SuYun Jie

Synthesis and CO2 Capture Behavior of Porous Cross-Linked Polymers Containing Pendant Triazole Groups

Co-reporter:Junjie Zhu, Linbo Wu, Zhiyang Bu, Suyun Jie, and Bo-Geng Li

Industrial & Engineering Chemistry Research September 13, 2017 Volume 56(Issue 36) pp:10155-10155

Publication Date(Web):July 26, 2017

DOI:10.1021/acs.iecr.7b01961

Porous cross-linked polymers containing pendant triazole groups were synthesized from glycidyl methacrylate (GMA) in the presence of divinylbenzene via high internal phase emulsion (HIPE) templating method followed by functionalization with sodium 3-amino-1,2,4-triazole (ATANa). They were characterized with FTIR, SEM, BET, and mercury intrusion and assessed as CO2 adsorbents. With interconnected hierarchical porous structure and abundant triazole groups which absorbed CO2 chemically in 1:1 stoichiometry, the adsorbents exhibited high CO2 adsorption capacity (3.6 mmol g–1, at 25 °C and 1 atm) and rate, and good CO2/N2 selectivity (∼30). The adsorbents also displayed easy CO2 desorption with medium desorption heat (58 kJ/mol CO2), acceptable moisture endurance, and excellent recyclability. The results suggest that these functionalized porous polymers are potential adsorbents for CO2 capture.

Preparation of Hydroxyl-Terminated Polybutadiene with High Cis-1,4 Content

Co-reporter:Qinzhuo Zhou;Bo-Geng Li

Industrial & Engineering Chemistry Research November 19, 2014 Volume 53(Issue 46) pp:17884-17893

Publication Date(Web):Publication Date (Web): October 31, 2014

DOI:10.1021/ie503652g

Hydroxyl-terminated polybutadiene (HTPB) with high cis-1,4 content (>95.0%) has been prepared via a two-step method by taking commercial butadiene rubber (BR9000) as a starting material, including the one-pot synthesis of aldehyde-group-terminated polybutadiene (ATPB) in high efficiency and the subsequent reduction reaction. The double bonds distributed in linear polybutadiene were first epoxidized and then cleaved at the exact epoxidized sites. The epoxidation reaction by 3-chloroperbenzoic acid and chain-cleavage reaction by periodic acid are controllable, highly efficient, selective, and quantitative. Along with an epoxy percent increase, the molecular weight of ATPB prepared via a one-pot method decreased with a relatively narrow polydispersity index. The aldehyde groups in the chain ends were reduced by NaBH4 to produce HTPB, in which the high cis-1,4 content of BR was retained.

High cis-1,4 Hydroxyl-Terminated Polybutadiene-Based Polyurethanes with Extremely Low Glass Transition Temperature and Excellent Mechanical Properties

Co-reporter:Zhe Cao, Qinzhuo Zhou, Suyun Jie, and Bo-Geng Li

Industrial & Engineering Chemistry Research 2016 Volume 55(Issue 6) pp:1582-1589

Publication Date(Web):February 4, 2016

DOI:10.1021/acs.iecr.5b04921

A series of polyurethanes have been prepared from hydroxyl-terminated polybutadiene (HTPB) with high cis-1,4 content and commercial free-radical-polymerized HTPB (FHTPB). The mechanical properties of cured polyurethane (PU) samples have been studied by tensile testing and dynamic mechanical analysis (DMA), and their thermal properties have been tested by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The NCO/OH ratio, chain extension coefficient (r), and microstructure of HTPB and FHTPB have a large influence on the mechanical properties of PUs. Meanwhile, the cyclic tensile testing indicated that the HTPB-based PUs had an outstanding elasticity. Both DSC and DMA analyses showed that the HTPB-based PUs had a glass transition temperature much lower than that of the FHTPB-based PUs. The hydrophobicity of the surface of PUs was verified by measuring their water contact angles.

