Synthesis of Polymers Containing Cross-Linkable Groups by Atom Transfer Radical Polymerization:  Poly(allyl methacrylate) and Copolymers of Allyl Methacrylate and Styrene

Abstract

Poly(allyl methacrylate) (PAMA) and random copolymers of styrene (St) with allyl methacrylate (AMA) were prepared via atom transfer radical polymerization. For the homopolymerization of AMA, the maximum conversion depends on the reaction conditions and on the monomer/initiator ratio. For the copolymerization, AMA conversions of up to 90% were obtained while no cross-linking occurred. Kinetic studies of the homopolymerization revealed a controlled polymerization up to a certain conversion whereas at higher conversions, multimodal molecular weight distributions caused by branching reactions and cross-linking were observed. The copolymerization of AMA with St allowed a controlled reaction up to conversions higher than 90%. The copolymers obtained were soluble in standard organic solvents. In a subsequent reaction, these copolymers were cross-linked both thermally and photochemically using suitable initiators. Moreover, pendant double bonds were brominated quantitatively.

Deposition Kinetics and Thermal Properties of Atmospheric Plasma Deposited Methacrylate-Like Films

“…However, due to the lower reactivity of the allylic C5 5C group compared to the methacrylic group, a fully cross-linked poly(AMA) benchmark system cannot be obtained. [26,42] The propyl isobutyrate precursor (see Figure 1, (PiB)) is the fully saturated analog of AMA, and therefore cannot be polymerized through conventional polymerization reactions. Methyl methacrylate (see Figure 1, (MMA)) has one C5 5C double bond and gives rise to a linear polymer, PMMA, through conventional free radical polymerization.…”

Multifunctional Polymethacrylates Obtained Via ATRP of Functional and Reactive Monomers Followed by Polymer Analogous Reaction with Functional Amines

“…In order to achieve this goal, the following synthetic concept was adopted: first, a reactive monomer, PCEMA, was synthesized, then it was copolymerized with MMA, BMA, and AMA in order to obtain reactive copolymers (coP), which upon quantitative reaction with functional amines lead to functional copolymers (fcoP) (Figure 2). The copolymerization of AMA with different monomers via ATRP has been studied on the one hand by our group [22,23] and on the other hand, Paris and de la Fuente, reported the copolymerization of AMA with butyl acrylate where three double bonds of different reactivity were used: methacrylic, acrylic, and allylic double bonds. [25] Synthesis and Polymerization of PCEMA For the synthesis of the monomer PCEMA, the commercially available HEMA was used as starting material (Figure 3).…”

“…The first two monomers were used to define the bulk properties of the copolymer, AMA was used for a potential cross-linking reaction, [22][23][24] and PCEMA was used to introduce a reactive repeating unit for polymer analogous reaction.…”

Molecular design and application of divinyl monomers to synthesis of UV-curable latex

“…13,14 The first approach is limited, however, by intricacy of technical process while the latter is limited by the choice of monomers and crosslinkers.…”