Triallyl Ether Research Articles

A study of poly(pentaerythritol triallyl ether) embolic granules with medium swelling properties using for vascular embolizations against hepatocellar carcinoma

A study of poly(pentaerythritol triallyl ether) embolic granules with medium swelling properties using for vascular embolizations against hepatocellar carcinoma

A micro-crosslinked amphoteric hydrophobic association copolymer as high temperature- and salt-resistance fluid loss reducer for water-based drilling fluids

During ultradeep oil and gas drilling, fluid loss reducers are highly important for water-based drilling fluids, while preparing high temperature- and salt-resistance fluid loss reducers with excellent rheology and filtration performance remains a challenge. Herein, a micro-crosslinked amphoteric hydrophobic association copolymer (i.e., DADC) was synthesized using N,N-dimethyl acrylamide, diallyl dimethyl ammonium chloride, 2-acrylamido-2-methylpropane sulfonic acid, hydrophobic monomer, and pentaerythritol triallyl ether crosslinker. Due to the synergistic effects of hydrogen bonds, electrostatic interaction, hydrophobic association, and micro-crosslinking, the DADC copolymer exhibited outstanding temperature- and salt-resistance. The rheological experiments have shown that the DADC copolymer had excellent shear dilution performance and a certain degree of salt-responsive viscosity-increasing performance. The DADC copolymer could effectively adsorb on the surface of bentonite particles through electrostatic interaction and hydrogen bonds, which bring more negative charge to the bentonite, thus improving the hydration and dispersion of bentonite particles as well as the colloidal stability of the drilling fluids. Moreover, the drilling fluids constructed based on the DADC copolymer exhibited satisfactory rheological and filtration properties (FLHTHP = 12 mL) after aging at high temperatures (up to 200 °C) and high salinity (saturated salt) environments. Therefore, this work provided new insights into designing and fabricating high-performance drilling fluid treatment agents, demonstrating good potential applications in deep and ultradeep drilling engineering.

Box–Behnken response surface method for the synthesis of high‐temperature‐ and salt‐resistant filter loss reducers

AbstractWellbores are destabilized by the immersion of a formation in drilling fluid during deep well drilling. To address this issue, in the present study, trimethylolethane triallyl ether (TMETE), 2‐acrylamide‐2‐methylpropanesulfonic acid (AMPS), acrylamide, and N‐vinylpyrrolidone undergo free radical copolymerization to produce a PTAAN filter loss reducer. The Box–Behnken response surface method is used to optimize the synthesis of PTAAN; the optimal conditions are 1 wt% TMETE and 0.1111 wt% initiator at 60°C. Fourier transform infrared spectroscopy, transmission electron microscopy, and thermogravimetric analysis are used to characterize the composition, micromorphology, and thermal stability of the PTAAN product, respectively. The synthesized product is resistant to high temperatures and salt under the optimal synthesis conditions. It has an API filtration loss of 8.2 mL for freshwater‐based mud, an API filtration loss of 13.8 mL for 20% by weight brine mud after aging at 220°C, and an API filtration loss of 29.5 mL at 150°C under high temperatures and pressures. Incorporating PTAAN into the base slurry prevents clay particle agglomeration at elevated temperatures and high mineralization, resulting in a broader clay particle size distribution and ultimately leading to the formation of a thin and compact filter cake.

Preparation of the amorphous embolic agents from glyceryl triallyl ether via a photo-driven radical-mediated [3 + 2] cyclopolymerization

Preparation of the amorphous embolic agents from glyceryl triallyl ether via a photo-driven radical-mediated [3 + 2] cyclopolymerization

Preparation and evaluation of high‐temperature filtrate reducer for solid‐free water‐based drilling fluid

