Neopentyl Glycol Diglycidyl Ether Research Articles

Epoxy (Meth)acrylate-Based Thermally and UV Initiated Curable Coating Systems.

Recently, photocurable coatings are being used frequently. However, it is worth mentioning that the use of photopolymerization has its drawbacks, especially in the case of curing coatings on three-dimensional surfaces and in places that are difficult to access for UV radiation. However, it is possible to develop a system in which UV technology and thermal methods for curing coatings can be combined. Moreover, the obtained resins are derived from low-viscosity epoxy resins or diglycidyl ethers, making them an ideal building material for photopolymerization-based three-dimensional printing techniques. Due to the need to improve this method, a series of epoxy (meth)acrylates containing both epoxy and (meth)acrylate groups were obtained via the addition of acrylic or methacrylic acid to epoxy resin, diglycydylether of bisphenol A epoxy resin (DGEBA), cyclohexane dimethanol diglycidyl ether (CHDMDE) and neopentyl glycol diglycidyl ether (NPDE). The structures of the synthesized copolymers were confirmed through spectroscopic analysis (FTIR) and studied regarding their nonvolatile matter content (NV) and acid values (PAVs), as well as their epoxy equivalent values (EEs). Due to the presence of both epoxy and double carbon-carbon pendant groups, two distinct mechanisms can be applied: cationic and radical. Hence, the obtained resins can be cured using UV radiation with thermally appropriate conditions and initiators. This type of method can be used as a solution to many problems currently encountered in using UV technology, such as failure to cure coatings in underexposed areas as well as deformation of coatings. Synthesized epoxy (meth)acrylate prepolymers were employed to formulate photocurable coating compositions. Furthermore, the curing process and properties of cured coatings were investigated regarding some structural factors and parameters. Among the synthesized materials, the most promising are those based on epoxy resin, characterized by their high glass transition temperature values and satisfactory functional properties.

Organic-inorganic building block of phytic acid intercalated graphene oxide for performance enhancement of plant-derived adhesives

The introduction of 2D graphene into the soybean protein (SP) adhesive is expected to enhance its mechanical performance. However, insufficient binding of the two materials inevitably leads to the resulting composite having limited mechanical strength. Using phytic acid (PA) and a supramolecular self-assembly strategy, hard graphene oxide (GO) was first assembled with PA to form a supramolecular polymer, PA-co-GO, that has a “bricks and mortar” structure as a result of strong non-covalent interactions. PA-co-GO was then further combined with SP in the presence of the long-chain epoxy compound neopentyl glycol diglycidyl ether (NG) to produce a novel biopolymer-based adhesive PA-co-GO/NG/SP. The prepared adhesive has a moisture-insensitive interface as a result of non-covalent/covalent bonds and a “bricks and mortar” microstructure that allows the dissipation of energy, resulting in an enhancement in the water-resistant bonding strength of the material, with a 345% increase in its wet bonding strength compared with the unmodified SP adhesive. Additionally, the combination of the heat shielding of the GO and catalytic carbonization of PA resulted in the adhesive having excellent flame retardant properties. The structure and morphology of the materials were characterized using atomic force microscopy (AFM), dynamic light scattering (DLS), Fourier-transform infrared (FTIR), X-ray photoelectron spectra (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and solid-state 13C NMR. Overall, a new clean route for preparing green high-performance biopolymer-based adhesives is described, with potential applications for sustainable agricultural byproducts.

Shape memory polymer composites (SMPCs) using interconnected nanowire network foams as reinforcements

