Propylene Glycol Diglycidyl Ether Research Articles

Characterisation and biocompatibility of crosslinked hyaluronic acid with BDDE and PEGDE for clinical applications

Hyaluronic acid (HA) is a versatile biomaterial frequently utilized in regenerative medicine due to its gel-like properties, making it well-suited for clinical applications. However, its linear form is susceptible to rapid enzymatic degradation, limiting its longevity within the body. To address this challenge, extensive research has focused on crosslinking mechanisms to enhance the durability of HA gels. One early approach involved crosslinking HA with 1,4-butanediol diglycidyl ether (BDDE) to create HA-BDDE, a clinically used product since the 1990s. However, the manufacturing process for HA-BDDE, primarily used in industry, lacks comprehensive documentation in the literature. More recently, poly(propylene glycol) diglycidyl ether (PEGDE) has emerged as an alternative to BDDE for crosslinking, offering improved gel elasticity and reduced cytotoxicity. In this study, we present the manufacturing process for producing both crosslinked gels, HA-BDDE and HA-PEGDE, with negligible residual crosslinkers, as confirmed by FTIR and NMR analysis. We characterize the crosslinking kinetics and the resulting formulations, revealing that HA-PEGDE gel exhibits comparable stiffness (G' = 60 Pa vs. 75 Pa) to HA-BDDE, despite a lower effective crosslinking ratio (CrR = 0.12 vs. 0.24). Intriguingly, our cytotoxicity testing demonstrates significantly greater cell viability for HA-PEGDE compared to HA-BDDE (151% versus 105%). Overall, both gels can be readily manufactured using a similar process and demonstrate excellent in vitro biocompatibility. This study elucidates why HA-BDDE is widely utilized in clinical settings and underscores the potential promise of HA-PEGDE as an emerging variant for clinical applications.

Synthesis and Phase Behavior of a Linear Amphiphilic Multiblock Copolymer.

Linear amphiphilic multiblock copolymer PPMPEs, obtained through a stepwise method, and linear amphiphilic random copolymer PPMPEs-1, obtained through a one-pot method, were synthesized using poly(propylene glycol) diglycidyl ether (PPGDGE), poly(ethylene glycol) diglycidyl ether (PEGDGE), and monoethanolamine (MEA) as the main raw materials. The structures of PPMPEs and PPMPEs-1 were characterized by FT-IR, 1H NMR, and gel permeation chromatography, which proved that the copolymers were synthesized with different components. Transmittance of the copolymer was tested by UV–vis. By changing the ratio of PEGDGE content and the concentration of the copolymer aqueous solution, the phase behaviors of PPMPEs and PPMPEs-1 were compared and studied in depth. It mainly highlighted the advantages of the stepwise method compared to the one-pot method. The transmittance of the polymer solutions could be improved by lowering the pH value in the acidic solution or increasing the pH value in the alkaline solution. Moreover, as the reaction degree of the PPMPEs hydrophobic chain segment increased, the transmittance decreased.

Microscopic ordered structure compactness and intrinsic thermal conductivity improvement of dispersed liquid crystal films of flexible epoxy-thiol polymers

Flexible epoxy-thiol polymers were fabricated by the reaction between N, N-Diglycidyl-4-glycidyloxyaniline (NDGA), poly (propylene glycol) diglycidyl ether (PGDE) and thiol curing agent with different functionality including 3,6-dioxa-1,8-octanedithiol (DET), pentaerythritol tetra(3-mercaptopropionate) (PETMP) and trimethylolpropane tris(3-mercaptopropionate) (TTMP). Liquid crystal monomer (LCM) was uniformly dispersed into epoxy-thiol polymers to prepare dispersed liquid crystal films of flexible epoxy-thiol polymers (E-PDLC films). The elongation at break and tensile strength of E-PDLC films increased to 195.9% and 25 MPa respectively. LCM showed favorable dispersibility and maintain ordered orientation of liquid crystal in E-PDLC films. The degree of order in molecular chain of epoxy-thiol polymers was increased, and chain interaction of epoxy-thiol polymers and LCM was enhanced by hydrogen-bonding. In E-PDLC films, with different thiol curing agent and LCM addition，different microscopic-ordered structure formed: ordered-layered structures and denser squamous ordered structures. Both of these two microscopic-ordered structures formed by different thiol curing agent and the addition of LCM, and afforded continuous phonon transfer paths. The thermal conductivity of E-PDLC films is up to 0.70 W m−1 K−1. This work offered a new way to design flexible epoxy resin and intrinsic thermal conductive polymers.

