Pt-H2SO4/Zr-montmorillonite: An efficient catalyst for the polymerization of octamethylcy-clotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane to low-hydro silicone oil

doi:10.1016/j.cjche.2017.04.004

Abstract

Abstract: The liquid phase ring-opening of octamethylcy-clotetrasiloxane (D₄) was investigated over Pt-H₂SO₄/Zrmontmorillonite catalyst. Montmorillonite (Mt), Zr-Mt, H₂SO₄/Mt, H₂SO₄/Zr-Mt and Pt-H₂SO₄/Zr-Mt were also detected for evaluation. The catalysts were characterized by X-ray fluorescence, X-ray diffraction, nitrogen adsorption-desorption, NH₃-TPD and pyridine-FTIR measurements. In comparison to activate clay which is used in the industry of catalyst, Zr-Mt catalyst displayed stronger acidity and more excellent catalytic activity in the polymerization of D₄, polymethylhydrosiloxane (D₄^H) and hexamethyldisiloxane (MM) to low-hydro silicone oil. Relative to Zr-Mt, the acidity of H₂SO₄/Zr-Mt was noticeably improved and the catalyst exhibited a higher capability of ring-opening of D₄ conversion and yield of low-hydro silicone oil. To enhance the stability of H₂SO₄/Zr-Mt catalyst, a small amount of metals (Pt) was doped. The nitrogen adsorption-desorption results indicated that pore textural parameters of the Pt-H₂SO₄/Zr-Mt had not changed with larger specific surface area. Compared with H₂SO₄/Zr-Mt, the total acidity of Pt-H₂SO₄-Zr/Mt catalyst retained, but the content of the Brønsted acid increased and the content of the Lewis acid decreased. The Pt-H₂SO₄-Zr/Mt catalyst displayed higher catalyst reproducibility. After 40 h reaction of polymerization, the yield of low-hydro silicone oil decreased from 93% to 42% over H₂SO₄/Zr-Mt catalyst, while the yield of low-hydro silicone oil reduced from 93% to 78% over Pt-H₂SO₄/Zr-Mt catalyst. A sharp decrease in catalytic activity after 35 h of Pt-H₂SO₄/Zr-Mt catalyst was detected. Furthermore, Pt-H₂SO₄/Zr-Mt was completely regenerated under appropriate condition and appeared good repeatability in the D₄, D₄^H and MM to low-hydro silicone oil.

Key words: Pt-H₂SO₄/Zr-montmorillonite, Low-hydro silicone oil, Catalyst, Stability, Regeneration

摘要： The liquid phase ring-opening of octamethylcy-clotetrasiloxane (D₄) was investigated over Pt-H₂SO₄/Zrmontmorillonite catalyst. Montmorillonite (Mt), Zr-Mt, H₂SO₄/Mt, H₂SO₄/Zr-Mt and Pt-H₂SO₄/Zr-Mt were also detected for evaluation. The catalysts were characterized by X-ray fluorescence, X-ray diffraction, nitrogen adsorption-desorption, NH₃-TPD and pyridine-FTIR measurements. In comparison to activate clay which is used in the industry of catalyst, Zr-Mt catalyst displayed stronger acidity and more excellent catalytic activity in the polymerization of D₄, polymethylhydrosiloxane (D₄^H) and hexamethyldisiloxane (MM) to low-hydro silicone oil. Relative to Zr-Mt, the acidity of H₂SO₄/Zr-Mt was noticeably improved and the catalyst exhibited a higher capability of ring-opening of D₄ conversion and yield of low-hydro silicone oil. To enhance the stability of H₂SO₄/Zr-Mt catalyst, a small amount of metals (Pt) was doped. The nitrogen adsorption-desorption results indicated that pore textural parameters of the Pt-H₂SO₄/Zr-Mt had not changed with larger specific surface area. Compared with H₂SO₄/Zr-Mt, the total acidity of Pt-H₂SO₄-Zr/Mt catalyst retained, but the content of the Brønsted acid increased and the content of the Lewis acid decreased. The Pt-H₂SO₄-Zr/Mt catalyst displayed higher catalyst reproducibility. After 40 h reaction of polymerization, the yield of low-hydro silicone oil decreased from 93% to 42% over H₂SO₄/Zr-Mt catalyst, while the yield of low-hydro silicone oil reduced from 93% to 78% over Pt-H₂SO₄/Zr-Mt catalyst. A sharp decrease in catalytic activity after 35 h of Pt-H₂SO₄/Zr-Mt catalyst was detected. Furthermore, Pt-H₂SO₄/Zr-Mt was completely regenerated under appropriate condition and appeared good repeatability in the D₄, D₄^H and MM to low-hydro silicone oil.

