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Catalyst-Free Construction of Versatile Article Cite This: Macromolecules 2019, 52, 8596−8603 pubs.acs.org/Macromolecules ‑ Catalyst-Free Construction of Versatile and Functional CS2 Based Polythioureas: Characteristics from Self-Healing to Heavy Metal Absorption † † ‡ † Shuang Wu, Ming Luo,*, Donald J. Darensbourg,*, and Xiaobing Zuo † School of Chemistry and Materials Engineering, Changshu Institute of Technology, Changshu, Jiangsu 215500, China ‡ Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States *S Supporting Information ABSTRACT: As typical of sulfur-containing polymers, polythiourea is a promising polymeric material because of its outstanding properties such as self-healing, high refractive index, high dielectric constant, and good coordinating ability to heavy metal ions. However, examples of versatile polythioureas are relatively scarce as a result of the limited methods for their synthesis. Herein, we report a mild and easily accessible strategy for the preparation of polythioureas by a catalyst-free copolymerization of CS2 and diamines in the absence of an inert/anhydrous atmosphere. The copolymerization of 1,8-diamino-3,6-dioxaoctane (DA1) and carbon disulfide was selected as the model reaction for optimizing conditions for the ff fi polymerization process. DA1 and CS2 a orded well-de ned polythiourea P1 with high molecular weight (25.5 kg/mol) in good yield (96%) at 45 °C, which was shown to be mechanically robust and readily self-healable. This method displayed a wide scope, providing 23 polythioureas with structural diversity and high molecular weights in excellent yields from CS2 and commercially available diamines. The aliphatic polythiourea P4 was examined for its ability as a heavy metal absorbent, effectively sequestering Hg2+ ions with greater than 99.9% efficiency. Hence, this study provides an easily accessible method for synthesizing various polythioureas with diverse structures and functionalities. ■ INTRODUCTION generally rely on a high hydrogen-bonding density or cross- The design and synthesis of sulfur-containing polymers have linking hydrogen bonds and generally require heat to recover experienced an increase in attention in recent years because of their original performance. In addition, the presence of lots of − their outstanding characteristics.1 19 Specifically, these poly- hydrogen bonds often leads to crystallinity, thereby making the meric materials possess enhanced thermal and chemical polymeric material brittle. Thus, P1’s ability to balance − stability,5,19,20 crystalline and optical properties,2,21 31 metal- mechanical strength and self-healing capability makes this binding ability,5,7,32 photocatalytic properties,33 and self- polythiourea a very special and promising polymeric material. healing capability.1,34 An additional incentive is that many of The sulfur atoms in polymer P1 are assumed to play a key these materials can be derived directly or indirectly from the role in achieving the properties of this material, since replacing large quantities of elemental sulfur which is produced from Downloaded via TEXAS A&M UNIV COLG STATION on October 26, 2020 at 20:23:37 (UTC). sulfur with oxygen provided an analog polyurea which was See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles. hydrodesulfurization processes. semicrystalline and not self-healing. The behavioral properties ff One very e ective sulfur-containing polymer was recently of P1 were attributed to interactions of the thiourea groups 1 reported by Aida and co-workers. These researchers described with the oxygen atoms of the linear polymer chain. That is, the an amorphous polythiourea (P1 in Scheme 1) which is oxygen atoms were thought to facilitate the exchange of mechanically robust yet readily repairable, i.e., the elastic hydrogen-bonded thiourea pairs by serving as temporal modulus of P1 (M of 22.3 kg/mol and Đ of 2.3) was found to w acceptors, thereby lowering the energy barrier for the gliding be as high as 1.4 GPa, which is equivalent to polypropylene. motion of the polymer chains. Moreover, a sheet of pristine P1 (2 × 10 × 20 mm3) when cut In the initial report, P1 was synthesized by the apart and manually compressed for 30 s at 21 °C withstood a 300 g load. It is well known that high mechanical robustness polycondensation of 1,8-diamino-3,6-dioxaoctane (DA1) and 1,1’-thiocarbonyldiimidazole (Scheme 1), a process which is and healing ability appear to be mutually exclusive in a 1 material. For instance, the ability to form hydrogen bonds in expensive and air/moisture sensitive. Moreover, additional fi polymers is a widely employed strategy for achieving self- puri cation of P1 is needed to remove the imidazole − healing in polymeric materials.35 37 However, these polymers are mostly soft and deformable, like gels or rubbers, and always Received: August 28, 2019 have good tensile strength with low elastic modulus. In other Revised: October 10, 2019 instances, healable materials with good elastic modulus Published: November 4, 2019 © 2019 American Chemical Society 8596 DOI: 10.1021/acs.macromol.9b01811 Macromolecules 2019, 52, 