Difunctional Monomers Research Articles

Radiation-induced cross-linking polymerization: Recent developments for coating and composite applications

Abstract Radiation-initiated cross-linking polymerization of multifunctional monomers is an attractive method used for drying solvent-free liquid coatings, inks, and adhesive as well as for fabricating high-performance composite materials. The method offers a number of advantages compared with thermal curing processes. Free radical and cationic polymerization have been investigated in detail over the past years. A high degree of control over curing kinetics and material properties can be exerted by adjusting the composition of matrix precursors and/or by acting on the process parameters (overall dose, dose rate, dose increment, initial temperature). Several pending issues that require deeper investigations are as follows: (i) the fast polymerization of multifunctional monomers generates micro-heterogeneous networks requiring detailed characterization and quantification by microscopic, thermal, and spectroscopic analyses; (ii) the adhesion and surface properties of radiation-cured coatings are quite sensitive to processing parameters; and (iii) significant enhancement of the toughness is needed to qualify potential matrices based on simple difunctional monomers for high-performance composites. Recent results show that the bulk and surface properties of radiation-cured materials can be improved by advanced formulation of matrix precursors and by a parametric study of the processing factors.

Enhanced Electromechanical Output in Liquid Crystal Elastomers Prepared by Thiol‐ene Photopolymerization

AbstractThe electrically‐directed, isothermal response of liquid crystal elastomers (LCEs) to an applied electric field is a compelling approach to realize spatially tailorable, sequence‐controllable, and high‐frequency deformation. The electromechanical response is facilitated by coating aligned LCEs with compliant electrodes. Upon application of an electric field, the electrodes attract and generate Maxwell stress. The directional difference in moduli for aligned LCEs produces directional deformation of the material and does not require mechanical bias or framing. Here, LCEs prepared from a newly reported thiol‐ene reaction are explored as DEAs with improved mechanical and dielectric properties. This report details that incorporating a difunctional liquid crystalline monomer composed of allyl ether functional groups reduces Young's modulus, increases the dielectric constant, and improves cyclic recovery compared to an analogous LCE prepared by thiol‐ene polymerization. Electrically‐induced, isothermal deformation of as much as 30% strain is reported. The facile chemistry and enhanced electromechanical response reported here may enable the functional integration of LCEs in applications such as robotics.

Multifunctional Separator for Li-Ion Batteries Enabling Acid Scavenging and Long Cyclability

The membrane separator is indispensable in lithium-ion batteries (LIBs), electrically isolating the electrodes while hosting liquid electrolyte for facile ion transport. Microporous polyolefin materials, consisting of polyethylene (PE) and/or polypropylene (PP), represent the state-of-the art in separator technology. They offer sufficient mechanical properties, chemical inertness, effective pore sizes <100 nm, porosity ranging from 30-78%, and relatively low costs. However, safety issues associated with thermal shrinkage above 70℃ and poor electrolyte wettability are significant limitations. Replacing these conventional polyolefin separators with multifunctional microporous membranes provides opportunities to address these limitations and other challenges in lithium ion batteries. LiMn2O4 cathodes, for example, attract widespread interest due to the abundance and low cost of Mn, especially in comparison to Co, and reasonable energy densities. However, these cathodes do not provide the calendar and cycle life of the layered oxide cathodes, especially at elevated temperatures (>50°C), due to dissolution of Mn and structural instabilities.1 One of the underlying reasons is the presence of HF in commercial LiPF6-carbonate electrolytes; HF will attack and dissolve the Mn, leading to severe capacity decay, as shown in Figure 1.2 Chemically active multifunctional separator can scavenge HF from the electrolyte, improving the stability of LiMn2O4, but they must be fabricated by low cost, scalable processes without compromising other separator properties.Herein, a multifunctional separator will be described, wherein poly(4-vinylpyridine) (P4VP) is incorporated into separators prepared by polymerization induced phase separation (PIPS). In PIPS, a homogenous solution of difunctional monomers and porogen is polymerized; the difunctional monomers polymerize and crosslink while the porogen phase separates into nanoscale domains. Our previous study employed PIPS to prepare highly porous and thermally stable separators, exhibiting comparable ion transport to conventional Celgard 2500 Polypropylene (PP) separators and negligible thermal shrinkage at 150 °C (digital images in Figure 1).3 Moreover, when incorporated into LIB half cells, these separators enable better electrochemical performance than Celgard 2500 separators due to their reduced thicknesses and superior electrolyte uptake. In the study, P4VP is integrated with the PIPS process to scavenge both HF and PF5 (precursor to HF) through acid-base interactions. A thin layer of P4VP coating was fabricated via initiated chemical vapor deposition (iCVD) process and makes full use of high porosity of separators due to the conformal nature of the coating, increasing the surface area to scavenge the acids. The P4VP-coated PIPS separator enables better capacity retention in Mn-based cathode materials, relative to cells using inert polyolefin separators. The scavenged concentration of HF and transition metal will be compared to validate the HF scavenging property. Post-mortem analysis of the Li anode also confirms the suppression of Mn dissolution and deposition on the anode at elevated temperatures (50°C).

