JP2014237850A - Multibranched polymer and method for producing the same - Google Patents
Multibranched polymer and method for producing the same Download PDFInfo
- Publication number
- JP2014237850A JP2014237850A JP2014190790A JP2014190790A JP2014237850A JP 2014237850 A JP2014237850 A JP 2014237850A JP 2014190790 A JP2014190790 A JP 2014190790A JP 2014190790 A JP2014190790 A JP 2014190790A JP 2014237850 A JP2014237850 A JP 2014237850A
- Authority
- JP
- Japan
- Prior art keywords
- group
- hydrocarbon
- anhydro
- general formula
- polymer
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000003505 polymerization initiator Substances 0.000 claims description 9
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 22
- 125000003843 furanosyl group Chemical group 0.000 abstract 1
- 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
- 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
- 238000000034 method Methods 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
- 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
- 229920000587 hyperbranched polymer Polymers 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
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 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
- 239000000126 substance Substances 0.000 description 1
- 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
Landscapes
- Polyethers (AREA)
Abstract
Description
本発明は、生体適合性のハイドロゲル等の医用基盤材料など種々の機能性材料として有用な糖またはその類縁体由来の多分岐ポリマー、及びその製造方法に関する。 The present invention relates to a multi-branched polymer derived from a sugar or an analog thereof useful as various functional materials such as a medical base material such as a biocompatible hydrogel, and a production method thereof.
有機合成的手法による糖及びその誘導体を用いる多分岐ポリマーの合成は、アンヒドロピラノース及びその誘導体の開環重合により行なわれている(特開2003-252904号公報;特許文献1)。また、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(特開2004-256804号公報;特許文献2)、あるいは、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開環重合により行なわれている(特開2005-248120号公報;特許文献3)。
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。
Synthesis of multi-branched polymers using sugars and their derivatives by organic synthetic techniques is carried out by ring-opening polymerization of anhydropyranose and its derivatives (Japanese Patent Laid-Open No. 2003-252904; Patent Document 1). Further, it is carried out by ring-opening polymerization of an anhydro sugar alcohol having an epoxy ring and a derivative thereof (Japanese Patent Laid-Open No. 2004-256804; Patent Document 2), or an anhydro sugar alcohol having a tetrahydrofuran ring and a derivative thereof (Japanese Patent Laid-Open No. 2004-256804). JP 2005-248120; Patent Document 3).
However, these methods are limited to polymerization of anhydropyranose having a pyranose ring and derivatives thereof, polymerization of anhydrosugar alcohol having an epoxy ring and derivatives thereof, polymerization of anhydrosugar alcohol having a tetrahydrofuran ring and derivatives thereof, and furanose. It is difficult to synthesize a multi-branched polymer by polymerizing anhydrofuranose having a ring and its analogs.
本発明の課題は、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及びその製造方法を提供することにある。 An object of the present invention is to provide a multi-branched polymer by polymerization of anhydrofuranose having a furanose ring and an analog thereof and a method for producing the same.
本発明は、前記課題を解決すべく鋭意研究を重ねた結果、完成されたものであり、下記の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を重合して得られる多分岐ポリマー及びその製造方法を提供する。 The present invention has been completed as a result of intensive studies to solve the above problems, and has been completed. A multibranched polymer obtained by polymerizing the following anhydrofuranose having a furanose ring and its analogs and a method for producing the same I will provide a.
[1] 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。
[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。
[1] General formula (1)
The multibranched polymer which consists of a polymer of the at least 1 sort (s) of compound shown by these.
[2] General formula (1)
At least one compound represented by formulas (2) to (7)
Or a group represented by the general formula (8)
Or a group represented by the general formula (9)
Or a group represented by the general formula (10)
The multibranched polymer which consists of a copolymer with the at least 1 sort (s) of compound chosen from the group shown by these.
[3] The multi-branched polymer according to [1] or [2], wherein the hydrocarbon group is an alkyl group, an aryl group, or an arylalkyl group.
[4] The multi-branched polymer according to [1] or [2], wherein the hydrocarbon-O- group is an alkoxy group.
[5] The multibranched polymer according to any one of [1] to [4], wherein the degree of branching is 0.05 to 1.00.
[6] General formula (1)
A method for producing a multi-branched polymer, wherein at least one compound represented by the formula (1) is polymerized in the presence of a cationic polymerization initiator.
[7] General formula (1)
At least one compound represented by formulas (2) to (7)
Or a group represented by the general formula (8)
Or a group represented by the general formula (9)
Or a group represented by the general formula (10)
A method for producing a multi-branched polymer, wherein at least one compound selected from the group represented by the formula (1) is copolymerized in the presence of a cationic polymerization initiator.
[8] The method for producing a multibranched polymer according to the above [6] or [7], wherein the hydrocarbon group is an alkyl group, an aryl group or an arylalkyl group.
[9] The method for producing a multi-branched polymer according to [6] or [7], wherein the hydrocarbon-O- group is an alkoxy group.
[10] The method for producing a multibranched polymer according to any one of [6] to [9], wherein the degree of branching of the multibranched polymer is 0.05 to 1.00.
