N-butyl Vinyl Ether Research Articles

The development of high-performance kinetic hydrate inhibitors by introducing N-vinyl caprolactam and vinyl ether homopolymers into PVCap

Low dosage kinetic hydrate inhibitors (KHIs) are a kind of alternative chemical additives to prevent gas hydrate formation in oil & gas production wells and transportation pipelines. In this work, a series of KHIs were experimentally synthesized with N-vinyl caprolactam (N-VCap) and vinyl ether including vinyl ether, vinyl n-butyl ether, vinyl isobutyl ether, triethylene glycol divinyl ether, with the mole ratio ranging from 9:1 to 5:5. The inhibition performance of new-synthesized KHIs on the formation process of methane hydrate were examined and compared with that of commercial N-vinyl caprolactam PVCap. Several ethylenediamine reagents were used as synergists and tested to improve the inhibition capacity of new-synthesized KHIs. The experimental results demonstrate that the introduction of ether groups on PVCap improves the performance of hydrate inhibitors. PVCap-VNBE (N-VCap: vinyl n-butyl ether = 5:5) showed the best inhibition performance for methane hydrate, which could extend the TVO to 1251 min under 6 K subcooling. N,N'-dimethylethylenediamine shows the best synergistic effect for PVCap-VNBE (5:5), and extends the TVO by 2.75 times at 7 K subcooling. Additionally, the relationship between hydrate inhibition performance and interfacial tension of newly-synthesized KHIs under high pressure were studied. It shows that the lower interfacial tension of KHIs would result in longer onset time, exhibiting better inhibition performance.

Design of sec-Benzyl Vinyl Ethers toward the Synthesis of Alternating Copolymers Composed of Vinyl Alcohol and Vinyl Ether Units.

In this work, we designed benzyl vinyl ethers carrying alkyl substituents at the benzyl position (i.e., sec-BnVEs) as bulky, reactive, and transformable monomers to realize the alternating cationic copolymerization with an alkyl vinyl ether (VE). In particular, the isopropyl substitution caused not only the bulkiness to suppress the successive propagation but also an enhancement of the vinyl group reactivity to promote crossover propagation with a less bulky VE comonomer. The isopropyl-substituted BnVE (iPr-BnVE) underwent living cationic alternating copolymerization with n-butyl VE (nBVE), and the alternating propagation was strongly suggested by the reactivity ratios. The subsequent deprotection of the sec-benzyl pendant afforded the vinyl alcohol (VA)-nBVE alternating copolymer, and the corresponding statistical copolymer was also synthesized by using the nonsubstituted monomer (BnVE) instead of iPr-BnVE. The alternating copolymer exhibited a higher glass transition temperature, which likely stems from the uniform and efficient hydrogen-bonding formation due to the periodic sequence.

Photocatalyzed HAT-Degradation of Vinyl Polymers: Cleavage of C-C Bond in Backbone Triggered by Radical Activation of C-H Bond in Pendant.

In this work, we achieved a triggering degradation of polymers composed of carbon-carbon (C-C) bonded backbone without relying on introduction of labile heteroatom-based bond. The crucial point for the achievement is using vinyl ether (VE) as a comonomer in radical copolymerization of (meth)acrylate for introduction of the carbon-hydrogen (C-H) bonds active for photocatalyzed hydrogen atom transfer (HAT) as triggers in the pendant. Interestingly, methyl methacrylate (MMA)-n-butyl vinyl ether (NBVE) copolymer underwent degradation in acetonitrile in the presence of benzophenone (Ph2CO) under UV irradiation at 80˚C. The degradation did not take place, when any one of UV, Ph2CO, heat, and NBVE unit was removed or HAT-active solvent such as toluene and 1,4-dioxane was used. These control experiments strongly supported the HAT-triggering degradation. Furthermore, the degradation behaviors of the copolymers with other vinyl ethers such as tert-butyl vinyl ether and methyl isopropenyl ether indicated that the C-H bond neighboring to oxygen on the pendant is mainly responsible for the trigger leading to degradation. The HAT-triggering degradation was also demonstrated even with the acrylate-based copolymer.

