XiaoLi Zhan

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Name: 詹晓力; XiaoLi Zhan
Organization: Zhejiang University
Department: Department of Chemical and Biological Engineering
Title: Professor
Co-reporter:Qinghua Zhang, Biyu Jin, Bing Wang, Yuchen Fu, Xiaoli Zhan, and Fengqiu Chen
Industrial & Engineering Chemistry Research March 15, 2017 Volume 56(Issue 10) pp:2754-2754
Publication Date(Web):February 21, 2017
DOI:10.1021/acs.iecr.6b04650
The stable superhydrophobic aluminum alloy surface with dual geometric architectures was prepared by a combination of simple processes of chemical etching, dip-coating, and modification of fluorosilicone. The Al surface with 20 min of acid etching and nanosilica dip-coating has the best superhydrophobicity, which showed water contact angles (WCAs) of >157° and water sliding angles (SAs) of <1°. The superhydrophobic surface showed excellent antifogging, antifrosting, and delayed icing performances, compared to hydrophobic and hydrophilic Al surfaces. Furthermore, the superhydrophobicity of as-prepared surfaces is mechanically durable after 11 tape tests and 120 cm wear (under a pressure of 0.8 kPa). The strong interfacial interactions among the SiO2 nanoparticles, fluorosilicone-modified polyester resin, and the Al surface contributed to superior abrasion resistance. This method could provide a facile, low-cost, and stable route to fabricate a large-area superhydrophobic Al surface for application in various harsh environments.
Co-reporter:Cunqian Wei, Yongqiang Tang, Guangfa Zhang, Qinghua Zhang, Xiaoli Zhan and Fengqiu Chen  
RSC Advances 2016 vol. 6(Issue 78) pp:74340-74348
Publication Date(Web):29 Jul 2016
DOI:10.1039/C6RA13367C
Liquid repellent surfaces are being promisingly applied in industry and our daily lives. Herein we report a facile and effective sol–gel method for fabricating hybrid coatings with highly omniphobic and self-cleaning properties. The fluorinated hybrid nanocomposite was synthesized via one-step hydrolytic condensation of a nanosilica sol, methyltriethoxysilane (MTES) and 3-[(perfluorohexyl sulfonyl) amino] propyltriethoxysilane (HFTES). The solvent mixture of water and 2-propanol surrounding the hydrophobic nanosilica is a key factor in the control of nanoparticle aggregation, which leads to the formation of a multi-scale roughness surface with different wettabilities. The fluorinated nano-sol can be easily coated on various hard and soft substrates by spraying or dipping methods, endowing the substrate with omniphobicity to different organic liquids and biofoulings especially solidified egg white. Furthermore, the designed coating shows excellent self-cleaning and anti-adhesion properties in various harsh environments such as high temperature, acid and alkaline treatment and oil contamination. Owing to the facile method and its remarkable omniphobic abilities, the fluorinated hybrid coatings can be expected to have potential industry applications in a material system requiring robust antifouling, protein resistance and self-cleaning functions.
Co-reporter:Qinghua Zhang, Hailong Liu, Xiaoli Zhan, Fengqiu Chen, Jie Yan and Hao Tang  
RSC Advances 2015 vol. 5(Issue 95) pp:77508-77517
Publication Date(Web):04 Sep 2015
DOI:10.1039/C5RA12945A
Multifunctional polyurethane based on polysiloxane tethered cationic biocides was designed for fouling resistance and antibacterial objectives. Quaternary ammonium salt (QAS) functionalized hydroxy-terminated polysiloxanes (PQMS) with different compositions were synthesized by hydrolytic polycondensation and subsequent quaternization. Then, a series of antibacterial polyurethane copolymers (PQMS–PU) with PQMS and PPG as soft segments were prepared by two-step condensation methods. GPC, FTIR and 1H-NMR were employed to analyze the chemical structural and composition. The surface migrations of polysiloxane segment tethered QAS groups and the distribution of N+ on the surface were quantitatively characterized by XPS. The microphase morphology and wettability properties of the copolymer films were investigated by AFM, TEM and dynamic contact angle tests. The migration of the biocide groups to the surface caused by the microphase separation between polysiloxane soft segments and hard segments was determined. The quantitative relationships of the polysiloxane segments and QAS group distribution on the surface with the wettability and antibacterial activity of the copolymer films were demonstrated. Within the designed range, the obtained copolymers exhibited very low surface free energy and excellent antibacterial activity towards Escherichia coli, which was of great environmental friendliness and industrial interest for textile and marine coating application.
Co-reporter:Qinghua Zhang;Hailong Liu;Xi Chen;Fengqiu Chen
Journal of Applied Polymer Science 2015 Volume 132( Issue 14) pp:
Publication Date(Web):
DOI:10.1002/app.41725

