Real‐time monitoring by proton relaxometry of radical polymerization reactions of acrylamide in aqueous solution

The potential of time‐domain nuclear magnetic resonance (TD‐NMR) for the real‐time monitoring of solution radical polymerizations is demonstrated. A model system composed of a redox‐pair initiator system, acrylamide as monomer and water as solvent was investigated. A second‐generation continuous wave free precession technique was employed to measure the longitudinal relaxation time constant (T₁) of the samples throughout the polymerization reactions. This parameter was shown to be sensitive to the reactant feed free‐radical enhancement of the water molecule relaxation time, making it a good probe to monitor monomer conversion in real time in an automated, non‐destructive fashion. It was found that the T₁ value was better than the transverse relaxation time constant (T₂) for describing the evolution of the polymerization reactions, due to its greater sensitivity to paramagnetic effects. The TD‐NMR signal variation observed was linked to the formation, propagation and termination steps of the radical polymerization kinetics scheme. These first results may contribute to the application of real‐time monitoring of radical polymerization reactions employing low‐cost and robust TD‐NMR spectrometers. © 2018 Society of Chemical Industry     

Post‐polymerization modification of bio‐based polymers: maximizing the high functionality of polymers derived from biomass

The renaissance of the bio‐based chemical industry over the last 20 years has seen an ever growing interest in the synthesis of new bio‐based polymers. The building blocks of these new polymers, so called platform molecules, contain significantly more chemical functionality than their petrochemical counterparts (such as ethene, propene and para‐xylene). As a result bio‐based polymers often contain greater residual chemical functionality in their chains, with groups such as alkenes and hydroxyls commonly observed. These functional groups can act as sites for post‐polymerization modification (PPM), thus further extending the range of applications for bio‐based polymers by tailoring the polymers' final properties. This mini‐review highlights some of the most recent and compelling examples of how to make use of bio‐based polymers with residual functional groups for PPM. It also looks at how the emerging interdisciplinary field of enzymatic polymer synthesis allows for increased functionality in polymers by avoiding side‐reactions as a result of milder reaction conditions, and additionally offers an alternative means of polymer surface modification. © 2018 Society of Chemical Industry     

Bi-supported Ziegler–Natta TiCl4/MCM-41/MgCl2 (ethoxide type) catalyst preparation and comprehensive investigations of produced polyethylene characteristics

Bi-supported Ziegler–Natta catalysts (TiCl₄/MCM-41/MgCl₂ (ethoxide type)) were synthesized to improve the morphology and the properties of polyethylene. The morphology control is a crucial issue in polymerization process, while tailoring the properties of polymers is needed for specific applications. The catalysts were synthesized in different ratios of two supports with impregnation method. The polymerization process was carried out in atmospheric slurry reactor. The catalysts were characterized with scanning electron microscopy - energy dispersive X-ray spectroscopy (SEM–EDX), inductively coupled plasma, Fourier transform infrared spectrometry (FTIR), and Brunauer-Emmett-Teller (BET) methods. The polymers were analyzed with scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry, FTIR, and tensile-strength analyses. Ubbelohde viscometer and frequency sweep measurements showed that the synthesized polymers are ultra-high-molecular-weight polyethylene. Mechanical properties of polymers showed higher Young's modulus in samples containing MCM-41, having higher thermal stability supported by TGA analysis. SEM images of bi-supported catalyst showed a controlled spherical morphology with uniform size distribution. SEM analysis support that the polymers replicate their morphology from catalyst, improving their morphology comparing to MgCl₂-supported catalyst. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48553.     

Recycling of multilayer packaging using a reversible cross-linking adhesive

Plastic-based multilayer packaging has an important function on the packaging market, but is currently not recyclable as the polymer layers used are usually thermodynamically immiscible. This work therefore follows the approach to prepare separable multilayer packaging using a packaging adhesive modified with thermally unstable adducts, and proposes a corresponding recycling process. For this purpose, typical multilayer structures (polyethylene (PE)// polyethylene terephtalate (PET), PET//aluminum, and PE//aluminum) were prepared by curing furan-/maleimide-functionalized polyurethane (PU)-prepolymers with a three-functional cross-linking agent. Adhesions of up to over 3N per 15 mm test specimen were measured or substrate failures of PET films were observed. However, heating in dimethylsulfoxide, the retro-Diels–Alder reaction takes place and the cross-linked adhesive turns thermoplastic and dissolves in the solvent. Thus, the laminate separates and the pure PE, PET, and aluminum foils can be recovered without any PU residue.     

低温水等离子体活化和表面接枝DMAE聚氯乙烯中空纤维膜研究

采用低温水等离子体技术，在三通道聚氯乙烯(PVC)膜表面接枝了甲基丙烯氧基苄基二甲基氯化铵(DMAE)单体，增强了膜亲水和抗菌性能。通过红外分析，表明DMAE成功接枝到了PVC膜上，水通量提高两倍，PVC-ir-H₂O膜(通过水等离子体处理的膜)对牛血清蛋白(BSA)的吸附能力下降67%，对BSA溶液的通量从7.7提高至40 kg?m^-2?h^-1，并且对BSA的截留能力不变。通过静态及动态抗菌实验，接枝后的PVC膜（PVC-g-PMAE膜）抗菌率达到100%，膜组件运行中的抗菌率也达到82%以上。在保证细菌截留率100%的同时，其渗透通量提高三倍。该膜表面修饰工程技术能实现膜表面的均一化改性，且绿色环保、操作简便、成本低，改性膜在饮用水处理领域，尤其是家用净水器中展现了很好的应用前景。     

