水滑石类功能材料的特性分析及其阻燃应用

摘要/Abstract

摘要： 水滑石类化合物(LDHs)是一类具有特殊结构与功能的新型层状材料。介绍了LDHs的化学组成、结构和性质,对典型LDHs(Mg₆Al₂(OH)₁₆CO₃·4H₂O)热分解行为和阻燃机理进行了分析。最后从主体层板调控、功能性客体插层、协同效应三个方面对LDHs在阻燃领域的应用进行了综述。

关键词: 水滑石类化合物, 化学组成, 结构, 性质, 阻燃机理, 阻燃应用

Abstract: Hydrotalcite-like compounds,also known as layered double hydroxides (LDHs),are a new type of layered materials with special structure and function. Chemical composition, structure and properties of LDHs were introduced, and the thermal decomposition behavior and flame retardant mechanism of typical LDHs (Mg₆Al₂(OH)₁₆CO₃·4H₂O) were analyzed. Finally, the application of LDHs in the field of flame retardant was reviewed from the three aspects of main layer regulation, functional guest intercalation, and synergistic effects.

Key words: LDHs, chemical component, structure, property, flame retardant mechanism, flame retardant application

中图分类号:

邹瑜. 水滑石类功能材料的特性分析及其阻燃应用[J]. 硅酸盐通报, 2020, 39(12): 4034-4042.

ZOU Yu. Characteristic Analysis of Layered Double Hydroxides Functional Materials and Its Flame Retardant Application[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2020, 39(12): 4034-4042.