Synthesis and Biological Evaluation of Substituted Fused Dipyranoquinolinones

New methyl-substituted, and diphenyl-substituted fused dipyranoquinolinones are prepared in excellent yields via the triple bond activation and 6-endo-dig cyclization of propargyloxycoumarin derivatives by gold nanoparticles supported on TiO2 in chlorobenzene under microwave irradiation. In the absence of gold nanoparticles, the methyl-substituted propargyloxycoumarin derivatives resulted in fused furopyranoquinolinones through Claisen rearrangement and 5-exo-dig cyclization. The intermediate propargyloxy-fused pyridocoumarins are prepared by propargylation of the corresponding hydroxy-fused pyridocoumarins. The methyl-substituted derivatives of the latter are synthesized in excellent yield by the three-component reaction of amino hydroxycoumarin with n-butyl vinyl ether under iodine catalysis. The diphenyl-substituted derivatives of hydroxy-fused pyridocoumarins are obtained, also, by the three-component reaction of amino hydroxycoumarin with benzaldehyde and phenyl acetylene catalyzed by iron (III) chloride. Preliminary biological tests of the title compounds indicated lipoxygenase (LOX) (EC 1.13.11.12) inhibitory activity (60–100 μM), whereas compound 28a, with IC50 = 10 μM, was found to be a potent LOX inhibitor and a possible lead compound. Only compounds 10b and 28b significantly inhibited lipid peroxidation.

Photocatalyzed Hydrogen Atom Transfer Degradation of Vinyl Polymers: Cleavage of a Backbone C−C Bond Triggered by Radical Activation of a C−H Bond in a Pendant

AbstractIn this work, we achieved a triggering degradation of polymers composed of carbon‐carbon (C−C) bonded backbone without relying on introduction of labile heteroatom‐based bond. The crucial point for the achievement is using vinyl ether (VE) as a comonomer in radical copolymerization of (meth)acrylate for introduction of the carbon‐hydrogen (C−H) bonds active for photocatalyzed hydrogen atom transfer (HAT) as triggers in the pendant. Interestingly, methyl methacrylate (MMA)‐n‐butyl vinyl ether (NBVE) copolymer underwent degradation in acetonitrile in the presence of benzophenone (Ph2CO) under UV irradiation at 80 °C. The degradation did not take place, when any one of UV, Ph2CO, heat, and NBVE unit was removed or HAT‐active solvent such as toluene and 1,4‐dioxane was used. These control experiments strongly supported the HAT‐triggering degradation. Furthermore, the degradation behaviors of the copolymers with other vinyl ethers such as tert‐butyl vinyl ether and methyl isopropenyl ether indicated that the C−H bond neighboring to oxygen on the pendant is mainly responsible for the trigger leading to degradation. The HAT‐triggering degradation was also demonstrated even with the acrylate‐based copolymer.

2,9-Dimethyl-4H-oxazolo[5’,4’:4,5]pyrano[3,2-f]quinolin-4-one

The new 2,9-dimethyl-4H-oxazolo[5’,4’:4,5]pyrano[3,2-f]quinolin-4-one was successfully prepared through the three-component iodine-catalyzed reaction of n-butyl vinyl ether with the new 8-amino-2-methyl-4H-chromeno[3,4-d]oxazol-4-one. The latter was prepared by the reduction of 2-methyl-8-nitro-4H-chromeno[3,4-d]oxazol-4-one with Pd/C in a hydrogen atmosphere. The above nitro compound was synthesized by the condensation of N-(4-hydroxy-6-nitro-2-oxo-2H-chromen-3-yl)acetamide with P2O5 under microwave irradiation. The above acetamide derivative was prepared during the nitration of 2-methyl-4H-chromeno[3,4-d]oxazol-4-one with H2SO4 and KNO3. The structure of the newly synthesized compounds was confirmed by FT-IR, LC-MS, 1H-NMR, and 13C-NMR analyses. Preliminary biological tests show significant anti-lipid peroxidation activity for the title compound and the other synthesized new intermediates, as well as interesting soybean lipoxygenase inhibition for acetamide 2 (IC50 55 μM) and nitro-compound 3 (IC50 27 μM).

