Juan Francisco Rodríguez

• PhD
• Head of Department at University of Castilla-La Mancha

Oleic-based trimethylolpropane (TMP) ester mixtures can be produced via esterification reaction between oleic acid (OA) and TMP, presenting important application as biobased lubricants. In this study, a new mathematical model that allows us to predict kinematic viscosities of such mixtures based on kinematic viscosity sensitivity parameters from pr...

The isocyanate-derived fraction resulting as the bottom phase from the split-phase glycolysis of conventional polyurethane flexible foams has been given a new life based on the formation of amine-based polymers (polyureas and polyamides). For that purpose, the bottom phase was first hydrolyzed, producing toluenediamine and diethylene glycol, and fu...

The glycolysis process of flexible polyurethane foams containing styrene–acrylonitrile and calcium carbonate as fillers was explored in detail. The use of DABCO as a catalyst allowed us to reduce the catalyst concentration and the polyurethane-to-glycol mass ratio to 0.1% and 1:1, respectively. The glycolysis process allowed us to obtain a high-pur...

The demand for natural products in the treatment of dermatological pathologies has boosted the use of bioactive substances such as lavender essential oil (LEO), which stands out for its anti-inflammatory and antioxidant properties and its antimicrobial potential. Biopolymers such as chitosan (CHT) and alginate (ALG) are biodegradable and biocompati...

There is a subpopulation of pancreatic tumor pluripotent cells with mechanisms of drug resistance that favor the locoregional recurrence and poor prognosis of the disease. In this work, the preclinical study of the safety of gemcitabine (GEM) impregnated in polymeric foams designed for intraoperative administration in pancreatic cancer (PC) is intr...

In the present work, the reprocessability of thermosetting polythiourethanes via supercritical CO2 foaming was explored. Firstly, the maximum crosslinking density susceptible to be foamed was determined employing samples with a crosslinking density between 4•10⁻⁴ and 7.4•10⁻⁵ mol of crosslinking bonds/g of sample. The foaming conditions explored we...

The scale-up and the economic feasibility of the synthesis of St-MMA-GMA-PEGMA particles biofunctionalized with HSA were studied. First, the geometrical similarity of laboratory and pilot plant reactors was checked to develop the scale up of the process according to a criterion of partial similarity. The selected criterion was constant Re number. T...

This work describes the development of styrene-divinylbenzene (St-DVB) particles with polyethylene glycol methacrylate (PEGMA) and/or glycidyl methacrylate (GMA) brushes for the removal of bilirubin from blood in haemodialyzed patients. Bovine serum albumin (BSA) was immobilized onto the particles using ethyl lactate as a biocompatible solvent, whi...

Garlic (Allium sativum) has historically been associated with antioxidant, immunomodulatory, and microbiocidal properties, mainly due to its richness in thiosulfates and sulfur-containing phytoconstituents. Sepsis patients could benefit from these properties because it involves both inflammatory and refractory processes. We evaluated the effects of...

Non-isocyanate polyurethanes (NIPUs) based on biobased polyamines and polycarbonates are a sustainable alternative to conventional polyurethanes (PU). This article discloses a novel method to control the crosslinking density of fully biobased isocyanate-free polyurethanes, synthesized from triglycerides carbonated previously in scCO2 and different...

The techno-economic feasibility of lavender essential oil supercritical CO2 extraction was studied. The process was scaled up to a pilot plant, and the extraction yield, composition, and antioxidant potential of the extracts were evaluated at 60 °C and 180 bar or 250 bar, achieving a maximum yield of 6.9% and a percentage inhibition of the extracts...

To date, there have been no new drugs or adjuvants able to decrease both morbidity and mortality in the context of sepsis and septic shock. Our objective was to evaluate the use of thiosulfinate-enriched Allium sativum and black garlic extracts as adjuvants in the management of sepsis. An experimental in vivo study was carried out with male Sprague...

Thermoplastic Polyurethanes (TPUs) are one of the most used materials, but they are hard to recycle and when their lifetime ends they are mostly incinerated or landfilled. For that reason, this work explores the transformation of these materials into foams using supercritical CO2, searching a new reprocessing approach. The influence of pressure, te...

Molecular hybridization consists of the combination of two or more non-identical pharmacophores in a single molecule. It has emerged as a promising strategy that allows the design of molecular frameworks with enhanced activity and affinity compared to their parent drugs. In this work, two novel hybrids that combine the well-known anticancer chemoth...

