Article
Chemistry, Multidisciplinary
Yu-Sheng Liu, Eva Harth
Summary: The introduction of m-xylyl substituents to alpha-diimine Pd-II catalyst promotes living ethylene polymerization, leading to high molecular weight polyethylene with low branching. The m-xylyl groups effectively block the axial sites of the catalytic center, preventing chain-transfer and easy accessibility of polar monomers, resulting in a living polymerization. Incorporating different acrylate block sequences can significantly modify the mechanical and chemical properties of block copolymers to be a hard plastic, elastomer, or semi-amorphous polymer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Polymer Science
Jie Li, Yu Wang, Wen Cai, Gang Yang, Qiuhui Tian, Yongshuang Huang, Dan Peng, Chen Zou, Chen Tan
Summary: Dual-site molecular heterogeneous catalysts have gained attention for synthesizing polyolefin in-reactor blends. A self-supporting strategy based on nickel-catalyzed precipitation coordination polymerization was used to heterogenize and spatially distribute catalyst components in the particles. These polymeric heterogeneous catalysts exhibited higher activities, high molecular weights, good morphological control, and improved compatibility with polar materials. The composition and physical properties of the blend can be controlled by the molar ratio of the two catalytic components. Interestingly, different spatial distribution types resulted in significant differences in thermal, mechanical, and rheological properties and applications of the obtained blends.
Article
Polymer Science
Yue Liu, Gang Yang, Chao Li, Chen Tan, Min Chen
Summary: In this study, alpha-diimine ligands with an allyl group were designed, and ligand pre-inserted palladium catalysts Pd1-ACN and Pd2-ACN were generated. The Pd2-ACN catalyst showed higher catalytic activity in ethylene polymerization and copolymerization with polar monomers, demonstrating good polar group tolerance. DFT calculations and mechanistic studies revealed the formation of Pd-H catalytically active species during the polymerization process. This research provides new insights and information for catalyst design in olefin polymerization.
Article
Chemistry, Inorganic & Nuclear
Weiqing Lu, Hui Wang, Weigang Fan, Shengyu Dai
Summary: In this study, a bulky hybrid catalyst was designed and synthesized, which exhibited high activity and efficient copolymerization performance in the polymerization of ethylene. The hybrid catalyst generated highly branched polyethylenes with high molecular weights, showing advantages over the corresponding symmetrical catalysts.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Shumpei Akita, Jing-Yao Guo, Falk W. Seidel, Matthew S. Sigman, Kyoko Nozaki
Summary: In this study, the impact of ligands in palladium complexes on the copolymerization of ethylene and methyl acrylate was analyzed using a statistical method. The electron density on the palladium center and the maximum width of the substituents on the phosphorus atom were found to be significant factors affecting the catalyst performance. Additionally, features such as the occupancy of the palladium d(z)(2) orbital and the bite angle of the ligand were shown to influence the reaction outputs. The experimental results were not always consistent with the predictions, possibly due to insufficient training data for certain catalysts. However, the unexpected finding that chlorination of the ligand backbone improved the overall catalyst performance provides inspiration for the development of PS catalysts.
Review
Chemistry, Multidisciplinary
Wasim Ullah Khan, Hassam Mazhar, Farrukh Shehzad, Mamdouh A. Al-Harthi
Summary: The synthesis of polar functionalized polyolefin (PFP) improves mixing properties, polymer surface, and rheological properties for upgraded polyolefins. Metal-based catalyzed olefin copolymerization with polar comonomers offers an energy-efficient and upfront methodology, with late transition metal-based catalysts making progress in recent years. The development of nickel-based catalysts for PFP synthesis has shown rigorous progress in the past half-decade. This review summarizes the research trends in both early and late transition metal-based catalyst development and highlights the influence of transition metal-based catalysts on polymer properties.
