➨୍⦅ ◊✲ືྥ㹙㹛

1-࣊࢟ࢭࣥ㑅ᢥ〇㐀ゐ፹ࡢ㛤Ⓨ୕஭໬Ꮫ㸦ᰴ㸧 ᕷᕝ┿୍㑻 ▼஭⪷୍ ୰㔝㝯ᚿ ⸨⏣↷඾㸯㸬ࡣࡌࡵ࡟㸯-࣊࢟ࢭࣥࡣȘ-࢜ࣞࣇ࢕ࣥࢆ௦⾲ࡍࡿ໬Ꮫရࡢ 1 ࡘ࡛࠶ࡾࠊ┤㙐≧పᐦᗘ࣏࢚ࣜࢳࣞࣥ㸦LLDPE㸧࡞࡝ࡢඹ㔜ྜ⏝ࣔࣀ࣐࣮࡜ࡋ࡚㔜せ࡛࠶ࡿࠋ୍⯡࡟ࠊ1-࣊࢟ࢭࣥࡣ࢚ࢳࣞࣥࡢ࢜ࣜࢦ࣓ࣜ໬཯ᛂ࡟ࡼࡾ〇㐀ࡉࢀࡓȘ-࢜ࣞࣇ࢕ࣥΰྜ≀࠿ࡽศ㞳ࡋ࡚ᚓࡽࢀࡿࠋ୍᪉ࠊ୕஭໬Ꮫ㸦ᰴ㸧ࡣ࢚ࢳࣞࣥࡢ㑅ᢥⓗ୕㔞໬ゐ፹ࢆ㛤Ⓨࡋࠊᕤᴗ໬࡟ᡂຌࡋࡓࠋ1) ᮏ✏࡛ࡣࠊ1-࣊࢟ࢭࣥ㑅ᢥ〇㐀ゐ፹ࡢ㛤Ⓨ࡟ࡘ࠸࡚⤂௓ࡍࡿࠋ㸰㸬࢜ࣞࣇ࢕ࣥ㢮ࡢ〇㐀ᢏ⾡࣏࢚ࣜࢳࣞࣥ㸦PE㸧࠾ࡼࡧ࣏ࣜࣉࣟࣆࣞࣥ㸦PP㸧࡟௦⾲ࡉࢀࡿ࣏ࣜ࢜ࣞࣇ࢕ࣥࡣࠊ࢚ࢳࣞࣥࡸࣉࣟࣆࣞࣥࢆ୺ཎᩱ࡜ࡋࠊඹ㔜ྜ⏝ࣔࣀ࣐࣮࡜ࡋ࡚ 1-ࣈࢸࣥࠊ1-࣊࢟ࢭࣥࡸ 1-࢜ࢡࢸࣥ࡞࡝ࢆ⏝࠸࡚〇㐀ࡉࢀ࡚࠸ࡿࠋࡇࢀࡽࡢ࣏ࣜ࢜ࣞࣇ࢕ࣥ〇㐀ࡢ࣮࢟࡜࡞ࡿ࢜ࣞࣇ࢕ࣥ㢮ࡣࠊ
ᅗ 1 ࡟♧ࡍࡼ࠺࡞✀ࠎࡢ᪉ἲ࡛〇㐀ࡉࢀࡿࠋࢼࣇࢧࡢࢫࢳ࣮࣒ࢡࣛࢵ࢟ࣥࢢ㸦↓ゐ፹㸧ࡸ㍍Ἔࡢὶື᥋ゐศゎ㸦USY ᆺࢮ࢜ࣛ࢖ࢺゐ፹㸧࡟ࡼࡾࠊ࢚ࢳࣞࣥࠊࣉࣟࣆࣞࣥ࠾ࡼࡧ 1-ࣈࢸࣥࡀ〇㐀ࡉࢀࡿࠋ㏆ᖺ࡛ࡣࢩ࢙࣮ࣝ㠉࿨࡟ࡼࡾኳ↛࢞ࢫࡢ᭷ຠ฼⏝ࡀ୍ẁ࡜㐍ࢇ࡛࠾ࡾࠊ࢚ࢱࣥࡢࢫࢳ࣮࣒ࢡࣛࢵ࢟ࣥࢢ㸦↓ゐ፹㸧࡟ࡼࡿ࢚ࢳࣞࣥࡢ〇㐀㔞ࡀⴭࡋࡃቑຍࡋࠊࣉࣟࣃࣥ⬺Ỉ⣲㸦Pt-Sn ゐ፹࡞࡝㸧࡟ࡼࡿࣉࣟࣆࣞࣥࡢ〇㐀㔞ࡶቑ኱ࡋ࡚࠸ࡿࠋࡲࡓࠊ࣓ࢱࣥࡸ▼Ⅳࢆཎᩱ࡜ࡋ࡚ᚓࡽࢀࡿྜᡂ࢞ࢫ㸦CO/H2㸧࠿ࡽࠊ࣓ࢱࣀ࣮ࣝࢆ⤒⏤ࡋ࡚࢚ࢳࣞࣥࡸࣉࣟࣆࣞࣥ㸦SAPO-34 ゐ፹ࠊZSM-5 ゐ፹㸧ࡀ〇㐀ࡉࢀࡿࡼ࠺࡟࡞ࡗ࡚ࡁࡓࠋࡉࡽ࡟ࠊ࣓ࢱࢭࢩࢫ཯ᛂ࡟ࡼࡿ࢚ࢳࣞࣥ࡜ࣈࢸࣥ࠿ࡽࡢࣉࣟࣆࣞࣥ〇㐀㸦WO3/SiO2 ゐ፹㸧ࡸ࢚ࢳࣞࣥࡢ㑅ᢥⓗ஧㔞໬࡟ࡼࡿ 1-ࣈࢸࣥࡢ〇㐀㹙Ti(OBu)4 ゐ፹㹛ࡀᕤᴗ໬ࡉࢀ࡚࠸ࡿࠋ᭱㏆ࠊ୕஭໬Ꮫࡣ࢚ࢳࣞࣥࡢ㑅ᢥⓗ஧㔞໬཯ᛂ㸦Ni/Al2O3 ゐ፹㸧ࠊ࠾ࡼࡧ࢚ࢳࣞࣥ࡜ࣈࢸࣥࡢ࣓ࢱࢭࢩࢫ཯ᛂ㸦WO3/SiO2 ゐ፹㸧ࢆ㐃⥆Ẽ┦཯ᛂ࡛ᐇ᪋ࡋ࡚ࠊ࢚ࢳࣞࣥ࠿ࡽࣉࣟࣆࣞࣥࢆ㑅ᢥⓗ࡟ྜᡂࡍࡿᢏ⾡ࢆ㛤Ⓨࡋࡓࠋ2) ࡲࡓࠊ࣓ࢱࣀ࣮ࣝ࡜࢚ࢳࣞࣥ࠿ࡽࡢࣉࣟࣆࣞࣥ〇㐀㸦⤖ᬗᛶ࢔࣑ࣝࣀ࣎ࣟࢩࣜࢣ࣮ࢺゐ፹࡞࡝㸧ࡸ࢚ࢳࣞࣥ࠿ࡽ┤᥋ࣉࣟࣆࣞࣥࢆ〇㐀㸦CHA ᆺ࢔࣑ࣝࣀࢩࣜࢣ࣮ࢺゐ፹㸧ࡍࡿᢏ⾡ࡢ㛤Ⓨࡶ㐍ࡵࡽࢀ࡚࠸ࡿࠋ3)
୍᪉ࠊ1-࣊࢟ࢭࣥ࡜ 1-࢜ࢡࢸࣥࡣࠊ୺࡜ࡋ࡚࢚ࢳࣞࣥࡢ࢜ࣜࢦ࣓ࣜ໬཯ᛂ࡟ࡼࡾ〇㐀ࡉࢀ࡚ ࠸ ࡿ ࠋ 4)  Chevron Phillips 㸦 Et3Al ゐ ፹ 㸸 1 ẁ ཯ ᛂ 㸧ࠊ Shell 㸦 Ni ゐ ፹ 㸧ࠊ ฟ ග ⯆ ⏘^ZrCl4/Et3Al/[(C2H5)2AlCl-(C2H5)AlCl2]ゐ፹㹻ࠊSABIC/LINDE㹙Zn(IV)࢝ࣝ࣎ࣥ㓟ሷ/࢔ࣝ࢟ࣝ࢔࣑ࣝࢽ࣒࢘ゐ፹㹛࡟ࡼࡾඃࢀࡓᕤᴗࣉࣟࢭࢫࡀ☜❧ࡉࢀ࡚࠸ࡿࡀࠊఱࢀࡢࣉࣟࢭࢫ࡟࠾࠸࡚ࡶ⏕ᡂ≀࡛࠶ࡿȘ-࢜ࣞࣇ࢕ࣥࡣࠊSchulz-Flory ศᕸ࡟ࡋࡓࡀࡗࡓⅣ⣲ᩘ 4 ࠿ࡽ 20 ⛬ᗘࡢȘ࢜ࣞࣇ࢕ࣥΰྜ≀࡜࡞ࡿ㸦౛㸸1-࣊࢟ࢭࣥ㑅ᢥ⋡ࠥ15wt%㸧ࠋINEOS ࡣࠊEt3Al ゐ፹ࢆ⏝࠸࡚ᡂ㛗཯ᛂ࡜஺᥮཯ᛂࢆูࡢ཯ᛂჾ࡛⾜࠺㸦2 ẁ཯ᛂ㸧ࡇ࡜࡟ࡼࡾ Poisson ศᕸ࡟ࡋࡓࡀࡗࡓȘ-࢜ࣞࣇ࢕ࣥࢆ〇㐀ࡋࠊࡉࡽ࡟ 1-ࣈࢸࣥࢆࣜࢧ࢖ࢡࣝࡍࡿࡇ࡜࡟ࡼࡾࠊ1-࣊࢟ࢭࣥࡸ 1-࢜ࢡࢸ㸫㸫ᕤᴗゐ፹ὀ┠ᢏ⾡ࣥࡢ㑅ᢥ⋡ࢆ 30wt%ᙅࡲ࡛ྥୖࡉࡏ࡚࠸ࡿࠋᅗ ࣏ࣜ࢜ࣞࣇ࢕ࣥ〇㐀ࡢ࣮࢟࡜࡞ࡿ࢜ࣞࣇ࢕ࣥࡢ〇㐀