Phase Change Dispersions (PCDs) of large colloidal stability were produced by sonication at an energy per liquid volume of ∼800 kJ L⁻¹, using gum arabic (GA) and sodium dodecyl sulfate (SDS) mixtures as dispersant agent and varying their mass ratios from 0 to 100 (GA/SDS). An important interplay between the PCD base properties and the final phase c...

Lightweight gypsum composites with improved thermal and waterproof properties were produced by using a concentrated slurry containing polystyrene nanoparticles (NPS) as an additive. The NPS/Hemihydrate mass ratio was varied between 0.00 and 0.42. The density of the composites decreased with the increase of the NPS/Hemihydrate mass ratio, due to the...

Hyperbilirubinemia is one of the main causes of death in patients with severe hepatic problems, which justifies the research for bilirubin removal solutions. In this study, St-MMA particles with PEGMA and/or GMA brushes were synthesized. First, the recipe for St-MMA was optimized and then adapted for PEGMA and GMA incorporation. Different solvents...

Thermoregulating composites were produced by using a thermoregulating slurry (NPCS) containing nanoencapsulated phase change material (NPCM) from poly(styrene-co-divinylbenzene) as shell and the commercial paraffin Rubitherm®RT27 as core material. These composites were synthesized by using the constitutive water of the slurry as setting water and c...

The production of oleic‐based trimethylolpropane (TMP) esters via the esterification reaction between oleic acid (OA) and TMP in a reactive distillation system, employing the environmentally friendly catalyst methanesulfonic acid, was explored. The homogeneous acid catalyst, the OA/TMP molar ratio within 1.0–3.0, the esterification reaction enhance...

The development of novel thermal fluids having large thermal energy storage (TES) capacity represents a research field of growing interest nowadays. One of the most explored alternatives is the employment of slurries containing encapsulated Phase Change Materials (PCM) at nano-scale range to avoid pumping problems. Slurries constituted by capsules...

Production of cyclic carbonates from epoxidized vegetable oils allows to introduce CO2 into the molecular structure of renewable and highly functional resources, obtaining high added value products, which also could serve as precursors for chemicals with a high potential, such as non-isocyanate polyurethanes (NIPUs). The selection of supercritical...

The copper(I)-catalyzed azide/alkyne cycloaddition is recognized as one of the most successful click reactions to access self-assembling amphiphilic polymer-drug conjugates (PDCs). In this way, poor water-soluble drugs can be linked covalently to hydrophilic poly(ethylene glycol) (PEG) to obtain PEGylated drug micelles that can be used as versatile...

The economic viability of the split-phase glycolysis process for the recycling of any kind of flexible polyurethane foam waste employing crude glycerol as cleavage agent has been demonstrated. First, experiments at pilot plant scale were carried out to check that the process can be extrapolated to larger scales. With the goal of scaling-up the proc...

Background: Chemical industry has increased the investment into and innovation capacity to supply chemicals from safe and sustainable sources, which will be essential to offering new solutions and supporting the green transition of the global economy and society. In this sense, the use of green solvents and reusable heterogeneous catalysts has emer...

The epoxidation of grape seed oil in supercritical CO2, to the best of our knowledge, has been only superficially described in the literature, apart from a short communication and our own previous published work on the topic. In this work, a thorough study of the performance of the supercritical epoxidation of grape seed oil is performed in a wide...

Gypsums with improved thermal properties have been obtained using a thermoregulatory nanocapsulated slurry (NPCS) as additive. In order to determine the effects of the slurries in the gypsum, physical, mechanical and thermal properties of the different composite materials (gypsum – polystyrene nanoparticles (PS) or nanocapsules (NPCM)) have been st...

The synthesis of rigid polyurethane (RPU) foams containing thermoregulatory microcapsules has been carried out under reduced pressure conditions with a new foaming formulation to reduce the final composite densities. These optimized RPU foams were able to overpass the drawbacks exhibited by the previous composites over the studied temperature range...

Polyurethane (PU) is one of the principal polymers in the global plastic market thanks to its versatility and continuous improvement. In this work, PU elastomeric materials having thermoregulating properties through the incorporation of microcapsules (mSD-(LDPE·EVA-RT27)) from low-density polyethylene and vinyl acetate containing paraffin®RT27 as P...

Flexible polyurethane foams (FPUs) having polystyrene (PS) stabilized by silica gel or polystyrene-acrylonitrile (SAN) particles were synthesized employing polymer polyether polyols (PPPs). The filler and its content effect on physical, mechanical and thermal properties of FPUs were studied. The FPU thermal stability increased with PS content into...