ABSTRACT

To obtain a copolymer network with low surface energy and antibacterial properties, a series of hydroxyl-terminated poly(dimethyl siloxane)s (PDMSs) modified by a quaternary ammonium salt (QAS) side chain was synthesized via hydrolytic polycondensation and quaternization. The structures of the intermediate and final products were confirmed by Fourier transform infrared spectroscopy, 1H-NMR, and gel permeation chromatography. The results show that each step was successfully carried out, and objective products were obtained. The modified PDMSs were crosslinked with a commercial polyisocyanate to obtain cured QAS-modified PDMS coatings. The target functional coatings exhibited excellent antibacterial performance with a low surface energy. When the molar content of QAS in PDMS was varied from 10 to 30%, the critical surface energy of the coatings remained in the range 24.05–26.88 mN/m; this indicated that the coatings had minimal adhesion with fouling according to the Baier curve. The bactericidal tests showed that the antibacterial activity was independent of the PDMS molecular weight but was closely correlated with the QAS content in PDMS. The bactericidal rate of the coatings to Escherichia coli and Staphylococcus aureus was higher than 97% when the molar content of QAS in PDMS was above 20%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41725.

Co-reporter:Qinghua Zhang, Qiongyan Wang, Jingxian Jiang, Xiaoli Zhan, and Fengqiu Chen
Langmuir 2015 Volume 31(Issue 16) pp:4752-4760
Publication Date(Web):April 7, 2015
DOI:10.1021/la504467m
Novel fluorinated copolymers of stearyl acrylate (SA) and (perfluorohexyl)ethyl acrylate (C6A), (perfluorohexyl)ethyl methacrylate (C6MA), 2-[[[[2-(perfluorohexyl)]-sulfonyl]methyl] amino]ethyl acrylate (C6SA), and methacrylate (C6SMA) were synthesized via miniemulsion copolymerization. The extremely hydrophobic monomers perfluoroalkyl acrylate (FA) and SA acted as the reactive costabilizer in the miniemulsion system. The microstructure and surface wetting properties of the copolymers were characterized by 1H NMR, FT-IR, and dynamic contact angle test. The crystallization behaviors and fine surface structures of the copolymer films were determined by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) analysis. The self-assembled aggregation and roughness of the copolymer films were investigated by atomic force microscopy (AFM). The results showed that the fluorinated side chains interrupted and impeded the crystallizable side chains of SA from forming complete crystals. And the Tm and ΔHf of the copolymers were decreased as a consequence of this effect. The fluorinated side chains in P(C6A/SA) and P(C6MA/SA) arranged between the crystallizable hydrocarbon side chains of SA, while the crystallization structure of fluorinated and nonfluorinated pendant groups existed all at once in copolymers P(C6SA/SA) and P(C6SMA/SA). The four copolymers exhibited very low surface free energy and excellent dynamic water repellency attributed to the restriction of perfluoroalkyl groups combined with crystallization of stearyl pendant groups.
Co-reporter:Qinghua Zhang, Qiongyan Wang, Xiaoli Zhan, and Fengqiu Chen
Industrial & Engineering Chemistry Research 2014 Volume 53(Issue 19) pp:8026
Publication Date(Web):April 14, 2014
DOI:10.1021/ie404217d
Developing novel fluorinated monomers and polymer materials with a short perfluoroalkyl group is attracting the attention of researchers. The synthesis of fluorinated monomers, [N-methyl-perfluorobutane-1-sulfonamide]ethyl acrylate (C4SA) and methacrylate (C4SMA), [N-methyl-perfluorohexane-1-sulfonamide]ethyl acrylate (C6SA), and methacrylate (C6SMA) were presented from a three-step procedure, which combined the reaction of perfluorobutanesulfonyl fluoride or perfluorohexanesulfonyl fluoride with an excess of methylamine, alkylation reaction with 2-bromoethanol, and esterification reaction with acryloyl chloride or methacryloyl chloride. The outcome compounds structures of each step were confirmed by 1H NMR, 19F NMR, FT-IR, and elemental analysis. Free radical copolymerizations of fluorinated acrylates and butyl methacrylate (BMA) in butyl acetate (BuOAc) were performed to determine the comonomers reactivity ratios and Q-e values. The surface wetting properties of fluorinated homopolymers were investigated by surface tension and dynamic contact angles. As a result, the target polymers showed extreme low surface energies and dynamic surface properties.
