Diethylene Glycol Divinyl Ether Research Articles

Hydrolysis of Poly(fluoroacrylate) Thin Films Synthesized from the Vapor Phase.

The post-synthesis surface reaction of vapor-deposited polymer thin films is a promising technique in engineering heterogeneous surface chemistry. Because the existing research has neglected marginally reactive precursor films in preference of their highly reactive counterparts, our knowledge of kinetics and loss of film integrity during the reaction are limited. To address these limitations, we characterize hydrolysis of two fluoroacrylates, poly(1H,1H,2H,2H-perfluorooctyl acrylate) (pPFOA) and poly(2,2,3,4,4,4-hexafluorobutyl acrylate) (pHFBA), with sodium hydroxide using X-ray photoelectron spectroscopy. Without crosslinking with di(ethylene glycol)divinyl ether (DEGDVE) and grafting with trichlorovinyl silane, the films degrade rapidly during hydrolysis. An SN2 mechanism describes hydrolysis well, with rate constants of 0.0029 ± 0.0004 and 0.011 ± 0.001 L mol-1s-1 at 30 °C for p(PFOA-co-DEGDVE) and p(HFBA-co-DEGDVE), respectively. Our detailed study of hydrolysis kinetics of marginally reactive fluoroacrylates demonstrates the full capability and limitations of the post-synthesis reaction. Importantly, copolymers are characterized using a density correction new to polymer chemical vapor deposition.

Synthesis and Resist Sensitive Property of Iodine-Containing Materials using Extreme Ultraviolet (EUV) Exposure Tool

We examined the synthesis, physical properties, and resist properties of various iodine-containing molecules and polymers as resist materials. By condensation reaction of 2,6-dimethylphenol (DMP) with 4-iodebenzaldehyde (IBA), 3,5-diiodesalicylaldehyde (DISA) and 4-hydroxy-3,5-diiodebenzaldehyde (HDIA), the corresponding iodine containing compounds DIPM, 2-DIPM, and 4-DIPM were synthesized. The reaction of these compounds with adamantyl bromo acetate, yielding corresponding compounds with adamanty ester groups DIPM-AD, 2-DIPM-AD, and 4-DIPM-AD. The polyaddition of 4-DIPM with divinyl ethers such as diethylene glycol divinyl ether (DGDE), 1,4-bis(allyloxymethyl)cyclohexane (BAC), 2,2'-bis(4-vinyloxyethoxyphenyl)perfluoropropane (BVFP) was investigated to give iodine containing hyperbranched polyacetals poly(4-DIPM-co-DGDE), poly(4-DIPM-co-BAC), poly(4-DIPM-co-BVFP). In the same way, tri(4-hydoroxyphenyl)methane (THM) was used instead of 4-DIPM, the corresponding hyperbranched polyacetals poly(THM-co-DGDE), poly(THM-co-BAC), and poly(THM-co-BVFP) were also synthesized. Almost all resist materials had good physical properties (solubility, film formation, high thermal stability,) and excellent thickness loss property. The resist sensitivity in the extreme ultraviolet (EUV) exposure tool showed that these resist materials were good candidate to offer higher resolution resist pattern, i.e., E0 = 7.0 mJ/cm2 for DIPM-AD, E0 = 7.0 mJ/cm2 for 2-DIPM-AD, E0 = 2.0 mJ/cm2 for 4-DIPM-AD, poly(THM-co-DGDE) and poly(THM-co-BAC), E0 = 1.0 mJ/cm2 for poly(4-DIPM-co-DGDE) and poly(4-DIPM-co- BVFP).

