Investigating the Effect of Silica Aerogel Nanoparticles on the Kinetics of AGET ATRP of Methyl Methacrylate

2019 ◽  
Vol 233 (3) ◽  
pp. 393-411 ◽  
Author(s):  
Maryam Karimi ◽  
Soroush Davoudizadeh ◽  
Saeed Bahadorikhalili ◽  
Khezrollah Khezri

Abstract Hexamethyldisilazane-modified silica aerogel nanoparticles were used for in situ polymerization of methyl methacrylate by activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP) to synthesize tailor-made PMMA nanocomposites. Appropriate dispersion of silica aerogel nanoparticles in the monomer solution and improvement in interfacial interaction between the PMMA matrix and nanoparticles are two main reasons for application of HMDS-modified silica aerogel nanoparticles. Nitrogen adsorption/desorption isotherm was employed to examine surface area and structural characteristics of the HMDS-modified silica aerogel nanoparticles. Evaluation of size distribution and morphological studies were also performed by SEM and TEM. Conversion and molecular weight determinations were carried out using GC and SEC, respectively. Addition of 3 wt% HMDS-modified silica aerogel nanoparticles leads to decrement of conversion from 85 to 64%. Molecular weight of PMMA chains also decreases from 13,912 to 10,810 g⋅mol−1 by addition of only 3 wt% HMDS-modified silica aerogel nanoparticles; however, polydispersity index values increases from 1.18 to 1.51. Linear increase of ln(M0/M) with time for all the samples shows that polymerization proceeds in a living manner. In addition, suitable agreement between theoretical and experimental molecular weight in combination with low PDI values can appropriately demonstrate the living nature of the polymerization. TGA results indicate that by increasing HMDS-modified silica aerogel nanoparticles content, slight improvements in thermal stability of the nanocomposites were obtained. DSC results show a decrease in Tg from 86.9 to 80.1°C by addition of 3 wt% HMDS-modified silica aerogel nanoparticles.

2019 ◽  
pp. 089270571988167
Author(s):  
Khezrollah Khezri ◽  
Yousef Fazli

Surface of pristine silica aerogel nanoparticles was hydrophobically modified with hexamethyldisilazane (HMDS). Then, the resultant modified nanoparticles were used for in situ atom transfer radical copolymerization of styrene and methyl methacrylate. Surface area and structural characteristics of the HMDS-modified silica aerogel nanoparticles (H-SANs) were examined by nitrogen adsorption/desorption isotherm. Evaluation of size distribution and morphological studies were also performed by scanning electron microscopy and transmission electron microscopy. Conversion and molecular weight determinations were carried out using gas chromatography and size exclusion chromatography, respectively. Adding of H-SAN by 3 wt% results in decrement of conversion from 98% to 79%. In addition, molecular weight of copolymer chains decreases from 20,372 g·mol−1 to 16,487 g·mol−1. However, polydispersity index values increases from 1.38 to 1.76. Linear increase of ln( M 0/ M) with time for all the samples shows that polymerization proceeds in a living manner. Increasing thermal stability of the nanocomposites is demonstrated by thermal gravimetric analysis. Differential scanning calorimetry shows a decrease in glass transition temperature from 67.4°C to 59.8°C by the addition of 3 wt% of the H-SAN.


2018 ◽  
Vol 33 (2) ◽  
pp. 180-197 ◽  
Author(s):  
Khezrollah Khezri ◽  
Yousef Fazli

Pristine mesoporous diatomite was employed to prepare polystyrene/diatomite composites. Diatomite platelets were used for in situ polymerization of styrene by atom transfer radical polymerization to synthesize tailor-made polystyrene nanocomposites. X-Ray fluorescence spectrometer analysis and thermogravimetric analysis (TGA) were employed for evaluating some inherent properties of pristine diatomite platelets. Nitrogen adsorption/desorption isotherm is applied to examine surface area and structural characteristics of the diatomite platelets. Evaluation of pore size distribution and morphological studies were also performed by scanning and transmission electron microscopy. Conversion and molecular weight determinations were carried out using gas and size exclusion chromatography, respectively. Linear increase of ln ( M0/M) with time for all the samples shows that polymerization proceeds in a living manner. Addition of 3 wt% pristine mesoporous diatomite leads to an increase of conversion from 72% to 89%. Molecular weight of polystyrene chains increases from 11,326 g mol−1 to 14134 g mol−1 with the addition of 3 wt% pristine mesoporous diatomite; however, polydispersity index values increases from 1.13 to 1.38. Increasing thermal stability of the nanocomposites is demonstrated by TGA. Differential scanning calorimetry shows an increase in glass transition temperature from 81.9°C to 87.1°C by adding 3 wt% of mesoporous diatomite platelets.