୍᪉ࠊ1-࣊࢟ࢭࣥࡢ㑅ᢥ〇㐀ᢏ⾡ࡢ㛤Ⓨࡀ㐍ࢇ࡛࠸ࡿࠋ1977 ᖺ࡟ Union Carbide㸦⡿ᅜ㸧ࡣࠊ
Cr[O2CCH(C2H5)C4H9]3 ࡜[(CH3)2CHCH2]3Al ࡢ㒊ศຍỈศゎ≀ࢆ⏝࠸ࡓゐ፹⣔ࡀࠊPE ࡀ୺⏕ᡂ≀㸦㑅ᢥ⋡ 84wt%㸧࡛࠶ࡿࡶࡢࡢࠊ1-࣊࢟ࢭࣥࢆ㑅ᢥ⋡ 15%㸦⏕ᡂ࢜ࣞࣇ࢕ࣥ୰ࡢ 1-࣊࢟ࢭࣥࡢ㑅ᢥ⋡ࡣ 93wt%㸧࡛୚࠼ࡿࡇ࡜ࢆሗ࿌ࡋࡓࠋ5) ࡇࡢሗ࿌ࢆዎᶵ࡜ࡋ࡚ࠊCr ゐ፹ࢆ୰ᚰ࡟࢚ࢳࣞࣥࡢ㑅ᢥⓗ࢜ࣜࢦ࣓ࣜ໬཯ᛂ㸦1-࣊࢟ࢭࣥࠊ1-࢜ࢡࢸࣥ㸧ࡢ᳨ウࡀάⓎ໬ࡋࡓࠋ6) ࡇࡇ࡛ࠊ࢚ࢳࣞࣥࡢ㑅ᢥⓗ࢜ࣜࢦ࣓ࣜ໬ࢆᐇ⌧ࡍࡿࡓࡵ࡟ࡣࠊ࣓ࢱࣛࢧ࢖ࢡࣝᶵᵓ࡛཯ᛂࢆ㐍⾜ࡉࡏࡿࡇ࡜ࡀᚲ㡲࡛࠶ࡿ㸦3.1.⠇࡛㏙࡭ࡿ㸧ࠋ2003 ᖺ࡟ࡣ Qatar Chemical㸦࢝ࢱ࣮ࣝ㸧࡟ࡼࡗ࡚ Cr ゐ፹ࢆ⏝࠸ࡿ࢚ࢳࣞࣥࡢ㑅ᢥⓗ୕㔞໬ࡀึࡵ࡚ᕤᴗ໬ࡉࢀࡓࠋ≉チ᝟ሗ࡟ࡼࢀࡤࠊゐ፹⣔࡜ࡋ࡚ Cr[O2CCH(C2H5)C4H9]3ࠊ2,5-ࢪ࣓ࢳࣝࣆ࣮ࣟࣝ࠾ࡼࡧ(C2H5)3Al/(C2H5)2AlCl ࢆ⏝࠸ࡿ࡜ࠊ115Υࠊ཯ᛂᅽຊ 10 MPaࠊゐ፹άᛶ 8.2kg/mmol-Cr࣭h ࡛ 1-࣊࢟ࢭࣥࡢ㑅ᢥ⋡ࡣ 93wt%࡛࠶ࡿࠋ6d) ㏆ᖺ࡛ࡣࠊPࠊNࠊO ࡞࡝ᵝࠎ࡞࣊ࢸࣟཎᏊከᗙ㓄఩Ꮚࢆࡶࡘ Cr ゐ፹ࡢ◊✲㛤Ⓨࡀ⢭ຊⓗ࡟⾜ࢃࢀ࡚࠾ࡾࠊSasol㸦༡࢔ࣇࣜ࢝㸧ࡣ Cr ゐ፹ࢆ⏝࠸ࡿ 1-࣊࢟ࢭࣥ㸭1-࢜ࢡࢸࣥ㸦ే⏘㸧ࢆ 2013 ᖺ࡟ᕤᴗ໬ࡍࡿ࡜Ⓨ⾲ࡋࡓࠋࡇࡢࣉࣟࢭࢫ࡛ࡣࠊ[P,N,P]㓄఩Ꮚ㸭Cr㸦III㸧ሷ㸭࣓ࢳࣝ࢔࣑ࣝࣀ࢟ࢧࣥ(MAO)࠿ࡽ࡞ࡿゐ፹⣔ࡢ฼⏝ࡀ᥎ࡉࢀࡿࠋ6e)୍᪉ࠊ㠀 Cr ゐ፹࡜ࡋ࡚ࠊTi ࡸ Ta ࡞࡝ࢆ୰ᚰ㔠ᒓ࡜ࡍࡿゐ፹ࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋ7) ౛࠼ࡤࠊHessen ࡽࡣࣇ࢙ࢽࣝᇶࢆ࣌ࣥࢲࣥࢺᇶ࡜ࡍࡿࢩࢡࣟ࣌ࣥࢱࢪ࢚ࢽࣝ㓄఩Ꮚࢆࡶࡘ Ti ゐ፹ࡀ
MAO ࢆຓゐ፹࡜ࡋ࡚ 30Υࠊ࢚ࢳࣞࣥᅽ 0.2 MPaࠊゐ፹άᛶ 1.2 kg/mmol-Ti࣭h ࡛ 1-࣊࢟ࢭࣥࢆ㑅ᢥ⋡ 87wt%࡛୚࠼ࡿ࡜ሗ࿌ࡋࡓࠋ7a)㸫㸫➨୍⦅ ◊✲ືྥ㸱㸬࣊࢟ࢭࣥ㑅ᢥ〇㐀ゐ፹ࡢ㛤Ⓨ㸱㸬㸯㸬ゐ፹タィᣦ㔪ᅗ 2 ࡟㑄⛣㔠ᒓ㘒యゐ፹࡟ࡼࡿ࢚ࢳࣞࣥࡢ࢜ࣜࢦ࣓ࣜ໬㸭㔜ྜ࡜㑅ᢥⓗ୕㔞໬ࡢ཯ᛂᶵᵓࢆ♧ࡍࠋ࢚ࢳࣞࣥࡢ࢜ࣜࢦ࣓ࣜ໬㸭㔜ྜ࡛ࡣࠊ୰ᚰ㔠ᒓ࡬ࡢ࢚ࢳࣞࣥࡢ㓄఩࡜ࠊ㓄఩ࡋࡓ࢚ࢳࣞࣥࡢ㔠ᒓ㸫࢔ࣝ࢟ࣝ⤖ྜ࡬ࡢᤄධࡀ⧞ࡾ㏉ࡉࢀࡿࡇ࡜࡟ࡼࡾ㐍⾜ࡍࡿ㸦Cossee-Arlman ᶵᵓ㸧ࠋࡋࡓࡀࡗ࡚ࠊ཯ᛂࢧ࢖ࢺ࡜ࡋ࡚࢔ࣝ࢟ࣝ㙐ࡢ⤖ྜ࡜࢚ࢳࣞࣥ㓄఩ࡢࡓࡵ࡟ 2 ᗙࡀᚲせ࡛࠶ࡿࠋࡲࡓࠊ཯ᛂ㐣⛬࡛㔠ᒓࡢཎᏊ౯ࡣኚ໬ࡋ࡞࠸ࠋ୍᪉ࠊ࢚ࢳࣞࣥࡢ㑅ᢥⓗ୕㔞໬ࡣ 2 ศᏊࡢ࢚ࢳࣞࣥࡀపཎᏊ౯ࡢ㔠ᒓ㸦ཎᏊ౯㸸Mn㸧࡟㓄఩ࡋࡓᚋࠊ㓟໬ⓗ௜ຍ࡟ࡼࡾ 5 ဨ⎔ࡢ࣓ࠋ⥆࠸࡚㔠ᒓ࡟࢚ࢳࣞࣥࡀ㓄఩ࡋࠊࡇࡢ㓄఩ࢱࣛࢧ࢖ࢡࣝࢆᙧᡂࡍࡿ㸦㔠ᒓࡢཎᏊ౯㸸Mn+2㸧ࡋࡓ࢚ࢳࣞࣥࡀ㔠ᒓ㸫࣓ࢱࣛࢧ࢖ࢡࣝࡢ࢔ࣝ࢟ࣝ⤖ྜ࡟ᤄධࡉࢀ 7 ဨ⎔ࡢ࣓ࢱࣛࢧ࢖ࢡࣝࢆ
ᙧᡂࡋࡓᚋࠊ㑏ඖⓗ⬺㞳ࢆక࠺࣓ࢱࣛࢧ࢖ࢡࣝࡢ㛤⿣࡟ࡼࡾ 1-࣊࢟ࢭࣥࡀ⏕ᡂࡍࡿ㸦㔠ᒓࡢཎᏊ౯㸸MnࠊపཎᏊ౯ࡢ㔠ᒓࡀ෌⏕㸧ࠋ8) ࡋࡓࡀࡗ࡚ࠊ཯ᛂࢧ࢖ࢺ࡜ࡋ࡚࣓ࢱࣛࢧ࢖ࢡࣝࡢ⤖ྜ࡜࢚ࢳࣞࣥࡢ㓄఩ࡢࡓࡵ࡟ 3 ᗙࡀᚲせ࡛࠶ࡿࠋࡲࡓࠊ㓟໬ⓗ௜ຍ࡜㑏ඖⓗ⬺㞳ࢆྵࡴࡓࠋࡵ㔠ᒓࡢཎᏊ౯ࡣኚ໬ࡍࡿ㸦Mn/Mn+2㸧ᅗ ࢚ࢳࣞࣥࡢ࢜ࣜࢦ࣓ࣜ໬㸭㔜ྜ࡜㑅ᢥⓗ୕㔞໬ࡢ཯ᛂᶵᵓࡇࡢࡼ࠺࡟࢜ࣜࢦ࣓ࣜ໬㸭㔜ྜ࡜㑅ᢥⓗ୕㔞໬ࡢ཯ᛂᶵᵓࡣ୍ぢࡍࡿ࡜␗࡞ࡿࡀࠊ୧⪅࡜ࡶ࡟㧗άᛶⓎ⌧ࡢせᅉࡣࠊ㔠ᒓ࡜㓄఩Ꮚࡢ㛫࡛㟁Ꮚࡢࡸࡾ࡜ࡾࡀ෇⁥࡟⾜ࢃࢀࡿࡇ࡜࡛࠶ࡿࠋࡋࡓࡀࡗ࡚ࠊ㧗άᛶ࡞࢜ࣜࢦ࣓ࣜ໬㸭㔜ྜゐ፹࡜㑅ᢥⓗ୕㔞໬ゐ፹࡟ồࡵࡽࢀࡿ㓄఩Ꮚࡢᛶ㉁㸦ࣇࣞ࢟ࢩࣈࣝ࡞㟁Ꮚᤵཷ⬟ຊ㸧ࡣඹ㏻࡛࠶ࡿ࡜⪃࠼ࡓࠋࡑࡇ࡛ࠊᙜ♫ࡀ㛤Ⓨࡋࡓ㧗άᛶ࡞࢜ࣞࣇ࢕ࣥ㔜ྜゐ፹ࠕFI ゐ፹ࠖ9) [ᅗ 3 ୰ࡢ(a)]ࡢᒎ㛤࡟ࡼࡿ࢚ࢳࣞࣥࡢ㑅ᢥⓗ୕㔞໬ゐ፹ࡢ㛤Ⓨࢆ┠ᣦࡋࡓࠋࡑࡢ㝿ࠊ1-࣊࢟ࢭࣥ⏕ᡂࡢ཯ᛂᶵᵓ㸦ᅗ 2㸧ࡢ⪃ᐹ࡟ᇶ࡙࠸࡚ࠊᅗ 3 ࡟♧ࡍࡼ࠺࡞ゐ፹タィࢆࡋࡓࠋࡍ࡞ࢃࡕࠊ୰ᚰ㔠ᒓ࡜ࡋ࡚ 2 ౯/4 ౯ࡀᏳᐃ࡟Ꮡᅾྍ⬟࡛࠶ࡾࠊ㧗࠸࢚ࢳࣞࣥ㔜ྜάᛶࢆ᭷ࡍࡿ Ti ࢆ㑅ᢥࡋࡓࠋࡲࡓࠊ࣓ࢱࣛࢧ࢖
ࢡࣝࡢᙧᡂ࡜࢚ࢳࣞࣥ㓄఩ࡢࡓࡵ࡟ᚲせ࡞ 3 ࡘࡢ㓄఩ᗙࢆ☜ಖࡍࡿࡓࡵ Ti ࡟㓄఩ࡉࡏࡿ FI㓄఩Ꮚࢆ 1 ࡘ࡜ࡋࠊࡉࡽ࡟ゐ፹άᛶ✀ࢆᏳᐃ໬ࡉࡏࡿࡓࡵࠊࡇࡢ FI 㓄఩Ꮚ࡟୰ᛶࡢࢻࢼ࣮ࢆ
1 ࡘᑟධࡋࡓ 3 ᗙࡢ FI 㓄఩Ꮚࢆタィࡋࡓࠋ㸫㸫

