Poly(phthalaldehyde), abbreviated as PPA, is a metastable stimuli-responsive polymer first synthesized in 1967. It has garnered significant attention during the past couple of years due to its ease of synthesis and outstanding transient and mechanical properties. For this reason, it has been exploited for a variety of applications including sensing, drug delivery, and EUV lithography. As of 2023, it is considered the only aromatic aldehyde polymerized through a living chain growth polymerization.
Discovery and history
Poly(phthalaldehyde) was first reported in 1967 by Chuji Aso and Sanae Tagami from the department of Organic Synthesis at Kyushu University by an addition homopolymerization reaction of aromatic o-phthalaldehyde. This polymer, consisting of a polyacetal main chain, is still to date, the only aromatic aldehyde that can be homopolymerized through a chain-growth polymerization method. It is a white brittle solid with a low ceiling temperature and significant self-immolative properties. It has gathered significant attention in recent years especially in the development of novel responsive materials and applications.
Synthesis techniques Since its first inception in 1967, many synthesis techniques have been developed and employed for the polymerization of o-phthalaldehyde. Most notably, living polymerization methods are among the most common and promising techniques used, as can be seen in the high number of publications in the literature depicting their usage in poly(phthalaldehyde) preparation.
Living cationic polymerization (LCP)
History and main idea Aso and Tagami were the first to report the polymerization of o-phthalaldehyde in 1967 using the cationic living polymerization technique. This technique, which was initially thought to require the usage of a strong Brönsted acid to initiate polymerization in addition to a strong nucleophile to depress polymerization and endcap the polymer chain was proven successful in a number of polymerization processes reported earlier. Interestingly, the authors were able to produce this polymer without using an initiator nor a terminator and determined the polymer's structure to be cyclic. In fact, they worked at liquid nitrogen temperature and relied on Boron trifluoride etherate catalyst which was sufficient to produce a polymer stable enough at room temperature for a few days.
Current trends In the following years, polymer chemists started studying the characteristics of this polymer and worked on enhancing its thermal stability and mechanical properties. In particular, Moore and coworkers conducted rigorous mechanistic studies on poly(phthalaldehyde) by modifying the type of catalyst used, as well as the starting monomer concentration in an effort to control the molar mass, decrease the polydispersity index, and increase the polymer's purity. Among the catalysts used were triethyloxonium borofluoride, tin chloride, and triphenylmethylium tetrafluoroborate.
Limitations While LCP was the first and sole method used to produce poly(phthalaldehyde), its usage nowadays has dramatically decreased in favor of other polymerization techniques which allow a better control over the polymer properties including molar mass and thermal stability.
Living anionic polymerization (LAP)
History and main idea While this polymerization technique did not typically gain fame and popularity until 2010, it was also reported by Aso and Tagami in 1969. In general, LAP involves the usage of a strong nucleophile to initiate polymerization in addition to the employment of an electrophile as a terminator to endcap the polymer chain. In Tagami's article, PPA was prepared by utilizing tert-butyllithium as an initiator and acetic anhydride as a terminator. However, the drawbacks faced when utilizing LCP (low polydispersity index (PDI), low yield, and no control over molecular weight) were also encountered in this polymerization technique.
Current trends It was not until 1987 when two chemists, Hedrick and Schlemper, from the University of Freiburg proposed the use of phosphazene bases to speed up the reaction and lower the polydispersity index. Up until 2023, three different phosphazene bases have been used in PPA polymerization. Moreover, most of the published research articles describing PPA synthesis between 2008 and 2023 revolve around the usage of LAP, rendering it the most common and effective polymerization technique.
Advantages The major advantage this polymerization technique presents over LCP lies in the fact that the polymer can be end capped on both sides of the chain with stimuli-responsive groups. The tuning process of PPA by these functional groups have not only expanded the set of applications this polymer can be used in, but has also improved its properties and attributes. For instance, by controlling the o-phthalaldehyde monomer/alcohol initiator concentration ratio, ultra-high molecular weights (50-150 KDa) PPA can be obtained. Furthermore, PPA synthesized through LAP is more thermally and mechanically stable. Generally, the presence of endcaps on both ends stabilizes the polymer and results in a more flexible chain with a high thermal stability. And because linear polymers synthesized by LAP method can be end capped whereas cyclic polymers prepared via LCP method cannot be end capped with functional groups, LAP results in more thermally stable polymers. It has a much lower PDI ranging between 1.3 and 1.9 as opposed to PPA synthesized through LCP which has a PDI ranging between 2 and 4.5. This is because of the ability to control the character, molecular weight, and end group of the polymer. Furthermore, the initiator used in LAP synthesis method, which is a strong nucleophile, acts as the first endcap, and hence by controlling the amount of initiator used, a control over the molar mass and PDI can be obtained. This is in contrary to cyclic PPA which is synthesized through LCP where the initiator (Lewis acid) will not be part of the final PPA product, and hence, controlling the amount of Lewis acid used will have no to little effect on the final molar mass and PDI of cyclic PPA polymer.
… excerpt ends here. Continue reading the full article.
