Monomer Systems Research Articles

Norbornadiene-Quadricyclane Photoswitches with Enhanced Solar Spectrum Match.

Herein, we report monomeric and dimeric norbornadiene-quadricyclane molecular photoswitch systems intended for molecular solar thermal applications. A series of six new norbornadiene derivatives conjugated with benzothiadiazole as the acceptor unit and dithiafulvene as the donor unit were synthesized and fully characterized. The photoswitches were evaluated by experimentally and theoretically measuring optical absorption profiles and thermal conversion of quadricyclane to norbornadiene. Computational insight by density functional theory calculations at the M06-2X/def2-SVPD level of theory provided geometries, storage energies, UV-vis absorption spectra, and HOMO-LUMO levels that are used to describe the function of the molecular systems. The studied molecules exhibit absorption onset ranging from 416 nm to 595 nm due to a systemic change in their donor-acceptor character. This approach was advantageous due to the introduction of benzothiadiazole and the dimeric nature of molecular structures. The best-performing system has a half-life of 3 days with quantum yields over 50 %.

Fast and Selective Main-Chain Scission of Vinyl Polymers Using the Domino Reaction in the Alternating Sequence for Transesterification.

This communication reports on vinyl polymers capable of selective and fast main-chain scission (MCS). The trick is the domino reaction in an alternating sequence of methyl 2-(trimethylsiloxymethyl)acrylate and 5,6-benzo-2-methylene-1,3-dioxepane, a cyclic ketene acetal for radical ring-opening polymerization. Removal of the trimethylsilyl group using Bu4N+·F- readily led to MCS via irreversible transesterification of the ester backbone, affording a five-membered lactone fragment. The molar mass decreased drastically within 5 min, and no side reactions were observed. Control experiments suggest that the formation of a five-membered ring via a domino reaction is critical for fast and selective MCS. The terpolymers with methyl methacrylate and styrene also exhibited a large decrease in molar mass within 5 min. In addition, MCS was also observed for the heterogeneous reaction system in acidic aqueous media; treatment of the binary copolymer in a 50 wt % acetic acid solution resulted in a significant decrease in molar mass after 30 min. These results suggest efficient construction of degradable sites using a binary monomer system corresponding to the pendant trigger and ester backbone. Because this molecular design using a binary monomer system provides selective and fast MCS for terpolymers containing other vinyl monomers, it can provide various degradable vinyl polymers.

Scaling the polymerization of polyaldehydes through continuous flow synthesis

A plug flow reactor was constructed to scale the synthesis of metastable, phthalaldehyde-based polymers to achieve production rates of 1–2 kg per day. The flow-induced mixing and in-line polymerization quench and precipitation sequences resulted in improved polymer purity and long-term stability compared to the same materials made from a conventional batch process. Cryogenic rheology was used to probe the complex fluid dynamics encountered during the polymerization of PPA homopolymers. It is envisioned that this continuous flow manufacturing approach could be extended to other low ceiling temperature or aldehyde monomer systems to help implement and support a plastic circular economy.Graphical abstract

Core-Tunable Dendritic Polymer: A Folate-Guided Theranostic Nanoplatform for Drug Delivery Applications.

Clinical application of anticancer drugs is mostly limited due to their hydrophobic nature, which often results in lower bioavailability and lesser retention in systemic circulation. Despite extensive research on the development of targeted drug delivery systems for cancer treatment, delivery of hydrophobic therapeutic drugs to tumor cells remains a major challenge in the field. To address these concerns, we have precisely engineered a new hyperbranched polymer for the targeted delivery of hydrophobic drugs by using a malonic acid-based A2B monomer and 1,6-hexanediol. The choice of monomer systems in our design allows for the formation of higher molecular weight polymers with hydrophobic cavities for the efficient encapsulation of therapeutic drugs that exhibit poor water solubility. Using several experimental techniques such as NMR, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier transform-infrared (FT-IR), and gel permeation chromatography (GPC), the synthesized polymer was characterized, which indicated its dendritic structure, thermal stability, and amorphous nature, making it suitable as a drug delivery system. Following characterizations, theranostic nanoplatforms were formulated using a one-pot solvent diffusion method to coencapsulate hydrophobic drugs, BQU57 and doxorubicin. To achieve targeted delivery of loaded therapeutic drugs in A549 cancer cells, the surface of the polymeric nanoparticle was conjugated with folic acid. The therapeutic efficacy of the delivery system was determined by various cell-based in vitro experiments, including cytotoxicity, cell internalizations, reactive oxygen species (ROS), apoptosis, migration, and comet assays. Overall, findings from this study indicate that the synthesized dendritic polymer is a promising carrier for hydrophobic anticancer drugs with higher biocompatibility, stability, and therapeutic efficacy for applications in cancer therapy.

