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CO_(2)-Sourced Poly(chloropropylene carbonate) with High Flame-Retardant Performance

Chinese Journal of polymer science 2025年第1期43卷 110-119,I0010页

作者： Yue Gong Xiao-Feng Zhu Guan-Wen Yang Meng Ma Xu Wang Jie Xu Xin Shu Guang-Peng Wu MOE Key Laboratory of Macromolecular Synthesis and Functionalization Key Laboratory of Adsorption and Separation Materials&Technologies of Zhejiang ProvinceDepartment of Polymer Science and EngineeringZhejiang UniversityHangzhou 310058China Zhejiang Key Laboratory of Plastic Modification and Processing Technology College of Materials Science and EngineeringZhejiang University of Technology Hangzhou 310014China Shanxi Coal Chemical Industry Technology Research Institute Co Ltd.Xi'an 710100China

The alternating copolymer of CO_(2) with epoxide is a green plastic that can efficiently transform CO_(2) into valuable chemicals. Despite the significant advances made, the restricted practical application of CO_(2)-sourced polycarbonates due to their lack of functionality has hindered field development. We successfully demonstrated the flame retardancy of poly(chloropropylene carbonate) (PCPC), a perfectly alternating copolymer of epichlorohydrin (ECH) and CO_(2). This was prepared at a 200-gram scale using a high-efficacy tetranuclear organoborane catalyst. PCPC’s excellent flame-retardant performance has been proven by both the vertical combustion test (UL94 V-0) and the limiting oxygen index (LOI) value (29.1%). The underlaid flame-retardant mechanism of PCPC was clearly elucidated. As a result, we confirmed that the generated cyclic carbonates and concurrently released flame-retardant chlorine radicals, hydrogen chloride, and CO_(2) during combustion render PCPC an excellent flame retardant. Furthermore, we investigated the practicability of PCPC as a halogen-rich polymeric flame retardant by blending it with commercial bisphenol A polycarbonate (BPA-PC). PCPC upgraded the flame retardancy rating of BPA polycarbonate from V-2 to V-0 even with a mere 1 wt% addition. It is our hope that this result will prove useful in future developments of advanced CO_(2)-sourced polymeric materials.

关键词： Carbon dioxide Ring-Opening polymerization Organocatalysis Sustainable materials Flame-retardant polymer

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A breathing A4 paper by in situ growth of green metal-organic frameworks for air freshening and cleaning

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Chinese Journal of chemical engineering 2022年第12期52卷 95-102页

作者： Bo Zhang Hongwen Chen Liming Jiang Youqing Shen Dan Zhao Zhuxian Zhou Key Laboratory of Biomass Chemical Engineering of Ministry of Education and Zhejiang Key Laboratory of Smart Biomaterials College of Chemical and Biological EngineeringZhejiang UniversityHangzhou 310027China Department of Polymer Science and Engineering Zhejiang UniversityHangzhou 310027China Department of Chemical&Biomolecular Engineering National University of Singapore117585Singapore Hangzhou Global Scientific and Technological Innovation Center Zhejiang UniversityHangzhou 311215China

Surface modification of natural cellulose fibers with nanomaterials is an effective strategy for producing functional textiles for multiple applications.A4-sized printing paper is a commonly used,cheap,and easily acquirable office supply which is mainly made of cellulose ***,we report green and simple nanofabrication of A4 paper to endow it with high capability for fragrance encapsulation and sustained release,and strong adsorption to indoor air *** method utilizes the sugar molecule of cellulose for in-situ growth ofγ-cyclodextrin(γ-CD)metal-organic frameworks(MOFs)on A4 *** obtainedγ-CD-MOF/A4 nanocomposites have superior specific surface area and high porous ***γ-CD-MOF/A4 nanocomposites can effectively encapsulate fragrant molecules through host-guest ***γ-CD-MOF/A4 nanocomposites also show strong absorption capability to formaldehyde and carbon dioxide through the formation of hydrogen bonding and chemical ***γ-CD-MOF/A4nanocomposites combine the advantages of both A4 paper andγ-CD-MOF,which can be used in indoor air freshening and cleaning.