本発明によれば、水溶性の多分岐ポリマーを再現性よく、かつ大量に合成することができ、これにより多分岐ポリマーを工業的規模で機能材料として使用することができる。また、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り得られる発明の多分岐ポリマーは、生分解性バイオプラスチック、バイオ接着剤などの化学原料、抗癌剤や抗HIV剤の原料、光学異性体分割剤などの機能性高分子材料として有用である。さらに、本発明により得られる多分岐ポリマーは、高い水溶性、低粘性、保水性、糖クラスター効果による分子認識性など多くの優れた機能性を有し、医用基盤材料や化粧品材料などへも利用可能である。 According to the present invention, it is possible to synthesize a water-soluble multi-branched polymer with high reproducibility and in large quantities, whereby the multi-branched polymer can be used as a functional material on an industrial scale. In addition, the multi-branched polymer of the invention obtained by polymerization of anhydrofuranose having a furanose ring and its analogs is composed of chemical raw materials such as biodegradable bioplastics and bioadhesives, raw materials for anticancer agents and anti-HIV agents, and optical isomers. It is useful as a functional polymer material such as a resolving agent. Furthermore, the multi-branched polymer obtained by the present invention has many excellent functions such as high water solubility, low viscosity, water retention, molecular recognition by sugar cluster effect, and can be used for medical base materials and cosmetic materials. Is possible.
前記一般式(1)〜(10)中、R及びR1〜R12が表す炭素数1〜30の炭化水素基の具体例としては、C1-30−アルキル基、例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、イソペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、エイコシル基、ヘンエイコシル基、ドコシル基、トリアコンチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基;C2-30−アルケニル基、例えばビニル基、1−プロペニル基、アリル基、1−ブテニル基、2−ブテニル基、ペンテニル基、ヘキセニル基、シクロヘキセニル基;C2-30−アルキニル基、例えばエチニル基、1−プロピニル基、2−プロピニル(プロパルギル)基、3−ブチニル基、ペンチニル基、ヘキシニル基;C6-30−アリール基、例えばフェニル基、トリル基、キシリル基、ビフェニリル基、1−ナフチル基、2−ナフチル基、アントリル基、フェナントリル基;C7-30−アリールアルキル基、例えばベンジル基、フェネチル基が挙げられる。これらの中でも、C1-30−アルキル基(例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基)、C5-7−シクロアルキル基(例えば、シクロペンチル基、シクロヘキシル基、シクロヘプチル基)、C2-7−アルケニル基(例えば、ビニル基、1−プロペニル基、アリル基、1−ブテニル基、2−ブテニル基、ペンテニル基、ヘキセニル基)、C5-7−シクロアルケニル基(例えば、シクロヘキセニル基)、C6-12−アリール基(例えば、フェニル基、トリル基、キシリル基、ビフェニリル基、1−ナフチル基、2−ナフチル基)、C7-10−アリールアルキル基(例えば、ベンジル基、フェネチル基)が好ましく、C1-4−アルキル基(例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基)、C6-12−アリール基(例えば、フェニル基、トリル基、キシリル基、ビフェニリル基、1−ナフチル基、2−ナフチル基)、C7-10−アリールアルキル基(例えば、ベンジル基、フェネチル基)が好ましい。 Specific examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R and R 1 to R 12 in the general formulas (1) to (10) include a C 1-30 -alkyl group such as a methyl group or an ethyl group. Propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, eicosyl group, heneicosyl group, Docosyl group, triacontyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group; C 2-30 -alkenyl group such as vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2- Butenyl, pentenyl, hexenyl, cyclohexenyl; C 2-30 -alkynyl, such as ethynyl, 1-propynyl, 2-propyl Lopinyl (propargyl) group, 3-butynyl group, pentynyl group, hexynyl group; C 6-30 -aryl group such as phenyl group, tolyl group, xylyl group, biphenylyl group, 1-naphthyl group, 2-naphthyl group, anthryl group Phenanthryl group; C 7-30 -arylalkyl group such as benzyl group and phenethyl group. Among these, C 1-30 -alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group), C 5-7 -cycloalkyl Group (for example, cyclopentyl group, cyclohexyl group, cycloheptyl group), C 2-7 -alkenyl group (for example, vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group) Group), C 5-7 -cycloalkenyl group (eg, cyclohexenyl group), C 6-12 -aryl group (eg, phenyl group, tolyl group, xylyl group, biphenylyl group, 1-naphthyl group, 2-naphthyl group) ), C 7-10 - aryl group (e.g., benzyl group, phenethyl group) are preferred, C 1-4 - alkyl group (e.g., methyl group, ethyl group, propyl group Isopropyl group, butyl group, isobutyl group, sec- butyl group, tert- butyl group), C 6-12 - aryl group (e.g., phenyl group, tolyl group, xylyl group, biphenylyl group, a 1-naphthyl group, 2-naphthyl Group) and a C 7-10 -arylalkyl group (for example, benzyl group, phenethyl group) are preferable.
