Poly(meth)acrylates Obtained by Cascade Reaction

Abstract

Preparation, purification, and stabilization of functional (meth)acrylates with a high dipole moment are complex, laborious, and expensive processes. In order to avoid purification and stabilization of the highly reactive functional monomers, a concept of cascade reactions was developed comprising enzymatic monomer synthesis and radical polymerization. Transacylation of methyl acrylate (MA) and methyl methacrylate (MMA) with different functional alcohols, diols, and triols (1,2,6-hexanetriol and glycerol) in the presence of Novozyme 435 led to functional (meth)acrylates. After the removal of the enzyme by means of filtration, removal of excess (meth)acrylate and/or addition of a new monomer, e.g., 2-hydroxyethyl (meth)acrylate the (co)polymerization via free radical (FRP) or nitroxide mediated radical polymerization (NMP) resulted in poly[(meth)acrylate]s with predefined functionalities. Hydrophilic, hydrophobic as well as ionic repeating units were assembled within the copolymer. The transacylation of MA and MMA with diols and triols carried out under mild conditions is an easy and rapid process and is suitable for the preparation of sensitive monomers.

CaLB Catalyzed Conversion of ε-Caprolactone in Aqueous Medium. Part 1: Immobilization of CaLB to Microgels

“…In natural environment lipases are known to hydrolyze fats at the lipid-water interface with formation of fatty acids and glycerol [4,5]. In organic solvents it was shown that lipases also catalyze esterification reactions [6] with the formation of polyesters [7]. In order to reduce the use of ecologically harmful organic solvents, which are always found in traces in the final products, we attempt to engineer the micro surrounding of the lipase such, that in the future it can be used for the catalysis of polyesterifications in pure water.…”

One‐Pot Synthesis of Multifunctional Polymers by Light‐Controlled Radical Polymerization and Enzymatic Catalysis with Candida antarctica Lipase B

“…[ 1,2 ] Polymers with functional groups, such as hydroxyl, amine, and thiol groups, have gained increased attention in drug delivery systems, additives for motor oils, and a wide variety of smart materials. [ 3,4 ] Although the demand for multifunctional polymers is quickly growing, effi cient synthetic strategies to these versatile macromolecules remain still a challenge, since functional groups can interact in the polymerization process and cause unwanted side reactions.…”

“…The renaissance of multifunctional polymers and their synthesis by controlled radical polymerization processes and postpolymerization modifications has recently been one of the major developments in the field of polymer chemistry . Polymers with functional groups, such as hydroxyl, amine, and thiol groups, have gained increased attention in drug delivery systems, additives for motor oils, and a wide variety of smart materials .…”

Copolymerization of a dendronized monomer with styrene and different acrylates: Determination of reactivity ratios

“…Possible comonomers should be already established compounds in copolymerizations, and in view of future applications of the products should possess a certain industrial interest and be cheap and easily available. Styrene (S),11 tert ‐butyl acrylate ( t BuA),12 tert ‐butyl methacrylate ( t BuMA),13 and methyl methacrylate (MMA)14 all fit the aforementioned conditions, and were chosen as reaction partners for first‐generation monomer MG1. The reactivity ratios for each reaction were determined and are summarized in Table 1.…”