Shape memory polymers (SMPs), although offer a suite of advantages such as ease of processability and lower density, lag behind their shape memory alloy counterparts, in terms of mechanical properties such as recovery stress and cyclability. Reinforcing SMPs with inorganic nanowires and carbon nanotubes (CNTs) is a sought-after pathway for tailoring their mechanical properties. Here, inorganic nanowires also offer the added advantage of covalently binding the fillers to the surrounding polymer matrices via organic molecules. The SMP composites (SMPCs) thus obtained have well-engineered nanowire-polymer interfaces, which could be used to tune their mechanical properties. A well-known method of fabricating SMPCs involving casting dispersions of nanowires (or CNTs) in mixtures of monomers and crosslinkers typically results in marginal improvements in the mechanical properties of the fabricated SMPCs. This is owed to the constraints imposed by the rule-of-mixture principles. To circumvent this limitation, a new method for SMPC fabrication is designed and presented. This involves infiltrating polymers into pre-fabricated nanowire foams. The pre-fabricated foams were fabricated by consolidating measured quantities of nanowires and a sacrificial material, such as (NH4)2CO3, followed by heating the consolidated mixtures for subliming the sacrificial material. Similar to the case of traditional composites, use of silanes to functionalize the nanowire surfaces allowed for the formation of bonds between both the nanowire-nanowire and the nanowire-polymer interfaces. SMPCs fabricated using TiO2 nanowires and SMP composed of neopentyl glycol diglycidyl ether and poly(propylene glycol) bis(2-aminopropyl ether) (Jeffamine D230) in a 2:1 molar ratio exhibited a 300% improvement in the elastic modulus relative to that of the SMP. This increase was significantly higher than SMPC made using the traditional fabrication route. Well-known powder metallurgy techniques employed for the fabrication of these SMPCs make this strategy applicable for obtaining other SMPCs of any desired shape and chemical composition.

Dielectric and Mechanical Properties of Silicone Rubber Composites Reinforced by Conductive Carbon Black and Neopentyl Glycol Diglycidyl Ether

Dielectric and Mechanical Properties of Silicone Rubber Composites Reinforced by Conductive Carbon Black and Neopentyl Glycol Diglycidyl Ether

A Convenient U-Shape Microreactor for Continuous Flow Biocatalysis with Enzyme-Coated Magnetic Nanoparticles-Lipase-Catalyzed Enantiomer Selective Acylation of 4-(Morpholin-4-yl)butan-2-ol

This study implements a convenient microreactor for biocatalysis with enzymes immobilized on magnetic nanoparticles (MNPs). The enzyme immobilized onto MNPs by adsorption or by covalent bonds was lipase B from Candida antarctica (CaLB). The MNPs for adsorption were obtained by covering the magnetite core with a silica shell and later with hexadecyltrimethoxysilane, while for covalent immobilization, the silica-covered MNPs were functionalized by a layer forming from mixtures of hexadecyl- and 3-(2-aminoethylamino)propyldimethoxymethylsilanes in 16:1 molar ratio, which was further activated with neopentyl glycol diglycidyl ether (NGDE). The resulting CaLB-MNPs were tested in a convenient continuous flow system, created by 3D printing to hold six adjustable permanent magnets beneath a polytetrafluoroethylene tube (PTFE) to anchor the MNP biocatalyst inside the tube reactor. The anchored CaLB-MNPs formed reaction chambers in the tube for passing the fluid through and above the MNP biocatalysts, thus increasing the mixing during the fluid flow and resulting in enhanced activity of CaLB on MNPs. The enantiomer selective acylation of 4-(morpholin-4-yl)butan-2-ol (±)-1, being the chiral alcohol constituent of the mucolytic drug Fedrilate, was carried out by CaLB-MNPs in the U-shape reactor. The CaLB-MNPs in the U-shape reactor were compared in batch reactions to the lyophilized CaLB and to the CaLB-MNPs using the same reaction composition, and the same amounts of CaLB showed similar or higher activity in flow mode and superior activity as compared to the lyophilized powder form. The U-shape permanent magnet design represents a general and easy-to-access implementation of MNP-based flow microreactors, being useful for many biotransformations and reducing costly and time-consuming downstream processes.