A comparative study on the mechanical and antibacterial properties of BPA-free dental resin composites

ObjectiveThe commonly used base monomer utilized in resinous commercial dental restorative products is bis-GMA which is derived from bisphenol-A (BPA) - a well-known compound which may disrupt endocrine functions. To address concerns about its leaching into the oral environment and to optimize the quality of dental composites, a BPA-free alternative base monomer, fluorinated urethane dimethacrylate (FUDMA), was designed by modifying a UDMA monomer system. MethodsNine groups of composites were prepared by mixing the base monomers and TEGDMA in a ratio of 70/30 wt% to which were added silanized glass particles (mean diameter: 0.7 µm) in 3 different volume fractions (40, 45, and 50 vol%). Bis-GMA and UDMA base monomers were used as control groups in the same ratios. Various properties including degree of conversion (DC), flexural strength (FS) and flexural modulus (FM), water sorption (WS), solubility (SL), surface hardness and roughness, and initial adhesion property against S.mutans were investigated. One-way analysis of variance followed by Bonferroni test at α = 0.05 was used to analyze the results. ResultsA significant difference in FS between FUDMA-based composite with 40 vol% filler (120.3 ± 10.4 MPa) and Bis-GMA-based composite with the same filler fraction (105.8 ± 10.0 MPa) was observed but there was no significant difference among other groups. The UDMA based group exhibited the highest WS (1.3 ± 0.3 %). Bis-GMA showed greater initial bacterial adhesion but was not statistically different from the other groups (p = 0.082). SignificanceFUDMA-based resin composites exhibit comparable mechanical and bacterial adhesion properties compared with Bis-GMA and UDMA-based composites. The FUDMA composites show positive outcomes indicating they could be used as substitute composites to Bis-GMA-based composites.

Leveraging Electron Push-Pull Effect for Catalytic Polymerization and Degradation of a Cyclobutane Monomer System.

Ring-opening polymerization (ROP) offers a striking solution to solve problems encountered in step-growth condensation polymerization, including precise control over molecular weight, molecular weight distribution, and topology. This has inspired our interest in ROP of cycloalkanes with an ultimate goal to rethink polyolefins, which clearly poses a number of challenges. Practicality of ROP of cycloalkanes is actually limited by their low polymerizability and elusive mechanisms which arise from significantly varied ring size and non-polar C-C bonds in monomers. In this work, by using Lewis acid/Brønsted base/C(sp3)-H initiator system previously developed in our laboratory, we focus on cyclobutanes and explore the positional and electronic effects of substituents on the ring, namely electron push-pull effect, in promoting controlled polymerization to afford densely functionalized poly(cyclobutanes), as well as catalytic degradation of obtained polymers for upcycling. More importantly, experiments and DFT calculations unveil considerable population of Lewis-acid-induced thermostabilized 1,4-zwitterions, which distinguish cyclobutanes from cyclopropanes and others. All these findings would shed light on catalytic synthesis and degradation of saturated all-carbon main-chain polymers, as well as small molecule transformations of cyclobutanes.

Leveraging Electron Push‐Pull Effect for Catalytic Polymerization and Degradation of a Cyclobutane Monomer System

AbstractRing‐opening polymerization (ROP) offers a striking solution to solve problems encountered in step‐growth condensation polymerization, including precise control over molecular weight, molecular weight distribution, and topology. This has inspired our interest in ROP of cycloalkanes with an ultimate goal to rethink polyolefins, which clearly poses a number of challenges. Practicality of ROP of cycloalkanes is actually limited by their low polymerizability and elusive mechanisms which arise from significantly varied ring size and non‐polar C−C bonds in monomers. In this work, by using Lewis acid/Brønsted base/C(sp3)‐H initiator system previously developed in our laboratory, we focus on cyclobutanes and explore the positional and electronic effects of substituents on the ring, namely electron push‐pull effect, in promoting controlled polymerization to afford densely functionalized poly(cyclobutanes), as well as catalytic degradation of obtained polymers for upcycling. More importantly, experiments and DFT calculations unveil considerable population of Lewis‐acid‐induced thermostabilized 1,4‐zwitterions, which distinguish cyclobutanes from cyclopropanes and others. All these findings would shed light on catalytic synthesis and degradation of saturated all‐carbon main‐chain polymers, as well as small molecule transformations of cyclobutanes.