AbstractThe object of this work was to improve the temperature and salt resistance of filtrate reducers used in solid‐free water‐based drilling fluids at 200°C. This copolymer (PAD) was obtained by reacting pentaerythritol triallyl ether (PTE) with acrylamide AM, N‐isopropyl acrylamide (N‐AM), methacrylic acid (MAA), and 2‐acrylamide‐2‐methylpropanesulfonic acid sodium (AMPS‐Na) in radical polymerization with potassium peroxydisulfate (KPS) and sodium bisulfite as initiators. The molar ratio of each monomer shown as follow: nAm:nN−Am:nMAA:nAmps: = 1:1.6:0.9:1.5. The functional groups of each monomer were revealed by Fourier transformation infrared. Moreover, 13C nuclear magnetic resonance confirmed the PAD was synthesized by addition polymerization through these monomers. Scanning electron microscopy showed that the surface of the filter cake was smooth and dense, indicating that PAD can effectively block small pores and thus reduce filter loss. The analysis suggested the PAD produced a “ball” structure at high temperature and salt which controlled the filtration of drilling fluid. The maximum temperature resistance boundary of PAD was 210°C. PAD maintained filtration performance in nearly saturated sodium chloride, 1.4 g/cm3 HCOOK and 1.37 g/cm3 HCOONa, at 210°C for 16 h.

Surface engineering of Si wafers with tunable surface morphology and stiffness via visible light induced thiol‐ene click polymerization with 4‐(N,N‐diphenylamino)benzaldehyde as an organocatalyst

AbstractA facile strategy is developed to fabricate a two‐layer grafted polymer coatings on silicon wafers, specifically soft crosslinked polythioether as middle damping layer and stiff poly(methyl methacrylate) (PMMA) as top protecting layer. At first, a highly crosslinked polythioether layer was constructed on the surface of the silicon wafer with tunable thickness and smooth morphology with trimethylolpropane tris(2‐mercaptoacetate) and pentaerythritol triallyl ether as monomers and 4‐(N,N‐diphenyl‐amino)benzaldehyde as an organocatalyst. The Young's modulus of the grafted crosslinked polythioether layer is about 300–400 MPa and the roughness is about 11.3 nm measured by atomic force microscope. There are about 9000 ea reactive –SH in a cuboid cell with 1 nm2 base area and 7–14 μm height in the grafted crosslinked polythiolether layer. Then, a flatten PMMA coating layer with Young's modulus as high as ~2.4 GPa was grafted from/onto the surface of the crosslinked polythiolether with surface –SH groups as initiating or chain transfer sites.

Fabrication of a state of the art mesh lock polymer for water based solid free drilling fluid

Polymers are used widely in various kinds of drilling fluid to maintain the proper rheological properties. However, most of them are not available for high-temperature or salt solutions due to poor temperature and salt resistance. To ameliorate the temperature and salt resistance of polymer used in the solid-free water-based drilling fluid, a novel polymer with a kind of "Mesh-Lock" reinforced network cross structure, named PLY-F [main monomer acrylic acid (AA), acrylamide (AM), functional monomers 2-acrylamide-2-methylpropanesulfonic acid (AMPS) N-vinylpyrrolidone (NVP) and C16DMAAC] were prepared through free radical polymerization of an aqueous solution of organic cross-linking agent pentaerythritol triallyl ether (PTE) as a cross-linking system, Potassium persulfate (KPS) and sodium bisulfite as the initiator for the first time. The surface morphology, crosslinking architecture and temperature and salt resistance of the PLY-F were fully characterized with several means including SEM, FT-IR, 13CNMR, dynamic rheology, and long-term thermal stability. The SEM observation indicated that the PLY-F exhibits a regular “Mesh-Lock” reinforced network cross structure. FT-IR, 13CNMR analysis indicated that the characteristic functional groups of each monomer such as AM, AA, AMPS and NVP were all together in the polymer. The results show that the apparent viscosity retention rate of the PLY-F in the potassium formate solution (with a density of 1.3 g/cm3) was more than 80% after heat rolling for 72 h at 200 °C and the plastic viscosity retention rate reached 90.3%. Moreover, the salt resistance of the polymer can reach the density of 1.4 g/cm3 (potassium formate solution) under 200 °C and the temperature resistance can reach 220 °C under the density of 1.3 g/cm3 (potassium formate solution). Besides, the PLY-F still has good rheological properties in other saturated solutions (NaCl, HCOONa) under 210 °C.