参考文献

[1] Cavani F, Trifirò F, Vaccari A. Hydrotalcite-type anionic clays: preparation, properties and applications[J]. Catalysis today, 1991, 11(2): 173-301.
[2] Feitknecht W, Gerber M. Zur Kenntnis der Doppelhydroxyde und basischen Doppelsalze II. Űber Mischfällungen aus Calcium-Aluminiumsalzlösungen[J]. Helvetica Chimica Acta, 1942, 25(1): 106-131.
[3] Allmann R, Jepsen H P. Die struktur des hydrotalkits[J]. Neues Jahrbuch fur Mineralogie Monatshefte, 1969, 12: 544-551.
[4] Kovanda F, Jindová E, Lang K, et al. Preparation of layered double hydroxides intercalated with organic anions and their application in LDH/poly(butyl methacrylate) nanocomposites[J]. Applied Clay Science, 2010, 48(1-2): 260-270.
[5] Evans D G, Xue D A. Preparation of layered double hydroxides and their applications as additives in polymers, as precursors to magnetic materials and in biology and medicine[J]. Chemical Communications, 2006, 37(5): 485-496.
[6] Rives V. Layered double hydroxides: present and future[M]. New York: Nova Science, 2001.
[7] Dubey A, Rives V, Kannan S. Catalytic hydroxylation of phenol over ternary hydrotalcites containing Cu, Ni and Al[J]. Journal of Molecular Catalysis A: Chemical, 2002, 181(1): 151-160.
[8] Rives V, Prieto O, Dubey A, et al. Synergistic effect in the hydroxylation of phenol over CoNiAl ternary hydrotalcites[J]. Journal of Catalysis, 2003, 220(1): 161-171.
[9] Auer S M, Gredig S V, Koppel R A, et al. Synthesis of methylamines from CO₂, H₂ and NH₃ over Cu-Mg-Al mixed oxides[J]. Journal of Molecular Catalysis A: Chemical, 1999, 141(1-3): 193-203.
[10] Velu S, Ramaswamy V, Ramani A, et al. New hydrotalcite-like anionic clays containing Zr in the layers[J]. Chem Inform, 1998, 29(7): 2107-2108.
[11] Velu S, Suzuki K, Osaki T, et al. Synthesis of new Sn incorporated layered double hydroxides and their evolution to mixed oxides[J]. Materials Research Bulletin, 1999, 34(10): 1707-1717.
[12] Carrado K A, Kostapapas A, Suib S L. Layered double hydroxides (LDHs)[J]. Solid State Ionics, 1988, 26(2): 77-86.
[13] Leroux F, Besse J P. Polymer interleaved layered double hydroxide: a new emerging class of nanocomposites[J]. Chemistry of Materials, 2001, 13(10): 3507-3515.
[14] Roland S C, Besse J P, Leroux F. Polymerization of sulfopropyl methacrylate, a surface active monomer, within layered double hydroxide[J]. Chemistry of Materials, 2004, 16(25): 5512-5517.
[15] Choy J H, Kwak S Y, Park J S, et al. Cellular uptake behavior of [γ-32P] labeled ATP-LDH nanohybrids[J]. Journal of Materials Chemistry, 2001, 11(6): 1671-1674.
[16] Choy J H, Park J S, Kwak S Y, et al. Layered double hydroxide as gene reservoir[J]. Molecular Crystals & Liquid Crystals, 2000, 341: 425-429.
[17] Evans D G, Slade R C T. Structural aspects of layered double hydroxides[M]. Springer Berlin Heidelberg, 2005.
[18] Gastuche M C. Mixed magnesium-aluminium hydroxides[J]. Clay Minerals, 1967, 7(2): 177-192.
[19] Wu J S, Xiao Y K, Wan J Y, et al. The growth mechanism of hydrotalcite crystal[J]. Science China Technological Sciences, 2012, 55(4): 872-878.
[20] Naghash A, Etsell T H, Lu B. Mechanisms involved in the formation and growth of Al-Cu-Ni hydrotalcite-like precipitates using the urea hydrolysis scheme[J]. Journal of Materials Chemistry, 2008, 18(22): 2562.
[21] Gomes J F P, Puna J F B, GonÇalves L M, et al. Study on the use of MgAl hydrotalcites as solid heterogeneous catalysts for biodiesel production[J]. Energy, 2011, 36(12): 6770-6778.
[22] Lei X D, Lu W, Peng Q, et al. Activated MgAl-layered double hydroxide as solid base catalysts for the conversion of fatty acid methyl esters to monoethanolamides[J]. Applied Catalysis A: General, 2011, 399(1-2): 87-92.
[23] Huang Y Y, Chen X P, Deng Y F, et al. A novel nickel catalyst derived from layered double hydroxides (LDHs) supported on fluid catalytic cracking catalyst residue (FC3R) for rosin hydrogenation[J]. Chemical Engineering Journal, 2015, 269: 434-443.
[24] Ma W, Ma R, Wang C, et al. A Superlattice of alternately stackedNi-Fe hydroxide nanosheets and graphene for efficient splitting of water[J]. Acs Nano, 2015, 9(2): 1977-1984.