ROS-Responsive 4D Printable Acrylic Thioether-Based Hydrogels for Smart Drug Release.

Reactive oxygen species (ROS) play a key role in several biological functions like regulating cell survival and signaling; however, their effect can range from beneficial to nondesirable oxidative stress when they are overproduced causing inflammation or cancer diseases. Thus, the design of tailor-made ROS-responsive polymers offers the possibility of engineering hydrogels for target therapies. In this work, we developed thioether-based ROS-responsive difunctional monomers from ethylene glycol/thioether acrylate (EGnSA) with different lengths of the EGn chain (n = 1, 2, 3) by the thiol-Michael addition click reaction. The presence of acrylate groups allowed their photopolymerization by UV light, while the thioether groups conferred ROS-responsive properties. As a result, smart PEGnSA hydrogels were obtained, which could be processed by four-dimensional (4D) printing. The mechanical properties of the hydrogels were determined by rheology, pointing out a decrease of the elastic modulus (G') with the length of the EG segment. To enhance the stability of the hydrogels after swelling, the EGnSA monomers were copolymerized with a polar monomer, 2-hydroxyethyl acrylate (HEA), leading to P[(EGnSA)x-co-HEAy] with improved compatibility in aqueous media, making it a less brittle material. Swelling properties of the hydrogels increased in the presence of hydrogen peroxide, a kind of ROS, reaching values of ≈130% for P[(EG3SA)7-co-HEA93] which confirms the stimuli-responsive properties. Then, the P[(EG3SA)x-co-HEAy] hydrogels were employed as matrixes for the encapsulation of a chemotherapeutic drug, 5-fluorouracil (5FU), which showed sustained release over time modulated by the presence of H2O2. Finally, the effect of the 5-FU release from P[(EG3SA)x-co-HEAy] hydrogels was tested in vitro with melanoma cancer cells B16F10, pointing out B16F10 growth inhibition values in the range of 40-60% modulated by the EG3SA percentage and the presence or absence of ROS agents, thus confirming their excellent ROS-responsive properties for the treatment of localized pathologies.

Waxes from Long-Chain Aliphatic Difunctional Monomers.

Petrochemical polyethylene waxes (Mn = 800-8000 g/mol for commercial Ziegler waxes) as additives, lubricants, and release agents are essential to numerous products and production processes. The biodegradability of this class of compounds when unintentionally released to the environment is molar mass dependent and subject to ongoing discussions, and alternatives to conventional polyethylene waxes are desirable. By employing bottom-up and top-down approaches, that is nonstoichiometric A2 + B2 polycondensation and chain scission, respectively, linear waxes with multiple in-chain ester groups as biodegradation break points could be obtained. Specifically, waxes with 12,12 (WLE-12,12, WLE = waxes linear ester) and 2,18 (WLE-2,18) carbon atom linear ester repeat unit motifs were accessible over a wide range of molar masses (Mn ≈ 600-10 000 g/mol). In addition to the molar mass, the type of end group functionality (i.e., methyl ester, hydroxy, or carboxylic acid end groups) significantly impacts the thermal properties of the waxes, with higher melting points observed for carboxylic acid end groups (e.g., Tm = 83 °C for carboxylic acid-terminated WLE-12,12 with Mn,NMR = 1900 g/mol, Tm = 92 °C for WLE-2,18 with Mn,NMR = 2200 g/mol). A HDPE-like orthorhombic crystalline structure and rheological properties comparable to a commercial polyethylene wax suggest WLE-12,12 and WLE-2,18 are viable biodegradable and biosourced alternatives to conventional, petrochemical polyethylene waxes.