Phosphate-Based Cross-Linked Polymers from Iodo-ene Photopolymerization: Tuning Surface Wettability through Thiol-ene Chemistry.

Motivated by the various reported potential applications of poly(phosphine oxide) materials, a visible light photoinitiated iodo-ene reaction was successfully employed in network polymerization between the phosphorus-containing multifunctional monomer, tris(allyloxymethyl)phosphine oxide (TAOPO), and diiodoperfluorobutane. The cross-linked poly(phosphine oxide) network exhibited a higher glass transition temperature than a similarly cross-linked polymer formulated with trimethylolpropane triallyl ether (TMPTAE). Interestingly, the TMPTAE/DIPFB cross-linked polymer, changed color from clear to yellow within 10 min of exposure to air, whereas the cross-linked poly(phosphine oxide) underwent a similar change only upon heating. Upon investigation, it was determined that alkenes were generated within the polymer network, presumably via elimination, accounting for the observed color. These double bonds, formed in the polymer matrix, permitted surface modification via radical thiol-ene reaction. The successful surface functionalization with PEG-SH resulted in increasing the surface wettability. Additionally, the phosphorus-containing network polymer with double bonds in the polymer matrix showed shape memory capability, this representing an exciting and versatile materials platform.

Modified soybean oil as a reactive diluent: Synthesis and characterization

ABSTRACTSoybean oil was modified in two steps: (1) conjugation of soybean oil and (2) Diels‐Alder addition with 3‐(trimethoxysilyl)propyl methacrylate, 2,2,2‐trifluoroethyl methacrylate and triallyl ether acrylate. The structures were characterized using 1H NMR, 13C NMR, 13C‐1H gradient heteronuclear single quantum coherence (gHSQC) NMR spectroscopy, and MALDI‐TOF mass spectrometry. The 13C‐1H gHSQC NMR spectra helped confirm the formation of a cyclohexene ring in all reactions, indicating a Diels‐Alder addition. The diluent efficiency of modified soybean oil was evaluated in long oil alkyd formulation. Triallyl ether functionalized soybean oil resulted in the highest reduction in the viscosity of the alkyd formulations. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 3045–3059

Mussel-Inspired Thiol–Ene Polymer Networks: Influencing Network Properties and Adhesion with Catechol Functionality

In this work, we report the synthesis of photocurable, ternary polymer networks prepared by incorporating dopamine acrylamide (DAm) into a cross-linked thiol–ene network based on pentaerythritol triallyl ether (APE) and pentaerythritol tetra(3-mercaptopropionate) (PETMP). We systematically evaluate the effect of DAm, in the nonoxidized catechol form, on photopolymerization kinetics and thermal, thermomechanical, and mechanical properties of the modified thiol–ene networks. We show that while DAm only affects photopolymerization kinetics at high concentrations, the presence of the catechol moiety significantly increases the glass transition temperature of the networks across the compositional range (0–50 mol % DAm) due to hydrogen bonding interactions between the catechol and various hydrogen bonding acceptors (ethers, amides, esters) within the network, despite an obvious decrease in cross-link density with increasing concentration of the monofunctional acrylamide. Similarly, trends in the mechanical properties of the DAm–APE–PETMP networks reflect the interplay that exists between competing network design parameters, including the catechol hydrogen bonding interactions and the decrease in cross-link density derived from the use of a monofunctional acrylamide—both of which simultaneously influence network properties. Additionally, we report improved macroscopic adhesion of DAm–APE–PETMP coatings to a range of substrates—including glass, aluminum, steel, and marble—by systematically varying the amount of DAm in the network. Adhesion of the DAm–APE–PETMP coatings were evaluated using two methods, including pull-off and crosshatch adhesion tests.