R及びR1〜R12が表す炭素数1〜30の炭化水素−O−基とは、水酸基が前記の炭素数1〜30の炭化水素基で置換された置換基を意味し、具体例としては、C1-30−アルコキシ基、C2-30−アルケニルオキシ基、C2-30−アルキニルオキシ基、C6-30−アリールオキシ基、C7-30−アリールアルコキシ基が挙げらる。これらの中でも、C1-4−アルコキシ基(例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、sec−ブトキシ基、tert−ブトキシ基)、C6-12−アリールオキシ基(例えば、フェノキシ基、1−ナフトキシ基、2−ナフトキシ基)、C7-10−アリールアルコキシ基(例えば、ベンジルオキシ基、フェネチルオキシ基)が好ましい。 The hydrocarbon group having 1 to 30 carbon atoms represented by R and R 1 to R 12 means a substituent group in which a hydroxyl group is substituted with the above hydrocarbon group having 1 to 30 carbon atoms. C 1-30 -alkoxy group, C 2-30 -alkenyloxy group, C 2-30 -alkynyloxy group, C 6-30 -aryloxy group, C 7-30 -arylalkoxy group. Among these, C 1-4 -alkoxy groups (for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group), C 6-12 -aryl An oxy group (for example, phenoxy group, 1-naphthoxy group, 2-naphthoxy group) and a C 7-10 -arylalkoxy group (for example, benzyloxy group, phenethyloxy group) are preferable.
前記一般式(8)において、a、b、c及びdは同一または異なっていてもよく、0または1〜10の整数であるが、好ましくは0または1〜4の整数である。 In the general formula (8), a, b, c and d may be the same or different, and are 0 or an integer of 1 to 10, preferably 0 or an integer of 1 to 4.
前記一般式(9)において、nは1〜10の整数であるが、好ましくは1〜4の整数である。 In the said General formula (9), although n is an integer of 1-10, Preferably it is an integer of 1-4.
前記一般式(10)において、m及びnは同一または異なっていてもよく、0または1〜20の整数であり、好ましくは0または1〜4の整数である。 In the general formula (10), m and n may be the same or different, and are 0 or an integer of 1 to 20, preferably 0 or an integer of 1 to 4.
前記一般式(1)で示される化合物の具体例として、1,6−アンヒドロヘキソフラノース、少なくとも一つは水酸基を有するそのメチルエーテル体、エチルエーテル体、アリルエーテル体、ベンジルエーテル体が挙げられる。中でも1,6−アンヒドロヘキソフラノースである1,6−アンヒドロアロフラノース、1,6−アンヒドロアルトフラノース、1,6−アンヒドログルコフラノース、1,6−アンヒドロマンノフラノース、1,6−アンヒドログロフラノース、1,6−アンヒドロイドフラノース、1,6−アンヒドロガラクトフラノース、1,6−アンヒドログルコフラノースが好ましい。 Specific examples of the compound represented by the general formula (1) include 1,6-anhydrohexofuranose, and at least one of its methyl ether, ethyl ether, allyl ether, and benzyl ether having a hydroxyl group. It is done. Among these, 1,6-anhydrohexofuranose is 1,6-anhydroallofuranose, 1,6-anhydroaltofuranose, 1,6-anhydroglucofuranose, 1,6-anhydromannofuranose, , 6-Anhydroglofuranose, 1,6-anhydrofuranose, 1,6-anhydrogalactofuranose, 1,6-anhydroglucofuranose are preferred.
前記一般式(2)で示される化合物の具体例として、1,6−アンヒドロヘキソピラノース、少なくとも一つは水酸基を有するそのメチルエーテル体、エチルエーテル体、アリルエーテル体、ベンジルエーテル体が挙げられる。中でも1,6−アンヒドロヘキソピラノースである1,6−アンヒドロアロピラノース、1,6−アンヒドロアルトピラノース、1,6−アンヒドログルコピラノース、1,6−アンヒドロマンノピラノース、1,6−アンヒドログロピラノース、1,6−アンヒドロイドピラノース、1,6−アンヒドロガラクトピラノース、1,6−アンヒドログルコピラノースが好ましい。 Specific examples of the compound represented by the general formula (2) include 1,6-anhydrohexopyranose, and at least one of its methyl ether, ethyl ether, allyl ether, and benzyl ether having a hydroxyl group. It is done. Among these, 1,6-anhydrohexopyranose is 1,6-anhydroallopyranose, 1,6-anhydroaltopyranose, 1,6-anhydroglucopyranose, 1,6-anhydromannopyranose, , 6-Anhydroglopyranose, 1,6-Anhydroidpyranose, 1,6-Anhydrogalactopyranose, 1,6-Anhydroglucopyranose are preferred.
前記一般式(3)で示される化合物の具体例として、1,4−アンヒドロペントピラノース、少なくとも一つは水酸基を有するそのメチルエーテル体、エチルエーテル体、アリルエーテル体、ベンジルエーテル体が挙げられる。中でも1,4−アンヒドロペントピラノースである1,4−アンヒドロリボピラノース、1,4−アンヒドロキシロピラノース、1,4−アンヒドロアラビノピラノース、1,4−アンヒドロリキソピラノースが好ましい。 Specific examples of the compound represented by the general formula (3) include 1,4-anhydropentopyranose, and at least one of its methyl ether, ethyl ether, allyl ether, and benzyl ether having a hydroxyl group. . Of these, 1,4-anhydropentopyranose, 1,4-anhydroribopyranose, 1,4-anhydroxyropyranose, 1,4-anhydroarabinopyranose, and 1,4-anhydrolyxopyranose are preferable. .