Thiol-acrylate based polymer wall-stabilized cholesteric liquid crystal enables flexible bistable states light shutter

Bistable-states mode light shutter boost the applications in smart windows or transparent displays due to the significant energy efficiency. In this study, polymer wall-stabilized cholesteric liquid crystals (PWSCLC) with regular microstructures and outstanding electric field frequency-controlled bistability were prepared using non-liquid crystalline thiol-acrylate monomers system and polymerization under a photomask. The addition and proportion of the thiol monomer played an essential role in the morphology structures of the polymer network. Thanks to the effectively modulation of polymerization speed, periodic regular polymer wall morphology was obtained, which improved the transmittance and the long-term stability. Under a suitable voltage, repeatedly reversible switch between transparent and scattering states was successfully realized via frequency regulation, and both states remained stable for more than 10 days after removing electric field. Remarkably, the mechanical strength of the PSWCLC film was significantly improved due to the relatively high polymer concentration, proving feasibility for the flexible applications and large-scale preparation.

Encapsulation of Cadmium-Free InP-based Quantum Dots in Cross-Linked Core-Shell Microparticles via Coaxial Electrospraying.

Quantum dots (QDs) are inorganic semiconductornanocrystalscapable of emitting light. The current major challenge lies in theuseofheavy metals, which are known to be highly toxic to humans and pose significant environmental risks. Researchers have turned to indium (In) as a promising option for more environmentally benign QDs, specifically indium phosphide (InP). A significant obstacle remains in sustaining the long-term photostability of InP-based QDs when exposed to the environment. To tackle this, electrospraying is used in this work to protect indium phosphide/zinc selenide/zinc sulfide (InP/ZnSe/ZnS) QDs by embedding them within polymer core-shell microparticles of poly[(lauryl methacrylate)-co-(ethylene glycol dimethacrylate)]/poly(methyl methacrylate)(poly(LMA-co-EGDMA)/PMMA). During the flight of droplets, the liquid monomer core of LMA and EGDMA with QDs is encapsulated by the solid shell of PMMA formed due to solvent evaporation, resulting in a liquid-core/solid-shell particle structure. After that, the captured core of monomers is polymerized into a cross-linked polymer with the embedded QDs via a thermal initiation. They demonstrate how a successful core-shell particle formation is achieved to produce structures for initially liquid monomer systems via coaxial electrospraying that are used for cross-linked polymers, which are of major interest for the encapsulation of InP-based QDs for generally improved photostability over pristineQDs.

Ultrahighly Li-selective nanofiltration membranes prepared via tailored interfacial polymerization

Nanofiltration (NF) membrane-based separation has gained significant attention as an efficient technology for recovering lithium (Li) from salt-lake brines. However, many previously developed NF membranes are not commercially feasible because they lack sufficient Li selectivity and require the use of new monomers/chemicals or complicated fabrication processes. Herein, we propose a commercially viable method to fabricate ultrahighly Li-selective polyamide (PA) membranes by carefully tailoring a conventional interfacial polymerization process using an established piperazine (PIP)/trimesoyl chloride monomer system. The use of excess PIP endowed the fabricated membrane with enhanced PA crosslinking density and a positive surface charge, reinforcing both its size and Donnan exclusion mechanisms. Furthermore, the addition of benzyltributylammonium chloride, a cationic surfactant, to the PIP solution effectively improved the water permeance of the membrane without impairing its magnesium ion (Mg2+) rejection by loosening its PA network while enhancing its positive surface charge. Consequently, our tailor-made PA membranes with the proper pore structures and strong positive surface charges exhibited ultrahigh Li+/Mg2+ selectivity of up to 150 (under single-salt conditions) and 887 (under mixed-salt conditions), significantly outperforming commercial and other reported laboratory-made NF membranes. Our strategy provides a facile and effective means to manufacture Li-selective membranes with high commercial viability.

Effects of Activation Barriers on Quenching to Stabilize Prebiotic Chemical Systems.

