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Three representative types of WAXD/SAXS patterns to establish the bimodal structure concept of stacked lamellae in isotactic polypropylene spherulites 三种具有代表性的 WAXD/SAXS 图样,用于建立同素异形聚丙烯球粒中叠层的双峰结构概念
IF 2.8 4区 化学 Q2 Materials Science Pub Date : 2024-03-14 DOI: 10.1038/s41428-024-00893-x
Kohji Tashiro, Hiroko Yamamoto, Ken-ichi Funaki, Hiroyasu Masunaga, Yuichi Miyake
Two types of lamellar stacking model were proposed for the inner structure of the melt-grown spherulites of isotactic polypropylene (iPP): the edge-on structure (flat lamellar planes stand on the spherulite plane, and a*-axis // growth direction of spherulite, b-axis ┴ spherulite plane, and c-axis // spherulite plane) and the flat-on structure (flat lamellar planes lay on the spherulite plane, a*-axis // growth direction, b-axis // spherulite plane, and c-axis ┴ spherulite plane). After a literature review was performed, the observed X-ray scattering data were not high quality and could not be used to establish these bimodal structures; moreover, the X-ray data analyses were not performed satisfactorily. As a result, the derivations of actual structures were still debatable. We performed simultaneous time-resolved WAXD/SAXS measurements using a synchrotron X-ray microbeam technique. The collected data were classified into three sets of completely different WAXD/SAXS patterns. Detailed quantitative analysis enabled the determination of the spatial orientations of the stacked lamellae and related crystallographic axes. Although the bimodal structure of iPP spherulites was considered to be a well-known and already-established concept for long years, the bimodal structure was successfully confirmed for the first time in the present study, making the concrete discussions on the growth mechanism of the iPP spherulites possible. The in situ wide-angle (WAXD) and small-angle X-ray scattering (SAXS) measurements have been performed using a synchrotron microbeam technique for the melt-isothermally-growing iPP spherulites. The thus-collected data were found to be classified into three sets of totally different WAXD/SAXS patterns, from which the three different orientation modes of the stacked lamellae and related crystallographic axes were deduced. These structural information allowed us to discuss the growth mechanism of stacked lamellae in the iPP spherulites from the microscopic point of view.
针对熔融生长的异方性聚丙烯(iPP)球粒的内部结构,提出了两种层状堆积模型:边缘结构(扁平片层平面位于球粒体平面上,球粒体的生长方向为 a*轴//球粒体平面、b 轴┴球粒体平面和 c 轴//球粒体平面)和平面结构(扁平片层平面位于球粒体平面上,生长方向为 a*轴//球粒体平面、b 轴//球粒体平面和 c 轴┴球粒体平面)。在查阅文献后发现,观测到的 X 射线散射数据质量不高,无法用于确定这些双模结构;此外,X 射线数据分析的效果也不理想。因此,实际结构的推导仍有争议。我们使用同步辐射 X 射线微束技术同时进行了时间分辨 WAXD/SAXS 测量。收集到的数据被分为三组完全不同的 WAXD/SAXS 模式。通过详细的定量分析,确定了叠层的空间取向和相关的晶体学轴线。尽管 iPP 球粒的双峰结构多年来一直被认为是一个众所周知且早已确立的概念,但本研究首次成功证实了其双峰结构,从而使对 iPP 球粒的生长机制进行具体讨论成为可能。
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引用次数: 0
Micropatterned microplastic generation via degradation of polymeric films with micropatterned structures 通过具有微图案结构的聚合物薄膜降解生成微图案微塑料
IF 2.3 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2024-03-07 DOI: 10.1038/s41428-024-00897-7
Haruki Uchida, Wakako Uchiyama, Erika Kurita, Masayuki Kirihara, Yohei Kotsuchibashi
Water-insoluble micropatterned films were prepared from poly(vinyl alcohol) (PVA) (or ethylene-vinyl alcohol copolymer (EVOH)) and poly(methacrylic acid) (poly(MAAc)). The carboxy groups in poly(MAAc) underwent dehydration reactions with the hydroxy groups in the vinyl alcohol units during heating at 135 °C, which resulted in crosslinking with ester bonds and formation of a polymeric network in the micropatterned films. The surface structures of the micropatterned films and the shapes of the peeled microplastics in the supernatant were measured after decomposition in an oxidizing environment, after ultrasonic irradiation, and with both. The results revealed that the micropatterns could be peeled off from the films after they were subjected to appropriate decomposition conditions and maintained their patterned shapes. Water-insoluble micropatterned films were prepared from poly(vinyl alcohol) (PVA) (or ethylene-vinyl alcohol copolymer (EVOH)) and poly(methacrylic acid) (poly(MAAc)). The carboxy groups in poly(MAAc) underwent dehydration reactions with the hydroxy groups in the vinyl alcohol units during heating at 135 °C, which resulted in the introduction of a crosslinked structure with ester bonds into the polymeric network of the micropatterned films. The micropatterns could be peeled off from the films after decomposition and maintained their patterned shapes.