Novel polyethylene-b-polyurethane-b-polyethylene triblock copolymers: Facile synthesis and application

Co-reporter:Zhixian Xu;Yulu Liu;Song Guo;Bo-Geng Li

Journal of Applied Polymer Science 2016 Volume 133( Issue 6) pp:

Publication Date(Web):

DOI:10.1002/app.42967

ABSTRACT

A series of novel polyethylene-b-polyurethane-b-polyethylene (EUE) triblock copolymers is successfully prepared through a facile route combining the thiol-ene chemistry, addition polymerization, and coupling reaction. The resulting EUE triblock copolymers are characterized by Nuclear magnetic resonance (¹H NMR), Fourier transform-infrared spectra (FT-IR), High temperature gel permeation chromatography (HT-GPC), Differential scanning calorimetry (DSC), Thermogravimetric analysis (TGA), and Transmission electron microscopy (TEM). In addition, the EUE triblock copolymers have been evaluated as compatibilizers in the polymer blends of thermoplastic polyurethane elastomer (TPU) and high-density polyethylene (HDPE). The SEM results show that the compatibility of immiscible blends is enhanced greatly after the addition of EUE triblock copolymers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42967.

Nickel(II) α-diimine catalysts with carboxyl groups for ethylene oligomerization and polymerization

Co-reporter:Bing Liu;Meng-zhe Fang;Su-yun Jie 介素云;Zhi-yang Bu

Chinese Journal of Polymer Science 2016 Volume 34( Issue 2) pp:221-228

Publication Date(Web):2016 February

DOI:10.1007/s10118-016-1734-3

A series of nickel(II) α-diimine complexes with strong electron-withdrawing carboxyl groups, having reactive hydrogen atoms, were prepared and used as precatalysts for ethylene oligomerization and/or polymerization. The influence of metal halides and ligand structure on the catalytic activity and properties of products was investigated. The results showed that nickel bromide was much more active than nickel chloride, and the substituents at the ortho-position of aryl ring had large influence on the properties of products. Therefore, the products ranging from liquid oligomers to polymers could be readily obtained by the variation of the substituents on the ligands and reaction conditions.

Cleavable polybutadiene rubber: A versatile precursor to hydroxyl-terminated or multi-hydroxyl polybutadiene and polyethylene

Co-reporter:Qinzhuo Zhou, Anqi Wang, Lu Dai, Suyun Jie, Bo-Geng Li

Polymer 2016 Volume 107() pp:306-315

Publication Date(Web):19 December 2016

DOI:10.1016/j.polymer.2016.11.033

•MHPB with α,ω- and controllable intrachain hydroxyl groups was synthesized.•Hydroxyl functionalized polyethylenes (HTPE, FHTPE and MHPE) were synthesized.•Linear HTPE has high degree of crystallinity (70%) and melting temperature (123.2 °C).•MHPE has lower degree of crystallinity (47%) and melting temperature (110.9 °C).A series of hydroxyl functionalized polybutadienes has been prepared by combining the oxidolysis and reduction of cis-polybutadiene rubber (BR). For the first time, multi-hydroxyl polybutadiene (MHPB) with α,ω- and intrachain hydroxyl groups was synthesized through the simultaneous reduction of –CHO and epoxy groups in epoxidized aldehyde group terminated polybutadiene (EATPB) by sodium dihydro-bis-(2-methoxyethoxy) aluminate (Red-Al). The corresponding hydroxyl functionalized polyethylenes, including hydroxyl-terminated polyethylene (HTPE), multi-hydroxyl polyethylene (MHPE) and hydroxyl-terminated polyethylene with ethyl branches (FHTPE), were readily obtained via the hydrogenation of C=C double bonds in the functionalized polybutadienes with TSH/TPA regents. The microstructures of all the products were confirmed by 1H NMR, 13C NMR and FT-IR, and their thermal properties were determined by TGA and DSC. It has been indicated that the linear HTPE and MHPE possessed high initial thermal degradation temperature, high degree of crystallinity, and high melting temperature due to their stereoregular microstructure. However, the FHTPE obtained through the hydrogenation of HTPB from free radical polymerization had much lower degree of crystallinity and melting temperature due to the presence of more ethyl branches.