We have previously shown in model studies that rapid quenches of systems of monomers interacting to form polymer chains can fix nonequilibrium chemistries with some lifelike properties. We suggested that such quenching processes might have occurred at very high rates on early Earth, giving an efficient mechanism for natural sorting through enormous numbers of nonequilibrium chemistries from which the most lifelike ones could be naturally selected. However, the model used for these studies did not take account of activation barriers to polymer scission (peptide bond hydrolysis in the case of proteins). Such barriers are known to exist and are expected to enhance the quenching effect. Here, we introduce a modified model which takes activation barriers into account and we compare the results to data from experiments on quenched systems of amino acids. We find that the model results turn out to be sensitive to the width of the distribution of barrier heights but quite insensitive to its average value. The results of the new model are in significantly better agreement with the experiments than those found using our previous model. The new parametrization of the model only requires one new parameter and the parametrization is more physical than the previous one, providing a chemical interpretation of the parameter p in our previous models. Within the model, a characteristic temperature Tc emerges such that if the temperature of the hot stage is above Tc and the temperature of the cold stage is below it, then the 'freezing out', in a quench, of a disequilibrium ensemble of long polymers is expected. We discuss the possible relevance of this to models of the origin of life in emissions from deep ocean rifts.

Epoxy-Acrylic Polymer In-Situ Filling Cell Lumen and Bonding Cell Wall for Wood Reinforcement and Stabilization.

Under a global carbon-neutralizing environment, renewable wood is a viable alternative to non-renewable resources due to its abundance and high specific strength. However, fast-growing wood is hard to be applied extensively due to low mechanical strength and poor dimensional stability and durability. In this study, epoxy-acrylic resin-modified wood was prepared by forming a functional monomer system with three monomers [glycidyl methacrylate (GMA), maleic anhydride (MAN), and polyethylene glycol-200-dimethylacrylic acid (PEGDMA)] and filling into the wood cell cavity. The results showed that in the case of an optimal monomer system of nGMA:nPEGDMA = 20:1 and an optimal MAN dosage of 6%, the conversion rate of monomers reached 98.01%, the cell cavity was evenly filled by the polymer, with the cell wall chemically bonded. Thus, a bonding strength of as high as 1.13 MPa, a bending strength of 112.6 MPa and an impact toughness of 74.85 KJ/m2 were applied to the modified wood, which presented excellent dimensional stability (720 h water absorption: 26%, and volume expansion ratio: 5.04%) and rot resistance (loss rates from white rot and brown rot: 3.05% and 0.67%). Additionally, polymer-modified wood also exhibited excellent wear resistance and heat stability. This study reports a novel approach for building new environmentally friendly wood with high strength and toughness and good structural stability and durability.

Strong and Durable Wood Designed by Cell Wall Bulking Combined with Cell Lumen Filling.

Traditional wood-polymer composite (WPC) based on the in situ polymerization of ethylene unsaturated monomers in the cellular cavity of wood is significant for the high-value-added utilization of low-quality wood. However, this type of WPC has the problems of volatile monomers, low conversion rates, odor residue, and poor compatibility between the polymer and wood interface, which hinder its promotion and application. In this study, a two-step process of cell wall bulking in combination with cell lumen filling was prepared to modify wood using Maleic anhydride (MAN) as the bulking agent and GMA-EGDMA (molar ratio 2:1) as the active monomer system. The results indicate that the modulus of rupture (MOR) (125.19 ± 8.41 MPa), compressive strength (116.38 ± 7.69 MPa), impact toughness (55.4 ± 2.95 KJ m-2), and hardness (6187 ± 273 N) of the bulking-filling wood composite materials were improved by 54%, 56%, 36%, and 66%, respectively, compared with those of poplar wood. These properties were superior to those of the traditional styrene (PSt)-WPC and even exceeded the performance of Xylosma congesta (Lour.) Merr, a high-quality wood from northeast China. Meanwhile, the mass loss of wood composite materials with bulking-filling treatment was only 2.35 ± 0.05%, and the internal structure remained intact, presenting excellent decay resistance. Additionally, the treatment also significantly improved the thermal and dimensional stability of the wood composites. This study provides a theoretical basis and guidance for realizing the high-value-added application of low-quality wood and the preparation of highly durable wood-based composites.

