Topology Controlled All-(Meth)acrylic Thermoplastic Elastomers by Multi-Functional Lewis Pairs-Mediated Polymerization.

It remains challenging to synthesize all-(meth)acrylic triblock thermoplastic elastomers (TPEs), due to the drastically different reactivities between the acrylates and methacrylates and inevitable occurrence of side reactions during polymerization of acrylates. By taking advantage of the easy structural modulation features of N-heterocyclic olefins (NHOs), we design and synthesize strong nucleophilic tetraphenylethylene-based NHOs varying in the number (i.e. mono-, dual- and tetra-) of initiating functional groups. Its combination with bulky organoaluminum [iBuAl(BHT)2] (BHT=bis(2,6-di-tBu-4-methylphenoxy)) constructs Lewis pair (LP) to realize the living polymerization of both acrylates and methacrylates, furnishing polyacrylates with ultrahigh molecular weight (Mn up to 2174 kg ⋅ mol-1) within 4 min. Moreover, these NHO-based LPs enable us to not only realize the control over the polymers' topology (i.e. linear and star), but also achieve triblock star copolymers in one-step manner. Mechanical studies reveal that the star triblock TPEs exhibit better mechanical properties (elongation at break up to 1863 % and tensile strength up to 19.1 MPa) in comparison with the linear analogs. Moreover, the presence of tetraphenylethylene group in the NHOs entitled the triblock TPEs with excellent AIE properties in both solution and solid state.

Heterogeneous self-healing assembly of MXene and graphene oxide enables producing free-standing and self-reparable soft electronics and robots.

Self-healing materials (SHMs) with unique mechanical and electronic properties are promising for self-reparable electronics and robots. However, the self-healing ability of emerging two-dimensional (2D) materials, for instance, MXenes, has not been systematically investigated, which limits their applications in self-healing electronics. Herein, we report the homogeneous self-healing assembly (homo-SHA) of MXene and the heterogeneous self-healing assembly (hetero-SHA) of MXene and graphene oxide (GO) under moisture treatments. The self-healing mechanism has been attributed to the hydration induced interlayer swelling of MXene and GO and the recombination of hydrogen bond networks after water desorption. The multiform hetero-SHA of MXene and GO not only enables facile fabrication of free-standing soft electronics and robots, but also endows the resultant devices with damage-healing properties. As proof-of-concept demonstrations, free-standing soft electronic devices including a generator, a humidity sensor, a pressure sensor, and several robotic devices have been fabricated. The hetero-SHA of MXene and GO is simple yet effective, and it may pioneer a new avenue to develop miniature soft electronics and robots based on 2D materials.

Boron-Based Lewis Pairs Catalyzed Living, Regioselective, and Topology-Controlled Polymerization of (E, E)-Alkyl Sorbates.

It remains as a great challenge to realize living and controlled polymerization of renewable monomers by the boron-based Lewis pairs. Here, strong nucleophilic N-heterocyclic olefins (NHOs) or N-heterocyclic carbenes (NHCs) as Lewis bases, and boron-based compounds as Lewis acids, are employed to construct LPs for polymerization of alkyl sorbates, including (E, E)-methyl sorbate and (E, E)-ethyl sorbate. Systematic investigation reveals that the combinations of B(C6 F5 )3  with appropriate acidity and steric hindrance, and strong nucleophilic NHOs promote living and controlled polymerization of alkyl sorbates in 100% 1,4-addition manner, furnishing polymers with predicted molecular weight (Mw up to 56.6 kg mol-1 ) and narrow molecular weight distribution (D as low as 1.12). Furthermore, topology analysis shows that NHC1/B(C6 F5 )3  LP produce PMS possessing cyclic structure.

Single-Step Expeditious Synthesis of Diblock Copolymers with Different Morphologies by Lewis Pair Polymerization-Induced Self-Assembly.

Lewis pair polymerization has demonstrated its unique advantages and powerful capability in polymer synthesis. Here we employ strong nucleophilic N-heterocyclic olefin (NHO) and bulky organoaluminum to construct a frustrated Lewis pair, which can realize the compounded sequence control (CSC) copolymerization and self-assembly the mixture of dimethylaminoethyl acrylate and fluoride-functionalized methacrylate into diblock copolymers (di-BCPs) nano-assemblies through polymerization-induced self-assembly in one-pot, single-step manner within minutes. These di-BCPs were characterized by 1 H and 13 C NMR, GPC, DSC, and TEM. By utilizing appropriate solvophilic block and solvophobic block, such Lewis pair polymerization-induced self-assembly strategy enables the expeditious, room-temperature synthesis of di-BCP nanoparticles with different morphologies, including spheres, worms, vesicles, and even fibers, thus suggesting the great application potential of such method in the future.

Lewis Pair Catalyzed Regioselective Polymerization of (E,E)-Alkyl Sorbates for the Synthesis of (AB)n Sequenced Polymers.