Rigid polyurethane (RPU) foams have been successfully glycolyzed by using diethylene glycol (DEG) and crude glycerol (CG) as transesterification agents. However, DEG did not allow to achieve a split-phase process, obtaining a product with low polyol purity (61.7 wt %). On contrary, CG allowed to achieve a split-phase glycolysis improving the recove...

Hydrophilic, flexible polyurethane (FPU) foams made from Hypol prepolymers are capable of retaining large amounts of water and saline solutions. The addition of different catalysts and surfactant agents to Hypol JM 5008 prepolymer was assayed to obtain a foam with good structural stability and elasticity. The combination of three catalysts, stannou...

A novel form-stable phase-change material (PCM) based on facing bricks was developed by incorporating thermoregulating PEG-SiO2, synthetized by sol-gel method and based on polyethylene glycol as phase-change material and silica as stabilizer compound. The PEG-SiO2 in its liquid form (sol) is firstly adsorbed inside the porous brick and lastly stabi...

A new sustainable green protocol for obtaining polyethylene glycol (PEG) conjugates, with a prototype molecule, which in this work was coumarin, by means of click chemistry is presented. The organic solvents commonly used for this type of reaction were replaced by supercritical carbon dioxide (scCO2). The synthesis and characterization of PEG-couma...

In this work, it is proposed to check the viability of the epoxidation process of grape seed oil under supercritical conditions, select and optimize the ratios of the different reagents and/or additives that take part in it. Different experiments were performed involving oil, hydrogen peroxide, CO2 (as the supercritical fluid), sodium bicarbonate a...

The understanding of the phase behaviour of the mixture mPEG-alkyne and supercritical CO2 (scCO2) and the study of the variation of the polymer melting point are essential prerequisites in order to determine appropriate operating conditions and develop high pressure processes that allow the obtention of a conjugate mPEG-alkyne with a drug or a prot...

This article contains data related to the research article entitled “Carbon dioxide sorption and melting behaviour of mPEG-alkyne”. The presented data gives information on the thermodynamics properties of the solvent and the polymer. The time saturation of mPEG-alkyne in supercritical carbon dioxide (scCO2) was evaluated in a high-pressure variable...

Thermoregulating microcapsules (MC) with flame-retardant properties were used to produce polyurethane (PU) foams. Thermogravimetric analyses of the microcapsules performed under atmospheric air and nitrogen confirmed that the hexa(methacryloylethylenedioxy) cyclotriphosphazene (PNC-HEMA) monomer raised the amount of residue after exposure to high t...

Slurries with low viscosity and polystyrene (PS) nanoparticle concentration up to 52 wt.% have been synthesized in one-step process with no waste generation, by suspension polymerization and optimizing the concentration of dispersants (sodium dodecyl sulfate, SDS, and the cosurfactant, CS). The CS was manufactured in situ from tetraethyl orthosilic...

The use of supercritical fluids technology, in particular the use of CO2, is an important advantage over other production techniques of controlled release systems. The impregnation and foaming process can be carried out in a single step. By adjusting the conditions of pressure, temperature, depressurization time or type of polymer used, microcellul...

Microcellular scaffolds were prepared using high pressure fluids. Solutions of biodegradable material Poly (lactic-co-glycolic) acid (PLGA) in a green solvent such as ethyl lactate was used as the scaffold matrix. To carry out polymer foaming from polymer solutions allows the possibility of reducing the working temperature. The effect of the ratio...

In this work, we sought to investigate the effects of a thiosulfinate-enriched garlic extract, co-administered with 5-fluorouracil (5-FU) or oxaliplatin chemotherapy, on the viability of colon cancer cells (Caco-2 and HT-29). We also addressed the economic feasibility of a new combined treatment of this thiosulfinate-enriched garlic extract, with o...

Coumarin is successfully incorporated in poly(ethylene oxide)‐poly(propylene oxide) block copolymers functionalized with terminal alkynes, PEO‐b‐PPO‐b‐GPE, by click reactions at atmospheric pressure and in CO2 supercritical conditions (scCO2). The presence of glycidyl propargyl ether (GPE), an alkynyl‐terminated monomer, in the copolymer chain allo...

Poly (lactic-co-glycolic acid) (PLGA) is a copolymer used as drug carrier in controlled release systems as microparticles or scaffolds. Foamed structures are industrially obtained by injecting gas at temperatures above the melting point of the polymer that may promote PLGA degradation. High temperatures are avoidable in this foaming process if a po...

Currently, the PU industry is developing new products with enhanced physical, mechanical and structural properties. One of the specialties that is attracting more and more attention from managers and enterprises all over the world are the PUs based on polymer polyether polyols (graft polyols). In this work, the synthesis of graft polyols was devel...