2016 ◽  
Vol 230 (10) ◽  
Author(s):  
Khezrollah Khezri ◽  
Hossein Mahdavi

AbstractPristine silica aerogel nanoparticles surface was functionalized with 3-(trimethoxysilyl)propyl methacrylate (MPS). Then, the resultant functionalized nanoparticles were used in grafting through polymerization of styrene by reverse initiation technique for atom transfer radical polymerization. Nitrogen adsorption/desorption isotherm is applied to examine surface area and structural characteristics of the synthesized nanoparticles. Evaluation of size distribution and morphological studies were also performed by scanning and transmission electron microscopy. Conversion and molecular weight determinations were carried out using gas and size exclusion chromatography respectively. Addition of MPS-functionalized nanoparticles by 3 wt % results in a decrease of conversion from 98 to 81%. Molecular weight (


Author(s):  
Khezrollah Khezri ◽  
Moosa Ghasemi ◽  
Yousef Fazli

Abstract Mesoporous diatomite particles were employed to prepare different poly(styrene-co-butyl acrylate)/diatomite nanocomposites. Diatomite nanoplatelets were used for in situ copolymerization of styrene and butyl acrylate by SR&NI ATRP to synthesize well-defined poly(styrene-co-butyl acrylate) nanocomposites. Nitrogen adsorption/desorption isotherm is applied to examine surface area and structural characteristics of the diatomite nanoplatelets. Evaluation of pore size distribution and morphological studies were also performed by SEM and TEM. Conversion and molecular weight determinations were carried out using gas and size exclusion chromatography respectively. Addition of 3 wt% pristine mesoporous diatomite nanoplatelets leads to increase of conversion from 73 to 89%. Molecular weight of poly(styrene-co-butyl acrylate) chains increases from 17,115 to 20,343 g·mol−1 by addition of 3 wt% pristine mesoporous diatomite; however, polydispersity index values increases from 1.14 to 1.37. Increasing thermal stability of the nanocomposites is demonstrated by TGA. Differential scanning calorimetry shows an increase in glass transition temperature from 35.26 to 39.61°C by adding 3 wt% of mesoporous diatomite nanoplatelets.


NANO ◽  
2014 ◽  
Vol 09 (02) ◽  
pp. 1450023 ◽  
Author(s):  
KHEZROLLAH KHEZRI ◽  
VAHID HADDADI-ASL ◽  
HOSSEIN ROGHANI-MAMAQANI

Mesoporous silica nanoparticles (MCM-41) surface was functionalized with 3-(trimethoxysilyl)propyl methacrylate (MPS). Then, the resultant double bond containing nanoparticles were used in grafting through simultaneous reverse and normal initiation technique for atom transfer radical polymerization (SR&NI ATRP) of styrene to synthesize well-defined polystyrene nanocomposites with twofold chains. Nitrogen adsorption/desorption isotherm and X-ray diffraction analysis were used to evaluate characteristics of spherical MCM-41 nanoparticles. Morphological studies were also performed by scanning and transmission electron microscopy. Conversion and molecular weight determinations were carried out using gas and size exclusion chromatography respectively. Addition of MCM-41 nanoparticles by 3 wt.% results in a decrease of conversion from 93% to 82%. Molecular weight of the free and attached polystyrene chains decreases by adding 3 wt.% MCM-41 nanoparticles; however, PDI values increases from 1.27 to 1.78 for free chains and 1.87 to 2.48 for attached chains. A peak around 4.1 ppm which originates from hydrogen atom of terminal units of polystyrene chains in proton nuclear magnetic resonance spectra in combination with low PDI values can appropriately demonstrate the living nature of the polymerization. Increasing thermal stability of the nanocomposites is demonstrated by Thermogravimetric analysis. Differential scanning calorimetry also shows a decrease in glass transition temperature by increasing MCM-41 nanoparticles.


2018 ◽  
Vol 32 (2) ◽  
pp. 248-266 ◽  
Author(s):  
Khezrollah Khezri ◽  
Hassan Alijani ◽  
Yousef Fazli ◽  
Zahra Shariatinia

Mesoporous diatomite nanoplatelets were employed to prepare various poly (styrene-co-butyl acrylate)/diatomite nanocomposites by in situ reverse atom transfer radical polymerization of styrene and butyl acrylate. Fourier-transform infrared spectroscopy, thermogravimetric analysis (TGA), and nitrogen adsorption/desorption isotherm were employed for evaluating some properties of the pristine diatomite nanoplatelets. Evaluation of pore size distribution and morphological studies were also performed by scanning and transmission electron microscopy. Conversion and molecular weight determinations were carried out using gas and size exclusion chromatography, respectively. Addition of 3 wt% pristine mesoporous diatomite nanoplatelets leads to an increase in conversion from 77% to 92%. Molecular weight of poly (styrene-co-butyl acrylate) chains increases from 17,348 g mol−1 to 21,346 g mol−1 with the addition of 3 wt% pristine mesoporous diatomite nanoplatelets; however, polydispersity index values increases from 1.38 to 1.65. Increasing thermal stability of the nanocomposites is demonstrated by TGA. Differential scanning calorimetry shows an increase in glass transition temperature from 35.5°C to 39.4°C with the addition of 3 wt% mesoporous diatomite nanoplatelets.


RSC Advances ◽  
2016 ◽  
Vol 6 (77) ◽  
pp. 73842-73847 ◽  
Author(s):  
Zhecheng Zhu ◽  
Guorong Shan ◽  
Pengju Pan

4,4′-Dimethoxydiphenyl nitroxide-based alkoxyamine was prepared and used to control the polymerization of methyl methacrylate. Linear increase in molecular weight with conversion and narrow molecular weight distribution was up to 65% conversion.


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