Gamma Radiation- and Ultraviolet-Induced Polymerization of Bis(amino acid)fumaramide Gel Assemblies

Controlling the polymerization of supramolecular self-assembly through external stimuli holds great potential for the development of responsive soft materials and manipulation at the nanoscale. Vinyl esters of bis(leu or val)fumaramide (1a and 2a) have been found to be gelators of various organic solvents and were applied in this investigation of the influence of organogelators’ self-assembly on solid-state polymerization induced by gamma and ultraviolet irradiation. Here, we report our investigation into the influences of self-assemblies of bis(amino acid vinyl ester)fumaramides on gamma-ray- and ultraviolet-induced polymerization. The gelator molecules self-assembled by non-covalent interactions, mainly through hydrogen bonds between the amide group (CONH) and the carboxyl group (COO), thus forming a gel network. NMR and FTIR spectroscopy were used to investigate and characterize supramolecular gels. TEM and SEM microscopy were used to investigate the morphology of gels and polymers. Morphology studies showed that the gels contained a filamentous structure of nanometer dimensions that was exhaustive in a three-dimensional network. The prepared derivatives contained reactive alkyl groups suitable for carrying out the polymerization reaction initiated by gamma or ultraviolet radiation in the supramolecular aggregates of selected gels. It was found that the polymerization reaction occurred only in the network of the gel and was dependent on the structure of aggregates or the proximity and orientation of double bonds in the gel network. Polymers were formed by the gels exposure to gamma and ultraviolet radiation in toluene, and water/DMF gels with transcripts of their gel structure into polymers. The polymeric material was able to immobilize various solvents by swelling. Furthermore, methyl esters of bis(leu and val)fumaramide (1b and 2b) were synthesized; these compounds showed no gelling properties, and the crystal structure of the valine derivative 2b was determined.

In situ polymerization monitoring of a diacrylate in an electrically conducting mesoporous nanoparticle scaffold

The properties of nanoparticle–polymer composites strongly depend on the network structure of the polymer matrix. By introducing nanoparticles into a monomer (solution) and subsequently polymerizing it, the formation of the polymer phase influences the mechanical and physicochemical properties of the composite. In this study, semi-conducting indium tin oxide (ITO) nanoparticles were prepared to form a rigid nanoparticle scaffold in which 1,6-hexanediol diacrylate (HDDA), together with an initiator for photo-polymerization, was infiltrated and subsequently polymerized by UV light. During this process, the polymerization reaction was characterized using rapid scan Kubelka–Munk FT-IR spectroscopy and compared to bulk HDDA. The conductivity change of the ITO nanoparticles was monitored and correlated with the polymerization process. It was revealed that the reaction rates of the radical initiation and chain propagation are reduced when cured inside the voids of the nanoparticle scaffold. The degree of conversion is lower for HDDA infiltrated into the mesoporous ITO nanoparticle scaffold compared to purely bulk-polymerized HDDA. Graphical abstract

Coupling Oil Increase by Coal Liquefaction Residue Pyrolysis and Coal Pyrolysis Depolymerization Based on Big Data

With the continuous improvement of big data technology, my country’s coal liquefaction technology has also continued to mature, maintaining a stable industrial development. Traditional coal pyrolysis technology for tar production with the purpose of increasing tar production, such as coal hydropyrolysis, has problems such as high cost of pure hydrogen atmosphere and complex process and equipment operations, which severely restrict its industrial operation process. Based on this, this paper proposes a new technology of coal pyrolysis and depolymerization coupled with oil increase by using hydrogen precipitated by the condensation polymerization reaction at relatively high temperature under big data technology to study the effect of this process on coal pyrolysis for oil production. Experiments show that at 700°C, the tar yield reaches 21.5wt.%, which is 6% and 7% higher than the pyrolysis tar yield under the same conditions under hydrogen and nitrogen atmospheres. At 600°C, the methane aromatization reaction is relatively weak, and it can be seen that the tar yield is only slightly higher than that under hydrogen and nitrogen atmospheres. As the temperature of the methane anaerobic aromatization reaction increases, the equilibrium conversion rate increases accordingly. Therefore, as the reaction temperature increases, the tar yield also begins to increase.