Copolymers from ethylene oxide (EO) and propylene oxide (PO) functionalized with glycidyl propargyl ether (GPE) are synthesized. The GPE allows further attachment of drugs but its influence on the polymeric micelle formation is unknown. In this work, the influence of the structure of these copolymers on their critical micellar concentration (CMC) i...

Three different approaches to estimate the vapor pressure by thermogravimetric analyses (TGA) of commercial paraffins-based phase change materials (PCMs) have been compared. The known Langmuir vaporization relation and two additional models based on the mass transfer by molecular diffusion at isothermal and non-isothermal conditions, using the Full...

Aminophosphonated polyols with flame retardant properties are synthesized by ring opening polymerization using diethyl‐N,N‐bis(2‐hydroxyethyl) aminomethyl phosphonate (Fyrol‐6) as initiator. The influence of the catalyst type and its concentration on the polymerization rate are studied. The catalyst system formed by potassium methoxide (MeOK) in DM...

The effect of frost conditions on the physical and mechanical properties of geopolymer concrete (GPC) and Portland cement concrete (PCC) containing two different micro-encapsulated phase change materials (MPCM) was examined. Microstructural studies revealed that the freeze-thaw induced concrete deterioration can be contributed to microcracks appear...

An in situ shape-stabilized phase change material (ssPCM) from polyethylene glycol (PEG) has been produced by sol–gel method. The inorganic matrix was in situ formed from tetraethyl orthosilicate (TEOS), controlling the condensation rate in a second alkaline step using NaOH. ssPCMs having a latent heat up to 113.8 J/g were synthetized using a sol w...

Hydrophobic release agents were developed from SiO2-CH3 submicron-sized particles containing hydrophilic and hydrophobic functional groups dispersed into a vegetable oil as support. The SiO2-CH3 submicron-sized particles were synthesized by changing the molar ratio between the precursors Tetraethyl orthosilicate (TEOS) and Methyltriethoxysilane (MT...

Renewable resources are playing a key role on the synthesis of biodegradable polyols. Moreover, the incorporation of covalently linked additives is increasing in importance in the polyurethane (PU) market. In this work, previously epoxidized grape seed oil and methyl oleate were transformed into phosphorylated biopolyols through an acid-catalyzed r...

The potential of utilizing geopolymer concrete (GPC) walls containing microencapsulated phase change material (MPCM) in buildings at different environmental conditions has been investigated. The effect of climate conditions (temperature, solar radiation) and MPCM design (shell thickness, concentration) on the energy efficiency of buildings was syst...

Use of copper wire bits as simple catalyst in a click chemistry reaction using supercritical CO2 has been achieved. The use of this catalyst in the reaction between polylactic acid (PLA) and coumarin allows to remove the whole amount of catalyst in the final product with a simple purification step using a green solvent where no toxic solvent is use...

The morphology and encapsulation efficiency of thermoregulating microcapsules based on a spreading coefficient theory and polar surface energy component were evaluated. For this purpose the microencapsulation of phase change materials (PCMs) with different copolymer shells and using different suspending agents by the suspension-like polymerization...

Polyether polyols with flame‐retardant properties are synthesized using glycerol phosphate disodium salt as an initiator and dimethyl sulfoxide (DMSO) as a solvent. The molecular weight of the polyol decreased when higher solvent to initiator ratios were used, revealing that a larger amount of salt was activated. In addition, the larger the amount...

The effect of microencapsulated phase change materials (MPCM) on the rheological properties of geopolymer paste (GPP) was investigated. In order to quantify the time dependent viscosity increase of the geopolymer paste containing MPCM (GPP-MPCM), a new rheological model was successfully developed. Three different MPCMs were compared, in order to ex...

Geopolymer concrete (GPC) containing microencapsulated phase change materials (MPCM) were fabricated in order to achieve a high thermal energy storage capacity of an environmental friendly concrete. Different kinds of MPCM were utilized to investigate the influence of the hygroscopic nature, latent heat, and size of microcapsules on the microstruct...

Microencapsulated phase change materials (MPCM) were added to geopolymer concrete (GPC) for utilization as a thermal energy storage concrete for passive building applications. Three different MPCM were compared to examine the influence of the hygroscopic nature of the MPCM shell, the PCM core/polymer shell ratio, and the MPCM size on the microstruc...

The thermal and rheological properties of suspensions of microencapsulated phase change materials (MPCM) in glycerol were investigated. When the microcapsule concentration is raised, the heat storage capacity of the suspensions becomes higher and a slight decline in the thermal conductivity of the suspensions is observed. The temperature-dependent...