Polymerization of renewable itaconic acid in deep eutectic monomers: Effect of the quaternary ammonium cation structure

A systematic investigation has been carried out on the synthesis of poly(itaconic acid) (PIA) in Deep Eutectic Monomer (DEM) systems, composed of bio-derived itaconic acid (IA) and quaternary ammonium chlorides (QCl) varying in their cation structure. The physicochemical properties including density, viscosity, Kamlet-Taft parameters and polarity as Nile Red transition energy of DEMs supported with spectroscopic studies (FT-IR, 1H and 13C NMR) are reported. It was observed that cation structure of the ammonium chloride impacts on the physicochemical properties and radical polymerization of DEMs. More notably, the correlations between the Kamlet-Taft hydrogen bonding accepting ability (β) of the DEMs and both IA polymerization rate and the molecular weight of the synthesized PIA were found. These findings provided theoretical guidance on designing DEMs tailored to specific polymerization process.

Integration of knee-shaped self-written waveguides between optical fibers by direct illumination and tip to tip coupling

Optical transmission efficiency of self-written polymer waveguide has been investigated. The polymer couplers were fabricated from a photopolymerizable monomer system by direct illumination from two pre-aligned single mode fibers, and by butt coupling of two extended long polymer tips at the end of fibers. Regarding direct illumination, the writing beams exhibit quasi-solitonic behavior and both show a tendency to attract each other to be merged at the middle point where the droplet deposited between the aligned fiber. Optical transmission gives insertion loss of 4.3 dB and 5.7 dB with total knee angles of (5° and 10°) respectively. Polymer bridges with larger deviation angles were not formed, since the induced beams were not merged properly to form a decent waveguide. Therefore, long polymer tips were fabricated separately and then they were butt coupled at different knee-angles. Optical transmission efficiency was measured over broadband from Ultraviolet to Infrared (UV-IR). In the butt-coupling approach average loss of 1.7 dB, 5.4 dB, 8.6 dB, 10.4 dB and 14.6 dB at measured wavelength 1550 nm were obtained for 300 μm- 300 μm coupling tips corresponding to knee-angles of (0°,5°,10°,15°, and 20°) respectively.

The Preparation of Electrolyte Hydrogels with the Water Solubilization of Polybenzoxazine.

Polybenzoxazine (PBZ) exhibits excellent heat resistance, and PBZ derivatives have been designed and synthesized to achieve high performance. However, the application range of PBZ is limited by the strong interactions between molecular chains and its low solubility in organic solvents, thereby limiting its processability. This study focused on the benzoxazine structure as the molecular backbone of new hydrogel materials that can be applied as electrolyte materials and prepared functional gel materials. Here, we prepared hydrogels by water-solubilizing PBZ derivatives, which typically exhibit low solubility in organic solvents. Although studies on the hydrophilization of PBZ and its complexation with hydrophilic polymers have been conducted, no studies have been performed on the hydrogelation of PBZ. First, the phenol in the organic solvent-insoluble PBZ thin film obtained after the thermal ring-opening polymerization of the monomer was transformed into sodium phenoxide by immersion in a NaOH aqueous solution to water-solubilize it and obtain a hydrogel thin film. Although the hydrogel thin film exhibited low mechanical strength, a free-standing hydrogel film with improved strength was obtained through the double network gelation method with an acrylamide monomer system. The physical properties of the polymer composite hydrogel thin film were evaluated. The ionic conductivity of the hydrogel thin films was in the order of 10-4 S cm-1, indicating the potential of PBZ as an electrolyte hydrogel material. However, improving its ionic conductivity will be undertaken in future studies.

Dendritic Glycerol-Cholesterol Amphiphiles as Drug Delivery Systems: A Comparison between Monomeric and Polymeric Structures.

The application of micelles as drug delivery systems has gained a great deal of attention as a means to overcome the current several drawbacks present in conventional cancer treatments. In this work, we highlight the comparison of polymeric and monomeric amphiphilic systems with a similar hydrophilic-lipophilic balance (HLB) in terms of their biocompatibility, aggregation behavior in aqueous solution, and potential in solubilizing hydrophobic compounds. The polymeric system consists of non-ionic polymeric amphiphiles synthesized via sequential RAFT polymerization of polyglycerol first-generation [G1] dendron methacrylate and cholesterol methacrylate to obtain poly(G1-polyglycerol dendron methacrylate)-block-poly(cholesterol methacrylate) (pG1MA-b-pCMA). The monomeric system is a polyglycerol second-generation [G2] dendron end-capped to a cholesterol unit. Both amphiphiles form spherical micellar aggregations in aqueous solution, with differences in size and the morphology in which hydrophobic molecules can be encapsulated. The polymeric and monomeric micelles showed a low critical micelle concentration (CMC) of 0.2 and 17 μg/mL, respectively. The results of our cytotoxicity assays showed that the polymeric system has significantly higher cell viability compared to that of the monomeric amphiphiles. The polymeric micelles were implemented as drug delivery systems by encapsulation of the hydrophobic small molecule doxorubicin, achieving a loading capacity of 4%. In summary, the results of this study reveal that using cholesterol as a building block for polymer synthesis is a promising method of preparation for efficient drug delivery systems while improving the cell viability of monomeric cholesterol.

