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Mechanism and Nanosize Products of the Sol-Gel Reaction Using Diphenylsilanediol and 3-methacryloxypropyltrimethoxysilane as Precursors

Mechanism and Nanosize Products of the Sol-Gel Reaction Using Diphenylsilanediol and 3-methacryloxypropyltrimethoxysilane as Precursors

Se Yun Kim, Saji Augustine, Young Joo Eo, Byeong Soo Bae, Seong Ihl Woo, Jeung Ku Kang

J Phys Chem B. 2005 May 19;109(19):9397-403.

PMID: 16852126

Abstract:

We use a first-principles calculation and small-angle neutron scattering (SANS) to investigate the mechanism and the nanosize products of the sol-gel reaction with diphenylsilanediol (DPD) and 3-methacryloxypropyltrimethoxysilane (MEMO) precursors in synthesizing a hybrid waveguide material. It is predicted that switching between a DPD hydroxyl and a MEMO methoxy with a reaction rate of 6.8 x 10(-6) s(-1) at 300 K is the fastest process for the first reaction step, thus generating diphenylmethoxysilanol (DPM) and 3-methacryloxypropyldimethoxysilanol (MEDO) as products. However, we determine that this reaction pathway could be modified by the presence of the H2O released from a catalyst such as Ba(OH)2.H2O. Next, switching between the DPM hydroxyl and the MEDO methoxy is followed to generate diphenyldimethoxysilane (DPDM) and 3-methacryloxypropylmethoxysilanediol (MEMDO). However, condensation between a MEMDO hydroxyl and a DPDM methoxy is found to be most favorable for the third reaction step, which generates the DPDM-MEMDO dimer and CH3OH molecule as products. In a similar fashion, a DPDM methoxy of the DPDM-MEMDO dimer can condense with a MEMDO hydroxyl of the second DPDM-MEMDO dimer to increase the chain, but its reaction rate of 2.8 x 10(-11) s(-1) is predicted to be about 5 times smaller than that between a DPDM methoxy and a MEMDO hydroxyl. This implies that the reaction rate for the larger nanostructures becomes smaller. Additionally, our SANS measurements determine that the final products from our sol-gel reaction are on the nanometer scale, at sizes from 1.76 to 2.36 nm.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP947422	Diphenylsilanediol		947-42-2	Price

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