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Recent advances in flame retardant polymers via thiol-ene click chemistry 通过巯基化学研究阻燃聚合物的最新进展
3区 化学 Q3 POLYMER SCIENCE Pub Date : 2023-11-10 DOI: 10.1080/10601325.2023.2280237
Emrah Çakmakçı
AbstractWithin the toolbox of click chemistry, the utilization of thiol-ene reactions for polymer synthesis and modification is a current area of intense attention. Thiol-ene click reactions are used for a broad range of applications. One main area that needs particular attention, where thiol-ene click reactions are immensely employed, is the fabrication of coatings. Especially, when light is used to trigger the thiol-ene reactions, coatings can be prepared within seconds. This method is known as thiol-ene photopolymerization (TEP) and it is a marvelous advancement among light-induced crosslinking systems. TEP is a powerful tool for the preparation of coatings. The synthesis of phosphorous monomers for TEP has prominent importance for improved thermal properties and flame retardancy. Here, the existing literature on flame retardant TEP systems and reactive phosphorous monomers used in TEP are summarized. This review mainly highlights the studies on thermosets yet some linear polymer examples are also included. While this mini-review focuses mostly on TEP, relevant works involving other thiol-ene polymerization routes (i.e. thermal thiol-ene polymerization) rather than photopolymerization are presented. Finally, studies that utilize thiol-ene click reactions to synthesize phosphorous monomers and flame retardants are also given.Keywords: Thiol-ene clickthiol-ene photopolymerizationflame retardantphosphorusnitrogen AcknowledgmentsThis paper is dedicated to the memory of Prof. Atilla GÜNGÖR. The author would like to thank all colleagues and group members who have contributed over the years.Disclosure StatementThe author declares no conflict of interest.
摘要在化学的工具箱中,利用巯基反应合成和修饰聚合物是当前备受关注的一个领域。巯基点击反应的应用范围很广。需要特别注意的一个主要领域是涂料的制造,在这个领域中,巯基点击反应被大量使用。特别是,当光被用来触发巯基反应时,涂层可以在几秒钟内制备出来。这种方法被称为硫烯光聚合(TEP),是光诱导交联体系的一个了不起的进步。TEP是制备涂料的有力工具。合成用于TEP的含磷单体对改善TEP的热性能和阻燃性能具有重要意义。本文对现有的阻燃TEP体系和用于TEP的活性磷单体进行了综述。本文主要综述了热固性聚合物的研究,同时也介绍了一些线状聚合物的例子。虽然这篇小型综述主要集中在TEP,但涉及其他硫醇-烯聚合途径(即热硫醇-烯聚合)而不是光聚合的相关工作也被介绍。最后,介绍了利用巯基键合反应合成含磷单体和阻燃剂的研究进展。关键词:巯基,巯基,光聚合,阻燃,磷氮,致谢本文是为了纪念阿提拉教授GÜNGÖR。作者要感谢所有的同事和小组成员谁贡献了多年。声明作者声明无利益冲突。
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引用次数: 0
Determination of HOMO and LUMO of bis( β -diketonate)zirconium(IV) compound used as a catalyst in the ring opening polymerization of ε -Caprolactone and δ -Valerolactone ε -己内酯和δ -戊内酯开环聚合催化剂双(β -二酮酸)锆化合物HOMO和LUMO的测定
3区 化学 Q3 POLYMER SCIENCE Pub Date : 2023-10-27 DOI: 10.1080/10601325.2023.2273842
Muhammad Yusuf, None Nurfajriani, Rahmayani Siregar, None Eddiyanto, Asep W. Nugraha
AbstractPoly(ε-caprolactone) (PCL) and poly(δ-valerolactone) (PVL) are aliphatic polyesters that can generally be used for basic medical materials such as bone and dental implant materials, drug delivery systems, and scaffolds in tissue engineering. PCL and PVL belong to the polylactone group which have superior properties such as good biocompatibility, nontoxicity, flexibility, thermoplastic and can be biodegraded in a controlled manner. These superior properties make it the main choice in producing medical materials. This study aims to determine the degree of polymerization of PCL and PVL catalyzed using a bis(β-diketonate)zirconium(IV) complex. In addition, analysis of the Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) was also carried out on the catalyst complex. The ring-opening polymerization reaction (ROP) of ε-caprolactone (ε-CL) and δ-valerolactone (δ-VL) lasted for 4 h at 100 °C. The resulting PCL and PVL were then characterized for their chemical and thermal properties using FTIR, 1HNMR, XRD, DTA and TGA. Both PCL and PVL are semicrystalline. On the other hand, the resulting PCL has a melting point of 65.5 °C, with a degree of polymerization (DP) of 17. Meanwhile, the resulting PVL has a melting point of 63.4 °C with a DP of 8.Keywords: Bis(β-diketonate)zirconium(IV)poly(ε-caprolactone)poly(δ-valerolactone)ring-opening polymerization reactionsand implants Disclosure statementNo potential conflict of interest was reported by the author(s).Additional informationFundingWe are grateful for the financial support provided by Hibah Penelitian Fundamental Reguler DRTPM DIKTI RI (No. 012/UN33.8/DRTPM/PL/2023).