ᕤᴗゐ፹ὀ┠ᢏ⾡ᅗ FI ゐ፹ࢆ࣮࣋ࢫ࡟ࡋࡓ࢚ࢳࣞࣥ㑅ᢥⓗ୕㔞໬ゐ፹ࡢタィ㸱㸬㸰㸬SFI ゐ፹ࡢ㛤Ⓨᅗ 3 ࡛ࡲ࡜ࡵࡓ⪃࠼᪉࡟ᇶ࡙࠸࡚タィࡋࡓゐ፹ࡢࢫࢡࣜ
࣮ࢽࣥࢢ࡟ࡼࡾࠊᅗ 4 ࡟♧ࡍࡼ࠺࡞࢚࣮ࢸࣝࢆ୰ᛶࢻࢼ࣮
࡜ࡍࡿ Ti ゐ፹ A ࢆぢฟࡋࡓࠋࡇࡢゐ፹ࡣࠊMAO ࢆຓゐ፹࡜ࡋ࡚ࠊ࢚ࢳࣞࣥᅽ 0.8 MPaࠊ25Υࠊ0.5 h ࡢ᮲௳ୗࠊゐ፹άᛶ 0.1 kg/mmol-Ti࣭h ࡛ 1-࣊࢟ࢭࣥࢆ㑅ᢥ⋡ 34.5wt%࡛୚࠼ࡓࠋPE ࡀ㑅ᢥ⋡ 65.5wt%࡛