关键词: Pt-H₂SO₄/Zr-montmorillonite, Low-hydro silicone oil, Catalyst, Stability, Regeneration

Yuedong Zhou, Fengfu Li, Junwei Liu, Zhi Yun, Xia Gui. Pt-H₂SO₄/Zr-montmorillonite: An efficient catalyst for the polymerization of octamethylcy-clotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane to low-hydro silicone oil[J]. Chin.J.Chem.Eng., 2017, 25(12): 1771-1776.

References

[1] Z.J. Zhang, N. Zhou, C.H. Xu, Polymerization of octamethylcyclotetrasiloxane with hexamethyldisilazyl-lithium as initiator, Chin. J. Polym. Sci. 19 (1) (2001) 7-11.

[2] J. Bauer, N. Husing, G. Kickelbick, Preparation of functional block copolymers based on a polysiloxane backbone by anionic ring-opening polymerization, J. Polym. Sci. A Polym. Chem. 40 (10) (2002) 1539-1551.

[3] A. Degunzbourg, J.C. Favier, P. Hemery, Anionic-polymerization of octamethylcyclotetrasiloxane in aqueous emulsion. 1. Preliminary-results and kinetic-study, Polym. Int. 35 (2) (1994) 179-188.

[4] I. Yilgor, J.E. Mcgrath, Polysiloxane containing copolymers — A survey of recent developments, Adv. Polym. Sci. 86 (1998) 1-86.

[5] W.Z. Wang, Synthesis and characterization of UV-curable polydimethylsiloxane epoxy acrylate, Eur. Polym. J. 39 (6) (2003) 1117-1123.

[6] C. Iojoiu, M.J.M. Abadie, V. Harabagiu, Synthesis and photocrosslinking of benzyl acrylate substituted polydimethylsiloxanes, Eur. Polym. J. 36 (10) (2000) 2115-2123.

[7] F.Wang, J.L. Dubois,W. Ueda, Catalytic dehydration of glycerol over vanadium phosphate oxides in the presence of molecular oxygen, J. Catal. 268 (2) (2009) 260-267.

[8] H. Oki, T. Morita, K. Nakajima, MoO₃/ZrO₂ as a stable, reusable, and highly active solid acid catalyst for polyester polyol synthesis, Chem. Lett. 42 (10) (2013) 1314-1316.

[9] B.M. Reddy, M.K. Patil, Organic syntheses and transformations catalyzed by sulfated zirconia, Chem. Rev. 109 (6) (2009) 2185-2208.

[10] R.J. Stanis,M.C. Kuo, A.J. Rickett, Investigation into the activity of heteropolyacids towards the oxygen reduction reaction on PEMFC cathodes, Electrochim. Acta 53 (28) (2008) 8277-8286.

[11] C. Cativiela, J.M. Fraile, J.I. Garcia, Effect of clay calcination on clay-catalyzed Diels-Alder reactions of cyclopentadiene with methyl and (-)-menthyl acrylates, Tetrahedron 48 (31) (1992) 6467-6476.

[12] K. Li, E.M. Kennedy, B.Z. Dlugogorski, Non-oxidative reaction of CBrF₃ with methane over NiZSM-5 and HZSM-5, Catal. Today 63 (2-4) (2000) 355-362.

[13] X.F. Yang, Q. Shao, L.L. Yang, Preparation and performance of high refractive index silicone resin-type materials for the packaging of light-emitting diodes, J. Appl. Polym. Sci. 127 (3) (2013) 1717-1724.

[14] B. Yactine, A. Ratsimihety, F. Ganachaud, Do-it-yourself functionalized silicones part 2: synthesis by ring opening polymerization of commercial cyclosiloxanes, Polym. Adv. Technol. 21 (2) (2010) 139-149.

[15] X.F. Yang, Z.G. Chen, J. Liu, A convenientmethod for preparation of hydroxyl silicone oils with ring opening polymerization of octamethylcyclotetrasiloxane (D4), Phosphorus Sulfur Silicon Relat. Elem. 191 (1) (2016) 117-122.

[16] O.S. Ahmed, D.K. Dutta, Friedel-Crafts benzylation of benzene using Zn and Cd ions exchanged clay composites, J. Mol. Catal. A Chem. 229 (1-2) (2005) 227-231.

[17] G. Nagendrappa, Organic synthesis using clay and clay-supported catalysts, Appl. Clay Sci. 53 (2) (2011) 106-138.

