Supramolecular X-Shaped Homopolymers and Block Polymers by Midsegment Complementary Hydrogen Bonds: Design of Bifunctional Initiators with Interactive Sites for Metal-Catalyzed Living Radical Polymerization
作者:Sang-Ho Lee、Makoto Ouchi、Mitsuo Sawamoto
DOI:10.1021/ma300479s
日期:2012.5.8
homopolymers (PMMA and PS, respectively) with a DAD or an ADA unit at the backbone center. Upon mixing in CDCl3, for example, a pair of “complementary” polymers, such as PMMA-DAD-PMMA and PS-ADA-PS, formedsupramolecular X-shaped “block” polymers via the multiple hydrogen bond association between their midchain DAD and ADA sites, as demonstrated by in situ 1H NMR (association constant ∼102). 1H DOSY analysis
两条聚合物链,每条聚合物链的中心都带有一个互补的多个氢键结合位点,形成了超分子嵌段共聚物,其中两个链段以X形连接。为了精确合成配对的前体聚合物,设计了一组双功能引发剂X-DAD-X和Y-ADA-Y,它们由三个串联的氢键形成位点组成(DAD或ADA; D =氢供体) ; A =氢受体)和两个用于钌催化的活性自由基聚合的起始位点(X或Y);因此,DAD和ADA单元在超分子缔合时彼此互补。通常,DAD是衍生自2,6-二氨基吡啶的-NH–C–N–C–NH–单元,而ADA是衍生自2'-脱氧尿苷的–CO–NH–CO–单元。这些官能化的引发剂引发了甲基丙烯酸甲酯和苯乙烯的活性自由基聚合反应,从而在骨架中心带有DAD或ADA单元的均聚物(分别为PMMA和PS)。在CDCl中混合后参见图3,例如,一对“互补”聚合物,例如PMMA-DAD-PMMA和PS-ADA-PS,通过其中链DAD和ADA位点之间的多个氢
Convergent synthesis of digitally-encoded poly(alkoxyamine amide)s
Binary-encoded poly(alkoxyamine amide)s were prepared by oligomer ligation.
通过寡聚物连接制备了二进制编码的聚(烷氧基胺酰胺)。
POLYMER PRODUCTION METHOD AND RADICAL POLYMERIZATION INITIATING GROUP-CONTAINING COMPOUND
申请人:Dainichiseika Color & Chemicals Mfg. Co., Ltd.
公开号:EP3424960A1
公开(公告)日:2019-01-09
The present invention provides: a novel production technique that enables production of a polymer whose molecular weight and molecular weight distribution are controlled and production of a polymer having a complicated structure in a desirably controlled manner using commercially available materials without using a radical polymerization initiator or a special material for use in living radical polymerization and without the need for strict polymerization conditions; and a radical polymerization initiating group-containing compound for use in the technique. The present invention relates to:
a method for producing a polymer, the method including a polymerization step of mixing and warming (1) a radically polymerizable monomer, (2) an organic compound wherein at least one group that functions as a group for initiating polymerization of the monomer and that has a structure represented by formula 1 or formula 2 (X in the formula represents Cl or Br) is introduced in a molecule of the organic compound, and (3) an iodine-containing compound, thereby initiating, from the group having the structure, radical polymerization accompanied by a termination reaction; and the organic compound of (2) for use in the method.
PRODUCTION METHOD FOR POLYMER, COMPOUND CONTAINING RADICAL-POLYMERIZATION INITIATION GROUP, AND POLYMER
申请人:Dainichiseika Color & Chemicals Mfg. Co., Ltd.
公开号:EP3604354A1
公开(公告)日:2020-02-05
Provided are: a novel polymerization technique by which a polymer having a controlled molecular weight or molecular weight distribution or a polymer having a desirably regulated, complicated structure can be obtained using commercially available general-purpose materials without using any radical polymerization initiator, or any special material for use in living radical polymerization and without requiring any strict polymerization conditions; a radical polymerization initiation group-containing compound for use in the technique; and a polymer obtained thereby. Specifically, provided are: a method for producing a polymer, the method including a polymerization step of mixing and warming (1) a radically polymerizable monomer, (2) an organic compound having at least one group introduced in a molecule thereof, the group functioning as a polymerization initiation group for the monomer and having a structure represented by formula 1, and (3) a chloride ion-containing and/or bromide ion-containing compound selected from among specific compounds, thereby initiating radical polymerization from the group having the structure, the radical polymerization accompanying a termination reaction; a radical polymerization initiation group-containing compound; and a polymer.
NOVEL MACROINITIATOR, PRODUCTION METHOD THEREOF AND METHOD FOR PRODUCING BLOCK COPOLYMER
申请人:National University Corporation
Tokyo University of Agriculture and Technology
公开号:EP3680257A1
公开(公告)日:2020-07-15
Provided is an aliphatic polycarbonate applicable to the production of a block copolymer by radical polymerization. The aliphatic polycarbonate is represented by formula (1):
wherein R1, R2, R3, and R4 are identical or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; A and B are identical or different, and each represents a substituent that serves as an initiating group for living radical polymerization, a hydroxy group, an alkoxy group, an acyloxy group, or a carboxy group, provided that at least one of A and B is a substituent that serves as an initiating group for living radical polymerization; and m is an integer of 10 to 2500.
本发明提供了一种脂肪族聚碳酸酯,适用于通过自由基聚合生产嵌段共聚物。该脂肪族聚碳酸酯由式(1)表示:
其中 R1、R2、R3 和 R4 相同或不同,且各自代表氢原子、具有 1 至 15 个碳原子的取代或未取代的烷基或具有 6 至 20 个碳原子的取代或未取代的芳基;A 和 B 相同或不同,各自代表作为活自由基聚合引发基的取代基、羟基、烷氧基、酰氧基或羧基,条件是 A 和 B 中至少有一个是作为活自由基聚合引发基的取代基;以及 m 是 10 至 2500 的整数。