Maleimide Copolymers Research Articles

3D Printable Antimicrobial Polymer Blend

AbstractThree‐dimensional (3D) printing is an innovative manufacturing method for preparing designer materials with complex geometries. However, there are very few studies on the fabrication of antimicrobial polymer materials suitable for use in everyday clinical objects, via 3D printing. In this work, an antibacterial polymer material is prepared by blending polyamide 11 (matrix), a high‐performance engineering thermoplastic, and a styrene maleimide copolymer with pendant quaternary amine moieties, and the blend 3D printed via selective laser sintering. The quaternary amine functionalities confer permanent antimicrobial properties. Blend properties are studied prior to printing via differential scanning calorimetry, powder X‐ray diffraction, and FTIR spectroscopy. Additionally, the mechanical and antimicrobial properties of the polymer blends and printed material are also assessed. The microstructure of the 3D printed polymer materials is further characterized via DOSY NMR spectroscopy. This study indicates that this is a promising approach for preparing nonleaching antimicrobial 3D printable materials.

Thermal Behavior of Copolymers of Maleimide with Alkyl Methacrylates

Thermal Behavior of Copolymers of Maleimide with Alkyl Methacrylates

Waste to Treasure: Preparation of Functional Polymeric Particles from Waste Olefins in Carbolic Oil by Self-Stabilized Precipitation Polymerization

Carbolic oil is a fraction of coal tar with an enormous reserve, 40% of which are aromatic olefins such as indene, coumarone, styrene, etc. However, it is an underutilized r esource due to the lack of deep processing technology. In this study, we copolymerized olefins in the carbolic oil with maleic anhydride (MAh) by self-stabilized precipitation polymerization (2SP) method, to obtain uniform carbolic oil–maleic anhydride copolymer (CMA) particles with high yield (≥90%). Uniform CMA particles with a number-average molecular weight (Mn) in the range of 4400–24,100 g·mol–1 and particle sizes in the range of 150–2800 nm could be conveniently obtained by tuning the reaction factors. CMA exhibited good solubility in common organic solvents and possessed good thermal stability. After chemical modification of anhydride groups, CMA could be further converted into water-soluble carbolic oil–maleamic acid copolymers (CMAA), and heat-resistant and hydrophobic carbolic oil–maleimide copolymers (CMI). Overall, this research had provided a facile and green strategy for the effective utilization of waste olefins in carbolic oil, and the obtained copolymers had broad application prospects.

Molecular Properties of Comb-Shaped Maleimide Copolymers in Dilute Solutions: Effect of Alkyl Side Chains

Molecular Properties of Comb-Shaped Maleimide Copolymers in Dilute Solutions: Effect of Alkyl Side Chains

Thermal degradation behavior of maleimide-methacrylate copolymers bearing pendant allyl groups

Maleimide copolymers bearing pendant allyl groups were obtained by radical copolymerization of maleimide and allylmaleimide with methylmethacrylate and allylmethacrylate in bulk and methanol solution in the presence of AIBN. The structural features of the copolymers were studied using UV, IR, and NMR spectroscopy. During the copolymerization of maleimide with allylmethacrylate and N-allylmaleimide with methylmethacrylate at high conversions, an increase in the viscosity of the system is observed, which results in cross-linking along the “allyl bonds” of side polymer chains with the formation of insoluble copolymers that swell in DMSO. Copolymerization of N-allylmaleimide with allylmethacrylate already at initial conversions leads to the formation of crosslinked copolymers with high heat resistance. The thermal degradation behavior of copolymers was studied and the volatile products were investigated.

ТЕРМИЧЕСКОЕ ПОВЕДЕНИЕ СОПОЛИМЕРОВ МАЛЕИМИДА С АЛКИЛМЕТАКРИЛАТАМИ

Copolymers of maleimide with methyl- and allyl methacrylate have been prepared by the method of radical copolymerization in bulk. It was established that, regardless of the composition of the initial monomer mixture, copolymerization proceeded with the formation of random copolymers enriched with acrylate monomer units. Maleimide copolymers have high thermal stability up to 320 °C.