Influence of intraparticle cross-linking on polymer diffusion in latex films prepared from secondary dispersions

In this work, we synthesized surfactant-free latex dispersions of nanoparticles (NPs) based upon emulsification of a preformed proprietary BASF polymer (MnGPC = 5000 g/mol, Ð = 3, denoted as Pol), in which the —COOH groups were partially neutralized by ammonia. To obtain useful coatings with polymers of such low molecular weight (MW), we approached this problem through the reaction of carboxylated polymer dispersions with neopentyl glycol diglycidyl ether (NGDE, 20 to 60 mol% based on carboxyl groups) to increase the MW and to introduce gel content. We employed AFM to monitor the influence of cross-link density on the surface roughness and found the presence of cross-links increases the resistance of particles to deformation. Fluorescence resonance energy transfer (FRET) measurements were carried out to determine the extent of polymer mixing upon film formation. Our most important finding is that the gel content substantially limited the extent of molecular mixing at long annealing times or in corresponding solvent-cast films. In parallel, we carried out a series of similar reactions on the secondary dispersion particles with a monoepoxide, consisting of a mixture of dodecyl and tetradecyl glycidyl ether. This reaction maintained the size and size distribution of the latex particles. These polymers had no gel content, but the reaction with the epoxide lowered the Tg of the polymer. FRET studies showed a pronounced influence of Tg on the rates of polymer diffusion in these films.

Cross-Linked Enzyme-Adhered Nanoparticles (CLEANs) for Continuous-Flow Bioproduction.

Nanostructured but micro-sized biocatalysts were created by bottom-up technology using multi-functionalized silica nanoparticles (NPs) as nano-sized building blocks to form cross-linked enzyme-adhered nanoparticles (CLEANs) as robust micro-sized particles with beneficial internal structure and good mechanical properties. Systematic surface modification of NPs with a grafting mixture consisting of organosilanes with reactive (aminopropyl) and inert (e. g., vinyl, propyl, phenyl, or octyl) functions resulted in functional NPs enabling cross-linking agents, such as glutardialdehyde or bisepoxides (glycerol diglycidyl ether, neopentylglycol diglycidyl ether, and poly(propylene glycol) diglycidyl ether), to bind and cross-link enzymes covalently and to form macroporous microparticles. These CLEANs were able to diminish several weaknesses of traditional cross-linked enzyme aggregates as biocatalysts, such as poor mechanical resistance, difficult recovery, and storage, strengthening their use for packed-bed enzyme reactors. Lipase B from Candida antarctica (CaLB) was selected as model enzyme for development of robust CLEANs, which were successfully tested for various industrially relevant applications including a kinetic resolution of a racemic alcohol and the production of various natural fragrance compounds under continuous-flow conditions.

A SiO2 Microcarrier with an Opal-like Structure for Cross-Linked Enzyme Immobilization.

The opal-like SiO2 microcarriers with different pore diameters named opal-SiO2I and opal-SiO2II were synthesized and utilized as microcarriers to immobilize Rhizopus oryzae lipase (ROL) and Aspergillus oryzae α-amylases (AOA). ROL and AOA can be more stably immobilized on the cross-linked SiO2 opals by neopentyl glycol diglycidyl ether (NGDE), which is the first attempt to use it as a cross-linking agent compared with glutaraldehyde. According to the morphology analysis, multiple layers of SiO2 monodisperse microspheres were regularly packed and formed an opal-like structure, and enzymes were well scattered and immobilized throughout the SiO2 opals. The results showed that the performance of enzymes immobilized on opal-SiO2II with a larger specific surface area was much better than that of opal-SiO2I. The enzyme activity of ROL@opal-SiO2II and AOA@opal-SiO2II cross-linked with 1% NGDE increased 5.32 and 9.32 times compared with their free counterpart, respectively. Furthermore, pH and thermal stability and reusability of ROL/AOA@opal-SiO2II were significantly improved and higher than those of ROL/AOA@opal-SiO2I and free enzymes. This study provides an easily obtained microcarrier opal-SiO2II, which shows potential for efficient different enzyme immobilizations and further industrial applications.