Laboratory evaluation on water-based and flexible epoxy/SiO2 nanocomposites to enhance anti-sliding effectiveness of pavement

The anti-slip (AS) layer of the cement concrete pavement (CCP) can probability decrease traffic accidents and extend the service life of the road. Epoxy resin has excellent adhesion and mechanical strength, making it possible in this field. Herein, a flexible waterborne epoxy resin (WER) without a small molecule emulsifier was synthesized by bisphenol A epoxy resin, poly (propylene glycol) diglycidyl ether (PDE), diethylenetriamine (DETA). The mechanism of the group reaction was characterized by fourier transform infrared (FTIR), and dynamic scanning calorimetry (DSC) determined the heat of curing of WER. Then, the physical properties of WER were enhanced by the silane coupling agent modified nano-silica (SCA-NS) and the composite’s water absorption rate and mechanical propriety were evaluated. Finally, the pavement performance of the AS layer was prepared and tested as well as compared with the commercial waterborne epoxy resin (CWER) and emulsified asphalt (EA). The result shows EA has low durability and adhesion strength than epoxy resin. The small molecule emulsifier and low-flexible resistance of CWER decrease water stability and anti-sliding durability of the AS layer. Due to applied nanomaterial reinforced and without small molecule emulsifiers, the WER base AS layer shows extremely high adhesion strength, water stability, and skid-resistance durability at addition 3 wt% of SCA-NS, which have a great potential for CCP.

Synthesis and phase behavior of double sensitive linear amphiphilic prepolymers before gelation

A series of amphiphilic linear prepolymers for gelation, poly(poly(ethylene glycol) diglycidyl ether—monoethanolamine—poly(propylene glycol) diglycidyl ether), i.e. polyPEMPPs, were designed and synthesized by using poly(ethylene glycol) diglycidyl ether (PEGDGE), Poly(propylene glycol) diglycidyl ether (PPGDGE), and monoethanolamine (MEA) as main raw materials through nucleophilic addition/ring-opening reaction. The amphiphilic structure in the backbone of the prepolymers polyPEMPPs causes a phase transition in aqueous solution and has multiple stimuli responsiveness. The effects of hydrogen bonding and electrostatic interactions on phase transition behavior were discussed and analyzed structural reasons in detail. This has important guiding significance for further research on control sol–gel transition. The effects of polyPEMPPs concentration, content of PEGDGE and solution pH values on the phase transition temperature were examined. The experimental results show that increasing polyPEMPPs concentration promotes the phase transition, the transition temperature decreasing with increasing PEGDGE content. In the pH experiment, intra- and intermolecular association became difficult and the phase behavior will be inhibited, whether hydrochloric acid system or sodium hydroxide system. Moreover, we also experimented oscillatory phase transition, and the result exhibited a stably reversible phenomenon transition.

Optimizing support properties of heterogeneous catalysts for the coupling of carbon dioxide with epoxides

The study deals with the catalytic cyclocarbonation of epoxides to produce monomers used in the synthesis of polyurethane. A benchmark study of the textural properties of silica-based, doped or not, supports enabling the identification and optimization of the key parameters affecting the catalytic activity is reported. The results reveal that ammonium catalysts immobilized onto mesostructured supports with high surface area and low aggregation show better catalytic performances than analogue catalysts grafted onto microstuctured ones. While a high external surface area favours the grafting of ammonium salt, pore size must be large enough to enhance the accessibility of both carbon dioxide and epoxides to the catalytic sites. The activity of heterogeneous catalysts was evaluated for a model coupling reaction between carbon dioxide and propylene glycol diglycidylether. Using appropriated supports, cyclocarbonation yields are found to be higher in the presence of the heterogeneous catalyst in comparison with the homogeneous one. These results allow to confirm the beneficial effect of the presence of residual OH silanol groups at the surface of the support, which activate epoxide through forming of hydrogen bonds.

A Flexible Reversible Material Curing at Room Temperature Based on Diels‐Alder Reversible Reaction Characteristics

AbstractReversible materials have been extensively studied for their good application potential. In this work, a series of materials with thermal reversible properties were synthesized by Diels‐Alder (DA) reaction of furan/BMI. The main structure of the thermoreversible polymer was poly (propylene glycol) diglycidyl ether (PPGGE) which was chain‐extended by furfurylamine. Bismaleimide (BMI) was set as crosslinking agent. The conversion rates of DA reaction and retro‐DA reaction were calculated by Fourier Transform Infrared Spectroscopy. The material could react quickly at room temperature and achieve high conversion rate to 90%. Differential Scanning Calorimetry and Thermogravimetric Analysis were used to study the thermal properties of the materials, and the obvious reversible transformation temperature of the materials occurred in the range of 90 °C to 120 °C. The thermomechanical properties and tensile properties of the materials were obtained by DMA and tensile tests, respectively. Compared to the previous studies, these materials exhibited a relatively high breaking elongation of 230%.

Solubilities of CO2 in, densities and kinematic viscosities of poly(propylene glycol) diglycidyl ether and poly(ethylene glycol) monooleate

Densities and kinematic viscosities of polymer absorbents such as poly(propylene glycol) diglycidyl ether(PPDE) with molecular weights of 380 and 640, and poly(ethylene glycol) monooleate(PEGM) with molecular weight of 460 were respectively measured at atmosphere and temperatures ranging from 273.15 K to 333.15 K, and correlated with linear equation and Vogel-Fulcher-Tamman equation respectively. The density declines slightly while the kinematic viscosity decreases greatly with the increase of temperature. The result also showed that increasing the molecular weight is beneficial for the decrease of density and the increase of kinematic viscosity. In addition, CO2 solubilities in the selected polymer absorbents were determined by using an isothermal synthetic method, under pressures up to 1.2 MPa and at temperatures ranging from 273.15 K to 303.15 K. The four-parameter nonrandom two-liquid (NRTL) model was used to fit the experimental data, and model parameters were obtained. According to the absorbents as PPDE380, PEGM460, and PPDE640, the mean relative deviations of the pressure between the experimental and fitted data were 1.03%, 1.15%, and 1.31%, and the maximum deviations of that were 2.73%, 2.57%, and 2.55%. The result showed that decreasing the absorption temperature has a large effect on improving absorption capacity. Henry’s constants were calculated from NRTL model and compared with those of experimental data. Relatively good correspondence was obtained with the experimental and calculated data. To assess the selected absorbents for CO2 capture preliminarily, densities and kinematic viscosities of, CO2 solubilities in selected absorbents were compared with common solvents used in industrial plants, other polymer absorbents, and some ionic liquids. The result showed the selected absorbent as PPDE640 has moderate density and kinematic viscosity, the highest CO2 absorption capacities of all the compared absorbents, which showed that PPDE640 has potential research value for CO2 capture.

Antimicrobial paper obtained by dip-coating with modified guanidine-based particle aqueous dispersion

Nonbiodegradable features and the lack of antimicrobial activity for conventional synthetic polymer-based packaging materials remain as extensive concerns for environmental issues and food safety. In this work, an antimicrobial copolymer PHGH–PPGDE was synthesized via a reaction between polyhexamethylene guanidine hydrochloride (PHGH) and poly(propylene glycol)diglycidyl ether (PPGDE). The obtained PHGH–PPGDE was amphiphilic, antimicrobial and reactive due to the terminal reactive group. The TEM images indicated that PHGH–PPGDE formed aggregated particles dispersed in water. The antimicrobial paper was conveniently prepared by dip-coating a paper matrix in the PHGH–PPGDE aqueous dispersion, or mixing the dispersion with pulp. The resultant paper showed excellent antimicrobial activities against Escherichia coli and improved durability for the nonleaching effect.

Breathable Microgel Colloidosome: Gas-Switchable Microcapsules with O2 and CO2 Tunable Shell Permeability for Hierarchical Size-Selective Control Release.