[18] G.B.B. Varadwaj, S. Ran, K. Parida, Pd(0) nanoparticles supported organofunctionalized clay driving C-C coupling reactions under benign conditions through a Pd(0)/Pd(Ⅱ) redox interplay, J. Phys. Chem. C 118 (3) (2014) 1640-1651.

[19] W. Pu, S. Pang, H. Jia, Using DSC/TG/DTA techniques to re-evaluate the effect of clays on crude oil oxidation kinetics, J. Pet. Sci. Eng. 134 (2014) 123-130.

[20] L. Zatta, L.P. Ramos, F. Wypych, Acid-activated montmorillonites as heterogeneous catalysts for the esterification of lauric acid acid with methanol, Appl. Clay Sci. 80-81 (2013) 236-244.

[21] A. Hachemaoui, A. Yahiaoui, M. Belbachir, Synthesis of perfluorohexyl-terminated poly(ethylene oxide) using Maghnite-H as clay catalyst, J. Appl. Polym. Sci. 118 (6) (2010) 3445-3452.

[22] F. Junges, M.S. Beauvalet, B.C. Leal, UHMWPE-layered silicate nanocomposites by in situ polymerization with tris(pyrazolyl)borate titanium/clay catalyst, J. Braz. Chem. Soc. 20 (3) (2009) 472-477.

[23] R. Issaadi, F. Garin, C.E. Chitour, Catalytic behaviour of combined palladium-acid catalysts: use of Al and Zr-pillared montmorillonite as supports part I. Reactivity of linear, branched and cyclic hexane hydrocarbons, Appl. Catal. A Gen. 207 (1-2) (2001) 323-332.

[24] W. Li,W. Ding, Y. Nie, Enhancing the stability and activity by anchoring Pt nanoparticles between the layers of etched montmorillonite for oxygen reduction reaction, Sci. Bull. 61 (18) (2016) 1435-1439.

[25] S.Y. Feng, M.Z. Cui, Study of polysiloxanes containing epoxy groups I. Synthesis and characterization of polysiloxanes containing 3-(2,3-epoxypropoxy)propyl groups, React. Funct. Polym. 45 (2) (2000) 79-83.

[26] R.Mokaya,W. Jones, Pillared clays and pillared acid-activated clays—A comparativestudy of physical, acidic, and catalytic properties, J. Catal. 153 (1) (1995) 76-85.

[27] B. Tyagi, C.D. Chudasama, R.V. Jasra, Characterization of surface acidity of an acid montmorillonite activated with hydrothermal, ultrasonic and microwave techniques, Appl. Clay Sci. 31 (1-2) (2006) 16-28.

[28] N. Belaidi, S. Bedrane, A. Choukchou-Braham, Novel vanadium-chromium-bentonite green catalysts for cyclohexene epoxidation, Appl. Clay Sci. 107 (2015) 14-20.

[29] I. Kun, G. Szollosi, M. Bartok, Crotonaldehyde hydrogenation over clay-supported platinum catalysts, J. Mol. Catal. A Chem. 169 (1-2) (2001) 235-246.

[30] K. Balazsik, B. Torok, G. Szakonyi, Homogeneous and heterogeneous asymmetric reactions. Part X: enantioselective hydrogenations over K-10 montmorillonite supported noble metal catalysts with immobilized modifier, Appl. Catal. A Gen. 182 (1) (1999) 53-63.

[31] C.A. Emeis, Determination of integrated molar extinction coefficients for infraredabsorption bands of pyridine adsorbed on solid acid catalysts, J. Catal. 141 (2) (1993) 347-354.

[32] E.L.Warrick,W.A. Piccoli, F.O. Stark, Melt viscosities of dimethylpolysiloxanes, J. Am. Chem. Soc. 77 (1955) 5017.

[33] D. Tyagi, I. Yilgor, J.E. Mcgrath, Segmented organosiloxane copolymers. 2. Thermal and mechanical-properties of siloxane urea copolymers, Polymer 25 (12) (1984) 1807-1816.

[34] P.R. Dvornic, J.D. Jovanovic, M.N. Govedarica, On the critical molecular chain-length of polydimethylsiloxane, J. Appl. Polym. Sci. 49 (9) (1993) 1497-1507.

[35] O.B. Ayodele, J.K. Lim, B.H. Hameed, Pillared montmorillonite supported ferric oxalate as heterogeneous photo-Fenton catalyst for degradation of amoxicillin, Appl. Catal. A Gen. 413-314 (2012) 301-309.

