+34 902 204 100 ext. 3615 ó 90325 (dirección ITQUIMA) itquima@uclm.es

Polymer Technology

 The laboratory is dedicated to the development and characterization of new polymeric materials, as well as the improvement of existing polymers. In this way, the intention is cover new needs in several fields such as housing, industry, transport, health, etc. 

Furthermore, this unit works in the improvement and optimization of polymerization process, and in the valorization and recycling of polymeric materials, giving the companies more efficient and eco-friendly solutions.

 ANIONIC POLYMERIZATION REACTOR

 The preparation of the initiator solution and the reactions of polyol polymerizations, take place in a reactor BUCHI BEP 280 Type II (Büchi, Uster Switzerland) with a glass heating jacket, and digital control of pressure, temperature and stirring. The vacuum is controlled by a vacuum digital controller DT Divatronic (Kölb, Germany), which acts on a solenoid valve.

 

 

 

POLYOL PURIFICATION REACTOR

To obtain high quality and purity polyols, adsorption and ion exchange processes are taken place. These processes are made in a 2 L glass reactor BUCHI AUTOCLAVE Type 1B with digital control of the pressure, temperature and stirring. The vacuum is controlled by a digital vacuum controller DT Divatronic (Köln, Germany), which acts on a solenoid valve.

 

 

 

KARL-FISCHER TITRATOR

Karl Fischer valorator is used to determine the quantity of humidity in samples. The measures are made by a Methrom 701 KF Titrino equipment. 

 

GEL PERMEATION CHROMATOGRAPH (GPC) 

Gel Permeation Chromatography is used to determine the molecular weight distribution of polymers, polydispersity and viscosity. The measures are performed with a Viscotek TDAmax chromatograph with two columns (Styragel HR2 and Styragel HR0.5), at 35ºC with a flow rate of 1 mL/min and using THF as eluent. The calibration curves for the GPC analysis were obtained using polyethylenglycol. 

 

FOURIER TRANSFORM INFRARED SPECTROSCOPY (FT-IR) 

Infrared Spectroscopy is used to identify and study several chemical products. The measures are performed with a Varian 640-IR FTIR spectrometer. 

 

THERMOGRAVIMETRIC ANALYSIS (TGA) 

The thermogravimetric is used to determine de thermal stability of materials and the composition of the parts which form them. 

Measures are carried out by a SDT Simultaneous DSC-TGA (TA Instruments) thermobalance.

 

INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION SPECTROMETRY (ICP-OES) 

Inductively Coupled Plasma Optical Emission Spectrometry is used to determine the metal content of the samples. The measures are made with a VARIAN 710-ES ICP spectrometer, using organic or aqueous medium. 

 

TITRATOR + SPECTROPHOTOMETER

Automatic system to measure conductivity and pH (Metrohm), connected with a spectrophotometer (AvaSpec, 3648 model, wavelength range between 200 and 750 nm), which allows to identify organic and inorganic compounds. 

The determination of equilibrium isotherms and kinetic curves is also possible. In the same way, it can make titrations.

 

OPTICAL (OM) AND SCANNING ELECTRON (SEM) MICROSCOPIES 

These technologies are used to study the morphology and structural characteristics of materials. 

For OM, an optical microscopy Axio Imager.A1 model (Carl Zeiss) connected with a digital camera Digital Sight DS-2Mv (Nikon) is used. 

In the case of SEM, an equipment Quanta 250 (FEI Company) with a wolfram filament is used. SEM is connected with an energy dispersive spectrometer (Apollo X) to determine elemental composition. This microscope works under different pressure modes: ambient, low vacuum and high vacuum. It has also available different detectors: GSED, ETD, LFD and BSED. 

 

MICROCAPSULES SYNTHESIS INSTALLATION

Microcapsules synthesis reactions are carried out by a suspension like-polymerization, in 0.250, 0.5, 1, 2 and 10 L (scale-up experiments) jacketed glass reactors, with Rushton impellers, digital control of stirring and temperature and under a nitrogen atmosphere. 

Furthermore, a membrane module SPG (Shirasu porous glass) with pore size of 5.5 μm can be used to obtain particles with a closer particle size distribution.