用聚(乙烯醇)(PVA)(或乙烯-乙烯醇共聚物(EVOH))和聚(甲基丙烯酸)(poly(MAAc))制备了不溶于水的微图案薄膜。在 135 °C 的加热过程中,聚(甲基丙烯酸)中的羧基与乙烯醇单元中的羟基发生脱水反应,从而与酯键交联,在微图案薄膜中形成聚合物网络。测量了微图案薄膜在氧化环境中分解后、超声波辐照后以及两者同时分解后的表面结构和上清液中剥离的微塑料的形状。结果表明,在适当的分解条件下,微图案可以从薄膜上剥离,并保持其图案形状。
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引用次数: 0
Click synthesis of an adhesive block copolymer with poly(3-hexylthiophene) and poly(vinyl catechol) segments 聚(3-己基噻吩)和聚(乙烯基邻苯二酚)段的粘合嵌段共聚物的单击合成
IF 2.3 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2024-03-06 DOI: 10.1038/s41428-024-00898-6
Shin Inagaki, Kazuhiro Nakabayashi, Tomoya Higashihara
Semiconducting polymers have garnered considerable attention from researchers, as these polymers are potentially applicable to flexible/stretchable organic electronics. However, although the adhesiveness of these materials on substrates is an important characteristic, it has rarely been investigated. Herein, we synthesized and characterized a novel block copolymer, poly(3-hexylthiophene)-b-poly(vinyl catechol) (P3HT-b-PVC), with improved adhesion properties. P3HT-b-PVC was successfully synthesized via a copper-catalyzed azide–alkyne cycloaddition reaction between chain-end-functionalized P3HT with an alkyne group (P3HT-Alkyne) and chain-end-functionalized poly(3,4-di-tert-butyldimethylsilyloxystyrene) with an azide group (PSVC-Azide), followed by deprotection of tert-butyldimethylsilyloxy groups from the PSVC-Azide segment. Tape test results showed that the adhesion property of the P3HT-b-PVC film was considerably better than that of the corresponding P3HT film. Furthermore, despite the presence of an insulating PVC block in P3HT-b-PVC, the P3HT-b-PVC thin film exhibited a hole mobility of 1.1 × 10−5 cm2V−1s−1, which was comparable to that of the corresponding P3HT thin film (1.8 × 10−5 cm2V−1s−1). To the best of our knowledge, this is the first study to elucidate the primitive adhesion properties and charge mobility of P3HT-based block copolymers. The proposed synthetic approach may be extended to develop various block copolymers with other π-conjugated polymer segments, providing new avenues for various applications that require highly-adhesive materials. A novel block copolymer, poly(3-hexylthiophene)-b-poly(vinyl catechol) (P3HT-b-PVC) was successfully synthesized via a Click reaction between chain-endfunctionalized P3HT with an alkyne group (P3HT-Alkyne) and chain-end-functionalized poly(3,4-di-tert-butyldimethylsilyloxystyrene) with an azide group (PSVC-Azide), followed by deprotection of tert-butyldimethylsilyloxy groups from the PSVC-Azide segment. Tape test results showed that the adhesion property of the P3HT-b-PVC film was considerably better than that of the corresponding P3HT film. Furthermore, despite the presence of an insulating PVC block in P3HT-b-PVC, the P3HT-b-PVC thin film exhibited a hole mobility comparable to that of the corresponding P3HT thin film.