Multilayer, Broadband Infrared Reflectors Based on the Photoinduced Preparation of Cholesteric Liquid Crystal Polymers.

This paper focuses on preparing broadband reflective liquid crystal films through the diffusion of monofunctional and bifunctional monomers in a photoinduced trilayer system. By combining the hydrophilic and hydrophobic liquid crystal glass surface treatment technologies, the polymer network of polymer-stabilized cholesteric liquid crystal (PSCLC) itself serves as a diffusion channel to form a trilayer cholesteric liquid crystal composite system containing bifunctional monomers, a nematic liquid crystal composite system, and a cholesteric liquid crystal composite system containing monofunctional monomers. Utilizing the difference in the polymerization rates of monofunctional and difunctional polymerizable monomers, the monomers and chiral compounds diffuse relative to each other, so that the liquid crystal pitch exhibits a gradient distribution, and the broadened reflective width can reach up to 1570 nm. There is no doubt that new and improved processes and technologies offer important possibilities for preparing and applying PSCLC films.

Synthesis of Crosslinked Microparticles Based on Glycidyl Methacrylate and N‐Vinylimidazole

AbstractIn this study, suspension polymerization technique is used to obtain 3D porous networks based on two monofunctional monomers (glycidyl methacrylate and N‐vinylimidazole) and one of the following difunctional monomers known as crosslinking agents: mono‐, di‐, and triethylene glycol dimethacrylate or divinylbenzene. The influence of various operational parameters like: monomer molar ratio, amount and type of crosslinkers, composition of stabilization system, stirring speed, amount of porogenic agent on the reaction yield, surface morphologies, particle size distribution, and porous characteristics are investigated in order to find the optimal conditions for the synthesis of microparticles possessing the desired properties for further chemical modification. Crosslinked porous microparticles are structurally characterized by Fourier transform inrared (FTIR) spectroscopy, X‐ray photoelectron spectroscopy, and elemental analysis by determination of nitrogen and epoxy groups. The microparticle morphologies as a function of investigated parameters are revealed by scanning electron microscopy, whereas the porous structure is highlighted by mercury porosimetry and dynamic water vapor sorption methods. All the crosslinked networks exhibit porous structures with different surface morphologies and specific surface area values (1.15–48.32 m2 g−1) depending on the operational parameters. These microparticles can be considered precursors for the preparation of various functional polymeric materials.

Contribution of Dynamic Rheology Coupled to FTIR and Raman Spectroscopies to the Real-Time Shaping Ability of a Hyperbranched Polycarbosilane.

In the field of non-oxide ceramics, the polymer-derived ceramic (PDC) approach appears to be very promising, especially for obtaining easily shaped and homogeneous materials in terms of structure and composition. However, in order to reach a suitable form during the process, it is often necessary to study the rheology of preceramic polymers while they are modified during polymerisation or crosslinking reactions. Given this need in the understanding of the real-time rheology of macromolecules during their synthesis, a rheometer coupled with both an infrared spectrometer and a Raman probe is described as a powerful tool for monitoring in situ synthesised polycarbosilanes. Indeed, this original device allows one to control the viscosity of a hyberbranched polycarbosilane from defined difunctional and tetrafunctional monomers. Meanwhile, it links this evolution to structural modifications in the macromolecular structure (molar masses, dispersity and conformation), based on SEC-MALS analyses, synchronised by the monomer conversion determined by using Raman and infrared spectroscopies, a common denominator of the aforementioned instrumental platform.

Step-growth polymerization of supracolloidal chains from patchy micelles of diblock copolymers

HypothesisThe formation of supracolloidal chains from the patchy micelles of diblock copolymers bears a close resemblance to traditional step-growth polymerization of difunctional monomers in many aspects, including chain-length evolution, size distribution, and initial-concentration dependence. Thus, understanding the colloidal polymerization based on the step-growth mechanism can offer potential control over the formation of supracolloidal chains in terms of chain structure and reaction rate. ExperimentsWe analyzed the size evolution of supracolloidal chains of patchy micelles of PS-b-P4VP by investigating a large number of colloidal chains visualized in SEM images. We varied the initial concentration of patchy micelles to achieve a high degree of polymerization and a cyclic chain. To manipulate the polymerization rate, we also changed the ratio of water to DMF and adjusted the patch size by employing PS(25)-b-P4VP(7) and PS(145)-b-P4VP(40). FindingsWe confirmed the step-growth mechanism for the formation supracolloidal chains from patchy micelles of PS-b-P4VP. Based on this mechanism, we were able to achieve a high degree of polymerization early in the reaction by increasing the initial concentration and form cyclic chains by diluting the solution. We also accelerated colloidal polymerization by increasing the ratio of water to DMF in the solution and patch size by using PS-b-P4VP with a larger molecular weight.