 

PILOT PLAN OF SUSPENSION LIKE POLYMERIZATION

From the laboratory scale design, the design and construction of a suspension like polymerization pilot plant was carried out. The pilot plant has two different reactors where the synthesis of thermoregulating microcapsules with paraffin core and polystyrene shell take place. The plant consists of a 1400 L stainless steel reactor and a 100 L glass reactor. The first one, which is built in stainless steel, has a Rushton stirrer with 6 blades made of stainless steel and is equipped with a frequency converter until 500 rpm. It has also available pressure and temperature sensors with digital displays. The glass reactor has a stirrer with speed variator until 800 rpm. 

 

MICROCAPSULES SULFONATION INSTALLATION

The functionalization of the microcapsules shell with sulphuric acid is carried out in a 0.25 L glass reactor. The temperature and stirring is controlled by a hot-plate (Agimatec-ED, Selecta). The process take place under a nitrogen atmosphere.

 

EQUILIBRIUM STUDIES INSTALATION

Exchange equilibrium studies is performed with an installation which consists of 0.1 L glass bottles hermetically closed, and immersed in a thermostatic bath with temperature control. The suspension formed by the microcapsules or resins is kept under stirring with a stirring platform. 

 

ION EXHANGE AND RESIN REGENERATION COLUMN

The glass column has a volume of 1 L. At the bottom, it has available a porous membrane plate to support the resin bed.

 

GLYCOLYSIS INSTALLATION

The installation consists of a 1 L glass reactor, with a digital stirring head (Heidolph RZR 2041), a reflux condenser, a display temperature and an outlet to keep the system under inert atmosphere. 

The feed system of foams is made up of a glass coupler attached to the reactor and a high accuracy feeder GAC 232.5 (Gericke), where polyurethane foams is conducted from a hopper to the reactor by means of an endless screw. 

From the conceptual design of the integrated glycolysis process which is commented on the line of research, the design and building of a pilot unit was carried out. This unit, which can work in continuous mode, allows the treatment of 5 kg/h foam cut-outs.

 

DIFFERENTIAL SCANNING CALORIMETRY (DSC) 

The Differential Scanning Calorimetry (DSC) is a thermoanalytical technique where the difference between the heat of a sample and the heat of a reference is measured as a function of the temperature. The sample and the reference are kept at the same temperature while the experiment takes place. Generally, the temperature program for a DSC analysis is designed in such a way that the temperature of the sample carrier, increases with the time lineally. The reference sample should have a well-defined heat capacity in the temperature range where the scanning will take place. The basic principle underlying this technique is that, when a sample suffers a physical transformation, for example a phase transition, more (or less) heat flow will be needed to maintain both samples at the same temperature. The heat flow needed will depend on whether the process is exothermic or endothermic. 

The thermal characterization of materials like thermoregulating microcapsules, is carried out by a calorimeter DSC Q100 model (TA Instruments) with temperature modulation equipped with a cooling system and using high purity nitrogen atmosphere (99,999%). 

 

PARTICLE SIZE DISTRIBUTION DETERMINATION

The Malver Mastersizer 2000 equipment uses the laser diffraction technique to measure the particle size. This is made by the measure of the intensity of the light dispersed as a laser beam passing through a sample of scattered particles. This information is analyzed to calculate the size of the particle which created the dispersion pattern. The equipment can measure in the range between 0.02 to 2,000 micrometers. 

The samples dispersion can be made both wet with 2000SM Hydro accessory and dry with the Scirocco 2000 accesory. These units of dispersion make sure that the particles are delivered to the optical bench measurement area at the correct concentration and in a suitable and stable state of dispersion.

 

SPRAY DRYER

The spray-drying technique is a physical method whose aim is the production of a dry powder by means of the atomization of an emulsion or solution in a stream of hot air in a drying chamber. The solvent is immediately evaporated, allowing the active material present in the solution, to be trapped within a film of an encapsulating material. The spray drying process consists of four steps: atomization of the fluid to have it sprayed, the contact of the spray fluid with air, its dehydration and the separation of the dry product. The production of thermoregulating microcapsules with a PCM core and a polymer shell is performed with this MiniSpray Dryer B-290 (Büchi). 

 

SPRAY DRYING MICROENCAPSULATION PILOT PLANT

From the laboratory scale design and considering the differences due to the scale-up, the design and building of a pilot plant to operate in continuous mode was carried out. 

The Spray Drying pilot plant is designed to produced 6.7 kg/h of thermoregulating microcapsules with low density polyethylene and polyethylene-vinyl acetate shell and paraffin core. 