Polythioethers with Controlled α,ω‐End Groups Prepared by Visible Light Induced Thiol–Ene Click Polymerization of Dithiol and Divinyl Ether with 4‐(N,N‐diphenylamino)benzaldehyde as Organocatalyst

AbstractThis study reports a step‐growth click‐polymerization of 1,4‐benzenedimethane (BDMT) and diethylene glycol divinyl ether (DEGVE) with 4‐(N,N‐diphenylamino)‐benzaldehyde (DPAB) as a photoredox catalyst under irradiation of visible light. DPAB exhibits a strong UV–vis absorption at 350 nm and a strong fluorescence emission at 480 nm in anisole. There is a strong fluorescence quenching between BDMT and DPAB. The molecular weight of the polythiolether can be controlled by reaction time and monomer feed ratios. More importantly, α,ω‐dithiol and α,ω‐divinyl telechelic polythiolether oligomers are successfully synthesized by simply changing the molar ratios of BDMT to DEGVE. 1H NMR and MALDI‐TOF MS spectra demonstrate that the oligomers have high end group fidelity. In addition, strong fluorescence is observed when the α,ω‐dithiol terminated polythiolether adds with N‐(1‐pyrenyl) maleimide, indicating that the as‐prepared polythiolether bears reactive thiol end groups. Furthermore, high molecular weight polythiolether are prepared by chain extension with reactive polythiolether oligomers as macro‐monomers. For example, α,ω‐divinyl oligomer (Mn = 2000 g mol−1) could further react with α,ω‐dithiol oligomer (Mn = 2400 g mol−1) to form high molecular weight polythiolether (Mn = 6000 g mol−1).

Synthesis and properties of degradable gels and porous polymers including acetal group in the network structure by addition reaction of multi-functional phenols and divinyl ether compounds

Gels containing acetal group have been synthesized by addition reaction of multi-functional phenols, 1,1,1-tris(4-hydroxyphenyl)ethane (THPE) or tannic acid (TA) and divinylethers, diethylene glycol divinyl ether (DEGVE) or polyethylene glycol divinyl ether (PEGVE) in tetrahydrofuran (THF) or 1,4-dioxane (DO) using pyridinium p-toluenesulfonate as a catalyst under nitrogen atmosphere. The gels synthesized from DEGVE showed higher Young’s modulus, breaking stress, and lower breaking strain than the gels synthesized from PEGVE. The gels in DO showed higher mechanical properties than those in THF due to the high affinity between the network structure and the solvent used. The gels with TA showed lower Young’s modulus than those with THPE derived from flexible molecular structure of TA. The reaction of THPE and PEGVE in acetonitrile induced phase separation, and yielded porous polymer formed by connected globules about 10 μm diameter. The dried porous polymers showed remarkable increase in the Young’s modulus in comparison with the corresponding gels in THF or DO. The gels and porous polymers were degraded under atmospheric conditions caused by hydrolytic degradation of acetal groups in the network structure. The present hydrolytic degradable materials would be applicable for drug carriers or sensors for humidity or water.

Synthesis and sorption activity of copolymers of vinyltriazole with diethylene glycol divinyl ether

New cross-linked insoluble polyfunctional copolymers with triazole fragments and vinyloxy groups in the side chain were synthesized by radical copolymerization of 1-vinyl-1,2,4-triazole with diethylene glycol divinyl ether. The dependence of the sorption activity with respect to the gold ions in acidic solutions on their nature and concentration was studied. The copolymers obtained were found to possess high sorption activity; they efficiently extracted gold ions from solutions of complex composition.

Flexible, Low-Power Thin-Film Transistors Made of Vapor-Phase Synthesized High-k, Ultrathin Polymer Gate Dielectrics.