关键词： Metal-organic frameworks A4 printing paper In situ synthesis Fragrance encapsulation Formaldehyde removal Carbon dioxide capture

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Potential use of Ulva intestinalis-derived biochar adsorbing phosphate ions in the cultivation of winter wheat Tristicum aestivum

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Bioresources and Bioprocessing 2024年第1期11卷 371-394页

作者： Natalia Niedzbała Ewa Lorenc-Grabowska Piotr Rutkowski Jacek Chęcmanowski Anna Szymczycha-Madeja Maja Wełna Izabela Michalak Department of Advanced Material Technologies Faculty of ChemistryWrocław University of Science and TechnologyWrocławPoland Department of Process Engineering and Technology of Polymer and Carbon Materials Faculty of ChemistryWrocław University of Science and TechnologyWrocławPoland Department of Analytical Chemistry and Chemical Metallurgy Faculty of ChemistryWrocław University of Science and TechnologyWrocławPoland

In this work,the properties of biochar produced from green macroalga Ulva intestinalis by pyrolysis were studied at temperatures of 300,500,and 700°*** biochar was characterized in terms of multielemental composition,BET surface area,total pore volume,and biosorption properties toward phosphate *** produced at 700°C-25 m2/g had the highest surface *** kinetics and isotherms of sorption processes of phosphate ions as sorbate by these sorbents were *** biochar was able to remove 84.3%of phosphate ions from wastewater,whereas non-modified biochar-only 40.6%.Hence,biochar enriched with phosphate ions can serve as a valuable soil *** experiments performed on winter wheat(Triticum aestivum)with a 3%addition of dry Ulva intestinalis,pristine biochar,and Mg-modified biochar enriched with phosphate ions showed that these amendments stimulated plant growth(length and fresh weight of plants)as well as enlarging the chlorophyll content in *** results indicate that the production of biochar(pristine and Mg-impregnated)is a sustainable option to valorize the biomass of seaweeds,and to recycle phosphorus from wastewater.

关键词： Green seaweed Pyrolysis Biochar Phosphate ions Wastewater treatment Soil additives

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Polyethylene interfacial dielectric layer for organic semiconductor single crystal based field-effect transistors

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Chinese chemical Letters 2024年第4期35卷 431-435页

作者： Min Chen Boyu Peng Xuyun Guo Ye Zhu Hanying Li Department of Polymer Science and Engineering MOE Key Laboratory of Macromolecular Synthesis and FunctionalizationInternational Research Center for X PolymersShanxi-Zheda Institute of Advanced Materials and Chemical EngineeringZhejiang UniversityHangzhou 310027China Department of Applied Physics Research Institute for Smart EnergyThe Hong Kong Polytechnic UniversityHong Kong 999077China

Organic semiconductor single crystals(OSSCs) have shown their promising potential in high-performance organic field-effect transistors(OFETs). The interfacial dielectric layers are critical in these OFETs as they not only govern the key semiconductor/dielectric interface quality but also determine the growth of OSSCs by their wetting properties. However, reported interfacial dielectric layers either need rigorous preparation processes, rely on certain surface chemistry reactions, or exhibit poor solvent resistance, which limits their applications in low-cost, large-area, monolithic fabrication of OSSC-based OFETs. In this work, polyethylene(PE) thin films and lamellar single crystals are utilized as the interfacial dielectric layers, providing solvent resistive but wettable surfaces that facilitate the crystallization of 6,13-bis(tri-isopropylsilylethynyl)pentacene(TIPS-PEN) and 6,13-bis(triisopropylsilylethynyl)-5,7,12,14-tetraazapentacene(TIPS-TAP). As evidenced by the presence of ambipolar behavior in TIPS-PEN single crystals and the high electron mobility(2.3 ± 0.34 cm^(2)V^(-1)s^(-1)) in TIPS-TAP single crystals, a general improvement on electron transport with PE interfacial dielectric layers is revealed, which likely associates with the chemically inertness of the saturated C-H bonds. With the advantages in both processing and device operation, the PE interfacial dielectric layer potentially offers a monolithic way for the enhancement of electron transport in solution-processed OSSC-based OFETs.

