JP6179953B2 - 多分岐ポリマー - Google Patents
多分岐ポリマー Download PDFInfo
- Publication number
- JP6179953B2 JP6179953B2 JP2014190790A JP2014190790A JP6179953B2 JP 6179953 B2 JP6179953 B2 JP 6179953B2 JP 2014190790 A JP2014190790 A JP 2014190790A JP 2014190790 A JP2014190790 A JP 2014190790A JP 6179953 B2 JP6179953 B2 JP 6179953B2
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- JP
- Japan
- Prior art keywords
- group
- anhydro
- hydrocarbon
- general formula
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 229920000587 hyperbranched polymer Polymers 0.000 title description 3
- 229920000642 polymer Polymers 0.000 claims description 44
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 21
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 21
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 16
- 238000000569 multi-angle light scattering Methods 0.000 description 12
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 10
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 10
- 238000001542 size-exclusion chromatography Methods 0.000 description 10
- -1 biphenylyl group Chemical group 0.000 description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 235000010344 sodium nitrate Nutrition 0.000 description 8
- 239000004317 sodium nitrate Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000010538 cationic polymerization reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 150000002243 furanoses Chemical class 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000001226 reprecipitation Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 230000011987 methylation Effects 0.000 description 3
- 238000007069 methylation reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 125000005023 xylyl group Chemical group 0.000 description 3
- YBIARWIJKVMPBV-WISUUJSJSA-N (1S,2R)-1-[(2S)-oxiran-2-yl]propane-1,2,3-triol Chemical compound C1[C@H](O1)[C@@H](O)[C@H](O)CO YBIARWIJKVMPBV-WISUUJSJSA-N 0.000 description 2
- KRBIHOANUQUSRV-QWWZWVQMSA-N (1r)-1-[(2r)-oxiran-2-yl]ethane-1,2-diol Chemical compound OC[C@@H](O)[C@H]1CO1 KRBIHOANUQUSRV-QWWZWVQMSA-N 0.000 description 2
- TWNIBLMWSKIRAT-FPRJBGLDSA-N (1r,2r,3s,4r,5r)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol Chemical compound O1[C@@]2([H])OC[C@]1([H])[C@H](O)[C@H](O)[C@H]2O TWNIBLMWSKIRAT-FPRJBGLDSA-N 0.000 description 2
- GYNYBVOAJFHCRG-IVMDWMLBSA-N (1r,2r,6r,7r)-4,8-dioxabicyclo[3.2.1]octane-2,6,7-triol Chemical compound O1C2OC[C@@H](O)[C@]1([H])[C@H](O)[C@H]2O GYNYBVOAJFHCRG-IVMDWMLBSA-N 0.000 description 2