Factors affecting the sieving behavior of anti-fouling thin-layer cross-linked hydrogel polyethersulfone composite ultrafiltration membranes

Anti-fouling thin-layer hydrogel composite membranes based on polyethersulfone (PES) ultrafiltration (UF) membranes were synthesized by addition of the crosslinking agents N,N′-methylene bisacrylamide (MBAA) and pentaerythritol triallyl ether (PETAE) to the modifier solution of poly(ethylene glycol)400 methacrylate (PEGMA) in water under variation of the UV irradiation intensity and dose. The resulting membrane properties were characterized by means of water permeability, degree of grafting (DG), modification depth and skin-layer cross-section structure (scanning electron microscopy; SEM) as well as sieving/rejection behavior via filtration of polyethylene glycol (PEG) and dextran mixtures with wide molecular weight distribution (MWD) in water, the latter as additional study to already performed experiments on protein rejection [1]. For better understanding of the obtained results, bulk hydrogels were also prepared and the degree of swelling (DS) was determined. The performed experiments showed that the used crosslinkers changed the hydrogel layer structure and properties, which significantly affected the sieving/rejection behavior of the composite membranes. Using test solutions with low fouling tendency facilitated the validation of the obtained data in comparison to the previously reported protein rejection results. It was shown that polyPEGMA/MBAA composite membranes exhibited higher solute rejection, while polyPEGMA/PETAE showed lower solute rejection compared to uncrosslinked polyPEGMA composite membranes prepared with the same UV irradiation dose. Increasing the amount of crosslinkers amplified these effects. Furthermore, a trade-off analysis between water permeability and molecular weight cut-off (MWCO) for virgin and composite membranes was done in order to evaluate the membrane performance improvement by the composite membranes. The obtained results showed that the prepared composite membranes exhibited better fluxes and selectivity compared to commercial membranes with analogous characteristics.

PLA-based biodegradable and tunable soft elastomers for biomedical applications

Although desirable for biomedical applications, soft degradable elastomers having balanced amphiphilic behaviour are rarely described in the literature. Indeed, mainly highly hydrophobic elastomers or very hydrophilic elastomers with hydrogel behaviours are found. In this work, we developed thermoset degradable elastomers based on the photo-cross-linking of poly(lactide)-poly(ethylene glycol)-poly(lactide) (PLA-PEG-PLA) triblock prepolymers. The originality of the proposed elastomers comes from the careful choice of the prepolymer amphiphilicity and from the possible modulation of their mechanical properties and degradation rates provided by cross-linkers of different nature. This is illustrated with the hydrophobic and rigid 2,4,6-triallyloxy-1,3,5-triazine compared to the hydrophilic and soft pentaerythritol triallyl ether. Thermal properties, mechanical properties, swelling behaviours, degradation rates and cytocompatibility have been evaluated. Results show that it is possible to generate a family of degradable elastomers covering a broad range of properties from a single biocompatible and biodegradable prepolymer.

Tung based reactive diluents for alkyd systems: Film properties

Reactive diluents were prepared from tung oil via a Diels–Alder reaction with three different dienophiles: methacryloxypropyl trimethoxysilane (TOMAS), 2,2,2-trifluoroethyl methacrylate (TOF) and triallyl ether acrylate (TOTAE). The reactive diluents were mixed with a long oil soya alkyd, a metal drier package, and a wetting agent; and then cured. Formulations were prepared as a function of reactive diluent type and wt%. Tensile, thermomechanical, and coatings properties were evaluated after curing the films. The addition of two reactive diluents, TOMAS and TOTAE, improved the tensile strength and tensile modulus of the alkyd. The addition of the diluents, however, did not significantly change the elongation at break compared to the alkyd in any of the systems. Also, the addition of TOMAS and TOTAE increased both the crosslink density and glass transition temperature of the alkyd. Basic film properties including hardness, solvent resistance, impact resistance, adhesion, and gloss were not adversely affected by the introduction of any of the tung oil based diluents.

Synthesis and properties of acrylate functionalized alkyds via a Diels–Alder reaction

The α-eleosterate pendent fatty acid of a tung oil based alkyd was functionalized via a Diels–Alder reaction with three different acrylate groups: (1) 2,2,2-trifluoroethyl methacrylate, (2) 3-methacryloxypropyl trimethoxysilane, and (3) triallyl ether acrylate. The modified alkyds were characterized by using 1H NMR, 13C NMR, and gel permeation chromatography (GPC). The drying time was measured at ambient temperature. The viscoelastic properties of the alkyd-modified films were measured using dynamic mechanical thermal analysis. The viscoelastic and drying time results show that the alkyd modified with siloxane and triallyl group affords a faster drying time, higher crosslink density, and higher glass transition temperature compared to the unmodified alkyd, whereas the fluorinated alkyd possesses surface active properties, but suffers in terms of drying and crosslinking density.

