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ÐÎËÜ ÍÎÑÈÒÅËÅÉ Â ÔÎÐÌÈÐÎÂÀÍÈÈ ÀÊÒÈÂÍÎÃÎ ÊÎÌÏÎÍÅÍÒÀ ÍÀÍÅÑÅÍÍÛÕ ÊÀÒÀËÈÇÀÒÎÐÎÂ ÏÎËÈÌÅÐÈÇÀÖÈÈ ÎËÅÔÈÍÎÂ Çàõàðîâ Â.À. Èíñòèòóò êàòàëèçà èì. Ã.Ê. Áîðåñêîâà ÑÎ ÐÀÍ, Íîâîñèáèðñê E-mail: zva@catalysis.nsk.su Ïèîíåðñêèå ðàáîòû Þ.È. Åðìàêîâà, âûïîëíåííûå åùå â êîíöå 60õíà÷àëå 70õ ãîäîâ ïðîøëîãî âåêà, âíåñëè ñóùåñòâåííûé âêëàä â ðàçâèòèå ïðåäñòàâëåíèé îá àêòèâíîì êîìïîíåíòå íàíåñåííûõ êàòàëèçàòîðîâ ïîëèìåðèçàöèè êàê ïîâåðõíîñòíûõ ñîåäèíåíèÿõ ïåðåõîäíûõ ìåòàëëîâ, îáðàçóþùèõñÿ ïðè âçàèìîäåéñòâèè íàíîñèìîãî êîìïëåêñà ñ ïîâåðõíîñòíûìè ôóíêöèîíàëüíûìè ãðóïïàìè íîñèòåëÿ. Ýòè ïðåäñòàâëåíèÿ ïîñëóæèëè îñíîâîé äëÿ ðàçðàáîòêè è èññëåäîâàíèÿ áîëüøîãî ÷èñëà íîâûõ íàíåñåííûõ êàòàëèçàòîðîâ ïîëèìåðèçàöèè ðàçëè÷íîãî ñîñòàâà. Â íàñòîÿùåì ñîîáùåíèè îáñóæäàþòñÿ èçâåñòíûå ëèòåðàòóðíûå äàííûå è ïðåäñòàâëåíû íîâûå ýêñïåðèìåíòàëüíûå ðåçóëüòàòû, íà îñíîâàíèè êîòîðûõ ðàññìàòðèâàþòñÿ ðàçëè÷íûå ñõåìû ôîðìèðîâàíèÿ àêòèâíîãî êîìïîíåíòà íàíåñåííûõ êàòàëèçàòîðîâ ïîëèìåðèçàöèè îëåôèíîâ ðàçëè÷íîãî ñîñòàâà. Ìåòîäîì ÈÊÑÄÎ ïîëó÷åíû äàííûå î ôîðìèðîâàíèè àêòèâíîãî êîìïîíåíòà îêèñíîõðîìîâîãî êàòàëèçàòîðà ïðè âçàèìîäåéñòâèè ïàðîâ CrO 3 ñ ñèëèêàãåëåì, ïðåäâàðèòåëüíî äåãèäðîêñèëèðîâàííûì ïðè òåìïåðàòóðàõ 250-800 î Ñ. Ïîêàçàíî, ÷òî CrO 3 âçàèìîäåéñòâóåò ñ ãèäðîêñèëüíûìè ãðóïïàìè ñèëèêàãåëÿ ñ îáðàçîâàíèåì õðîìàòîâ ðàçëè÷íîãî ñîñòàâà (ìîíîõðîìàòîâ, äèõðîìàòîâ è ïîëèõðîìàòîâ). Ìîíîõðîìàòû îáðàçóþòñÿ ïðè èñïîëüçîâàíèè ñèëèêàãåëÿ, äåãèäðîêñèëèðîâàííîãî ïðè 250 î Ñ, ìîíî- è áèõðîìàòû â ñëó÷àå ñèëèêàãåëÿ, äåãèäðîêñèëèðîâàííîãî ïðè 400 î Ñ, áèõðîìàòû è ïîëèõðîìàòû îáðàçóþòñÿ íà ñèëèêàãåëå, äåãèäðîêñèëèðîâàííîì ïðè 800 î Ñ. Íà îñíîâàíèè ýòèõ äàííûõ è äàííûõ îá àêòèâíîñòè êàòàëèçàòîðîâ â ïîëèìåðèçàöèè ýòèëåíà ïðåäïîëàãàåòñÿ, ÷òî àêòèâíûì êîìïîíåíòîì îêèñíîõðîìîâûõ êàòàëèçàòîðîâ ïîëèìåðèçàöèè ÿâëÿþòñÿ ïîâåðõíîñòíûå äèõðîìàòû è ïîëèõðîìàòû. 13
Ñóùåñòâåííî èíûå ñõåìû ôîðìèðîâàíèÿ àêòèâíîãî êîìïîíåíòà ðåàëèçóþòñÿ â íàíåñåííûõ êàòàëèçàòîðàõ íà îñíîâå ìåòàëëîöåíîâûõ (öèðêîíîöåíîâûõ) êîìïëåêñîâ. Â ýòîì ñëó÷àå â êà÷åñòâå àêòèâíîãî êîìïîíåíòà âûñòóïàþò ïîâåðõíîñòíûå êàòèîíîïîäîáíûå êîìïëåêñû öèðêîíèÿ, îáðàçîâàíèå êîòîðûõ ïðîèñõîäèò ñ ó÷àñòèåì ëüþèñîâñêèõ êèñëîòíûõ öåíòðîâ íîñèòåëåé. Ïðåäñòàâëåíû ýêñïåðèìåíòàëüíûå äàííûå è ðàññìîòðåíû ñõåìû ôîðìèðîâàíèÿ òàêèõ ñòðóêòóð ïðè èñïîëüçîâàíèè â êà÷åñòâå íîñèòåëÿ ñèëèêàãåëÿ ñ íàíåñåííûì íà íåãî ïîëèìåòèëàëþìîêñàíîì (íîñèòåëü SiO 2 /MAO), îêñèäîâ àëþìèíèÿ ñ ðàçëè÷íîé ëüþèñîâñêîé êèñëîòíîñòüþ è âûñîêîäèñïåðñíîãî äèõëîðèäà ìàãíèÿ. Íàéäåíî, ÷òî ïðèðîäà íîñèòåëÿ ñóùåñòâåííî âëèÿåò íà ðåàêöèîííóþ ñïîñîáíîñòü àêòèâíûõ öåíòðîâ ýòèõ êàòàëèçàòîðîâ, ÷òî ïðèâîäèò ê ðåçêîìó èçìåíåíèþ ìîëåêóëÿðíîé ñòðóêòóðû ïîëèìåðà ïðè ïåðåõîäå îò íàíåñåííûõ êàòàëèçàòîðîâ SiO 2 (MAO)/öèðêîíîöåí ê íàíåñåííûì öèðêîíîöåíîâûì ñèñòåìàì, ïðèãîòîâëåííûì ñ èñïîëüçîâàíèåì â êà÷åñòâå íîñèòåëåé îêñèäà àëþìèíèÿ è äèõëîðèäà ìàãíèÿ. Èñêëþ÷èòåëüíûì ñëó÷àåì, êîãäà ïðèðîäà íîñèòåëÿ ïðàêòè÷åñêè íå âëèÿåò íà ñîñòàâ àêòèâíîãî êîìïîíåíòà, ÿâëÿþòñÿ êàòàëèçàòîðû, ïîëó÷àåìûå íàíåñåíèåì áèñ(èìèíî)ïèðèäèëüíîãî êîìïëåêñà Fe(II) íà ñèëèêàãåëü (âçàèìîäåéñòâèå ñ ãèäðîêñèëüíûìè ãðóïïàìè) è òàêèå íîñèòåëè êàê îêñèä àëþìèíèÿ è äèõëîðèä ìàãíèÿ (âçàèìîäåéñòâèå ñ ëüþèñîâñêèìè êèñëîòíûìè öåíòðàìè). Â ýòîì ñëó÷àå ðåàêöèîííàÿ ñïîñîáíîñòü àêòèâíûõ öåíòðîâ â ïîëèìåðèçàöèè ýòèëåíà è ìîëåêóëÿðíàÿ ñòðóêòóðà ïîëó÷àåìîãî ïîëèìåðà ïðàêòè÷åñêè íå çàâèñÿò îò ïðèðîäû íîñèòåëÿ. 14