The main element of the installation is a dryer with spray nozzles, built in stainless steel AISI 316. The feed is stored in a stainless steel AISI 316 tank of 1.2 m3 capacity, which is equipped with a drain valve and a Rushton type stirrer with hermetic shaft of 300 rpm. It also has a cladding in which thermal oil and ATEX heating is, a temperature probe Pt-100 and a digital controller to keep the feed temperature in the desired value. The other elements that form the plant are: a high efficiency cyclone, a deposit where the microcapsules are collected, a venture scrubber where the gaseous stream is mixed with a liquid stream of heptane to clean the gas, a self-cleaning filter, an exchange-cooler, a blower and a electric heater. 

The entire assembly is robustly mounted on a stainless steel frame in the ITQUIMA pilot plant. All equipment that can generate an ignition source are suitable for use in ATEX zone (zone 1, class 2): rotatory equipment (pumps, motors…), electrical equipment, thermal resistances, etc.

 

THERMAL CHARACTERIZATION EQUIPMENT

This equipment allows to determine the influence of the incorporation of microcapsules containing PCMs in building materials. These materials are subjected to controlled temperature changes, being the temperature variation recorded. The dimensions of the samples analyzed should be 10 cm large, 6 cm wide and 3 cm thick. 

The experimental device consists of a metal hollow aluminum box, through which the refrigerant flows constantly by means of a peristaltic pump from a thermostatic bath to the desired temperature. This refrigerant allows the temperature control in the aluminum cell. The dimensions of the aluminum cell were 10x6x3 cm with a wall thickness of 1 mm. The tested material, with the same dimensions of the aluminum cell, is placed on the upper surface of the aluminum cell and is insulted with 4 cm thick insulation foam. Two PUT22 heat flow sensors are used to control online both the incoming heat flow and the outgoing heat flow on the top surface of the tested piece. Two PUT11T heat flow sensors are used to monitor online heat flow output on the sides. 

Type K thermocouples are used to measure the temperature: two are placed in the outer surface of the test specimen, and the other two are placed at the entrance and exit of the cell boundaries (liquid flow) and two others in the middle of the studied material. Finally, two thermocouples are used to measure atmospheric and insulating foam temperatures. All these signals are continuously recorded in a computer using the NOKEVAL program. 

 

ZETA POTENTIAL AND SIZE PARTICLE IN NANOMETRIC RANGE DETERMINATIONS 

Zeta potential is a measure of the magnitude of the electrostatic interactions of attraction or repulsion between the particles of a colloidal suspension, giving an idea about the suspension stability. 

The measure is made by a Z-Sizer Nano ZS (Malvern Instruments) that uses the technique of Doppler laser microelectrophoresis. This technique consists of applying an electric field to the particles suspension, which move at a speed related to their zeta potential. The speed of the particles is measured by an interferometric laser technique that detects the dispersion of the laser beam in the particles. From the speed data, the zeta potential is calculated. 

The equipment measures the zeta potential in particle suspensions with diameter between 3.8 and 100 micrometers. It also measures the particle size in the same range.

 

ROTATIONAL RHEOMETRY

Rotational rheometry is a technique used to measure the sear rheology of both low viscosity and highly viscous fluids. The shear rheology studies the behavior of a fluid under a shear stress. This technique allows to detect changes in the structure and composition of the materials. Such changes can modify the flow and deformation properties, and even the stability of the fluid. The measures are made by a BOHLIN GEMINI ™ 200 rheometer (Malvern Instruments). 

SLURRY PUMPING SYSTEM

The pumping system is widely used to know both the durability of the nano or microparticles that are forming the PCM slurry and the amount of energy that this fluid is able to exchanging. The system is equipped with heat exchangers, impeller pump flexible, a hot bulb and a cold bulb, obtaining a heating system at the laboratory scale by exchanging energy using a slurry PCM. 

MECHANICAL CHARACTERIZATION

The mechanical properties of the building materials containing PCMs are measured in an INSTRON 5548 model equipment, equipped with a load cell of 1 kN according to the ASTM D1621 Regulation. To determine the mechanical resistance of the samples, the equipment performs unidirectional compression tests where the load head speed used is 2.5 mm/min. 

The dimensions of the tested samples should be 5.1 cm x 5.1 cm x 2.6 cm. Then the samples are compressed up to 13% of their original thickness, in perpendicular direction to the growth of the foam. 

