Synthesis of New Aprotic Polar Polymers

新型非质子极性聚合物的合成

• 批准号: 11450357
• 负责人: CHUJO Yoshiki
• 金额: $ 8.58万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11450357/
• 关键词: Aprotic Polar Polymers; Aprotic Polar Solvents; DMAC; DMSD; HMPA; Amphiphilicity; Miscibility; Polymer Reaction

N, N-Dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), and hexamethyl-phosphoric triamide (HMPA) are unique and useful aprotic polar solvents in organic synthesis. In this research project, the polymer homologues of these polar solvents were synthesized.First, the polymer homologue of DMSO was prepared. Aliphatic polysulfoxides were successfully synthesized from the corresponding aliphatic polysulfides by the oxidation using hydrogen peroxide. The polysulfoxides obtained were used as oxidizing reagents in Swern oxidation. A real polymer homologue of DMSO, poly-(ethylene sulfoxide) was prepared by selective oxidation of poly (ethylene sulfide).The poly (HMPA) was synthesized by the polymer reaction of linear poly (ethyleneimine) with bis (dimethylamino) phosphoryl chloride in the presence of DBU.The poly (HMPA) obtained showed good miscibility with commodity polymers such as polystyrene. The poly (HMPA) was also prepared by ring-opening polymerization of bis (dimethylamino) phosphorylpropylenimine.As an example of poly (DMAc), poly (N, N-dimethylcarbamoylmethylene) having amide groups on all main chain carbons was successfully prepared by the polymer reaction of poly (fumaric acid).

N， N-二甲基乙酰胺（DMAc）、二甲基亚砜（DMSO）和六甲基磷酸三酰胺（HMPA）是有机合成中独特而有用的非质子极性溶剂。在本研究项目中，合成了这些极性溶剂的聚合物同源物。首先，制备了DMSO的聚合物同系物。以相应的脂肪族聚硫化物为原料，用双氧水氧化合成了脂肪族聚亚砜。所制得的聚亚砜作为氧化试剂用于Swern氧化。通过对聚硫乙烯的选择性氧化，制备了一种真正的DMSO聚合物同系物——聚亚砜。在DBU的存在下，采用线性聚乙亚胺与二（二甲胺）磷酸氯酯的聚合反应合成了HMPA。所制得的HMPA与聚苯乙烯等商品聚合物具有良好的混相性。采用开环聚合法制备了双（二甲胺）磷酸丙胺聚合物。以聚富马酸为例，成功制备了主链上全酰胺基团的聚（N， N-二甲基氨基甲酰亚甲基）。

项目成果

Toshiyuki Oyama, Kensuke Naka, Yoshiki Chujo: "Polymer Homolog of DMSO.Synthesis of Poly (ethylene sulfoxide) by Selective Oxidation of Poly (ethylene sulfide)."Macromolecules. 32. 5240 (1999)

Toshiyuki Oyama、Kensuke Naka、Yoshiki Chujo：“DMSO 的聚合物同系物。通过聚（乙硫醚）选择性氧化合成聚（乙撑亚砜）。”大分子。

T.Oyama,Y.Chujo: "Synthesis of Highly Optically Active Poly - sulfoxides by Assymmetric Oxidation."Macromolecules. 32・23. 7732-7736 (1999)

T.Oyama，Y.Chujo：“通过不对称氧化合成高光学活性聚亚砜。”32・23（1999）。

T.Oyama,K.Naka,Y.Chujo: "Polymer Homolog of DMSO: Synthesis of Polylethy line sulfoxide) by Selective Oxidation"Macromolecules. 32・16. 5240-5242 (1999)

T.Oyama、K.Naka、Y.Chujo：“DMSO 的聚合物同系物：通过选择性氧化合成聚乙烯亚砜”32・16（1999）。

Y.Imai,K.Adachi,K.Naka,Y.Chujo: "Photochromic Organic-Inorganic Polymer Hybrids from Spiropyron-Modified Poly (DMAc)"Polymer Bulletin. 44・1. 9-15 (2000)

Y. Imai、K. Adachi、K. Naka、Y. Chujo：“来自螺吡喃改性聚 (DMAc) 的光致变色有机-无机聚合物杂化物”聚合物通报 44・1 (2000)。

T.Oyama,K.Naka,Y.Chujo: "Polymer Homolog of DMSO : Synthesis of Polylethylene sulforidel by Selective Oxidation"Macromolecules. 32・16. 5240-5242 (1999)

T.Oyama、K.Naka、Y.Chujo：“DMSO 的聚合物同系物：通过选择性氧化合成聚亚乙基硫醚”32・16（1999）。