Self-Accelerating Diels-Alder Reaction for Preparing Polymers of Intrinsic Microporosity.

It is a formidable challenge in polycondensation to simultaneously construct multiple covalent bonds to prepare double-stranded polymers of intrinsic microporosity (PIMs) with fused multicyclic linkages. To the best of our knowledge, this is the first study to develop a self-accelerating Diels-Alder reaction for successfully preparing double-stranded PIMs with fused multicyclic backbone structures. A self-accelerating Diels-Alder reaction was developed based on the [4+2] cycloaddition of sym-dibenzo-1,5-cyclooctadiene-3,7-diyne (DIBOD) and ortho-quinone compounds. In this reaction, the cycloaddition of ortho-quinone with the first alkyne of DIBOD activates the second alkyne, which reacts with ortho-quinone at a rate constant 192 times larger than that of the original alkyne. Using this self-accelerating reaction to polymerize DIBOD and spirocyclic/cyclic difunctional ortho-quinone monomers, a novel stoichiometric imbalance-promoted step-growth polymerization method was developed to prepare PIMs. The resultant PIMs possess intrinsic ultramicropores with pore sizes between 0.45 to 0.7 nm, high specific surface areas above 646 m2 g-1 , and good H2 separation performance.

In Situ Synthesis of Branched Block Copolymer Assemblies via RAFT Dispersion Polymerization Using Branched Macro‐RAFT Agents†

Comprehensive SummaryHere, we demonstrate the use of branched macromolecular reversible addition‐fragmentation chain transfer (macro‐RAFT) agents in RAFT dispersion polymerization, to access branched block copolymers as well as well‐defined branched block copolymer assemblies. Two types of branched macro‐RAFT agents were first synthesized by using either a monofunctional chain transfer monomer or a difunctional chain transfer monomer in RAFT polymerization, and subsequently utilized in RAFT dispersion polymerization. It was found that only branched macro‐RAFT agents synthesized from the difunctional chain transfer monomer could lead to colloidally stable assemblies with well‐defined morphologies. Reaction conditions including monomer concentration, degree of polymerization (DP) of the core‐forming block, and DP of the solvophilic segment on morphologies of branched block copolymer assemblies were investigated in detail. Size exclusion chromatography (SEC) analysis further confirmed the successful formation of branched block copolymers by using branched macro‐RAFT agents. This work on the synthesis of branched block copolymer assemblies by RAFT dispersion polymerization offers new opportunities for the rational design of polymer assemblies with well‐defined structures.

Molecular dynamics simulation of molecular network structure and mechanical properties of polymer matrix in PBT propellant

3,3-Bis(azidomethyl)oxetane (BAMO)/tetrahydrofuran (THF) copolymer (PBT) constitutes the polymer matrix of PBT solid propellant and influences the mechanical properties of the propellant. In this work, the molecular network structure of the PBT propellant matrix was constructed by molecular dynamics method, the influence of different component contents on the mechanical properties was studied, and the structure - mechanical properties relationship at the molecular level was established. The simulation results showed that changes in the content of crosslinker (TMP) and chain extender (DEG) had slight effects on Young's modulus. The tensile strength of the polymer matrix network was positively correlated with the molecular chain length and the number of cross-linking sites formed by TMP. When the isocyanate index R was less than 1, increasing the content of TMP crosslinker led to low conversion rate due to insufficient curing agent, thereby reducing the number of cross-linking sites and the strength of the system. When the isocyanate index R was less than 0.87, the increase of DEG content increased the chain length of the main chain and strengthened the system. Due to the competitive reaction with the curing agent, the difunctional (-OH) chain extender monomer showed stronger reactivity than the trifunctional crosslinker monomer, and the excess chain extender reduced the number of crosslinking sites, destroyed the crosslinking network structure and reduced the strength.

Cationic and radical polymerization using a boron–thienothiophene–triphenylamine based D–π–A type photosensitizer under white LED irradiation

A D–π–A type pull–push photosensitizer, possessing thieno[3,2-b]thiophene, triphenylamine and boron units, was synthesized and used in both free-radical and cationic photopolymerization using DPI salt under white light irritation.