关键词： Polyethylene Interfacial dielectric layer Organic semiconductor Single crystal Organic field-effect transistors

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Effect of poly(4-tert-butylstyrene)block length on the microphase structure of poly(ethylene oxide)-b-poly(4-vinylbenzyl chloride)-b-poly(4-tert-butylstyrene)triblock terpolymers

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Chinese chemical Letters 2023年第6期34卷 551-555页

作者： Kun An Jia Gao Yihang Chen Jingjing Nie Yongjin Li Junting Xu Binyang Du State Key Laboratory of Motor Vehicle Biofuel Technology Department of Polymer Science&EngineeringZhejiang UniversityHangzhou 310027China College of Material Chemistry and Chemical EngineeringHangzhou Normal UniversityHangzhou 310036China Department of Chemistry Zhejiang UniversityHangzhou 310027China

A series of linear poly(ethylene oxide)-b-poly(4-vinylbenzyl chloride)-b-poly(4-tert-butylstyrene)(PEO_(113)-b-PVBC_(130)-b-Pt BS_(x)or E_(113)V_(130)T_(x))triblock terpolymers with various lengths x(=20,33,66,104,215)of Pt BS block were synthesized via a two-step reversible addition-fragmentation chain transfer(RAFT)*** E_(113)V_(130)T_(x)triblock terpolymers were non-crystalline because the PVBC and Pt BS blocks strongly hindered the crystallization of PEO *** effects of Pt BS block length x on the phase structures of E_(113)V_(130)T_(x)triblock terpolymers were investigated by combined techniques of small-angle X-ray scattering(SAXS)and transmission electron microscopy(TEM).It was found that with increasing x from20 to 215,the phase structure of E_(113)V_(130)T_(x)triblock terpolymers became more ordered and changed from disordered structure,hexagonally-packed cylinder(HEX),hexagonally perforated layer(HPL),to lamellar(LAM)phase ***-variable SAXS measurements showed that the HEX,HPL and LAM phase structures obtained for E_(113)V_(130)T_(66),E_(113)V_(130)T_(104)and E_(113)V_(130)T_(215)by thermal annealing,respectively,were thermodynamically stable in the temperature range of 30-170℃.

关键词： ABC triblock terpolymer Phase structure SAXS HPL Thermodynamically stable

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Revealing the Effect of Branched Side Chain Length on polymer Aggregation and Paracrystallinity for Improved Mobility-Stretchability Properties

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ACS Applied Electronic Materials 2024年第3期6卷 1797-1808页

作者： Shih, Yen-Han Chen, Guan-Lin Liu, Pang-Hsiao Tseng, Kai-Wei Lee, Wen-Ya Chen, Wen-Chang Wang, Leeyih Chueh, Chu-Chen Department of Chemical Engineering National Taiwan University Taipei10617 Taiwan Center for Condensed Matter Science National Taiwan University Taipei10617 Taiwan Center of Atomic Initiative for New Materials National Taiwan University Taipei10617 Taiwan Institute of Polymer Science and Engineering National Taiwan University Taipei10617 Taiwan Department of Chemical Engineering & Biotechnology National Taipei University of Technology Taipei10608 Taiwan Advanced Research Center for Green Materials Science and Technology National Taiwan University Taipei10617 Taiwan

Alkyl side chain engineering has long been used to improve the solubility of conjugated polymers. However, systematic studies on the effect of different alkyl branch lengths on morphological modulation and mobility-stretchability properties are still lacking. Here, we synthesize three fluorinated benzothiadiazole-based polymers (PC12BTDFT, PC16BTDFT, and PC20BTDFT) with different alkyl branch lengths and evaluate their structure-aggregation-stretchability correlations. The results show that longer side chains alleviate severe aggregation and form short-range aggregates, leading to a higher stretching ability without sacrificing high mobility (∼0.1 cm2 V-1 s-1). Also, a higher degree of paracrystallinity produced by longer side chains improves the release of tensile stresses, resulting in more significant retention of crystalline structural domains and the maintenance of higher mobility after being subjected to mechanical forces, as evidenced by the significant difference in mobility after 60% strain (7.64 × 10-4 cm2 V-1 s-1 for PC12BTDFT and 0.011 cm2 V-1 s-1 for PC20BTDFT). Our results show the effect of the side chain length on the aggregation behavior and microstructure between polymer chains. Furthermore, a clear dependence between paracrystallinity and stretchability is identified from the changes in morphology and charge transport behavior, providing a valuable perspective for the design of high-performance stretchable conjugated polymers. © 2024 The Authors. Published by American chemical Society.

