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.

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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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