Supporting information
Synthesis and Catalytic Performance of a New Post-Metallocene Titanium Complex Having Asymmetric Tetradentate [ONSO]-type Amino Acid Based Chelating Ligand for Acrylate Polymerization at Room Temperature in Aqueous Emulsion
Sudip K. De*a, K. Sharmab and C. Sharmab
aDepartment of Chemistry, Bangabasi Evening College, Kolkata, 700009, India
bDepartment of Chemistry, Jaypee University of Engineering and Technology, Guna, 473226, India
Fig.S1 1H NMR Spectrum of the complex 1 in CDCl3
Fig.S2 13C NMR Spectrum of the complex 1 in CDCl3
Fig.S3 UV-Visible Spectrum of Complex 1 in Methanol (10-3 M)
Fig.S4 IR Spectrum of Complex
Fig.S5 Variation of Yield with Time in the Homopolymerization of MA and MMA
Fig.S6 Variation of Turn over Number with Time in the Homopolymerization of MA and MMA
Fig.S7 Variation of Activity with Time in the Homopolymerization of MA and MMA
Fig.S8 Changes in Number Average Molecular Weight with Yield in the Homopolymerization of MMA
Fig.S9 Changes in Number Average Molecular Weight with Yield in the Homopolymerization of MA
Fig. S10 Changes in Number Average Molecular Weight with Time in the Homopolymerization of MMA and MA
Fig.S11 Representative GPC of PMMA
Fig.S12 1 H NMR Spectrum of the PMMA
Fig.S13 13 C NMR Spectrum of the PMMA
Fig.S14 Representative 1H NMR Spectrum of PMA Synthesized.
Fig.S15 Representative 13C NMR Spectrum of PMA Synthesized.
Fig.S16 DSC Curve of Polymethyl acrylate
Fig.S17 DSC Curve of Polymethyl methacrylate
Fig.S18 Representative 13 C NMR Spectrum of PMMA-co-PMA Synthesized.
Determination of the most abundant species in catalyst solution: Identifying the actual active catalyst species
For the determination of the structure of the “real catalyst”, at first, based on literature review we have predicted the several possible structures (A-D in the following figure S19) of the real catalyst and then conducted two experiments: a) Chloride estimation and b) pH measurement to identify the most abundant species in solution. For these studies we dissolved 48.4 mg (0.1 mmol) of catalyst in deionised water and diluted upto 100 ml to give 0.001 M solution. Following standard argentometric method, the chloride concentration in this catalyst solution was found to be 0.0019 moles/L which is almost double than catalyst concentration indicating that both the chlorides have hydrolyzed resulting in the formation of B. Now if both the coordinated water molecules give up one proton each then [H+] in the catalyst solution should be ~0.002M and pH of the solution should be ~2.69 whereas if only one coordinated water gives up a proton, i.e., species C predominates in solution then [H+] in the catalyst solution should be ~0.001M and pH of the solution should be ~3. Experimentally with the help of pH meter we found the pH of the solution prepared to be 2.92 slightly less than 3 indicating that the predominant species in solution to be C. C being a cationic species gets stabilized by the formation of ion-pair with the cocatalyst BPh4- in the solvent cage which in turn helps the real active catalytic species C to enter inside the micelle (actual site of polymerization) through the negatively charged outer surface of SDS and hence the role of cocatalyst NaBPh4 is justified.
Fig.S19 Various species present in equilibrium in an aqueous solution of the catalyst
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