半导体聚合物引起了研究人员的极大关注,因为这些聚合物可能适用于柔性/可拉伸有机电子产品。然而,尽管这些材料在基底上的粘附性是一个重要特性,但却很少有人对此进行研究。在此,我们合成了一种新型嵌段共聚物--聚(3-己基噻吩)-b-聚(乙烯基邻苯二酚)(P3HT-b-PVC),并对其进行了表征,该聚合物具有更好的粘附性能。P3HT-b-PVC 是通过铜催化叠氮-炔烃环加成反应成功合成的,该反应是在链端官能化的带有炔烃基(P3HT-Alkyne)的 P3HT 和带有叠氮基(PSVC-Azide)的链端官能化的聚(3,4-二叔丁基二甲基硅氧基苯乙烯)之间进行的,然后对 PSVC-Azide 部分的叔丁基二甲基硅氧基基团进行脱保护。胶带测试结果表明,P3HT-b-PVC 薄膜的粘附性能大大优于相应的 P3HT 薄膜。此外,尽管在 P3HT-b-PVC 中存在绝缘 PVC 块,P3HT-b-PVC 薄膜仍表现出 1.1 × 10-5 cm2V-1s-1 的孔迁移率,与相应的 P3HT 薄膜(1.8 × 10-5 cm2V-1s-1)相当。据我们所知,这是首次阐明基于 P3HT 的嵌段共聚物的原始粘附特性和电荷迁移率的研究。所提出的合成方法可扩展用于开发具有其他 π 共轭聚合物段的各种嵌段共聚物,为需要高粘合性材料的各种应用提供新的途径。
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引用次数: 0
Cage octasilsesquioxane-pendant polynorbornenes connected with short spacers exhibiting optical transparency 用短间隔物连接的笼状八叠苯并二噁烷附聚降冰片烯具有光学透明性
IF 2.3 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2024-03-06 DOI: 10.1038/s41428-024-00903-y
Yu Tomioka, Ryota Tanaka, Thu Thao Pham, Shin-ichi Yusa, Hiroaki Imoto, Kensuke Naka
Heptaisobutyl-norbornenylethyl-substituted cage octasilsesquioxane (POSS) (1a) and heptaphenyl-norbornenylethyl-substituted POSS (1b) were subjected to ring-opening metathesis polymerizations (ROMP) at room temperature with the Grubbs 2nd generation catalyst. The metathesis polymerizations of 1a and 1b were performed at room temperature for 3 h with initial monomer molar concentrations of [1a, 1b] = 10 mM, and the number average molecular weights (Mn) of 2a and 2b were 82,000 g/mol and 87,000 g/mol, respectively. Dynamic light scattering (DLS) and static light scattering (SLS) measurements showed that the Rg/Rh value for 2a was 4.91, suggesting the formation of polydisperse rod-shaped particles. Chloroform solutions of 2a and 2b were cast onto glass substrates and dried at room temperature to obtain optically transparent free-standing films. X-ray diffraction (XRD) analyses of the casted films revealed their amorphous natures. Thermogravimetric analyses (TGA) of 2a and 2b under N2 atmospheres showed 5 wt% losses (Td5) at 416 °C and 451 °C, respectively. The POSS-pendant polynorbornenenes connected with short spacers exhibited showed high optical transparencies owing to the prevention of POSS crystallization and the excellent thermal stability. Side-chain typed POSS-based polynorbornenes connecting with a short spacer exhibiting optical transparency owing to prevention of POSS crystallization to provide amorphous character. In addition, the resulting amorphous polymers exhibited excellent thermal stability.
使用 Grubbs 第二代催化剂在室温下对七异丁基-降冰片烯乙基取代的笼状八硅氧烷(POSS)(1a)和七苯基-降冰片烯乙基取代的 POSS(1b)进行开环元合成聚合反应(ROMP)。1a 和 1b 的开环聚合反应在室温下进行了 3 小时,初始单体摩尔浓度为 [1a, 1b] = 10 mM,2a 和 2b 的平均分子量(Mn)分别为 82,000 g/mol 和 87,000 g/mol。动态光散射(DLS)和静态光散射(SLS)测量显示,2a 的 Rg/Rh 值为 4.91,表明形成了多分散的棒状颗粒。将 2a 和 2b 的氯仿溶液浇铸到玻璃基底上,并在室温下干燥,得到光学透明的独立薄膜。对浇铸薄膜进行的 X 射线衍射(XRD)分析表明,它们具有无定形性质。在氮气环境下对 2a 和 2b 进行的热重分析(TGA)显示,在 416 ℃ 和 451 ℃ 时分别有 5 wt% 的损失(Td5)。由于防止了 POSS 结晶和优异的热稳定性,与短间隔相连的 POSS 附聚降冰片烯显示出很高的光学透射率。
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引用次数: 0
Construction of peptide/plasmid DNA complexes for plant gene transfection via the basic leucine zipper domain 通过基本亮氨酸拉链结构域构建用于植物基因转染的肽/质粒 DNA 复合物
IF 2.3 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2024-03-05 DOI: 10.1038/s41428-024-00901-0
Kota Nomura, Seiya Fujita, Yuki Shimatani, Taichi Kurita, Chonprakun Thagun, Naoya Abe, Kazusato Oikawa, Kousuke Tsuchiya, Hirotaka Uji, Keiji Numata
An important method for plant genetic modification is using peptide/pDNA complexes to transfer genes into plant cells. With conventional carrier peptides, the peptide sequence must contain a high amount of cationic amino acids to condense and introduce pDNA. As a result, the dissociation of pDNA from the complex is inefficient, often causing problems. Herein, we designed a new peptide carrier that mimics the basic leucine zipper (bZIP) domain of DNA-binding proteins, in which (LU)4 is the leucine zipper motif and (KUA)3 is the basic DNA-binding and cell-penetrating motif (U = α-aminoisobutyric acid). After (KUA)3-(LU)4 peptide was mixed with pDNA, DNA molecules were condensed to form nanoparticles of approximately 130 nm. Furthermore, when complexes of (KUA)3-(LU)4 peptide and pDNA were introduced into the leaves of Arabidopsis thaliana (A. thaliana), expression of the reporter protein was detected in the plant cells. Thus, (KUA)3-(LU)4 peptide that mimics the bZIP domain is a novel and efficient carrier for pDNA with high dissociation efficiency. A new peptide carrier that mimics the basic leucine zipper domain (bZIP) of DNA-binding proteins was designed, in which (LU)4 is the leucine zipper motif and (KUA)3 is the basic DNA-binding motif (U = α-aminoisobutyric acid). When mixed with pDNA, (KUA)3-(LU)4 peptide condensed DNA molecules to form nanoparticles. Furthermore, when complexes of the (KUA)3-(LU)4 peptide and pDNA were introduced into the leaves of Arabidopsis thaliana (A. thaliana), the reporter protein was expressed in plant cells. Thus, (KUA)3-(LU)4 is an efficient carrier of pDNA with high dissociation efficiency.
植物基因改造的一个重要方法是利用肽/pDNA 复合物将基因转移到植物细胞中。使用传统的载体肽时,肽序列必须含有大量阳离子氨基酸才能凝结并导入 pDNA。因此,pDNA 从复合物中解离的效率很低,经常会造成问题。在这里,我们设计了一种新的肽载体,它模仿了 DNA 结合蛋白的碱性亮氨酸拉链(bZIP)结构域,其中 (LU)4 是亮氨酸拉链结构域,(KUA)3 是碱性 DNA 结合和细胞穿透结构域(U = α-氨基异丁酸)。(KUA)3-(LU)4肽与pDNA混合后,DNA分子凝结成约130纳米的纳米颗粒。此外,将(KUA)3-(LU)4 多肽和 pDNA 复合物导入拟南芥(A. thaliana)叶片后,可在植物细胞中检测到报告蛋白的表达。因此,模仿 bZIP 结构域的 (KUA)3-(LU)4 多肽是一种新型高效的 pDNA 载体,具有很高的解离效率。
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引用次数: 0
Predicting the effects of degradation on viscoelastic relaxation time using model transient networks 利用模型瞬态网络预测降解对粘弹性松弛时间的影响
IF 2.3 4区 化学 Q3 POLYMER SCIENCE Pub Date : 2024-03-05 DOI: 10.1038/s41428-024-00902-z
Ryunosuke Kobayashi, Mitsuru Naito, Kanjiro Miyata, Takamasa Sakai, Ung-il Chung, Takuya Katashima
In this study, we utilized tetra-armed polyethylene glycol (Tetra-PEG) slimes, which are model transient networks with well-controlled structures, to predict the effects of long-term degradation on the viscoelastic properties of liquids. Viscoelastic liquids, such as sodium hyaluronate, are frequently used in biomedical applications within the human body. However, precisely controlling the viscoelastic properties of these liquids in the long-term is challenging, as the main chains of the liquids undergo stochastic degradation. To establish a predictable model for studying long-term degradation effects, we employed Tetra-PEG slime, and modifications were performed to introduce specific cleavage sites in areas with connections. The Tetra-PEG slimes were characterized by single relaxation modes, and these modes were independent from the degree of degradation, which was determined by hydrolyzing the cleavage sites. Overall, this work provides a universal design for viscoelastic liquids with precisely-controllable degradation. This study explores the effects of long-term degradation on the viscoelastic properties of viscoelastic liquids using tetra-armed polyethylene glycol (Tetra-PEG) slimes as model material. It aims to enhance control over the viscoelasticity of biomedical materials, like sodium hyaluronate, by introducing specific cleavage sites into the Tetra-PEG slimes to simulate degradation. The study reveals that despite degradation, the slimes maintain a single relaxation mode, offering a method to design viscoelastic liquids with predictable and controllable degradation for biomedical applications.
在这项研究中,我们利用四臂聚乙二醇(Tetra-PEG)淤泥(具有良好结构的瞬态网络模型)来预测长期降解对液体粘弹性特性的影响。透明质酸钠等粘弹性液体经常用于人体的生物医学应用。然而,由于这些液体的主链会发生随机降解,因此长期精确控制这些液体的粘弹性能具有挑战性。为了建立一个研究长期降解效应的可预测模型,我们采用了四聚乙二醇(Tetra-PEG)粘液,并对其进行了改性,在有连接的区域引入了特定的裂解位点。Tetra-PEG 黏液以单一弛豫模式为特征,这些模式与降解程度无关,降解程度由水解裂解位点决定。总之,这项工作为可精确控制降解的粘弹性液体提供了一种通用设计。
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引用次数: 0
Humidity responsiveness of a poly(N-isopropylacrylamide) gel with a PEG/water mixed solvent 含 PEG/水混合溶剂的聚(N-异丙基丙烯酰胺)凝胶的湿度响应性
IF 2.8 4区 化学 Q2 Materials Science Pub Date : 2024-02-28 DOI: 10.1038/s41428-024-00900-1
Ryotaro Makita, Aya M. Akimoto, Takafumi Enomoto, Taihei Nishimoto, Xiang Li, Mitsuhiro Shibayama, Ryo Yoshida
This manuscript presents the humidity responsiveness of a poly(N-isopropylacrylamide) (PNIPAAm) gel, which was capable of exhibiting volume changes. The strategy for inducing volume changes in the gel capitalized on the differences in PNIPAAm solubility, which stemmed from variations in the polyethylene glycol (PEG) proportions of PEG/water solvent mixtures. Due to the hygroscopic nature of PEG, PNIPAAm gels using PEG as the solvent (weight fraction of PEG, φPEG = 1.00) absorbed ambient moisture, resulting in a decrease in φPEG over time. In concert with this moisture absorption process, the PNIPAAm gel contracted owing to phase separation at a consistent room temperature, which was attributed to the diminished solubility of PNIPAAm in the solvent. During this investigation, we scrutinized the temperature dependency of the optical transmittance and conducted differential scanning calorimetry (DSC) assessments on free PNIPAAm in water across various φPEG values to substantiate phase separation of the system. We then demonstrated that a PNIPAAm gel with a PEG/water mixed solvent underwent volume changes in response to humidity changes. Additionally, humidity-induced shape deformations were realized with a PNIPAAm and poly(N,N-dimethylacrylamide) (PDMAAm) composite gel. This study introduces, for the first time, a humidity-responsive PNIPAAm gel with a PEG/water mixed solvent. We report the humidity-responsive volume changes of a poly(N-isopropylacrylamide) (PNIPAAm) gel and bending deformation of a PNIPAAm and poly(N,N-dimethylacrylamide) (PDMAAm) complex gel.