前記一般式(4)で示される化合物の具体例として、1,3−アンヒドロヘキソピラノース、少なくとも一つは水酸基を有するそのメチルエーテル体、エチルエーテル体、アリルエーテル体、ベンジルエーテル体が挙げられる。中でも1,3−アンヒドログルコピラノース、1,3−アンヒドロマンノピラノースが好ましい。 Specific examples of the compound represented by the general formula (4) include 1,3-anhydrohexopyranose, and at least one of its methyl ether, ethyl ether, allyl ether, and benzyl ether having a hydroxyl group. It is done. Of these, 1,3-anhydroglucopyranose and 1,3-anhydromannopyranose are preferable.
前記一般式(5)で示される化合物の具体例として、1,2−アンヒドロヘキソピラノース、少なくとも一つは水酸基を有するそのメチルエーテル体、エチルエーテル体、アリルエーテル体、ベンジルエーテル体が挙げられる。中でも1,2−アンヒドログルコピラノース、1,2−アンヒドロマンノピラノースが好ましい。 Specific examples of the compound represented by the general formula (5) include 1,2-anhydrohexopyranose, and at least one of its methyl ether, ethyl ether, allyl ether, and benzyl ether having a hydroxyl group. It is done. Of these, 1,2-anhydroglucopyranose and 1,2-anhydromannopyranose are preferable.
前記一般式(6)で示される化合物の具体例として、5,6−アンヒドロヘキソフラノース、少なくとも一つは水酸基を有するそのメチルエーテル体、エチルエーテル体、アリルエーテル体、ベンジルエーテル体が挙げられる。中でも5,6−アンヒドログルコフラノース、5,6−アンヒドロアロフラノースが好ましい。 Specific examples of the compound represented by the general formula (6) include 5,6-anhydrohexofuranose, and at least one of its methyl ether, ethyl ether, allyl ether, and benzyl ether having a hydroxyl group. It is done. Of these, 5,6-anhydroglucofuranose and 5,6-anhydroallofuranose are preferable.
前記一般式(7)で示される化合物の具体例として、1,4:3,6−ジアンヒドロ−D−グルシトール、1,4:3,6−ジアンヒドロ−D−マンニトール、及び少なくとも一つは水酸基を有するそれらのメチルエーテル体、エチルエーテル体、アリルエーテル体、ベンジルエーテル体が挙げられる。中でも1,4:3,6−ジアンヒドロ−D−グルシトール及び1,4:3,6−ジアンヒドロ−D−マンニトールが好ましい。 Specific examples of the compound represented by the general formula (7) include 1,4: 3,6-dianhydro-D-glucitol, 1,4: 3,6-dianhydro-D-mannitol, and at least one of which has a hydroxyl group. Examples thereof include methyl ether, ethyl ether, allyl ether, and benzyl ether. Of these, 1,4: 3,6-dianhydro-D-glucitol and 1,4: 3,6-dianhydro-D-mannitol are preferable.
前記一般式(8)で示される化合物の具体例として、1,4−アンヒドロ−メソ−エリスリトール、1,4−アンヒドロ−L−トレイトール、2,5−アンヒドロ−D−マンニトール、2,5−アンヒドロ−ガラクチトール、2,5−アンヒドロ−グルシトール、及び少なくとも一つは水酸基を有するそれらのメチルエーテル体、エチルエーテル体、アリルエーテル体、ベンジルエーテル体、3−ヒドロキシテトラヒドロフラン、テトラヒドロフルフリルアルコール等が挙げられる。中でも1,4−アンヒドロ−メソ−エリスリトール、1,4−アンヒドロ−L−トレイトール、2,5−アンヒドロ−D−マンニトール、2,5−アンヒドロ−ガラクチトール、2,5−アンヒドロ−グルシトールが好ましい。 Specific examples of the compound represented by the general formula (8) include 1,4-anhydro-meso-erythritol, 1,4-anhydro-L-threitol, 2,5-anhydro-D-mannitol, 2,5- Anhydro-galactitol, 2,5-anhydro-glucitol, and at least one of them having a hydroxyl group such as methyl ether, ethyl ether, allyl ether, benzyl ether, 3-hydroxytetrahydrofuran, tetrahydrofurfuryl alcohol, etc. Can be mentioned. Among these, 1,4-anhydro-meso-erythritol, 1,4-anhydro-L-threitol, 2,5-anhydro-D-mannitol, 2,5-anhydro-galactitol, and 2,5-anhydro-glucitol are preferable. .