Facile synthesis of novel HTPBs and EHTPBs with high cis-1,4 content and extremely low glass transition temperature

Co-reporter:Qinzhuo Zhou, Suyun Jie, Bo-Geng Li

Polymer 2015 Volume 67() pp:208-215

Publication Date(Web):12 June 2015

DOI:10.1016/j.polymer.2015.04.078

•Novel HTPBs and EHTPBs were synthesized through a facile route.•HTPBs and EHTPBs had high cis-1,4 content.•HTPBs and EHTPBs had extremely low glass transition temperature.•HTPBs and EHTPBs had controllable Mn and PDI.Hydroxyl-terminated polybutadiene (HTPB) and epoxidized HTPB (EHTPB) with high cis-1,4 content, controllable molecular weight and relatively low PDI have been prepared via the selective oxidolysis process using commercial butadiene rubber (BR9000) as a starting material, including the one-pot synthesis of aldehyde group-terminated polybutadiene (ATPB) and the subsequent reduction reaction by sodium borohydride. The full process could be conducted in mild conditions and without complicated manipulations. By tuning the epoxy percent and chain-cleavage percent in the first step, liquid telechelic HTPBs with full-scale molecular weight and EHTPBs with various epoxy percent were readily obtained. The microstructure, molecular weight and PDI of products in each step were determined by FT-IR, 1H NMR, 13C NMR and GPC, respectively. The thermal properties of HTPBs and EHTPBs were tested by DSC and TGA.

Solvent effect on cis-1,4-specific polymerization of 1,3-butadiene with CoCl2(PRPh2)2–EASC catalytic systems

Co-reporter:Qinzhuo Zhou, Bo-Geng Li, Suyun Jie and Na Zheng

Catalysis Science & Technology 2014 vol. 4(Issue 3) pp:773-779

Publication Date(Web):17 Dec 2013

DOI:10.1039/C3CY00634D

A series of phosphine-containing cobalt complexes [CoCl2(PRPh2)2, R = Ph (1), Cy (2), nPr (3), Et (4), Me (5), H (6)] has been used for the highly active and stereospecific polymerization of 1,3-butadiene upon activation with ethylaluminum sesquichloride (EASC). The high catalytic activities and polybutadienes with high cis-1,4 selectivity were obtained in the solution polymerization in toluene. The conversion of butadiene and the microstructure and molecular weight of the resulting polymers were affected by reaction parameters and the R group on the phosphine ligand. The dispersion medium was also a sensitive factor for the current catalytic systems, influencing the catalytic activity and properties of products. In comparison with the solution polymerization in toluene, the heterogeneous polymerization in isooctane yielded slightly lower catalytic activity, cis-1,4 content and molecular weight under similar reaction conditions.

Postsynthetic modification of mixed-linker metal–organic frameworks for ethylene oligomerization

Co-reporter:Bing Liu, Suyun Jie, Zhiyang Bu and Bo-Geng Li

RSC Advances 2014 vol. 4(Issue 107) pp:62343-62346

Publication Date(Web):13 Nov 2014

DOI:10.1039/C4RA10605A

A series of mixed-linker metal–organic frameworks (Zn4O(BDC)x(ABDC)3−x) has been synthesized, and then transformed into nickel catalysts for ethylene oligomerization through quantitative postsynthetic modification. These complexes were more manageable, more stable, and more economic than analogues of IRMOF-3 (x = 0) by post-modification.

Well-defined PE-b-PDMS diblock copolymers via the combination of thiol-ene click and esterification reactions: Facile synthesis and compatibilization for HDPE/silicone oil blends

Co-reporter:Zhixian Xu;Bo-Geng Li

Journal of Polymer Science Part A: Polymer Chemistry 2014 Volume 52( Issue 22) pp:3205-3212

Publication Date(Web):

DOI:10.1002/pola.27381

ABSTRACT

Well-defined diblock copolymers of linear polyethylene (PE) and poly(dimethylsiloxane) (PDMS) have been synthesized through a facile route combining the thiol-ene click chemistry of vinyl-terminated polyethylene (PE-ene) and the sequential esterification reaction. The resulting diblock copolymers are characterized by ¹H NMR, FT-IR, DSC, TGA, and TEM. In addition, the PE-b-PDMS diblock copolymers have been evaluated as compatibilizers in the blends of high-density polyethylene (HDPE) and silicone oil. The morphological analysis and mechanical properties demonstrate that the compatibilized blends with low loading concentration of PE-b-PDMS display significant improvements in modulus of elasticity and elongation at break as compared to the uncompatibilized binary blends. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 3205–3212

