To develop an efficient and bio-compatible way to improve the thermal and mechanical properties of addition type liquid silicone rubber(LSR), a series of modified LSR samples were prepared by introducing octavinyl-p...To develop an efficient and bio-compatible way to improve the thermal and mechanical properties of addition type liquid silicone rubber(LSR), a series of modified LSR samples were prepared by introducing octavinyl-polyhedral oligosilsesquioxanes(VPOSS) and high purity silicon sol singly or in combination before vulcanization. Significant correlation was found between the loading rate of VPOSS and thermal properties. However, mechanical properties were negatively correlated with VPOSS content within the range experimented, which may be ascribed to material defect caused by uneven distribution and aggregation. Furthermore, test results approved that the introducing of silicon sol indeed affected the stabilities of the polymer by restraining the material defect caused by the aggregation of POSS molecules and improving cross link density. For example, adding 10%-20% of silicon sol into VPOSS(1.0%) modified LSR will increase tear resistance by 43.9%-85.7%, elongation at break by 31.7%-57.3%, residue at 800 ℃ in N2 atmosphere by 32.0%-37.9%, residue at 650 ℃ in air atmosphere by 70.9%-91.6%, respectively. This work proves that, to incorporate VPOSS into LSR by hydrosilylation, and to use silicon sol as dispersant and reinforce filler can become an efficient way to improve the mechanical property, thermal stability and bio-compatibility of LSR in the future.展开更多
The liquid phase ring-opening of octamethylcy-clotetrasiloxane (D4) was investigated over Pt-H2SO4/Zr- montmorillonite catalyst. Montmorillonite (Mt), Zr-Mt, H2SO4/Mt, H2SO4/Zr-Mt and Pt-H2SO4/Zr-Mt were also dete...The liquid phase ring-opening of octamethylcy-clotetrasiloxane (D4) was investigated over Pt-H2SO4/Zr- montmorillonite 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 (DH) and hexamethyldisiloxane (MM) to low-hydro sili- cone 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 Bransted 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, DH and MM to low-hydro silicone oil.展开更多
基金Funded by the National Natural Science Foundation of China(No.31170558)
文摘To develop an efficient and bio-compatible way to improve the thermal and mechanical properties of addition type liquid silicone rubber(LSR), a series of modified LSR samples were prepared by introducing octavinyl-polyhedral oligosilsesquioxanes(VPOSS) and high purity silicon sol singly or in combination before vulcanization. Significant correlation was found between the loading rate of VPOSS and thermal properties. However, mechanical properties were negatively correlated with VPOSS content within the range experimented, which may be ascribed to material defect caused by uneven distribution and aggregation. Furthermore, test results approved that the introducing of silicon sol indeed affected the stabilities of the polymer by restraining the material defect caused by the aggregation of POSS molecules and improving cross link density. For example, adding 10%-20% of silicon sol into VPOSS(1.0%) modified LSR will increase tear resistance by 43.9%-85.7%, elongation at break by 31.7%-57.3%, residue at 800 ℃ in N2 atmosphere by 32.0%-37.9%, residue at 650 ℃ in air atmosphere by 70.9%-91.6%, respectively. This work proves that, to incorporate VPOSS into LSR by hydrosilylation, and to use silicon sol as dispersant and reinforce filler can become an efficient way to improve the mechanical property, thermal stability and bio-compatibility of LSR in the future.
基金Supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘The liquid phase ring-opening of octamethylcy-clotetrasiloxane (D4) was investigated over Pt-H2SO4/Zr- montmorillonite 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 (DH) and hexamethyldisiloxane (MM) to low-hydro sili- cone 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 Bransted 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, DH and MM to low-hydro silicone oil.