Preparation of UV-curable PSAs by grafting isocyanate-terminated photoreactive monomers and the effect of the functionality of grafted monomers on the debonding properties on Si wafers.

Photoreactive pressure-sensitive adhesives (PSAs) were prepared by grafting mono- or difunctional photoreactive monomers onto acrylic PSA, and their adhesion properties were evaluated before and after ultraviolet (UV) curing for application as dicing tape. In this study, the NCO-terminated difunctional photoreactive monomer (NDPM) was newly synthesized and compared with 2-acryloxyloxyethyl isocyanate (AOI), a monofunctional monomer. The 180° peel strengths of pristine and photoreactive PSAs were similar before UV curing (1850-2030 gf/25 mm). After UV curing, the 180° peel strengths of the photoreactive PSAs decreased significantly and converged to nearly zero. When a UV dose of 200 mJ cm-2 was used, the 180° peel strength of 40% NDPM-grafted PSA decreased to 8.40 gf/25 mm, which was much lower than that of 40% AOI-grafted PSA (39.26 gf/25 mm). NDPM-grafted PSA also showed that its storage modulus shifted more to the upper right side of Chang's viscoelastic window than AOI-grafted PSA, and this is because NDPM provided a higher degree of crosslinking than AOI. Furthermore, SEM-EDS analysis showed that UV-cured NDPM-grafted PSA retained almost no residue on the silicon wafer after debonding.

Bio-based monomers for amide-containing sustainable polymers.

The field of sustainable polymers from renewable feedstocks is a fast-reviving field after the decades-long domination of petroleum-based polymers. Amide-containing polymers exhibit a wide range of properties depending on the type of amide (primary, secondary, and tertiary), amide density, and other molecular structural parameters (co-existing groups, molecular weight, and topology). Engineering amide groups into sustainable polymers via the "monomer approach" is an industrially proven strategy, while bio-based monomers are of enormous importance to bridge the gap between renewable sources and amide-containing sustainable polymers (AmSPs). This feature article aims at conceptualizing the monomer-design philosophy behind most of the reported AmSPs and is organized by discussing di-functional monomers for step-growth polymerization, cyclic monomers for ring-opening polymerization and amide-containing monomers for chain-growth polymerization. We also give a perspective on AmSPs with respect to monomer design and performance enhancement.

Controlled functionalization of polypropylene by VETEMPO-mediated radical chemistry

New chemistry for grafting maleic anhydride (MAn) and N-aryl maleimides to a propylene homopolymer is described. Whereas conventional peroxide-initiated maleations are accompanied by extensive degradation, formulations containing a small amount of 4-vinyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (VETEMPO) can meet graft content targets while minimizing melt viscosity losses. The first stage of a VETEMPO-mediated process involves alkyl radical trapping by nitroxyl to yield polymer-bound alkoxyamines bearing pendant vinyl ether functionality. Subsequently, copolymerization between vinyl ether and MAn builds polymer molecular weight while offsetting the degradation incurred by the standard MAn grafting mechanism. The result is a lightly branched, maleated product with a melt viscosity close to that of the starting material. This VETEMPO-based copolymerization strategy is adapted to generate thermoset PP derivatives by peroxide-initiated reactions of VETEMPO with an appropriate difunctional monomer such as N,N′-1,3-phenylene dimaleimide (PDM).

Synthesis of a transesterification vitrimer activated by fluorine from an α,α-difluoro carboxylic acid and a diepoxy

An α,α-difluorodicarboxylic acid (P-DAF) was easily synthesized in two steps from diiodobenzene and reacted with a commercial diepoxy (BDGE). The electron-withdrawing effect of the fluorinated group activated the polymerization and gelation readily happened at room temperature. After curing at 150 °C a novel dynamic material was obtained. The P-DAF/BDGE material exhibited a high gel content (94 %) and was able to flow when heated. This material could be successfully reshaped by compression molding under mild conditions (1.5 h at 150 °C). This new material demonstrates that catalyst-free transesterification vitrimers can be prepared from difunctional monomers.