Isolation and characterization of 2-butoxyethanol degrading bacterial strains

A total of 11 bacterial strains capable of completely degrading 2-butoxyethanol (2-BE) were isolated from forest soil, a biotrickling filter, a bioscrubber, and activated sludge, and identified by 16S rRNA gene sequence analysis. Eight of these strains belong to the genus Pseudomonas; the remaining three strains are Hydrogenophaga pseudoflava BOE3, Gordonia terrae BOE5, and Cupriavidus oxalaticus BOE300. In addition to 2-BE, all isolated strains were able to grow on 2-ethoxyethanol and 2-propoxyethanol, ethanol, n-hexanol, ethyl acetate, 2-butoxyacetic acid (2-BAA), glyoxylic acid, and n-butanol. Apart from the only gram-positive strain isolated, BOE5, none of the strains were able to grow on the nonpolar ethers diethyl ether, di-n-butyl ether, n-butyl vinyl ether, and dibenzyl ether, as well as on 1-butoxy-2-propanol. Strains H. pseudoflava BOE3 and two of the isolated pseudomonads, Pseudomonas putida BOE100 and P. vancouverensis BOE200, were studied in more detail. The maximum growth rates of strains BOE3, BOE100, and BOE200 at 30 °C were 0.204 h−1 at 4 mM, 0.645 h−1 at 5 mM, and 0.395 h−1 at 6 mM 2-BE, respectively. 2-BAA, n-butanol, and butanoic acid were detected as potential metabolites during the degradation of 2-BE. These findings indicate that the degradation of 2-BE by the isolated gram-negative strains proceeds via oxidation to 2-BAA with subsequent cleavage of the ether bond yielding glyoxylate and n-butanol. Since Gordonia terrae BOE5 was the only strain able to degrade nonpolar ethers like diethyl ether, the degradation pathway of 2-BE may be different for this strain.

Impacts of Mixed Gaseous and Particulate Pollutants on Secondary Particle Formation during Ozonolysis of Butyl Vinyl Ether

To clarify how coexisting atmospheric pollutants affect secondary organic aerosol (SOA) formation, we investigated the effects of mixed gaseous pollutants (CO and SO2) and mixed organic-inorganic (MOI) particles on SOA formation during n-butyl vinyl ether (BVE) ozonolysis. Higher CO levels (90 ppm) were found to significantly change the chemical composition of SOA (prompting monomers while reducing oligomer formation) without causing much change in the overall SOA mass. Based on the positive matrix factorization (PMF) analysis, heterogeneous chemical conversions between preformed and newly formed SOA were the major pathways of SOA formation in the presence of MOI particles. Furthermore, MOI particles had an enhancing effect on SOA formation at 1% relative humidity (RH) but a negligible effect at higher RH (10 and 55%). The enhancing effect was attributed to the formation of multifunctional products resulting from high functionalization of preformed and newly formed SOA. The negligible effect observed was ascribed to the cleavage of unstable oligomers as a result of the reversible oligomerization of preformed and newly formed SOA. Even so, MOI particles could still affect the composition of newly formed SOA. These results highlight the need to account for the significant effect of mixed gaseous and particulate pollutants on both SOA constituents and their evolution.

Chemiluminescence-Induced Free Radical-Promoted Cationic Polymerization.

Chemiluminescence (CL) has recently been featured as a new external light source for various photoinduced reactions with attractive features such as eliminating continuous energy supply and advanced light source setups. In the present study, the free-radical-promoted cationic polymerization of cyclohexene oxide, n-butyl vinyl ether, and N-vinyl carbazole under CL irradiation is described. The method is based on the visible-light-induced generation of electron donor radicals from bis-(4-methoxybenzoyl)diethyl germane (BAG), bis(2,4,6-trimethylbenzoyl) phenyl phosphinate, and camphorquinone by CL illumination followed by electron transfer to diphenyl iodonium hexafluorophosphate (Ph2 I+ PF6 - ) to form corresponding cations capable of initiating cationic polymerization. The applicability of the process to network formation is also demonstrated by using a bifunctional monomer, tri(ethylene glycol) divinyl ether.

Statistical Copolymers of n-Butyl Vinyl Ether and 2-Chloroethyl Vinyl Ether via Metallocene-Mediated Cationic Polymerization. A Scaffold for the Synthesis of Graft Copolymers.