Microcapsules enabling precise delivery and controlled release are highly desirable. However, it is still challenging to control the release profile by regulating the microcapsule shell permeability. In this work, gas-switchable microgel colloidosome (MGC) with oxygen (O2) and carbon dioxide (CO2) dual gas-tunable shell permeability has been developed and tested for control release of water-soluble cargo molecules, based on the size exclusion mechanism. The O2 and CO2 dual gas-switchable poly(2-(diethylamino)ethyl methacrylate-co-2,3,4,5,6-pentafluorostyrene), P(DEA-co-FS), microgels having surface modified with amino group (-NH2) were synthesized and used to stabilize oil-in-water (O/W) Pickering emulsions. The oil-soluble poly(propylene glycol) diglycidyl ether (PPGDGE) was added as an intermicrogel cross-linker. The cross-linking between adjacent microgel particles at the water-oil interface was achieved through the amine-epoxy reaction of PPGDGE with the amine groups at the particle surface. Fluorescent-labeled dextran model cargo molecules of 10 kDa (D1) and 2000 kDa (D2) were uploaded under CO2 treatment and locked inside the MGC with N2 treatment. The O2 and CO2 dual-gas switchable properties offered the MGC with tunable shell permeability, which allowed the hierarchical release of D1 and D2 based on size exclusive mechanism. This work provides a robust method for preparation of gas-switchable microcapsules with tunable permeability and size-exclusive hierarchical release profile, promising for multiple ingredient controllable release, separation, and reaction.

Broadband terahertz dynamics of propylene glycol monomer and oligomers

We investigated the broadband terahertz spectra (0.1–5.0 THz) of glass-forming liquids, propylene glycol (PG), its oligomers poly (propylene glycol)s (PPGs), and poly (propylene glycol) diglycidyl ether (PPG-de) using broadband terahertz time-domain spectroscopy and low-frequency Raman scattering. The numerical value of the dielectric loss at around 1.5 THz, which is the peak position of broad peaks in all samples, decreased as the molecular weight increased. Furthermore, the peak at around 1.5 THz is insensitive to the molecular weight. For PPGs, the side chain effect of the oligomer was observed in the terahertz region. Based on the experimental and calculation results for the PPGs and PPG-de, whose end groups are epoxy groups, the beginnings of the increases in the observed dielectric loss above 3.5 THz of the PPGs are assigned to the OH bending vibration. The higher value of the dielectric loss in the terahertz region for the PPG-de can be the tail of a broad peak located in the MHz region. The difference between the Raman susceptibility and dielectric loss reflects the difference in the observable molecular dynamics between the infrared and Raman spectroscopies.

The effects of crosslink density on thermo-mechanical properties of shape-memory hydro-epoxy resin

Abstract

Thermomechanical properties of shape-memory hydro-epoxy resin

The thermomechanical properties and shape-memory performance of a novel shape-memory hydro-epoxy resin system are studied. The system is prepared using hydro-epoxy, maleic anhydride, and poly(propylene glycol) diglycidyl ether (PPGDGE). The glass transition temperature (Tg) is determined using dynamic mechanical analysis, and the results indicate that Tg linearly decreases from 124 to 60 °C as the PPGDGE content increases. The tensile strength drastically increases after the addition of PPGDGE but gradually decreases as the PPGDGE content continues to increase. The room-temperature bend strength decreases as the PPGDGE content increases but increases slightly and then continues to decrease when the PPGDGE content is increased to 6.67 mol%. Moreover, the room-temperature elongation at break increases as the PPGDGE content increases but decreases slightly and then continues to increase when the PPGDGE content is increased to 6.67 mol%. These phenomena are attributed to flexible segment crystallization, which increases the rigidity of hydro-epoxy resin. Finally, investigation of shape-memory behavior of the resin reveals that full recovery can be observed after only a few minutes when the temperature is equal to or above Tg. The shape recovery time first increases and then decreases as the PPGDGE content is increased at Tg, Tg + 10 °C, and Tg + 20 °C, showing a polymer peak value at 6.67 mol% PPGDGE content. These results are attributed to the increase in PPGDGE content.