Article
Chemistry, Physical
Chiara Alberoni, Massimo C. D'Alterio, Gabriele Balducci, Barbara Immirzi, Maurizio Polentarutti, Claudio Pellecchia, Barbara Milani
Summary: The microstructure of copolymers can be controlled by modifying the ligands in the catalyst. Different reaction media and ligands can result in different ways of polar monomer insertion into copolymers.
Article
Chemistry, Inorganic & Nuclear
Babak Tahmouresilerd, Dawei Xiao, Loi H. Do
Summary: In this study, two nickel complexes with conformationally rigid bisphosphine mono-oxide ligands were synthesized, showing competent catalytic activities for ethylene homopolymerization and copolymerization. The addition of Li+ to one of the complexes led to a significant enhancement in catalyst activity and polar monomer incorporation, making the nickel-alkali catalysts competitive with other efficient Ni-based systems for ethylene and methyl acrylate copolymerization.
INORGANIC CHEMISTRY
(2021)
Review
Polymer Science
Handou Zheng, Zonglin Qiu, Donghui Li, Lixia Pei, Haiyang Gao
Summary: Nickel- and palladium-catalyzed insertion copolymerization of ethylene and acrylate comonomers has drawn significant attention from academia and industry, yet remains highly challenging. This review provides an overview of the developments in this field, including mechanistic interpretation, different catalysts, and their effects on copolymerization performance and microstructure. The aim is to promote the design and development of nickel and palladium catalysts for ethylene/acrylate copolymerizations and synthesis of ethylene-acrylates copolymers.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Chemistry, Physical
Minghang Ji, Guifu Si, Yao Pan, Chen Tan, Min Chen
Summary: In this study, a series of α-diimine palladium complexes with two vinyl units were designed and synthesized, and they were employed as chain-transfer agents in tandem ring opening metathesis polymerization/cross metathesis reactions. Well-defined polymeric Pd catalysts with improved catalytic performances were successfully prepared. These catalysts exhibited enhanced catalytic activities in ethylene and 1-hexene polymerization, as well as improved tolerance to polar comonomers. The catalyst performance could be tuned by varying the structure or amount of cyclic monomer used in their preparation.
JOURNAL OF CATALYSIS
(2022)
Article
Polymer Science
Zijuan Hai, Zhou Lu, Shuaikang Li, Zhong-Yan Cao, Shengyu Dai
Summary: The study focused on the development of alpha-diimine catalysts with rigid steric hindrance groups, showing great potential in olefin polymerization. Significant progress has been made in the synthesis and characterization of unsymmetrical alpha-diimine ligands with flexible cycloalkyl and rigid diphenylmethyl moieties, as well as their corresponding Ni(ii) and Pd(ii) complexes, demonstrating high catalytic activities and the production of high-quality polymers.
Article
Chemistry, Inorganic & Nuclear
Weiqing Lu, Guoyong Xu, Guanru Chang, Hui Wang, Shengyu Dai
Summary: The types and sizes of N-o-aryl substituents strongly influence the activity of α-diimine Pd(II) catalysts; unsymmetrical acenaphthene-based α-diimine Pd(II) catalysts significantly enhance the branching of polyethylene and copolymerization ratio of E-MA copolymers in ethylene polymerization reactions.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Hongwei Peng, Shuaikang Li, Gen Li, Shengyu Dai, Mingjun Ji, Zhe Liu, Lihua Guo
Summary: The addition of bulky rotation-restricted substituents into iminopyridyl Ni (II) and Pd (II) catalysts was shown to effectively retard chain transfer, resulting in high molecular weight polyethylene or ethylene-MA copolymers with high MA incorporation ratio. Systematic studies on the (co)polymerization behavior as a function of rotation-restricted substituent variations led to the successful synthesis of various molecular weight polyethylene and ethylene-MA copolymer products.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Polymer Science
Xin Ma, Yixin Zhang, Zhongbao Jian
Summary: Introducing polyethylene glycol units into the seminal alpha-diimine framework led to the design of a new family of polyethylene glycol sandwich alpha-diimine nickel and palladium catalysts, which exhibited enhanced catalytic activities and the ability to tune branching densities of the polymer. The unique ligand-cocatalyst effect via secondary coordination interaction was proposed as the key mechanism behind the improved performance of the nickel catalysts.