Synthesis of non-isocyanate poly(hydroxyurethane)s (NI-PHUs) using diglycidyl ethers

In this study, we synthesized non-isocyanate poly(hydroxyurethane)s (NI-PHUs) via the polyaddition of bis(cyclic carbonate)s and diamines. Bis(cyclic carbonate)s were prepared by reacting resorcinol diglycidyl ether and neopentyl glycol diglycidyl ether with CO2. NI-PHUs were obtained through the reaction of the bis(cyclic carbonate)s with either an aliphatic or a cycloaliphatic diamine. The identities of the synthesized products were confirmed via 1H NMR and FT-IR spectroscopy. The glass transition temperatures (Tgs) of the NI-PHUs were higher when resorcinol diglycidyl ether was used to synthesize the bis(cyclic carbonate) instead of neopentyl glycol diglycidyl ether. The NI-PHUs prepared with isophorone diamine had significantly higher Tgs than those prepared with 1,4-diaminobutane.

Cold programming of epoxy-based shape memory polymer

Shape Memory Polymers (SMPs) are the class of smart materials that show ability to memorize different shapes and regain original shape. The conventional method is to heat SMP above its glass transition temperature (Tg) and deform it to obtain the desired shape. It reverts to original shape upon heating. This is known as hot programming. Recent advances in the programming of SMP have shown promising results of a new programming method also known as cold programming. The SMP is plastically deformed at a temperature below Tg to impart the desired shape. This paper aims at the experimental investigation of shape memory properties of Epoxy-based SMPs using the cold programming method. The polymers of Epoxy used in this work are Diglycidyl Ether of Bisphenol-A (DGEBA) and Neopentyl Glycol Diglycidyl Ether (NGDE). The mechanical properties like elastic modulus, tensile strength, and failure strain have been found for different ratios of DGEBA and NGDE at various temperatures. The Tg of different compositions has been measured using Differential Scanning Calorimetry (DSC). In this work, a candidate material has been identified based on its mechanical and shape memory properties. It has been demonstrated that important properties of material like glass transition temperature, elastic modulus, and strength can be tailored according to the need by changing the ratio of constituents. A dedicated experimental setup consisting of Uniaxial Tensile Machine (UTM), temperature control chamber, and a camera for Digital Image Correlation (DIC) has been used to carryout thermomechanical cycles of SMP. The parameters that affect the performance of cold programming like stress-relaxation time, structural relaxation time, and operating temperature have been studied. The stress-strain response for a complete shape memory cycle has been measured. Parameters determining the shape memory capabilities like shape fixity, recovery ratio, recovery speed of the material were evaluated. The merits and demerits of cold programming over other programming methods have been discussed by carrying out required experiments. The differences in both the programming methods and the underlying mechanism of shape memory effect have been discussed briefly in this paper. Present work is limited to the study of SMP for uniaxial tensile cases undergoing large deformation with small strain-rate and low rate of heating and cooling.

Incorporation of dumbbell-shaped and Y-shaped cross-linkers in adjustable pullulan/polydopamine hydrogels for selective adsorption of cationic dyes

Hydrogel adsorbents have attracted considerable attention due to their sludge minimization, good water permeability and renewable performance. Here, a promising strategy for the one-step preparation of pullulan/polydopamine hybird hydrogels (PPGels) was presented. Dumbbell-shaped cross-linker neopentyl glycol diglycidyl ether (NGDE, 2 arms) and Y-shaped cross-linker trimethylolpropane triglycidyl ether (TTE, 3 arms) were selected to study the relationship between cross-linker structure and hydrogel performances. The NGDE possessing less molecular repulsive force and higher reactivity demonstrated more effective cross-linking with the pullulan, which leaded to a decrease in pore size of the hydrogel. Meanwhile, the introduction of polydopamine significantly enhanced the adsorption ability and gave the resulting hybrid gel the specific selectivity toward cationic dyes (96 mg/g for crystal violet, 25.8 mg/g for methylene blue and barely not adsorption for azophloxine). Our data suggested that the electrostatic interaction played a vital role in the dye adsorption process, and the adsorption data could be explained by pseudo-second-order model and Langmuir isotherm model. Furthermore, the obtained PPGel could be easily separated after adsorption. This study describes the relationship between cross-linker structure and properties of pullulan/polydopamine hybrid gels, which provides a new strategy to create polysaccharide-based adsorbents for wastewater remediation.

Effect of nanoclay content on the thermal, mechanical and shape memory properties of epoxy nanocomposites

The bright future of shape memory epoxy polymer (SMEP), to be used in critical industries, can be refined by enhancing its properties and overcoming its limitations. Depicting the great performance of nanofillers in polymer composites, their inclusion in SMEP is expected to emphasize the properties of SMEP. In this study, experimental analyses are conducted to study the effects of nanoclay content on the thermal and mechanical properties of SMEP through dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), X-ray diffraction (XRD), flexural testing and shape memory cyclic testing. The epoxy systems, made of EPON 826 and neopentyl glycol diglycidyl ether (NGDE) and incorporated with 1 wt%, 3 wt% and 5 wt% montmorillonite (MMT) nanoclay, are prepared for characterization. It is found that increasing the nanoclay content decreases the glass transition temperature and increases the thermal stability of SMEP, through DMA and TGA, respectively. The highest values of both the storage modulus at glassy region from DMA and the flexural modulus from the flexural testing are observed for the nanocomposites with 3 wt% nanoclay content. The XRD analysis and TEM micrograph support these results. Meanwhile, only a small difference is observed based on TGA data. Addressing the main use of SMEP, the increment of nanoclay content has improved the shape recovery and shape fixity through the shape memory cyclic testing.

Smart Nanoparticles for Selective Immobilization of Acid Phosphatases.

An easy to use method combining the selectivity of metal chelate affinity binding with strong covalent linking was developed for immobilization of non‐specific acid phosphatases bearing a His‐tag from crude cell lysate. Silica nanoparticles were grafted with aminopropyl functions which were partially transformed further with EDTA dianhydride to chelators. The heterofunctionalized nanoparticles charged with Ni2+ as the most appropriate metal ion were applied as support. First, the His‐tagged phosphatases were selectively bound to the metal‐chelate functions of the support. Then, the enzyme‐charged silica nanoparticles were further stabilized by forming a covalent linkage between nucleophilic moieties at the enzyme surface and free amino groups of the support using neopentylglycol diglycidylether as the most effective bifunctional linking agent. The phosphatase biocatalysts obtained by this method exhibited better phosphate transfer activity with a range of alcohols and PPi as phosphate donor in aqueous medium applying batch and continuous‐flow modes than the ones immobilized on conventional supports. Furthermore, this novel strategy opens up novel possibility for efficient immobilization of other His‐tagged recombinant enzymes.

Direct characterization of cotton fabrics treated with di-epoxide by nuclear magnetic resonance

A non-acid-based, di-functional epoxide, neopentyl glycol diglycidyl ether (NPGDGE), was used to modify cotton fabrics. Direct characterization of the modified cotton was conducted by Nuclear Magnetic Resonance (NMR) without grinding the fabric into a fine powder. NaOH and MgBr2 were compared in catalyzing the reaction between the epoxide groups of NPGDGE and the hydroxyl groups of cellulose. Possible reaction routes were discussed. Scanning electron microscopy (SEM) images showed that while the MgBr2-catalyzed reaction resulted in self-polymerization of NPGDGE, the NaOH-catalyzed reaction did not. Fourier transform infrared spectroscopy (FTIR) showed that at high NaOH concentration cellulose restructures from allomorph I to II. NMR studies verified the incorporation of NPGDGE into cotton fabrics with a clear NMR signal, and confirmed that at higher NaOH concentration the efficiency of grafting of NPGDGE was increased. This demonstrates that use of solid state NMR directly on woven fabric samples can simultaneously characterize chemical modification and crystalline polymorph of cotton. No loss of tensile strength was observed for cotton fabrics modified with NPGDGE.

A New Flexible Soy-Based Adhesive Enhanced with Neopentyl Glycol Diglycidyl Ether: Properties and Application.