关键词： Organic field effect transistors

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Manipulating noncovalent conformational lock via side-chain engineering for luminescence at aggregate level

Aggregate

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Aggregate 2024年第4期5卷 349-359页

作者： Mingbing Lian Yingxiao Mu Zecong Ye Ziying Lu Jingping Xiao Jianyu Zhang Shaomin Ji Haoke Zhang Yanping Huo Ben Zhong Tang School of Chemical Engineering and Light Industry Analytical and Testing CenterGuangdong University of TechnologyGuangzhouChina Stratingh Institute for Chemistry and Zernike Institute for Advanced Materials University of GroningenGroningenThe Netherlands MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and EngineeringZhejiang UniversityHangzhouChina School of Science and Engineering Shenzhen Institute of Aggregate Science and TechnologyThe Chinese University of Hong KongGuangdongChina

The unfavorable photochemical processes at the molecular level have become a bar-rier limiting the use of aromatic amides as high-performance luminescent ***,we propose a reliable strategy for manipulating noncovalent conformational lock(NCL)via side-chain engineering to burst out eye-catching luminescence at the aggregate *** to the invisible emission in dilute solutions,dyad OO with a three-centered H-bond gave the wondrous crystallization-induced emis-sion with a quantum yield of 66.8%and clusterization-triggered emission,which were much brighter than those of *** calculations demonstrate that crystallization-induced planarized intramolecular charge transfer(PICT),con-formation rigidification,and through-space conjugation(TSC)are responsible for aggregate-state *** NCL composed of intramolecular N-H⋅⋅⋅Ointeractions could boost molecular rigidity and planarity,thus greatly facilitating PICT and *** study would inspire researchers to design efficient luminescent materials at the aggregate level via rational conformational control.

关键词： aromatic amide clusterization-triggered emission crystallization-induced emission noncovalent confor-mational lock side-chain engineering

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Low-Temperature Methanolysis of Polycarbonate over Solid Base Sodium Aluminate

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Langmuir 2024年第10期40卷 5338-5347页

作者： Krisbiantoro, Philip Anggo Sato, Miyu Lin, Tzu-Ming Chang, Yu-Chia Peng, Tzu-Yun Wu, Yun-Chih Liao, Weisheng Kamiya, Yuichi Otomo, Ryoichi Wu, Kevin C.-W. Molecular Science and Technology Program Taiwan International Graduate Program Academia Sinica Taipei11529 Taiwan International Graduate Program of Molecular Science and Technology National Taiwan University Taipei10617 Taiwan Department of Chemical Engineering College of Engineering National Taiwan University Taipei10617 Taiwan Graduate School of Environmental Science Hokkaido University Nishi 5 Kita 10 Sapporo060-0810 Japan Faculty of Environmental Earth Science Hokkaido University Nishi 5 Kita 10 Sapporo060-0810 Japan Center of Atomic Initiative for New Materials National Taiwan University Taipei10617 Taiwan Department of Chemical Engineering and Materials Science Yuan Ze University Taoyuan320 Taiwan

Herein, a low-cost and readily available sodium aluminate (NaAlO2) was used as a solid base catalyst for the depolymerization of polycarbonate (PC) via methanolysis in the presence of tetrahydrofuran (THF) as a solvent. NaAlO2 was highly active for the reaction, and the performance was comparable to that of soluble strong base SrO and much higher than those of MgO and CaO. By the reaction over the catalyst, a highly pure and crystalline bisphenol A (BPA) was obtained. Among tested organic solvents, THF was the best in aiding PC methanolysis over NaAlO2 due to the polarity similar to PC according to Hansen solubility parameters (HSPs). At 60 °C, 98.1% PC conversion and 96.8% BPA yield were achieved within just 2 h. NaAlO2 was reusable without any severe catalyst deactivation in at least four runs. The mechanistic study revealed that the reaction proceeded via the methoxide pathway, with THF aiding the dissolution of PC. The reaction over NaAlO2 possessed a low apparent activation energy (Ea) of 75.1 kJ mol-1, which is the lowest ever reported so far for the reaction over solid catalysts. © 2024 The Authors. Published by American chemical Society.