Thermal, Mechanical, and Optical Properties of Maleimide Copolymers Containing Twisted N‐Phenyl Substituents in the Side Chain

AbstractUV absorption spectroscopic measurements and DFT calculations revealed that N‐(alkyl‐substituted phenyl)maleimides with substituents at the ortho position favored a twisted N‐phenyl conformation, due to the steric hindrance between the maleimide ring and the substituted N‐phenyl moiety. High‐molecular‐weight copolymers were synthesized by radical copolymerization of the N‐(alkyl‐substituted phenyl)maleimides with n‐butyl vinyl ether and n‐butyl acrylate. The thermal properties of the copolymers were determined by thermogravimetric analysis and differential scanning calorimetry. The mechanical tensile tests under temperature control revealed the mechanical features of the copolymers depending on their repeating structure and composition. The significant temperature dependence of the modulus and strain of the copolymers was also clarified. Then, the transparency, refractive indices, and birefringence properties of the copolymer films were evaluated. It was confirmed that the maleimide copolymers had negative orientational birefringence with small absolute values and positive photoelastic birefringence. The effect of the conformational structure of the N‐phenyl groups on the thermal, mechanical, and optical properties of the copolymers was discussed.

Synthesis of Heat‐resistant Polymers by Thiol–Ene Reaction of N‐Allylmaleimide Copolymers Using Glycoluril Crosslinkers with Rigid Molecular Structures

ABSTRACTWe carried out the thermal curing of the copolymers of N‐allylmaleimide (AMI) and 2‐ethylhexyl acrylate (2EHA) using 1,3,4,6‐tetra(2‐mercaproethyl)glycoluril (G1), 1,3,4,6‐tetra(3‐mercaptopropyl)glycoluril (G2), 1,3,4,6‐tetraallylglycoluril (G3), triallylisocyanurate (TAIC), and pentaerythritol tetrakis(3‐mercaptobutyrate) (PEMB) as the crosslinkers. Based on the results for the analysis of thiol–ene reactions monitored by IR spectroscopy, it was confirmed that the curing rate significantly depended on the combination of the used crosslinkers. The insoluble fraction after curing was more than 90% for the systems using the glycoluril crosslinkers, while the conversion of the allyl groups was suppressed due to the rigid structure of these crosslinkers. The heat resistance and the mechanical properties of the crosslinked polymers were investigated by thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and mechanical tensile tests. For the products cured using the glycoluril crosslinkers, the glass transition temperature (Tg) and the maximum temperature of thermal decomposition (Tmax) were 54–59 °C and 395–409 °C, respectively, being higher than those for the cured product prepared with PEMB and TAIC as the conventional crosslinkers. The elasticity (75–139 MPa), the maximum strength (3.0–4.1 MPa), and the adhesion strength (6.7–10.7 MPa) for the polymers cured with the glycoluril crosslinkers, determined by the mechanical tensile and single lap‐shear adhesion tests, were higher than those for cured materials produced with PEMB. Thus, the thermal and mechanical properties of the maleimide copolymers were efficiently enhanced by crosslinking using the rigid glycoluril compounds. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 923–931

Maleimide Copolymers of MMA / Styrene: Microwave -Preparation And Their Properties

This study focused ona convenient, fast and rapid process to synthesis of N-substituted maleimide [4-N-Phenylethanamide azo-3-N-(4-chlorophenyl)Maleimide] [PAChMI] and their copolymers in domestic microwave as an energy source. The monomer was prepared by the reaction of maleic anhydride with 4-aminochlorobenzene in the presence of ml volume of DMF and P2O5 to provide a homogenous solution for chemical transformation. The copolymerization were also done under microwave heating conditions, in presence of ml volume of DMF with AIBN as free radical initiator. The structures of all compounds were confirmed by FT-IR, 1H-NMR and molecular weight was determined by GPC

Role of N-substituents of maleimides on penultimate unit effect for sequence control during radical copolymerization