ᅗ ࢚࣮ࢸࣝࢆ୰ᛶࢻࢼ࣮
࡜ࡍࡿ Ti ゐ፹ A๪⏕ࡍࡿࡀࠊ࢜ࣜࢦ࣐࣮ᡂศ୰ࡢ 1-࣊࢟ࢭࣥࡢ㑅ᢥ⋡ࡣ
100wt%࡛࠶ࡗࡓࠋࡇࡇ࡛ࠊ࢜ࣜࢦ࣐࣮࡜ PE ࢆ⏕ᡂࡍࡿゐ፹άᛶ✀ࡣ␗࡞ࡿ࡜᥎

ࡉࢀࠊ1-࣊࢟ࢭࣥࢆ㧗㑅ᢥⓗ࡟୚࠼ࡿάᛶ✀ࡢᏑᅾࡀ♧၀ࡉࢀࡓࠋࡑࡇ࡛ࠊTi ゐ፹ A ࢆ࣮࣋ࢫ࡟ゐ፹ࢆ᥈⣴ࡋࡓ⤖ᯝࠊ࢔࣮࢚࣮ࣜࣝࢸࣝࢆ୰ᛶࢻࢼ࣮࡜ࡍࡿ㧗ᛶ⬟ Ti ゐ፹ࢆぢฟࡋࡓࠋࡑࢀࡽࡢゐ፹ࢆ⏝࠸ࡓ཯ᛂ⤖ᯝࢆ⾲ 1 ࡟ࡲ࡜ࡵࡓࠋ⾲ 㧗ᛶ⬟ Ti ゐ፹ࢆ⏝࠸ࡓ࢚ࢳࣞࣥࡢ㑅ᢥⓗ୕㔞໬཯ᛂ

R1R2

R3R4⏕⏘ᛶ㑅ᢥ⋡ (wt%)
1-࣊࢟ࢭࣥ⏕⏘ᛶ
(kg/mmol-Tih) 1-࣊࢟ࢭࣥࢹࢭࣥ PE (kg/mmol-Tih)
MeMeH
H
20.0
91.0
7.6
1.4
18.2
1i-Bu MeH
H
4.4
93.6
2.5
3.9
4.1
2
MeF
H
H
34.2
93.3
5.9
0.8
31.9
3
MeOMe H
H
16.6
87.2
11.1
1.7
14.54MeMei-Pr H
5.1
70.5
27.9
1.2
3.65MeMeH
Me
30.5
50.1
49.7
0.2
15.36
཯ᛂ᮲௳: ࢺ࢚ࣝࣥ 30 mL, ゐ፹ 0.25 μmol, MAO 0.5 mmol (Al ࡜ࡋ࡚), ࢚ࢳࣞࣥᅽຊ 0.8 MPa, 25 °C, 1 h.
ゐ፹㸫㸫

➨୍⦅ ◊✲ືྥゐ፹ 1 ࡣࠊMAO ࢆຓゐ፹࡜ࡋ࡚ࠊ࢚ࢳࣞࣥᅽ 0.8 MPaࠊ25Υࠊ1 h ࡢ᮲௳ୗࠊ1-࣊࢟ࢭࣥࡢ
⏕ᡂάᛶ 18.2 kg/mmol-Ti࣭h ࡛ 1-࣊࢟ࢭࣥࢆ㑅ᢥ⋡ 91.0wt%࡛୚࠼ࠊ㧗άᛶ࠿ࡘ㧗㑅ᢥᛶࢆ᭷ࡍࡿ࢚ࢳࣞࣥ୕㔞໬ゐ፹࡟࡞ࡿࡇ࡜ࢆぢฟࡋࡓࠋ࢔࣮࢚࣮ࣜࣝࢸࣝࡣࠊ࢔࢚࣮ࣝ࢟ࣝࢸࣝࡼ
ࡾࡶࠕࣇࣞ࢟ࢩࣈࣝ࡞㟁Ꮚᤵཷ⬟ຊࠖࢆࡶࡘࡓࡵ࡟ࠊ㧗άᛶࡀᐇ⌧ࡉࢀࡓ࡜᥎ࡉࢀࡿࠋ10)

ࡲࡓࠊ๪⏕≀࡜ࡋ࡚ 2-ࣈࢳࣝ-1-࣊࢟ࢭࣥࢆ୺ᡂศ㸦ࢹࢭࣥ୰ࡢ㑅ᢥ⋡ࡣ⣙ 90wt%㸧࡜ࡍࡿࢹࢭࣥ㢮ࡀ㑅ᢥ⋡ 7.6wt%࡛⏕ᡂࡋࡓ㸦཯ᛂᶵᵓࡣᚋ㏙ࡍࡿ㸧ࠋ
ゐ፹ 1 ࡢάᛶࡣࠊ࢚ࢳࣞࣥᅽࡢ 2 ḟ࡟ẚ౛ࡋ࡚኱ࡁࡃྥୖࡋࡓࠋࡍ࡞ࢃࡕࠊ࢚ࢳࣞࣥᅽࢆ
0.8 ࠿ࡽ 5.0 MPa ࡟ࡍࡿ࡜ 1-࣊࢟ࢭࣥ⏕ᡂάᛶࡣ 7.4 ࠿ࡽ 315.5 kg/mmol-Ti࣭h ࡟㐩ࡋࡓ
㸦30Υࠊ1 h 㸹1-࣊࢟ࢭࣥ㑅ᢥ⋡ࡣࡑࢀࡒࢀ 91.4%ࠊ92.3%㸧ࠋ1a) ࡇࡢ 1-࣊࢟ࢭࣥ⏕ᡂάᛶࡣྠ୍᮲௳
࡛ࡢ Cr ゐ፹ࡢ 100 ಸ௨ୖ࡛࠶ࡾࠊ1-࣊࢟ࢭࣥ〇㐀ゐ፹࡜ࡋ࡚ୡ⏺᭱㧗ࣞ࣋ࣝࡢ್࡛࠶ࡿࠋゐ፹ 1 ࡣࠊX ⥺༢⤖ᬗᵓ㐀ゎᯒ࠿ࡽᨃඵ㠃యᵓ㐀ࢆࡶࡕࠊࣇ࢙ࣀ࢟ࢩ࣭࢖࣑࣭࢚࣮ࣥࢸࣝ㓄఩Ꮚࡀ 3 ᗙ࡛ facial 㓄఩ࡋ࡚࠾ࡾࠊ཯ᛂࢧ࢖ࢺ࡜࡞ࡿ 3 ࡘࡢሷ⣲ཎᏊࡀ஫࠸࡟ cis ఩࡟఩⨨ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸦ᅗ 5㸧ࠋࡇࡢ㓄఩ᵓ㐀ࡣࠊ࣓ࢱࣛࢧ࢖ࢡࣝᶵᵓ࡟ᇶ࡙ࡃ࢚ࢳࣞࣥ୕
㔞໬཯ᛂࡢ㏿ᗘྥୖ࡟᭷฼࡜⪃࠼ࡽࢀࡿࠋ

