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Îñíîâíûå ïîäõîäû ê ìîëåêóëÿðíîìó äèçàéíó ãåòåðîãåííûõ<br />
êàòàëèçàòîðîâ ÷åðåç ìåòàëëîïîëèìåðíûé ñèíòåç.<br />
Ëèòåðàòóðà<br />
1. Yu. I. Ermakov, V.A. Likholobov (Eds.). Homogeneous and Heterogeneous<br />
Catalysis. Utecht: VNU Science Press. 1987.<br />
2. D.Wohrle, A.D. Pomogailo. Metal Complexes and Metals in Macromolecules.<br />
Weinheim: Wiley-VCH. 2003.<br />
3. À.Ä. Ïîìîãàéëî. Êàòàëèç ãåòåðîãåíèçèðîâàííûìè ìåòàëëîïîëèìåðíûìè<br />
êîìïëåêñàìè: äîñòèæåíèÿ è ïåðñïåêòèâû. Êèíåòèêà è êàòàëèç. 2004. Ò.45,<br />
¹1. Ñ.67-114.<br />
48
ãèäðîãåíèçàöèè, âåðîÿòíî, íàèáîëåå ïðîñòûõ äëÿ òàêèõ ñèñòåì, â êà÷åñòâå ïðîìåæóòî÷íûõ îáíàðóæåíû ñîåäèíåíèÿ Ì-Í, óñòàíîâëåíî ñòóïåí÷àòîå ïðèñîåäèíåíèå âîäîðîäà, óìåíüøåíèå ñêîðîñòè ãèäðèðîâàíèÿ îëåôèíîâ â ïðèñóòñòâèè ïðî÷íî êîîðäèíèðóþùèõñÿ ñ ìåòàëëîöåíòðîì àöåòèëåíîâûõ ëèáî ñîïðÿæåííûõ äèåíîâûõ ñóáñòðàòîâ, îòðàâëåíèå îäíîòèïíûìè êàòàëèòè÷åñêèìè ÿäàìè è ò.ï. Ýòî æå îòíîñèòñÿ è ê ïîëèìåðèçàöèîííûì ïðîöåññàì. ×àñòî óäàåòñÿ âûäåëèòü èíòåðìåäèàòû, ìåòîäàìè íåðàçðóøàþùåãî êîíòðîëÿ èçó÷èòü ñîñòîÿíèå ïåðåõîäíîãî ìåòàëëà, ñîîòíåñòè êàòàëèòè÷åñêèå ñâîéñòâà ñ åãî âàëåíòíûì ñîñòîÿíèåì, äèñïåðñíîñòüþ Ì 0 , åãî äîëåé íà ïîâåðõíîñòè è äð.[3]. Àíàëèçèðóþòñÿ ñëåäóþùèå ÿâëåíèÿ â êàòàëèçå ïîëèìåðèììîáèëèçîâàííûìè êîìïëåêñàìè. Òåìïåðàòóðíûé ôàêòîð. Àíîìàëüíàÿ àððåíèóñîâñêàÿ çàâèñèìîñòü ñêîðîñòè ðåàêöèè, êàòàëèçèðóåìîé èììîáèëèçîâàííûìè ìåòàëëîêîìïëåêñàìè: ñêîðîñòü ðåàêöèè êàê ïðàâèëî óâåëè÷èâàåòñÿ äî òåìïåðàòóðû ñòåêëîâàíèÿ ïîëèìåðà, à çàòåì ðåçêî óìåíüøàåòñÿ. Ýòî ñâÿçàíî ñ èçìåíåíèåì ïîäâèæíîñòè ïîëèìåðíûõ ñåãìåíòîâ è ñâÿçàííûõ ñ íèìè àêòèâíûõ öåíòðîâ. Êîíöåíòðàöèîííûå ýôôåêòû. Ñóùåñòâåííîå âëèÿíèå íà êàòàëèòè÷åñêèå ñâîéñòâà îêàçûâàåò íå òîëüêî îáùàÿ êîíöåíòðàöèÿ èììîáèëèçîâàííûõ êîìïëåêñîâ, íî è èõ ðàñïðåäåëåíèå íà ïîëèìåðíîé ìàòðèöå (òîïîãðàôèÿ). Êîîïåðàòèâíûå ýôôåêòû. Ðàçìåðíûå ýôôåêòû. Âûñîêàÿ ëîêàëüíàÿ êîíöåíòðàöèÿ ñóáñòðàòà âîêðóã àêòèâíîãî öåíòðà (ò.í. ñóáñòðàòíîå îáîãàùåíèå). Ñïåöèôèêà êàòàëèçà ïîëèìåð-èììîáèëèçîâàííûìè êëàñòåðàìè. Íàíîêàòàëèç. Îñîáåííîñòè ãåòåðîãåíèçàöèè ìåòàëëîöåíîâ. Ïîëèìåð-îïîñðåäîâàííîå êîíñòðóèðîâàíèå áèôóíêöèîíàëüíûõ êàòàëèçàòîðîâ. Âîçìîæíîñòü âûäåëåíèÿ è èññëåäîâàíèÿ ïðîìåæóòî÷íûõ è àêòèâíûõ êîìïëåêñîâ. Àñèììåòðè÷åñêàÿ èíäóêöèÿ 47
Îñíîâíûå ïîäõîäû ê ìîëåêóëÿðíîìó äèçàéíó ãåòåðîãåííûõ êàòàëèçàòîðîâ ÷åðåç ìåòàëëîïîëèìåðíûé ñèíòåç. Ëèòåðàòóðà 1. Yu. I. Ermakov, V.A. Likholobov (Eds.). Homogeneous and Heterogeneous Catalysis. Utecht: VNU Science Press. 1987. 2. D.Wohrle, A.D. Pomogailo. Metal Complexes and Metals in Macromolecules. Weinheim: Wiley-VCH. 2003. 3. À.Ä. Ïîìîãàéëî. Êàòàëèç ãåòåðîãåíèçèðîâàííûìè ìåòàëëîïîëèìåðíûìè êîìïëåêñàìè: äîñòèæåíèÿ è ïåðñïåêòèâû. Êèíåòèêà è êàòàëèç. 2004. Ò.45, ¹1. Ñ.67-114. 48
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