- TWNIBLMWSKIRAT-GASJEMHNSA-N (1r,2s,3s,4r)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@H]2COC1O2 TWNIBLMWSKIRAT-GASJEMHNSA-N 0.000 description 2
- AAFJXZWCNVJTMK-GUCUJZIJSA-N (1s,2r)-1-[(2s)-oxiran-2-yl]-2-[(2r)-oxiran-2-yl]ethane-1,2-diol Chemical compound C([C@@H]1[C@H](O)[C@H](O)[C@H]2OC2)O1 AAFJXZWCNVJTMK-GUCUJZIJSA-N 0.000 description 2
- HUFWTKSCHWVPCM-KVTDHHQDSA-N (1s,2r,3r)-1-[(2r)-oxiran-2-yl]butane-1,2,3,4-tetrol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H]1CO1 HUFWTKSCHWVPCM-KVTDHHQDSA-N 0.000 description 2
- MCHWWJLLPNDHGL-KVTDHHQDSA-N (2r,3s,4s,5r)-2,5-bis(hydroxymethyl)oxolane-3,4-diol Chemical compound OC[C@H]1O[C@H](CO)[C@@H](O)[C@@H]1O MCHWWJLLPNDHGL-KVTDHHQDSA-N 0.000 description 2
- MCHWWJLLPNDHGL-GUCUJZIJSA-N (2s,3s,4r,5r)-2,5-bis(hydroxymethyl)oxolane-3,4-diol Chemical compound OC[C@H]1O[C@@H](CO)[C@@H](O)[C@H]1O MCHWWJLLPNDHGL-GUCUJZIJSA-N 0.000 description 2
- MCHWWJLLPNDHGL-JGWLITMVSA-N (2s,3s,4s,5r)-2,5-bis(hydroxymethyl)oxolane-3,4-diol Chemical compound OC[C@H]1O[C@@H](CO)[C@@H](O)[C@@H]1O MCHWWJLLPNDHGL-JGWLITMVSA-N 0.000 description 2
- KLDXJTOLSGUMSJ-KVTDHHQDSA-N (3r,3ar,6r,6ar)-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound O[C@@H]1CO[C@@H]2[C@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-KVTDHHQDSA-N 0.000 description 2
- SSYDTHANSGMJTP-IMJSIDKUSA-N (3s,4s)-oxolane-3,4-diol Chemical compound O[C@H]1COC[C@@H]1O SSYDTHANSGMJTP-IMJSIDKUSA-N 0.000 description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 2
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000006017 1-propenyl group Chemical group 0.000 description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000000811 xylitol Substances 0.000 description 2
- 229960002675 xylitol Drugs 0.000 description 2
- TWNIBLMWSKIRAT-YIDFTEPTSA-N (1R,2R,3R,4S)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol Chemical compound O1C2OC[C@]1([H])[C@H](O)[C@@H](O)[C@@H]2O TWNIBLMWSKIRAT-YIDFTEPTSA-N 0.000 description 1
- HUFWTKSCHWVPCM-DPYQTVNSSA-N (1S,2S,3R)-1-[(2S)-oxiran-2-yl]butane-1,2,3,4-tetrol Chemical compound C1[C@H](O1)[C@@H](O)[C@@H](O)[C@H](O)CO HUFWTKSCHWVPCM-DPYQTVNSSA-N 0.000 description 1
- TWNIBLMWSKIRAT-SVZMEOIVSA-N (1r,2r,3s,4r)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol Chemical compound O1C2OC[C@]1([H])[C@H](O)[C@H](O)[C@H]2O TWNIBLMWSKIRAT-SVZMEOIVSA-N 0.000 description 1
- OYJJPEGOLXZHDM-ZRMNMSDTSA-N (1r,2s,3s)-5,7-dioxabicyclo[2.2.1]heptane-2,3-diol Chemical compound O1C[C@@H]2[C@@H](O)[C@H](O)C1O2 OYJJPEGOLXZHDM-ZRMNMSDTSA-N 0.000 description 1
- HFWNXHAGJNLQRO-GASJEMHNSA-N (1r,2s,3s,4r)-4-(hydroxymethyl)-5,7-dioxabicyclo[4.1.0]heptane-2,3-diol Chemical compound O[C@H]1[C@H](O)[C@@H](CO)OC2O[C@@H]21 HFWNXHAGJNLQRO-GASJEMHNSA-N 0.000 description 1
- GYNYBVOAJFHCRG-TVIMKVIFSA-N (1s,2r,5s,6r,7r)-4,8-dioxabicyclo[3.2.1]octane-2,6,7-triol Chemical compound O1[C@]2([H])[C@H](O)[C@@H](O)[C@@]1([H])OC[C@H]2O GYNYBVOAJFHCRG-TVIMKVIFSA-N 0.000 description 1
- GYNYBVOAJFHCRG-RSVSWTKNSA-N (1s,2r,6r,7r)-4,8-dioxabicyclo[3.2.1]octane-2,6,7-triol Chemical compound O1C2OC[C@@H](O)[C@@]1([H])[C@H](O)[C@H]2O GYNYBVOAJFHCRG-RSVSWTKNSA-N 0.000 description 1
- NGMRVZJUVCLGQY-IVMDWMLBSA-N (3R,4R,5S)-5-[(2R)-oxiran-2-yl]oxolane-2,3,4-triol Chemical compound O[C@@H]1[C@@H](O)C(O)O[C@@H]1[C@@H]1OC1 NGMRVZJUVCLGQY-IVMDWMLBSA-N 0.000 description 1
- JZZPVMIZFNNQNP-RSVSWTKNSA-N (3R,4R,5S,7R)-3-(hydroxymethyl)-2,6-dioxabicyclo[3.1.1]heptane-4,7-diol Chemical compound C12[C@H](O)[C@@H](O2)[C@H](O)[C@H](O1)CO JZZPVMIZFNNQNP-RSVSWTKNSA-N 0.000 description 1
- GYNYBVOAJFHCRG-GASJEMHNSA-N (4R,5R,6R,7S)-2,8-dioxabicyclo[3.2.1]octane-4,6,7-triol Chemical compound C12[C@@H](O)[C@@H](O)[C@H](O1)[C@H](O)CO2 GYNYBVOAJFHCRG-GASJEMHNSA-N 0.000 description 1
- OYJJPEGOLXZHDM-AGQMPKSLSA-N (4R,5R,6S)-2,7-dioxabicyclo[2.2.1]heptane-5,6-diol Chemical compound C12[C@@H](O)[C@@H](O)[C@H](O2)CO1 OYJJPEGOLXZHDM-AGQMPKSLSA-N 0.000 description 1
- OYJJPEGOLXZHDM-SOOFDHNKSA-N (4R,5S,6R)-2,7-dioxabicyclo[2.2.1]heptane-5,6-diol Chemical compound O1C[C@@H]2[C@@H](O)[C@@H](O)C1O2 OYJJPEGOLXZHDM-SOOFDHNKSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000006705 (C5-C7) cycloalkyl group Chemical group 0.000 description 1
- BROQXILFDWZSAC-UHFFFAOYSA-N 1,2-dimethylimidazolidine Chemical compound CC1NCCN1C BROQXILFDWZSAC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- XDPCNPCKDGQBAN-UHFFFAOYSA-N 3-hydroxytetrahydrofuran Chemical compound OC1CCOC1 XDPCNPCKDGQBAN-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- JZZPVMIZFNNQNP-QTVWNMPRSA-N C12[C@@H](O)[C@@H](O2)[C@H](O)[C@H](O1)CO Chemical compound C12[C@@H](O)[C@@H](O2)[C@H](O)[C@H](O1)CO JZZPVMIZFNNQNP-QTVWNMPRSA-N 0.000 description 1
- HFWNXHAGJNLQRO-QTVWNMPRSA-N C12[C@@H](O2)[C@@H](O)[C@H](O)[C@H](O1)CO Chemical compound C12[C@@H](O2)[C@@H](O)[C@H](O)[C@H](O1)CO HFWNXHAGJNLQRO-QTVWNMPRSA-N 0.000 description 1
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 description 1
- AVVWPBAENSWJCB-RSVSWTKNSA-N D-galactofuranose Chemical compound OC[C@@H](O)[C@@H]1OC(O)[C@H](O)[C@H]1O AVVWPBAENSWJCB-RSVSWTKNSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- TWNIBLMWSKIRAT-QTVWNMPRSA-N O1C2OC[C@]1([H])[C@@H](O)[C@H](O)[C@@H]2O Chemical compound O1C2OC[C@]1([H])[C@@H](O)[C@H](O)[C@@H]2O TWNIBLMWSKIRAT-QTVWNMPRSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- CLGXAFATQCNQCF-GKHXCVKOSA-N [C@@H]12[C@H](O)[C@@H](O)[C@@H](O1)[C@H](O)CO2.[C@@H]21[C@H](O)[C@@H](O)[C@@H](O2)[C@H](O)CO1 Chemical compound [C@@H]12[C@H](O)[C@@H](O)[C@@H](O1)[C@H](O)CO2.[C@@H]21[C@H](O)[C@@H](O)[C@@H](O2)[C@H](O)CO1 CLGXAFATQCNQCF-GKHXCVKOSA-N 0.000 description 1
- CLGXAFATQCNQCF-NMYAFYTPSA-N [C@H]12[C@@H](O)[C@@H](O)[C@H](O1)[C@H](O)CO2.[C@H]21[C@@H](O)[C@@H](O)[C@H](O2)[C@H](O)CO1 Chemical compound [C@H]12[C@@H](O)[C@@H](O)[C@H](O1)[C@H](O)CO2.[C@H]21[C@@H](O)[C@@H](O)[C@H](O2)[C@H](O)CO1 CLGXAFATQCNQCF-NMYAFYTPSA-N 0.000 description 1
- CLGXAFATQCNQCF-NPSHZYPLSA-N [C@H]12[C@@H](O)[C@@H](O)[C@H](O1)[C@H](O)CO2.[C@H]21[C@H](O)[C@@H](O)[C@H](O2)[C@H](O)CO1 Chemical compound [C@H]12[C@@H](O)[C@@H](O)[C@H](O1)[C@H](O)CO2.[C@H]21[C@H](O)[C@@H](O)[C@H](O2)[C@H](O)CO1 CLGXAFATQCNQCF-NPSHZYPLSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000002259 anti human immunodeficiency virus agent Substances 0.000 description 1
- 229940124411 anti-hiv antiviral agent Drugs 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229960003082 galactose Drugs 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 125000000755 henicosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000000832 lactitol Substances 0.000 description 1
- VQHSOMBJVWLPSR-JVCRWLNRSA-N lactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-JVCRWLNRSA-N 0.000 description 1
- 229960003451 lactitol Drugs 0.000 description 1
- 235000010448 lactitol Nutrition 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000003214 pyranose derivatives Chemical group 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
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- Polyethers (AREA)
Description
しかしながら、これらの方法では、ピラノース環を有するアンヒドロピラノース及びその誘導体の重合、エポキシ環を有するアンヒドロ糖アルコール及びその誘導体の重合、テトラヒドロフラン環を有するアンヒドロ糖アルコール及びその誘導体の重合に限定され、フラノース環を有するアンヒドロフラノース及びその類縁体の重合による多分岐ポリマーの合成が困難である。
で示される少なくとも1種の化合物の重合体からなる多分岐ポリマー。
[2] 一般式(1)
で示される少なくとも1種の化合物と、一般式(2)〜(7)
で示される群、または一般式(8)
で示される群、または一般式(9)
で示される群、または一般式(10)
で示される群から選ばれる少なくとも1種の化合物との共重合体からなる多分岐ポリマー。
[3] 前記炭化水素基が、アルキル基、アリール基またはアリールアルキル基である前記[1]または[2]に記載の多分岐ポリマー。
[4] 前記炭化水素−O−基が、アルコキシ基である前記[1]または[2]に記載の多分岐ポリマー。
[5] 分岐度が、0.05〜1.00である前記[1]〜[4]のいずれかに記載の多分岐ポリマー。
[6] 一般式(1)
で示される少なくとも1種の化合物を、カチオン重合開始剤の存在下で重合させることを特徴とする多分岐ポリマーの製造方法。
[7] 一般式(1)
で示される少なくとも1種の化合物と、一般式(2)〜(7)
で示される群、または一般式(8)
で示される群、または一般式(9)
で示される群、または一般式(10)
で示される群の中から選ばれる少なくとも1種の化合物を、カチオン重合開始剤の存在下で共重合させることを特徴とする多分岐ポリマーの製造方法。
[8] 前記炭化水素基が、アルキル基、アリール基またはアリールアルキル基である前記[6]または[7]に記載の多分岐ポリマーの製造方法。
[9] 前記炭化水素−O−基が、アルコキシ基である前記[6]または[7]に記載の多分岐ポリマーの製造方法。
[10] 前記多分岐ポリマーの分岐度が、0.05〜1.00である前記[6]〜[9]のいずれかに記載の多分岐ポリマーの製造方法。
重合開始剤の使用量は、原料化合物に対して、10質量%以下であり、好ましくは2質量%以下である。
重合反応の温度は、通常60〜220℃、好ましくは100〜160℃であり、重合時間は、通常1〜600分、好ましくは5〜120分である。
窒素雰囲気下、シュレンク管内に1,6−アンヒドロ−β−D−マンノフラノース(1.0g、メチルマンノフラノシドより合成した。)及び乾燥プロピレンカーボネート(1.5mL、アルドリッチ、モノマー濃度4.0mol・L-1)を入れ、130℃に加熱して均一溶液とした後、重合開始剤として2−ブテニルテトラメチレンスルフォニウムヘキサフルオロアンチモネート(4.4μL、66wt%プロピレンカーボネート溶液、旭電化工業)を滴下し、重合を開始した。20分後、重合溶液をメタノール中に注ぎ重合を停止した。溶媒を留去後、残渣を水、メタノールで再沈殿することにより精製した。生成物(多分岐ポリマー)の収量610mg、重量平均分子量7.4×103(サイズ排除クロマトグラフィー(SEC),0.2mol・L-1硝酸ナトリウム水溶液、40℃)、分散度2.47。絶対分子量18.8×103(多角度光散乱法(MALS),0.2mol・L-1硝酸ナトリウム水溶液、40℃)、分岐度0.42(メチル化分析)。
窒素雰囲気下、シュレンク管内に1,6−アンヒドロ−α−D−ガラクトフラノース(1.0g、ガラクトースより合成した。)及び乾燥プロピレンカーボネート(1.5mL、アルドリッチ、モノマー濃度4.0mol・L-1)を入れ、150℃に加熱して均一溶液とした後、重合開始剤として2−ブテニルテトラメチレンスルフォニウムヘキサフルオロアンチモネート(4.4μL、66wt%プロピレンカーボネート溶液、旭電化工業)を滴下し、重合を開始した。20分後、重合溶液をメタノール中に注ぎ重合を停止した。溶媒を留去後、残渣を水、メタノールで再沈殿することにより精製した。生成物(多分岐ポリマー)の収量550mg、重量平均分子量6.6×103(サイズ排除クロマトグラフィー(SEC),0.2mol・L-1硝酸ナトリウム水溶液、40℃)、分散度2.06。絶対分子量22.7×103(多角度光散乱法(MALS),0.2mol・L-1硝酸ナトリウム水溶液、40℃)、分岐度0.46(メチル化分析)。
窒素雰囲気下、シュレンク管内に1,6−アンヒドロ−β−D−マンノフラノース(1.0g、メチルグルコフラノシドより合成した。)及び乾燥プロピレンカーボネート(1.5mL、アルドリッチ、モノマー濃度4.0mol・L-1)を入れ、150℃に加熱して均一溶液とした後、重合開始剤として2−ブテニルテトラメチレンスルフォニウムヘキサフルオロアンチモネート(4.4μL、66wt%プロピレンカーボネート溶液、旭電化工業)を滴下し、重合を開始した。20分後、重合溶液をメタノール中に注ぎ重合を停止した。溶媒を留去後、残渣を水、メタノールで再沈殿することにより精製した。生成物(多分岐ポリマー)の収量600mg、重量平均分子量8.0×103(サイズ排除クロマトグラフィー(SEC),0.2mol・L-1硝酸ナトリウム水溶液、40℃)、分散度2.15。絶対分子量34.7×103(多角度光散乱法(MALS),0.2mol・L-1硝酸ナトリウム水溶液、40℃)、分岐度0.40(メチル化分析)。
窒素雰囲気下、シュレンク管内に1,6−アンヒドロ−α−D−ガラクトフラノースと1,6−アンヒドロ−β−D−ガラクトピラノース(それぞれ0.5g)及び乾燥プロピレンカーボネート(1.5mL、アルドリッチ、モノマー濃度4.0mol・L-1)を入れ、150℃に加熱して均一溶液とした後、重合開始剤として2−ブテニルテトラメチレンスルフォニウムヘキサフルオロアンチモネート(4.4μL、66wt%プロピレンカーボネート溶液、旭電化工業)を滴下し、重合を開始した。20分後、重合溶液をメタノール中に注ぎ重合を停止した。溶媒を留去後、残渣を水、メタノールで再沈殿することにより精製した。生成物(多分岐ポリマー)の収量520mg、重量平均分子量6.9×103(サイズ排除クロマトグラフィー(SEC),0.2mol・L-1硝酸ナトリウム水溶液、40℃)、分散度2.47。絶対分子量17.3×103(多角度光散乱法(MALS),0.2mol・L-1硝酸ナトリウム水溶液、40℃)。
Claims (4)
- 一般式(1)
で示される少なくとも1種の化合物の重合体からなる多分岐ポリマー。 - 前記炭化水素基が、アルキル基、アリール基またはアリールアルキル基である請求項1に記載の多分岐ポリマー。
- 前記炭化水素−O−基が、アルコキシ基である請求項1に記載の多分岐ポリマー。
- 分岐度が、0.05〜1.00である請求項1〜3のいずれかに記載の多分岐ポリマー。
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