O(1)

N(1)
O(2)
Cl(3)

Ti(1)
Ti

Cl(1)

Cl(2)

Ti(1)–O(1)Ti(1)–O(2)Ti(1)–N(1)Ti(1)–Cl(1)Ti(1)–Cl(2)Ti(1)–Cl(3)⤖ྜ㊥㞳 Å
2.182(2)1.827(2)2.197(3)2.324(1)2.262(9)2.274(1)N(1)–Ti(1)–O(1)Cl(2)–Ti(1)–Cl(3)N(1)–Ti(1)–O(2)Cl(2)–Ti(1)–Cl(1)O(1)–Ti(1)–O(2)Cl(3)–Ti(1)–Cl(1)⤖ྜゅᗘ deg 
78.7(1)99.97(4)79.9(1)96.86(4)92.0(1)91.29(4)ᅗ ゐ፹ 1 ࡢศᏊᵓ㐀ゐ፹άᛶࡣࠊ㓄఩Ꮚࡢ⨨᥮ᇶ࡟኱ࡁࡃᙳ㡪ࡉࢀࡿ㸦⾲ 1㸧
ࠋR1 ࡢ⨨᥮ᇶࢆ኱ࡁࡃࡍࡿ࡜ࠊ㑅ᢥᛶࡣ࡯࡜ࢇ࡝ኚ໬ࡍࡿࡇ࡜࡞ࡃࠊゐ፹άᛶࡀపୗࡍࡿࠋ౛࠼ࡤࠊ࣓ࢳࣝᇶ㸦ゐ፹ 1㸧ࡢ௦ࢃࡾ࡟࢖ࢯࣈࢳࣝᇶ㸦ゐ፹ 2㸧ࢆᑟධࡍࡿ࡜ࠊ1-࣊࢟ࢭࣥ⏕ᡂάᛶࡣ⣙ 1/4 ࡟࡞ࡗࡓࠋࡇࡢཎᅉࡣࠊάᛶⅬ㏆ഐࡢ❧య㞀ᐖ࡟ࡼࡾ 5 ဨ⎔ࡢ࣓ࢱࣛࢧ࢖ࢡࣝ࡬ࡢ࢚ࢳࣞࣥࡢ㓄఩ࡸᤄධ཯ᛂࡀ㜼ᐖࡉࢀࡿࡓࡵ࡛࠶ࡿ࡜᥎ࡉࢀࡿࠋࡲࡓࠊR2 ࡢ⨨᥮ᇶ࡛ࡣࠊF㸦ゐ፹ 3㸧>Me㸦ゐ፹ 1㸧>OMe㸦ゐ፹ 4㸧ࡢ㡰࡟άᛶࡀ㧗ࡃ࡞ࡗࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊ㟁Ꮚ྾ᘬᛶ⨨᥮ᇶ࡞࡝ࡢᑟධ࡟ࡼࡾ୰ᚰ㔠ᒓࡢồ㟁Ꮚᛶࢆ㧗ࡵࡿࡇ࡜ࡀゐ፹άᛶࡢྥୖ࡟᭷ຠ࡛࠶ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋࡇࡢࡼ࠺࡞⨨᥮ᇶຠᯝࡣ࢚ࢳࣞࣥ㔜ྜゐ፹࡛ࡶㄆࡵࡽࢀ࡚࠾ࡾࠊ࢚ࢳࣞࣥ㔜ྜ࠾ࡼࡧ㑅ᢥⓗ୕㔞໬ゐ፹ࡢ㓄఩Ꮚ࡬ࡢせồᛶ⬟ࡀඹ㏻࡛࠶ࡿ࡜࠸࠺➹⪅ࡽࡢ⪃࠼᪉࡜▩┪ࡋ࡞࠸ࠋ㓄఩Ꮚࡢ⨨᥮ᇶࡣ⏕ᡂ≀ࡢ㑅ᢥ⋡࡟ࡶ኱ࡁ࡞ᙳ㡪ࢆ୚࠼ࡿ㸦⾲ 1㸧ࠋR3 ࠶ࡿ࠸ࡣ R4 ࡢ⨨᥮ᇶࢆ኱ࡁࡃࡍࡿ࡜ࢹࢭࣥ㢮㸦2-ࣈࢳࣝ-1-࣊࢟ࢭࣥࡀ୺ᡂศ㸧ࡢ㑅ᢥ⋡ࡀྥୖࡍࡿࠋ౛࠼ࡤࠊ
R3 ࡢ⨨᥮ᇶࢆỈ⣲㸦ゐ፹ 1㸧࠿ࡽ࢖ࢯࣉࣟࣆࣝᇶ㸦ゐ፹ 5㸧࡟ࠊ࠶ࡿ࠸ࡣ R4 ࡢ⨨᥮ᇶࢆỈ⣲㸦ゐ፹ 1㸧࠿ࡽ࣓ࢳࣝᇶ㸦ゐ፹ 6㸧࡟ࡍࡿ࡜ࠊࢹࢭࣥ㑅ᢥ⋡ࡣ 7.6wt%㸦ゐ፹ 1㸧࠿ࡽ 27.9wt%
㸦ゐ፹ 5㸧࠾ࡼࡧ 49.7wt%㸦ゐ፹ 6㸧࡟኱ᖜ࡟ྥୖࡋࡓࠋࡇࡢ⌮⏤࡟ࡘ࠸࡚ࡣ 4.㡯࡛㏙࡭ࡿࠋ
ゐ፹ 1 ࡣࠊ࢚ࢳࣞࣥࡔࡅ࡛࡞ࡃ 1-࣌ࣥࢸࣥࡸ 1-࣊࢟ࢭࣥࠊ1-ࢹࢭࣥ࡞࡝ࡢ㑅ᢥⓗ୕㔞໬཯ᛂࡢゐ፹࡜ࡋ࡚ࡶඃࢀ࡚࠾ࡾࠊᚓࡽࢀࡓ୕㔞యࡣࢹ࢕࣮ࢮ࣭ࣝࢪ࢙ࢵࢺ⇞ᩱࠊ₶⁥Ἔ࡞࡝࡬㸫㸫ᕤᴗゐ፹ὀ┠ᢏ⾡ࡢᒎ㛤ࡀᮇᚅࡉࢀ࡚࠸ࡿࠋ11)௨ୖࡢࡼ࠺࡟ࡋ࡚㛤Ⓨࡉࢀࡓࣇ࢙ࣀ࢟ࢩ࣭࢖࣑࣭࢚࣮ࣥࢸࣝ 3 ᗙ㓄఩Ꮚࢆࡶࡘ࢚ࢳࣞࣥࡢ
㧗άᛶ࡞㑅ᢥⓗ୕㔞໬ゐ፹ࡣ FI 㓄఩Ꮚࢆ 1 ࡘࡶࡘࡇ࡜࠿ࡽࠊSFI ゐ፹㸦Single FI-based ligand㸧࡜ྡ௜ࡅࡓࠋ㸲㸬㹂㹄㹒ィ⟬࠾ࡼࡧ㏿ᗘㄽ࡟ࡼࡿ཯ᛂゎᯒ
SFI ゐ፹ 1 ࢆࣔࢹࣝ࡜ࡋ࡚ DFT ィ⟬㸦B3LYP/LANL2DZ㸧ࢆ⏝࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮㸦ǼG 㸧ࡢ⟬ฟ࡟ࡼࡾ࢚ࢳࣞࣥࡢ㑅ᢥⓗ୕㔞໬ࡢ཯ᛂᶵᵓࢆゎᯒࡋࡓ㸦25Υࠊ0.1 MPa㸹Gaussian09 Rev.
ࠋ
A.02 ࣉࣟࢢ࣒ࣛ 12)㸧ࡣࡌࡵ࡟ࠊSFI ゐ፹ 1 ࡢάᛶ✀ࡢ⏕ᡂᶵᵓࢆゎᯒࡋࡓࠋࡇࡢゐ፹ࡣ MAO ࡟ࡼࡾࠊࡲࡎࢪ࣓ࢳࣝ໬ࡉࢀࡿ࡜⪃࠼ࡽࢀࡿࡓࡵࠊࢪ࣓ࢳࣝయ࡜࢚ࢳࣞࣥ࡜ࡢ཯ᛂ⤒㊰ࢆㄪ࡭ࡓࠋᅗ 6 ࡟♧ࡍࡼ࠺࡟ࠊ࢚ࢳࣞࣥࡀ Ti-C ⤖ྜ࡟ᤄධࡉࢀࡓᚋࠊș-⬺㞳཯ᛂࡀ㐍⾜ࡍࡿࠋș-⬺㞳཯ᛂ࡜ࡋ࡚
