Synthesis and applications of oligoetherols with perhydro‐1,3,5‐triazine ring and boron

A new method of preparation of oligoetherols containing perhydro‐1,3,5‐triazine rings and boron atoms is presented. The oligoetherols were obtained in the reaction of 1,3,5‐tris(2‐hydroxyethyl) isocyanurate with boric acid followed by reaction with alkylene carbonates. The structure and physical properties of the products render them good candidate for preparing the polyurethane foams. The foams were obtained and their properties were compared with those synthesized from isocyanuric acid and alkylene carbonates. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Oligoetherols Obtained from Uric Acid,Glycidol, and Alkylene Carbonates and Their Use to Obtain Polyurethane Foams of Enhanced Thermal Resistance

A new method of preparation of oligoetherols containing purine rings from uric acid and an excess of glycidol and alkylene carbonates was presented. The course of reaction was studied at various molar concentrations of glycidol. The structure of the products was established, and some physical properties were measured. The oligoetherols were demonstrated to be useful substrates for rigid polyurethane foams of enhanced thermal stability.     

Application of products of reaction between melamine and glycidol as substrates for oligoetherols and polyurethane foams containing 1,3,5‐triazine rings

Hydroxyalkyl derivatives of melamine were obtained by addition of melamine to glycidol. These derivatives were then used to obtain multifunctional oligoetherols by reaction with oxiranes and alkylene carbonates. The structure and properties of the oligoetherols were studied in detail. The oligoetherols were then used to obtain polyurethane foams of enhanced thermal stability. The foams showed marked thermal resistance at 200 °C. The beneficial feature of the obtained foams was their increased compression strength after thermal exposure. © 2013 Society of Chemical Industry     

Application of reactive solvents of melamine for synthesis of polyetherols with perhydro‐1,3,5‐triazine rings

The application of reactive solvents (RSs), namely hydroxymethyl derivatives of acetone for digestion of isocyanuric acid, which is insoluble in most organic solvents except for DMSO, makes the substrate available for further conversions. At this step, the incorporation of perhydro‐1,3,5‐triazine ring into RS takes place. The obtained solutions were used for synthesis of polyetherols containing perhydro‐1,3,5‐triazine rings in reaction with oxiranes: ethylene and propylene oxides. The polyetherols were then used to obtain foamed polyurethanes with enhanced thermal stability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of porous poly(sodium acrylate‐co‐acrylamide) salt‐resistant superabsorbent composite

A novel semi‐interpenetrating polymer networks (semi‐IPNs) porous salt‐resistant superabsorbent composite was prepared by copolymerization of partially neutralized acrylic acid and acrylamide using polyethylene glycol as semi‐IPNs composite, N,N′‐methylenebisacrylamide, triene propanol phosphate, and trihydroxymethyl propane glycidol ether as crosslinking agents, methanol, propanol, and butanol as foaming agents, and L ‐ascorbic acid and peroxide hydrogen as initiators. To improve the properties of swollen hydrogel, such as strength, resilience, permeabilities, and dispersion, the copolymer was surface‐crosslinked, and then blended with aluminum sulfate, sodium carbonate, and sodium 1‐octadecanol phosphate in the course of post treatment. The influences of reaction conditions on properties of superabsorbent composite were investigated and optimized, and the water absorbency of superabsorbent composite prepared at optimal conditions in 0.9 wt% NaCl aqueous solution under atmospheric pressure and certain load (P ≈ 2 × 10³ Pa) were 61 g g^?1 and 16.7 g g^?1, respectively. Moreover, the swelling rate reached 22.003 × 10^?3 g (g s)^?1. And the excellent hydrogel properties, such as hydrogel strength, resilience, permeabilities, and dispersion were also obtained. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Star poly(2‐ethyl‐2‐oxazoline)s—synthesis and thermosensitivity

A series of star‐shaped poly(2‐ethyl‐2‐oxazoline)s was prepared by cationic polymerization. The polymerization was initiated by dipentaerythrityl hexakis(4‐nitrobenzene sulfonate) and a tosylated hyperbranched polymer of glycidol. The polymerization proceeded in a controlled manner. The star structure of the products was determined by nuclear magnetic resonance. The molar mass distributions that were measured by gel permeation chromatography with multiangle laser light scattering were narrow, and the experimental values of the molar masses were close to those predicted. The very compact structure of the polymers obtained (compared with the linear counterparts) confirmed the star formation. The star poly(2‐ethyl‐2‐oxazoline)s show a phase transition temperature in the range 62–75 °C. Comparison of this phase transition temperature with that of the linear poly(2‐ethyl‐2‐oxazoline)s with the same molar masses indicates the influence of molar mass and topological structure of the macromolecule on temperature behavior. The prepared copolymers are spherical, which might be useful for the controlled transport and release of active compounds. Copyright © 2011 Society of Chemical Industry     

