JP3721389B2 - Multi-branched polymer chain derived from anhydrosugar and method for producing the same - Google Patents
Multi-branched polymer chain derived from anhydrosugar and method for producing the same Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 42
- 235000000346 sugar Nutrition 0.000 claims description 37
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 150000005846 sugar alcohols Chemical class 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 150000008163 sugars Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 13
- 235000010344 sodium nitrate Nutrition 0.000 description 13
- 239000004317 sodium nitrate Substances 0.000 description 13
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 11
- 238000001370 static light scattering Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000004676 glycans Chemical class 0.000 description 6
- 229920001282 polysaccharide Polymers 0.000 description 6
- 239000005017 polysaccharide Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 0 *CC1OC(C2*)OC2C1* Chemical compound *CC1OC(C2*)OC2C1* 0.000 description 5
- -1 alicyclic hydrocarbon Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229930182478 glucoside Natural products 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- PENWRXZLRDTNBI-ZXZARUISSA-N [(2s,3r)-3-(hydroxymethyl)oxiran-2-yl]methanol Chemical compound OC[C@H]1O[C@H]1CO PENWRXZLRDTNBI-ZXZARUISSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002243 furanoses Chemical group 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 235000010355 mannitol Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- YBIARWIJKVMPBV-WISUUJSJSA-N (1S,2R)-1-[(2S)-oxiran-2-yl]propane-1,2,3-triol Chemical class C1[C@H](O1)[C@@H](O)[C@H](O)CO YBIARWIJKVMPBV-WISUUJSJSA-N 0.000 description 1
- HUFWTKSCHWVPCM-DPYQTVNSSA-N (1S,2S,3R)-1-[(2S)-oxiran-2-yl]butane-1,2,3,4-tetrol Chemical class C1[C@H](O1)[C@@H](O)[C@@H](O)[C@H](O)CO HUFWTKSCHWVPCM-DPYQTVNSSA-N 0.000 description 1
- KRBIHOANUQUSRV-QWWZWVQMSA-N (1r)-1-[(2r)-oxiran-2-yl]ethane-1,2-diol Chemical class OC[C@@H](O)[C@H]1CO1 KRBIHOANUQUSRV-QWWZWVQMSA-N 0.000 description 1
- TWNIBLMWSKIRAT-RWOPYEJCSA-N (1r,2s,3s,4s,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-RWOPYEJCSA-N 0.000 description 1
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 150000002303 glucose derivatives Chemical class 0.000 description 1
- 150000002337 glycosamines Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000003214 pyranose derivatives Chemical group 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 238000010189 synthetic method Methods 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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Description
本発明は、生体適合性のハイドロゲルとして増粘剤や人工被覆剤などの医用材料として有用なアンヒドロ糖由来の多分岐ポリマー鎖及びその製造方法に関する。 The present invention relates to an anhydrosugar-derived multi-branched polymer chain useful as a biocompatible hydrogel as a medical material such as a thickener and an artificial coating agent, and a method for producing the same.
有機合成的手法による多分岐多糖の合成は、Ｓｃｈｕｅｒｃｈ等により、グルコース誘導体などの無水糖（アンヒドロ糖）をカチオン開環重合する事により行なっている［Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．１９５９，８１，４０５４（非特許文献１）］。
しかしながら、この方法では、分岐度および分子量の制御は困難である。さらに、生成多分岐多糖は天然に存在するピラノース環からなるグルコシド結合を有するものに限定され、例えばフラノース環からなるものやグルコシド結合を有しないものなど多分岐多糖の多様な設計は困難である。
最近では多分岐多糖を得る化学合成的な例として、糖オキサゾリン誘導体のグルコシル化反応による多分岐アミノ多糖の合成が門川等によって報告されている［Ａｎｇｅｗ．Ｃｈｅｍ．Ｉｎｔ．Ｅｄ．１９９８，３７，２３７３−２３７６（非特許文献２）、Ｐｏｌｙｍ．Ａｄｖ．Ｔｅｃｈｎｏｌ．２０００，１１，１２２（非特許文献３）］。しかしながら、この方法の適合範囲はアミノ糖のみに限られ、その他の糖類への応用が困難である。
Synthesis of multi-branched polysaccharides by an organic synthetic method is performed by cation ring-opening polymerization of anhydrosugar (anhydrosugar) such as a glucose derivative by Schuerch et al. [J. Am. Chem. Soc. 1959, 81, 4054 (Non-Patent Document 1)].
However, with this method, it is difficult to control the degree of branching and the molecular weight. Furthermore, the resulting multibranched polysaccharide is limited to those having a glucoside bond consisting of a naturally occurring pyranose ring, and it is difficult to design various multibranched polysaccharides such as those consisting of a furanose ring and those having no glucoside bond.