ࡣࠊn-ࣉࣟࣆࣝᇶࡢș-Ỉ⣲ࡀ Ti ࡟⛣ືࡋࣄࢻࣜࢻ୰㛫యࢆ⤒⏤ࡍࡿ⤒㊰࡜ș-Ỉ⣲ࡀ┤᥋࣓ࢳࣝᇶࡢⅣ⣲࡟⛣ືࡋ࡞ࡀࡽ࣓ࢱࣥ࡜ࡋ࡚⬺㞳ࡍࡿ༠ዌⓗࣄࢻࣜࢻ⛣ື཯ᛂࡀ⪃࠼ࡽࢀࡿࠋィ⟬ࡢ⤖ᯝࠊᚋ⪅ࡢ⤒㊰࡟ࡼࡾ཯ᛂࡀ㐍⾜ࡋࠊάᛶ✀ V ࡀ⏕ᡂࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ
ᅗ 7 ࡟ࠊゐ፹άᛶ✀ V ࡟࠾ࡅࡿゐ፹ࢧ࢖ࢡࣝ඲యࡢ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ǼG ࢆ♧ࡍࠋᅗ୰ࡢ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝ࠿ࡽࢃ࠿ࡿࡼ࠺࡟ࠊ5 ဨ⎔ࡢ࣓ࢱࣛࢧ࢖ࢡࣝ࡬ࡢ࢚ࢳࣞࣥᤄධࡢ
཯ᛂ㞀ቨ㸦VIIIэIX㸧ࡀ᭱ࡶ኱ࡁࡃࠊࡇࡢ⣲཯ᛂࡀᚊ㏿ẁ㝵࡟࡞ࡗ࡚࠸ࡿࠋࡉࡽ࡟ࠊ7 ဨ⎔ࡢ࣓ࢱࣛࢧ࢖ࢡࣝ࠿ࡽࡢ 1-࣊࢟ࢭࣥ⏕ᡂ㐣⛬ࡣࠊ3 ఩ࡢỈ⣲ࡀ 7 ఩ࡢⅣ⣲࡟⛣ືࡍࡿ༠ዌ཯ᛂ㸦IXэX㸧࡛࠶ࡾࠊTi ࡢࣄࢻࣜࢻ୰㛫యࢆ⤒⏤ࡍࡿ཯ᛂ㸦IXэXIэX㸧࡛ࡣ࡞࠸ࡇ࡜ࢆぢฟࡋࡓࠋࡇࢀࡣࠊࣄࢻࣜࢻ୰㛫యࡢ⏕ᡂࡀ྾⇕཯ᛂ࡟࡞ࡿࡓࡵ࡛࠶ࡿࠋ1-࣊࢟ࢭࣥࡀ⏕ᡂࡉࢀࡿ࡜✵㓄఩ᗙ࡟࢚ࢳࣞࣥࡀ㓄఩ࡋ㸦XэXII㸧ࠊ1-࣊࢟ࢭࣥࡀ࢚ࢳࣞࣥ࡟ᢲฟࡉࢀࡿᙧ࡛࢜ࣞࣇ࢕ࣥ஺᥮཯ᛂࡀ㐍⾜ࡋ࡚άᛶ✀ V ࡀ෌⏕ࡉࢀࡿ㸦XIIэV㸧ࠋ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝࡢほⅬ࠿ࡽࡣࠊάᛶ✀ V ࠿ࡽゐ፹ࢧ࢖ࢡࣝࢆ 1 ࿘ࡋ࡚άᛶ✀ V ࡀ෌⏕ࡉࢀࡿ࡜ࠊ࢚ࢳࣞࣥ୕㔞໬཯ᛂࡢ⮬⏤࢚ࢿࣝࢠ࣮ᕪࡔࡅᏳᐃ໬ࡍࡿࠋᅗ SFI ゐ፹㸦ゐ፹ 1㸧࡟࠾ࡅࡿάᛶ✀⏕ᡂᶵᵓ(ΔG ࡣ⮬⏤࢚ࢿࣝࢠ࣮ᕪࠊΔG‡ࡣάᛶ໬⮬⏤࢚ࢿࣝࢠ࣮ࢆ♧ࡍࠋ༢఩ࡣ kJ/mol)㸫㸫➨୍⦅ ◊✲ືྥḟ࡟ࠊ࡞ࡐ 1-࣊࢟ࢭࣥࡀ㑅ᢥⓗ࡟⏕ᡂࡍࡿࡢ࠿ࢆゎᯒࡋࡓࠋ1-ࣈࢸࣥࡣ 5 ဨ⎔ࡢ࣓ࢱࣛࢧ
࢖ࢡࣝ VII ࡢ 3 ఩ࡢỈ⣲ࡀ⛣ືࡍࡿࡇ࡜࡟ࡼࡾ⏕ࡌࡿࡀࠊᅗ 8 ࡟♧ࡍࡼ࠺࡟ࠊTi ࡬ࡢș-Ỉ⣲⛣ື࠾ࡼࡧ༠ዌⓗ 3,5-ࣄࢻࣜࢻ⛣ື཯ᛂࡣࠊ࡜ࡶ࡟㠀ᖖ࡟኱ࡁ࡞⎔ṍࡀ⏕ࡌࡿࡓࡵ࡟ࠊάᛶ
ୖ㏙ࡋࡓࡼ࠺࡟ࠊ
໬⮬⏤࢚ࢿࣝࢠ࣮ǼG͋ࡀࡑࢀࡒࢀ 142.8 kJ/molࠊ195.0 kJ/mol ࡜኱ࡁࡃ࡞ࡿࠋ5 ဨ⎔ࡢ࣓ࢱࣛࢧ࢖ࢡࣝ࡬ࡢ࢚ࢳࣞࣥᤄධ཯ᛂࡣࠊ1-࣊࢟ࢭࣥ⏕ᡂ㐣⛬࡛ࡢᚊ㏿ẁ㝵࡛ࠊάᛶ໬⮬⏤࢚ࢿࣝࢠ࣮ࡀ 123.1 kJ/mol ࡜኱ࡁ࠸࡟ࡶ㛵ࢃࡽࡎࠊ1-ࣈࢸࣥ⏕ᡂ཯ᛂ࡟ẚ࡭༑ศ࡟㏿࠸ࠋࡑࡢࡓࡵࠊ1-ࣈࢸࣥࡣ⏕ᡂࡋ࡞࠸࡜⪃࠼ࡽࢀࡿࠋ
୍᪉ࠊ1-࢜ࢡࢸࣥࡲࡓࡣࡑࢀ௨ୖࡢ㙐㛗ࢆᣢࡘȘ-࢜ࣞࣇ࢕ࣥࡢ⏕ᡂࡣࠊ7 ဨ⎔ࡢ࣓ࢱࣛࢧ
࢖ࢡࣝ IX ࠿ࡽࡢ࢚ࢳࣞࣥᤄධ཯ᛂࢆ⤒⏤ࡍࡿᚲせࡀ࠶ࡿࠋࡋ࠿ࡋࠊᅗ 8 ࠿ࡽࢃ࠿ࡿࡼ࠺࡟ࠊ
ࡇࡢ࢚ࢳࣞࣥᤄධ཯ᛂࡣࠊྠࡌ 7 ဨ⎔ࡢ࣓ࢱࣛࢧ࢖ࢡࣝ IX ࠿ࡽ⏕ࡌࡿ༠ዌⓗ 3,7-ࣄࢻࣜࢻ⛣ື཯ᛂ࡟ẚ࡭࡚άᛶ໬⮬⏤࢚ࢿࣝࢠ࣮ࡀ㠀ᖖ࡟኱ࡁࡃࠊ࢚ࢳࣞࣥᤄධ཯ᛂࡣ㉳ࡇࡽ࡞࠸࡜⪃࠼ࡽࢀࡿࠋ༠ዌⓗ 3,7-ࣄࢻࣜࢻ⛣ື཯ᛂࡀ⏕ࡌ᫆ࡃ࡞ࡿせᅉࡣࠊ7 ဨ⎔࠿ࡽࡢ཯ᛂ࡛࠶ࡿࡓࡵ
⎔ṍࡀ༑ศゎᾘࡋ࡚࠸ࡿࡇ࡜࡜㛤⎔཯ᛂ࡛࠶ࡿࡓࡵ࢚ࣥࢺࣟࣆ࣮ࡀቑ኱ࡍࡿࡇ࡜ࠊࡉࡽ࡟࢚ࢳࣞࣥᤄධ཯ᛂ⮬యࡀ఍ྜ཯ᛂ࡛࠶ࡿࡓࡵ࡟࢚ࣥࢺࣟࣆ࣮ⓗ࡟୙฼࡛࠶ࡿࡇ࡜ࡀᣲࡆࡽࢀࡿࠋࡇࢀࡽࡢ⌮⏤࡟ࡼࡾࠊSFI ゐ፹ 1 ࡛ࡣ 1-࣊࢟ࢭࣥࡀ㑅ᢥⓗ࡟⏕ᡂࡍࡿࠋࡲࡓࠊ࢚ࢳࣞࣥࡢ㑅ᢥⓗᅄ㔞໬ゐ፹࡟ࡼࡿ 1-࢜ࢡࢸࣥࡢ⏕ᡂࡣࠊୖ㏙ࡋࡓ⪃ᐹ࠿ࡽ࣓ࢱࣛࢧ࢖ࢡࣝ࡬ࡢ㏲ḟⓗ࡞࢚ࢳࣞࣥᤄධ཯ᛂ࡟ᇶ࡙ࡃࡶࡢ࡛࡞࠸ྍ⬟ᛶࡀ㧗࠸ࠋᅗ SFI ゐ፹ 1 ࡟࠾ࡅࡿゐ፹ࢧ࢖ࢡࣝ඲యࡢ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝ

㸫㸫

ᕤᴗゐ፹ὀ┠ᢏ⾡ᅗ 1-࣊࢟ࢭࣥ࠾ࡼࡧ௚ࡢ Ș-࢜ࣞࣇ࢕ࣥࡢ⏕ᡂࡢࡋ᫆ࡉ㸦ΔG‡ࡢ༢఩㸸kJ/mol㸧࡞࠾ࠊ๪⏕≀࡛࠶ࡿࢹࢭࣥ㢮ࡣ 1-࣊࢟ࢭࣥ 1 ศᏊ࡜࢚ࢳࣞࣥ 2 ศᏊ࡜ࡢඹ୕㔞໬࡟ࡼࡾ⏕ᡂࡍࡿࡀࠊ୺せᡂศ࡛࠶ࡿ 2-ࣈࢳࣝ-1-࣊࢟ࢭࣥࡣࠊᅗ 7 ࡟♧ࡋࡓ 1-࣊࢟ࢭࣥ⏕ᡂ┤ᚋࡢ࢜ࣞࣇ࢕ࣥ஺᥮཯ᛂ㸦XIIэV㸧ࡢ௦ࢃࡾ࡟ࠊ1-࣊࢟ࢭࣥ࡜࢚ࢳࣞࣥࡢ 2 ศᏊ㓄఩≧ែ㸦XII㸧࠿ࡽ㓟໬ⓗ௜ຍ࡟ࡼࡾ⏕ᡂࡍࡿ 3-ࣈࢳ࣓ࣝࢱࣛࢩࢡࣟ࣊ࣉࢱࣥࢆ⤒⏤ࡋ࡚⏕ᡂࡍࡿࡇ࡜ࡀ DFT ィ⟬࠿ࡽ♧၀ࡉࢀ࡚࠸ࡿࠋ3.2.⠇࡛ゐࢀࡓ SFI ゐ፹ 6 ࡣࢹࢭࣥࡢ㑅ᢥ⋡ࢆ኱ᖜ࡟ቑ኱ࡉࡏࡿࡀࠊ
SFI ゐ፹ 1 ࡢ R4 ࢆỈ⣲࠿ࡽ࣓ࢳࣝᇶ࡟ኚ᥮ࡍࡿࡇ࡜࡛ 1-࣊࢟ࢭࣥࡢ⬺㞳ࢆ㜼ᐖࡋࠊ࢜ࣞࣇ࢕ࣥ஺᥮཯ᛂ㸦XIIэV㸧ࡀ㐜ࡃ࡞ࡗࡓࡓࡵ࡜⪃࠼ࡽࢀࡿࠋࡇࢀࡽ୍㐃ࡢ DFT ィ⟬ࡢ⤖ᯝࢆཷࡅ࡚㏿ᗘㄽゎᯒࢆ⾜ࡗࡓࠋᅗ 9 ࡟࢚ࢳࣞࣥࡢ㑅ᢥⓗ୕㔞໬ࡢ᥎ᐃ཯ᛂᶵᵓࢆ♧ࡍࠋᅗ ࢚ࢳࣞࣥ㑅ᢥⓗ୕㔞໬ࡢ᥎ᐃ཯ᛂᶵᵓ㸦㏿ᗘㄽゎᯒࡢ๓ᥦ㸧ィ⟬⤖ᯝࡼࡾ཯ᛂࡢᚊ㏿ẁ㝵ࡣ཯ᛂ D㸦㏿ᗘᐃᩘ kD㸧࡛࠶ࡾࠊࡑࢀ௨እࢆᖹ⾮཯ᛂ㸦ᖹ⾮ᐃᩘ㸸KA㹼KC, KE㹼KG㸧࡜௬ᐃࡋࡓࠋゐ፹௙㎸ࡳ㔞ࢆ C㸦୍ᐃ್㸧࡜ࡋࠊࡉࡽ࡟ kDKAKBKCC=k࡜ࡍࡿ࡜ࠊ1-࣊࢟ࢭࣥࡢ⏕ᡂ㏿ᗘ R ࡣࠊᘧ㸦1㸧࡛⾲ࡍࡇ࡜ࡀ࡛ࡁࡿࠋ
R=k[C2H4]3/{(1+KE)[C6H12]/KEKFKG+(1+[C6H12]/KG)[C2H4]+KA(1+KB)[C2H4]2+KAKBKC[C2H4]3}