摘要聚(ε-己内酯)(PCL)和聚(δ-戊内酯)(PVL)是脂肪族聚酯,一般用于骨、牙种植材料、药物输送系统、组织工程支架等基础医用材料。PCL和PVL属于聚内酯类,具有良好的生物相容性、无毒性、柔韧性、热塑性和可控的生物降解性。这些优越的性能使其成为生产医用材料的主要选择。本研究旨在确定双(β-二酮酸)锆(IV)配合物催化PCL和PVL的聚合程度。此外,还对催化剂配合物进行了最高占据分子轨道(HOMO)和最低未占据分子轨道(LUMO)的分析。ε-己内酯(ε-CL)和δ-戊内酯(δ-VL)的开环聚合反应(ROP)在100℃下持续4 h。然后用FTIR、1HNMR、XRD、DTA和TGA对所得PCL和PVL的化学和热性能进行了表征。PCL和PVL都是半结晶的。另一方面,所得PCL的熔点为65.5℃,聚合度(DP)为17。同时,所得PVL熔点为63.4℃,DP为8。关键词:双(β-二酮酸)锆(IV)聚(ε-己内酯)聚(δ-戊内酯)开环聚合反应和植入物披露声明作者未报告潜在利益冲突。我们非常感谢Hibah Penelitian Fundamental Reguler DRTPM DIKTI RI (No. 012/UN33.8/DRTPM/PL/2023)提供的资金支持。
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引用次数: 0
Nanohybrid materials using gold nanoparticles and RAFT-synthesized polymers for biomedical applications 使用金纳米粒子和raft合成聚合物的纳米杂化材料用于生物医学应用
3区 化学 Q3 POLYMER SCIENCE Pub Date : 2023-10-26 DOI: 10.1080/10601325.2023.2271040
Mahua Dhara (Ganguly)
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引用次数: 0
Emerging trends in olefin polymerization: a perspective 烯烃聚合的新趋势:展望
3区 化学 Q3 POLYMER SCIENCE Pub Date : 2023-10-22 DOI: 10.1080/10601325.2023.2269971
Rajkumar S. Birajdar, Dnyaneshwar Bodkhe, Poonam Gupta, Maulali H. Shaikh, Rohan Ramekar, Samir H. Chikkali
AbstractThe seemingly matured field of olefin polymerization still poses several challenges and holds enormous potential to meet contemporary material requirements. In this feature article, we examine the progress of olefin polymerization in the last two decades. Among the several emerging trends, we identify four most impactful discoveries, namely, (i) disentangled ultra-high molecular weight polyethylene (dUHMWPE), (ii) disubstituted functional olefin copolymerization, (iii) incorporation of bioderived comonomers in polyolefins, and (iv) application of above (ii, iii) functional polyolefins as compatibilizers. The dUHMWPE has attracted significant attention and heterogeneous Ziegler-type catalysts, homogenous metallocene, and post-metallocene catalysts have been reported to produce disentangled ultrahigh molecular weight polyethylene. Insertion copolymerization of difunctional disubstituted olefins has been reported only recently and ortho-phosphinobenzene sulfonate palladium catalyst outperforms the other catalysts. Interestingly, insertion copolymerization of bioderived olefins has witnessed a surge in the number of reports. Sugar and plant oil-derived olefins have been copolymerized with ethylene to obtain relatively hydrophilic polyethylene. The functional polyethylene is finding a new application as compatibilizer or displays better adhesion to surfaces. Thus, the feature article offers a succinct account of emerging trends in polyolefins, identifies the most impactful contributions, and debates the application potential of these new materials.Keywords: Insertion (co)polymerizationuHMWPEfunctional polyethylenerenewable monomerscompatibilizer Disclosure statementNo potential conflict of interest was reported by the author(s).Additional informationFundingWe gratefully acknowledge the financial support from DST-SERB (CRG/2021/005385), CSIR-NCL (HCP46), and DSIR (CRTDH@NCL) India. RSB is thankful to DST for the DST-INSPIRE fellowship. DVB and PG are thankful to UGC for the fellowship.