Article
Chemistry, Physical
Mahsa Karimi, Hassan Arabi, Samahe Sadjadi
Summary: The use of catalysts in olefin homo- and copolymerization has become increasingly important. Nickel and palladium-based complexes with symmetrical cationic a-diimine and non-symmetrical neutral phosphine-sulfonate ligands have been widely utilized as olefin (co)polymerization catalysts. The unique properties of phosphine-sulfonate-based catalysts have attracted significant attention from researchers.
JOURNAL OF CATALYSIS
(2022)
Article
Polymer Science
Shenming Wang, Lingzhi Wang, Liu Zhong, Renwei Xu, Xiong Wang, Wenqian Kang, Haiyang Gao
EUROPEAN POLYMER JOURNAL
(2020)
Article
Chemistry, Physical
Liu Zhong, Handou Zheng, Cheng Du, Wenbo Du, Guangfu Liao, Chi Shing Cheung, Haiyang Gao
JOURNAL OF CATALYSIS
(2020)
Review
Materials Science, Multidisciplinary
Guangfu Liao, Fei He, Qing Li, Liu Zhong, Ruizheng Zhao, Huinan Che, Haiyang Gao, Baizeng Fang
PROGRESS IN MATERIALS SCIENCE
(2020)
Article
Polymer Science
Zefan Xiao, Liu Zhong, Cheng Du, Wenbo Du, Handou Zheng, Chi Shing Cheung, Lingzhi Wang, Haiyang Gao
Summary: This study investigates the substituent effects of vinyl arene in palladium-catalyzed copolymerization with different substituted styrenes. The electronic and steric effects of substituents on the copolymerization reaction are quantitatively evaluated. Results show significant impact of substituents on turnover number, copolymer molecular weight, and stereoregularity, highlighting the positioning effects of substituents on the reaction.
Article
Chemistry, Inorganic & Nuclear
Jiongzhe Wu, Wei Li, Shanyue Guan, Xiaohong Chen, Haiyang Gao, Xiaolong Liu
Summary: In this study, Vanadium-doped NaNbO3 powder was successfully prepared by adjusting the mass ratio of Nb2O5, NaOH and V2O5 using the hydrothermal synthesis method. The photocatalytic degradation activity of Vanadium-doped NaNbO3 for antibiotics in wastewater showed promising results, suggesting its potential application in antibiotic wastewater treatment.
INORGANIC CHEMISTRY COMMUNICATIONS
(2021)
Article
Nanoscience & Nanotechnology
Cheng Du, Chi Shing Cheung, Handou Zheng, Donghui Li, Wenbo Du, Heng Gao, Guodong Liang, Haiyang Gao
Summary: This study successfully developed an efficient strategy for adjusting the emission color of nontraditional intrinsic luminescent polymers through through-space acceptor-donor charge transfer, with experiments showing that the emission color can be tuned by changing postfunctionalization conversion and monomer substituents.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Materials Science, Multidisciplinary
Wenjie Tao, Yusheng Zhou, Faxu Lin, Haiyang Gao, Zhenguo Chi, Guodong Liang
Summary: This study reports a new type of mechanically responsive materials, RTP polymers, which possess both mechanochromic and mechanodecay characteristics. These polymers exhibit abundant changes in fluorescence intensity, emission color, RTP intensity, and RTP lifetime under force stimuli, enabling the detection of material deformation. Through phosphorescence lifetime and image analysis, early damage warning for engineering polymers can be achieved.