[36] H. Gao, B.X. Zhao, J.C. Luo, D. Wu, W. Ye, Q. Wang, X.L. Zhang, Fe-Ni-Al pillared montmorillonite as a heterogeneous catalyst for the catalytic wet peroxide oxidation degradation of orange acid Ⅱ: preparation condition and properties study, Microporous Mesoporous Mater. 196 (2014) 208-215.

[37] G.R. Rao, B.G. Mishra, A comparative UV-vis-diffuse reflectance study on the location and interaction of cerium ions in Al- and Zr-pillared montmorillonite clays, Mater. Chem. Phys. 89 (1) (2005) 110-115.

[38] W.J. Zhang, M.K.S. Li, R.J.Wang, Preparation of stable exfoliated Pt-clay nanocatalyst, Langmuir 25 (14) (2009) 8226-8234.

[39] X. Xu, X. Zhang,W. Zou, Conversion of carbohydrates tomethyl levulinate catalyzed by sulfated montmorillonite, Catal. Commun. 62 (2015) 67-70.

[40] N. Bouchenafa-Saib, R. Issaadi, P. Grange, Hydroconversion of n-heptane: A comparative study of catalytic properties of Pd/Sulfated Zr-pillared montmorillonite, Pd/ Sulfated zirconia and Pd/gamma-alumina, Appl. Catal. A Gen. 259 (1) (2004) 9-15.

[41] D. Das, H.K. Mishra, K.M. Parida, Preparation and characterisation of Zr, Ti and Zr-Ti mixed oxide pillared montmorillonite and their catalytic activity towards nitration of chlorobenzene, Indian J. Chem. Sect. A-Inorg. Bio-Inorg. Phys. Theor. Anal. Chem. 41 (11) (2002) 2238-2243.

[42] P. Berteau, M.A. Kellens, B. Delmon, Acid-base properties of modified aluminas, J. Am. Chem. Soc. 87 (9) (1991) 1425-1431.

[43] F. Kooli, Y. Liu, K. Hbaieb, Characterization and catalytic properties of porous clay heterostructures from zirconium intercalated clay and its pillared derivatives, Microporous Mesoporous Mater. 226 (2016) 482-492.

[44] T. Ma, Z. Yun, W. Xu, Pd-H₃PW₁₂O₄₀/Zr-MCM-41: an efficient catalyst for the sustainable dehydration of glycerol to acrolein, Chem. Eng. J. 294 (2016) 343-352.

[45] D. Olszewska, Characterization of ZrO₂-acid activated montmorillonite doped with Cu, Ni or Mn ions, Appl. Clay Sci. 53 (2) (2011) 353-358.

[46] H.A. Patel, S. Bocchini, A. Frache, Platinum nanoparticle intercalatedmontmorillonite to enhance the char formation of polyamide 6 nanocomposites, J. Mater. Chem. 20 (42) (2010) 9550.

[47] E.J.M. Hensen, D.G. Poduval, V. Degirmenci, Acidity characterization of amorphous silica-alumina, J. Phys. Chem. C 116 (40) (2012) 21416-21429.

[48] K. Oussadi, V. Montembault, M. Belbachir, Ring-opening bulk polymerization of five- and six-membered cyclic phosphonates using maghnite, a nontoxic proton exchanged montmorillonite clay, J. Appl. Polym. Sci. 122 (2) (2011) 891-897.

[49] A. Schutz, W.E.E. Stone, G. Poncelet, J.J. Fripiat, Preparation and characterization of bidimensional zeolitic structures obtained from synthetic beidellite and hydroxyaluminum solutions, Clay Clay Miner. 35 (4) (1987) 251-262.

[50] M.R.S. Kou, S. Mendioroz, M.I. Guijarro, A thermal study of Zr-pillared montmorillonite, Thermochim. Acta 323 (1-2) (1998) 145-157.

[51] S. Yariv, L. Heller-Kallai, Iron-bearing kaolinite in Venezuelan laterites. 1. Infrared spectroscopy and chemical dissolution evidence, Clay Clay Miner. 21 (1973) 199.

[52] V.C. Farmer, Transverse and longitudinal crystal modes associated with OH stretching vibrations in single crystals of kaolinite and dickite, Spectrochim. Acta A 56 (5) (2000) 927-930.

Pt-H₂SO₄/Zr-montmorillonite: An efficient catalyst for the polymerization of octamethylcy-clotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane to low-hydro silicone oil

Pt-H₂SO₄/Zr-montmorillonite: An efficient catalyst for the polymerization of octamethylcy-clotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane to low-hydro silicone oil

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