Structural Study of Four-Armed Amphiphilic Star-Block Copolymers: Pristine and End-Linked Tetronic T1307
Structural Study of Four-Armed Amphiphilic Star-Block Copolymers: Pristine and End-Linked Tetronic T1307
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四臂两亲星形嵌段共聚物的结构研究：原始和末端连接的 Tetronic T1307
DOI：
10.1021/acsmacrolett.5b00936
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发表时间：
2016
影响因子：
7.015
通讯作者：
Kell Mortensen and Masahiko Annaka
中科院分区：
文献类型：
--
作者：
Satoshi Minakata;Arata Hirayama;Shino Tanaka;Kell Mortensen and Masahiko Annaka
我们提出了一个比较的结构研究的30重量%的水悬浮液的两个相关系统的基础上4臂PEO-PPO型的大分子（Tetronic T1307，巴斯夫）与PPO块附近的星星中心。一种体系涉及原始的4臂PEO-PPO星星嵌段共聚物T1307。第二种体系是1：1共混物，分别由四胺（达特）和四-N-羟基琥珀酰亚胺（TNT）封端的T1307组成。这两种体系显示出共同的特征，这些特征也是从线性PEO-PPO型共聚物（Pluronic，BASF）中已知的：在低温下，测量的结构由单个分子的特征主导，而在较高温度下，PPO结构域的疏水效应导致自组装成球形或棒状胶束。这些胶束在两个系统中形成有序的中间相。原始T1307共聚物悬浮液的行为通常非常类似于线性PEO-PPO类型的二嵌段和三嵌段共聚物：在低温下的单聚物在较高温度下缔合成胶束，在温度进一步升高时随后形成立方相和六方相。30重量% Tetronic T1307的立方相具有FCC对称性。交联的30wt%1：1 TAT-TNT体系的结构基本上被组织成二维网络片。在低温下，系统是相当无序的，但仍然有一个尖锐的相关峰，这是与相邻网络片之间的距离。在升高温度时，PPO自组装导致相邻片材上的组织，导致垂直于片材的圆柱状组装。这些圆柱体形成六边形结构。
We present a comparative structural study of 30 wt % aqueous suspensions of two related systems based on 4-arm PEO–PPO type of macromolecules (Tetronic T1307, BASF) with the PPO block near the star center. One system concerns the pristine 4-arm PEO–PPO star block copolymer T1307. The second system is a 1:1 blend consisting of, respectively, tetra-amine (TAT) and tetra-N-hydroxysuccinimide (TNT) terminated T1307. The two systems show common characteristics which are also known from linear PEO–PPO type of copolymers (Pluronic, BASF): at low temperatures the measured structure is dominated by the characteristics of individual molecules, while at higher temperatures hydrophobic effects of the PPO domains cause self-assembly into spherical or rodlike micelles. These micelles form in both systems ordered mesophases. The pristine T1307 copolymer suspension behaves generally very similarly to linear PEO–PPO type of di- and triblock copolymers: unimers at low temperatures associating into micelles at higher temperatures, forming subsequently cubic and hexagonal phases upon further increase in temperatures. The cubic phase of the 30 wt % Tetronic T1307 has FCC symmetry. The structure of the cross-linked 30 wt % 1:1 TAT–TNT system is basically organized into two-dimensional network sheets. At low temperatures the system is rather disordered but still with a sharp correlation peak which is associated with the distance between neighboring network sheets. Upon raising temperatures, PPO self-assembly causes organization across neighboring sheets, resulting in cylinder-like assemblies perpendicular to the sheets. These cylinders form hexagonal structure.