Co-reporter:Qinghua Zhang, Ying Shi, Xiaoli Zhan, Fengqiu Chen
Colloids and Surfaces A: Physicochemical and Engineering Aspects 2012 Volume 393() pp:17-26
Publication Date(Web):5 January 2012
DOI:10.1016/j.colsurfa.2011.10.016
Isocyanates hydrolysis, an important side reaction in direct synthesis of waterborne polyurethanes by miniemulsion polymerization has been studied experimentally and theoretically in the paper. A kinetic model has been developed considering the resistances due to the diffusion through the formed polymer and interfacial reaction in monomer miniemulsion. This model studied the hydrolysis process quantitatively by reaction degree as a function of time in terms of the reaction rate-controlling step. Both experimental results and reported data from literatures fit the kinetic model well. It has been found that the hydrolysis of aromatic isocyanate with high reactivity is a diffusion controlled fast reaction process, while the hydrolysis of aliphatic isocyanate with moderate reactivity is a reaction-controlled process. The hydrolysis of aliphatic isocyanate at different temperatures has also been studied and it was also found a reaction-controlled process.Graphical abstract. The hydrolysis of isocyanate is an important side reaction during the direct synthesis of waterborne polyurethanes (PUs) by miniemulsion polymerization. The hydrolysis mechanisms and the interplay of the physical diffusion and the chemical rate process were investigated. A kinetic model has been developed considering the resistances due to the diffusion through the formed polymer and interfacial reaction in monomer miniemulsion. It has been found that the hydrolysis of aromatic isocyanate with high reactivity is a diffusion controlled fast reaction process, while the hydrolysis of aliphatic isocyanate with moderate reactivity is a reaction-controlled process.Highlights► Synthesis of waterborne polyurethanes by in situ miniemulsion polymerization. ► Interfacial hydrolysis of isocyanate in synthesis of waterborne polyurethanes. ► Kinetic model of the interfacial reaction describes the hydrolysis process. ► Hydrolysis of IPDI over a range of temperature is controlled by reaction.
Co-reporter:Yitao Yu;Qinghua Zhang ;Fengqiu Chen
Polymer Engineering & Science 2011 Volume 51( Issue 6) pp:1041-1050
Publication Date(Web):
DOI:10.1002/pen.21921

Abstract

We have conducted reversible addition-fragmentation chain transfer (RAFT) polymerizations of styrene (St) and maleic anhydride (MAh) and n-butyl acrylate (BA) to produce a well-defined triblock copolymer having alternating structure, P(St-alt-MAh)-b-PSt-b-PBA, via bulk, miniemulsion and seed miniemulsion polymerizations. The polymerization kinetics and living characters were investigated. The results followed by gel permeation chromatography (GPC) showed that bulk and miniemulsion polymerizations exhibited controlled nature such as narrow polydispersity index (PDI), controlled molecular weight, and first-order polymerization kinetics, whereas triblock copolymer owned a rather wider PDI. Comparison of GPC RI and UV traces revealed that alternating copolymer and diblock copolymer have a very high percentage of living chains. For seed miniemulsion polymerization, when the molecular weight of triblock copolymer is more than 36,000 g/mol, the formation of homopolymer of BA resulted in broadening of PDI. 1H NMR method was used to identify the compositions of block copolymers. Differential scanning calorimetry analysis showed that the copolymers exhibited distinct glass temperatures. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers

Co-reporter:Zhen Xi Wang, Qing Hua Zhang, Yi Tao Yu, Xiao Li Zhan, Feng Qiu Chen, Ji Hai Xiong
Chinese Chemical Letters 2010 Volume 21(Issue 12) pp:1497-1500
Publication Date(Web):December 2010
DOI:10.1016/j.cclet.2010.06.001
Polystyrene–styrene/butadiene diblock copolymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) miniemulsion polymerization. During the polymerization process, the molecular weight distribution was narrow and the numerical molecular weight of the copolymers increased with increasing conversion of monomers, which was close to the theoretical. FT-IR and 1H NMR results indicated that the microstructure of the polymer was mainly 1,4-trans-butadiene with small amount of 1,2-units, and composition in the copolymers was obtained.
Co-reporter:Qinghua Zhang;Zhongbing Yang;Fengqiu Chen
Journal of Applied Polymer Science 2009 Volume 113( Issue 1) pp:207-215
Publication Date(Web):
DOI:10.1002/app.29631

Abstract

Hollow polymer latex particles containing a hydrophilic core were prepared by seeded emulsion polymerization with MAA/BA/MMA/St as comonomers, followed by stepwise alkalization treatment with ammonia. The size and morphology of composite latex particles was determined by TEM. The effects of the seeded emulsion polymerization conditions and alkalization treatment on the size and hollow structure of latex were investigated. The results showed that the optimum content of crosslinking agent in the shell polymers was about 0.5–1.0 wt %, emulsifier was about 0.8–1.1 wt %, and the core/shell weight ratio was 1/7. To obtain uniform hollow latex particles with large size, the starved feeding technique should be adopted in seeded emulsion polymerization, and the neutralization temperature should equal to the Tg of the shell polymer. Then, the obtained polymer particles under this condition had an excellent hollow structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Co-reporter:Qing Hua Zhang, Zhen Huan Luo, Xiao Li Zhan, Feng Qiu Chen
Chinese Chemical Letters 2009 Volume 20(Issue 4) pp:478-482
Publication Date(Web):April 2009
DOI:10.1016/j.cclet.2008.12.041
Miniemulsion copolymerization of butyl mathacrylate (BMA) with fluoroacrylate (HFMA, TFMA) was carried out at 70 °C by employing potassium persulphate (KPS) as initiator. Copolymer compositions at low conversion levels were determined by 1H NMR spectra techniques. The reactivity ratios were evaluated by employing Kellen–Tudos (K–T) methods, which yields the apparent reactivity ratios, rBMA = 0.74, rHFMA = 0.87 and rBMA = 0.73, rTFMA = 0.75, respectively, and Q- and e-values of HFMA and TFMA were calculated by the Alfrey–Price method. The results show that HFMA and TFMA are more active than BMA, and the cross-propagation rate constant is greater than the self-propagation one in these two copolymerizations.
Co-reporter:Qinghua Zhang;Qiongyan Wang;Zhenhuan Luo;Fengqiu Chen
Polymer Engineering & Science 2009 Volume 49( Issue 9) pp:1818-1824
Publication Date(Web):
DOI:10.1002/pen.21419