Radical copolymerization of N-substituted maleimides (RMIs) and olefins provides AAB sequence-controlled copolymers by penultimate unit (PU) control. In this study, we investigated the steric, resonance, and polar effects of N-substituents on sequence control during copolymerization of RMIs as the M2 monomer with diisobutene (DIB) and d-limonene (Lim) as the M1 monomer in chloroform at 60 °C. The monomer reactivity ratios (i.e., r2 (= k22/k21), r12 (= k122/k121), and r22 (= k222/k221)) were determined based on the terminal and PU models using a nonlinear least-squares method. For the copolymerization of RMIs with DIB, the introduction of a bulky N-alkyl group suppressed the PU effect and led to the formation of alternating copolymers. The copolymerization of N-phenylmaleimides with o- and p-substituents was also investigated to reveal the steric, resonance, and polar effects of the substituents. In conclusion, less bulky and more electron-donating substituents effectively induced the PU effect during the radical copolymerization of RMIs and olefins. Radical copolymerization of N-substituted maleimides and olefins provides AAB sequence-controlled copolymers by penultimate unit control. In this study, we investigated the steric, resonance, and polar effects of N-substituents on sequence control during copolymerization of various N-substituted maleimides with diisobutene and limonene in chloroform at 60 °C, and concluded that less bulky and more electron-donating substituents effectively induced the penultimate unit effect. We also demonstrated that 2:1 sequence-controlled maleimide copolymers was efficiently produced during radical copolymerization of limonene and N-phenylmaleimides with an electron-donating substituent.

Control of thermal, mechanical, and optical properties of three‐component maleimide copolymers by steric bulkiness and hydrogen bonding

ABSTRACT N‐substituted maleimides polymerize in the presence of a radical initiator to give polymers with excellent thermal stabilities and transparency. In this study, we synthesized various maleimide copolymers with styrenes and acrylic monomers to control their thermal and mechanical properties by the introduction of bulky substituents and intermolecular hydrogen bonding. Three‐component copolymers of N‐(2‐ethylhexyl)maleimide in combination with styrene, α‐methylstyrene (MSt), or 1‐methylenebenzocyclopentane (BC5) as the styrene derivatives, and n‐butyl acrylate, 2‐hydroxyethyl acrylate, 4‐hydroxybutyl acrylate, or acrylic acid as the acrylic monomers were prepared by radical copolymerization. These copolymers were revealed to exhibit excellent heat resistance by thermogravimetric analysis. Glass transition temperatures increased by the introduction of bulky MSt and BC5 repeating units. The mechanical properties of the copolymer films were improved by the introduction of intermolecular hydrogen bonding. Optical properties, such as transmittance, refractive index, Abbe number, and birefringence, were determined for the copolymers. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1569–1579

Physical gelation of AB-alternating copolymers made of vinyl phenol and maleimide units: cooperation between precisely incorporated phenol and long alkyl pendant groups

Alternating copolymers of vinyl phenol and alkyl maleimide gave organogel in aromatic solvents. The gelation was induced by segregation.

Dependence of color change of vinylethylene carbonate copolymers having N-substituted maleimides on chemical structure by acid-base switching in solution and solid state

The copolymers of vinylethylene carbonate (VEC) and N-substituted maleimide (NMI) having various N-substituents were synthesized by radical polymerization. The color of P(VEC/NMI)s changed from colorless to red reversibly based on the acid-base switching in solution and solid state. Furthermore, the color depth of P(VEC/NMI) solution and powder changed systematically depending on the electric effect of N-substituents. However, the copolymers of styrene and NMIs barely changed under the same conditions. These color change and depth behaviors of NMI copolymers were analyzed in detail by UV–vis and IR spectra, and the results were also supported by the density functional theory (DFT) calculation for the model compound of maleimide tautomers. Additionally, the powder color of P(VEC/NMI)s changed reversibly before and after exposure to cigarette smoke and vinegar.