Fast‐swelling oxidized starch phosphate–poly(acrylate/acrylamide/2‐acryloylamino‐2‐methyl‐1‐propanesulfonic acid) superabsorbent composite

A fast‐swelling superabsorbent composite was prepared by solution polymerization of acrylate, acrylamide, 2‐acryloylamino‐2‐methyl‐1‐propanesulfonic acid and oxidized starch phosphate. Ethanol, propyl alcohol, butyl alcohol, and sodium bicarbonate were used as foaming agents to produce fast‐swelling characteristics. The structure of the superabsorbent composite was characterized using Fourier transform infrared spectroscopy (FTIR). The influences of the amount of water, acrylamide, 2‐acryloylamino‐2‐methyl‐1‐propanesulfonic acid, oxidized starch phosphate, initiator, and trihydroxymethyl propane glycidol ether, as well as the neutralization degree of acrylic acid on the equilibrium swelling degree and swelling rate of the superabsorbent composite, were investigated. The equilibrium swelling degree of the superabsorbent composite prepared in a 0.9 wt% NaCl aqueous solution was 52 g g^?1, and the swelling rate reached 0.86 mL g^?1 s^?1. The swelling kinetics was also investigated, and the results indicate that swelling of the superabsorbent composites obeys Schott's pseudo second‐order kinetics model. POLYM. ENG. SCI., 56:1267–1274, 2016. © 2016 Society of Plastics Engineers     

The application of dynamic modeling for thermal risks analysis of the acid‐catalyzed hydrolysis of glycidol

The aim of this work was to determine the limits of safe operation of continuous flow stirred‐tank reactor (CSTR) for the acid‐catalyzed hydrolysis of glycidol. The stability analysis was performed by dynamic modelling. The obtained results were compared with the experimental data reported in the open literature. For this purpose, dimensionless variables and parameters were introduced and unstable material and energy balances were defined. The system equations were solved using Matcont (Matlab^® software). Thus, bifurcation diagrams (in one and two dimensions) were mapped. All different dynamic states were identified and studied (thermal stability and instability, with unique and multiple solutions; Hopf bifurcations; turning points and envelope of periodic solutions). Finally, the intrinsic thermal unstable and cycle behavior of the acid‐catalyzed hydration of glycidol to produce glycerol was identified. The appropriate conditions to guarantee safe operation of CSTR were found. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4418–4426, 2016     

Curing reaction of amino‐terminated aqueous‐based polyurethane dispersions with triglycidyl‐containing compound

Amino‐terminated anionic aqueous‐based polyurethane (PU) dispersion was obtained from NCO‐terminated PU prepolymer, which was neutralized with an excess triethylamine (TEA) and chain extended by ethylenediamine (EDA) during water dispersion process. That PU prepolymer was obtained from a polyaddition reaction of isophorone diisocyanate (IPDI), polypropylene glycol‐2000 (PPG‐2000), and 2,2′‐dimethylol propanoic acid (DMPA). This aqueous‐based PU dispersion was treated with trimethylolpropane triglycidyl ether (TMPTGE) as a latent curing agent and resulted in a self‐cured PU resin on drying. A model ring‐opening curing reaction between oxirane group of TMPTGE with terminal amino group of PU was demonstrated by glycidol with n‐butyl amine. The physical and mechanical properties as well as thermogravimetric analyses of these self‐cured PU resins were evaluated in this article. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Generation of 3‐monochloro‐1,2‐propanediol and related materials from tri‐, di‐, and monoolein at deodorization temperature

Heating tests of pure tri‐, di‐, and monoolein (TO, DO, and MO, respectively) with and without the addition of tetrabutylammonium chloride as a chloride source at 240°C revealed the characteristic reactions that generate 3‐monochloro‐1,2‐propanediol‐related materials (3‐MCPD‐RM) in each acylglycerol. 3‐MCPD‐RM were formed mainly from DO and MO, with only a small amount from TO. Glycidyl ester was the predominant class of 3‐MCPD‐RM generated from both DO and MO, and was increased continuously throughout the heating period with comparable rates in both DO and MO, which also generated 3‐MCPD esters with chloride in a short completion time with an achieved level that was fourfold higher for MO than for DO. The production of free glycidol and 3‐MCPD was confirmed only in heated MO, but not from TO and DO, in a closed heating system, although these compounds were never detected in oils heated under simulated distillation conditions using a gas stream. In a closed system, both free glycidol and 3‐MCPD were increased throughout the heating period, which differed from the esters. Since an interesterification reaction, which produced free glycerol, was observed only in heated MO, free glycerol might be one of the precursors for those free forms. For clarification, further investigation is required.     