摘要烯烃聚合这一看似成熟的领域,在满足当代材料需求方面仍面临着一些挑战,并具有巨大的潜力。在这篇专题文章中,我们研究了近二十年来烯烃聚合的进展。在几个新兴趋势中,我们确定了四个最具影响力的发现,即:(i)解结超高分子量聚乙烯(dUHMWPE), (ii)双取代功能烯烃共聚,(iii)生物衍生共聚体在聚烯烃中的掺入,以及(iv)上述(ii, iii)功能聚烯烃作为相容剂的应用。dUHMWPE引起了广泛的关注,非均相齐格勒型催化剂、均相茂金属催化剂和后茂金属催化剂已被报道用于制备脱缠超高分子量聚乙烯。双官能二取代烯烃的插入共聚反应最近才有报道,邻膦苯磺酸钯催化剂的催化性能优于其他催化剂。有趣的是,生物衍生烯烃的插入共聚已经见证了报告数量的激增。糖和植物油衍生的烯烃已与乙烯共聚得到相对亲水的聚乙烯。功能性聚乙烯正在寻找一种新的应用,作为相容剂或显示更好的表面附着力。因此,这篇专题文章简要介绍了聚烯烃的新兴趋势,确定了最具影响力的贡献,并讨论了这些新材料的应用潜力。关键词:插入(co)聚合;超高分子量聚乙烯;功能化聚乙烯;我们感谢DST-SERB (CRG/2021/005385)、CSIR-NCL (HCP46)和DSIR (CRTDH@NCL)印度的资金支持。RSB感谢DST提供DST- inspire奖学金。DVB和PG感谢教资会提供奖学金。
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引用次数: 0
A hyaluronic-based prodrug with aggregation-induced emission for drug delivery and cellular imaging 一种基于透明质酸的前药,具有聚集诱导发射,用于药物传递和细胞成像
3区 化学 Q3 POLYMER SCIENCE Pub Date : 2023-10-10 DOI: 10.1080/10601325.2023.2265961
Hoang-Phuc Pham, Vijayakameswara Rao Neralla
AbstractA novel drug molecule (R6) is conjugated to hyaluronic acid (HA) to form a pH-responsive prodrug with aggregation-induced emission (AIE) property. Owing to its amphiphilic nature, the prodrug could self-assemble into nanoparticles (NP) in an aqueous solution. This formulation thereby gave rise to AIE of the R6 moieties which resided in the NP core. The polymer could release the drug at the tumor microenvironment (TME) acidic condition (99% release after 72 h), while remaining stable at the physiological pH. In addition, fluorescence signals by AIE from the NP could be used for cellular imaging. The hyaluronic acid shell can target the overexpressed CD44 receptors in cancer cells, which gives the NP active targeting property. The prodrug showed toxicity against the mouse breast cancer cell line 4T1 while being harmless to the L929 fibroblast cells. Fluorescence microscopy images confirmed the imaging ability of the NP in 4T1 cells. The HA-R6 polymer prodrug promises to be a versatile pH-sensitive drug delivery platform.Keywords: Hyaluronic acidprodrugdrug deliveryaggregation-induced emissionimaging AcknowledgmentsWe would like to express their gratitude to National Taiwan University of Science and Technology (NTUST) and the Department of Chemical Engineering for their support to this project. For the chemical characterization and cell studies, Taiwan Ministry of Science and Technology funding (NSTC 111-2221-E-011-025) was used. Hyluronic acid was purchased from the NSTC 109-2222-E-011-004 grant.Disclosure statementThe authors declare no competing financial interest.
