A library of thermoresponsive PEG‐based methacrylate homopolymers: How do the molar mass and number of ethylene glycol groups affect the cloud point?

In this study, a novel library of thermoresponsive homopolymers based on poly (ethylene glycol) (EG) (m)ethyl ether methacrylate monomers is presented. Twenty‐seven EG based homopolymers were synthesized and three parameters, the molar mass (MM), the number of the ethylene glycol groups in the monomer, and the chemistry of the functional side group were varied to investigate how these affect their thermoresponsive behavior. The targeted MMs of these polymers are varied from 2560, 5000, 8200 to 12,000 g mol−1. Seven PEG‐based monomers were investigated: ethylene glycol methyl ether methacrylate (MEGMA), ethylene glycol ethyl ether methacrylate (EEGMA), di(ethylene glycol) methyl ether methacrylate (DEGMA), tri(ethylene glycol) methyl ether methacrylate (TEGMA), tri(ethylene glycol) ethyl ether methacrylate (TEGEMA), penta(ethylene glycol) methyl ether methacrylate (PEGMA), nona(ethylene glycol) methyl ether methacrylate (NEGMA). Homopolymers of 2‐(dimethylamino) ethyl methacrylate (DMAEMA) were also synthesized for comparison. The cloud points of these homopolymers were tested in different solvents and it was observed that it decreases as the number of EG group was decreased or the MM increased. Interestingly, the end functional group (methoxy or ethoxy) of the side group has an effect as well and is even more dominant than the number of EG groups. Ethylene glycol based methacrylate homopolymers have great potential in many biological applications. In this study, 27 homopolymers are synthesized and characterized in terms of their thermoresponsive properties. Interestingly the cloud point is not only affected by the number of ethylene glycol group and the molar mass but also by the terminal group on the ethylene glycol functional side group.