前記一般式(9)で示される化合物の具体例として、1,2:5,6−ジアンヒドロ−D−マンニトール、1,2:5,6−ジアンヒドロ−L−イジトール、1,2:5,6−ジアンヒドロ−アリトール、1,2:5,6−ジアンヒドロ−ガラクチトール、1,2:5,6−ジアンヒドロ−グルシトール、1,2:5,6−ジアンヒドロ−キシリトール、及び少なくとも一つは水酸基を有するそれらのメチルエーテル体、エチルエーテル体、アリルエーテル体、ベンジルエーテル体が挙げられる。中でも1,2:5,6−ジアンヒドロ−D−マンニトール、1,2:5,6−ジアンヒドロ−L−イジトール、1,2:5,6−ジアンヒドロ−アリトール、1,2:5,6−ジアンヒドロ−ガラクチトール、1,2:5,6−ジアンヒドロ−グルシトール、1,2:5,6−ジアンヒドロ−キシリトールが好ましい。 Specific examples of the compound represented by the general formula (9) include 1,2: 5,6-dianhydro-D-mannitol, 1,2: 5,6-dianhydro-L-iditol, 1,2: 5,6. -Dianhydro-allitol, 1,2: 5,6-dianhydro-galactitol, 1,2: 5,6-dianhydro-glucitol, 1,2: 5,6-dianhydro-xylitol, and at least one has a hydroxyl group Examples thereof include methyl ether, ethyl ether, allyl ether, and benzyl ether. Among them, 1,2: 5,6-dianhydro-D-mannitol, 1,2: 5,6-dianhydro-L-iditol, 1,2: 5,6-dianhydro-allitol, 1,2: 5,6-dianhydro -Galactitol, 1,2: 5,6-dianhydro-glucitol, 1,2: 5,6-dianhydro-xylitol are preferred.
前記一般式(10)で示される化合物の具体例として、1,2−アンヒドロ−D−マンニトール、1,2−アンヒドロ−L−イジトール、1,2−アンヒドロ−アリトール、1,2−アンヒドロ−ガラクチトール、1,2−アンヒドロ−グリシトール、1,2−アンヒドロ−キシリトール、1,2−アンヒドロ−スレイトール、及び少なくとも一つは水酸基を有するそれらのメチルエーテル体、エチルエーテル体、アリルエーテル体、ベンジルエーテル体が挙げられる。中でも1,2−アンヒドロ−D−マンニトール、1,2−アンヒドロ−L−イジトール、1,2−アンヒドロ−アリトール、1,2−アンヒドロ−ガラクチトール、1,2−アンヒドロ−グリシトール、1,2−アンヒドロ−キシリトール、1,2−アンヒドロ−スレイトールが好ましい。 Specific examples of the compound represented by the general formula (10) include 1,2-anhydro-D-mannitol, 1,2-anhydro-L-iditol, 1,2-anhydro-allitol, 1,2-anhydro-ga. Lactitol, 1,2-anhydro-glycitol, 1,2-anhydro-xylitol, 1,2-anhydro-threitol, and at least one of them having a hydroxyl group methyl ether, ethyl ether, allyl ether, benzyl ether The body is mentioned. Among them, 1,2-anhydro-D-mannitol, 1,2-anhydro-L-iditol, 1,2-anhydro-allitol, 1,2-anhydro-galactitol, 1,2-anhydro-glycitol, 1,2- Anhydro-xylitol, 1,2-anhydro-threitol are preferred.
本発明の多分岐ポリマーは、前記一般式(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を用いて重合させることによって製造することができる。 The multi-branched polymer of the present invention can be produced by polymerizing at least one compound represented by the general formula (1) using a cationic polymerization initiator.
カチオン重合開始剤としては、従来公知のもの、例えば、スルフォニウムアンチモネートなどの熱カチオン開始剤や光カチオン開始剤、三フッ化ホウ素エーテラート、四塩化スズ、五塩化アンチモン、五フッ化リンなどのルイス酸、トリフルオロメタンスルホン酸やフルオロスルホン酸などのブレンステッド酸等を用いることができる。
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。
As the cationic polymerization initiator, conventionally known ones such as thermal cation initiators such as sulfonium antimonate, photocation initiators, boron trifluoride etherate, tin tetrachloride, antimony pentachloride, phosphorus pentafluoride, etc. Lewis acids, Bronsted acids such as trifluoromethanesulfonic acid and fluorosulfonic acid can be used.
The usage-amount of a polymerization initiator is 10 mass% or less with respect to a raw material compound, Preferably it is 2 mass% or less.
重合反応は、溶媒を用いない塊状重合及び有機溶媒を用いる溶液重合により行うことができる。有機溶媒としては、プロピレンカーボネート、エチレンカーボネート、ジメチルイミダゾリジン、1,4−ジオキサンなどの非プロトン性有機溶媒を用いることができる。
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。
The polymerization reaction can be performed by bulk polymerization without using a solvent and solution polymerization using an organic solvent. As the organic solvent, an aprotic organic solvent such as propylene carbonate, ethylene carbonate, dimethylimidazolidine, 1,4-dioxane can be used.
The temperature of the polymerization reaction is usually from 60 to 220 ° C, preferably from 100 to 160 ° C, and the polymerization time is usually from 1 to 600 minutes, preferably from 5 to 120 minutes.
本発明における重合反応は、原料である1,6位のエーテル結合が開環し、他の原料のエーテル結合へ求電子攻撃することで重合、さらに他の原料の水酸基と結合して進行し、その結果、分岐を繰り返した多分岐ポリマーが形成される。本発明による多分岐ポリマーは、樹枝状に近い形をしており、分岐鎖からもさらに分岐ができていると考えられる。 The polymerization reaction in the present invention, the ether bond at the 1,6-position that is the raw material is ring-opened, proceeds by electrophilic attack to the ether bond of the other raw material, and further proceeds by bonding with the hydroxyl group of the other raw material, As a result, a multi-branched polymer with repeated branching is formed. The multi-branched polymer according to the present invention has a shape close to a dendritic shape and is considered to be further branched from a branched chain.