Studies on reactivity ratio and thermal studies of copolymers of N-substituted maleimide with vinyl pyridine [VP]/2-hydroxy ethylmethacrylate [OHEMA

The copolymers (C-NACPMI) with various proportions of N-[4-N'-(4-nitrophenyl) aminocarbonyl] phenyl) maleimide [NACPMI] with Vinyl Pyridine [VP] and 2-hydroxy ethylmethacrylate (OHEMA) were prepared by free radical polymerization. The structure of synthesized copolymers was characterized by FT - IR and 1 H-NMR spectroscopic methods. The nine copolymer samples were synthesized from different feed ratio of comonomers. The monomer reactivity ratio r NACPMI, r VP and r OHEMA are determined by Finemann Ross method. Copolymers showed solubility in polar solvent. Thermal behavior of copolymers was evaluated by TGA and DSC. The investigated copolymers degrade in one steps. The molecular weight was determined by GPC.

Side chain length impacting thermal transitions and water uptake of acrylate–maleimide copolymers with pendent catechols

Significant moisture uptake was observed for a family of catechol side-chain poly(alkyl acrylate-maleimide)s (PAMs) intended to probe the effects of Tg and polarity.

Maleimide copolymers containing azobenzene moieties – synthesis and study of liquid crystalline and optical properties

New reactive copolymers have been synthesized by copolymerization of two functional N-substituted-maleimides with styrene.

Modification of acrylic adhesives with maleimides and copolymers of maleimide with methacrylic monomers

The thermal properties of acrylic reactive adhesives modified with maleimides and copolymers of maleimide with methacrylic copolymers are studied. It is shown that such modification allows one to improve the operability of anaerobic and thermosetting adhesives upon exposure to elevated temperatures.

シークエンス制御したマレイミド共重合体の合成と耐熱透明ポリマー材料設計への応用

シークエンス制御したマレイミド共重合体の合成と耐熱透明ポリマー材料設計への応用

Synthesis and Characterization of Thermoresistant Maleimide Copolymers and their Crosslinked Polymers

Synthesis and Characterization of Thermoresistant Maleimide Copolymers and their Crosslinked Polymers

Transferrin receptor antibody-modified α-cobrotoxin-loaded nanoparticles enable drug delivery across the blood–brain barrier by intranasal administration

A novel drug carrier for brain delivery, maleimide–poly(ethyleneglycol)–poly(lactide) (maleimide–PEG–PLA) nanoparticles (NPs) conjugated with mouse–anti-rat monoclonal antibody OX26 (OX26–NPs), was developed and its brain delivery property was evaluated. The diblock copolymers of maleimide–PEG–PLA were synthesized and applied to α-cobrotoxin (αCT)-loaded NPs which were characterized by transmission electron micrograph imaging, Fourier-transform IR, and X-ray diffraction. The NPs encapsulating αCT had a round and vesicle-like shape with a mean diameter around 100 nm, and the OX26 had covalently conjugated to the surface of NPs. MTT studies in brain microvascular endothelial cells (BMEC) revealed a moderate decrease in the cell viability of αCT, when incorporated in OX26–NPs compared to free αCT in solution. A higher affinity of the OX26–αCT–NPs to the BMEC was shown in comparison to αCT–NPs. Then, OX26–αCT–NPs were intranasally (i.n.) administered to rats, and αCT in the periaqueductal gray was monitored for up to 480 min using microdialysis technique in free-moving rats, with i.n. αCT–NPs, i.n. OX26–αCT–NPs, intramuscular injection (i.m.) αCT–NPs, and i.m. OX26–αCT–NPs. The brain transport results showed that the corresponding absolute bioavailability (F abs) of i.n. OX26–αCT–NPs were about 125 and 155 % with i.n. αCT–NPs and i.m. OX26–αCT–NPs, respectively, and it was found that both the C max and AUC of the four groups were as follows: i.n. OX26–αCT–NPs > i.n. αCT–NPs > i.m. OX26–αCT–NPs > i.m. αCT–NPs, while αCT solution, as control groups, could hardly enter the brain. These results indicated that OX26–NPs are promising carriers for peptide brain delivery.