Polymer Chemistry最新文献

英文中文

Poly(butylene succinate) filaments for fused deposition modelling (FDM) 3D-printing†

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2025-01-24 DOI: 10.1039/d4py01351d

Yong Chen , Jielin Xu , Ye Chen , Chaosheng Wang , Huaping Wang , Jing Wu

Polybutylene succinate (PBS) is an aliphatic degradable polyester prepared by melt polycondensation of succinic acid and 1,4-butanediol; the highly symmetrical molecular structure and linear polymerization monomer result in a polymer exhibiting rapid crystallization and low melt strength, limiting its fiber development and application in melt processing. In order to investigate the feasibility of using PBS as a printing consumable, in this work, a series of long-chain branched PBS filaments were synthesized by using branching agents including glycerol, diglycerol, pentaerythritol and di-pentaerythritol. The chemical structure of different branching agents significantly affects the crystallization properties of PBS polyesters. The branched structure disturbs the symmetry and regularity of the polymer and reduces the crystallization ability of the polymer. Chain topology was obtained through rheological investigations and the synthesized polymers showed a typical behavior of linear and branched PBS. The complex viscosity, storage modulus and loss modulus of long chain branched PBS at low frequency were significantly enhanced compared to those of linear PBS. To reduce the fluidity of the polymer, the melt strength of the polymer was increased by about 2.7 times. PBS filaments have been developed for the application of 3D-printing via fused deposition modeling (FDM), which provides a broader research field for PBS polymers.

{"title":"Poly(butylene succinate) filaments for fused deposition modelling (FDM) 3D-printing†","authors":"Yong Chen , Jielin Xu , Ye Chen , Chaosheng Wang , Huaping Wang , Jing Wu","doi":"10.1039/d4py01351d","DOIUrl":"10.1039/d4py01351d","url":null,"abstract":"<div><div>Polybutylene succinate (PBS) is an aliphatic degradable polyester prepared by melt polycondensation of succinic acid and 1,4-butanediol; the highly symmetrical molecular structure and linear polymerization monomer result in a polymer exhibiting rapid crystallization and low melt strength, limiting its fiber development and application in melt processing. In order to investigate the feasibility of using PBS as a printing consumable, in this work, a series of long-chain branched PBS filaments were synthesized by using branching agents including glycerol, diglycerol, pentaerythritol and di-pentaerythritol. The chemical structure of different branching agents significantly affects the crystallization properties of PBS polyesters. The branched structure disturbs the symmetry and regularity of the polymer and reduces the crystallization ability of the polymer. Chain topology was obtained through rheological investigations and the synthesized polymers showed a typical behavior of linear and branched PBS. The complex viscosity, storage modulus and loss modulus of long chain branched PBS at low frequency were significantly enhanced compared to those of linear PBS. To reduce the fluidity of the polymer, the melt strength of the polymer was increased by about 2.7 times. PBS filaments have been developed for the application of 3D-printing <em>via</em> fused deposition modeling (FDM), which provides a broader research field for PBS polymers.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 9","pages":"Pages 1072-1084"},"PeriodicalIF":4.1,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Living cascade enyne metathesis polymerization of an allylic acetate monomer and post-polymerization modification via a Tsuji–Trost reaction†

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2025-01-24 DOI: 10.1039/d4py01453g

Zhixiong Luo , Yuhuai Tian , Bixia Xie , Liangbing Fu

Here we report the design and synthesis of an allylic acetate-containing monomer suitable for post-polymerization modification through a Tsuji–Trost reaction. This monomer is capable of living cascade enyne metathesis polymerization, as evidenced by the kinetics studies as well as a diblock copolymer formation. The resultant polymers are amenable to efficient palladium-catalyzed Tsuji–Trost reactions using a range of nitrogen, oxygen, and sulfur nucleophiles to furnish structural elaboration. Additionally, the pristine and modified polymers possessed acid-responsive degradability and further tunability depending on the structure.

引用次数: 0

Giant molecules with varying geometric features by programming the unit sequence† 具有不同几何特征的大分子单元序列的编程

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2025-01-24 DOI: 10.1039/d4py01274g

Ze Yang , Zhongguo Liu , Shuai Wang , Gang Li , Xue-Hui Dong

In this study, we modularly prepared a library of giant molecules using molecular nanoparticles – polyhedral oligomeric silsesquioxane (POSS) – as repeat units, with precise control over composition, regio-configuration, and sequence. Benefiting from the enlarged unit size, the assembly behaviors of these giant molecules are found to be sensitive to subtle structural variations. The precise chemical structure rules out molecular “defects” and serves as an ideal platform to resolve minute differences. The regio-configuration directly impacts the spatial arrangement of the neighboring POSS units, resulting in distinct phase behaviors. Molecular geometry, which stems from the monomer sequence, plays a crucial role in the self-assembly process. Simply changing the position of the alkyl ligands on the peripheries of particles generates substantial differences in the period spacing and phase stability, and in some cases even triggers a phase transition toward distinct structures.

在这项研究中，我们以分子纳米粒子——多面体低聚硅氧烷（POSS）作为重复单元，模块化地制备了一个大分子文库，精确控制了组成、区域构型和序列。得益于扩大的单位尺寸，这些大分子的组装行为被发现对细微的结构变化敏感。精确的化学结构排除了分子“缺陷”，作为解决微小差异的理想平台。区域构型直接影响相邻POSS单元的空间排列，从而导致不同的相行为。分子几何，源于单体序列，在自组装过程中起着至关重要的作用。仅仅改变烷基配体在粒子外围的位置，就会在周期间隔和相稳定性方面产生实质性的差异，在某些情况下甚至会引发向不同结构的相变。

引用次数: 0

Functionalized cyclic olefin copolymers: chemoselective polymerization of a cyclopropane-containing norbornadiene dimer using a titanium catalyst and post-polymerization modification†

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2025-01-24 DOI: 10.1039/d4py01310g

Yusuke Iwata , Takeshi Shiono , Shin-ichi Matsuoka

The synthesis of functionalized polyolefins is important for tuning their properties and expanding their application range. However, the copolymerization of olefins with polar monomers using early transition-metal catalysts remains a formidable challenge. Here, we demonstrate a synthesis strategy through the Ti-catalyzed addition polymerization of a cyclopropane-containing norbornadiene dimer (), followed by post-polymerization modification (PPM). The polymerization of using a constrained-geometry Ti catalyst afforded poly with narrow molecular weight distributions (Đ < 1.3), wherein the molecular weight increased linearly with the monomer conversion. Additionally, the copolymerization of with 1-octene proceeded rapidly, and was consumed faster than 1-octene to form gradient copolymers. The ¹³C nuclear magnetic resonance (NMR) spectroscopic analysis of the polymers indicated that the coordination–insertion of the alkenyl group of occurred selectively without side reactions at the cyclopropane moiety. The polymerizations were highly controlled and chemoselective owing to the lack of cyclopropane coordination to the active Ti species involved in the polymerization. The PPM of poly(-co-1-octene) via the protic acid-catalyzed ring-opening reaction of the cyclopropane introduced aromatic, acyloxyl, and alkoxy groups in high incorporation ratios without cross-linking reactions. Thus, this work demonstrates a promising procedure for the modification of cyclic olefin copolymers using specific cyclopropane reactivity.

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引用次数: 0

Highly efficient synthesis of random isobutylene/alkenyl styrene copolymers with pendant vinyl groups via cationic polymerization for versatile functionalization†

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2025-01-24 DOI: 10.1039/d4py01242a

He-Ying Wang , Feng-Yu Zhang , Si-Hao Li , Zi-Yang Song , Yang Wang , Yi-Xian Wu

The controlled/living cationic copolymerizations of isobutylene (IB) with alkenyl styrenes including 4-allylstyrene (AS), p-(3-butenyl)-styrene (BS) and p-(5-hexenyl)-styrene (HS) were carried out in n-hexane/CH₂Cl₂ (6/4 v/v) at −80 °C using a t-BuCl/FeCl₃/iPrOH initiating system. The random copolymers of IB with AS, BS or HS could be obtained without crosslinking and the contents of AS units in the copolymers linearly increased from 0.71 mol% to 14.23 mol% with an increase in the feed ratio of AS. The monomer reactivity ratios (r) were determined to be r_AS = 4.16 and r_IB = 1.66 by the Fineman–Ross method, respectively. The livingness of cationic copolymerization of IB with AS was confirmed by All Monomer In (AMI) and Incremental Monomer Addition (IMA) techniques at −80 °C. The yields, M_n and M_w/M_n of the resulting copolymers decreased with increasing polymerization temperature (T_p) and the apparent activation energy (E_a) depended on T_p. The pendant vinyl groups in the above poly(IB-co-AS) copolymers can be completely converted into hydroxyl groups, carboxyl groups or epoxy groups via hydroboration/oxidation, thiol–ene click reaction or epoxidation. The hydrophilicity on the film surface of functionalized copolymers with hydroxyl, carboxyl or epoxy pendant groups could be improved by introduction of the functional groups and the water contact angle (WCA) of poly(IB-co-AS) with epoxy pendant groups decreased from 134.9° to 78.7° upon increasing the molar content of epoxy groups from 0 to 3.99%. Therefore, the random isobutylene/alkenyl styrene copolymers containing plentiful pendant vinyl groups and versatile polar groups would have potential applications in highly reactive elastomers, adhesives and amphiphilic materials with inorganic fillers.

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引用次数: 0

A dual-initiating organic frustrated Lewis pair catalyst for living polymerizations of (bio)acrylates to facilitate the synthesis of metal-free multiblock copolymers† 用于（生物）丙烯酸酯活聚合的双引发有机沮灭路易斯对催化剂，促进无金属多嵌段共聚物的合成

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2025-01-23 DOI: 10.1039/d4py01067a

Zhen-Hua Zhang , Yuyang Chen , Yuesheng Li , Miao Hong

The development of powerful catalysis or methodologies for the synthesis of fundamentally and technologically important multiblock copolymers is a perpetual task. Dual-initiating Lewis pair (LP) catalysts for living/controlled polymerizations of methacrylates have been demonstrated to be an effective approach towards all-acrylic multiblock copolymers. However, the utilization of metal-based Lewis acids (LAs) and complicated Lewis bases (LBs) that typically require laborious syntheses are essential. This article reports the first organic dual-initiating frustrated Lewis pair (FLP) catalysts consisting of tris(2,4-difluorophenyl)borane [B(2,4-F₂C₆H₃)₃] LA and commercially available 1,2-bis[(di-tert-butylphosphino)methyl]benzene (DP^tBu₂) LB, which can mediate efficient and living polymerizations of various (bio)acrylates. Accordingly, all-acrylic multiblock copolymers (up to hepta blocks) with well-defined structures can be readily prepared via sequential monomer addition, thus successfully establishing DP^tBu₂/B(2,4-F₂C₆H₃)₃ FLP as a green/sustainable and user-friendly polymerization catalyst for the convenient synthesis of metal-free all-acrylic multiblock copolymers.

为合成具有重要基础和技术意义的多嵌段共聚物而开发功能强大的催化剂或方法是一项长期任务。用于甲基丙烯酸酯活/可控聚合反应的双引发路易斯对（LP）催化剂已被证明是一种有效的全丙烯酸多嵌段共聚物方法。然而，利用金属基路易斯酸（LAs）和复杂的路易斯碱（LBs）通常需要费力的合成。本文报告了由三(2,4-二氟苯基)硼烷[B(2,4-F2C6H3)3] LA 和市售的 1,2-双[(二叔丁基膦)甲基]苯 (DPtBu2) LB 组成的首个有机双引发受挫路易斯对 (FLP) 催化剂，它可以介导各种（生物）丙烯酸酯的高效活聚合反应。因此，通过顺序添加单体，可以轻松制备出具有明确结构的全丙烯酸多嵌段共聚物（最多可达七嵌段），从而成功地将 DPtBu2/B(2,4-F2C6H3)3 FLP 确立为一种绿色/可持续和用户友好型聚合催化剂，用于方便地合成不含金属的全丙烯酸多嵌段共聚物。

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引用次数: 0

Amphiphilic block-random copolymer stabilisers: extension to other monomer types† 两亲性嵌段无规共聚物稳定剂：扩展到其他单体类型

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2025-01-23 DOI: 10.1039/d4py01321b

Arthur Werner , Connor A. Sanders , Sandra E. Smeltzer , Sean R. George , Andreas Gernandt , Bernd Reck , Michael F. Cunningham

Block-random copolymers (BRCs) incorporating acrylics were synthesised using nitroxide-mediated polymerisation (NMP) to form macro-stabilisers for the preparation of polymer latexes. These hybrids of block copolymers and random copolymers are traditionally composed of a polystyrene hydrophobic block coupled with a hydrophilic random block of styrene and acrylic acid. Their aqueous dispersions exhibit unique behaviour compared to conventional block copolymers, including being responsible for a unique nucleation mechanism in emulsion polymerisation. However, all previous work has only used styrene as the hydrophobic monomer, and only styrene emulsion polymerizations have been conducted. To explore the versatility of BRCs for the polymerisation of monomers other than styrenics (e.g. acrylates, methacrylates), the BRC library was explored with the introduction of methyl methacrylate (MMA) and n-butyl acrylate (n-BuA) units as the hydrophobic monomers. With blocks composed of one or multiple monomers, all the BRCs were successfully dispersed in water at high concentrations (>100 g L⁻¹), with similar behaviour compared to previously reported for styrene-based BRCs. Semi-batch emulsion polymerisation of styrene or acrylates latexes was also performed. A hydrophobic block consisting of a n-BuA and styrene copolymer was found to be of the most interest, showing promising stability over the range of latexes polymerised.

利用氮氧化物介导聚合（NMP）合成了含丙烯酸酯的嵌段无规共聚物（BRCs），以形成用于制备聚合物乳胶的宏观稳定剂。这些嵌段共聚物和无规共聚物的杂化物传统上由聚苯乙烯疏水嵌段与苯乙烯和丙烯酸的亲水性无规嵌段耦合组成。与传统嵌段共聚物相比，它们的水相分散体表现出独特的行为，包括在乳液聚合中具有独特的成核机制。然而，以往的工作都只使用苯乙烯作为疏水单体，并且只进行了苯乙烯乳液聚合。为了探索BRC在苯乙烯类以外的单体聚合（如丙烯酸酯、甲基丙烯酸酯）中的多功能性，研究人员引入了甲基丙烯酸甲酯（MMA）和丙烯酸正丁酯（n-BuA）作为疏水单体，探索了BRC库。用由一个或多个单体组成的块体，所有BRCs都成功地以高浓度（100 g.L-1）分散在水中，与先前报道的苯乙烯基BRCs具有相似的行为。还进行了苯乙烯或丙烯酸酯乳液的半间歇乳液聚合。发现由正丁腈橡胶和苯乙烯共聚物组成的疏水嵌段是最感兴趣的，在聚合的乳液范围内显示出有希望的稳定性

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引用次数: 0

Implementing a sulfur-substitution approach toward a high-performance recyclable polythioester† 采用硫代法制备高性能可回收聚硫酯

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2025-01-23 DOI: 10.1039/d4py01425a

Si-Qi Wang , Long-Hai Liu , Kun Li , Wei Xiong , Hua-Zhong Fan , Qing Cao , Zhongzheng Cai , Jian-Bo Zhu

Developing new chemically recyclable polymers is highly demanded for a circular plastic economy. Herein, we implement a sulfur-substitution approach for improving the chemical recyclability and material performance of polycaprolactone (PCL). This thiocaprolactone (tCL) displayed excellent reactivity towards ring-opening polymerization, affording P(tCL) products with high thermal stability (T_d = 330 °C), high air stability, high crystallinity, and outstanding mechanical and transport properties (σ_B = ∼20 MPa, ε_B = ∼600%, PO₂ = 0.38 Barrer) comparable to commercial low-density polyethylene. Impressively, chemical recycling of P(tCL) to its monomer could be accomplished with excellent yield and purity, thus establishing its circular life cycle.

开发新的化学可回收聚合物是循环塑料经济的高度要求。本文采用硫代法提高聚己内酯（PCL）的化学可回收性和材料性能。该产物具有高的热稳定性（Td = 330℃）、高的空气稳定性、高的结晶度、优异的机械性能和输运性能（σB = ~20 MPa, σB = ~600%, PO2 = 0.38 Barrer），可与工业低密度聚乙烯相比较。令人印象深刻的是，P（tCL）可以以优异的收率和纯度实现化学再循环到其单体，从而建立其循环生命周期

引用次数: 0

An eco-friendly adhesive with ultra-strong adhesive performance† 具有超强粘合性能的环保粘合剂

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2025-01-23 DOI: 10.1039/d4py01398k

Zhenyu Yang , Xiaoting Ji , Xin-long Sha , Jincheng Ding , Lin Cheng , Guangfeng Li

With the increasing global attention on energy and environmental issues, there is a growing push towards the eco-friendly transformation of adhesive materials. However, designing and developing eco-friendly adhesive materials with ultra-strong adhesion has always been a significant challenge in the field of adhesion. Herein, we present an eco-friendly adhesive (CBA) derived from bio-based thioctic acid (TA) that combines synergistic covalent and dynamic covalent polymeric segments, demonstrating strong adhesive strength and closed-loop recyclability. Specifically, leveraging the synergistic effects of dynamic covalent and covalent chain segments within the polymer network, the adhesive CBA exhibits ultra-strong adhesive strength (16.1 MPa), exceptional antifreeze performance (11.6 MPa at −196 °C), high reusability with 12.1 MPa retained after ten cycles, and resistance to common organic solvents. Importantly, the main chains of disulfide bonds formed through the solid-phase thermal-induced ring-opening polymerization of TA, combined with robust reversible amide bonds to crosslink into a network, enable closed-loop recyclability. This approach of using bio-based materials with synergistic dynamic covalent and covalent bonds effectively balances adhesive strength with environmental sustainability, offering an excellent solution for designing and developing new adhesive materials.

随着全球对能源和环境问题的日益关注，胶粘剂材料的生态友好型转型日益受到推动。然而，设计和开发具有超强附着力的环保型粘接材料一直是粘接领域的重大挑战。在此，我们提出了一种由生物基硫辛酸（TA）衍生的环保粘合剂（CBA），它结合了协同共价和动态共价聚合物段，具有很强的粘合强度和闭环可回收性。具体而言，利用聚合物网络中动态共价链段和共价链段的协同效应，粘合剂CBA具有超强的粘接强度（16.1 MPa），出色的防冻性能（- 196℃时11.6 MPa），高可重复使用性（10次循环后仍保留12.1 MPa），并且耐常见有机溶剂。重要的是，通过固相热诱导的TA开环聚合形成的二硫键主链，与强大的可逆酰胺键交联成一个网络，实现了闭环可回收性。这种使用具有协同动态共价键和共价键的生物基材料的方法有效地平衡了粘合强度和环境可持续性，为设计和开发新型粘合材料提供了一种极好的解决方案。

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引用次数: 0

Photoresponsive polymers for carbodiimide-fueled transient hydrogels† 碳二酰亚胺燃料瞬态水凝胶的光响应聚合物

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2025-01-23 DOI: 10.1039/d4py01244e

Ibrahim O. Raji , Torin C. Wilcox , C. Scott Hartley , Dominik Konkolewicz

Light- and carbodiimide-responsive hydrogels were synthesized. An “AND” gate was developed using ortho-nitrobenzyl (ONB) protected carboxylic acids in the polymer backbone. Crosslinking was only realized in the presence of both UV stimulus to photocleave the ONB group and carbodiimide fuels to induce anhydride bonds. In the presence of water, the anhydride bonds eventually hydrolyze to carboxylic acids and the system returns to the solution state. The mechanical properties of the out-of-equilibrium hydrogels were investigated using oscillatory rheology to examine the effects of deprotection efficiency, carbodiimide concentration and chain architecture on the hydrogels’ moduli and decrosslinking time. Higher moduli and longer decrosslinking times were found with increased carbodiimide concentration and deprotection efficiency. These discoveries unveil new possibilities for photoresponsive chemically fueled soft materials.

合成了光响应和碳二亚胺响应水凝胶。利用邻硝基苯基（ONB）在聚合物主链中保护羧酸，建立了“与”门。交联仅在UV刺激光裂解ONB基团和碳二亚胺燃料诱导酸酐键的情况下才能实现。在有水存在的情况下，酸酐键最终水解成羧酸，系统回到溶液状态。采用振荡流变学方法研究了失平衡水凝胶的力学性能，考察了脱保护效率、碳二亚胺浓度和链结构对水凝胶模量和脱交联时间的影响。随着碳二亚胺浓度的增加和脱保护效率的提高，模量增大，脱交联时间延长。这些发现揭示了光反应化学燃料软材料的新可能性。

引用次数: 0

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