前記一般式(1)において、R1、R2の2個が水酸基である化合物の重合体からなる多分岐ポリマーは、下記一般式(11)で示される形態をしているものと推定される。 In the general formula (1), it is presumed that the multi-branched polymer composed of a polymer of a compound in which two of R 1 and R 2 are hydroxyl groups has a form represented by the following general formula (11). .
本発明の多分岐ポリマーにおいて、その分岐度は、好ましくは0.05〜1.00、より好ましくは0.35〜1.0である。この場合の多分岐度は、Frechetの式:[分岐度=(分岐ユニット数+ポリマー末端数)/(分岐ユニット数+ポリマー末端数+直鎖ユニット数)]によって算出される。このFrechetの式によると、直鎖状ポリマーの分岐度は0で、デンドリマーの分岐度は1となる。 In the multibranched polymer of the present invention, the degree of branching is preferably 0.05 to 1.00, more preferably 0.35 to 1.0. The degree of multi-branching in this case is calculated by the Frechet equation: [degree of branching = (number of branch units + number of polymer terminals) / (number of branch units + number of polymer terminals + number of straight chain units)]. According to this equation for Frech e t, at 0 degree of branching linear polymers the degree of branching of the dendrimer is 1.
本発明による一般式(1)の化合物の重合体において、その分子量は(多角度光散乱法(MALS))は、5千以上、好ましくは1万以上である。 In the polymer of the compound of the general formula (1) according to the present invention, the molecular weight (multi-angle light scattering method (MALS)) is 5,000 or more, preferably 10,000 or more.
以下、本発明を実施例により例証するが、本発明は下記の例に限定されるものではない。 Hereinafter, the present invention is illustrated by examples, but the present invention is not limited to the following examples.
実施例1:1,6−アンヒドロ−β−D−マンノフラノースのカチオン重合
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)。
Example 1: Cationic polymerization of 1,6-anhydro-β-D-mannofuranose 1,6-Anhydro-β-D-mannofuranose (1.0 g, methyl mannofuranoside in a Schlenk tube under a nitrogen atmosphere And dried propylene carbonate (1.5 mL, Aldrich, monomer concentration 4.0 mol·L −1 ), heated to 130 ° C. to make a homogeneous solution, and then 2-butenyltetra Methylene sulfonium hexafluoroantimonate (4.4 μL, 66 wt% propylene carbonate solution, Asahi Denka Kogyo) was added dropwise to initiate polymerization. After 20 minutes, the polymerization solution was poured into methanol to stop the polymerization. After the solvent was distilled off, the residue was purified by reprecipitation with water and methanol. Yield 610 mg of product (multi-branched polymer), weight average molecular weight 7.4 × 10 3 (size exclusion chromatography (SEC), 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.), dispersity 2.47. Absolute molecular weight 18.8 × 10 3 (multi-angle light scattering method (MALS), 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.), branching degree 0.42 (methylation analysis).
実施例2:1,6−アンヒドロ−α−D−ガラクトフラノースのカチオン重合
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)。
Example 2: Cationic polymerization of 1,6-anhydro-α-D-galactofuranose 1,6-Anhydro-α-D-galactofuranose (1.0 g, synthesized from galactose) and Schlenk tube under nitrogen atmosphere. Add dry propylene carbonate (1.5 mL, Aldrich, monomer concentration 4.0 mol·L −1 ), heat to 150 ° C. to make a homogeneous solution, and then use 2-butenyltetramethylenesulfonium hexafluoro as a polymerization initiator. Antimonate (4.4 μL, 66 wt% propylene carbonate solution, Asahi Denka Kogyo) was added dropwise to initiate polymerization. After 20 minutes, the polymerization solution was poured into methanol to stop the polymerization. After the solvent was distilled off, the residue was purified by reprecipitation with water and methanol. Yield of product (multi-branched polymer) 550 mg, weight average molecular weight 6.6 × 10 3 (size exclusion chromatography (SEC), 0.2 mol·L −1 aqueous sodium nitrate solution, 40 ° C.), dispersity 2.06. Absolute molecular weight 22.7 × 10 3 (multi-angle light scattering method (MALS), 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.), branching degree 0.46 (methylation analysis).