POLYMERIZATION BY INTERACTION a-HALOACRYLIC ACIDS WITH TERTIARY AMINES

Приведены результаты самопроизвольной полимеризации а -хлоракриловой и а -бромакриловой кислот с третичными аминами при невысокой температуре. В результате самопроизвольной полимеризации при взаимодействии а -галоидакриловых кислот с третичными аминами образуются полимеры, содержащие четвертичные аммониевые группы. С целью подтверждения данного предположения были проведены ЯМР- и ИК-спектроскопические исследования продуктов самопроизвольной полимеризации. Показано, что сопутствующая реакция кватернизации, спонтанной полимеризации, имеет место как в смеси реагентов, так и в присутствии растворителя, т.е. и при смешении непредельного амина и галоидного алкила. Изучены кинетические закономерности реакции полимеризации и показано, что реакция кватернизации, являющаяся лимитирующей стадией процесса самопроизвольной полимеризации, протекает по S 2 - механизму. Описываются первые попытки получения новых нанокомпозиционных материалов на основе синтезированных сополимеров и модифицированного монтмориллонита. Анализ литературных данных показывает, что особенности получения нанокомпозитов на основе Na - монтмориллонита и водорастворимых сополимеров ранее не изучались. The results of spontaneous polymerization of а -chloroacrylic and а -bromoacrylic acids with tertiary amines at a low temperature are presented. As a result of spontaneous polymerization during the interaction of а -halodacrylic acids with tertiary amines, polymers containing quaternary ammonium groups are formed. In order to confirm this assumption, nuclear magnetic resonance and infrared spectroscopic studies of the products of the spontaneous polymerization were carried out. Spontaneous polymerization proceeds, consisting of two stages: the quaternization reaction and the polymerization reaction. The kinetic regularities of the polymerization reaction were studied and it was shown that the quaternization reaction, which is the limiting stage of the spontaneous polymerization process, proceeds according to the S 2 - mechanism. It has described the first attempts to obtain new nanocomposite materials based on synthesized copolymers and modified montmorillonite. Analysis of the literature data shows that the features of the preparation of nanocomposites based on Na - montmorillonite and water-soluble copolymers have not been previously studied.

The Preparation of High-Performance and Stable MXene Nanofiltration Membranes with MXene Embedded in the Organic Phase

Nanomaterials embedded in nanofiltration membranes have become a promising modification technology to improve separation performance. As a novel representation of two-dimensional (2D) nanomaterials, MXene has nice features with a strong negative charge and excellent hydrophilicity. Our previous research showed that MXene nanosheets were added in the aqueous phase, which enhanced the permeselectivity of the membrane and achieved persistent desalination performance. Embedding the nanomaterials into the polyamide layer through the organic phase can locate the nanomaterials on the upper surface of the polyamide layer, and also prevent the water layer around the hydrophilic nanomaterials from hindering the interfacial polymerization reaction. We supposed that if MXene nanosheets were added in the organic phase, MXene nanosheets would have more negative contact sites on the membrane surface and the crosslinking degree would increase. In this study, MXene were dispersed in the organic phase with the help of ultrasound, then MXene nanocomposite nanofiltration membranes were achieved. The prepared MXene membranes obtained enhanced negative charge and lower effective pore size. In the 28-day persistent desalination test, the Na2SO4 rejection of MXene membrane could reach 98.6%, which showed higher rejection compared with MXene embedded in aqueous phase. The results of a long-time water immersion test showed that MXene membrane could still maintain a high salt rejection after being soaked in water for up to 105 days, which indicated MXene on the membrane surface was stable. Besides MXene membrane showed high rejection for high-concentration brine and good mono/divalent salt separation performance in mono/divalent mixed salt solutions. As a part of the study of MXene in nanofiltration membranes, we hoped this research could provide a theoretical guidance for future research in screening different addition methods and different properties.

Visible Light-Controlled Living Cationic Polymerization of Methoxystyrene

Photo-controlled living polymerization has received great attention in recent years. However, despite the great success therein, the report on photo-controlled living cationic polymerization has been greatly limited. We demonstrate here a novel decolorable, metal-free and visible light-controlled living cationic polymerization system by using tris(2,4-dimethoxyphenyl)methylium tetrafluoroborate as the photocatalyst and phosphate as the chain transfer agent (CTA) for polymerization of 4-methoxystyrene. This polymerization reaction under green LED light irradiation shows clear living characteristics including predictable molar mass, narrow molar-mass dispersity (Đ = 1.25), and sequential polymerization capability. In addition, the photocata-lytic system exits excellent “on-off” photo switchability and shows the longest “off period” of 36 h up to now for photo-controlled cationic polymerization. Furthermore, the residual photo-catalyst is easily deactivated and decolored with addition of a base after the polymerization.