Unraveling Triplet Formation Mechanisms in Acenothiophene Chromophores.

The evolution of molecular platforms for singlet fission (SF) chromophores has fueled the quest for new compounds capable of generating triplets quantitatively at fast time scales. As the exploration of molecular motifs for SF has diversified, a key challenge has emerged in identifying when the criteria for SF have been satisfied. Here, we show how covalently bound molecular dimers uniquely provide a set of characteristic optical markers that can be used to distinguish triplet pair formation from processes that generate an individual triplet. These markers are contained within (i) triplet charge-transfer excited state absorption features, (ii) kinetic signatures of triplet-triplet annihilation processes, and (iii) the modulation of triplet formation rates using bridging moieties between chromophores. Our assignments are verified by time-resolved electron paramagnetic resonance (EPR) measurements, which directly identify triplet pairs by their electron spin and polarization patterns. We apply these diagnostic criteria to dimers of acenothiophene derivatives in solution that were recently reported to undergo efficient intermolecular SF in condensed media. While the electronic structure of these heteroatom-containing chromophores can be broadly tuned, the effect of their enhanced spin-orbit coupling and low-energy nonbonding orbitals on their SF dynamics has not been fully determined. We find that SF is fast and efficient in tetracenothiophene but that anthradithiophene exhibits fast intersystem crossing due to modifications of the singlet and triplet excited state energies upon functionalization of the heterocycle. We conclude that it is not sufficient to assign SF based on comparisons of the triplet formation kinetics between monomer and multichromophore systems.

Exploring pulse mitigation in heterogeneous granular metamaterials

Recognizing the need for effective control of vibration and sound propagation in various industries, this study investigates the potential of designing heterogeneous granular networks for vibroacoustic transmission mitigation. It introduces new models of granular systems: decorated, stepped, and tapered 2-level branching structures. The research assesses changes in particle size (5–10 mm radii) and material properties (density and Young's Modulus) to create finely-tuned composites that significantly modulate pulse waves. The discrete element method predicts wave propagation in these granular metamaterials, comparing monodispersed chains, conventional chain networks, and the proposed heterogeneous structures. Their pulse diffusion capacity is evaluated, showing how collective responses can be adjusted by altering physical parameters like particle size and composition. Preliminary findings underscore the utility of these configurations in advancing the development of elastic and acoustic metamaterials, demonstrating a peak amplitude reduction more than five times greater than an equivalent monomer system. With versatility across a wide frequency range, these metamaterials could pioneer a new direction in impact mitigation.

Synthesis and applications of a Y‐inimer with two orthogonal controlled free radical polymerization initiators

AbstractWe report the synthesis of a Y‐shaped inimer that contains two orthogonal initiators for ATRP and NMP. The inimer is synthesized through a one‐pot multi‐component reaction that vastly simplifies the typically cumbersome synthesis of similar compounds. The Y‐inimer has the versatility to be homopolymerized into a backbone for A/B Janus bottlebrush synthesis or copolymerized with glycidyl methacrylate (GMA) and cross‐linked into an ultra‐thin coating for mixed A/B brush growth from planar surfaces. Importantly, the Y‐shaped nature of the inimer ensures growth of A and B brushes are consistently in a 1:1 ratio. We demonstrate the application of the Y‐inimer in the synthesis of a PMMA/PS Janus bottlebrush as well as two different mixed A/B polymer brushes, one with the ability to microphase separate, and a second mixed polyelectrolyte brush with opposite charges. The inimer is compatible with various A/B monomer systems and offers a universal approach to the “grafting‐from” polymerization of dual vinyl polymer side chains. This study provides a unique way of utilizing multi‐component reactions in polymer chemistry to access complex functional architectures.