ADVANCED OPTICAL MATERIALS
(2022)
Review
Polymer Science
Chi Shing Cheung, Xinbo Shi, Lixia Pei, Cheng Du, Heng Gao, Zonglin Qiu, Haiyang Gao
Summary: In this review, we introduce the present status and synthesis methods of aromatic polyketones made from vinyl arene and CO. The use of [N,N] bidentate palladium catalysts in catalytic synthesis is discussed, along with the effects of vinyl arene monomer, counteranion, and solvent on copolymerization. The stereochemistry of copolymerization is also addressed.
JOURNAL OF POLYMER SCIENCE
(2022)
Article
Polymer Science
Wenbo Du, Handou Zheng, Yinwu Li, Chi Shing Cheung, Donghui Li, Heng Gao, Huiyun Deng, Haiyang Gao
Summary: This study developed a new neutral nickel catalyst with good thermal stability and high tolerance towards polar monomers. The copolymerization reaction using this catalyst produced branched copolymers with high molecular weight and high monomer incorporation, similar to commercially prepared products. Density functional theory calculations provided insights into the mechanism of copolymer formation.
Review
Chemistry, Physical
Huiyun Deng, Handou Zheng, Heng Gao, Lixia Pei, Haiyang Gao
Summary: This review focuses on late transition metal catalysts with chelating amines for olefin polymerization. A variety of catalysts with different amine donors are surveyed, and the relationship between catalyst structure and catalytic performance is discussed. The aim is to promote the development of high-performance polyolefin materials.
Article
Polymer Science
Lingzhi Wang, Donghui Li, He Ren, Yuru Wang, Wei Wu, Yuxin Gao, Xiong Wang, Haiyang Gao
Summary: In this study, the stereospecific polymerization of 1-alkenes was investigated using nonconventional pyridylamido hafnium catalysts with different bridgehead substituents. It was found that the bridgehead substituents significantly affected the polymerization activity and molecular weight distribution of the resultant poly(4-methylpentene)s.
Article
Chemistry, Multidisciplinary
Jing Ma, Yusheng Zhou, Haiyang Gao, Fangming Zhu, Guodong Liang
Summary: Photoluminescent materials are widely used in various fields, with a recent study reporting rare full-type photoluminescence from a single organic molecule, showing properties like aggregation-induced phosphorescence and thermoresponsive persistent phosphorescence. The materials can provide multiple visual signals upon temperature variation, and their luminescence thermoresponse is amplified when incorporated into polymers. A facile method based on phosphorescence lifetime and image analysis is used for quick, visual, and quantitative temperature sensing, showing promise for applications in quantitative temperature sensing.
MATERIALS CHEMISTRY FRONTIERS
(2021)
Article
Materials Science, Multidisciplinary
Xin Li, Zhen Liu, Zekun Zhou, Haiyang Gao, Guodong Liang, Daniel Rauber, Christopher W. M. Kay, Peng Zhang
Summary: The study found that doping salts with small-sized cations can enhance the electrical conductivity of PEDOT:PSS films by improving crystalline order and p-doped levels. These findings will be beneficial in developing recipes based on PEDOT:PSS/salt composites for printed flexible electronics applications.
ACS APPLIED POLYMER MATERIALS
(2021)
Article
Chemistry, Physical
Handou Zheng, Liu Zhong, Cheng Du, Wenbo Du, Chi Shing Cheung, Jingjing Ruan, Haiyang Gao
Summary: The development of thermally robust palladium-based catalysts for (co)polymerization of ethylene and polar monomers with high activities remains a challenging task. By combining hydrogen bonding interactions with steric and electronic modifications, new dibenzobarrelene-based alpha-diimine palladium complexes with different substituents have been synthesized and characterized. Through the steric and electronic effects as well as hydrogen bonding contributions, chloro- and methoxy-substituted palladium catalysts showed excellent performance in ethylene polymerization and copolymerization with high MA incorporation, respectively.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Polymer Science
Cheng Du, Hongling Chu, Zefan Xiao, Liu Zhong, Yusheng Zhou, Wei Qin, Guodong Liang, Haiyang Gao