Synthesis of Tung‐Oil‐Based Reactive Diluents

AbstractThree new reactive diluents were prepared from tung oil using a Diels‐Alder reaction. The dienophiles were methacryloxypropyl trimethoxysilane (MAS), 2,2,2‐trifluoroethyl methacrylate (TFM) and triallyl ether acrylate (TAEA). The chemical structures were evaluated using 1H NMR, 13C NMR, FT‐IR, GPC and MALDI‐TOF‐MS. Spectra evidence (NMR, MS) indicated that a six‐member ring were formed in all three reactions indicating a Diels‐Alder adduct. The reactive diluents were formulated with a soya‐based alkyd to evaluate viscosity reduction and drying time. The viscosity of alkyd was reduced up to 70% using the reactive diluents. The drying time for the autoxidative reactive diluents with alkyds were 1.8‐1‐7 times faster than alkyd alone. magnified image

Tuning the ultrafiltration properties of anti-fouling thin-layer hydrogel polyethersulfone composite membranes by suited crosslinker monomers and photo-grafting conditions

Anti-fouling composite membranes were prepared via photo-initiated “grafting-from” of the hydrophilic monomer poly(ethylene glycol) methacrylate on commercial polyethersulfone ultrafiltration membranes. A fine adjustment of the sieving properties of the modified membranes could be achieved by addition of suited crosslinker monomers in appropriate ratio to the reaction mixture. In this study, two crosslinkers were used: N,N′-methylene bisacrylamide (MBAA) and pentaerythritol triallyl ether (PETAE). Systematic variations of UV intensity and UV irradiation time in combination with varied monomer mixtures have been performed. The resulting membranes have been characterized with respect to degree of functionalization, contact angle and zeta potential as well as water flux and protein ultrafiltration performance with bovine serum albumin and myoglobin, yielding data for solute rejection and permeability loss due to membrane fouling. A minimum degree of functionalization was necessary to achieve fouling resistance, and especially in this range, the effects of the two crosslinker monomers were largely different. Crosslinking with the “two-armed” MBAA yielded denser hydrogel layers on the porous base membrane and, consequently, enhanced protein rejection with increasing crosslinker ratio. In contrast, on the same membrane pore size, hydrogel layers crosslinked with the “three-armed” PETAE yielded a more open barrier structure and the protein rejection decreased with increasing crosslinker ratio. Overall, this study delivered fundamental results for the preparation of high performance composite membranes with enhanced selectivity and anti-fouling properties for ultrafiltration.

Photopolymerization of thiol‐ene systems based on oligomeric thiols

AbstractThiol oligomers were copolymerized with a triallyl ether by a photoinduced polymerization process. These oligomeric thiol‐ene systems comprise the same components as a photopolymerized thiol‐ene‐acrylate ternary system, yet the photopolymerized networks have much lower glass transition temperatures. An investigation into the effect of oligomeric thiol design on network formation was conducted by analyzing the reaction kinetics and thermal/mechanical properties of the thiol‐ene networks. Real‐time FTIR analysis shows that total conversion is >90% for all thiols investigated. Photo‐DSC analysis shows that the maximum exotherm rate is roughly equivalent for all of the thiols when the equivalent weight of the thiol is taken into account. As would be expected, the glass transition temperature and tensile strength increase with thiol functionality and lower thiol equivalent weight for thiols with functionality from 2 to 4. Films made using the oligomeric thiols have essentially the same glass transition temperatures and tensile modulus values regardless of thiol design. These results distinguish the method for generation of networks consisting of an initial Michael reaction of thiols and acrylates followed by a photoinitiated copolymerization with a multifunctional ene from the traditional photolysis of the corresponding thiol‐ene‐acrylate ternary systems with no Michael reaction. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 14–24, 2009