Page 1 and 2: Èíñòèòóò êàòàëèçà
Page 3 and 4: Îðãàíèçàòîðû êîíôå
Page 6 and 7: SINGLE SITE CATALYSTS - IDEAL MODEL
Page 8 and 9: ÑÒÀÁÈËÈÇÈÐÎÂÀÍÍÛÅ
Page 10 and 11: ÈÇÓ×ÅÍÈÅ ÌÅÕÀÍÈÇÌÎ
Page 12 and 13: Ñðàâíåíèå äèíàìèêè
Page 16 and 17: ÒÐÈÈÇÎÁÓÒÈËÀËÞÌÈÍ
Page 18: ÏÐÎÃÐÅÑÑ Â ÎÁËÀÑÒÈ
Page 22 and 23: MOLECULAR DESIGN OF NEW TYPE OF CAT
Page 24 and 25: PALLADIUM AND COBALT CATALYZED OXID
Page 26 and 27: ÍÎÂÛÉ ÏÎÄÕÎÄ Ê ÔÎÐÌ
Page 28 and 29: Èîííûé îáìåí Al 2O 3 2+
Page 30 and 31: êîòîðûõ èììîáèëèçî
Page 32 and 33: ïðèâåäøàÿ ê ñîçäàí
Page 34 and 35: ÐÀÇÐÀÁÎÒÊÀ ÊÀÒÀËÈÇ
Page 36 and 37: ðàñïðåäåëåíèÿ ÷àñò
Page 38 and 39: ÷òî äåôåêòû ýòîãî â
Page 40 and 41: ÈÇÓ×ÅÍÈÅ ÔÎÐÌÈÐÎÂÀ
Page 42 and 43: Ñîäåðæàíèå äèîêñèä
Page 44 and 45: Òàáë. 1. Äàííûå õåìî
Page 46 and 47: ñëàáîñâÿçàííîì ñîñ
Page 48 and 49: ãèäðîãåíèçàöèè, âå
Page 50 and 51: ÑÅËÅÊÒÈÂÍÀß ÎÊÈÑËÈ
Page 52 and 53: ÌÎÄÈÔÈÖÈÐÎÂÀÍÈÅ ÀË
Page 54 and 55: ãèäðîîêèñüþ àëþìèí
Page 56 and 57: ïðîìûñëîâûõ ìèíè-Í
Page 58 and 59: ÏÎËÓ×ÅÍÈÅ ÆÈÄÊÈÕ Ó
Page 60 and 61: ÈÇÎÌÅÐÈÇÀÖÈß ÓÃËÅÂ
Page 62 and 63: ÊÀÒÀËÈÒÈ×ÅÑÊÈÅ ÏÐÅ
Page 64 and 65:
îáðàçîâàíèÿ öèêëîï
Page 66 and 67:
ïðåèìóùåñòâåííîå ï
Page 68 and 69:
ÈÍÒÅÐÊÀËÈÐÎÂÀÍÍÛÅ
Page 70 and 71:
ÊÐÅÊÈÍÃ Ñ 10 -Ñ 15 - ÀË
Page 72 and 73:
Â ÈÊ- ñïåêòðàõ àäñî
Page 74 and 75:
Ïî âëèÿíèþ íà êàòàë
Page 76 and 77:
Ïðåîáëàäàþùèìè ïðè
Page 78 and 79:
ÃÈÄÐÎÏÅÐÅÐÀÁÎÒÊÀ Í
Page 80 and 81:
Ïîñëå ãèäðîïåðåðàá