A series of high-k, ultrathin copolymer gate dielectrics were synthesized from 2-cyanoethyl acrylate (CEA) and di(ethylene glycol) divinyl ether (DEGDVE) monomers by a free radical polymerization via a one-step, vapor-phase, initiated chemical vapor deposition (iCVD) method. The chemical composition of the copolymers was systematically optimized by tuning the input ratio of the vaporized CEA and DEGDVE monomers to achieve a high dielectric constant (k) as well as excellent dielectric strength. Interestingly, DEGDVE was nonhomopolymerizable but it was able to form a copolymer with other kinds of monomers. Utilizing this interesting property of the DEGDVE cross-linker, the dielectric constant of the copolymer film could be maximized with minimum incorporation of the cross-linker moiety. To our knowledge, this is the first report on the synthesis of a cyanide-containing polymer in the vapor phase, where a high-purity polymer film with a maximized dielectric constant was achieved. The dielectric film with the optimized composition showed a dielectric constant greater than 6 and extremely low leakage current densities (<3 × 10-8 A/cm2 in the range of ±2 MV/cm), with a thickness of only 20 nm, which is an outstanding thickness for down-scalable cyanide polymer dielectrics. With this high-k dielectric layer, organic thin-film transistors (OTFTs) and oxide TFTs were fabricated, which showed hysteresis-free transfer characteristics with an operating voltage of less than 3 V. Furthermore, the flexible OTFTs retained their low gate leakage current and ideal TFT characteristics even under 2% applied tensile strain, which makes them some of the most flexible OTFTs reported to date. We believe that these ultrathin, high-k organic dielectric films with excellent mechanical flexibility will play a crucial role in future soft electronics.

Visible light‐induced thiol‐ene reaction: A new strategy to prepare Α,ω‐dithiol and Α,ω‐divinyl telechelic polythiolether oligomers

ABSTRACTA new strategy is developed to prepare both α,ω‐dithiol and α,ω‐divinyl linear telechelic polythiolether oligomers by visible light induced thiol‐ene chemistry in the presence of a fac‐Ir(ppy)3 photoredox catalyst. Polythiolether oligomers of well‐defined end groups and controlled molecular weights have been successfully synthesized at varying monomer molar ratios of 1,4‐benzenedimethanethiol (BDMT) to diethylene glycol divinyl ether (DEGVE). 1H NMR and MALDI‐TOF MS analyses demonstrate that as‐prepared polythiolethers possess high end‐group fidelity, which is further supported by the successful polyaddition of polythiolethers bearing α,ω‐dithiol and α,ω‐divinyl groups. For example, with the α,ω‐dithiol‐ (Mn = 1900 g mol−1, PDI = 1.25) and α,ω‐divinyl‐terminated (Mn = 2000 g mol−1, PDI = 1.29) polythiolethers as macromonomers, the molecular weight of resulting polythiolether is up to 7700 g mol−1 with PDI as 1.67. The reactivity of the terminal thiol group is further confirmed by the addition reaction with N‐(1‐pyrenyl)maleimide. UV‐vis spectra and fluorescene measurements suggest that fac‐Ir(ppy)3 undergo a redox quenching process reacted with BDMT to generate thiyl free radicals. With these results, the mechanism of the thiol‐ene reaction catalyzed by photoredox catalyst is proposed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 740–749

Synthesise of Polythioether and Heat Resistant Property of Polythioether Sealants

Polythioether sealants are considered as new generational aeronautical sealants. First, by changing molecular structure, the feasibility of forming certain molecular weight of polythioethers was studied. Experiment show that most terminal dienes can react with dithiol generating certain molecular polythioethers. Then, analysis show that the linear polythioethers owning high degree of molecular regularity usually have rather low glass transition temperature (Tg), below -50oC, however, those polythioethers are very easily to crystalize. If they are not liquid at room temperature they can be used as raw rubber. If main chain of polythioether contains benzene ring, 5% weight loss temperatures will be improved, however, Tg will increase a lot, which cannot allow them to be used at low temperature. At last, using those polythioethers which are liquid at room temperature as raw rubber and Manganese Dioxide (MnO2) as curing agent, prepare kinds of sealants. The result shows that polythioether sealant prepared by reaction product of 1,6-Hexanedithiol and diethylene glycol divinyl ether(DGDE) has the highest tensile strength, which is 5.84MPa. After hot air aging (at 160oC and 100h), the sealant employing the polythioether synthesized by 2,2’-oxydiethanethiol and DGDE has the best thermal stability, the tensile strength only decrease 28%.