[25] Zhao Y F, He S, Wei M, et al. Hierarchical films of layered double hydroxides by using a sol-gel process and their high adaptability in water treatment[J]. Chemical Communications, 2010, 46(17): 3031-3033.
[26] Ardau C, Frau F, Lattanzi P. Antimony removal from aqueous solutions by the use of Zn-Al sulphate layered double hydroxide[J]. Water, Air, & Soil Pollution, 2016, 227(9): 1-15.
[27] Li T, Li G H, Li L H, et al. Large-scale self-assembly of 3D flower-like hierarchical Ni/Co-LDHs microspheres for high-performance flexible asymmetric supercapacitors[J]. ACS Applied Materials & Interfaces, 2016, 8(4): 2562-2572.
[28] Song Q L, Liu W, Bohn C D, et al. A high performance oxygen storage material for chemical looping processes with CO₂ capture[J]. Energy & Environmental Science, 2013, 6(1): 288-298.
[29] Li B, Wu P X, Ruan B, et al. Study on the adsorption of DNA on the layered double hydroxides (LDHs)[J]. Spectrochimica Acta Part A: Molecular & Biomolecular Spectroscopy, 2014, 121: 387-393.
[30] Liu Y, Gao Y, Wang Q, et al. The synergistic effect of layered double hydroxides with other flame retardant additives for polymer nanocomposites: a critical review[J]. Dalton Transactions, 2018, 47(42): 14827-14840.
[31] Costa F R, Saphiannikova M, Wagenknecht U, et al. Layered double hydroxide based polymer nanocomposites[M]. Springer Berlin Heidelberg, 2007.
[32] Bitinis N, Hernandez M, Verdejo R, et al. Recent advances in clay/polymer nanocomposites[J]. Advanced Materials, 2011, 23(44): 5229-5236.
[33] Liang J B, Ma R Z, Iyi N, et al. Topochemical synthesis, anion exchange, and exfoliation of Co-Ni layered double hydroxides: a route to positively charged Co-Ni hydroxide nanosheets with tunable composition[J]. Chemistry of Materials, 2010, 22(2): 371-378.
[34] Tarasov K A, Isupov V P, Chupakhina L E, et al. A time resolved, in-situ X-ray diffraction study of the de-intercalation of anions and lithium cations from [LiAl₂(OH)₆]nX·qH₂O (X = Cl^-, Br^-, NO^-₃, SO^2-₄)[J]. Journal of Materials Chemistry, 2004, 14(9): 1443-1447.
[35] Aramendía M A, Avilés Y, Borau V, et al. Thermal decomposition of Mg/Al and Mg/Ga layered-double hydroxides: a spectroscopic study[J]. Journal of Materials Chemistry, 1999, 9(7): 1603-1607.
[36] Crepaldi E L, Valim J B. Layered double hydroxides: structure, synthesis, properties and applications[J]. Química Nova, 1998, 21(3): 300-311.
[37] Das J, Patra B S, Baliarsingh N, et al. Adsorption of phosphate by layered double hydroxides in aqueous solutions[J]. Applied Clay Science, 2006, 32(3): 252-260.
[38] Zhang Z J, Lan B, Mei X J, et al. Study on fire retardant mechanism of nano-LDHs in intumescent system[J]. Science in China Series B: Chemistry, 2007, 50(3): 392-396.
[39] Valcheva-Traykova M L, Davidova N P, Weiss A H. Thermal decomposition of Mg, Al-hydrotalcite material[J]. Journal of Materials Science, 1993, 28(8): 2157-2162.
[40] Stanimirova T, Piperov N, Petrova N, et al. Thermal evolution of Mg-Al-CO₃ hydrotalcites[J]. Clay Minerals, 2004, 39(2): 177-191.
[41] Deng X, Fang Z, Zeng H, et al. Thermal decomposition mechanism and kinetics of Mg-Al hydrotalcite[J]. Chemical Reaction Engineering & Technology, 2010, 26(4): 309-314.
[42] Ren Q L, Luo Q. Preparation and thermal decomposition mechanism of Mg,Al-hydrotalcite nano-crystals with titania doping[J]. Transactions of Nonferrous Metals Society of China, 2006, 16: s402-s405.
[43] Rives V. Characterisation of layered double hydroxides and their decomposition products[J]. Materials Chemistry & Physics, 2002, 75(1): 19-25.
[44] Kissinger H E. Reaction kinetics in differential thermal analysis[J]. Analytical Chemistry, 1957, 29(11): 1702-1706.
[45] 谢鲜梅,胡秋霞,严凯,等.镁铝水滑石热分解机理函数研究[J].太原理工大学学报,2008,39(4):347-350.
[46] Wang Z, Han E, Wei K. Influence of nano-LDHs on char formation and fire-resistant properties of flame-retardant coating[J]. Progress in Organic Coatings, 2005, 53(1): 29-37.
[47] Nyambo C, Chen D, Su S P, et al. Variation of benzyl anions in MgAl-layered double hydroxides: fire and thermal properties in PMMA[J]. Polymer Degradation & Stability, 2009, 94(4): 496-505.