摘要一种新型药物分子(R6)与透明质酸(HA)偶联形成具有聚集诱导发射(AIE)特性的ph响应前药。由于其两亲性,前体药物可以在水溶液中自组装成纳米颗粒(NP)。因此,这种配方引起了位于NP核心的R6部分的AIE。该聚合物可在肿瘤微环境(TME)酸性条件下释放药物(72 h后释放99%),并在生理ph下保持稳定。此外,NP的AIE荧光信号可用于细胞成像。透明质酸外壳可以靶向癌细胞中过表达的CD44受体,这使得NP具有活性靶向特性。前药对小鼠乳腺癌细胞系4T1有毒性作用,对L929成纤维细胞无害。荧光显微镜图像证实了NP在4T1细胞中的成像能力。HA-R6聚合物前药有望成为一种通用的ph敏感药物输送平台。关键词:透明质酸;药物;药物传递;聚集诱导发射成像致谢感谢国立台湾科技大学(NTUST)和化学工程系对本项目的支持。化学表征和细胞研究使用了台湾科技部基金(NSTC 111-2221-E-011-025)。Hyluronic acid由NSTC 109-2222-E-011-004基金购买。披露声明作者声明没有与之竞争的经济利益。
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引用次数: 0
The effect of cross-linking system and reinforcement on the cross-linking reaction of peroxide vulcanized ethylene-propylene-diene terpolymer (EPDM) matrix 研究了交联体系和增强剂对过氧化物硫化三元共聚物(EPDM)基体交联反应的影响
3区 化学 Q3 POLYMER SCIENCE Pub Date : 2023-10-09 DOI: 10.1080/10601325.2023.2265974
Panayiotis Ketikis, Ioannis Ketikis, Petroula A. Tarantili
AbstractIn this work, the effect of using of dicumyl-peroxide (DCP) (2, 5 & 8 phr) and co-agent triallyl-cyanurate (TAC) (2, 4 & 6 phr) as cross-linking system as well as multi-walled carbon nanotubes (MWCNTs) (5, 8 και 10 phr) as a filler, for ethylene-propylene-diene terpolymer (EPDM) was investigated. Differential scanning calorimetry (DSC) was employed in order to study the progress of the cross-linking reaction, based on the exothermic vulcanization peaks of isothermal (at 160, 170, 180, 190 °C) and non-isothermal experiments (with heating rates 5, 10, 25, 50 °C min−1). The autocatalytic model was successfully applied to the results of isothermal experiments and the activation energy (Ea) of the reaction was calculated, based on the Arrhenius equation. The Ozawa-Kissinger equations were also applied to the data obtained from the non-isothermal study. From the results obtained from isothermal DSC experiments, an increase was observed in the reaction rates accompanied with a decrease in Ea with the increase of DCP content, whereas a proportional relationship between TAC content and the enthalpy and Ea of the reaction was recorded. The incorporation of MWCNT’s in EPDM increased its Ea. From the non-isothermal DSC experiments, a significant increase in the enthalpy and Ea of the cross-linking reaction was observed at higher DCP content, whereas TAC content did not show any notable effect on the reaction. Based on the results of this research, it is concluded that the increase of peroxide content facilitates the vulcanization of EPDM, whereas inhibition was observed by the incorporation of MWCNT’s.Keywords: EPDM elastomerperoxideco-agentcarbon nanotubesvulcanizationdifferential scanning calorimetry AcknowledgmentsSpecial thanks go to Dr. Dimitrios Korres for his assistance in DSC experiments.Disclosure statementNo potential conflict of interest was reported by the authors.
摘要本文研究了过氧化二氨基(DCP)(2,5和8 phr)和助剂三烯丙基氰脲酸酯(TAC)(2,4和6 phr)作为交联体系,以及多壁碳纳米管(MWCNTs) (5,8 και 10 phr)作为填料对乙烯-丙烯-二烯三元共聚物(EPDM)的交联效果。根据等温(160、170、180、190℃)和非等温实验(升温速率为5、10、25、50℃min - 1)的放热硫化峰,采用差示扫描量热法(DSC)研究交联反应的进展。将自催化模型应用于等温实验结果,并根据Arrhenius方程计算了反应的活化能(Ea)。小泽-基辛格方程也适用于从非等温研究得到的数据。等温DSC实验结果表明,随着DCP含量的增加,反应速率增加,Ea降低,TAC含量与反应焓和Ea成正比关系。在非等温DSC实验中,高DCP含量显著增加了交联反应的焓和Ea,而TAC含量对交联反应的影响不显著。研究结果表明,过氧化氢含量的增加促进了EPDM的硫化,而MWCNT的加入则抑制了EPDM的硫化。关键词:三元乙丙橡胶弹性体过氧化物生态剂碳纳米管硫化差示扫描量热法致谢特别感谢Dimitrios Korres博士在DSC实验中的帮助。披露声明作者未报告潜在的利益冲突。
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引用次数: 0