Synthesis of Novel Hexathiolated Squalene and Its Thiol-Ene Photopolymerization with Unsaturated Monomers

In this work is described the synthesis of a multifunctional thiolated squalene. Thiol-ene coupling reactions were employed to functionalize the six double bonds of squalene, using thiolacetic acid. Hydrolysis of the resulting thioacetates, rendered the corresponding hexathiolated squalene SQ6SH. This compound was further photopolymerized separately with triallyl cyanurate, pentaerythritol triacrylate and diethyleneglycol divinyl ether. Real Time FTIR kinetics revealed that homopolymerization of the ene monomers took place in addition to the thiol-ene photopolymerization. Flexible films were obtained when SQ6SH was photopolymerized in bulk with the above mentioned unsaturated monomers.

Silver recovery with complexing sorbents based on 1-vinyl-1,2,4-triazole

The sorption activity of copolymers based on 1-vinyl-1,2,4-triazole toward silver ions was studied in relation to the copolymer structure and to the kind and concentration of acids. The copolymers were prepared by radical copolymerization of 1-vinyl-1,2,4-triazole with 1,1,3-trihydrotetrafluoropropyl methacrylate and divinylbenzene, with 1,1,3-trihydrotetrafluoropropyl methacrylate, methyl methacrylate, and N,N′-methylenebisacrylamide, with diethylene glycol divinyl ether, and with divinyl sulfide. The copolymers exhibit high sorption activity. They efficiently recover silver cations from acid solutions and behave as anion exchangers.

An acid-labile temperature-responsive sol–gel reversible polymer for enhanced gene delivery to the myocardium and skeletal muscle cells

The work demonstrates the development of acid-labile temperature-responsive sol–gel reversible polymer for enhanced in vivo myocardium and skeletal muscle gene delivery. In this report, multi-block copolymers (MBCPs) synthesized from pluronic ® and di-(ethylene glycol) divinyl ether (DEGDVE) were used as a delivery vehicle for controlled and sustained release of plasmid DNA (pDNA) in in vitro as well as in vivo experiments. The non-ionic MBCP/pDNA complex showed remarkable transfection efficiencies against the myocardium cells as well as muscle cells in vivo, which is otherwise very difficult to achieve by using cationic polymers. In in vitro experimental settings, this intelligent stimuli-responsive polymer is shown to improve the transfection efficiency of branched polyethylenimine (BPEI)/pDNA complex when used together. The effect of MBCP on the surface charge and particle size of its various complexes with pDNA and BPEI was also studied. The release profile of pDNA from the MBCP gel was investigated and pH of the degraded polymer was also monitored to ascertain its non-cytotoxicity arising due to the increased acidity as observed with other PLGA-based polymers. The rapid sol–gel transition of MBCP under thermal stimuli with concomitant release of pDNA under acidic stimulation has potential for site specific, efficient and controlled transfection of therapeutic gene. In short, MBCP provides the silver lining in combat against the hurdles encountered in transfection to myocardial or other muscle cells.

UV absorption cross-sections of a series of vinyl ethers

UV absorption cross-sections of six vinyl ethers (ethyl vinyl ether, 1,4-butanediol divinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 4-hydroxybutylvinyl ether and diethyleneglycol divinyl ether) have been determined in the gas phase between 190 and 230 nm at 303 ± 2 K and pressures up to the corresponding saturation vapor pressures. The main band maxima of the vinyl ethers are below 200 nm with values under 8 × 10 −17 cm 2 molecule −1. The absorption vanishes above 225 nm with values of σ smaller than 1 × 10 −21 cm 2 molecule −1. Weak, overlaying vibrational progressions with spacings of 1400 cm −1 are observed for the alkyl vinyl ethers and are less pronounced for vinyl ethers with an extra O atom. Shifts of the positions and intensities are discussed on the basis of the differences in the chemical structure of this series.