Bifunctional oligoetherols with carbazole ring

A new synthetic method for bifunctional oligoetherols with carbazole ring was presented. 9‐(2,3‐Epoxypropyl)carbazole was obtained from carbazole and epichlorohydrine. The epoxide ring opening occurred upon the consecutive reaction with ethylene glycol to give the semiproduct well soluble in ethylene oxide and propylene oxide and reactive toward these epoxides at temperatures above 60–90°C to form oligoetherols. Structure of these oligoetherols and their physical properties and application for synthesis of linear polyurethanes were studied in details. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Composition and long‐term stability of polyglycidol prepared by cationic ring‐opening polymerization

Polyglycidol synthesized by cationic ring‐opening polymerization of glycidol (boron trifluoride initiation in dichloromethane) was purified of low molecular weight contaminants by centrifugal filtration. The high and low molecular weight fractions were characterized by NMR, GPC, osmometry, viscometry, DSC, and FTIR. The ¹³C‐NMR spectrum of this polymer was completely annotated by proposing a new step in the reaction mechanism. The four thermal dimers of glycidol were also isolated and identified as 2,5‐bis(hydroxymethyl)‐1,4‐dioxane and 2,6‐bis(hydroxymethyl)‐1,4‐dioxane, each of which can exist in cis and trans configurations. Polyglycidol was found to be hygroscopic, picking up about 5% by weight of atmospheric moisture. It was also found that, over time (ca. 1–2 years), polyglycidol crosslinks into a rubbery, insoluble mass. It is therefore recommended that this polymer be stored dry and used within a few months of synthesis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1344–1351, 2004     

Synthesis of polyaminostyrene‐based and polyallylamine‐based sorbents for boron removal

Hydroxyalkyl derivatives of polyaminostyrene (PAS), polyallylamine (PAA), and polyethyleneimine (PEI) containing a 2,3‐dihydroxypropyl moiety with a high degree of modification were synthesized. The chemical structures of the polymer transformation products were characterized with elemental analysis, Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, and ¹³C‐NMR spectroscopy in the solid state. PAS reacted with glycidol and formed poly[N‐(2,3‐dihydroxypropyl)aminostyrene] with a high degree of functionalization. PAA revealed primarily the graft polymerization of glycidol. In the case of PEI, primary amino groups allowed the formation of an N‐derivative of 3‐aminopropanediol‐1,2. The PAA‐based sorbent showed a high sorption capacity toward boron ions in both acidic and alkaline media. From the sorption isotherm data, the maximum sorption capacity of this sorbent at pH 4 was determined to be 3 mmol/g. The PAS‐based resin maintained a high capacity between pH 9 and 12; the optimum pH was 12. The sorption capacity was 1.7 mmol/g. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43939.     

Microwave‐assisted synthesis of polyglycerol from glycerol carbonate

Microwave irradiation of glycerol carbonate allows formation of glycidol, which readily polymerizes to form polyglycerol under mild conditions comparatively to the classical polyetherification reaction involving high temperature and basic conditions. Analysis of the crude reactional mixture indicated the presence of low‐molecular weight oligomers constituted mainly of di, tri, and tetraglycerols with small quantities of higher molecular weights oligomers. Molecular size distribution was relatively similar to that of polyglycerols obtained under basic condition, even if these latter contained slightly higher amounts of high‐molecular weight oligomers. Structure of oligomers differs slightly according to the conditions of polymerization, and polyglycerols are obtained under microwave activation containing higher contents of cyclic isomers, whereas polyglycerols obtained under basic conditions contain more ramified isomers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Photooxygenation Catalysis with a Polyol‐Decorated Disc‐Shaped Porphyrin Sensitizer: Shell‐Recognition Effects

Polar meso‐tetraarylporphyrins 2 – 4 were synthesized from tetrakis‐4‐hydroxyphenylporphyrin 1 as the central building block by consecutive base‐induced reactions with glycidol. The decorating units form a polar hydrogen‐bonded shell around the sensitizer core which is proposed as the binding site for polar substrates in photocatalyzed oxygenation reactions. As substrate, the polarity‐sensor mesitylol ( 5 ) was applied and the reaction constrained in a polystyrene matrix. Increasing shell dimensions lead to increased diastereoselectivities for the allylic hydroperoxides 6 and thus clearly demonstrate the concept of shell‐induced substrate stereoselectivity in singlet oxygen reactions.     