8596−8603 Macromolecules Article Scheme 1. (A) Synthetic Approaches to the Self-Healing Polythiourea (P1); (B) Previously Reported Work byproduct. All of these downsides should increase the and a variety of diamines. This process proceeds effectively at production cost of P1, and thereby limit its wide application. mild temperatures (20−80 °C) in the absence of an inert/ Besides the aforementioned method, detailed studies related anhydrous atmosphere. The reaction is carried out catalyst-free to the synthesis of polythioureas are relatively scarce. As is to provide a broad scope of polythioureas with a great deal of shown in Scheme 1, polythioureas can also be prepared by structural diversity with high molecular weights in good yields. reactions of diamines with thiourea,38,39 thiophosgene,40 Many of these well-characterized polythioureas are reported diisothiocyanate,40 and elemental sulfur/diisocyanides.7 All of for the first time. The synthesized polythioureas possess these procedures have significant drawbacks. For example, the various outstanding properties, such as self-healing, high reaction of thiourea with diamines requires a catalyst such as p- dielectric constant, high refractive index, and heavy metal toluenesulfonic acid, as well as microwave irradiation.38,39 absorption ability. Thiophosgene is a very toxic monomer which requires special handling,40 whereas, for both of the diisothiocyanate/ ■ RESULTS AND DISCUSSION diamine40 and elemental sulfur/diisocyanides/diamines7 sys- fi Catalyst-Free Polycondensation of CS2 and DA1. To tems, synthesis and puri cation of the sulfur-containing examine and optimize the synthesis of polythioureas of monomers are elaborate. Furthermore, the restricted diversity fi diamines in the presence of CS2,we rst carried out the of structures of the diisocyanates and diisocyanides severely process with DA1 without added solvent at ambient limits the variety of possible polythioureas. temperature. Under these conditions, the reaction solution From a general viewpoint, all of the sulfur-containing rapidly became highly viscous. Hence, in an effort to decrease monomers in this array of synthetic methods serve as the rate of polymerization and improve its controllability, all thiocarbonyl (C S) providers in the preparation of reactions were performed in N,N-dimethylformamide (DMF), polythioureas. Based on our previous research on synthesizing where the polymer P1 was highly soluble. During the fi 41−43 carbon disul de derived polymers, we speculate that CS2 optimization of the reaction temperature (entries 1−5in may be a much cheaper, less sensitive, and easy-handling Table 1), the feed ratio of DA1 and CS2 was set at 1:5, with source of thiocarbonyl than the aforementioned origins for the concentration of DA1 maintained at 1.5 M and a reaction synthesizing polythioureas. To our knowledge, the only time of 5 h. Upon increasing the reaction temperature from 0 reported related studies were carried out by Yamazaki and to 100 °C, the polymer yields and molecular weights increased co-workers during their investigation of the polycondensation up to 45 °C, followed by a steady decrease at higher 44,45 of CO2 and diamines in the early 1970s. In these initial temperatures. Therefore, the optimum reaction temperature ° inquiries, a few experiments of the polycondensation of CS2 was chosen as 45 C, which is close to the boiling point of CS2, and diamines under diphenyl phosphite in pyridine were thereby efficiently affording P1 in a yield of 96% and a carried out with limited success. In addition, a few aliphatic molecular weight (Mw) of 25.5 kg/mol with a polydispersity of polythioureas were synthesized by similar methods reported by 1.46. This is an improvement over that previously reported by Ohishi and Tasaka,46,47 where the focus was on the electrical the polycondensation of DA1 and 1,1’-thiocarbonyldiimida- and ferroelectric properties of these aliphatic polythioureas. zole.1 Herein, we report a novel strategy for the synthesis of The main-chain sequence of the resulting copolymer (P1) fi 1 13 polythioureas from the catalyst-free copolymerization of CS2 was con rmed by H and C NMR spectroscopy (Figure 1). 8597 DOI: 10.1021/acs.macromol.9b01811 Macromolecules 2019, 52, 8596−8603 Macromolecules Article Table 1. Catalyst-Free Polycondensation of CS and DA1 adjacent to the NH groups appears at 43.98 ppm, and the a 2 under Different Reaction Conditions signals of the CH2 next to the oxygen atoms are observed at 70.05 and 69.47 ppm. The carbon resonance of the b Đb DA1:CS2 [DA1] Mw fi (molar (mol/ T time yield of (kg/ (M / thiocarbonyl (C S) is found down eld at 183.3 ppm. ° w entry ratio) L) ( C) (h) P1 (%) mol) Mn) These NMR spectral data are completely in accord with 1 1 1:5 1.5 20 5 82 23.8 1.40 those previously reported. 2 1:5 1.5 45 5 96 25.5 1.46 To further validate the alternating structure of P1, matrix- fl 3 1:5 1.5 60 5 90 18.8 1.48 assisted laser desorption time-of- ight mass (MALDI-TOF- fi 4 1:5 1.5 80 5 75 12.1 1.45 MS) spectrometry was employed to con rm the polymeric 5 1:5 1.5 100 5 70 7.0 1.18 chain sequence.
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