Kinetics analysis and physical properties of photocured silicate-based thiol-ene nanocomposites: The effects of vinyl POSS ene on the polymerization kinetics and physical properties of thiol-triallyl ether networks

The kinetics and thermal/physical properties of the trithiol-TAE (triallyl ether) system were measured with respect to increasing polyoligomeric silsesquioxane (POSS) concentrations in order to understand how the presence of POSS nanoparticles affects network formation at low loadings. Vinyl POSS monomer (vPOSS-Bu4) with both vinyl and carboxylate pendant groups was synthesized via a thermally initiated, free-radical reaction to improve the compatibility of the inorganic particles with the trithiol and triallyl ether comomoners. Chemically modified vPOSS-Bu4 particles were incorporated into the trithiol-TAE polymer networks by a thiol-ene free-radical photopolymerization at molar concentrations of 0, 1, and 5 ene mol%. The polymerization rates were analyzed using real-time FTIR and photo-DSC. The polymerization rates showed no significant changes with increasing vPOSS-Bu4 concentration. Thermal analyses of the films by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) demonstrated that thermal stability improves without affecting T g as the POSS concentration increased. Additionally, scratch resistance increased and flame spread decreased markedly with increasing POSS concentration for concentrations up to 5 mol% vPOSS-Bu4.

Holographic polymer dispersed liquid crystals (HPDLCs) containing triallyl isocyanurate monomer

The morphology and corresponding performance of holographic polymer dispersed liquid crystals (HPDLCs) based on thiol–ene polymer are dependent on a number of factors including the gel point conversion of the polymer, polymerization kinetics, and extent of liquid crystal (LC) phase separation. Previous research of HPDLC reflection gratings made from thiol–allyl ether polymer indicates that increasing polymerization rate in systems with moderate gel point conversion can improve diffraction efficiency (DE). This work examines HPDLC reflection gratings that contain the ene monomer triallyl isocyanurate (TATATO). In HPDLCs, thiol–TATATO polymerization is two times faster than the thiol–ene polymerization of triallyl ether. By substituting TATATO for triallyl ether, the LC droplet size within HPDLC reflection gratings decreases from 100nm to 25nm. The dramatic reduction in LC droplet size for thiol–TATATO HPDLCs increases baseline transmission from 55% in thiol–triallyl ether HPDLCs to 90% at 450nm. Unfortunately, the DE of thiol–TATATO HPDLCs is only approximately 10% due to poorly defined lamellae in the grating morphology. As determined with real-time IR (RTIR) spectroscopy, thiol–TATATO HPDLCs have significantly faster LC demixing kinetics in comparison to thiol–allyl ether HPDLCs. During holographic photopolymerization, the increased rate of LC demixing causes formation of LC droplets throughout the grating. The low DE of thiol–TATATO HPDLCs can be improved by mixing TATATO and allyl ether monomer. The morphology of ternary thiol–ene HPDLC formulations containing TATATO and allyl ether has a well-defined grating structure due to increased LC solubility in the system, an average LC droplet size of 50nm, and baseline transmission of nearly 85% at 450nm.

Photopolymerization of ternary thiol–ene/acrylate systems: Film and network properties

AbstractPhotocurable, ternary‐component mixtures of a 1:1 molar multifunctional thiol–ene (trithiol and triallyl ether) blend and a 16‐functional acrylate based monomer have been photopolymerized, and the final film properties of the ternary crosslinked networks have been measured. The photopolymerization kinetics, morphology, and mechanical and physical properties of the films have been investigated with real‐time infrared, atomic force microscopy, and dynamic mechanical analysis. The photopolymerization process is a combination of acrylate homopolymerization and copolymerizations of thiol with allyl ether and acrylate functionalities. The tan δ peaks of the photopolymerized ternary systems are relatively narrow and tunable over a large temperature range. The morphology is characterized by a distinct phase‐separated nanostructure. The photocured thiol–ene/acrylate ternary systems can be made to exhibit good mechanical properties with enhanced energy absorption at room temperature by the appropriate selection of each component concentration. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 822–829, 2007.