生成物の1HNMRスペクトル及び13CNMRスペクトルをそれぞれ図1及び図2に示す。図2の13CNMRスペクトルにおいて、1,6位のエーテル結合のみが開環して重合した直鎖のポリマー鎖では、60〜85ppm領域にC1からC5炭素に由来する5本の鋭いピーク及び100〜110ppm領域にC6炭素に由来する1本の鋭いピークが想定されるが、図2では100〜110ppm領域にC6炭素に由来するピークが、いくつにも分裂し、幅広くなっている。さらに他の炭素に由来するピークもいくつにも分裂し、幅広くなっていることから、多分岐状になっていることがわかる。サイズ排除クロマトグラフィー(SEC)で測定した重量平均分子量が多角度光散乱法(MALS)で測定した絶対分子量よりも小さく出る。この傾向はポリマーの有効体積のちがいによるもので、多分岐ポリマーにはよく観察される現象である。 The 1 HNMR spectrum and 13 CNMR spectrum of the product are shown in FIGS. 1 and 2, respectively. In the 13 C NMR spectrum of FIG. 2, in the linear polymer chain polymerized by ring opening of only the ether bond at the 1 and 6 positions, 5 sharp peaks derived from C1 to C5 carbon and 100 to One sharp peak derived from C6 carbon is assumed in the 110 ppm region, but in FIG. 2, the peak derived from C6 carbon in the 100 to 110 ppm region is divided into many and widened. Furthermore, since the peaks derived from other carbons are also divided and broadened, it can be seen that they are multi-branched. The weight average molecular weight measured by size exclusion chromatography (SEC) is smaller than the absolute molecular weight measured by multi-angle light scattering method (MALS). This tendency is due to the difference in the effective volume of the polymer and is a phenomenon often observed in multi-branched polymers.
実施例3:1,6−アンヒドロ−β−D−グルコフラノースのカチオン重合
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)。
Example 3: Cationic polymerization of 1,6-anhydro-β-D-glucofuranose 1,6-anhydro-β-D-mannofuranose (1.0 g, synthesized from methyl glucofuranoside in a Schlenk tube under nitrogen atmosphere And dried propylene carbonate (1.5 mL, Aldrich, monomer concentration 4.0 mol·L −1 ), heated to 150 ° C. to make a homogeneous solution, and then 2-butenyltetramethylenesulfuric acid as a polymerization initiator. Phonium hexafluoroantimonate (4.4 μL, 66 wt% propylene carbonate solution, Asahi Denka Kogyo) was added dropwise to initiate polymerization. After 20 minutes, the polymerization solution was poured into methanol to stop the polymerization. After the solvent was distilled off, the residue was purified by reprecipitation with water and methanol. Yield of product (hyperbranched polymer) 600 mg, weight average molecular weight 8.0 × 10 3 (size exclusion chromatography (SEC), 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.), dispersity 2.15. Absolute molecular weight 34.7 × 10 3 (multi-angle light scattering method (MALS), 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.), branching degree 0.40 (methylation analysis).
実施例4:1,6−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のカチオン共重合
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℃)。
Example 4: Cationic copolymerization of 1,6-anhydro-α-D-galactofuranose and 1,6-anhydro-β-D-galactopyranose 1,6-anhydro-α-D- in a Schlenk tube under a nitrogen atmosphere Add galactofuranose, 1,6-anhydro-β-D-galactopyranose (each 0.5 g) and dry propylene carbonate (1.5 mL, Aldrich, monomer concentration 4.0 mol·L −1 ) and heat to 150 ° C. Then, 2-butenyltetramethylenesulfonium hexafluoroantimonate (4.4 μL, 66 wt% propylene carbonate solution, Asahi Denka Kogyo Co., Ltd.) was added dropwise as a polymerization initiator to initiate polymerization. After 20 minutes, the polymerization solution was poured into methanol to stop the polymerization. After the solvent was distilled off, the residue was purified by reprecipitation with water and methanol. Yield 520 mg of product (multi-branched polymer), weight average molecular weight 6.9 × 10 3 (size exclusion chromatography (SEC), 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.), dispersity 2.47. Absolute molecular weight 17.3 × 10 3 (multi-angle light scattering method (MALS), 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.).
生成物(多分岐ポリマー)の各種溶媒に対する溶解度(濃度:30mg/mL、溶解時間1時間)を表1に示す。表中、○は室温で可溶、△は50℃で可溶、×は不溶を表す。 Table 1 shows the solubility of the product (multi-branched polymer) in various solvents (concentration: 30 mg / mL, dissolution time 1 hour). In the table, ◯ is soluble at room temperature, Δ is soluble at 50 ° C., and x is insoluble.
Claims (8)
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。 General formula (1)
The multibranched polymer which consists of a polymer of the at least 1 sort (s) of compound shown by these.