Recently, as a chemical synthesis example of obtaining a multibranched polysaccharide, the synthesis of a multibranched aminopolysaccharide by glucosylation reaction of a sugar oxazoline derivative has been reported by Kadokawa et al. [Angew. Chem. Int. Ed. 1998, 37, 2373-2376 (Non-Patent Document 2), Polym. Adv. Technol. 2000, 11, 122 (non-patent document 3)]. However, the applicable range of this method is limited to amino sugars only, and application to other sugars is difficult.
本発明は、簡便に合成することのできるアンヒドロ糖由来の多分岐ポリマー鎖及びその製造方法を提供することをその課題とする。 An object of the present invention is to provide an anhydrosugar-derived multi-branched polymer chain that can be easily synthesized and a method for producing the same.
本発明によれば、以下に示す多分岐ポリマー鎖及びその製造方法が提供される。
（１）下記一般式（１）
で表されるジアンヒドロ糖アルコール及び下記一般式（２）
で表されるアンヒドロ糖アルコールの中から選ばれる少なくとも１種の糖由来化合物の重合体からなる多分岐ポリマー鎖。
（２）下記一般式（１）
で表されるジアンヒドロ糖アルコール及び下記一般式（２）
で表されるアンヒドロ糖アルコールの中から選ばれる少なくとも１種の糖由来化合物と、下記一般式（３）〜（７）で表されるアンヒドロ糖の中から選ばれる少なくとも１種の糖化合物との共重合体からなる多分岐ポリマー鎖。
（３）該炭化水素基が、アルキル基、アリール基又はアリールアルキル基である前記（１）〜（２）のいずれかに記載の多分岐ポリマー鎖。
（４）分岐度が、０．０５〜１．００である前記（１）〜（３）のいずれかに記載の多分岐ポリマー鎖。
（５）下記一般式（１）
で表されるジアンヒドロ糖アルコール及び下記一般式（２）
で表されるアンヒドロ糖アルコールの中から選ばれる少なくとも１種の糖由来化合物を、カチオン開始剤又はアニオン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鎖の製造方法。
（６）下記一般式（１）
で表されるジアンヒドロ糖アルコール及び下記一般式（２）
で表されるアンヒドロ糖アルコールの中から選ばれる少なくとも１種の糖由来化合物と、下記一般式（３）〜（７）で表されるアンヒドロ糖の中から選ばれる少なくとも１種の化合物とを、カチオン開始剤又はアニオン開始剤の存在下で反応させることを特徴とする多分岐ポリマー鎖の製造方法。
（７）該炭化水素基が、アルキル基、アリール基又はアリールアルキル基である前記（５）〜（６）のいずれかに記載の方法。
（８）該多分岐ポリマー鎖の分岐度が、０．０５〜１．００である前記（５）〜（６）のいずれかに記載の方法。
According to the present invention, the following multi-branched polymer chain and a method for producing the same are provided.
(1) The following general formula (1)
Dianhydrosugar alcohol represented by the following general formula (2)
A multi-branched polymer chain comprising a polymer of at least one sugar-derived compound selected from the anhydrosugar alcohols represented by the formula:
(2) The following general formula (1)
Dianhydrosugar alcohol represented by the following general formula (2)
At least one sugar-derived compound selected from among the anhydro sugar alcohols represented by the formula: and at least one sugar compound selected from among the anhydro sugars represented by the following general formulas (3) to (7): A multi-branched polymer chain made of a copolymer.
(3) The multi-branched polymer chain according to any one of (1) to (2), wherein the hydrocarbon group is an alkyl group, an aryl group, or an arylalkyl group.
(4) The multi-branched polymer chain according to any one of (1) to (3), wherein the degree of branching is 0.05 to 1.00.
(5) The following general formula (1)
Dianhydrosugar alcohol represented by the following general formula (2)
A method for producing a multi-branched polymer chain, comprising polymerizing at least one sugar-derived compound selected from the group consisting of an anhydro sugar alcohol represented by the above formula in the presence of a cationic initiator or an anionic initiator.
(6) The following general formula (1)
Dianhydrosugar alcohol represented by the following general formula (2)
At least one sugar-derived compound selected from among anhydrosugar alcohols represented by: and at least one compound selected from among anhydrosugars represented by the following general formulas (3) to (7): A method for producing a multi-branched polymer chain, wherein the reaction is carried out in the presence of a cationic initiator or an anionic initiator.
(7) The method according to any one of (5) to (6), wherein the hydrocarbon group is an alkyl group, an aryl group, or an arylalkyl group.
(8) The method according to any one of (5) to (6), wherein the degree of branching of the multi-branched polymer chain is 0.05 to 1.00.
本発明によれば、水溶性の多分岐多ポリマー鎖を再現性よく、かつ大量に合成することが出来、これにより工業的規模で多分岐ポリマー鎖を機能材料として使用することができる。さらに、本発明は、アミロペクチンなどの天然分岐糖鎖からの調達では不可能であった構造を有し、分子量、分岐度の調整も可能となり、用途に応じた多分岐糖鎖を得ることができる。
本発明の多分岐ポリマー鎖は、ハイドロゲルとしての増粘剤や生体適合性医用基盤材料等として用いられる。
According to the present invention, a water-soluble multi-branched multi-polymer chain can be synthesized with high reproducibility and in large quantities, whereby the multi-branched polymer chain can be used as a functional material on an industrial scale. Furthermore, the present invention has a structure that was impossible by procurement from natural branched sugar chains such as amylopectin, the molecular weight and the degree of branching can be adjusted, and a multi-branched sugar chain according to the application can be obtained. .
The multi-branched polymer chain of the present invention is used as a thickener as a hydrogel, a biocompatible medical base material, or the like.
前記一般式（１）において、分子中に含まれるｎ個のＲは水素原子又は炭素数１〜３０、好ましくは１〜１０の炭化水素基を示すが、この場合の炭化水素基には、鎖状及び環状の炭化水素基が包含される。鎖状炭化水素基には、炭素数１〜３０、好ましくは１〜４のアルキル基及び炭素数２〜３０、好ましくは２〜５のアルケニル基等の鎖状脂肪族炭化水素由来の炭化水素基が包含される。環状の炭化水素基には、炭素数３〜３０、好ましくは５〜７のシクロアルキル基又はシクロアルケニル基等の脂環族炭化水素由来の炭化水素基及び芳香族炭化水素基が包含される。
芳香族炭化水素基には、炭素数６〜３０、好ましくは６〜１２のアリール基及び炭素数７〜３０、好ましくは７〜１０のアリールアルキル基等の芳香族炭化水素由来の炭化水素基が包含される。
本発明で好ましく用いられる炭化水素基は、アルキル基、アリール基及びアリールアルキル基の中から選ばれる炭化水素基である。
In the general formula (1), n R contained in the molecule represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms. In this case, the hydrocarbon group includes a chain. Shaped and cyclic hydrocarbon groups are included. The chain hydrocarbon group includes a hydrocarbon group derived from a chain aliphatic hydrocarbon such as an alkyl group having 1 to 30 carbon atoms, preferably 1 to 4 carbon atoms and an alkenyl group having 2 to 30 carbon atoms, preferably 2 to 5 carbon atoms. Is included. The cyclic hydrocarbon group includes a hydrocarbon group and an aromatic hydrocarbon group derived from an alicyclic hydrocarbon such as a cycloalkyl group or a cycloalkenyl group having 3 to 30, preferably 5 to 7 carbon atoms.
The aromatic hydrocarbon group includes a hydrocarbon group derived from an aromatic hydrocarbon such as an aryl group having 6 to 30 carbon atoms, preferably 6 to 12 carbon atoms, and an arylalkyl group having 7 to 30 carbon atoms, preferably 7 to 10 carbon atoms. Is included.
The hydrocarbon group preferably used in the present invention is a hydrocarbon group selected from an alkyl group, an aryl group and an arylalkyl group.
前記一般式（１）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。
また、前記一般式（１）のジアンヒドロ糖アルコールに含まれるｎ個のＲのうちその少なくとも１つは水素原子である。この水素原子は、ジアンヒドロ糖アルコールの重合反応において、その反応に関与し、得られる多分岐ポリマー鎖（多分岐多糖）の分岐度を高める。
In the said General formula (1), although n is an integer of 1-10, Preferably it is an integer of 1-4.
In addition, at least one of n R contained in the dianhydrosugar alcohol of the general formula (1) is a hydrogen atom. This hydrogen atom participates in the polymerization reaction of dianhydrosugar alcohol and increases the degree of branching of the resulting multibranched polymer chain (multibranched polysaccharide).
前記一般式（１）で表されるジアンヒドロ糖アルコールを例示すると、１，２：５，６−ジアンヒドロ−Ｄ−マンニトール系化合物、１，２：５，６−ジアンヒドロ−Ｌ−イジトール系化合物、１，２：５，６−ジアンヒドロ−アリトール系化合物、１，２：５，６−ジアンヒドロ−ガラクチトール系化合物、１，２：５，６−ジアンヒドロ−グルシトール系化合物、１，２：４，５−ジアンヒドロ−キシリトール系化合物等が挙げられる。 Examples of the dianhydrosugar alcohol represented by the general formula (1) include 1,2: 5,6-dianhydro-D-mannitol compound, 1,2: 5,6-dianhydro-L-iditol compound, , 2: 5,6-dianhydro-allitol compound, 1,2: 5,6-dianhydro-galactitol compound, 1,2: 5,6-dianhydro-glucitol compound, 1,2: 4,5- Examples thereof include dianhydro-xylitol compounds.
前記一般式（２）において、分子中に含まれるＲ１、ｍ個のＲ２、ｐ個のＲ３及びＲ４は水素原子又は炭素数１〜３０の炭化水素基を示す。
この場合の炭化水素基には、前記前記一般式（１）のＲに関して示したものと同様の炭化水素基が包含される。好ましい炭化水素基は、アルキル基、アリール基又はアリールアルキル基である。
In the general formula (2), R 1 , m R 2 , p R 3 and R 4 contained in the molecule represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
The hydrocarbon group in this case includes the same hydrocarbon groups as those shown for R in the general formula (1). Preferred hydrocarbon groups are alkyl groups, aryl groups or arylalkyl groups.
一般式（２）において、ｍは０〜２０、好ましくは０〜４の整数を示し、ｐは１〜２０、好ましくは１〜４の整数を示し、ｍ＋ｐは１〜２０の整数を示す。
また、前記一般式（２）のアンヒドロ糖アルコールに含まれるｍ個のＲ２及びｐ個のＲ３のうちその少なくとも１つは水素原子である。この水素原子は、アンヒドロ糖アルコールの重合反応において、その反応に関与し、得られる多分岐ポリマー鎖（多分岐ポリエーテル）の分岐度を高める。
In the general formula (2), m represents an integer of 0 to 20, preferably 0 to 4, p represents an integer of 1 to 20, preferably 1 to 4, and m + p represents an integer of 1 to 20.
In addition, at least one of m R 2 and p R 3 contained in the anhydrosugar alcohol of the general formula (2) is a hydrogen atom. This hydrogen atom participates in the polymerization reaction of an anhydro sugar alcohol and increases the degree of branching of the resulting multi-branched polymer chain (multi-branched polyether).
前記一般式（２）で表されるアンヒドロ糖アルコールを例示すると、１，２−アンヒドロ−Ｄ−マンニトール系化合物、１，２−アンヒドロ−Ｌ−イジトール系化合物、１，２−アンヒドロ−アリトール系化合物、１，２−アンヒドロ−ガラクチトール系化合物、１，２−アンヒドロ−グリシトール系化合物、１，２−アンヒドロ−キシリトール系化合物、１，２−アンヒドロ−スレイトール系化合物系化合物等が挙げられる。 Examples of the anhydrosugar alcohol represented by the general formula (2) include 1,2-anhydro-D-mannitol compound, 1,2-anhydro-L-iditol compound, 1,2-anhydro-allitol compound. 1,2-anhydro-galactitol compounds, 1,2-anhydro-glycitol compounds, 1,2-anhydro-xylitol compounds, 1,2-anhydro-threitol compounds, and the like.
本発明の多分岐ポリマー鎖は、前記一般式（１）及び一般式（２）で表されるアンヒドロ糖アルコールの中から選ばれる少なくとも１種の糖由来化合物を、重合開始剤として、カチオン開始剤又はアニオン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 chain of the present invention is a cationic initiator using, as a polymerization initiator, at least one sugar-derived compound selected from the anhydrosugar alcohols represented by the general formula (1) and the general formula (2). Alternatively, it can be produced by polymerization using an anionic initiator.
カチオン開始剤としては、従来公知のもの、例えば、スルフォニウムアント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などのブレンステッド酸等を用いることができる。
アニオン開始剤としては、従来公知のもの、例えば、ＫＯＨなどの水酸化物、ｔｅｒｔ−ＢｕＯＫやＺｎ（ＯＣＨ３）２などの金属アルコラート等の使用が好ましい。
開始剤の使用量は、原料糖化合物に対して、１〜１０ｗｔ％程度である。
As the cationic initiator, conventionally known ones, for example, thermal cationic initiators such as sulfonium anemonate, photocationic initiators, boron trifluoride etherate, tin tetrachloride, antimony pentachloride, phosphorus pentafluoride, etc. Bronsted acids such as Lewis acid and trifluoromethanesulfonic acid can be used.
As the anion initiator, conventionally known ones such as hydroxides such as KOH, metal alcoholates such as tert-BuOK and Zn (OCH 3 ) 2 are preferably used.
The usage-amount of an initiator is about 1-10 wt% with respect to a raw material sugar compound.
重合反応においては、有機溶媒を使用することができるが、この場合の有機溶媒としては、テトラヒドロフラン、ジクロロメタン、プロピレンカーボネートなどを用いることができる。 In the polymerization reaction, an organic solvent can be used. In this case, tetrahydrofuran, dichloromethane, propylene carbonate, or the like can be used as the organic solvent.
本発明におけるアンヒドロ糖アルコールの重合のメカニズムを示すと、前記一般式（１）のジアンヒドロ糖アルコールの重合反応の場合は、原料であるジアンヒドロ糖アルコールの一方のアンヒドロ基が開環し、他方のアンヒドロ基へ求核あるいは求電子攻撃することで環化、さらに他の糖の水酸基と結合する。その結果、グルコシド結合を有しない天然にはない構造単位からなる分岐した糖鎖ポリマー（多分岐糖鎖ポリマー）が形成される。一方、前記一般式（２）のアンヒドロ糖アルコールの場合には、１，２−、１，４−、１，５−、２，３−、３，５−等のアンヒドロ結合が開環し、他の糖の水酸基と結合することで、分岐したポリエーテル鎖（多分岐ポリエーテル）が形成される。また、一般式（１）および（２）のアンヒドロ糖アルコールを混合した場合の重合反応は、上記のメカニズムが共存し、多分岐多糖と多分岐ポリエーテルが共存した重合体が形成される。 The polymerization mechanism of the anhydrosugar alcohol in the present invention is shown. In the case of the polymerization reaction of the dianhydrosugar alcohol of the general formula (1), one anhydro group of the starting dianhydrosugar alcohol is ring-opened, and the other anhydrosugar is opened. By nucleophilic or electrophilic attack on the group, it cyclizes and binds to the hydroxyl group of other sugars. As a result, a branched sugar chain polymer (multi-branched sugar chain polymer) composed of a non-natural structural unit having no glucoside bond is formed. On the other hand, in the case of the anhydrosugar alcohol of the general formula (2), anhydro bonds such as 1,2-, 1,4-, 1,5-, 2,3-, 3,5-and the like are opened, A branched polyether chain (multi-branched polyether) is formed by bonding with a hydroxyl group of another sugar. In addition, in the polymerization reaction when the anhydrosugar alcohols of the general formulas (1) and (2) are mixed, the above mechanism coexists and a polymer in which the multibranched polysaccharide and the multibranched polyether coexist is formed.
前記一般式（１）のジアンヒドロ糖アルコール（ｎ＝２）の重合体の構造式を示すと、下記一般式（ａ）で表される。
前記一般式（２）のアンヒドロ糖アルコール（Ｒ１＝Ｒ４＝Ｈ、ｍ＝ｐ＝２）の重合体の構造式を示すと、下記一般式（ｂ）で表される。 The structural formula of the polymer of the anhydrosugar alcohol (R 1 = R 4 = H, m = p = 2) of the general formula (2) is represented by the following general formula (b).
本発明の多分岐ポリマー鎖において、その分岐度は、好ましくは０．０５〜１．００、より好ましくは０．４５〜１．０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 multi-branched polymer chain of the present invention, the degree of branching is preferably 0.05 to 1.00, more preferably 0.45 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 linear units)]. According to the Frechet equation, the degree of branching of the linear polymer is 0 and the degree of branching of the dendrimer is 1.
本発明による多分岐ポリマー鎖は、樹枝状に近い形をしており、分岐鎖からもさらに分岐が出来ていると考えられる。本発明の多分岐ポリマー鎖は、フラノース型の糖ユニットからなるグルコシド結合を有しない天然にはない特殊な構造単位からなる糖鎖である。 The multi-branched polymer chain according to the present invention has a shape close to a dendritic shape and is considered to be further branched from the branched chain. The multi-branched polymer chain of the present invention is a sugar chain composed of a special structural unit that does not have a glucoside bond composed of a furanose type sugar unit and does not have a natural structure.
本発明による前記一般式（１）及び（２）の糖化合物（アンヒドロ糖アルコール）の重合体において、その分子量は（静的光散乱法）は、通常、１万以上、好ましくは２０万以上である。 In the polymer of the sugar compounds (anhydro sugar alcohol) of the general formulas (1) and (2) according to the present invention, the molecular weight (static light scattering method) is usually 10,000 or more, preferably 200,000 or more. is there.
以下、本発明を実施例により詳述する。 Hereinafter, the present invention will be described in detail by way of examples.
実施例１
（１，２：５，６−ジアンヒドロ−Ｄ−マンニトールのカチオン重合）
窒素雰囲気下、シュレンク管内に１，２−５，６−ジアンヒドロ−Ｄ−マンニトール（０．５ｇ，Ｄ−マンニトールより合成した）、乾燥ジクロロメタン（６．８ｍＬ、関東化学、モノマー濃度０．５ｍｏｌ・Ｌ−１）を入れ、０℃に冷却後、開始剤として三フッ化ホウ素エーテラート２．６μＬ、関東化学）を滴下し、重合を開始した。２００時間後、重合溶液をメタノール中に注ぎ重合を停止した。アンモニア水溶液にて中和後、溶媒を留去し、水中で透析膜（スペクトラポアＭＷ５００）を用いて精製した。収量０．２０９ｇ、収率４１．８％。重量平均分子量１，９００（ＳＥＣ，０．２ｍｏｌ・Ｌ−１硝酸ナトリウム水溶液、４０℃）、分散度２．２３。重量平均分子量３．１×１０５（ＳＬＳ，０．２ｍｏｌ・Ｌ−１硝酸ナトリウム水溶液、４０℃）。慣性半径８３ｎｍ（ＳＬＳ，０．２ｍｏｌ・Ｌ−１硝酸ナトリウム水溶液、４０℃）。流体力学半径６７ｎｍ（ＤＬＳ，０．２ｍｏｌ・Ｌ−１硝酸ナトリウム水溶液、４０℃）。
生成物（多分岐糖鎖）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。
Example 1
(Cationic polymerization of 1,2: 5,6-dianhydro-D-mannitol)
In a Schlenk tube under a nitrogen atmosphere, 1,2-5,6-dianhydro-D-mannitol (0.5 g, synthesized from D-mannitol), dry dichloromethane (6.8 mL, Kanto Chemical, monomer concentration 0.5 mol·L) -1 ) was added, and after cooling to 0 ° C, boron trifluoride etherate (2.6 µL, Kanto Chemical) was added dropwise as an initiator to initiate polymerization. After 200 hours, the polymerization solution was poured into methanol to stop the polymerization. After neutralization with an aqueous ammonia solution, the solvent was distilled off and the residue was purified in water using a dialysis membrane (Spectrapore M W 500). Yield 0.209 g, yield 41.8%. Weight average molecular weight 1,900 (SEC, 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.), dispersity 2.23. Weight average molecular weight 3.1 × 10 5 (SLS, 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.). Inertia radius 83 nm (SLS, 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.). Hydrodynamic radius 67 nm (DLS, 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.).
Table 1 shows the solubility (concentration: 30 mg / mL, dissolution time 1 hour) of the product (multi-branched sugar chain) in various solvents.
生成物の１ＨＮＭＲスペクトルおよび１３ＣＮＭＲスペクトルをそれぞれ図１および図２に示す。直鎖の糖鎖では末端（Ｃ１）の炭素由来のピークがほとんどみられないのに対し、本発明の糖鎖末端（Ｃ１）の炭素由来のピーク（６０ｐｐｍ付近）が大きく見られる。さらに他の炭素に由来するピークも数本に***していることから、多分岐状になっていることがわかる。ＳＥＣで測定した重量平均分子量が静的光散乱法で測定した重量平均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。 The 1 HNMR spectrum and 13 CNMR spectrum of the product are shown in FIGS. 1 and 2, respectively. In the linear sugar chain, the carbon-derived peak at the terminal (C1) is hardly observed, whereas the carbon-derived peak (around 60 ppm) at the sugar chain terminal (C1) of the present invention is greatly observed. Furthermore, since the peaks derived from other carbons are also split into several, it can be seen that they are multi-branched. The weight average molecular weight measured by SEC appears smaller than the weight average molecular weight measured by the static light scattering method. This tendency is due to differences in the effective volume of the polymer and is often observed for multi-branched polymers.
実施例２
（１，２：５，６−ジアンヒドロ−Ｄ−マンニトールのアニオン重合）
窒素雰囲気下、シュレンク管内に１，２−５，６−ジアンヒドロ−Ｄ−マンニトール（０．５ｇ，Ｄ−マンニトールより合成した）、乾燥テトラヒドロフラン（３．４ｍＬ、関東化学、モノマー濃度１．０ｍｏｌ・Ｌ−１）を入れ、開始剤として１．０ｍｏｌ・Ｌ−１ ｔｅｒｔ−ブトキシカリウム／ＴＨＦ溶液（０．１７ｍＬ、関東化学）を滴下し、重合を開始した。３０時間後、重合溶液をメタノール中に注ぎ重合を停止した。ドライアイスにて中和後、溶媒を留去し、水中で、透析膜（スペクトラポアＭＷ５００）を用いて精製した。収量０．０８５ｇ、収率１７．０％、比旋光度＋１９．７（ｃ １．０，Ｈ２Ｏ，２３℃）。重量平均分子量１６００（ＳＥＣ，０．２ｍｏｌ・Ｌ−１硝酸ナトリウム水溶液、４０℃）、分散度５．０７、重量平均分子量１３．１×１０５（ＳＬＳ，０．２ｍｏｌ・Ｌ−１硝酸ナトリウム水溶液、４０℃）、慣性半径１３１ｎｍ（ＳＬＳ，０．２ｍｏｌ・Ｌ−１硝酸ナトリウム水溶液、４０℃）、流体力学半径１３２ｎｍ（ＤＬＳ，０．２ｍｏｌ・Ｌ−１硝酸ナトリウム水溶液、４０℃）。
生成物の１ＨＮＭＲスペクトルおよび１３ＣＮＭＲスペクトルをそれぞれ図３および図４に示す。
Example 2
(Anionic polymerization of 1,2: 5,6-dianhydro-D-mannitol)
In a Schlenk tube under a nitrogen atmosphere, 1,2-5,6-dianhydro-D-mannitol (0.5 g, synthesized from D-mannitol), dry tetrahydrofuran (3.4 mL, Kanto Chemical, monomer concentration 1.0 mol·L) −1 ) was added, and 1.0 mol·L −1 tert-butoxy potassium / THF solution (0.17 mL, Kanto Chemical) was added dropwise as an initiator to initiate polymerization. After 30 hours, the polymerization solution was poured into methanol to stop the polymerization. After neutralized with dry ice, the solvent was distilled off in water and purified using dialysis membrane (Spectra Pore M W 500). Yield 0.085 g, Yield 17.0%, Specific rotation + 19.7 (c 1.0, H 2 O, 23 ° C.). Weight average molecular weight 1600 (SEC, 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.), dispersity 5.07, weight average molecular weight 13.1 × 10 5 (SLS, 0.2 mol·L −1 sodium nitrate aqueous solution , 40 ° C.), radius of inertia 131 nm (SLS, 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.), hydrodynamic radius 132 nm (DLS, 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.).
The 1 H NMR spectrum and 13 C NMR spectrum of the product are shown in FIGS. 3 and 4, respectively.
実施例３
（２，３−アンヒドロ−エリスリトールのカチオン重合）
窒素雰囲気下、シュレンク管内に２，３−アンヒドロ−エリスリトール（１．０ｇ，シス−２−ブテン−1，４−ジオールより合成した）を入れ、１００℃に加熱後、開始剤として三フッ化ホウ素エーテラート（６．２μＬ、関東化学）を滴下し、重合を開始した。１２０時間後、重合溶液を水中に注ぎ重合を停止した。アンモニア水溶液にて中和後、溶媒を留去し、水中で透析膜（スペクトラポアＭＷ５００）を用いて精製した。収量 ０．２９４ｇ、収率２９．４％。重量平均分子量９７０（ＳＥＣ，０．２ｍｏｌ・Ｌ−１硝酸ナトリウム水溶液、４０℃）。重量平均分子量３．０×１０５（ＳＬＳ，０．２ｍｏｌ・Ｌ−１硝酸ナトリウム水溶液、４０℃）。慣性半径１１６ｎｍ（ＳＬＳ，０．２ｍｏｌ・Ｌ−１硝酸ナトリウム水溶液、４０℃）。固有粘度０．０２２ｄＬ・ｇ−１。
生成物（多分岐糖鎖）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。
Example 3
(Cationic polymerization of 2,3-anhydro-erythritol)
2,3-Anhydro-erythritol (1.0 g, synthesized from cis-2-butene-1,4-diol) was placed in a Schlenk tube under a nitrogen atmosphere, heated to 100 ° C., and boron trifluoride as an initiator. Etherate (6.2 μL, Kanto Chemical) was added dropwise to initiate polymerization. After 120 hours, the polymerization solution was poured into water to stop the polymerization. After neutralization with an aqueous ammonia solution, the solvent was distilled off and the residue was purified in water using a dialysis membrane (Spectrapore M W 500). Yield 0.294 g, yield 29.4%. Weight average molecular weight 970 (SEC, 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.). Weight average molecular weight 3.0 × 10 5 (SLS, 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.). Inertia radius 116 nm (SLS, 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.). Intrinsic viscosity 0.022 dL · g −1 .
Table 1 shows the solubility (concentration: 30 mg / mL, dissolution time 1 hour) of the product (multi-branched sugar chain) in various solvents.
生成物の１ＨＮＭＲスペクトルおよび１３ＣＮＭＲスペクトルをそれぞれ図５および図６に示す。直鎖の糖鎖でわずかに見られる末端（Ｃ３）の炭素由来のピークが本発明の糖鎖では、７０ｐｐｍ付近に大きく見られる。さらに他の炭素に由来するピークも数本に***していることから、多分岐状になっていることがわかる。ＳＥＣで測定した重量平均分子量が静的光散乱法で測定した重量平均分子量よりも小さく出る。さらに動粘度測定において固有粘度が小さな値を示した。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。 The 1 HNMR spectrum and 13 CNMR spectrum of the product are shown in FIGS. 5 and 6, respectively. The peak derived from the carbon at the terminal (C3), which is slightly seen in the straight-chain sugar chain, is greatly seen in the vicinity of 70 ppm in the sugar chain of the present invention. Furthermore, since the peaks derived from other carbons are also split into several, it can be seen that they are multi-branched. The weight average molecular weight measured by SEC appears smaller than the weight average molecular weight measured by the static light scattering method. Furthermore, the intrinsic viscosity showed a small value in the kinematic viscosity measurement. This tendency is due to differences in the effective volume of the polymer and is often observed for multi-branched polymers.
実施例４
窒素雰囲気下、シュレンク管内に２，３−アンヒドロ−エリスリトール（１．０ｇ）、１，６−アンヒドロ−β−Ｄ−マンノピラノース（０．１６２ｇ）、そしてプロピレンカーボネート（２．５ｍＬ）を入れ、１３０℃で原料を溶解し、６６重量％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溶液を添加して重合を開始した。１９２時間重合した。重合溶液を水中に注ぎ重合を停止した。アンモニア水溶液にて中和後、溶媒を留去し、水中で透析膜（スペクトラポアＭＷ５００）を用いて精製した。収量 ０．３０４ｇ、収率２６．２％。重量平均分子量１２００（ＳＥＣ，０．２ｍｏｌ・Ｌ−１硝酸ナトリウム水溶液、４０℃）。重量平均分子量７．３×１０５（ＳＬＳ，０．２ｍｏｌ・Ｌ−１硝酸ナトリウム水溶液、４０℃）。
Example 4
Under a nitrogen atmosphere, 2,3-anhydro-erythritol (1.0 g), 1,6-anhydro-β-D-mannopyranose (0.162 g), and propylene carbonate (2.5 mL) were placed in a Schlenk tube. The raw material was dissolved at 130 ° C., and a polymerization was started by adding a 66 wt% 2-butenyl-tetramethylenesulfonium hexafluoroantimonate solution. Polymerized for 192 hours. The polymerization solution was poured into water to stop the polymerization. After neutralization with an aqueous ammonia solution, the solvent was distilled off and the residue was purified in water using a dialysis membrane (Spectrapore M W 500). Yield 0.304 g, yield 26.2%. Weight average molecular weight 1200 (SEC, 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.). Weight average molecular weight 7.3 × 10 5 (SLS, 0.2 mol·L −1 sodium nitrate aqueous solution, 40 ° C.).
Claims (8)
で表されるジアンヒドロ糖アルコール及び下記一般式（２）
で表されるアンヒドロ糖アルコールの中から選ばれる少なくとも１種の糖由来化合物の重合体からなる多分岐ポリマー鎖。 The following general formula (1)
Dianhydrosugar alcohol represented by the following general formula (2)
A multi-branched polymer chain comprising a polymer of at least one sugar-derived compound selected from the anhydrosugar alcohols represented by the formula:
で表されるジアンヒドロ糖アルコール及び下記一般式（２）
で表されるアンヒドロ糖アルコールの中から選ばれる少なくとも１種の糖由来化合物と、下記一般式（３）〜（７）で表されるアンヒドロ糖の中から選ばれる少なくとも１種の糖化合物との共重合体からなる多分岐ポリマー鎖。
Dianhydrosugar alcohol represented by the following general formula (2)
At least one sugar-derived compound selected from among the anhydro sugar alcohols represented by the formula: and at least one sugar compound selected from among the anhydro sugars represented by the following general formulas (3) to (7): A multi-branched polymer chain made of a copolymer.
で表されるジアンヒドロ糖アルコール及び下記一般式（２）
で表されるアンヒドロ糖アルコールの中から選ばれる少なくとも１種の糖由来化合物を、カチオン開始剤又はアニオン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鎖の製造方法。 The following general formula (1)
Dianhydrosugar alcohol represented by the following general formula (2)
A method for producing a multi-branched polymer chain, comprising polymerizing at least one sugar-derived compound selected from the group consisting of an anhydro sugar alcohol represented by the above formula in the presence of a cationic initiator or an anionic initiator.
で表されるジアンヒドロ糖アルコール及び下記一般式（２）
で表されるアンヒドロ糖アルコールの中から選ばれる少なくとも１種の糖由来化合物と、下記一般式（３）〜（７）で表されるアンヒドロ糖の中から選ばれる少なくとも１種の化合物とを、カチオン開始剤又はアニオン開始剤の存在下で反応させることを特徴とする多分岐ポリマー鎖の製造方法。
Dianhydrosugar alcohol represented by the following general formula (2)
At least one sugar-derived compound selected from among anhydrosugar alcohols represented by: and at least one compound selected from among anhydrosugars represented by the following general formulas (3) to (7): A method for producing a multi-branched polymer chain, wherein the reaction is carried out in the presence of a cationic initiator or an anionic initiator.
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