Swelling and drug release profile of poly(2‐ethyl‐2‐oxazoline)‐based hydrogels prepared by gamma radiation‐induced copolymerization

Poly(2‐ethyl‐2‐oxazoline) and acrylic acid were copolymerized in different compositions using γ‐rays‐induced polymerization and cross‐linking to obtain a series of pH‐sensitive hydrogels. The preparation parameters that may affect the copolymerization process such as the feed solution composition and irradiation dose were optimized. Swelling characteristics of the obtained polymeric hydrogels were evaluated. The results show the significant effects of the hydrogel composition, soaking time, and pH on the swelling equilibrium. The diffusion parameters obtained at pH 1 and 7 show the possibility of using the prepared hydrogels in the field of colon‐specific drug delivery systems. Ibuprofen as a model drug was loaded into (poly(2‐ethyl‐2‐oxazoline)/acrylic acid) copolymer hydrogel to investigate their drug release behavior at different pH values. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of polydopamine‐mediated PP hollow fibrous membranes with good hydrophilicity and antifouling properties

Membrane fouling remains a major barrier to membrane separation, particularly obvious in polymer membranes. Dopamine (DA) is of great value as a precursor for conjugation hydrophilic molecules. In this study, PP hollow fibrous membranes were first modified by DA to form a layer of polydopamine (PDA) coating. Then taurine and glycidol were introduced respectively with assisted by PDA reactive layer, the prepared membranes corresponding to PP‐T and PP‐G membranes, respectively. PP and the modified PP membranes were confirmed by a thorough membrane characterization of ATR‐FTIR, XPS, and FESEM measurements. The hydrophilic properties and permeability were measured by water contact angle (WCA) and permeation flux test. BSA was used to as model protein to evaluate the antifouling properties of the membranes. The results showed that taurine and glycidol were successfully introduced onto the membrane surface. The WCA of PP‐T and PP‐G membranes can be reduced to 32° and 26°, and the flux recovery ratio increased around 90.6% and 89.8%, respectively. Based on the experimental results, taurine and glycidol effectively improved the hydrophilic and anti‐fouling performance of PP membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44430.     

Characterization of poly(1‐methyl‐1,4‐butanediol‐1,4‐diyl/2,3,4‐trihydro‐5‐methylfuran‐2,5‐diyl) prepared from natural rubber through 2D NMR spectroscopy

Poly(1‐methyl‐1,4‐butanediol‐1,4‐diyl/2,3,4‐trihydro‐5‐methylfuran‐2,5‐diyl) was prepared by epoxidation of deproteinized natural rubber with m‐chloroperbenzoic acid followed by hydrolysis with sulfuric acid. Characterization of the resulting product was performed through FT‐IR, ¹H NMR, and ¹³C NMR spectroscopies. All signals appearing in the ¹H and ¹³C NMR spectra were assigned by distortionless enhancement by polarization transfer (DEPT), quaternary carbon observation (QUAT), correlation spectroscopy (COSY), and heteronuclear multiple quantum correlation (HMQC) measurements. After proving the primary structure of the product, one pot synthesis of poly(1‐methyl‐1,4‐butanediol‐1,4‐diyl/2,3,4‐trihydro‐5‐methylfuran‐2,5‐diyl) from deproteinized natural rubber latex was carried out with peracetic acid and 2‐propanol. The resulting product was characterized by ¹H NMR spectroscopy on the basis of the assignments established in this study, and its gas permeability was measured for a practical application as a film. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Solvent‐free synthesis of glycerol carbonate and glycidol from 3‐chloro‐1,2‐propanediol and potassium (hydrogen) carbonate

BACKGROUND: An indirect solvent‐free synthetic approach for obtaining glycerol carbonate and glycidol from glycerol and CO₂ through their more reactive and easily synthesizable derivatives 3‐chloro‐1,2‐propanediol (HAL) and potassium (hydrogen) carbonate has been studied. RESULTS: The reaction is fast with source of carbonation and temperature having a strong influence on the results. A yield of 80% glycerol carbonate together with a simultaneous substantial production of glycidol (0.56 mol mol^?1 glycerol carbonate) are obtained using K₂CO₃ as the carbonation source at 80 °C, a reaction time of 30 min and a 3:1 HAL/K₂CO₃ molar ratio. A lower yield of glycerol carbonate (60%) is obtained from KHCO₃ after 50 min with the other experimental conditions remaining unchanged. In this case, glycidol formation is zero or insignificant. Glycerol is also obtained in high yields, although in much lower amounts from KHCO₃ (～0.59 mol mol^?1 glycerol carbonate independent of operating conditions) than from K₂CO₃ (0.84–1.1 mol mol^?1 glycerol carbonate, depending on experimental conditions). CONCLUSIONS: The proposed synthetic strategy overcomes the currently difficult direct reaction between glycerol and CO₂, leading to the simultaneous synthesis of two valuable chemicals: glycerol carbonate and glycidol. However, glycerol is also obtained in substantial amounts thus decreasing the overall yield of the process. Thus, methods for preventing its formation must be developed for industrial feasibility. Copyright © 2010 Society of Chemical Industry