High-Performance UV-Vis Light Induces Radical Photopolymerization Using Novel 2-Aminobenzothiazole-Based Photosensitizers

The popularity of using the photopolymerization reactions in various areas of science and technique is constantly gaining importance. Light-induced photopolymerization is the basic process for the production of various polymeric materials. The key role in the polymerization reaction is the photoinitiator. The huge demand for radical and cationic initiators results from the dynamic development of the medical sector, and the optoelectronic, paints, coatings, varnishes and adhesives industries. For this reason, we dealt with the subject of designing new, highly-efficient radical photoinitiators. This paper describes novel photoinitiating systems operating in UV-Vis light for radical polymerization of acrylates. The proposed photoinitiators are composed of squaraine (SQ) as a light absorber and various diphenyliodonium (Iod) salts as co-initiators. The kinetic parameters of radical polymerization of trimethylolpropane triacrylate (TMPTA), such as the degree of double bonds conversion (C%), the rate of photopolymerization (Rp), as well as the photoinitiation index (Ip) were calculated. It was found that 2-aminobenzothiazole derivatives in the presence of iodonium salts effectively initiated the polymerization of TMPTA. The rates of polymerization were at about 2 × 10−2 s−1 and the degree of conversion of acrylate groups from 10% to 36% were observed. The values of the photoinitiating indexes for the most optimal initiator concentration, i.e., 5 × 10−3 M were in the range from 1 × 10−3 s−2 even to above 9 × 10−3 s−2. The photoinitiating efficiency of new radical initiators depends on the concentration and chemical structure of used photoinitiator. The role of squaraine-based photoinitiating systems as effective dyeing photoinitiators for radical polymerization is highlighted in this article.

Visible Light-Controlled Living Cationic Polymerization of Methoxystyrene

Photo-controlled living polymerization has received great attention in recent years. However, despite the great success therein, the report on photo-controlled living cationic polymerization has been greatly limited. We demonstrate here a novel decolorable, metal-free and visible light-controlled living cationic polymerization system by using tris(2,4-dimethoxyphenyl)methylium tetrafluoroborate as the photocatalyst and phosphate as the chain transfer agent (CTA) for polymerization of 4-methoxystyrene. This polymerization reaction under green LED light irradiation shows clear living characteristics including predictable molar mass, narrow molar-mass dispersity (Đ = 1.25), and sequential polymerization capability. In addition, the photocata-lytic system exits excellent “on-off” photo switchability and shows the longest “off period” of 36 h up to now for photo-controlled cationic polymerization. Furthermore, the residual photo-catalyst is easily deactivated and decolored with addition of a base after the polymerization.

Novel Polymerization of Dental Composites Using Near-Infrared-Induced Internal Upconversion Blue Luminescence

Blue light (BL) curing on dental resin composites results in gradient polymerization. By incorporating upconversion phosphors (UP) in resin composites, near-infrared (NIR) irradiation may activate internal blue emission and a polymerization reaction. This study was aimed to evaluate the competency of the NIR-to-BL upconversion luminance in polymerizing dental composites and to assess the appropriate UP content and curing protocol. NaYF4 (Yb3+/Tm3+ co-doped) powder exhibiting 476-nm blue emission under 980-nm NIR was adapted and ball-milled for 4–8 h to obtain different particles. The bare particles were assessed for their emission intensities, and also added into a base composite Z100 (3M EPSE) to evaluate their ability in enhancing polymerization under NIR irradiation. Experimental composites were prepared by dispensing the selected powder and Z100 at different ratios (0, 5, 10 wt% UP). These composites were irradiated under different protocols (BL, NIR, or their combinations), and the microhardness at the irradiated surface and different depths were determined. The results showed that unground UP (d50 = 1.9 μm) exhibited the highest luminescence, while the incorporation of 0.4-μm particles obtained the highest microhardness. The combined 20-s BL and 20–120-s NIR significantly increased the microhardness on the surface and internal depths compared to BL correspondents. The 5% UP effectively enhanced the microhardness under 80-s NIR irradiation but was surpassed by 10% UP with longer NIR irradiation. The combined BL-NIR curing could be an effective approach to polymerize dental composites, while the intensity of upconversion luminescence was related to specific UP particle size and content. Incorporation of 5–10% UP facilitates NIR upconversion polymerization on dental composites.