Cyclization assisted iterative growth method for synthesizing monodisperse polymers

A fast iterative growth method is reported to prepare monodisperse polymers assisted by a cyclization technique. This novel method uses a di-functional and a tri-functional compounds as monomer pairs. The di-functional monomer is designed to have an azide and a hydroxyl end groups, while the tri-functional monomer is designed to have an alkyne and a sym-dibenzo-1,5-cyclooctadiene-3,7-diyne containing two strained alkynes. One iterative cycle of this novel method is composed by four step reactions. First, the self-accelerating double-strain-promoted azide-alkyne click reaction is used to couple two monomers/oligomers having an azide and a hydroxyl end group pairs with one tri-functional monomer by reacting the azide and strained alkyne groups. This coupling reaction increases chain length and produces an elongated oligomers having two hydroxyl end groups and one alkyne group in the middle position of main-chain. Second, the esterification between anhydride and hydroxyl is used to modify the hydroxyl end groups to endow the elongated oligomers with two azide end groups. Third, copper(I)-catalyzed azide-alkyne click reaction is then used to ring-close the elongated oligomers by reacting the middle alkyne and one terminal azide groups to prepare a tadpole-shaped oligomers with one azide end group. Fourth, the 2,3-dichloro-5,6-dicyano-p-benzoquinone oxidized deprotection reaction is used to cleave the preset methoxybenzyl ether bond in the ring of the tadpole-shaped oligomers and rebuild an azide and a hydroxyl end group pairs for the elongated oligomers. The repetition of above iterative cycle can synthesize the monodisperse polymers with a fast chain-growth manner of 2n+1-1.

Synthesis of a bio-based and intrinsically anti-flammable epoxy thermoset and the application of its carbonized foam as an efficient CO2 capture adsorbent

The production of multifunctional carbon foams from biomass has attracted great interest due to the increasing awareness of green and sustainable development. Here, we report a bio-based epoxy thermoset prepared by curing a furan-derived di-functional epoxy monomer (5-hydroxymethyl-2-furaldehyde (HMF)-3, 5-diamino-1,2,4-triazole (GU)-EP) with a furan-derived curing agent, 5,5′-methylenedifurfurylamine (DFA). For comparison, the cured commercial diglycidyl ether of bisphenol-A was used as a thermoset epoxy resin. Due to its unique structure rich in aromatic and nitrogenous structures, the cured HMF-GU-EP/DFA thermoset possessed exceptional charring ability. This fully bio-based epoxy thermoset had a very high char yield (55.8 wt%) at 800 °C under nitrogen, while the cured diglycidyl ether of bisphenol-A/4, 4′-diaminodiphenylmethane was only 13.6 wt%. Due to this excellent carbonization ability, the cured HMF-GU-EP/DFA was carbonized at 700 °C to obtain a carbon foam as a CO2 absorbent. The Brunauer–Emmett–Teller surface area and total pore volume were measured to be 472 m2/g and 0.22 cm3/g, respectively. The amounts of CO2 adsorbed with this carbon foam were 4.72 and 2.15 mmol/g at 273 and 298 K, respectively. In conclusion, this study provides a bio-based, strong and rigid, inherently flammable, and highly carbonizable epoxy thermoset and the potential application of its carbonized foam as an efficient adsorbent for CO2 capture.

Synthesis and properties of cationic multiblock polyaramides and polyimides

AbstractPoly(diallyldimethylammonium chloride) (PDADMAC) is a useful material due to its high charge density and alkaline stability, but its hydrophilic nature limits applications to those where the dissolved polymer is appropriate. To make polymers suitable for applications as films and membranes containing the diallyldimethylammonium moiety, multiblock copolymers of polyaramides (PA) and polyimides (PI), materials known for their excellent physical properties and stabilities, were synthesized. Aminophenyl difunctionalized PDADMAC oligomers were synthesized using a disulfide iniferter then counterion exchanged to the hexafluorophosphate anion to produce telechelic oligomers with good solubility in polar aprotic solvents. The oligomers were reacted in situ with the proper difunctional monomers to produce PA, polyetheraramides, PI, and polyetherimides. All the classes of copolymers were synthesized over a range of compositions at high yield and material properties were demonstrated to be a result of both the backbone chemistry and the composition. Several of the synthesized copolymers formed films with good clarity, strength, and flexibility. The copolymers containing ether linkages had increased backbone flexibility and demonstrated better film‐forming properties. The multiblock copolyaramides and copolyimides demonstrate a method to produce materials with excellent thermal stability and good strength and flexibility, making them uniquely capable of serving as water insoluble, cationic films, and membranes.