Norbornenyl-pendant aromatic (co)poly(ether ether ketone)s 降冰片烯基悬垂芳香(co)聚醚醚酮
3区 化学 Q3 POLYMER SCIENCE Pub Date : 2023-10-05 DOI: 10.1080/10601325.2023.2261462
Aniket A. Talanikar, Samadhan S. Nagane, Prakash P. Wadgaonkar, Gajanan S. Rashinkar
Abstract4, 4'-(Bicyclo (2.2.1) hept-5-en-2 yl methylene) bis (2-methoxyphenol) (BPA-NB) was utilized as a step-growth monomer for the synthesis of (co)poly(ether ether ketone)s (PEEK-NBs) via nucleophilic aromatic substitution polycondensation. A homo and five PEEK-NBs were synthesized by polycondensation of 4, 4'-difluorobenzophenone with BPA-NB and various compositions of BPA-NB and bisphenol-A, respectively. 1H NMR spectroscopy confirmed the chemical structure and composition of PEEK-NBs. Inherent viscosity and number-average molecular weight values of PEEK-NBs were in the range 0.64 to 0.78 dL g−1 and 62,670 to 84,470 g mol−1, respectively, indicating the formation of polymers of reasonably high molecular weight. It was easy to dissolve PEEK-NBs in common organic solvents such as chloroform, dichloromethane, and tetrahydrofuran. Tough, transparent, and flexible films of PEEK-NBs could be cast from chloroform solution. X-Ray diffraction studies indicated amorphous nature of PEEK-NBs. Glass transition temperature (Tg) values, determined by DSC analysis, of PEEK-NBs were in the range 163 to190 °C and Tg values increased with the increase in mol % of BPA-NB. The post-polymerization modification of a representative PEEK-NB was demonstrated using two azido compounds, namely, 4-(azidomethyl)-7-methoxy-2H-chromen-2-one and 9-(azidomethyl)anthracene, via metal-free azide-alkene 1,3-dipolar cycloaddition reaction to obtain copoly(ether ether ketone)s appended with coumarinyl and anthracenyl moieties, respectively.Keywords: (Co)poly(ether ether ketone)snorbornenyl groupspost-polymerization modificationazide-alkene click reaction AcknowledgementsAuthors are grateful to Dr. P. R. Rajamohanan for help with interpretation of NMR data.Disclosure statementNo potential conflict of interest was reported by the author(s).
摘要以4,4′-(双环(2.2.1)庚-5-烯-2基亚甲基)双(2-甲氧基酚)(BPA-NB)为阶梯生长单体,采用亲核芳香取代缩聚法合成(co)聚醚醚酮(peek - nb)。以4,4′-二氟苯甲酮为原料,分别与BPA-NB、BPA-NB和双酚A的不同组分缩聚合成了1个homo和5个peek - nb。1H核磁共振谱证实了peek - nb的化学结构和组成。PEEK-NBs的固有粘度和数均分子量分别在0.64 ~ 0.78 dL g−1和62,670 ~ 84,470 g mol−1之间,表明形成了相当高的分子量聚合物。peek - nb在氯仿、二氯甲烷、四氢呋喃等常见有机溶剂中易于溶解。从氯仿溶液中可以铸出坚韧、透明、柔韧的PEEK-NBs薄膜。x射线衍射研究表明peek - nb具有无定形性质。通过DSC分析,peek - nb的玻璃化转变温度(Tg)值在163 ~ 190℃之间,Tg值随着BPA-NB摩尔百分比的增加而升高。用4-(叠氮多甲基)-7-甲氧基- 2h - chromen2 - 1和9-(叠氮多甲基)蒽两种叠氮化合物,通过无金属叠氮烯1,3-偶极环加成反应,对具有代表性的PEEK-NB进行聚合后改性,得到分别附有香豆素基和蒽基的共聚物(醚醚酮)s。关键词:(Co)聚醚醚酮鼻甲烯基后聚合改性叠氮烯烃点击反应作者感谢Dr. p.r. Rajamohanan对NMR数据的解释。披露声明作者未报告潜在的利益冲突。
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引用次数: 0
Nanomolar detection of hypochlorite in ground water samples by a norbornene-based polymeric sensor via unusual fluorescence turn-on response 基于降冰片烯的聚合物传感器通过异常荧光开启响应检测地下水样品中的次氯酸盐
3区 化学 Q3 POLYMER SCIENCE Pub Date : 2023-09-22 DOI: 10.1080/10601325.2023.2257767
Jyotirlata Singha, Narayan Das, Raja Shunmugam