Rate Coefficients for the Gas-Phase Reactions of OH and NO3Radicals and O3with Ethyleneglycol Monovinyl Ether, Ethyleneglycol Divinyl Ether, and Diethyleneglycol Divinyl Ether

Kinetic studies have been performed on the reactions of OH and NO(3) radicals and ozone with three ethyleneglycol vinyl ethers (EGVEs), that is, ethyleneglycol monovinyl ether (EGMVE, HOCH(2)CH(2)OCH=CH(2)), ethyleneglycol divinyl ether (EGDVE, H(2)C=CHOCH(2)CH(2)OCH=CH(2)), and diethyleneglycol divinyl ether (DEGDVE, H(2)C=CHOCH(2)CH(2)OCH(2)CH(2)OCH=CH(2)). Using a relative rate technique, rate coefficients have been determined for the reactions in a 405 L borosilicate glass chamber at (298 +/- 3) K in one atmosphere of synthetic air using in situ FTIR spectroscopy to monitor the reactants. The following rate coefficients (in units of cm(3) molecule(-1) s(-1)) were obtained: (1.04 +/- 0.22) x 10(-10), (1.23 +/- 0.33) x 10(-10), and (1.42 +/- 0.30) x 10(-10) for the reaction of OH with EGMVE, EGDVE, and DEGDVE, respectively; (2.23 +/- 0.46) x 10(-12), (1.95 +/- 0.50) x 10(-12), and (6.14 +/- 1.38) x 10(-12) for the reaction of NO(3) with EGMVE, EGDVE, and DEGDVE, respectively; and (2.02 +/- 0.41) x 10(-16), (1.69 +/- 0.41) x 10(-16), and (2.70 +/- 0.56) x 10(-16) for ozonolysis of EGMVE, EGDVE, and DEGDVE, respectively. Using the kinetic rate data, tropospheric lifetimes for EGMVE, EGDVE, and DEGDVE with respect to their reactions with OH, NO(3), and ozone have been estimated for typical ambient air concentrations of these oxidants.

Modified copolymers of bifunctional vinyl ethers with methyl vinyl sulfide as active matrices of solid superbases

Reactive linear and crosslinked copolymers of diethylene glycol divinyl ether and ethylene glycol vinyl glycidyl ether with methyl vinyl sulfide have been synthesized in the presence of 2,2′-azobis(isobutyronitrile) (2%, 60 °C, 45–55 h) in ∼53% yield. The hydrolyzed at the residual vinyloxy and epoxy groups and oxidized at the methylthio groups copolymers upon treatment with KOH afford alkoxide (complex) and crown-like superbases. They are capable of catalyzing the acetone ethynylation, as well as the prototropic isomerization of methyl propargyl ether to allenyl methyl ether and vinylation of ethylene and diethylene glycols with acetylene.

Nanoporous crosslinked macrocyclic polyethers based on diethylene glycol divinyl ether and their superbase complexes with KOH

Nanoporous (11–12 nm) crosslinked macrocyclic polyethers with vinyloxy and hydroxyl groups have been synthesized by the free-radical polymerization of diethylene glycol divinyl ether (AIBN, 80°C, i-octane), followed by acidic hydrolysis. It has been shown that the polymers react with KOH to form insoluble superbase complexes and alcoholates capable of catalyzing vinylation of ethylene glycol by acetylene.