The cationic statistical copolymerization of n-butyl (be) and 2-chloroethyl vinyl ether (CEVE), is efficiently conducted using bis(η5-cyclopentadienyl)dimethyl zirconium (Cp2ZrMe2) in combination with tetrakis(pentafluorophenyl)borate dimethylanilinum salt [B(C6F5)4]–[Me2NHPh]+, as an initiation system. The reactivity ratios are calculated using both linear graphical and non-linear methods. Structural parameters of the copolymers are obtained by calculating the dyad sequence fractions and the mean sequence length, which are derived using the monomer reactivity ratios. The glass transition temperatures (Tg) of the copolymers are measured by Differential Scanning Calorimetry (DSC), and the results are compared with predictions based on several theoretical models. The statistical copolymers are further employed as scaffolds for the synthesis of graft copolymers having poly(vinyl ether)s as a backbone and either poly(ε-caprolactone) (PCL) or poly(l-lactide) (PLLA) as side chains. Both the grafting “onto” and the grafting “from” methodologies are employed. The reaction sequence is monitored by Size Exclusion Chromatography (SEC), NMR and IR spectroscopies. The advantages and limitations of each approach are thoroughly examined.

Characteristics and Mechanism of Vinyl Ether Cationic Polymerization in Aqueous Media Initiated by Alcohol/B(C₆F₅)₃/Et₂O.

Aqueous cationic polymerizations of vinyl ethers (isobutyl vinyl ether (IBVE), 2-chloroethyl vinyl ether (CEVE), and n-butyl vinyl ether (n-BVE)) were performed for the first time by a CumOH/B(C6F5)3/Et2O initiating system in an air atmosphere. The polymerization proceeded in a reproducible manner through the careful design of experimental conditions (adding initiator, co-solvents, and surfactant or decreasing the reaction temperature), and the polymerization characteristics were systematically tested and compared in the suspension and emulsion. The significant difference with traditional cationic polymerization is that the polymerization rate in aqueous media using B(C6F5)3/Et2O as a co-initiator decreases when the temperature is lowered. The polymerization sites are located on the monomer/water surface. Density functional theory (DFT) was applied to investigate the competition between H2O and alcohol combined with B(C6F5)3 for providing a theoretical basis. The effectiveness of the proposed mechanism for the aqueous cationic polymerization of vinyl ethers using CumOH/B(C6F5)3/Et2O was confirmed.

Near-Infrared-Induced Cationic Polymerization Initiated by Using Upconverting Nanoparticles and Titanocene.

A new near-infrared (NIR)-sensitized photoinitiating system for free-radical-promoted cationic polymerization of oxirane and vinyl monomers such as cyclohexene oxide, and n-butyl vinyl ether (BVE), and N-vinyl carbazole (NVC) is described. A three-component photoinitiating system consists of upconverting nanoparticles (UCNPs), titanium-complex free radical photoinitiator (Irgacure 784, titanocene), and diphenyl iodonium hexafluorophosphate (Ph2 I+ PF6 - ). Upon NIR laser irradiation at 980 nm, the radicals generated from titanocene by the visible light emitted by UCNP abstract hydrogen or add to the monomer, forming electron donor radicals that can be oxidized by iodonium salt to initiate cationic polymerization.

Transformation from xanthate-type cationogen mediated metal-free RAFT cationic polymerization with “HCl·Et2O” into RAFT radical polymerization to form poly(alkyl vinyl ether)-b-polyvinyl alcohol amphiphiles

To elucidate the applicable range of metal-free RAFT cationic polymerization (MRCP) with “HCl·Et2O”, the effects of the monomer structure on the transformation from MRCP to RAFT radical polymerization were investigated. The MRCP with HCl·Et2O was conducted using the xanthate-type cationogen, O-ethyl S-(1-ethoxyethyl) carbonodithioate (EVEX) at 0 °C for alkyl vinyl ethers (ALVE) such as n-butyl (NBVE), isobutyl (IBVE), isopropyl (IPVE), and tert-butyl vinyl ethers (TBVE). It was demonstrated that EVEX acted efficiently as a RAFT cationogen for the cationic polymerization initiated by HCl·Et2O with good control over the molecular weight, polydispersity, and chain ends of the resulting poly(ALVE), regardless of the monomer structure of ALVE. The resulting chain-transfer constants indicate that EVEX is a substantially effective RAFT cationogen for MRCP of ALVE with HCl·Et2O. The resulting poly(ALVE) was utilized as a macromolecular chain transfer agent (macro-CTA) for RAFT radical polymerization since it had 0.72–0.76 of ω-end functionality for the xanthate group [–S–C(=S)OC2H5], as determined from 1H NMR and MALDI-TOF-MS spectra under the optimal conditions. However, when the resulting poly(TBVE) was employed for subsequent RAFT radical polymerization, no block copolymerization proceeded due to the poor stability of the vinyl ether radical. Thus, poly(ALVE) but not poly(TBVE) obtained by MRCP was available as a macro-CTA for RAFT radical polymerization to synthesize novel block copolymers such as poly(IPVE)-b-poly(vinyl acetate). In addition, the selectively saponified block copolymer, poly(IPVE)-b-polyvinyl alcohol, formed spherical micelles in water, demonstrating the successful results of the one-pot transformation from MRCP to RAFT radical polymerization.