本手稿介绍了一种聚(N-异丙基丙烯酰胺)(PNIPAAm)凝胶的湿度响应性,这种凝胶能够显示体积变化。诱导凝胶体积变化的策略是利用 PNIPAAm 溶解度的差异,这种差异源于 PEG/ 水溶剂混合物中聚乙二醇 (PEG) 比例的变化。由于 PEG 具有吸湿性,使用 PEG 作为溶剂的 PNIPAAm 凝胶(PEG 的重量分数,φPEG = 1.00)会吸收环境中的水分,导致φPEG 随时间推移而降低。在吸湿的同时,PNIPAAm 凝胶在室温下会发生相分离而收缩,这是因为 PNIPAAm 在溶剂中的溶解度降低了。在这项研究中,我们仔细研究了透光率的温度依赖性,并对水中的游离 PNIPAAm 在不同 φPEG 值下的表现进行了差示扫描量热法 (DSC) 评估,以证实系统的相分离。然后,我们证明了含有 PEG/ 水混合溶剂的 PNIPAAm 凝胶会随着湿度的变化而发生体积变化。此外,我们还利用 PNIPAAm 和聚(N,N-二甲基丙烯酰胺)(PDMAAm)复合凝胶实现了湿度引起的形状变形。本研究首次介绍了一种含有 PEG/ 水混合溶剂的湿度响应型 PNIPAAm 凝胶。
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引用次数: 0
Optimal conditions for the use of polyrotaxane as a cross-linker in preparing elastomers with high toughnesses 在制备高韧性弹性体过程中使用聚二十六烷作为交联剂的最佳条件
IF 2.8 4区 化学 Q2 Materials Science Pub Date : 2024-02-28 DOI: 10.1038/s41428-024-00896-8
Sizhe Liu, Tomoya Hayashi, Mitsuo Hara, Takahiro Seki, Kohzo Ito, Yukikazu Takeoka
The effects of the cyclic molecules within polyrotaxanes moving over axial molecules serving as cross-linking points in a polymeric network preclude observation of the cyclic effects in polymer networks composed of conventional cross-linking agents. As a result, polymer networks with movable cross-linking points behave more gently and stretch better than conventional polymer networks. These polymer networks can be composed of various polymers when using cross-linkers obtained by modifying the vinyl groups on the polyrotaxanes. In this study, the effects of the polyrotaxane cross-linker concentration and solvent content on elastomer preparation were investigated to obtain elastomers with high toughnesses due to the properties of the polyrotaxane cross-linking agent. If elastomers were prepared in a state in which the cyclic effect of the polyrotaxane was easily expressed by the concentration of the polyrotaxane cross-linker and the amount of solvent, the elastomers obtained elongated more and were tougher than elastomers made from conventional cross-linkers. In this study, the effects of the polyrotaxane cross-linker concentration and solvent content on elastomer preparation were investigated to obtain elastomers with high toughnesses due to the properties of the polyrotaxane cross-linking agent. If elastomers were prepared in a state in which the slide-ring effect of the polyrotaxane was easily expressed by the concentration of the polyrotaxane cross-linker and the amount of solvent, the elastomers obtained elongated more and were tougher than elastomers made from conventional cross-linkers.
在聚合物网络中作为交联点的轴向分子上移动的聚罗他赛内环状分子所产生的效应,排除了在由传统交联剂组成的聚合物网络中观察环状效应的可能性。因此,与传统的聚合物网络相比,具有可移动交联点的聚合物网络表现得更加平缓,伸展性更好。如果使用通过改变聚对苯二甲酸乙烯基而获得的交联剂,这些聚合物网络可以由各种聚合物组成。本研究调查了聚二十六烷交联剂浓度和溶剂含量对弹性体制备的影响,以获得因聚二十六烷交联剂的特性而具有高韧性的弹性体。如果在制备弹性体时,聚二十六烷的循环效应很容易通过聚二十六烷交联剂的浓度和溶剂量表现出来,那么获得的弹性体比使用传统交联剂制成的弹性体伸长更多,韧性更高。
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引用次数: 0
Postpolymerization modification of poly(2-alkoxyethoxycarbonylmethylene)s: Efficient formation and reactivity of the ketene silyl acetal repeating units in the polymer main chain 聚(2-烷氧基乙氧羰基亚甲基)的聚合后改性:聚合物主链中酮烯硅基缩醛重复单元的高效形成和反应活性
IF 2.8 4区 化学 Q2 Materials Science Pub Date : 2024-02-21 DOI: 10.1038/s41428-024-00891-z
Hiroaki Shimomoto, Shota Inouchi, Tomomichi Itoh, Eiji Ihara
Postpolymerization modifications of poly(2-methoxyethoxycarbonylmethylene) (pMEDA’) and poly(2-phenoxyethoxycarbonylmethylene) (pPEDA’) are described. The reactions of these polymers with mixtures of chlorotrimethylsilane (Me3SiCl) and lithium diisopropylamide (LDA) efficiently transformed the alkoxycarbonylmethylene repeating units to ketene silyl acetals to yield a product with up to 93 mol% composition of the latter unit. The ketene silyl acetal composition of the product was controlled by changing the feed ratio of Me3SiCl/LDA with respect to the alkoxycarbonylmethylene unit. Tetrabutylammonium fluoride (TBAF)-mediated benzylation of the highly silylated polymer with benzyl bromide yielded a polymer containing side chain O (major)- and main chain C (minor)-benzylated units along with the unreacted ketene silyl acetal unit. Postpolymerization modifications of poly(2-methoxyethoxycarbonylmethylene) and poly(2-phenoxyethoxycarbonylmethylene) with mixtures of Me3SiCl and LDA efficiently transformed the alkoxycarbonylmethylene repeating units to ketene silyl acetals to yield a product with up to 93 mol% composition of the latter unit. TBAF-mediated benzylation of the highly silylated polymer with benzyl bromide yielded a polymer containing side chain O (major)- and main chain C (minor)-benzylated units along with the unreacted ketene silyl acetal unit.