In this contribution, Lewis pairs (LPs) composed of N-heterocyclic olefins (NHOs) with different steric hindrance and nucleophilicity as Lewis bases (LBs) and Al-based compounds with comparable acidity but different steric hindrance as Lewis acids (LAs) were applied for 1,4-selective polymerization of (E,E)-methyl sorbate (MS) and (E,E)-ethyl sorbate (ES). The effects of steric hindrance, electron-donating ability, and acidity of LPs on MS and ES polymerization were systematically investigated. High catalytic activity and high initiation efficiency can be achieved, leading to the formation of PMS with 100 % 1,4-selectivity, tunable molecular weight (Mw up to 333 kg mol-1 ), and narrow molecular weight distribution (MWD). Block copolymerization of ES and methyl methacrylate (MMA) was also realized. Meanwhile, this system can be applied to other homologous conjugated diene substrates. Furthermore, simple chemical reactions can efficiently convert PMS to different polymers with strict (AB)n sequence structures, such as poly(sorbic acid), poly(propylene-alt-methyl acrylate), poly(propylene-alt-acrylic acid), poly(propylene-alt-allyl alcohol), and poly(ethylene-alt-2-butylene).

Highly efficient cyclotrimerization of isocyanates using N-heterocyclic olefins under bulk conditions.

With a catalyst loading as low as 0.005%, high to excellent yields of isocyanurates could be achieved from N-heterocyclic olefin mediated organocatalytic cyclotrimerization of a wide range of isocyanates under bulk conditions. Experimental details coupled with structural characterization of the key intermediates led to comprehensive mechanistic studies of cyclotrimerization.

Lewis pairs polymerization of polar vinyl monomers.

The globally increasing demands for polymer materials stimulate the significantly intense attention focused on the Lewis pair polymerization (LPP) of various polar vinyl monomers catalyzed by Lewis pairs (LPs) composed of Lewis acid (LA) and Lewis base (LB). According to the degree of interaction between LA and LB, LPs could be divided into classical Lewis adduct (CLA), interacting Lewis pair (ILP) and frustrated Lewis pair (FLP). Regulation of the Lewis basicity, Lewis acidity, and steric effects of these LPs has a significant impact on the polymer chain initiation, propagation and termination as well as chain transfer reaction during polymerization. Compared with other polymerization strategies, LPP has shown several unique advantages towards the polymerization of polar vinyl monomers such as high activity, control or livingness, mild conditions, and complete chemo- or regioselectivity. We will comprehensively review the recent advances achieved in the LPP of polar vinyl monomers according to the classification of the employed LPs based on different LAs, by highlighting the key polymerization results, polymerization mechanisms as well as the currently unmet challenges and the future research directions of LPP chemistry.

Living/controlled ring-opening (co)polymerization of lactones by Al-based catalysts with different sidearms.

It remains a challenging task to synthesize well-defined multi-block copolymers through the controlled/living ring-opening polymerization (ROP) of lactones without transesterification, the most common side reaction occurring during copolymerization. A series of Al-based complexes with different sidearms were prepared for living ROP of lactones such as ε-caprolactone (ε-CL) and δ-valerolactone (δ-VL) in the presence of BnOH at room temperature (RT), affording medium to high molecular weight (MW) linear polyesters with Mw up to 303 kg mol-1 and narrow molecular weight distributions (MWD, D as low as 1.12). The coordination-insertion polymerization mechanism was proposed based on the combination of the detailed experimental data and polymerization kinetics. It should be noted that the sidearm plays a significant important role in the reactivity of these Al-based catalyst systems. More specifically, the Al2 system with a butyl substituent on the sidearm exhibited the highest polymerization activity and the Al5 system with the bulkiest sidearm showed the lowest one among the investigated catalysts. Moreover, the Al4 system with a pyridine group on the sidearm could effectively inhibit transesterification and maintain a well-defined block copolymer structure even after heating at 50 °C for 10 h, which could also be confirmed by chain-end analyses of the produced polymers with the MALDI-TOF MS measurement.

Silyl Ketene Acetals/B(C6F5)3 Lewis Pair-Catalyzed Living Group Transfer Polymerization of Renewable Cyclic Acrylic Monomers.

This work reveals the silyl ketene acetal (SKA)/B(C6F5)3 Lewis pair-catalyzed room-temperature group transfer polymerization (GTP) of polar acrylic monomers, including methyl linear methacrylate (MMA), and the biorenewable cyclic monomers γ-methyl-α-methylene-γ-butyrolactone (MMBL) and α-methylene-γ-butyrolactone (MBL) as well. The in situ NMR monitored reaction of SKA with B(C6F5)3 indicated the formation of Frustrated Lewis Pairs (FLPs), although it is sluggish for MMA polymerization, such a FLP system exhibits highly activity and living GTP of MMBL and MBL. Detailed investigations, including the characterization of key reaction intermediates, polymerization kinetics and polymer structures have led to a polymerization mechanism, in which the polymerization is initiated with an intermolecular Michael addition of the ester enolate group of SKA to the vinyl group of B(C6F5)3-activated monomer, while the silyl group is transferred to the carbonyl group of the B(C6F5)3-activated monomer to generate the single-monomer-addition species or the active propagating species; the coordinated B(C6F5)3 is released to the incoming monomer, followed by repeated intermolecular Michael additions in the subsequent propagation cycle. Such neutral SKA analogues are the real active species for the polymerization and are retained in the whole process as confirmed by experimental data and the chain-end analysis by matrix-assisted laser desorption/ionization time of flight mass spectroscopy (MALDI-TOF MS). Moreover, using this method, we have successfully synthesized well-defined PMMBL-b-PMBL, PMMBL-b-PMBL-b-PMMBL and random copolymers with the predicated molecular weights (Mn) and narrow molecular weight distribution (MWD).