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。 General formula (1)
A method for producing a multi-branched polymer, wherein at least one compound represented by the formula (1) is polymerized in the presence of a cationic polymerization initiator.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014190790A JP6179953B2 (en) | 2014-09-19 | 2014-09-19 | Hyperbranched polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014190790A JP6179953B2 (en) | 2014-09-19 | 2014-09-19 | Hyperbranched polymer |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2010108168A Division JP5649161B2 (en) | 2010-05-10 | 2010-05-10 | Multi-branched polymer and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2014237850A true JP2014237850A (en) | 2014-12-18 |
JP6179953B2 JP6179953B2 (en) | 2017-08-16 |
Family
ID=52135222
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014190790A Expired - Fee Related JP6179953B2 (en) | 2014-09-19 | 2014-09-19 | Hyperbranched polymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6179953B2 (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4961193A (en) * | 1973-05-30 | 1974-06-13 | ||
JP2003252904A (en) * | 2002-03-04 | 2003-09-10 | Japan Science & Technology Corp | Multi-branched polysaccharose |
JP2004256804A (en) * | 2003-02-03 | 2004-09-16 | National Institute Of Advanced Industrial & Technology | Anhydrosugar derived multi-branched polymer chain and method for preparation of the same |
JP2005248120A (en) * | 2004-03-08 | 2005-09-15 | National Institute Of Advanced Industrial & Technology | Multi-branched polyol derived from alcohol containing tetrahydrofuran ring |
JP2007106685A (en) * | 2005-10-12 | 2007-04-26 | National Institute Of Advanced Industrial & Technology | Method for producing anhydrosugar |
JP2007217386A (en) * | 2006-02-20 | 2007-08-30 | National Institute Of Advanced Industrial & Technology | Method for producing anhydrosugar |
WO2008084705A1 (en) * | 2007-01-09 | 2008-07-17 | Kanazawa University | Method for production of anhydro sugar in ionic liquid |
-
2014
- 2014-09-19 JP JP2014190790A patent/JP6179953B2/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4961193A (en) * | 1973-05-30 | 1974-06-13 | ||
JP2003252904A (en) * | 2002-03-04 | 2003-09-10 | Japan Science & Technology Corp | Multi-branched polysaccharose |
JP2004256804A (en) * | 2003-02-03 | 2004-09-16 | National Institute Of Advanced Industrial & Technology | Anhydrosugar derived multi-branched polymer chain and method for preparation of the same |
JP2005248120A (en) * | 2004-03-08 | 2005-09-15 | National Institute Of Advanced Industrial & Technology | Multi-branched polyol derived from alcohol containing tetrahydrofuran ring |
JP2007106685A (en) * | 2005-10-12 | 2007-04-26 | National Institute Of Advanced Industrial & Technology | Method for producing anhydrosugar |
JP2007217386A (en) * | 2006-02-20 | 2007-08-30 | National Institute Of Advanced Industrial & Technology | Method for producing anhydrosugar |
WO2008084705A1 (en) * | 2007-01-09 | 2008-07-17 | Kanazawa University | Method for production of anhydro sugar in ionic liquid |
Also Published As
Publication number | Publication date |
---|---|
JP6179953B2 (en) | 2017-08-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8283410B2 (en) | Ring-opening metathesis polymerization of norbornene and oxanorbornene moieties and uses thereof | |
Mangold et al. | PEG-based multifunctional polyethers with highly reactive vinyl-ether side chains for click-type functionalization | |
Hu et al. | Ring-opening alternating copolymerization of epoxides and dihydrocoumarin catalyzed by a phosphazene superbase | |
Chen et al. | ABA and Star Amphiphilic Block Copolymers Composed of Polymethacrylate Bearing a Galactose Fragment and Poly (ε‐caprolactone) | |
Rajput et al. | Sustainable polyacetals from isohexides | |
Tran et al. | Efficient synthesis of 2-methylene-4-phenyl-1, 3-dioxolane, a cyclic ketene acetal for controlling the NMP of methyl methacrylate and conferring tunable degradability | |
Isono et al. | Controlled/living ring-opening polymerization of glycidylamine derivatives using t-Bu-P4/alcohol initiating system leading to polyethers with pendant primary, secondary, and tertiary amino groups | |
Bednarek et al. | Multihydroxyl branched polyethers. 2. Mechanistic aspects of cationic polymerization of 3-ethyl-3-(hydroxymethyl) oxetane | |
CN104245791A (en) | Multi-arm polyethylene glycol derivative, intermediate of same, and production method of same | |
Becker et al. | Joining two natural motifs: catechol-containing poly (phosphoester) s | |
US20120035341A1 (en) | Procede de polymerisation par voie catalytique de 1,4-dioxanes-2,5-diones et les polymeres correspondants | |
Unold et al. | Stereo-and regioselective cyclopolymerization of chiral 1, 7-octadiynes | |
KR20120080247A (en) | A process for the production of polysilalkylenesiloxanes | |
Zhang et al. | Dendritic polymers from vinyl ether | |
Li et al. | Diblock brush-arm star copolymers via a core-first/graft-from approach using γ-cyclodextrin and ROMP: a modular platform for drug delivery | |
JP6179953B2 (en) | Hyperbranched polymer | |
JP5649161B2 (en) | Multi-branched polymer and method for producing the same | |
JPH0768336B2 (en) | Process for producing polyether copolymer having oligooxyethylene side chain | |
Basko et al. | Cationic copolymerization of L, L‐lactide with hydroxyl substituted cyclic ethers | |
Jaworska et al. | Biodegradable polycarbonates containing side carboxyl groups—synthesis, properties, and degradation study | |
JP3721389B2 (en) | Multi-branched polymer chain derived from anhydrosugar and method for producing the same | |
JP4280824B2 (en) | Multi-branched polyol derived from alcohol containing tetrahydrofuran ring | |
JP2017515943A (en) | Cycloolefin copolymer and method for preparing the same | |
JP4170641B2 (en) | Hyperbranched polysaccharide | |
Tamaki et al. | Hyperbranched 5, 6-glucan as reducing sugar ball |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20141017 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20141113 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20150916 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150918 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20160322 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160520 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20160527 |
|
A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20160624 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170712 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6179953 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |