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The Extreme of Disentanglement: 100-fold Viscosity Reduction in Model Single-Chain Nanoparticles 解缠的极限:单链纳米粒子模型粘度降低 100 倍
IF 5.5 1区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-07-13 DOI: 10.1021/acs.macromol.3c02650
Yifu Ruan, Qingzhi Zou, Haoyan Zhang, Yipeng Zhang, Hao Zhang, Weiwei Wu, Hao Liu, Jiajun Yan, GengXin Liu
The melt rheology of single-chain nanoparticles (SCNPs), which are synthesized by intrachain cross-linking of linear precursors, remains an unresolved issue. In this study, we synthesized linear precursors with different molecular weights (MW) and varying mole percentages of cross-linkers (CrF). The cross-linker, 4-vinylbenzocyclobutene, undergoes thermal-induced coupling. The resulting SCNPs in the melt state exhibited four distinct types of linear viscoelastic behavior: 1) reduced entanglement, 2) viscous-dominant liquids, 3) viscoelastic liquid with an elastic plateau and terminal relaxation, and 4) viscoelastic solid, a persistent elastic plateau with unmeasurable long terminal relaxation times. We observed a nonmonotonic change in viscoelastic behavior as the cross-linking increases. At CrF equal to 4%, Type 1 SCNP is still polymer-like, but the degree of entanglement is reduced. When CrF increased to 8%, the elastic plateau completely disappeared, and the viscous-dominant behavior is similar to the Zimm or Rouse model. Complete disentanglement is achieved even for high MW. In Type 2, the relaxation times and zero-shear viscosities show weaker dependence (a power of 1) on MW compared to linear polymers (a power of 3.4). Thus, the relaxation times and viscosities of such SCNPs can be 100 times smaller than their linear counterparts of the same MW. At even higher CrF, the storage modulus would surpass the loss modulus again if the MW is sufficiently high. This elasticity is due to a mechanism other than entanglements but is analogous to the colloidal domain. Relaxation times or viscosities increase divergently and exceed the experimental measurability in Type 4. The boundary between Types 3 and 4 might be considered as the boundary between polymers and colloids. Using SCNPs as a model system for detailed rheological characterization, we demonstrate the dynamics of the transition from linear polymers to particles. Type 2 SCNPs could be regarded as the extreme of disentanglement, achieved by an appropriate amount of intrachain cross-linking. Such a significant viscosity reduction might support the development of more energy-efficient polymers.
单链纳米粒子(SCNPs)是通过线性前驱体链内交联合成的,其熔体流变学仍是一个悬而未决的问题。在本研究中,我们合成了不同分子量(MW)和不同摩尔百分比交联剂(CrF)的线性前体。交联剂 4-乙烯基苯并环丁烯会发生热诱导耦合。由此产生的 SCNPs 在熔融状态下表现出四种不同类型的线性粘弹性行为:1)缠结性降低;2)粘性为主的液体;3)具有弹性高原和末端松弛的粘弹性液体;4)粘弹性固体,即具有难以测量的长末端松弛时间的持久弹性高原。我们观察到,随着交联度的增加,粘弹性行为发生了非单调变化。当 CrF 等于 4% 时,1 型 SCNP 仍类似聚合物,但缠结程度降低。当 CrF 增加到 8% 时,弹性高原完全消失,粘性主导行为类似于 Zimm 或 Rouse 模型。即使是高 MW 也能实现完全解缠。在 2 型聚合物中,与线性聚合物相比,松弛时间和零剪切粘度对分子量的依赖性较弱(1 的幂次)(3.4 的幂次)。因此,这类 SCNPs 的松弛时间和粘度比相同分子量的线性聚合物小 100 倍。在 CrF 更高的情况下,如果截留分子量足够高,储存模量将再次超过损耗模量。这种弹性是由缠结以外的机制造成的,但与胶体域类似。松弛时间或粘度会发散性增加,并超过第 4 类的实验可测量性。第 3 类和第 4 类之间的界限可视为聚合物和胶体之间的界限。我们以 SCNPs 为模型系统进行了详细的流变学表征,展示了从线性聚合物向颗粒过渡的动态过程。第 2 类 SCNPs 可视为解缠的极致,可通过适量的链内交联实现。这种粘度的显著降低可能有助于开发更节能的聚合物。
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引用次数: 0
Modulation of π-Conjugation of Polymer Main Chain Containing π-Extended Benzoxaborin by Molecular Addition 通过分子添加调控含π-扩展苯并氧硼烷的聚合物主链的π-共轭作用
IF 5.5 1区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-07-12 DOI: 10.1021/acs.macromol.4c00799
Shuhei Morimoto, Kazuya Tanimura, Masayuki Gon, Takatoshi Suematsu, Ken Okamoto, Hiroyuki Watanabe, Hideo Taka, Hiroshi Kita, Kazuo Tanaka
We synthesize novel cyclic boronic acids incorporated into the main-chain π-conjugated system. The optical measurements under basic conditions reveal that the oligomer binds one-to-one to the sugar containing the cis-1,2-diol structure at the cyclic boronic acid moiety. In particular, the binding is accompanied by a bathochromic shift in absorption and emission spectra. The π-conjugated polymer maintained similar characteristics to the oligomer but showed emission in the longer wavelength region (λPL = 493–525 nm) where the color change was clearly detectable before and after the coordination of diols. Theoretical calculations with density functional theory reveal that the diol bonding to the cyclic boronic acid moiety elevates the energy levels of frontier molecular orbitals, especially the highest occupied molecular orbital. This study demonstrates that the introduction of cyclic boronic acid into π-conjugated polymers is effective for detecting diols with emission color change under mild conditions as well as for manipulating the electronic structures of polymer main chains.
我们合成了融入主链 π 共轭体系的新型环硼酸。在基本条件下进行的光学测量显示,低聚物能与环硼酸分子上含有顺式-1,2-二醇结构的糖一对一地结合。特别是,这种结合伴随着吸收光谱和发射光谱的浴色偏移。π-共轭聚合物保持了与低聚物相似的特性,但在较长的波长区域(λPL = 493-525 nm)显示出发射光谱,在二元醇配位前后可明显检测到颜色的变化。密度泛函理论的理论计算显示,二元醇与环硼酸分子的结合提高了前沿分子轨道的能级,尤其是最高占据的分子轨道。这项研究表明,在 π 共轭聚合物中引入环硼酸可以有效地检测二元醇,并在温和的条件下产生发射颜色变化,还可以操纵聚合物主链的电子结构。
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引用次数: 0
Leveraging Impurities in Macromonomers from Direct-Growth Polymerizations to Produce Supersoft Bottlebrush Networks with Tunable Mechanical Properties 利用直接生长聚合反应产生的大单体中的杂质,生产具有可调机械特性的超软底刷网络
IF 5.5 1区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-07-12 DOI: 10.1021/acs.macromol.4c01419
Yutong Liu, Henry L. Cater, Anthony J. Arrowood, Gabriel E. Sanoja, Zachariah A. Page
Bottlebrush polymers are coveted for their supersoft, tissue-like properties. Accordingly, several approaches have emerged to create these materials, yet synthetic challenges remain regarding the number of iterative reactions required to prepare precursors and the cocreation of difficult-to-remove impurities, such as unfunctionalized or bis-functionalized macromonomers (MMs). In this work, we develop a tandem photoiniferter and ring-opening metathesis polymerization method to furnish poly(n-butyl acrylate) bottlebrush polymers and networks without the requirement for MM postfunctionalization or the addition of further cross-linking agents. Systematic optimization of polymerization conditions enabled the preparation of ultrahigh-molecular-weight bottlebrush polymers (∼1000 kDa) with narrow dispersity (∼1.2) along with solvent-free elastomers having moduli akin to those of supersoft biological tissues (∼10 kPa). Mechanical properties of the networks were easily tailored by controlling the conversion of photoiniferter polymerization due to its correlation with the amount of in situ cross-linker formed. This report provides a streamlined approach to generate bottlebrush polymers while simultaneously providing structure–property relationships that will inform their preparation and utility in biomedical applications, such as tissue engineering and adhesives.
Bottlebrush 聚合物因其超软、类似组织的特性而备受青睐。因此,出现了几种制造这些材料的方法,但合成方面的挑战依然存在,包括制备前体所需的迭代反应次数,以及难以去除的杂质(如未官能化或双官能化的大单体 (MM))。在这项工作中,我们开发了一种串联光增塑剂和开环偏聚聚合法,用于制备聚丙烯酸正丁酯瓶丛聚合物和网络,而不需要 MM 后官能化或添加进一步的交联剂。通过系统优化聚合条件,制备出了具有窄分散度(1.2)的超高分子量瓶丛聚合物(1000 kDa)以及无溶剂弹性体,其模量与超软生物组织(10 kPa)类似。由于光增塑剂聚合的转化率与原位形成的交联剂数量相关,因此通过控制光增塑剂聚合的转化率可以轻松定制网络的机械性能。本报告提供了一种生成底层聚合物的简化方法,同时提供了结构-性能关系,为其制备及其在组织工程和粘合剂等生物医学应用中的实用性提供了参考。
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引用次数: 0
Mechanochromic Luminescence of π-Conjugated Polymer Based on Pyridylenolate Boron Complexes: Molecular Design and Application to Shear-Force Memory 基于吡啶烯酸硼配合物的π-共轭聚合物的机械变色发光:剪切力记忆的分子设计与应用
IF 5.5 1区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-07-12 DOI: 10.1021/acs.macromol.4c01149
Yuto Aoyama, Shunichiro Ito, Kazuo Tanaka
Mechanochromic luminescent (MCL) materials show emission color changes in response to external force. Although the development of MCL conjugated polymers is one of the hot topics because of their wide applicability for fabricating film-type mechanical and pressure sensors, it is still challenging to observe MCL behaviors from single-component polymer films. Herein, we report the MCL properties of the conjugated polymer consisting of boron pyridylenolate in film and its mechanism. We prepared copolymers involving pyridylenolate complexes bearing difluoride and diphenyl groups on boron and investigated their optical properties. Consequently, we found that the fluorine-substituted complex and especially its conjugated polymer showed clear MCL. From the mechanistic studies, we concluded that the degree of intermolecular interactions should play a key role in MCL behaviors. The boron complex units in the polymer main chain can detect microenvironmental changes in polymer morphology as luminescent color changes caused by the mechanical treatments owing to high environmental sensitivity. Finally, based on the sensitive MCL behaviors of the polymer, it was demonstrated that the polymer film was able to work as a shear-force memory at the tiny spot for needle puncture marks.
机械变色发光(MCL)材料在外力作用下会显示出发射颜色的变化。由于 MCL 共轭聚合物可广泛应用于制造薄膜型机械和压力传感器,因此开发 MCL 共轭聚合物是热门话题之一,但从单组分聚合物薄膜中观察 MCL 行为仍具有挑战性。在此,我们报告了由吡啶烯酸硼组成的共轭聚合物在薄膜中的 MCL 特性及其机理。我们制备了含有吡啶烯酸硼配合物的共聚物,这些配合物在硼上带有二氟化基和二苯基,并研究了它们的光学特性。结果我们发现,氟取代的配合物,尤其是其共轭聚合物显示出明显的 MCL。通过机理研究,我们得出结论:分子间相互作用的程度在 MCL 行为中起着关键作用。聚合物主链中的硼络合单元具有很高的环境灵敏度,可以检测聚合物形态的微环境变化,如机械处理引起的发光颜色变化。最后,基于聚合物灵敏的 MCL 行为,研究证明聚合物薄膜能够在针刺痕的微小位置上起到剪切力记忆的作用。
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引用次数: 0
Stearic Acid-Infused PDMS PolyMIPEs Exhibiting Shape Memory Behavior 注入硬脂酸的 PDMS 聚甲基丙烯酸酯具有形状记忆特性
IF 5.5 1区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-07-12 DOI: 10.1021/acs.macromol.4c00457
Anthony Smith, Anna Brown, Jack Newman, Neil Ayres
Emulsion-templated polymerizations are an attractive route to prepare porous materials that possess broad tunability by controlling the features of the emulsion template. Emulsion-templated polymer materials possessing shape memory behavior have also been reported, usually using (meth)acrylate monomers. However, achieving shape memory properties in emulsion-templated materials with polymers that do not possess accessible thermal transitions, including polydimethylsiloxane (PDMS), remains challenging. Here, porous PDMS materials have been prepared with stearic acid within the continuous phase of the emulsion template. The inclusion of stearic acid imparts the material with a transition temperature of ∼70 °C, and the porous materials in this work obtained fixity >90% and recovery >95% over multiple shape memory cycles. These results demonstrate how low glass-transition temperature emulsion-templated polymer materials can easily be given shape memory properties. This work should be a starting point for studies of elastomeric emulsion-templated polymer materials in applications, including in soft robotics.
通过控制乳液模板的特征来制备具有广泛可调性的多孔材料,乳液封装聚合是一种极具吸引力的方法。通常使用(甲基)丙烯酸酯单体制备具有形状记忆特性的乳液封装聚合物材料也有报道。然而,使用聚二甲基硅氧烷(PDMS)等不具备可获得热转变的聚合物来实现乳液模板材料的形状记忆特性仍然具有挑战性。在此,我们在乳液模板的连续相中加入硬脂酸,制备了多孔 PDMS 材料。硬脂酸的加入使材料的转变温度达到了 ∼ 70 °C,该研究中的多孔材料在多次形状记忆循环中获得了 90% 的固定性和 95% 的恢复性。这些结果表明,低玻璃化转变温度的乳液模板聚合物材料很容易获得形状记忆特性。这项工作应该成为研究弹性乳液模板聚合物材料在软机器人等领域应用的起点。
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引用次数: 0
Effect of Added Salt on the RAFT Polymerization of 2-Hydroxyethyl Methacrylate in Aqueous Media 添加盐对水介质中 2-羟乙基甲基丙烯酸酯 RAFT 聚合作用的影响
IF 5.5 1区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-07-12 DOI: 10.1021/acs.macromol.4c01078
Csilla György, Jacob S. Wagstaff, Saul J. Hunter, Esther U. Etim, Steven P. Armes
We report the effect of added salt on the reversible addition–fragmentation chain transfer (RAFT) polymerization of 2-hydroxyethyl methacrylate (HEMA) in aqueous media. More specifically, poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC26) was employed as a salt-tolerant water-soluble block for chain extension with HEMA targeting PHEMA DPs from 100 to 800 in the presence of NaCl. Increasing the salt concentration significantly reduces the aqueous solubility of both the HEMA monomer and the growing PHEMA chains. HEMA conversions of more than 99% could be achieved within 6 h at 70 °C regardless of the NaCl concentration when targeting PMPC26-PHEMA800 vesicles at 20% w/w solids. Significantly faster rates of polymerization were observed at higher salt concentration owing to the earlier onset of micellar nucleation. Transmission electron microscopy (TEM) was used to construct a pseudo-phase diagram for this polymerization-induced self-assembly (PISA) formulation. High-quality images required cross-linking of the PHEMA chains with glutaraldehyde prior to salt removal via dialysis. Block copolymer spheres, worms, or vesicles can be accessed at any salt concentration up to 2.5 M NaCl. However, only kinetically trapped spheres could be obtained in the presence of 3 M NaCl because the relatively low HEMA monomer solubility under such conditions leads to an aqueous emulsion polymerization rather than an aqueous dispersion polymerization. In this case, dynamic light scattering studies indicated a gradual increase in z-average diameter from 26 to 86 nm when adjusting the target PHEMA degree of polymerization from 200 to 800. When targeting PMPC26-PHEMA800 vesicles, increasing the salt content up to 2.5 M NaCl leads to a systematic reduction in the z-average diameter from 953 to 92 nm. Similarly, TEM analysis and dispersion viscosity measurements indicated a gradual reduction in worm contour length with increasing salt concentration for PMPC26-PHEMA600 worms. This new PISA formulation clearly illustrates the importance of added salt on aqueous monomer solubility and how this affects (i) the kinetics of polymerization, (ii) the morphology of the corresponding diblock copolymer nano-objects, and (iii) the mode of polymerization in aqueous media.
我们报告了在水介质中添加盐对甲基丙烯酸 2-羟乙基酯(HEMA)可逆加成-断裂链转移(RAFT)聚合的影响。更具体地说,采用聚(2-(甲基丙烯酰氧基)乙基磷酰胆碱)(PMPC26)作为耐盐水溶性嵌段,在氯化钠存在下与 HEMA 进行链延伸,目标 PHEMA DPs 为 100 至 800。盐浓度的增加会大大降低 HEMA 单体和生长的 PHEMA 链的水溶性。当 PMPC26-PHEMA800 囊泡的固体含量为 20% w/w 时,无论 NaCl 浓度如何,在 70 °C 下 6 小时内 HEMA 转化率均可达到 99% 以上。盐浓度越高,聚合速度越快,这是因为胶束成核开始得越早。透射电子显微镜(TEM)用于构建这种聚合诱导自组装(PISA)配方的伪相图。要获得高质量的图像,需要在通过透析去除盐分之前用戊二醛交联 PHEMA 链。嵌段共聚物球体、蠕虫或囊泡可在任何盐浓度(最高达 2.5 M NaCl)下进入。不过,只有在 3 M NaCl 的条件下才能获得动力学截留球,因为在这种条件下 HEMA 单体的溶解度相对较低,导致水乳液聚合而不是水分散聚合。在这种情况下,动态光散射研究表明,当目标 PHEMA 聚合度从 200 调整到 800 时,z 平均直径从 26 纳米逐渐增加到 86 纳米。当目标 PMPC26-PHEMA800 囊泡的盐含量增加到 2.5 M NaCl 时,z 平均直径从 953 纳米系统性地减小到 92 纳米。同样,TEM 分析和分散粘度测量结果表明,随着盐浓度的增加,PMPC26-PHEMA600 蠕虫的蠕虫轮廓长度逐渐缩短。这种新型 PISA 配方清楚地说明了添加盐对水性单体溶解度的重要性,以及盐对以下方面的影响:(i) 聚合动力学;(ii) 相应二嵌段共聚物纳米物体的形态;(iii) 水介质中的聚合模式。
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引用次数: 0
Radical Polymerization of Vinyl Boronate Involving Backbiting Chain Transfer and Postpolymerization Oxidation Affording Branched Poly(vinyl alcohol)s 涉及背向链转移和聚合后氧化的乙烯基硼酸酯的自由基聚合,生成支链聚乙烯醇
IF 5.5 1区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-07-12 DOI: 10.1021/acs.macromol.4c00744
Tomoaki Kanazawa, Tsuyoshi Nishikawa, Makoto Ouchi
We found that radical polymerization of vinyl boronic acid pinacol ester (VBpin) was accompanied by a backbiting chain transfer reaction to the polymer backbone, and thus, branched chains were generated via the propagation from the midchain radical. The subsequent oxidation for the boron pendant afforded a branched poly(vinyl alcohol) (PVA), which was certainly supported by NMR structural analyses. The synthesis of the branched PVA is inaccessible via radical polymerization of vinyl acetate (VAc) and subsequent saponification because the VAc polymerization favors the chain transfer reaction to pendant methyl groups over that to the backbone. Our effort was also directed to tuning the branch degree via copolymerization of VBpin with VAc for studies on effects of the branch degree on the physical properties, such as solubility in water and crystallization in the bulk state.
我们发现,乙烯基硼酸频哪醇酯 (VBpin) 的自由基聚合反应伴随着聚合物主链的反向链转移反应,因此,通过中链自由基的传播产生了支链。随后的硼垂饰氧化反应产生了支化聚乙烯醇(PVA),核磁共振结构分析也证实了这一点。由于醋酸乙烯酯(VAc)的聚合反应更倾向于链转移反应,因此无法通过醋酸乙烯酯(VAc)的自由基聚合反应和随后的皂化反应合成支链 PVA。我们还致力于通过 VBpin 与 VAc 的共聚来调整支化度,以研究支化度对物理性质的影响,如在水中的溶解度和块状结晶。
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引用次数: 0
Regulating the Chirality of the Superhelices Self-Assembled from Block Copolymer/Homopolymer Binary Systems by the Mixing Ratio of the Polymers 通过聚合物的混合比例调节嵌段共聚物/均聚物二元体系自组装超螺旋的手性
IF 5.5 1区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-07-11 DOI: 10.1021/acs.macromol.4c00474
Kexin Cao, Yue Du, Jiaping Lin, Chunhua Cai
Chirality control is one of the fundamental aspects of the research of chiral nanostructures. Currently, there are a few reports regarding the chirality variation of polymer nanostructures induced by ambient preparation conditions without changing the chiral sense of the polymer backbones. Herein, we report findings that the chirality of the superhelices self-assembled by a binary polymer system containing rodlike core-forming poly(γ-benzyl-l-glutamate) (PBLG) homopolymers and helical screw-forming poly(γ-benzyl-l-glutamate)-block-poly(ethylene glycol) (PBLG-b-PEG) block copolymers can be varied by the mixture ratio of the polymers. It was found that the chirality of the PBLG-b-PEG/PBLG superhelices can change from right-handed to left-handed by decreasing the fraction of the block copolymers. In such a process, the PBLG backbone of polymers retains their right-handed helical conformation, while the arrangement of the pendant phenyl groups varies from a contracted left-handed form to an extended right-handed form, which leads to the chirality evolution behaviors of the superhelices. This work presents a novel route regulating the chirality of chiral nanostructures formed by chiral polymers and enriches our knowledge for chirality evolution behaviors from polymers to nanostructures.
手性控制是手性纳米结构研究的基础之一。目前,有关在不改变聚合物骨架手性的情况下,通过环境制备条件诱导聚合物纳米结构手性变化的报道很少。在本文中,我们报告了一项发现:由二元聚合物体系自组装的超螺旋体的手性可以通过聚合物的混合比例来改变,该聚合物体系包含棒状核心形成的聚(γ-苄基-l-谷氨酸)(PBLG)均聚物和螺旋螺旋形成的聚(γ-苄基-l-谷氨酸)-嵌段-聚(乙二醇)(PBLG-b-PEG)嵌段共聚物。研究发现,通过降低嵌段共聚物的比例,PBLG-b-PEG/PBLG 超螺旋的手性可以从右手性变为左手性。在这一过程中,聚合物的 PBLG 主干保持其右手螺旋构象,而悬垂苯基的排列则从收缩的左手形式变为延伸的右手形式,从而导致了超螺旋的手性演变行为。这项研究提出了一种调节手性聚合物形成的手性纳米结构的新方法,丰富了我们对从聚合物到纳米结构的手性演化行为的认识。
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引用次数: 0
Multicomponent Polymerization of Sulfur, Diynes, and Aromatic Diamines and Facile Tuning of Polymer Backbone Structures 硫、二炔和芳香族二胺的多组分聚合以及聚合物骨架结构的便捷调节
IF 5.5 1区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-07-11 DOI: 10.1021/acs.macromol.4c00879
Yuzhang Huang, Rongrong Hu, Ben Zhong Tang
Polythioamides have attracted growing research interests owing to their structural similarity to extensively applied high-performance polyamide analogues, together with the additional properties endowed by sulfur such as strong metal coordination ability, high light refractivity, and unique photophysical properties. The synthesis of polythioamides, especially aromatic polythioamides, remained challenging due to the poor reactivity of aromatic amine monomers. In this work, through activation of sulfur by KF, a multicomponent polymerization (MCP) of elemental sulfur, aromatic diynes, and aromatic diamines was developed in the presence of KF in DMSO at 100 °C, affording aromatic polythioamides in high yields. Small molecular model reaction study suggested that under the reaction conditions, terminal alkyne could react with sulfur and aromatic amine to afford both thioamide and thiourea, depending on the loading ratio of alkyne and amine. With these competitive polymerization pathways, the backbone structures of the MCP product could be facilely tuned by simply changing the monomer loading ratio of diynes and diamines, producing random poly(thioamide-thiourea)s with decent molecular weights (Mns) of up to 19,200 g/mol in high yields of up to 98%. Through the polymer backbone structural tuning, the polymer thermal properties, including decomposition temperatures and glass transition temperatures, could be adjusted. The MCP has hence demonstrated facile synthesis of polythioamides and simple tuning of the backbone structure and property of sulfur-containing polymer materials.
聚硫酰胺在结构上与广泛应用的高性能聚酰胺类似物相似,而且硫还具有金属配位能力强、光折射率高和独特的光物理性质等额外特性,因此吸引了越来越多的研究兴趣。由于芳香胺单体的反应性较差,因此聚硫酰胺的合成,尤其是芳香族聚硫酰胺的合成仍然具有挑战性。在这项工作中,通过 KF 对硫的活化,在 KF 存在下于 100 ℃ 的二甲基亚砜中开发了元素硫、芳香族二炔和芳香族二胺的多组分聚合 (MCP),从而获得了高产率的芳香族聚硫酰胺。小分子模型反应研究表明,在该反应条件下,末端炔烃可与硫和芳香胺反应生成硫代酰胺和硫脲,具体取决于炔烃和胺的负载比例。有了这些竞争性聚合途径,只需改变二炔和二胺的单体负载比例,就能方便地调整 MCP 产物的骨架结构,生产出分子量(Mns)高达 19,200 g/mol 的无规聚(硫酰胺-硫脲),产率高达 98%。通过聚合物骨架结构调整,聚合物的热性能(包括分解温度和玻璃化转变温度)也可以得到调整。因此,MCP 证明了聚硫酰胺的简便合成以及含硫聚合物材料骨架结构和性能的简单调节。
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引用次数: 0
Ring-Opening Polymerization of α-Diazo Lactones: Access to Diazo-Containing Polyesters and Their Post-Polymerization Modifications α-重氮内酯的开环聚合:获得含重氮的聚酯及其聚合后改性
IF 5.5 1区 化学 Q1 POLYMER SCIENCE Pub Date : 2024-07-11 DOI: 10.1021/acs.macromol.4c00750
Lefei Yu, Yisong Wang, Qi Zhou, Xiaotong Wu, Zhenning Yu, Yan Xu, Zi-Chen Li, Jianbo Wang
The properties of polyesters can be enhanced by the introduction of various functional groups, while transformations of a diazo group via a carbene intermediate provide efficient approaches for functional group introduction. We herein report the first ring-opening polymerization (ROP) of 5, 6, and 7-membered α-diazo lactones using t-BuOK as the initiator. The diazo groups can be well tolerated in the polymerization condition, leading to stable, diazo-containing polyesters that can be readily isolated and characterized. Post-polymerization transformations of the diazo groups, including [1,2]-hydrogen migration, Si–H insertions, and S–H insertions, further provide polyesters that are nontrivial to access. Further, the introduction of diazo groups generally increases the ring strain of lactones and alters their polymerizability, which is more pronounced for α-diazo γ-butyrolactone. The ROP of α-diazo δ-valerolactone generates a new type of diazo-containing polyesters that can be depolymerized upon heating.
引入各种官能团可以增强聚酯的性能,而通过碳烯中间体转化重氮基团则为官能团的引入提供了有效的方法。我们在此首次报道了以 t-BuOK 为引发剂的 5、6 和 7 元 α-重氮内酯的开环聚合 (ROP)。重氮基团在聚合条件中具有良好的耐受性,可产生稳定的、含重氮的聚酯,且易于分离和表征。重氮基团的聚合后转化,包括[1,2]-氢迁移、Si-H 插入和 S-H 插入,可进一步提供难以获取的聚酯。此外,重氮基团的引入通常会增加内酯的环应变并改变其聚合性,这在α-重氮γ-丁内酯中更为明显。α-diazo δ-valerolactone 的 ROP 生成了一种新型含重氮的聚酯,这种聚酯在加热时可以解聚。
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引用次数: 0
期刊
Macromolecules
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