Rigid PU foams are properly recycled by a single-phase glycolysis process employing crude glycerol as transesterification agent. A high pure recovered polyol (71% of purity) was obtained using a mass ratio of PU scraps to crude glycerol of 1 to 1, a reaction temperature of 190 °C and stannous octoate as catalyst in a 1.3 wt% concentration. PU foam...

The recycling of any kind of plastic to convert it in valuable products is one of the main challenges of today’s society. Besides, if the recycling process is itself green, then it would be a great achievement. This paper reviews the way covered from the first attempts of reusing the polyurethane (PU) scraps as a filler for cushions to the last che...

Our study was focused on obtaining polyetherurethanes synthesized with using polymeric polyether based polyols differing in dispersed copolymer content (10, 20 and 40 wt%). The polyetherurethane materials were synthesized via two step method. The influence of different polymeric polyether based polyols on the chemical structure, morphology, mechani...

This work studies the feasibility of supercritical technology for the improvement of the loading and release of curcumin in PLGA. We synthetized the poly (lactic-co-glycolic acid (PLGA) support as a solid block, determining the effect of PLGA molar composition in the range (20:80 to 80:20). A curcumin solubility study selected acetone, methanol and...

An innovative approach to remove mercury from Hg-rich ground-waters of the Abbadia San Salvatore Hg-mining area (Italy) using microcapsules containing trioctyl-methyl-ammonium-chloride (MC-TOMAC) is presented. Waters from three selected locations with mercury concentrations between 1.43 and 256.8 μg L⁻¹ were studied. MC-TOMAC demonstrated high sele...

A new three step process has been developed and optimized in order to demonstrate that is possible to get complete conversion of free fatty acids (FFA) into estolide esters (biolubricant), biodiesel and choline carboxylates (biosurfactants). This new approach consists in the utilization of HClO4, a cheap and industrially available strong acid, to g...

Due to the increasing amount of polyurethane waste, chemical recycling of these materials is a topic of growing interest for many researchers. The primary purpose of polyurethane feedstock recycling is to recover the starting polyol. In this study glycerolysis using glycerine from two sources and two purity grades is proposed as a method of chemica...

The microencapsulation of linoleic (LinA), oleic, erucic, and palmitic acids (PAs) from styrene and divinylbenzene were studied by using the suspension-like polymerization technique. All materials exhibited a spherical shape, with a particle size between 166 and 416 μm. The phase change material (PCM) content decreased with the presence of double b...

The addition of a new shape-stabilized phase change material (ssPCM) in ceramic elements having large porosity has been carried out. In that way, a novel form-stable PCM based on bricks was developed. In order to study the incorporation of the thermoregulatory material in the composites, bricks with different porosities have been manufactured. In t...

Thermoregulating microcapsules containing phase change material (Rubitherm®RT27) was produced by using the suspension-like polymerization technique with styrene (St), divinylbenzene (DVB) and hexa(methacryloylethylenedioxy) cyclotriphosphazene (PNC-HEMA) as co-monomers. The effect of PNC-HEMA for improving the flame retardant properties of the micr...

For the first time the functionalization via click chemistry of polylactic acid (PLA) with coumarin in supercritical conditions CO2 has been achieved. Click reaction was performed at atmospheric pressure and supercritical carbon dioxide (scCO2) for comparison being observed that is possible to obtain similar yields, higher than 95% in both cases. O...

The adsorption of polyvinylpyrrolidone (PVP) by the thermoregulating microcapsules has been studied. The mass ratio of PVP has been changed from 1 to 20, with respect to the lowest amount of PVP value (4.08 g). The results confirmed that a large amount of PVP was adsorbed by the polymeric shell. Experimental data were perfectly fitted by Langmuir m...

Polyurethane (PU) is one of the most important polymers with a global production of 17.565 million tons, which makes its recycling an urgent task. Besides, the main goal of PU recycling is to recover constituent polyol as a valuable raw material that allows to obtain new PU with suitable properties. Split-phase glycolysis can be considered the most...

Rigid polyurethane foams with up to 50 wt% of microcapsules from LDPE-EVA containing Rubitherm®RT27 were synthesized. The influence of microcapsules on the foams density, microstructure and mechanical resistance was studied. Cell size and strut and wall thicknesses were analyzed by SEM. The relationships between densities and foam microstructures w...

Concretes with a high thermal energy storage capacity were fabricated by mixing microencapsulated phase change materials (MPCM) into Portland cement concrete (PCC) and geopolymer concrete (GPC). The effect of MPCM on thermal performance and compressive strength of PCC and GPC were investigated. It was found that the replacement of sand by MPCM resu...