Abstract

Reversible addition fragmentation chain transfer (RAFT) mediated and conventional miniemulsion copolymerizations of butyl methacrylate (BMA) with fluoromethacrylate (FMA) were carried out at 70°C with potassium persulphate as initiator. The kinetics of the copolymerizations was investigated comparatively. Copolymer compositions at low conversion levels were determined by 1H NMR and FTIR spectra techniques. In the presence of RAFT agent 2-cyanoprop-2-yl dithiobenzoate, the copolymerization of BMA with FMA in miniemulsion was obviously retarded. The copolymerization exhibited typical features of controlled molecular weights and narrow polydispersities. The reactivity ratios were evaluated by Kellen-Tudos (K-T) method, which yields the apparent reactivity ratios: rBMA = 0.73 and rFMA = 0.75 in conventional copolymerizations, and rBMA = 0.65 and rFMA = 0.70 in CPDB-mediated system. The results show that the monomer FMA with a perfluoroalkyl side chain is slightly more reactive than BMA, and the copolymerizations process have a tendency to crosspropagate and to produce a higher FMA content in the copolymers. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers

Co-reporter:Ying Shi;Zhenhuan Luo;Qinghua Zhang ;Fengqiu Chen
Journal of Polymer Science Part A: Polymer Chemistry 2008 Volume 46( Issue 7) pp:2433-2444
Publication Date(Web):
DOI:10.1002/pola.22577

Abstract

The purpose of this study is to propose a correlation between IR spectra and the urea fraction of waterborne polyurethanes (PUs) to investigate the side reaction, that is, isocyanate–water reaction, during polymerization. This method is based on the decomposition of the spectrum in amide I range, that is, 1600–1800 cm−1, where the bands of interest overlap. Several individual bands present in this region were resolved by employing Fourier self-deconvolution (FSD) and Gaussian curve-fitting techniques, and the intensity ratio of urethane's CO to urea's CO was determined. To realize some quantitative measurements, a calibration curve was established with some polyurethane-urea samples, characterized by 1H NMR, which were used as standards. The concentration ratios of urethane groups to urea groups were determined from 1H NMR. A good correlation was evidenced between IR and 1H NMR measurements. Moreover, waterborne PUs were prepared by miniemulsion polymerization of IPDI with diols. From quantitative IR analysis, it was shown that a vinylic monomer, as a solvent of polyaddition, restrained the isocyanate–water reaction, and this side reaction was influenced by the hydrophilicity of the vinylic monomers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2433–2444, 2008

Co-reporter:Qinghua Zhang;Fengqiu Chen
Journal of Applied Polymer Science 2007 Volume 104(Issue 1) pp:
Publication Date(Web):25 JAN 2007
DOI:10.1002/app.25639

A stable fluoroacrylate copolymer emulsion was successfully prepared by miniemulsion polymerization with fluoroacrylate, lauryl methylacrylate, and methyl methacrylate as monomers. Extremely hydrophobic fluoroacrylate, instead of conventional cosurfactants, was used as a reactive cosurfactant to stabilize the miniemulsions. The results indicated that fluoroacrylate retarded Ostwald ripening and allowed the production of stable miniemulsions. The chemical compositions of the copolymer were studied with Fourier transform infrared and 1H-NMR. The average composition of the copolymers prepared with miniemulsions was in good agreement with the feed ratio according to 1H-NMR from the integration ratios corresponding to typical protons of the individual monomers. The particle size distribution and morphology of the latex particles were determined with laser particle analysis and transmission electron microscopy. The particle size of the latex underwent no change in the process of miniemulsion polymerization, but the particle size distributions were broader than those of conventional emulsion polymerization. The effects of various reaction parameters, including the temperature and concentrations of the emulsifier and initiator, on the miniemulsion polymerization were also investigated, and the polymerization rate and conversion increased with increasing concentrations of nonylphenol polyethoxylate (with an average of 40 ethylene oxide units per molecule), cetyltrimethylammonium, and 2,2′-azobisisobutyronitrile. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 641–647, 2007

Co-reporter:Zhang Qinghua;Zhan Xiaoli;Chen Fengqiu;Shi Ying;Wang Qiongyan
Journal of Polymer Science Part A: Polymer Chemistry 2007 Volume 45(Issue 9) pp:1585-1594
Publication Date(Web):9 MAR 2007
DOI:10.1002/pola.21930