基于聚集诱导发光效应的高固低黏丙烯酸荧光树脂的制备及其性能研究

为了研制一种具有荧光功能特性的高固低黏羟基丙烯酸树脂。从聚集诱导发光效应（AIE）出发，将具有 AIE性质的二对丙烯酸四苯乙烯酯荧光分子通过自由基共聚连接于聚合物链段。由于聚合物链段对荧光分子化学键固定以及聚合物链的包裹束缚作用，导致荧光分子运动受限，从而实现涂层在紫外灯下荧光发光。通过荧光光谱的实时跟踪，探索高固低黏羟基丙烯酸树脂的合成以及固化规律。此外，由于聚合物链段对外界刺激具有实时响应性，从而间接影响了所连接的荧光分子的荧光发光行为。因此，文中也探索了涂层在外界温度与化学气体的影响下所发生的荧光变化的规律，以探索其在功能涂层中应用的可行性。     

负载羧基化球状介孔纳米颗粒TFN膜的研究

在薄层复合膜(thin-film composite membrane, TFC膜)中引入无机纳米颗粒，形成薄层纳米复合膜(thin-film nanocomposite membrane, TFN膜)，近几年作为反渗透膜开始应用于水处理研究。但是无机纳米颗粒在TFC膜中的性能的不稳定性和膜的机械强度等变成了突出问题。合成制备了粒径约为110 nm修饰羧基的介孔氧化硅球状纳米颗粒(MSN—COOH)，并将其成功地化学键合在TFC膜的表面功能层交联网络中。与TFC膜相比，键合有MSN—COOH的TFN膜，水通量提高了56.2%，保持高脱盐率；由于单分散介孔纳米颗粒表面亲水官能团的引入，使膜表面的亲水性有很大程度提高，单分散介孔纳米颗粒在基体中的有序排列，使膜表面粗糙度降低，提高了膜的抗污染能力。与普通TFN膜相比较，具有更好的稳定性和柔韧性，可以在长时间高压过滤操作下保持稳定。     

In situ emulsion polymerization and characterization of PVAc nanocomposites including colloidal silica nanoparticles for wood specimens bonding

Polyvinyl acetate (PVAc) nanocomposites for wood adhesives containing different amounts of colloidal silica nanoparticles (CSNs) were synthesized via in situ one-step emulsion polymerization. The adhesion strength of wood specimens bonded by PVAc nanocomposites was investigated by the tensile test. Thermal properties of PVAc nanocomposites were also characterized by differential scanning calorimetry and thermogravimetric analysis. Rheological and morphological properties of the PVAc nanocomposites were investigated using rheometric mechanical spectrometry and field emission scanning electron microscopy (FESEM), respectively. The obtaining results showed that the shear strength of PVAc nanocomposite including 1 wt. % CSNs has the highest shear and tensile strength about 4.7 and 3.2 MPa, respectively. A small increment of T_g (~3 °C) and considerable increment of the ash content proved the enhancement of PVAc thermal characterization in the presence of CSNs. FESEM results showed uniform dispersion of nanoparticles throughout the PVAc matrix due to using the in situ emulsion polymerization process. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48570.     

Unraveling the film-formation kinetics of interfacial polymerization via low coherence interferometry

Interfacial polymerization (IP) is one of the most important methods for fabricating thin film composite (TFC) membranes. Understanding the film-formation mechanisms is of great value for developing membranes with enhanced performance. This work proposed a novel method to in situ characterize the film-formation kinetics via low coherence interferometry (LCI). The polyamide film formed at the liquid–substrate interface was scanned in real time; the polymerization induced significant variations in the optical properties around the reaction zone. After mitigating the effects of the perturbed interface, the surface-averaged intensity profiles provide a solid basis for analyzing the film-formation kinetics at various depths. In particular, the effects of the monomer concentrations were investigated to reveal the asymmetric growth and development of irregular substructures. All the characterization results confirm that the LCI-based characterization is a powerful tool for studying the structural evolution of the IP layer and thereby providing deeper insights for optimizing TFC membranes.     

Synthesis and analysis of phase segregation of polystyrene-block-poly(methyl methacrylate) copolymer obtained by Steglich esterification from semitelechelic blocks of polystyrene and poly(methyl methacrylate)

Here, an alternative route to successfully synthesize polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) is reported. Steglich esterification was used as an effective, metal free approach for coupling carboxylic terminated PS and the hydroxyl end-functionalized PMMA chains obtained by nitroxide-mediated polymerization and atom transfer radical polymerization, respectively. α-Functionalization was obtained using 4,4′-azobis(4-cyanovaleric acid) and 2,2,2-tribromoethanol as initiators. The synthesis of PS-b-PMMA was confirmed by gel permeation chromatography and nuclear magnetic resonance (NMR), while the dependence of the diffusion coefficients of the polymers (PS, PMMA, PS/PMMA blend, and PS-b-PMMA) with their corresponding molecular weights was discussed based on the results of atomic force microscopy-based infrared spectroscopy, differential scanning calorimetry, and spectra of diffusion-ordered NMR spectroscopy. Differently from PS-b-PMMA, a partial segregation was observed for the PS/PMMA blend, affecting its thermal behavior and diffusion coefficient. The study here presented provides an easier and efficient strategy for the synthesis of PS-b-PMMA and new insights into the diffusion of polymers.