Abstract:In this work, we report the first molecular weight-controlled amphiphilic polybetaine synthesis using various hydrocarbons via reversible addition−fragmentation chain-transfer (RAFT) polymerization. The experimental separation of the alkyl aminocrotonate tautomers, which has been the subject of debate, was completed for the first time. The enamine form of these tautomers was further used as a monomer for the RAFT polymerization of amphiphilic polycarboxybetaines. Self-assembly of the amphiphilic polycarboxybet… Show more
“…In these applications, understanding of its kinetics is important for the large‐scale production of those polymers 14,15 . As usual, polymerization kinetics depends on many factors such as polymerization rate, initiator concentration, monomer concentration, and temperature 16‐19 . Production of polymer or copolymer with high yields also requires polymerization kinetics of the polmer 20 …”
The kinetics of copolymerization is one of the key factors for optimization the process in large scale of production. Copolymerization of N, N‐dimethyl‐N,N‐diallyammonium chloride (DMDAAC) with N,N‐dimethyl acrylamide (DMAA) was studied by a dilatometer technique using ammonium persulfate ([NH4]2S2O8) as an initiator. The effect of the parameters (including molar ratio of DMDAAC to DMAA, concentrations of monomers [M] and initiator [I], and the temperature) on the polymerization rate was analyzed. From these analyses it was found that the polymerization rate (Rp) with the above variables can be represented as the following relationship: Rp∝ [M]2.63; Rp∝ [I]0.40 andRp∝[MDMDAAC:MDMAA]‐0,86.The negative order found in the relationship of the reaction rate and the monomer composition indicated that the DMDAAC concentration in the monomers composition conversely affected the polymerization rate. The overall activation energy for the polymerization rate was 39.56 kJ/mol in the temperature range between 40°C and 60°C. Based on the experimental results, the mechanism of polymerization is discussed in detail. Different thermal properties for DMDAAC and DMDAAC‐DMAA were observed by differential scanning calorimetry (DSC), and thermogravimetry (TG) analysis. Addition of DMAA to DMDAAC lowered the thermal stability relative to the home polymer of DMDAAC.
“…In these applications, understanding of its kinetics is important for the large‐scale production of those polymers 14,15 . As usual, polymerization kinetics depends on many factors such as polymerization rate, initiator concentration, monomer concentration, and temperature 16‐19 . Production of polymer or copolymer with high yields also requires polymerization kinetics of the polmer 20 …”
The kinetics of copolymerization is one of the key factors for optimization the process in large scale of production. Copolymerization of N, N‐dimethyl‐N,N‐diallyammonium chloride (DMDAAC) with N,N‐dimethyl acrylamide (DMAA) was studied by a dilatometer technique using ammonium persulfate ([NH4]2S2O8) as an initiator. The effect of the parameters (including molar ratio of DMDAAC to DMAA, concentrations of monomers [M] and initiator [I], and the temperature) on the polymerization rate was analyzed. From these analyses it was found that the polymerization rate (Rp) with the above variables can be represented as the following relationship: Rp∝ [M]2.63; Rp∝ [I]0.40 andRp∝[MDMDAAC:MDMAA]‐0,86.The negative order found in the relationship of the reaction rate and the monomer composition indicated that the DMDAAC concentration in the monomers composition conversely affected the polymerization rate. The overall activation energy for the polymerization rate was 39.56 kJ/mol in the temperature range between 40°C and 60°C. Based on the experimental results, the mechanism of polymerization is discussed in detail. Different thermal properties for DMDAAC and DMDAAC‐DMAA were observed by differential scanning calorimetry (DSC), and thermogravimetry (TG) analysis. Addition of DMAA to DMDAAC lowered the thermal stability relative to the home polymer of DMDAAC.
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