Reversible addition-fragmentation chain transfer (RAFT) miniemulsion polymerization of butyl methacrylate (BMA) and dodecafluoroheptyl methacrylate (DFMA) was carried out with 2-cyanoprop-2-yl dithiobenzoate (CPDB) as chain transfer agent (CTA). Concentration effects of RAFT agent and initiator on kinetics and molecular weight were investigated. No obvious red oil layer (phase's separation) and coagulation was observed in the first stage of homopolymerization of BMA. The polymer molecular weights increased linearly with the monomer conversion with polydispersities lower than 1.2. At 75 °C, the monomer conversion could achieve above 96% in 3 h with [momomer]:[RAFT]:[KPS] = 620:4:1 (mole ratio). The results showed excellent controlled/living polymerization characteristics and a very fast polymerization rate. Furthermore, the synthesis of poly(BMA-b-DFMA) diblock copolymers with a regular structure (PDI < 1.30, PMMA calibration) was performed by adding the monomer of DFMA at the end of the RAFT miniemulsion polymerization of BMA. The success of diblock copolymerization was showed by the molecular weight curves shifting toward higher molar mass, recorded by gel permeation chromatography before and after block copolymerization. Compositions of block copolymers were further confirmed by 1H NMR, FTIR, and DSC analysis. The copolymers exhibited a phase-separated morphology and possessed distinct glass transition temperatures associated with fluoropolymer PDFMA and PBMA domains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1585–1594, 2007

Co-reporter:Xiaoli Zhan;Fengqiu Chen;Feng Du;Lingmin Yi;Linbing Huang
Journal of Polymer Science Part A: Polymer Chemistry 2005 Volume 43(Issue 19) pp:4431-4438
Publication Date(Web):12 AUG 2005
DOI:10.1002/pola.20927

A series of narrow molecular weight distribution (MWD) polystyrene-b-poly[methyl(3,3,3-trifluoropropyl)siloxane] (PS-b-PMTFPS) diblock copolymers were synthesized by the sequential anionic polymerization of styrene and trans-1,3,5-trimethyl-1,3,5-tris(3′,3′,3′-trifluoropropyl)cyclotrisiloxane in tetrahydrofuran (THF) with n-butyllithium as the initiator. The diblock copolymers had narrow MWDs ranging from 1.06 to 1.20 and number-average molecular weights ranging from 8.2 × 103 to 37.1 × 103. To investigate the properties of the copolymers, diblock copolymers with different weight fractions of poly[methyl(3,3,3-trifluoropropyl)siloxane] (15.4–78.8 wt %) were prepared. The compositions of the diblock copolymers were calculated from the characteristic proton integrals of 1H NMR spectra. For the anionic ring-opening polymerization (ROP) of 1,3,5-trimethyl-1,3,5-tris(3′,3′,3′-trifluoropropyl)cyclotrisiloxane (F3) initiated by polystyryllithium, high monomer concentrations could give high polymer yields and good control of MWDs when THF was used as the polymerization solvent. It was speculated that good control of the block copolymerization under the condition of high monomer concentrations was due to the slowdown of the anionic ROP rate of F3 and the steric hindrance of the polystyrene precursors. There was enough time to terminate the ROP of F3 when the polymer yield was high, and good control of block copolymerization could be achieved thereafter. The thermal properties (differential scanning calorimetry and thermogravimetric analysis) were also investigated for the PS-b-PMTFPS diblock copolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4431–4438, 2005

1-Dodecanaminium,N,N-dimethyl-N-[2-[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]-, bromide
2-Propenoic acid, 2-methyl-, hexafluorobutyl ester
tridecafluoro-N-(2-hydroxyethyl)-N-methylhexanesulphonamide
tridecafluoro-N-methylhexanesulphonamide
1-Hexanesulfonylfluoride
Mordenite
Nitric acid, cerium(3+)salt (3:1)
Benzene, (1-propylnonyl)-
Benzene,(1-butyloctyl)-
Benzene,(1-pentylheptyl)-