㸫㸫(1)➨୍⦅ ◊✲ືྥ

ࡇࡇ࡛ࠊ7 ဨ⎔ࡢ࣓ࢱࣛࢧ࢖ࢡࣝ໬ྜ≀ࡣ 1-࣊࢟ࢭࣥࡀ 1 ศᏊ㓄఩ࡋ࡚࠸ࡿゐ፹✀ࡼࡾࡶⴭࡋࡃ୙Ᏻᐃ࡞ࡓࡵ KE ࡣ㠀ᖖ࡟኱ࡁࡃࠊ(KE+1)KEҫ1 ࡜ぢ࡞ࡏࡿࠋࡼࡗ࡚ࠊᘧ㸦1㸧ࡣᘧ㸦2㸧࡟⡆␎໬ࡉࢀࡿࠋ
R=k[C2H4]3/{[C6H12]/KFKG+(1+[C6H12]/KG)[C2H4]+KA(1+KB)[C2H4]2+KAKBKC[C2H4]3}(2)

ᘧ㸦2㸧ࡣࠊ1-࣊࢟ࢭࣥࡢ⏕ᡂ㏿ᗘࡀ࢚ࢳࣞࣥᅽࡢ 0㹼3 ḟ࡟ẚ౛ࡍࡿࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋ
᪤㏙ࡢ㏻ࡾࠊᐇ㦂࡟⏝࠸ࡓ᮲௳ୗ࡛ࡣࠊ1-࣊࢟ࢭࣥ⏕ᡂάᛶࡣ࢚ࢳࣞࣥᅽࡢ 2 ḟ࡟ẚ౛ࡋࡓࠋࡇࡢࡇ࡜ࡣࠊ[C6H12]/KFKG+KA(1+KB)[C2H4]2+KAKBKC[C2H4]3 <<(1+[C6H12]/KG)[C2H4]࡛࠶ࡾࠊ(a)KAҫ0ࠊࡍ࡞ࢃࡕ཯ᛂ A ࡢᖹ⾮ࡀཎᩱഃ࡟೫ࡗ࡚࠸ࡿࡇ࡜࡜ࠊ(b) KF>>(1+[C6H12])࡛࠶ࡿࡇ࡜ࢆ
♧ࡋ࡚࠸ࡿࠋࡑࡢ㝿ࠊᘧ㸦2㸧ࡣୗᘧࡢࡼ࠺࡟⡆␎໬ࡉࢀࡿࠋ
R=k [C2H4]2/(1+[C6H12]/KG)
KG>>[C6H12]ࡢ࡜ࡁ

R=kDKAKBKCC[C2H4]2KG<<[C6H12]ࡢ࡜ࡁ

R={kDKAKBKCKGC/[C6H12]}[C2H4]2㸦࠾ࡼࡧ KG <<[C6H12]ࡢ࡜ࡁ
ࡋࡓࡀࡗ࡚ࠊࡼࡾ㧗άᛶ࡞ゐ፹ࢆᚓࡿࡓࡵ࡟ࡣࠊKAࠊKBࠊKCࠊ࡟ࡣࠊKG ࡶ㸧ࡢ್ࡀ኱ࡁࡃ࡞ࡿᚲせࡀ࠶ࡿࠋKA ࡜ KC ࢆ኱ࡁࡃࡍࡿ࡟ࡣゐ፹ࡢ㓄఩୙㣬࿴ᗘࢆ㧗ࡵࡿࡇ࡜ࡀ᭷ຠ࡛࠶ࡿࡀࠊ୍᪉࡛ࡣ Ti 㔠ᒓࡢ㟁Ꮚᐦᗘࢆ㧗ࡵࡓ᪉ࡀ KB ࡣ኱ࡁࡃ࡞ࡿ࡜᥎ࡉࢀࡿࠋࡇࢀࡽࡢ⤖ᯝࡣࠊSFI ゐ፹㛤Ⓨࡢ⪃࠼᪉࡛࠶ࡿࠕࣇࣞ࢟ࢩࣈࣝ࡞㟁Ꮚᤵཷ⬟ຊࠖࢆࡶࡘ㓄఩Ꮚࡢ㔜せᛶ࡟ᑐᛂࡋ࡚࠸ࡿࠋ㸳㸬࠾ࢃࡾ࡟㧗άᛶ࡞ 1-࣊࢟ࢭࣥ㑅ᢥ〇㐀ゐ፹࡛࠶ࡿࠕSFI ゐ፹ࠖࡢ㛤Ⓨ࡟ࡘ࠸࡚⤂௓ࡋࡓࠋᮏゐ፹ࡣࠊ㧗άᛶ࡞࢜ࣞࣇ࢕ࣥ㔜ྜゐ፹ࠕFI ゐ፹ࠖࢆ࣮࣋ࢫ࡜ࡋࠊ࢚ࢳࣞࣥࡢ㑅ᢥⓗ୕㔞໬ࡢ཯ᛂᶵᵓࢆ⪃៖ࡋ࡚㛤ⓎࡉࢀࡓࠋࠕSFI ゐ፹ࠖࢆ㛤Ⓨࡍࡿ㐣⛬࡛ࠊ㑅ᢥⓗ࢜ࣜࢦ࣓ࣜ໬࡜࢜ࣞࣇ࢕ࣥ㔜ྜࡢゐ፹ࡢ㓄఩Ꮚࡢඹ㏻ᛶࢆ☜ㄆ࡛ࡁࡓࠋ௒ᚋࡣࠊ⌧᫬Ⅼ࡛ࡣ㧗ᛶ⬟ゐ፹ࡀᏑᅾࡋ࡞࠸ 1-࢜ࢡࢸࣥࡸ 1-ࢹࢭࣥ࡞࡝ࡢ㑅ᢥ〇㐀ゐ፹ࡢ㛤Ⓨ࡟ࡶྲྀࡾ⤌ࢇ࡛࠸ࡁࡓ࠸ࠋᩥ ⊩1)(a) Y. Suzuki, S. Kinoshita, A. Shibahara, S. Ishii, K. Kawamura, Y. Inoue, T. Fujita,Organometallics, 29, 2394 (2010); (b) S. Kinoshita, K. Kawamura, T. Fujita, Chem. Asian J., 6,284 (2011); (c) ᮌୗ᫴௓, ୕㇂ㄔ, ⸨⏣↷඾, ࣇ࢓࢖ࣥࢣ࣑࢝ࣝ, 39, 12 (2010); (d) ᕷᕝ┿୍㑻, ୰㔝㝯ᚿ, ▼஭⪷୍, ⸨⏣↷඾, ゐ፹, 57, 271 (2015); (e) ᕷᕝ┿୍㑻, ▼஭⪷୍, ⸨⏣↷඾, ᕤᴗᮦᩱ, 64, 70 (2016); (f) S. Ishii, T. Nakano, K. Kawamura, S. Kinoshita, S.
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