[48] Fan G L, Li F, Evans D G, et al. Catalytic applications of layered double hydroxides: recent advances and perspectives[J]. Chemical Society Reviews, 2014, 45(20): 7040-7066.
[49] Kaul P K, Samson A J, Selvan G T, et al. Synergistic effect of LDH in the presence of organophosphate on thermal and flammable properties of an epoxy nanocomposite[J]. Applied Clay Science, 2017, 135: 234-243.
[50] 任庆利,刘斌,陈维,等.镁铝水滑石阻燃料的研究[J].绝缘材料,2003,36(5):17-19.
[51] Wang Z Y, Han E H, Wei K. Influence of nano-LDHs on char formation and fire-resistant properties of flame-retardant coating[J]. Progress in Organic Coatings, 2005, 53(1): 29-37.
[52] Costa F R, Wagenknecht U, Heinrich G. LDPE/Mg-Al layered double hydroxide nanocomposite: thermal and flammability properties[J]. Polymer Degradation & Stability, 2007, 92(10): 1813-1823.
[53] Du B X, Ma H Y, Fang Z P. How nano-fillers affect thermal stability and flame retardancy of intumescent flame retarded polypropylene[J]. Polymers for Advanced Technologies, 2011, 22(7): 1139-1146.
[54] Gu Z J, Jiang B, Zhu P, et al. Preparation and application of Mg/Al-LDHs nano flame retardant in veneer wood-based panel[J]. Journal of Forestry Engineering, 2016, 30(4): 39-44.
[55] Zhao W, Du Y C, Sun Y B, et al. Study on preparation of layered double hydroxides (LDHs) and properties of EPDM/LDHs composites[J]. Plastics, Rubber & Composites, 2014, 43(6): 192-201.
[56] Shi L, Li D Q, Li S F, et al. Structure, flame retarding and smoke suppressing properties of Zn-Mg-Al-CO₃ layered double hydroxides[J]. Chinese Science Bulletin, 2005, 50(11): 1101-1104.
[57] Han Y Q, Wu Y, Shen M X, et al. Preparation and flame retardancy of polystyrene nanocomposites based on layered double hydroxides[J]. Polymer Composites, 2017, 38(8): 1680-1688.
[58] Jiao C M, Wang Z Z, Chen X L, et al. Synthesis of a magnesium/aluminum/iron layered double hydroxide and its flammability characteristics in halogen-free, flame-retardant ethylene/vinyl acetate copolymer composites[J]. Journal of Applied Polymer Science, 2008, 107(4): 2626-2631.
[59] Qian Y, Li S S, Chen X L. Synthesis and characterization of LDHs using Bayer red mud and its flame-retardant properties in EVA/LDHs composites[J]. Journal of Material Cycles & Waste Management, 2015, 17(4): 646-654.
[60] Wang L L, Xu J. Effect of modified CoMgAl-LDHs on flame retardance and mechanical properties of EVA[J]. Polymer Materials Science and Engineering, 2018, 34(12): 52-58.
[61] 李素峰,李殿卿,史翎,等.硼酸根插层锌镁铝水滑石的制备及其阻燃抑烟性能研究[J].阻燃材料与技术,2005,(4):11-15.
[62] Wang Q, Undrell J P, Gao Y S, et al. Synthesis of flame-retardant polypropylene/LDH-borate nanocomposites[J]. Macromolecules, 2013, 46(15): 6145-6150.
[63] Xu W Z, Xu B L, Li A J, et al. Flame retardancy and smoke suppression of MgAl layered double hydroxides containing P and Si in polyurethane elastomer[J]. Industrial & Engineering Chemistry Research, 2016, 55(42): 11175-11185.
[64] Jin X D, Gu X Y, Chen C, et al. The fire performance of polylactic acid containing a novel intumescent flame retardant and intercalated layered double hydroxides[J]. Journal of Materials Science, 2017, 52(20): 12235-12250.
[65] Zhou X, Chen H, Chen Q, et al. Synthesis and characterization of two-component acidic ion intercalated layered double hydroxide and its use as a nanoflame-retardant in ethylene vinyl acetate copolymer (EVA)[J]. Rsc Advances, 2017, 7(84): 53064-53075.
[66] Yi Q, Li S Q, Chen X L. Preparation of mesoporous silica-LDHs system and its coordinated flame-retardant effect on EVA[J]. Journal of Thermal Analysis & Calorimetry, 2017, 130(1): 2055-2067.
[67] Mo H B, Xu L P, Zhou T. Novel synergistic flame-retardant system of Mg-Al-Co-LDHs/DPCPB for ABS resins[J]. Journal of Applied Polymer Science, 2018, 135(22): 46319.
[68] Sen P, Pugazhenthi G. Synergistic effect of dual nanofillers (MWCNT and Ni-Al LDH) on the electrical and thermal characteristics of polystyrene nanocomposites[J]. Journal of Applied Polymer Science, 2018, 135(22): 46513.