Synthesis of Highly Defined Graft Copolymers Using a Cyclic Acetal Moiety as a Two-Stage Latent Initiating Site for Successive Living Cationic Polymerization and Ring-Opening Anionic Polymerization,Macromolecules

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Synthesis of Highly Defined Graft Copolymers Using a Cyclic Acetal Moiety as a Two-Stage Latent Initiating Site for Successive Living Cationic Polymerization and Ring-Opening Anionic Polymerization
Macromolecules ( IF 5.1 ) Pub Date : 2018-01-30 00:00:00 , DOI: 10.1021/acs.macromol.7b02622
Norifumi Yokoyama ₁ , Arihiro Kanazawa ₁ , Shokyoku Kanaoka ₁ , Sadahito Aoshima ₁

Affiliation

The synthesis of well-defined graft copolymers with designed intervals between branches was achieved using cyclic acetal moieties as two-stage latent initiating sites. A cyclic acetal was shown to initiate the living cationic polymerization of vinyl ethers (VEs), yielding a polymer with a hydroxy group at the α-end derived from the cyclic acetal. The newly generated hydroxy group was able to efficiently induce the subsequent ring-opening anionic polymerization of l-lactide (LLA), and a diblock copolymer with a narrow molecular weight distribution (MWD) was obtained. For the synthesis of a graft copolymer, a five-membered cyclic acetal moiety was introduced at the ω-chain ends of poly(VE)s, which was employed as the initiating site for the living cationic polymerization of VEs. Repeated polymerization and acetalization generated a macroinitiator with several hydroxy groups on the side chain of a poly(VE) backbone. Graft copolymers possessing branches with narrow MWDs and regular spaces between the branches were synthesized by the ring-opening polymerization of LLA using this macroinitiator.

中文翻译：

连续的阳离子聚合和开环阴离子聚合的两步潜在起始位点，以环缩醛部分为原料合成高定义的接枝共聚物

使用环状缩醛基团作为两步潜在的起始位点，可以合成具有明确定义的支链间隔的接枝共聚物。环状缩醛显示出引发乙烯基醚（VEs）的活性阳离子聚合，从而产生了从环状缩醛衍生而来的在α-末端具有羟基的聚合物。新产生的羟基能够有效地诱导随后的l的开环阴离子聚合-丙交酯（LLA）和具有窄分子量分布（MWD）的二嵌段共聚物。为了合成接枝共聚物，在聚（VE）s的ω-链末端引入了五元环缩醛部分，将其用作VEs活性阳离子聚合的起始位点。重复的聚合和缩醛化反应生成了在聚（VE）主链的侧链上带有多个羟基的大分子引发剂。使用该大分子引发剂通过LLA的开环聚合反应合成了具有窄MWD的支链且支链之间有规则间隔的接枝共聚物。

更新日期：2018-01-30

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