Synthesis, Characterization and Biocompatibility of Novel Biodegradable Cross-linked Co-polymers Based on Poly(propylene oxide) Diglycidylether and Polyethylenimine

Novel biodegradable cross-linked co-polymers were prepared from poly(propylene glycol) diglycidylether (PPGDGE) and poly(ethylene imine) (PEI). PPGDGE and PEI were mixed at ambient temperature with varying PEI concentrations of 10, 15, 18.5, 25, 30, 40 and 50 wt%; the homogenous PPGDGE/PEI mixtures obtained were cured at elevated temperatures, resulting in formation of PPG–PEI cross-linked co-polymers via ring-opening reaction of PPGDGE with PEI. The physicochemical and biological properties of these co-polymers were dependent on the PEI content and the extent of curing reaction. The glass transition temperature of PPG–PEI cross-linked co-polymers varied in the range from −14 to +42°C, while the co-polymers displayed composition-dependent mechanical behavior, from brittle to ductile with increasing PEI content from 18.5 wt% to 40 wt%. Chinese hamster ovary (CHO) cells were cultured on the PPG–PEI co-polymers; the MTT assay was used to measure cell viability and determine the cytotoxicity. The cell viability rate, relative to tissue-culture polystyrene (TCPS), increased from 49% to 125% with increasing PEI content from 18.5 wt% to 40 wt%. Although epoxy monomers usually exhibit cytotoxicity, the epoxy groups were exhausted via curing reaction in the fully cross-linked co-polymers. The PEI-cured PPG epoxy resin, i.e., PPG–PEI cross-linked co-polymers obtained in this study, showed excellent biocompatibility.

Polyamine-Functional Sterically Stabilized Latexes for Covalently Cross-Linkable Colloidosomes

Sterically stabilized polystyrene latexes were prepared by aqueous emulsion polymerization using a poly(ethylene imine) (PEI) stabilizer in the presence of 4-vinylbenzyl chloride (4-VBC; 1.0 wt % based on styrene). Partial quaternization of the amine groups on the PEI chains by 4-VBC occurs in situ, hence producing a chemically grafted steric stabilizer. Such 4-VBC-modified PEI chains were grafted more efficiently onto the polystyrene particles than unmodified PEI, as judged by aqueous electrophoresis, XPS, and nitrogen microanalysis. Moreover, partially quaternized PEI gave significantly smaller polystyrene particles than those synthesized in the absence of any PEI stabilizer or those synthesized using unmodified PEI. The partially quaternized PEI-stabilized polystyrene latex proved to be an effective emulsifier at pH 9, forming stable oil-in-water Pickering emulsions when homogenized (12,000 rpm, 2 min, 20 °C) with four model oils, namely, n-dodecane, methyl myristate, isononyl isononanoate, and sunflower oil. The primary and/or secondary amine groups on the PEI stabilizer chains were successfully cross-linked using three commercially available polymeric reagents, namely, tolylene 2,4-diisocyanate-terminated poly(propylene glycol) (PPG-TDI), poly(propylene glycol) diglycidyl ether (PPG-DGE), or poly(ethylene glycol) diglycidyl ether (PEG-DGE). Cross-linking with the former reagent led to robust colloidosomes that survived the removal of the internal oil phase on washing with excess alcohol, as judged by optical microscopy and SEM. PPG-TDI reacted very rapidly with the PEI stabilizer chains, with cross-linking being achieved during homogenization. Well-defined colloidosomes could be formed only by using sunflower oil and isononyl isononanoate with this cross-linker at 20 °C. However, cooling to 0 °C allowed colloidosomes to be formed using n-dodecane, presumably because of the slower rate of cross-linking at this reduced temperature. PPG-DGE proved to be a more generic cross-linker because it formed robust colloidosomes with all four model oils. However, cross-linking was much slower than that achieved using PPG-TDI, with intact colloidosomes being formed only after ∼12 h at 20 °C. The PEG-DGE cross-linker allowed cross-linking to be conducted at 20 °C from the aqueous phase (rather from within the oil droplets for the oil-soluble PPG-TDI or PPG-DGE cross-linkers). In this case, well-defined colloidosomes were obtained at 50 vol % with surprisingly little intercolloidosome aggregation, as judged by laser diffraction studies.