AbstractHypochlorite anion has been widely used as a bleaching and disinfecting agent in daily life. Selective and sensitive identification ofOCl-ions from water is very important for researchers. For this purpose, monomeric (NPh), and polymeric (PNPh-Peg) novel fluorescent sensors have been established for the specific and excellently unique sensors that exhibit selective characteristics like excellent resistance to bleaching and a high fluorescence brightness. A multi-functional random polymer (PNPh-Peg) with ICT (intramolecular charge transfer) active para–amino phenol functionality and reactive oxygen species (ROS) responsive, PEG attached are readily prepared via ROMP (ring-opening metathesis polymerization).: An ICT-active random polymer (PNPh-Peg) exhibited an unexpectedly strong cyan blue emission in a water medium compared to that in other common organic solvents, which was dramatically increased by adding a trace amount of NaOCl.: Incorporating PEG moiety in the polymeric backbone increases the water solubility of a copolymer, and the ROS-responsive groups make the polymer a good ROS scavenger. Upon oxidation of the phenol group into carbonyl, both the monomeric (NPh) and polymeric (Norp-PEG oh) sensors showed a selective, noticeable, unusual fluorescence turn-on response towardsanalyteOCl-ions with a very fast response (within three minutes). The detection limit (59.14 nM) and (126.93 nM) were calculated for monomeric and polymeric sensors, respectively. This was a selective, specific oxidation reaction of the completely water-soluble random polymeric sensor (PNPh-Peg) for hypochlorite anions and can be applicable for quantitative measurement of aqueous OCl-. This ICT-active random polymeric molecule (PNPh-Peg) can also be used as a fluorescent sensor for unique OCl- detection from contaminated water by preparing a sensor-coated paper strip. Thus, these multi-functional monomeric (NPh) and polymeric (PNPh-Peg) sensors are anticipated to apply to the environment.Keywords: Bio-imagingbleaching propertyhygroscopicmulti-functionalpolymeric sensor AcknowledgmentsJ. S. thanks DBT for a research fellowship. R. S. thanks IISER-K, DBT, DST, and DRDO for funding. The authors thank IISER-K for the use of infrastructure and facilities.Authors’ contributionsJ.S. did all the reactions and wrote the manuscript. N.D. helps to do the reactions and write the manuscript. R.S. supervised every step of this project.Disclosure statementNo potential conflict of interest was reported by the author(s).
摘要阴离子次氯酸盐在日常生活中被广泛用作漂白剂和消毒剂。选择性、灵敏地鉴别水中的氯离子对研究人员来说是非常重要的。为此,已经建立了单体(NPh)和聚合物(PNPh-Peg)新型荧光传感器,它们具有特异性和非常独特的传感器,具有优异的抗漂白性和高荧光亮度等选择性特性。通过开环复分解聚合制备了具有ICT(分子内电荷转移)活性对氨基酚官能团和活性氧(ROS)响应的多功能无规聚合物(PNPh-Peg)。与其他常见有机溶剂相比,ict活性无规聚合物(PNPh-Peg)在水介质中表现出意想不到的强烈的青色蓝色发射,通过添加微量的NaOCl显著增加。在聚合物主链中加入PEG片段增加了共聚物的水溶性,并且ROS响应基团使聚合物成为良好的ROS清除剂。在苯酚基团氧化成羰基后,单体(NPh)和聚合物(Norp-PEG oh)传感器对分析的氯离子表现出选择性的、明显的、不寻常的荧光开启反应,反应非常快(在三分钟内)。单体传感器和聚合物传感器的检出限分别为59.14 nM和126.93 nM。这是一种完全水溶性无规聚合物传感器(PNPh-Peg)对次氯酸阴离子的选择性、特异性氧化反应,可用于水溶液OCl-的定量测量。这种信通技术活性随机聚合物分子(PNPh-Peg)也可以用作荧光传感器,通过制备传感器涂层纸条,从受污染的水中进行独特的OCl检测。因此,这些多功能单体(NPh)和聚合物(PNPh-Peg)传感器有望应用于环境。关键词:生物成像;漂白性能;吸湿;感谢DBT提供的研究奖学金。r.s.感谢IISER-K, DBT, DST和DRDO的资助。作者感谢IISER-K使用了基础设施和设施。作者的contributionsJ.S。做了所有的反应并写了手稿。N.D.帮助做反应和写手稿。R.S.监督了这个项目的每一步。披露声明作者未报告潜在的利益冲突。
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引用次数: 0
Fabrication of dense anion exchange membranes by filling polymer matrix into quaternized branched polyethyleneimine @cellulose aerogel through in-situ polymerization 原位聚合将聚合物基体填充到季铵化支化聚乙烯亚胺@纤维素气凝胶中制备致密阴离子交换膜