Thermoresponsive and bioactive poly(vinyl ether)-based hydrogels synthesized by radiation copolymerization and photochemical immobilization

A thermoresponsive hydrogel was synthesized by radiation copolymerization of ethylene glycol vinyl ether (EGVE) and butyl vinyl ether (BVE) in the presence of cross-linking agent diethylene glycol divinyl ether. The gel was modified by a cell adhesion factor RGD by photochemical immobilization technique. While the unmodified hydrogel shows fully hydrated form at low temperatures (+4 °C) and it extensively dehydrates at 37 °C, the biomodified hydrogel still kept its thermoresponsive character after immobilization. The effectiveness of immobilization was checked with FTIR-ATR and XPS. The use of bioactive thermoresponsive hydrogels in cell culture applications was investigated. For this purpose, cell culture experiments were realized by L929 mouse fibroblasts. Cell attachment experiments revealed the effect of immobilized RGD with higher values of cell attachment (∼85%), which were obtained especially in the absence of serum. The thermoresponsive character of the hydrogel was useful for the application of low-temperature treatment in order to recover the attached viable cells from the surface of the hydrogel without using trypsin. When the culture temperature was decreased from 37 to 10 °C for 30 min ∼80% of the cells were detached from the hydrogel surface.

Novel chlorhexidine releasing system developed from thermosensitive vinyl ether‐based hydrogels

The aim of this study is to determine the effective concentrations of chlorhexidine on the release for prolonged periods of time from a novel hydrogel system. A hydrogel that exhibits a volume phase transition in response to temperature was synthesized by radiation copolymerization of ethylene glycol vinyl ether and butyl vinyl ether in the presence of crosslinking agent, diethylene glycol divinyl ether. Hydrogel samples in the disc form (diameter, 10 mm and height, 1.5 mm) were utilized as a matrix for the release of an antimicrobial agent, chlorhexidine diacetate. Chlorhexidine loading into the hydrogel was performed by water sorption at 4 degrees C, which allows high swelling and thus high loading capacity, i.e., approximately 36 mg drug per gram of dry gel. Chlorhexidine release was examined as short-term (24 h) and long-term (27 days) by UV spectrophotometer. Microbial studies were carried out by micro-dilution method in order to determine the effectiveness of the drug release. Minimum inhibitory concentration values for the pathogens of Streptococcus mutans and Lactobacillus casei were determined. The long-term chlorhexidine release is initially very fast. After that, the drug release reaches a slow but a steady rate. Such a release pattern provides an effective drug release. The prolonged release of chlorhexidine is continued up to the 27th day. MIC values for the two pathogens have been shown that the release rate from disc is effective to inhibit the growth of pathogens. These in vitro drug release results suggested that the thermosensitive hydrogel system developed in this study can be evaluated as a delivery system for the release of chlorhexidine.

Release kinetics of bovine serum albumin from pH-sensitive poly(vinyl ether) based hydrogels

pH-Sensitive amphiphilic hydrogels were synthesized by radiation copolymerization of ethylene glycol vinyl ether (EGVE), butyl vinyl ether (BVE) and acrylic acid (AA) in the presence of crosslinking agent, diethylene glycol divinyl ether (DEGDVE). The results of the swelling experiments indicated that the hydrogel which has 60:40:5 comonomer ratio (mol% of EGVE:BVE:AA in monomeric mixture) is pH-sensitive. While the hydrogel is in a fully hydrated form at pH > 6, it extensively dehydrates below pH 6. A two-stage volume phase transition was observed in the range of pH 6.0–7.0 and 7.5–8.0. In addition, the equilibrium water contents of the gels decreased with increasing temperature from 4 to 37 °C by following the non-Fickian diffusion mechanism. The utility of pH-sensitive gels in delivery of protein based drugs was investigated. Bovine serum albumin (BSA) loaded gels were prepared and protein release was examined by fluorescence spectroscopy in the range of pH 2–9. While the protein release was very low at pH 2, readily high amount of BSA were released at pH > 6. It was concluded that the pH-sensitive EGVE–BVE–AA terpolymers may be suitable for the oral administration of protein based drugs as a carrier through gastrointestinal (GI) tract.