关键词： Sodium Aluminate

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Novel concept of nano-additive design:PTFE@silica Janus nanoparticles for water lubrication

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Friction 2024年第2期12卷 258-270页

作者： Yanfei LIU Hailing HE Meng YANG Ruize ZHANG Shengtao YU Tiantian YANG Wenzhong WANG Fuxin LIANG School of Mechanical Engineering Beijing Institute of TechnologyBeijing 100081China Institute of Polymer Science&Engineering Department of Chemical EngineeringTsinghua UniversityBeijing 100084China MOE Key Laboratory of Bioinformatics Center for Plant BiologySchool of Life SciencesTsinghua UniversityBeijing 100084China Tsinghua-Peking Center for Life Sciences Beijing 100084China College of Biological Sciences China Agricultural UniversityBeijing 100193China

Polytetrafluoroethylene(PTFE)has been widely used as a lubrication additive for reducing friction and wear;however,the hydrophobic nature of PTFE restricts its application in eco-friendly water-based lubrication *** this study,for the first time,we designed novel PTFE@silica Janus nanoparticles(JNs)to meet the requirement for additives in water-based lubricants,which have excellent dispersion stability in water attributed to the unique amphiphilic *** introducing the lubrication of the aqueous dispersion of the JNs with a concentration of 0.5 wt%,the coefficient of friction(COF)and wear volume were reduced by 63.8%and 94.2%,respectively,comparing to those with the lubrication of pure ***,the JNs suspension also exhibits better lubrication and wear-resistance performances comparing to commercial silica and PTFE *** excellent tribological behaviors of PTFE@silica JNs as nano-additives could be attributed to the synergetic effect of the two components,where the PTFE provided lubrication through the formed tribofilms on the friction pairs,and the rigid silica further enhanced the wear-resistance *** importantly,the unique structure of JNs makes it possible to use PTFE as an additive in water-lubrication *** study shed light on the design and application of novel JNs nanomaterials as additives to meet the requirements of future industrial applications.

关键词： Janus nanoparticles(JNs) polytetrafluoroethylene(PTFE) nano-additives friction lubrication

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Janus polymerization:A One-Shot Approach towards Amphiphilic Multiblock Poly(ester-acetal)s Directly from 1,3-Dioxolane withε-Caprolactone

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Chinese Journal of Chemistry 2022年第6期40卷 705-712页

作者： Huan Qiu Ting Shen Zhening Yang Feng Wu Xiaohong Li Yingfeng Tu Jun Ling MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and EngineeringZhejiang UniversityHangzhouZhejiang 310027China College of Chemistry Chemical Engineering and Materials ScienceSoochow UniversitySuzhouJiangsu 215123China

Janus polymerization consists of anionic and cationic ring opening polymerizations(AROP and CROP)at the two ends of a single propagating polymer chain,followed by a self-triggered chain extension generating multiblock copolymers(MBCPs)in one *** the contribution,Janus polymerization by Tm(OTf)_(3) or Er(OTf)_(3) catalyst with an epoxy initiator is applied to synthesize MBCPs of semi-crystalline poly(ε-caprolactone)(PCL)blocks from coordinated AROP and poly(1,3-dioxolane-co-ε-caprolactone)(P(DO-co-CL))blocks from CROP of DO with ***,amorphous random copolymers[P(DO-r-CL)]are synthesized as control by employing other rare earth triflates[RE(OTf)_(3),RE=Y,Nd,Gd and Lu]as catalysts or in the absence of an initiator via *** account of the distinguishable chemical structures and thermal properties between Janus MBCPs and cationic random copolymers,Janus features are confirmed including the CROP and AROP at a single propagating *** resultant amphiphilic copolymers self-assemble to nanoparticles in aqueous solution with designable diameters with the corresponding ratios of hydrophilic and hydrophobic *** exhibit good shape memory properties with appropriate deformation temperature close to human body's,providing a prospect on the applications in biomedical devices.

关键词： Janus polymerization Ring-opening polymerization Multiblock copolymers Homogeneous catalysis(?)Lanthanides

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