EFFECT OF CROSSLINKED CHITOSAN AS A CONSTRAINED VOLUME ON THE IN VITRO CALCIUM CARBONATE CRYSTALLIZATION

The present work deals with the effect of the constrained volume given by crosslinked chitosan (CHI) as a sphere on the in vitro CaC03 crystallization. Crosslinked CHI was obtained with formaldehyde (FA), glutaraldehyde (GA), epichlorhydrine (EPCH) and poly (propylene glycol) diglycidyl ether (PPDGE) as crosslinking agents. Determination of swelling percentage (%) of the crosslinked CHI spheres was carried out in TRIS buffer at pH 9. Spheres of high molecular weight were prepared using drops of CHI solution on NaOH. In vitro CaC03 crystallization using gas-diffusion method was done. In addition, a synthetically sulphonated containing polymethylsiloxane (S-PMS) was used as modifying additive on the CaC03 crystals growth in a confined space of CHI. The degree of the crosslinking altered the diffusion of C02 gas through the CHI spheres during the CaC03 crystallization resulting in different and specific crystals morphologies

Structural effect of photoinitiators on electro‐optical properties of polymer‐dispersed liquid crystal composite films

AbstractTwo types of photoinitiators were synthesized: (1) a α,ω‐telechelic oligomeric photoinitiator, by the reaction of poly(propylene glycol) diglycidylether (PPGDGE) and 2‐hydroxy‐2‐methyl‐1‐phenyl‐propan‐1‐one (Darocur 1173), and (2) a polymeric photoinitiator, by copolymerization of a monomer that had a liquid crystalline property, 4‐[ω‐(2‐methylpropenoyloxy)decanoxy]‐4′‐cyanobiphenyl, with a vinyl monomer that had a photosensitive group. For comparison, low‐molecular‐weight (low‐MW) photoinitiator (Darocur 1173) also was used. Attention was directed to the structural effect of the photoinitiators on the electro‐optical properties of polymer‐dispersed liquid crystal (PDLC) film in which the LC phase occupied a major volume (80 wt % of the composite film). For the preparation of PDLC films by the polymerization‐induced phase separation method, the optimum UV‐curing temperature was observed at 50°C, a temperature slightly higher than the cloud temperature (Tcloud) of the low‐MW LC/matrix‐forming material mixture. It was found that the electro‐optical performance of the PDLC cell fabricated with the oligomeric or polymeric photoinitiator was better than that of the PDLC cell made with a low‐MW photoinitiator (Darocur 1173), exhibiting lower driving voltage (V90) and higher contrast ratio under identical formulation conditions. Oligomeric photoinitiators allowed premature phase separation between the LC and matrix phases, resulting in relatively pure LC‐rich phases. For the polymeric photoinitiator, incorporation of mesogenic moieties into the photoinitiator resulted in not only a well‐defined LC/matrix morphology but also in low driving voltage (V90) because of reduced friction at the LC/matrix interfaces. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 162–169, 2006

Cyclodextrin Complexes of Bisepoxide and of α,ω-Diamine in Several Molar Ratios. Preparation and Characterization in the Solid State

Abstract Addition of 1,4-butanediol diglycidyl ether (glycidyl = 2,3-epoxypropyl) to aqueous solutions of α-cyclodextrin (CD) leads to separation of the 2 : 1 complex from the solution. The 13C CP/MAS NMR spectrum of the complex indicates the presence of diastereomeric oxirane groups formed via the complexation. 1,4-Butanediol diglycidyl ether forms the 1 : 1 or 2 : 2 complex with γ-CD similarly from the aqueous reactions of the two compounds. 2,2-Dimethyltrimethylene glycol diglycidyl ether also forms water-insoluble host–guest complexes with α-CD (2 : 1) and with γ-CD (1 : 1 or 2 : 2). Poly(propylene glycol diglycidyl ether) with an Mn of 640 reacts with β-CD to give the 1 : 4 complex. Poly(tetrahydrofuran) terminated with NH2 groups at both ends also forms the 1 : 4 complexes both with α-CD and with γ-CD.

Crease-Resistance Treatments of Cotton Fabrics with Non-Formaldehyde Crosslinking Agents

Various types of non-formaldehyde crosslinking agents for cotton fabrics were studied. Glyoxal, polyacetal, bis-β-hydroxyethyl sulfone, propylene glycol diglycidyl ether, and glyoxal adducts of urea and its derivatives were used as crosslinkers. Two crosslinking agents, 4,5-dihydroxy-1,3-dimethyleneurea and 4,5-dihydroxy-1,3-bis- (β-hydroxyethyl) ethyleneurea were the most promising ones for practical use among the many investigated.