Page 82 and 83:
óñëîâèé ïðîöåññà î
Page 84 and 85:
åå ðåàêöèè. Èìåííî
Page 86 and 87:
í-C 4 H 8 + Pd II + Í 2 Î ⎯⎯
Page 88 and 89:
ïðîäóêòîâ. Íàïðèìå
Page 90 and 91:
×ÈÑËÎ È ÐÅÀÊÖÈÎÍÍÀ
Page 92 and 93:
Äëÿ âñåõ ñèñòåì îïð
Page 94 and 95:
ñèíäèîòàêòè÷åñêèé
Page 96 and 97:
ñâÿçåé è ýêâèâàëåí
Page 98 and 99:
ÝËÅÊÒÐÎÕÈÌÈ×ÅÑÊÈÉ
Page 100 and 101:
ÑÒÅÍÄÎÂÛÅ ÄÎÊËÀÄÛ
Page 102 and 103:
ÈÇÓ×ÅÍÈÅ ÌÅÕÀÍÈÇÌÀ
Page 104 and 105:
Ðèñóíîê 2. Äèôôåðåí
Page 106 and 107:
âòîðîé ïî èíòåíñèâ
Page 108 and 109:
êîëåáàíèÿ â ìîñòèê
Page 110 and 111:
ÑÒÐÓÊÒÓÐÍÎ-ÎÐÃÀÍÈÇ
Page 112 and 113:
Òàáëèöà 2. Ðàñïðåäå
Page 114 and 115:
50 Rate/10 -8 mol g -1 s -1 40 30 2
Page 116 and 117:
ÐÀÇÐÀÁÎÒÊÀ È ÈÑÑËÅ
Page 118 and 119:
êèñëîðîäó øïèíåëè C
Page 120 and 121:
èçîìåðèçàöèè í-ãåê
Page 122 and 123:
ÃÅÍÅÇÈÑ ÔÀÇÎÂÎÃÎ Ñ
Page 124 and 125:
óïëîòíåíèÿ çàïîëíÿ
Page 126 and 127:
Ïðèðîäà èñõîäíûõ ñ
Page 128 and 129:
ÏÎËÈÌÅÐÍÛÅ ÐÎÄÈÉÑÎ
Page 130 and 131:
ïðîìîòîðîâ. Â ðàáîò
Page 132 and 133:
ôîðìàëüäåãèä, äè- è
Page 134 and 135:
Äàëüíåéøàÿ äåãèäðî
Page 136 and 137:
ÌÅÒÎÄÛ ÐÅÃÓËÈÐÎÂÀÍ
Page 138 and 139:
ÑÈÍÒÅÇ È ÈÑÑËÅÄÎÂÀ
Page 140 and 141:
ÂËÈßÍÈÅ ÎÁÐÀÁÎÒÎÊ
Page 142 and 143:
Íàðÿäó ñ óâåëè÷åíè
Page 144 and 145:
îáîðîòîâ êàòàëèçàò
Page 146 and 147:
Íàìè ðàçðàáîòàí ïð
Page 148 and 149:
äî 0,5 ÌÏà. Ôîðìû çàâ
Page 150 and 151:
Î ÏÐÎÖÅÑÑÀÕ ÏÐÅÄÎÒ
Page 152 and 153:
ÐÀÇÐÀÁÎÒÊÀ ÊÀÒÀËÈÒ
Page 154 and 155:
ÏÐÅÂÐÀÙÅÍÈß ÑÒÈÐÎË
Page 156 and 157:
ÆÈÄÊÎÔÀÇÍÀß ÈÇÎÌÅÐ
Page 158 and 159:
ÍÅÏÎËÍÎÅ ÎÊÈÑËÅÍÈÅ
Page 160 and 161:
ÍÀÍÎÑÒÐÓÊÒÓÐÍÛÅ ÊÀ
Page 162 and 163:
ÃÈÄÐÎÊÎÍÂÅÐÑÈß Í-Ã
Page 164 and 165:
ðàñòåò ñ ïîâûøåíèå
Page 166 and 167:
Èíäèâèäóàëüíàÿ àäñ
Page 168 and 169:
â ÑÍÃ ñíèæàåò òåìïå
Page 170 and 171:
Ïðîöåññ áèôîðìèíãà
Page 172 and 173:
ÈÑÏÎËÜÇÎÂÀÍÈÅ ÊÀÒÀ
Page 174 and 175:
Ïîâûøåíèå äàâëåíèÿ
Page 176 and 177:
Èç ïðèðîäíîãî öåîë
Page 178 and 179:
ÄÅÃÈÄÐÈÐÎÂÀÍÈÅ ËÅÃ
Page 180 and 181:
ðîäèåâûå è ðóòåíèå
Page 182 and 183:
Òàáëèöà 1. Âëèÿíèå ï
Page 184 and 185:
ÈÑÑËÅÄÎÂÀÍÈÅ ÏÐÎÖÅ
Page 186 and 187:
ÏÅÐÅÐÀÁÎÒÊÀ ÄÈÑÒÈË
Page 188 and 189:
ÃÈÄÐÎÏÅÐÅÐÀÁÎÒÊÀ í
Page 190 and 191:
ÊÐÅÊÈÍÃ ÒßÆÅËÎÃÎ Í
Page 192 and 193:
óãëåðîäà â äèîêñèä
Page 194 and 195:
ïîäà÷è ñûðüÿ 1,0-1,5 ÷
Page 196 and 197:
ëîêàëèçîâàííûå íà
Page 198 and 199:
CÓËÜÔÎÊÀÒÈÎÍÈÒÛ ÍÀ
Page 200 and 201:
Ïðè íàëè÷èè â ñèñòå
Page 202 and 203:
ãåêñàäåêàíîë-2 (ïðè
Page 204 and 205:
óñëîâèÿ îêèñëåíèÿ
Page 206 and 207:
ãàçîâ òåðìîäåñîðáö
Page 208 and 209:
ïîëèìåðèçàöèè ýòèë
Page 210 and 211:
ÊÀÒÀËÈÇÈÐÓÅÌÎÅ ÏÀË
Page 212 and 213:
ÈÑÑËÅÄÎÂÀÍÈÅ ÂËÈßÍ
Page 214 and 215:
ÄÈÌÅÐÈÇÀÖÈß ÝÒÈËÅÍ
Page 216 and 217:
ÈÇÓ×ÅÍÈÅ ÏÐÎÖÅÑÑÎÂ
Page 218 and 219:
ÐÀÑÏÐÅÄÅËÅÍÈÅ ÂÍÓÒ
Page 220 and 221:
ÃÎÌÎ - È ÑÎÏÎËÈÌÅÐÈ
Page 222 and 223:
ÏÎËÈÌÅÐÈÇÀÖÈß ÝÒÈË
Page 224 and 225:
Ñ ïðèìåíåíèåì ìåòî
Page 226 and 227:
àìîðôíûìè è êðèñòà
Page 228 and 229:
ÑÏÈÑÎÊ ÀÄÐÅÑÎÂ Ó×À
Page 230 and 231:
ÃÐÈÃÎÐÜÅÂÀ Íåëëè Ã
Page 232 and 233:
ÊÀÐÛÌÎÂÀ Ðàøèäà Õà
Page 234 and 235:
ÌÓÍØÈÅÂÀ Ìèíà Êåðè
Page 236 and 237:
ÓÑÌÀÍÎÂÀ Ìàíçóðà Ì
Page 238 and 239:
ÑÎÄÅÐÆÀÍÈÅ ÊËÞ×ÅÂÛ
Page 240 and 241:
Ñåêöèÿ II Êàòàëèç â
Page 242 and 243:
CÄ-I-3 CÄ-I-4 CÄ-I-5 CÄ-I-6 CÄ
Page 244 and 245:
CÄ-II-10 Çàêèðîâà À.Ã.,
Page 246 and 247:
CÄ-III-4 Ìèêåíàñ T.Á., Å
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