloropyrimidine derivatives, which were highly reactive and could revert to the more stable lactam form, were particularly useful for dehydration and dehydrosulfanylation reactions. Alkoxypyrimidines were thermally cleaved to give olefins or esters, causing lactim to lactam transformation. Dissociation of alkylthio groups from thioalkylpurines and thioalkylpyrimidines took place under basic conditions to give olefins, indicating another example of tautomeric transformation.</p></div>","PeriodicalId":101060,"journal":{"name":"Reactive Polymers, Ion Exchangers, Sorbents","volume":"9 1","pages":"Pages 71-79"},"PeriodicalIF":0.0,"publicationDate":"1988-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0167-6989(88)90052-9","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73422040","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1988-09-01Epub Date: 2003-06-11DOI: 10.1016/0167-6989(88)90120-1
{"title":"Electrochemical synthesis of polymer films with immobilized enzymes","authors":"","doi":"10.1016/0167-6989(88)90120-1","DOIUrl":"https://doi.org/10.1016/0167-6989(88)90120-1","url":null,"abstract":"","PeriodicalId":101060,"journal":{"name":"Reactive Polymers, Ion Exchangers, Sorbents","volume":"9 1","pages":"Page 144"},"PeriodicalIF":0.0,"publicationDate":"1988-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0167-6989(88)90120-1","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138260492","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1988-09-01Epub Date: 2003-06-11DOI: 10.1016/0167-6989(88)90121-3
{"title":"Catalytic oxidation of sodium sulphide in the presence of carboxylic ion exchangers","authors":"","doi":"10.1016/0167-6989(88)90121-3","DOIUrl":"https://doi.org/10.1016/0167-6989(88)90121-3","url":null,"abstract":"","PeriodicalId":101060,"journal":{"name":"Reactive Polymers, Ion Exchangers, Sorbents","volume":"9 1","pages":"Page 144"},"PeriodicalIF":0.0,"publicationDate":"1988-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0167-6989(88)90121-3","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138260493","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1988-09-01Epub Date: 2003-06-11DOI: 10.1016/0167-6989(88)90112-2
{"title":"The synthesis and properties of polymeric imidazoles based on glycidyl methacrylate gels","authors":"","doi":"10.1016/0167-6989(88)90112-2","DOIUrl":"https://doi.org/10.1016/0167-6989(88)90112-2","url":null,"abstract":"","PeriodicalId":101060,"journal":{"name":"Reactive Polymers, Ion Exchangers, Sorbents","volume":"9 1","pages":"Page 141"},"PeriodicalIF":0.0,"publicationDate":"1988-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0167-6989(88)90112-2","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138260494","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1988-09-01Epub Date: 2003-06-11DOI: 10.1016/0167-6989(88)90080-3
{"title":"Effect of N-bases on reactions of macroporous polymer-supported phenylboronic acid with mandelic acid","authors":"","doi":"10.1016/0167-6989(88)90080-3","DOIUrl":"https://doi.org/10.1016/0167-6989(88)90080-3","url":null,"abstract":"","PeriodicalId":101060,"journal":{"name":"Reactive Polymers, Ion Exchangers, Sorbents","volume":"9 1","pages":"Pages 129-130"},"PeriodicalIF":0.0,"publicationDate":"1988-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0167-6989(88)90080-3","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138305271","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1988-09-01Epub Date: 2003-06-11DOI: 10.1016/0167-6989(88)90065-7
{"title":"Problems arising in the synthesis of highly loaded polymer-supported macropolycyclic ligands","authors":"","doi":"10.1016/0167-6989(88)90065-7","DOIUrl":"https://doi.org/10.1016/0167-6989(88)90065-7","url":null,"abstract":"","PeriodicalId":101060,"journal":{"name":"Reactive Polymers, Ion Exchangers, Sorbents","volume":"9 1","pages":"Pages 122-123"},"PeriodicalIF":0.0,"publicationDate":"1988-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0167-6989(88)90065-7","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138304881","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1988-09-01Epub Date: 2003-06-11DOI: 10.1016/0167-6989(88)90045-1
Ignazio Renato Bellobono, Elena Selli, Rossana Tacchi, Mara Zeni , Francesco Muffato
The possibility of immobilizing reagents and catalysts by photochemical grafting of their composites with an epoxy-diacrylate resin has been investigated. Two model systems have been examined: (i) the catalytic decomposition of aqueous sodium hypochlorite by cobalt peroxide, with oxygen production; (ii) the reaction of alkali metals with alcohols. For case (i) the catalyst was embedded, in the form of a mixture with 90% of zeolite 13X, into the photografted polymer matrix; while for case (ii) the alkali metal reagent, supported onto 90% of zeolite 13X, was incorporated into the microporous membrane. Kinetics of reaction (i) were studied in standard conditions (1.0 M NaOCl; 1.0 M NaCl; 0.25 M NaOH) between 288.2 to 318.2 K, and the relation between pseudp-first order kinetic constants and amount of catalyst incorporated into the membrane determined. Isotope effects for reaction (ii), relative to H2, D2, HD production, were measured with mixtures of deuterated and non-deuterated CH3OH(D), C2H5OH(D), n-C3H7OH(D), and i-C3H7OH(D) at 25 °C, as a function of volume percent of non-deuterated alkanols in the liquid phase.