ESSAYS FOR RAW MATERIALS FOR POLYURETHANES (POLIOLS):

  • Determination of the hydroxyl index. (UNE 53985-1) (ASTM 4274:1999) 

  • Determination of the acid index. (UNE 53985-2) (ASTM D 4662:19989 

  • Determination of the basicity. (UNE 53985-3) (ISO 14899) 

  • Determination of the sodium (Na) and potassium (K) content. (UNE 53985-5)

  • Methods of preparation, titration and conservation of standard solutions for volumetric analysis of surface agents and formulations containing them. (UNE 55-539-94) 

DEVELOPMENT OF NEWS POLYURETHANES WITH FLAME RETARDANT PROPERTIES SINCE PHOSPHORYLATED POLYOLS 

Polyurethanes (Pus) are an important class of polymers that have wide application in a big number of industrials sectors. One of the main concerns of producers of Pus is the compliance of the flammability regulations. Phosphorus compounds have been widely used as flame retardant materials because of the high efficiency in lowering the flash point, the lower production of toxics gases, and the lower environmental destruction. In general, there is a growing interest in the incorporation of phosphorus compounds as additives or reagents in Pus formulations to improve their flammability resistance. The main objective of this research was the employment of the phosphorus compounds as initiator of the polyols polyether synthesis by anionic polymerization by ring opening. Subsequently, the synthesized polyols were used to develop new flame retardant polyurethanes. The proposed strategy opens a way for the production of polyols with fire retardant properties in a cost-effective way. 

 

 

Research staff: María M. Velencoso, María Jesús Ramos, Antonio De Lucas, Juan Francisco Rodríguez  

Publications:  

– M. M. Velencoso, M. J. Ramos, A. Serrano, A. de Lucas, J. F. Rodríguez. Fire retardant functionalized polyol by phosphonate monomer insertion. Polymer International. 2015. 54(12), 1706-1714.  

– M. M. Velencoso, M. J. Ramos, R. Klein, A. de Lucas, J. F. Rodríguez. Thermal degradation and fire behaviour of novel polyurethanes based on phosphate polyols. Polymer Degradation and Stability. 2014. 101(1), 40-51.  

– M. M. Velencoso, M. T. Villajos, A. C. Devic, M. J. Ramos, A. de Lucas, A, J. F. Rodríguez. Acidity removal and cesium catalyst recovery from polyol synthesis process. Organic Process Research and Development. 2013. 17(5), 792-797.  

– M. M. Velencoso, M. J. Ramos, J. C. Garcia-Martinez, A. de Lucas, J. F. Rodríguez. Synthesis of polyether polyols using glycerol phosphate disodium salt as initiator. Journal of Macromolecular Science, Part A: Pure and Applied Chemistry. 2013. 50(9), 905-913.  

– M. M. Velencoso, M. J. Ramos, J. C. García-Martínez, A. de Lucas y J. F. Rodríguez. Production of polyether polyols using phosphate calcium salt. Journal of Macromolecular Science, Part A: Pure and Applied Chemistry. 2011. 48, 1-9. 

Patents:  

– M. M. Velencoso, M. J. Ramos, J. C. García-Martínez, A. de Lucas y J. F. Rodríguez. Phosphate polyol and method of obtaining. Application number: 201031958. Spain. 2010. University of Castilla-La Mancha.  

 

FUNCTIONALIZATION OF POLYOLS AND POLYURETHANES BY CLICK CHEMISTRY 

In the last decades, the functionalization of polyurethanes and polyols has thrived by application of Click Chemistry (1,3-dipolar cycloaddition of azides and alkynes) in the synthesis of the process. In our research group, anionic polymerization with Click chemistry has been combined to synthesize polyols with fluorescent properties or high thermal stability. This route allows, through an easy, clean and very selective process, the incorporation of a wide range of functionalities in the polyols, compatible with several types of functional groups. The proposed strategy opens the way to cost-effectively producing polyurethanes with unconventional properties such as anti-acaric or antibacterial, flame retardant, hydrophobic or hydrophilic, etc. Thus, the synthesis process is carried out through the introduction of glycidyl propargyl ether into the polyol chains as a co-monomer with propylene oxide. Subsequently, this polyol with alkynil groups reacts with functionalized azides through of reactions of 1,3-dipolar cycloaddition catalyzed by copper.   

Figure 1. Polyurethanes functionalization with fluorescent properties by Click Chemistry.