A MOF-supported chromium catalyst for ethylene polymerization through post-synthetic modification

Co-reporter:Bing Liu, Suyun Jie, Zhiyang Bu, Bo-Geng Li

Journal of Molecular Catalysis A: Chemical 2014 Volume 387() pp:63-68

Publication Date(Web):June 2014

DOI:10.1016/j.molcata.2014.02.028

•A MOF-supported Cr(III) catalyst was prepared by postsynthetic modification.•The Cr(III) catalyst was active for ethylene polymerization.•Ethylene polymerization was largely influenced by diffusion.Isoreticular metal-organic framework-3 (IRMOF-3) has been post-synthetically modified to generate a Cr(III)-based heterogeneous catalyst (IRMOF-3-SI-Cr) for ethylene polymerization, which has been characterized by a variety of physical methods. The XRD analysis indicated that the structure integrity of the final solid was preserved after the functionalization with the imine and the subsequent coordination to chromium. The BET surface area of the final solid was slightly reduced as determined by N2 adsorption–desorption experiments. The material exhibited a unique behavior for ethylene polymerization upon activation with various alkylaluminium co-catalysts, and the polyethylenes formed featured high molecular weights and broad molecular weight distributions.

Polymerization of 1,3-butadiene catalyzed by ion-pair cobalt complexes with (benzimidazolyl)pyridine alcohol ligands

Co-reporter:Pengfei Ai, Lin Chen, Suyun Jie, Bo-Geng Li

Journal of Molecular Catalysis A: Chemical 2013 380() pp: 1-9

Publication Date(Web):

DOI:10.1016/j.molcata.2013.09.007

Stereospecific polymerization of 1,3-butadiene catalyzed by cobalt complexes bearing N-containing diphosphine PNP ligands

Co-reporter:Lin Chen, Pengfei Ai, Jianming Gu, Suyun Jie, Bo-Geng Li

Journal of Organometallic Chemistry 2012 716() pp: 55-61

Publication Date(Web):

DOI:10.1016/j.jorganchem.2012.05.051

Polymerization of 1,3-butadiene catalyzed by cobalt(II) and nickel(II) complexes bearing imino- or amino-pyridyl alcohol ligands in combination with ethylaluminum sesquichloride

Co-reporter:Pengfei Ai, Lin Chen, Yintian Guo, Suyun Jie, Bo-Geng Li

Journal of Organometallic Chemistry 2012 705() pp: 51-58

Publication Date(Web):

DOI:10.1016/j.jorganchem.2012.01.013

Mono- and di-nuclear nickel(II) complexes bearing 3-aryliminomethyl-2-hydroxybenzaldehydes: Synthesis, structures and vinyl polymerization of norbornene

Co-reporter:Yintian Guo, Pengfei Ai, Lingqin Han, Lin Chen, Bo-Geng Li, Suyun Jie

Journal of Organometallic Chemistry 2012 716() pp: 222-229

Publication Date(Web):

DOI:10.1016/j.jorganchem.2012.06.024

Highly active and stereospecific polymerization of 1,3-butadiene catalyzed by dinuclear cobalt(II) complexes bearing 3-aryliminomethyl-2-hydroxybenzaldehydes

Co-reporter:Suyun Jie, Pengfei Ai and Bo-Geng Li

Dalton Transactions 2011 vol. 40(Issue 41) pp:10975-10982

Publication Date(Web):14 Sep 2011

DOI:10.1039/C1DT11073J

A series of cobalt(II) complexes bearing 3-aryliminomethyl-2-hydroxybenzaldehydes (tridentate [NOO] ligands) was prepared and characterized by FT-IR and elemental analysis along with single-crystal X-ray diffraction. The X-ray diffraction analysis revealed that a dinuclear centrosymmetrical structure formed, in which each cobalt atom is surrounded by two bridged ligands and two acetate groups as a distorted octahedron. These dinuclear cobalt complexes displayed high catalytic activities for the polymerization of 1,3-butdiene on activation with organoaluminum cocatalysts to yield cis-1,4-polybutadiene with high selectivity. Ethylaluminum sesquichloride (EASC) was found to be the most efficient cocatalyst resulting in high conversion of butadiene and cis-1,4 content in the polymers with moderate molecular weight. The high catalytic activity and stereoselectivity could be achieved in a wide range of reaction conditions. All the dinuclear cobalt complexes (C1–C6) yielded predominantly cis-1,4-polybutadienes (> 96%) with negligible amounts of trans-1,4 (< 2.4%) and 1,2-vinyl (< 1.5%) products under the Al/Co molar ratio of 80 at 25 °C. The ligand modification by varying the substituents at the 4-position of phenol and on the imino-N aryl ring showed slight influence on the catalytic activity and microstructure of the resulting polymers.

Nickel and cationic palladium complexes bearing (imino)pyridyl alcohol ligands: Synthesis, characterization and vinyl polymerization of norbornene

Co-reporter:Suyun Jie, Pengfei Ai, Qimeng Zhou, Bo-Geng Li

Journal of Organometallic Chemistry 2011 696(7) pp: 1465-1473

Publication Date(Web):

DOI:10.1016/j.jorganchem.2011.01.024

Highly active and stereospecific polymerization of 1,3-butadiene catalyzed by dinuclear cobalt(II) complexes bearing 3-aryliminomethyl-2-hydroxybenzaldehydes

Co-reporter:Suyun Jie, Pengfei Ai and Bo-Geng Li

Dalton Transactions 2011 - vol. 40(Issue 41) pp:NaN10982-10982

Publication Date(Web):2011/09/14

DOI:10.1039/C1DT11073J

A series of cobalt(II) complexes bearing 3-aryliminomethyl-2-hydroxybenzaldehydes (tridentate [NOO] ligands) was prepared and characterized by FT-IR and elemental analysis along with single-crystal X-ray diffraction. The X-ray diffraction analysis revealed that a dinuclear centrosymmetrical structure formed, in which each cobalt atom is surrounded by two bridged ligands and two acetate groups as a distorted octahedron. These dinuclear cobalt complexes displayed high catalytic activities for the polymerization of 1,3-butdiene on activation with organoaluminum cocatalysts to yield cis-1,4-polybutadiene with high selectivity. Ethylaluminum sesquichloride (EASC) was found to be the most efficient cocatalyst resulting in high conversion of butadiene and cis-1,4 content in the polymers with moderate molecular weight. The high catalytic activity and stereoselectivity could be achieved in a wide range of reaction conditions. All the dinuclear cobalt complexes (C1–C6) yielded predominantly cis-1,4-polybutadienes (> 96%) with negligible amounts of trans-1,4 (< 2.4%) and 1,2-vinyl (< 1.5%) products under the Al/Co molar ratio of 80 at 25 °C. The ligand modification by varying the substituents at the 4-position of phenol and on the imino-N aryl ring showed slight influence on the catalytic activity and microstructure of the resulting polymers.

Solvent effect on cis-1,4-specific polymerization of 1,3-butadiene with CoCl2(PRPh2)2–EASC catalytic systems

Co-reporter:Qinzhuo Zhou, Bo-Geng Li, Suyun Jie and Na Zheng

Catalysis Science & Technology (2011-Present) 2014 - vol. 4(Issue 3) pp:NaN779-779

Publication Date(Web):2013/12/17

DOI:10.1039/C3CY00634D

A series of phosphine-containing cobalt complexes [CoCl2(PRPh2)2, R = Ph (1), Cy (2), nPr (3), Et (4), Me (5), H (6)] has been used for the highly active and stereospecific polymerization of 1,3-butadiene upon activation with ethylaluminum sesquichloride (EASC). The high catalytic activities and polybutadienes with high cis-1,4 selectivity were obtained in the solution polymerization in toluene. The conversion of butadiene and the microstructure and molecular weight of the resulting polymers were affected by reaction parameters and the R group on the phosphine ligand. The dispersion medium was also a sensitive factor for the current catalytic systems, influencing the catalytic activity and properties of products. In comparison with the solution polymerization in toluene, the heterogeneous polymerization in isooctane yielded slightly lower catalytic activity, cis-1,4 content and molecular weight under similar reaction conditions.

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