Soy-based adhesives inherently possess low water resistance and brittleness, which limit their application on plywood fabrication. This investigation involves using a long chain cross-linker, neopentyl glycol diglycidyl ether (NGDE), to produce an intrinsic toughening effect to reduce the brittleness and improve the water resistance of a soybean meal–based adhesive. The solids content, viscosity, functional groups, fracture surface micrographs, and thermal stability of the adhesives were measured. Three-layer plywood was fabricated using the resultant adhesive, and the tensile shear strength of the plywood was measured. All adhesive properties were compared with a soybean meal/polyamidoamine-epichlorohydrin (PAE) adhesive and commercial melamine urea formaldehyde resin. The results showed that adding 6 g NGDE improved the water resistance of the soybean meal-based adhesive by 12.5%. This improvement is attributed to the following reasons: (1) a dense cross-linked network is formed by the chemical reaction between NGDE and protein molecules; (2) the toughness of the adhesive increases and a smooth and homogeneous fracture surface is created, which effectively prevents moisture intrusion; (3) the addition of NGDE increases the thermostability of the cured adhesive. The tensile shear strength of the plywood bonded with the soybean meal-based adhesive with 6 g NGDE was 286.2% higher than that without NGDE and attained 1.12 MPa, which was attributed to the reduction in the adhesive’s viscosity, and the improvement in the water resistance and toughness of the adhesive. The tensile shear strength of the plywood bonded with 6 g NGDE was 19.1% higher than that with 6 g PAE and was similar to the MUF resin, which validated the novel adhesive being suitable for use as an industrial plywood adhesive.

Synthesis of a novel UV-curable prepolymer neopentyl glycol diglycidyl ether diacrylate and its cured film tensile property

A novel UV-curable prepolymer neopentyl glycol diglycidyl ether diacrylate (NPGGEA) was synthesized by using neopentyl glycol diglycidyl ether (NPGGE) and acrylic acid (AA) as starting materials, N, N-dimethylbenzylamine as catalyst and p-hydroxyanisole as inhibitor. The optimum synthetic conditions were taken as follows: The concentration of N,N-dimethylbenzylamine, 0.80% of reactants; the concentration of p-hydroxyanisole, 0.3% of reactants; the reaction temperature, 90–110 °C; the molar ratio of NPGGE to AA, 1:2.2. Meanwhile, 1-hydroxycyclohexyl phenyl ketone of a UV-cured initiator was added to the synthesized NPGGEA to prepare a kind of UV-cured coating. Mechanical properties of the UV-cured films were determined, giving 28.75 MPa of tensile strength, 923.82 MPa of Young’s modulus and 5.51% of elongation at tear.

Photopolymerization of neopentyl glycol diglycidylether and its compositions with 9-(2-oxiranylmethyl) carbazole

Photopolymerization of neopentyl glycol diglycidylether (NPG) initiated with diphenyl iodonium tetrafluoroborate (TB) in bulk has been studied. The influence of concentration of the photoinitiator on the rate of polymerization and monomer conversion is discussed. The initiator exponent was established for the photopolymerization of NPG with TB. Photopolymerization of the compositions consisting of NPG and 9-(2-oxiranylmethyl) carbazole (OMC) initiated with TB has been studied. It was established that OMC undergoes both homopolymerization and copolymerization during the UV irradiation of the composition. The effect of the temperature on the rate and conversion of epoxy groups for the photopolymerization of NPG alone and in the presence of OMC has been examined. It was established that 9-vinylcarbazole (VCz) acts as synergist of NPG photopolymerization as well of photopolymerization of the composition of NPG and OMC.

A novel one-pot oxidation polymerization of dithiols obtained from bifunctional five-membered cyclic dithiocarbonates with amines

One-pot oxidation polymerization of dithiols, obtained from bifunctional five-membered cyclic dithiocarbonates (4a and 4b) with two equivalents of amines, was studied. The monomers 4a and 4b were synthesized by the reactions of bisphenol A diglycidyl ether and neopentyl glycol diglycidyl ether with carbon disulfide, respectively. Polydisulfides with M̄ns 4600–20,200 were obtained quantitatively in the oxidation polymerization of the dithiols obtained in situ by the reactions of 4a with benzylamine, n-butylamine, and piperidine. On the other hand, dithiols obtained from 4b with benzylamine, afforded cyclic disulfides as well as the polydisulfide under similar conditions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 79–84, 1998