Synthesis and characterization of liquid molecular brush binder for coating applications

This report documents the facile synthesis of molecular brushes, via a grafting onto approach, with potential application as coating binders. Firstly, alternating copolymers of n-butyl vinyl ether (n-BVE) and maleic anhydride (MAh), i.e. n-BVEMAh, were synthesized via conventional radical polymerization. The anhydride reactive handle was subsequently utilised to access molecular brushes, via a grafting onto method, by imidizing the MAh repeat units with amine end-functional poly(ethylene glycol) oligomers, with 12 repeating units (PEG12-NH2). The product n-BVEMI-PEG12 brushes were viscous liquids at room temperature, hence we termed them liquid molecular brushes (LMBs). The LMBs displayed Newtonian flow behaviour at shear rates below 1000 s−1. We evaluated the applicability of this molecular brush system as coating binder, by grafting varying fractions of linoleamide (Lin) side chains, which has oxidative crosslinking ability, along with the PEG12 onto n-BVEMAh, to access n-BVEMI-PEG12/Lin. The n-BVEMI-PEG12/Lin binders underwent oxidative crosslinking at 50 °C in the presence of a drier. The challenges associated with the current binder system are highlighted.

A New Approach to the Synthesis of Benzo[b]naphtho[2,3-b]furan-6,11-diones and 2-Benzyl-3-hydroxynaphthalene-1,4-diones

Here we describe modified syntheses of o-acetylbenzoic acids­ and o-acetylphenylacetic acids by Heck palladium-catalysed aryl­ation of n-butyl vinyl ether with o-iodobenzoic acids or with o-iodo­phenylacetic acids, respectively. General syntheses of benzo[b]naphtho[2,3-b]furan-6,11-diones from o-acetylbenzoic acids and 2-benzyl-3-hydroxynaphthalene-1,4-diones from o-acetylphenylacetic acids are also reported.

HL2][P(1,2-O2C6Cl4)3] (L = THF, DMF): Brønsted acid initiators for the polymerization of n-butyl vinyl ether and p-methoxystyrene.

The development of solid, weighable Brønsted acids featuring the hexacoordinated phosphorous(v) anion [TRISPHAT]- are reported. H(DMF)2[1] and H(THF)2[1] {[1]- = [P(1,2-O2C6Cl4)3]-} were synthesized and fully characterized by 1H, 31P, 13C and 2D-NOESY NMR spectroscopy, X-ray crystallography, mass spectrometry and elemental analysis. Both, H(DMF)2[1] and H(THF)2[1] are found to be suitable initiators for the polymerization of n-butyl vinyl ether and p-methoxystyrene. Optimal polymerization results for these single-component initiators were generally obtained at -50 °C where high molecular weight polymers were isolated in high yield. 1H NMR spectroscopic analysis and dynamic light scattering of solutions of the isolated polymers provide evidence for a branched structure which presumably arises from chain transfer.

Influence of conditions for preparing butyl acrylate–vinyl butyl ether copolymers using the compensation procedure on their molecular-mass parameters and thickening power in dioctyl sebacate

New butyl acrylate–vinyl n-butyl ether copolymers were synthesized using initiating systems trialkylborane–oxygen, trialkylborane–di-tert-butylperoxytriphenylantimony, and azobis(isobutyronitrile) with compensation dosing of the active monomer. The kind of the initiator does not influence the composition and structure of the copolymers, according to the data of IR and 13С NMR spectroscopy, but influences their molecular-mass parameters, according to the data of gel permeation chromatography. The new copolymers dissolved in dioctyl sebacate (synthetic base of lubricating oils) well compete with related imported thickening additives in the thickening effect at temperatures from–40 to 100°С and in the resistance to mechanical degradation. Simple ways to control in the synthesis step the thickening effect of the polymers are suggested.

Metallocene-mediated cationic polymerization of vinyl ethers: Kinetics of polymerization and synthesis and characterization of statistical copolymers

ABSTRACTThe cationic polymerization of ethyl, n-butyl and iso-butyl vinyl ether, EVE, BVE and iBVE, respectively, was efficiently conducted using bis(η5-cyclopentadienyl)dimethyl hafnium, Cp2HfMe2, or bis(η5-cyclopentadienyl)dimethyl zirconium, Cp2ZrMe2 in combination with either tris(pentafluorophenyl)borate, B(C6F5)3, or tetrakis(pentafluorophenyl)borate dimethylanilinum salt, [B(C6F5)4]−[Me2NHPh]+, as initiation systems. The evolution of polymer yield, molecular weight and molecular weight distribution with time was examined. In addition, the influence of the initiating system, the monomer and the reaction conditions on the control of the polymerization was studied. Furthermore, statistical copolymers of EVE with BVE were prepared employing Cp2HfMe2 and [B(C6F5)4]−[Me2NHPh]+ as the initiation system. The reactivity ratios were estimated using both linear graphical and non-linear methods. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the mean sequence length, which were derived using the monomer reactivity ratios. The glass transition temperatures, Tg, of the copolymers were measured by Differential Scanning Calorimetry, DSC, and the results were compared with predictions based on several theoretical models. The kinetics of thermal decomposition of the copolymers along with the respective homopolymers was studied by thermogravimetric analysis within the framework of the Ozawa-Flynn-Wall and Kissinger methodologies.

Reaction products and mechanisms for the reaction of n-butyl vinyl ether with the oxidants OH and Cl: Atmospheric implications

Abstract A reaction product study for the degradation of butyl vinyl ether (CH3(CH2)3OCH CH2) by reaction with chlorine atoms (Cl) and hydroxyl radicals (OH) has been carried out using Fourier Transform Infrared absorption spectroscopy (FTIR) and/or Gas Chromatography-Mass Spectrometry with a Time of Flight analyzer (GC-TOFMS). The rate coefficient for the reaction of butyl vinyl ether (BVE) with chlorine atoms has also been evaluated for the first time at room temperature (298 ± 2) K and atmospheric pressure (708 ± 8) Torr. The rate coefficient obtained was (9.9 ± 1.5) × 10−10 cm3 molecule−1 s−1 and this indicates the high reactivity of butyl vinyl ether with Cl atoms. However, this value may be affected by the dark reaction of BVE with Cl2. The results of a qualitative study of the Cl reaction show that the main oxidation products are butyl formate (CH3(CH2)3OC(O)H), butyl chloroacetate (CH3(CH2)3OC(O)CH2Cl and formyl chloride (HCOCl). Individual yields in the ranges ∼16–40% and 30–70% in the absence and presence of NOx, respectively, have been estimated for these products. In the OH reaction, butyl formate and formic acid were identified as the main products, with yields of around 50 and 20%, respectively. Based on the results of this work and a literature survey, the addition of OH radicals and Cl atoms at the terminal C atom of the double bond in CH3(CH2)3OCH CH2 has been proposed as the first step in the reaction mechanism for both of the studied oxidants. The tropospheric lifetime of butyl vinyl ether is very short and, as a consequence, it will be rapidly degraded and will only be involved in tropospheric chemistry at a local level. The degradation products of these reactions should be considered when evaluating the atmospheric impact.

Direct generation of oxygen-stabilized radicals by H• transfer from transition metal hydrides.

Transition-metal hydrides generate α-alkoxy radicals by H• transfer to enol ethers. We have measured the rate constant for transfer from CpCr(CO)3H to n-butyl vinyl ether and have examined the chemistry of radicals generated by such transfers. Radicals from appropriate substrates undergo 5-exo cyclization, with higher diastereoselectivity than the analogous all-carbon radicals. From such radicals it is straightforward to make substituted tetrahydrofurans.