Vinyl ether/acrylic acid terpolymer hydrogels synthesized by [formula omitted]-radiation: characterization, thermosensitivity and pH-sensitivity

The radiation copolymerization of hydrophilic ethylene glycol vinyl ether (EGVE), hydrophobic butyl vinyl ether (BVE) and/or acidic comonomer acrylic acid (AA) was realized in the presence of crosslinking agent diethylene glycol divinyl ether (DEGDVE). The swelling studies which were carried out at 4 and 37 °C in phosphate buffer solution (PBS, pH 7.4) showed that equilibrium swelling ratios of the hydrogels (except EGVE homopolymer hydrogel) decreases with increasing temperature and swelling process obeys non-Fickian diffusion mechanism. The pH-dependent swelling behaviour of the hydrogels was examined in buffered solutions at various pHs. The swelling process is reversible and pH-dependent for the AA-containing hydrogel. While this hydrogel shows a fully hydrated form at pH>6; it extensively dehydrates below pH 6. The gels are stable after the repeated swelling experiments. The molecular structure of the hydrogels was studied by Fourier Transform Infrared Spectroscopy and their thermal behaviour was investigated by Differential Scanning Calorimetry and Thermal Gravimetric Analysis. The surface and cross-section structures of the gels were examined by a Scanning Electron Microscope.

Gel formation in cationic polymerization of divinyl ethers. III. Effect of oligooxyethylene chain versus oligomethylene chain as central spacer units

AbstractCationic polymerizations of two series of divinyl ethers were carried out to clarify the effects of their central spacer chain structure on their crosslinking polymerization behavior. One series of the monomers involves divinyl ethers with an oligooxyethylene central spacer chain: diethylene glycol divinyl ether (O‐3), triethylene glycol divinyl ether (O‐4), tetraethylene glycol divinyl ether (O‐5), pentaethylene glycol divinyl ether (O‐6), and heptaethylene glycol divinyl ether (O‐8) (see Scheme 1). The other series includes divinyl ethers with an oligomethylene central spacer chain: 1,4‐butanediol divinyl ether (C‐4), 1,6‐hexanediol divinyl ether (C‐6), and 1,8‐octanediol divinyl ether (C‐8). Cationic polymerizations of these monomers were carried out with the hydrogen chloride/zinc chloride (HCl/ZnCl2) initiating system in methylene chloride (CH2Cl2) at −30 °C ([Monomer]0 = 0.15 M; [HCl]0 = 5.0 mM; [ZnCl2]0 = 0.5 mM). The polymerizations of the oligomethylene‐based divinyl ethers C‐6 and C‐8 caused gel formation at high monomer conversions (∼90%), whereas C‐4 formed soluble polymers even at almost 100% monomer conversion. The oligooxyethylene‐based divinyl ethers O‐3, O‐4, O‐5, and O‐6 underwent gel‐free polymerizations up to 100% monomer conversion and O‐8 did so at least up to ∼80% conversion. The content of unreacted pendant vinyl groups of the obtained soluble polymers was measured by 1H NMR spectroscopy. In the polymerizations of the oligomethylene‐based divinyl ethers (C‐4, C‐6, and C‐8), the vinyl contents of the polymers decreased monotonously with increasing monomer conversion, and their number‐average molecular weights (Mn's) and polydispersity ratios (Mw/Mn's) increased considerably just before the gelation occurred. On the contrary, the vinyl contents of the polymers obtained from the oligooxyethylene‐based divinyl ethers (O‐3, O‐4, O‐5, O‐6, and O‐8) decreased steeply even in the early stage of the polymerizations and almost all the pendant vinyl ether groups were consumed in the soluble polymers at the final stage of the polymerizations. The oligooxyethylene spacer units adjacent to the pendant unreacted vinyl ether groups may solvate intramolecularly with the carbocationic active center to accelerate frequent occurrence of intramolecular crosslinking reactions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3729–3738, 2004