For reaction (i) reactivity was found to be substantially the same in the membrane reactor as in ordinary chemical conditions: loss of catalytic activity did not exceed 15%. For reaction (ii) isotope effects, the origin of which is discussed, fully coincided with those measured in the absence of the polymer matrix.
研究了环氧-二丙烯酸酯树脂光化学接枝固定化试剂和催化剂的可能性。研究了两种模型系统:(i)过氧化钴催化分解次氯酸钠，产生氧气;(ii)碱金属与醇的反应。对于情形(i)，催化剂以含有90%沸石13X的混合物的形式嵌入到光接枝聚合物基体中;在案例(ii)中，将支撑在90%沸石13X上的碱金属试剂并入微孔膜中。在标准条件下(1.0 M NaOCl;1.0 M NaCl;0.25 M NaOH)在288.2 ~ 318.2 K之间，测定了准一级动力学常数与催化剂入膜量的关系。在25°C下，用氘化和非氘化CH3OH(D)、C2H5OH(D)、n-C3H7OH(D)和i-C3H7OH(D)的混合物测量了反应(ii)相对于H2、D2、HD的同位素效应，作为液相中非氘化烷醇体积百分比的函数。对于反应(i)，发现膜反应器中的反应活性与普通化学条件下的反应活性基本相同:催化活性损失不超过15%。对于反应(ii)的同位素效应，其起源已被讨论，与没有聚合物基质时的测量结果完全一致。
{"title":"Immobilization of reagents and catalysts by photochemical grafting onto polymers","authors":"Ignazio Renato Bellobono, Elena Selli, Rossana Tacchi, Mara Zeni , Francesco Muffato","doi":"10.1016/0167-6989(88)90045-1","DOIUrl":"10.1016/0167-6989(88)90045-1","url":null,"abstract":"<div><p>The possibility of immobilizing reagents and catalysts by photochemical grafting of their composites with an epoxy-diacrylate resin has been investigated. Two model systems have been examined: (i) the catalytic decomposition of aqueous sodium hypochlorite by cobalt peroxide, with oxygen production; (ii) the reaction of alkali metals with alcohols. For case (i) the catalyst was embedded, in the form of a mixture with 90% of zeolite 13X, into the photografted polymer matrix; while for case (ii) the alkali metal reagent, supported onto 90% of zeolite 13X, was incorporated into the microporous membrane. Kinetics of reaction (i) were studied in standard conditions (1.0 <em>M</em> NaOCl; 1.0 <em>M</em> NaCl; 0.25 <em>M</em> NaOH) between 288.2 to 318.2 K, and the relation between pseudp-first order kinetic constants and amount of catalyst incorporated into the membrane determined. Isotope effects for reaction (ii), relative to H<sub>2</sub>, D<sub>2</sub>, HD production, were measured with mixtures of deuterated and non-deuterated CH<sub>3</sub>OH(D), C<sub>2</sub>H<sub>5</sub>OH(D), n-C<sub>3</sub>H<sub>7</sub>OH(D), and i-C<sub>3</sub>H<sub>7</sub>OH(D) at 25 °C, as a function of volume percent of non-deuterated alkanols in the liquid phase.</p><p>For reaction (i) reactivity was found to be substantially the same in the membrane reactor as in ordinary chemical conditions: loss of catalytic activity did not exceed 15%. For reaction (ii) isotope effects, the origin of which is discussed, fully coincided with those measured in the absence of the polymer matrix.</p></div>","PeriodicalId":101060,"journal":{"name":"Reactive Polymers, Ion Exchangers, Sorbents","volume":"9 1","pages":"Pages 11-18"},"PeriodicalIF":0.0,"publicationDate":"1988-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0167-6989(88)90045-1","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77013090","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1988-09-01Epub Date: 2003-06-11DOI: 10.1016/0167-6989(88)90083-9
{"title":"Immobilization of 2,4-ionene on an XAD-2 resin, and its effect on the cobaltphthalocyanine-catalyzed oxidative coupling of thiol","authors":"","doi":"10.1016/0167-6989(88)90083-9","DOIUrl":"https://doi.org/10.1016/0167-6989(88)90083-9","url":null,"abstract":"","PeriodicalId":101060,"journal":{"name":"Reactive Polymers, Ion Exchangers, Sorbents","volume":"9 1","pages":"Page 131"},"PeriodicalIF":0.0,"publicationDate":"1988-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0167-6989(88)90083-9","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138305311","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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