介绍了聚(2-甲氧基乙氧羰基亚甲基)(pMEDA')和聚(2-苯氧基乙氧羰基亚甲基)(pPEDA')的聚合后改性。这些聚合物与氯代三甲基硅烷(Me3SiCl)和二异丙基酰胺锂(LDA)的混合物反应,可有效地将烷氧羰基亚甲基重复单元转化为烯甲氧基硅基乙缩醛,从而得到后一种单元成分高达 93 摩尔%的产品。通过改变 Me3SiCl/LDA 与烷氧羰基亚甲基单元的进料比,可以控制产品中的乙缩酮硅烷成分。以四丁基氟化铵(TBAF)为介质,用溴化苄基对高度硅烷基化的聚合物进行苄基化反应,得到了含有侧链 O(主要)和主链 C(次要)苄基化单元以及未反应的酮烯硅基缩醛单元的聚合物。
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引用次数: 0
Ultrastretchable hydrogels with strong damping effects 具有强阻尼效应的超拉伸水凝胶
IF 2.8 4区 化学 Q2 Materials Science Pub Date : 2024-02-21 DOI: 10.1038/s41428-024-00894-w
Ming Ge, Lidong Zhang
Hydrogels can be stretched to several tens or even hundreds of times their original lengths, making them suitable for various applications. They have shown great potential for use in sensors and wearable devices. Although many attempts have been made to develop highly stretchable hydrogels, combining high stretchability and excellent damping remains a challenge. This study reports a method that significantly improved the stretchability and damping properties of hydrogels. The innovation is the replacement of traditional short-chain crosslinkers, such as N,N-methylenebis(acrylamide) (MBA), with long-chain crosslinkers. With increasing chain lengths, the spaces in the networks became larger, which reduced the interactions between the molecular chains in the network. As a result, the molecular chains of the network could slide when stretched, which greatly increased the mechanical elongation and enabled damping by the hydrogel (up to 85%). The maximum elongation reached 21800%, with a toughness of 11.32 MJ m−3. To the best of our knowledge, this elongation is superior to those in all previous reports. Our results provide a new approach for the development of highly stretchable and damping hydrogels. This study reports a method that significantly improved the stretchability and damping properties of hydrogels. The innovation is the replacement of traditional short-chain crosslinkers, such as N,N-methylenebis(acrylamide) (MBA), with long-chain crosslinkers. As a result, the molecular chains of the network could slide when stretched, which greatly increased the mechanical elongation and enabled damping by the hydrogel (up to 85%). The maximum elongation reached 21800%, with a toughness of 11.32 MJ m−3. This study provides a new approach for the development of highly stretchable and damping hydrogels.
水凝胶可以被拉伸到原始长度的几十倍甚至几百倍,因此适合各种应用。水凝胶在传感器和可穿戴设备方面显示出巨大的应用潜力。尽管人们已多次尝试开发高拉伸性水凝胶,但如何将高拉伸性和出色的阻尼结合起来仍是一项挑战。本研究报告介绍了一种可显著改善水凝胶拉伸性和阻尼特性的方法。创新之处在于用长链交联剂取代了传统的短链交联剂,如 N,N-亚甲基双(丙烯酰胺)(MBA)。随着链长的增加,网络中的空间变大,从而减少了网络中分子链之间的相互作用。因此,网络分子链在拉伸时可以滑动,这大大增加了机械伸长率,并使水凝胶产生阻尼(高达 85%)。最大伸长率达到 21800%,韧性为 11.32 MJ m-3。据我们所知,这一伸长率优于之前所有的报告。我们的研究结果为开发高伸展性和阻尼水凝胶提供了一种新方法。
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Polymer Journal
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