3区 化学 Q3 POLYMER SCIENCE Pub Date : 2023-09-22 DOI: 10.1080/10601325.2023.2257758
Wenting Lan, Dawei Dong, Minghua Zhang, Yafei Xiao, Zhixin Zhao, Zhaojie Yang, Ya Cao, Minmin Fan
AbstractIn order to construct interconnected three-dimensional ion transport structures within anion exchange membranes (AEMs), we proposed the idea of preparing AEMs by filling the aerogel three-dimensional network skeleton by in-situ polymerization. First, quaternized branched polyethyleneimine (QBPEI) with a large number of quaternary ammonium groups was cross-linked with cellulose to construct an aerogel with a three-dimensional network. Then, poly(4-vinylbenzyl chloride) (PVBC) was filled into the aerogel network through in-situ polymerization. Finally, dense AEMs with internal three-dimensional ion transport networks were prepared by hot pressing PVBC/QBPEI@cellulose. The prepared AEMs have low ion exchange capacity (IEC) values and high ionic conductivities, with the membrane with the best overall performance (IEC value of 1.58 meq./g) having a maximum hydroxide conductivity of 38.88 mS/cm at 80 °C. In addition, the optimized membrane has good chemical and dimensional stability, and the maximum power density of the fuel cell assembled based on it is 46.32 mW/cm2. Although the performance of the prepared composite membranes needs to be further improved due to the preparation process, the design idea in this work provides a feasible solution for the construction of continuous ion fast transport channels in AEMs.Keywords: anion exchange membranequaternized branched polyethyleneiminecellulose aerogelhot pressingpoly(4-vinylbenzyl chloride) Associated contentSupporting information is available free of charge.Author contributionsWenting Lan: Data curation, Writing- Original draft preparation; Dawei Dong: Writing- Reviewing and Editing; Minghua Zhang: Methodology and Software; Yafei Xiao: Conceptualization and Methodology; Zhixin Zhao: Visualization, Investigation; Zhaojie Yang: Software and Validation; Ya Cao: Supervision and Data curation; Minmin Fan: Writing- Reviewing and Editing.Disclosure statementNo potential conflict of interest was reported by the author(s).Additional informationFundingThis work was financially supported by the National Natural Science Foundation of China [No. 51803136], Sichuan Science and Technology Program [No. 2021YFG0245] and the Fundamental Research Funds for the Central Universities [No. 2022SCUH0001].
摘要为了在阴离子交换膜(AEMs)内部构建相互连接的三维离子传输结构,我们提出了通过原位聚合填充气凝胶三维网络骨架来制备AEMs的想法。首先,将具有大量季铵基团的季铵化支化聚乙烯亚胺(QBPEI)与纤维素交联,构建具有三维网络的气凝胶。然后,通过原位聚合将聚(4-乙烯基苄基氯)(PVBC)填充到气凝胶网络中。最后,通过热压PVBC/QBPEI@cellulose制备了具有内部三维离子输运网络的致密AEMs。制备的AEMs具有较低的离子交换容量(IEC)值和较高的离子电导率,其中综合性能最好的膜(IEC值为1.58 meq./g)在80℃时的最大氢氧化物电导率为38.88 mS/cm。此外,优化后的膜具有良好的化学稳定性和尺寸稳定性,基于其组装的燃料电池的最大功率密度为46.32 mW/cm2。虽然由于制备工艺的原因,所制备的复合膜的性能还有待进一步提高,但本文的设计思路为AEMs中连续离子快速传输通道的构建提供了可行的解决方案。关键词:阴离子交换膜均匀化支化聚乙烯亚胺纤维素气凝胶热压聚(4-乙烯基氯化苄)相关内容免费提供支持资料兰文婷:数据整理,写作-原稿准备;董大伟:写作-审校;张明华:方法论与软件;肖亚飞:概念与方法论;赵志新:可视化,调查;杨兆杰:软件与验证;曹亚:监管与数据策展;范敏敏:写作-审稿与编辑。披露声明作者未报告潜在的利益冲突。本研究由国家自然科学基金资助[No. 1];四川省科技计划项目[51803136];2021YFG0245]和中央高校基本科研业务费专项基金[No. 2021YFG0245];2022 scuh0001]。
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引用次数: 0
Diethylaluminum chloride-co-initiated cationic polymerization of isoprene: dramatic effect of the nature of alkyl halide on the properties of synthesized polymers 二乙基氯化铝-共引发异戊二烯阳离子聚合:烷基卤化物性质对合成聚合物性能的显著影响
