Copolymerize Conventional Vinyl Monomers to Degradable and Water‐Soluble Copolymers with a Fluorescence Property

Abstract

In the copolymerization of acrylamide (Am) and hydroxyethyl acrylate (HEA), the initial product is a carbon chain polymer with hydroxyl and amide side groups. However, in the present work, these two conventional vinyl monomers are combined into a degradable heterochain copolymer by using a phosphazene base, t‐BuP4, as a catalyst. NMR not only confirms that the backbone of the resulting copolymer is composed of ester–ether units and amide units but also suggests that the resulted secondary amide group retains an active hydrogen and can further react with another olefin, which would result in branching or gelation. Thermogravimetric analysis (TGA) shows a signal indicating decomposition at 205–509 °C, verifying the uniform composition of the sample. More interestingly, the synthesized copolymer can dissolve in water and exhibits aggregation‐enhanced emission (AEE). Additionally, the aqueous copolymer solution has a high selectivity and sensitivity for Ba2+, Fe2+, and Fe3+ cations. Hence, it is believed that this method for constructing degradable polymers may offer innovative insights into polymer synthesis and application.

Preparing Degradable Polymers with Promising Mechanical Properties by Hydrogen Transfer Polymerization

“…To seek a solution, we characterized in detail the polymer (PHEA-1, in Table 1) obtained from HTP of HEA according to our previous work by using a phosphate catalyst, t-BuP 2 . 21,27 The weight-average molecular weight of the resultant polymer HEA was first catalyzed by t-BuP 2 , and then BDDA with t-BuP 4 was added to the system at a fixed time. b The polymerization temperature was first set at −5 °C for 12 h and then increased to 80 °C.…”

“…26 Our previous work also suggested that hydrogen transfer copolymerization (HTcoP) could produce a degradable heterochain copolymer with a high selectivity and sensitivity for Ba 2+ , Fe 2+ , and Fe 3+ cations. 21,27 A milestone work in this area was achieved in 2016 by Chen et al, who found that N-heterocyclic carbenes could catalyze the HTP of dimethacrylate to an unsaturated polyester. 28 This work departed from both the typical HTP processes and traditional acrylic polymerization systems.…”

“…Subsequently, HTP was applied to many other vinyl monomers with active hydrogen atoms, including 2-hydroxyethyl acrylate (HEA), − acrylic acid (AA), − and 4-vinylpyridinium salts . Afterward, the scope of the catalyst and mechanistic insights into HTP were studied, and various polymers with abundant topological structures such as hyperbranched or porphyrin-containing polymers were prepared according to this strategy. − For example, Matsuoka’s group employed N -heterocyclic carbenes to catalyze the HTP and further combined HTP with condensation–addition polymerizations to produce a macromonomer for radical copolymerizing with styrene or methyl (meth)­acrylates. , Carlotti et al studied the sodium tert -butoxide-catalyzed HTP of Am and proposed a mechanism for this polymerization . Slugovc et al prepared a highly branched and amorphous Polyamide-3 by using nucleophiles as initiators .…”

Synthesis of Nonaromatic Macromolecular Luminogens, DFT Studies on Photophysics, and O‐Donor Selective On−Off Sensors: Contributions of In Situ N‐(Methylol)Acrylamido Comonomers

“…There is a continuously growing interest in developing nonconventional aliphatic macromolecular luminogens for diverse applications. [1][2][3][4][5][6] Notably, the conventional conjugated fluorescent polymers as well as aromatic probes are more susceptible toward photobleaching than those of aliphatic macromolecular sensors. [7] The cytotoxicity, small Stokes' shift, lack of durability, and self-quenching of conventional fluorescent polymers make these luminogens less attractive for diverse applications.…”

Unique Property of Nontraditional Intrinsic Luminescence in the Transforming of Solution‐Hydrogel‐Solid and Its Applications

“…Therefore, NTIL compounds may exhibit some unique features in the process of phase change. Unfortunately, although a lot of amine‐containing NTIL compounds including small molecules, oligomers, and polymers have been reported to possess remarkable fluorescence, [ 17–26 ] most of them were conducted in solution, and a few works in solid state. [ 9,27–29 ] Especially, a systematic research on the fluorescence variation from solution through gel to solid state has not been investigated.…”