Md. Monirul Islam

Synthesis and characterization of polycarbonates containing terminal and chain interior siloxane

Silicone polycarbonates having polydimethyl siloxane (PDMS) and heptamethyl trisiloxane (HMTS) were synthesized by the interfacial polymerization. Instead of common chain terminator p-tert-butyl phenol (PTBP), eugenol capped HMTS, and PDMS were used. PDMS was also attached into the chain interior of the polymer in different molar ratios. PDMS and HMTS were capped with eugenol through the hydrosilylation reaction using Karstedt’s catalyst. Both monohydroxy and dihydroxy terminated eugenosiloxanes were synthesized in order to use as chain terminator and interior subunit of polymer, respectively. Structural characterization and the study of the properties, such as thermal behavior, thermooxidative stability, surface morphology, wettability of the synthesized polymers were investigated. Flexibility and wettability of the synthesized polymers increases with increasing of silicone content. Polymers showed satisfactory thermo oxidative stability and transparency as good as bisphenol-A-polycarbonate.

Nano Composite Membranes of Sulfonated Amine-Poly(ether sulfone)s and SiO2 for Fuel Cell Application

Organic-inorganic Nano composite membranes were prepared by Sulfonated amine-poly(ether sulfone)s (S-APES)s and SiO2. S-APESs were prepared by nitration, reduction and sulfonation of poly(ether sulfone) (ultrason®-S6010). Poly(ether sulfone) was reacted with ammonium nitrate and trifluoroacetic anhydride to produce the nitrated poly(ether sulfone), and was followed by reduction using tin(Ⅱ)chloride and sodium iodide as reducing agents to give the amino-poly(ether sulfone). The S-APES was obtained by reaction of 1,3-propanesultone and the amino-poly(ether sulfone) (NH2-PES) with sodium methoxide. The different degrees of nitration and reduction of poly(ether sulfone) were successfully synthesized by an optimized process. Organic-inorganic nano composite membranes were obtained by mixing S-APES (45 %) with hydrophilic SiO2 (20 nm, 4-10 %) obtained by sol-gel process. Different contents of SiO2 of the S-APES were studied by FT-IR, 1H-NMR spectroscopy, differential scanning calorimetry (DSC), and thermo gravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and methanol. The ion exchange capacity (IEC), a measure of proton conductivity, was evaluated. The nano composite membranes exhibit conductivities (25 °C) from 3.51 x 10-3 to 4.10 x 10-3 S/cm, water swell from 57.25 to 60.50 %, IEC from 0.68 to 0.73 meq/g, and methanol diffusion coefficients from 2.81 x 10-7 to 3.33 x 10-7 cm2/S at 25 °C.

Synthesis and Characterization of Sulfonated Poly(diphenyl ether ketone sulfone)s Containing Dibenzoylbenzene Moiety for Proton Exchange Membrane Fuel Cell

Sulfonated poly (diphenyl ether ketone sulfone) s, SPDPEKSs were successfully synthesized for proton exchange membranes (PEMs). Poly (diphenyl ether ketone sulfone) s, PDPEKSs were prepared by the polycondensation of 4,4-sulfonyldiphenol with 1,2-bis (4-fluorobenzoyl)-3,6-diphenylbenzene (BFBDPB) and 4-fluorophenylsulfone respectively, at 210 °C using anhydrous potassium carbonate as catalyst in sulfolane. PDPEKSs were followed by sulfonation using chlorosulfonic acid and concentrated sulfuric acid at two step reactions. Different contents of sulfonated unit of SPDPEKS (25, 35, 45 mol% of BFBDPB) were studied by FT-IR, 1H NMR spectroscopy, and thermogravimetric analysis (TGA). The ion exchange capacity (IEC), water uptake and proton conductivity of SPDPEKS were evaluated with increase of degree of sulfonation.

Preparation and Characterization of Sulfonated Imide-Grafted Poly(ethersulfone)s

Poly(ethersulfone)s carrying pendant sulfonated imide side group. The first step in the preparation involved nitration of poly(ethersulfone) (ultrason®-S6010), with ammonium nitrate and trifluoroacetic anhydride resulting in the nitrated poly(ethersulfone) (NO2-PES). In the second step, the nitro groups on polymer were reacted with tin(II)chloride and sodium iodide as reducing agents for creating the amino poly(ethersulfone) (NH2-PES). The imide-poly(ethersulfone)s (IPES) were obtained by reaction of phthalic anhydride and the amino-poly(ethersulfone) with triethyl amine. The sulfonated imide-poly(ethersulfone)s (SIPES) were prepared by chlorosulfonic acid. The different degrees of sulfonated imide units of poly(ethersulfone) were successfully synthesized by an optimized condition. The Sulfonated imide-poly(ethersulfone)s (SIPES) were studied by FT-IR, 1H-NMR spectroscopy and thermo gravimetric analysis(TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water. The ion exchange capacity (IEC) and proton conductivity of SIPES membranes were evaluated with increase of degree of sulfonation. The water uptake of synthesized SIPES membranes exhibit 30 ~ 65 % compared with 28 % of Nafion 211®. The SIPES membranes exhibit proton conductivities (25 °C) of 1.21 ~ 2.62´10-3 S/cm compared with 3.37´10-3 S/cm of Nafion 211®.

Nano Composite Membranes of Sulfonated Poly(ether sulfone) Containing 4,4-Bis(4-hydroxylphenyl)valeric Acid and SiO2 for PEMFC

Poly(ether sulfone)s (PES) containing 25-75 mol % valeric acid were prepared with bisphenol A, bis(4-chlorophenyl)sulfone and 4,4-Bis(4-hydroxylphenyl)valeric acid using potassium carbonate in DMAc (dimethylacetamide) at 160 °C. Copolymers containing carboxylacid group were reduced to hydroxy group by BH3 solution 1M in THF and NaBH4 co-catalyst. Sulfonated poly(ether sulfone)s (S-PES) were obtained by reaction of 1,3-propanesultone and the reduced copolymer (PES-OH) with potassium t-butoxide. Composite membranes were prepared with copolymers and SiO2 nanoparticles(20 nm, 4-10 wt%). The composite membranes were cast from DMSO.A series of composite membranes were studied by 1H-NMR spectroscopy, differential scanning calorimetry (DSC), and thermo gravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and methanol.