3区 化学 Q3 POLYMER SCIENCE Pub Date : 2023-09-22 DOI: 10.1080/10601325.2023.2257739
Victor A. Rozentsvet, Daria M. Ulyanova, Nelly A. Sablina, Sergei V. Kostjuk, Nina V. Sidorenko, Peter M. Tolstoy
AbstractThe cationic polymerization of isoprene using alkyl halide/Et2AlCl initiating system (alkyl halide: tert-butyl chloride, tert-butyl bromide, 2-chloro-2-methylbutane and isopropyl chloride) at different temperatures has been studied. It was shown for the first time that using of tertiary alkyl halide in conjunction with Et2AlCl allowed to synthesize fully soluble solid thermoplastic polymers with reduced unsaturation (41–48 mol%) as well as relatively high glass transition temperature (52–60°С) and softening point (102–128°С). The substitution of tertiary alkyl halides on the secondary one (isopropyl chloride) results in the obtaining of cross-linked polymers due to the low activity of isopropyl chloride in chain transfer to alkyl halide. It was found that alkyl halide nature, the ratio of alkyl halide to Et2AlCl, duration and temperature of the polymerization of isoprene have dramatic effect on the unsaturation of synthesized polymers as well as their molecular weight, polydispersity, physical and chemical properties.Keywords: Alkyl halidescationic polymerizationdiethylaluminum chlorideisoprenesolid thermoplastic polymers Disclosure statementThe authors declare no conflict of interest.Author contributionsVictor A. Rozentsvet: Conceptualization, supervision, methodology, project administration, resources, writing-original draft, writing-review and editing. Daria M. Ulyanova: Investigation, formal analysis, data curation. Nelly A. Sablina: Investigation, data curation, software, visualization. Sergei V. Kostjuk: Formal analysis, writing-original draft, writing-review and editing. Nina V. Sidorenko: Investigation. Peter M. Tolstoy: Investigation, methodology, formal analysis.Additional informationFundingThe work was performed on the theme of research No. 1021060107217-0-1.6.19 of Samara Federal Research Scientific Center of Russian Academy of Science, Institute of Ecology of Volga River Basin of Russian Academy of Science and State Task of the Russian Federation No. АААА-А19-119091190094. This work is also partially supported by State Program for Scientific Research of Belarus “Chemical processes, reagents and technologies, bioregulators and bioorganic chemistry” (project 2.1.01.03).
摘要研究了在不同温度下,以烷基卤化物/乙二氯化铝引发体系(烷基卤化物:氯化叔丁基、溴化叔丁基、2-氯-2-甲基丁烷和氯异丙基)阳离子聚合异戊二烯的反应。首次证明叔烷基卤化物与Et2AlCl结合可以合成完全可溶的固体热塑性聚合物,其不饱和度降低(41-48 mol%),玻璃化转变温度(52-60°С)和软化点(102-128°С)相对较高。叔烷基卤化物取代仲烷基卤化物(异丙基氯),由于异丙基氯向烷基卤化物的链转移活性低,得到交联聚合物。结果表明,烷基卤化物的性质、烷基卤化物与乙二铝的比例、异戊二烯聚合的时间和温度对聚合产物的不饱和性、分子量、多分散性、理化性质等均有显著影响。关键词:卤代烷基阳离子聚合二乙基氯代铝异戊二烯固体热塑性聚合物披露声明作者声明无利益冲突。作者:victor A. Rozentsvet:概念、监督、方法、项目管理、资源、写作-原稿、写作-审查和编辑。Daria M. Ulyanova:调查,形式分析,数据管理。Nelly A. Sablina:调查,数据管理,软件,可视化。Sergei V. Kostjuk:形式分析,写作-原稿,写作-审查和编辑。尼娜·西多连科:调查。彼得·托尔斯泰:调查,方法论,形式分析。本研究由俄罗斯科学院萨马拉联邦研究科学中心(1021060107217-0-1.6.19)、俄罗斯科学院伏尔加河流域生态研究所和俄罗斯联邦国家课题(1021060107217-0-1.6.19)资助。ААААА19 - 119091190094。白俄罗斯国家科学研究计划“化学过程、试剂和技术、生物调节剂和生物有机化学”(项目2.1.01.03)。
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Journal of Macromolecular Science Part A-Pure and Applied Chemistry
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