Research staff: Maria M. Velencoso, Ana Borreguero, Maria Jesús Ramos, Antonio de Lucas, Juan Francisco Rodríguez  

Publications:  

– A. M. Borreguero, P. Sharma, C. Spiteri, M. M. Velencoso, M. S. Carmona, J. E. Moses, J. F. Rodríguez. A novel click-chemistry approach to flame retardant polyurethanes. Reactive and Functional Polymers. 2013. 73(9), 1207-1212.  

– M. M. Velencoso, A. S. González, J. C. García-Martínez, M. J. Ramos, A. de Lucas, J. F. Rodríguez. Click-ligation of coumarin to polyether polyols for polyurethane foams. Polymer International. 2012. 62(5), 783-790.  

 

RECYCLING OF FLEXIBLE POLYURETHANE FOAMS BY GLYCOLYSIS  

The main objective of this research line is the study and development of a process of chemical recovery of the polyols present in flexible polyurethane foams wastes. For the development of the recovery process of the polyol from the polyurethane wastes, due to its special characteristics, the process of “split phase” glycolysis was selected. This process consists of the treatment of polyurethane with low molecular weight glycols, in such a way that the final hydroxyl groups of the glycol cause an exchange in the urethane bond, the polyol being released into the reaction medium. The use of an excess of glycol and recovering a high molecular weight polyol provides phase separation in the reaction products, where one of the phase is composed, mainly, of the polyol revered with a low contamination. The “split phase” glycolysis has the important advantage that the final product recovered has a higher purity than in the homogeneous processes.  

The scheme of the “split phase” glycolysis process is shown under these lines:  

The subsequent treatment proposed for the phases obtained after the glycolysis of the foams not only improves the quality of the recovered polyol, but also take advantage of the by-products generated. Overall, the complete process developed for the treatment of flexible foams in the following figure: 

 

Research staff: Diego Simón, Ana Borreguero, Antonio de Lucas, Juan Francisco Rodríguez  

Publications:  

– D. Simón, A. de Lucas, J. F. Rodríguez, A. M. Borreguero. Flexible polyurethane foams synthesized employing recovered polyols from glycolysis: Physical and structural properties. Journal of Applied Polymer Science. 2017. 134(32), 450897.  

– J. Datta, P. Kopczyńska, D. Simón, J. F. Rodríguez. Thermo-chemical decomposition study of polyurethane elastomer through glycerolysis route with using crude and refined glycerine as a transesterification agent. Journal of Polymers and the Environment. 2017. 1-9.  

– D. Simón, A. de Lucas, J. F. Rodríguez, A. M. Borreguero. Glycolysis of high resilience flexible polyurethane foams containing polyurethane dispersion polyol. Polymer Degradation and Stability. 2016. 133, 119-130.  

– D. Simón, A. M. Borreguero, A. de Lucas, J. F. Rodríguez. Valorization of crude glycerol as a novel transesterification agent in the glycolysis of polyurethane foam waste. Polymer Degradation and Stability. 2015. 121, 126-136.  

– D. Simón, A. M. Borreguero, A. de Lucas, J. F. Rodríguez. Glycolysis of viscoelastic flexible polyurethane foam wastes. Polymer Degradation and Stability. 2015. 116, 23-35.  

– D. Simón, A. M. Borreguero, A. de Lucas, J. F. Rodríguez. Glycolysis of flexible polyurethane wastes containing polymeric polyols. Polymer Degradation and Stability. 2014. 109, 115-121.  

– D. Simón, A. M. Borregureo, A. de Lucas, C. Molero, J. F. Rodríguez. Novel polyol initiator form polyurethane recycling residue. Journal of Material Cycles Management. 2014. 16(3), 525-532.  

– D. Simón, M. T. García, A. de Lucas, A. M. Borreguero, J. F. Rodríguez. Glycolysis of flexible polyurethane wastes using stannous octoate as the catalyst: Study on the influence of reaction parameters. Polymer Degradation and Stability. 2013. 98, 144-149.  

– C. Molero, V. Mitova, K. Troev, J. F. Rodríguez. Kinetics and mechanism of the chemical degradation of flexible polyurethane foam wastes with dimethyl h-phosphonate with different catalysts. Journal of Macromolecular Science, Part A: Pure and Applied Chemistry. 2010. 47, 983-990.  

– C. Molero. A. de Lucas, J. F. Rodríguez. Glycolysis of flexible polyurethane wastes using stannous octoate as the catalyst. Journal of Material Cycles Waste Management. 2009. 11, 130-132.  

– C. Molero, A. de Lucas. J. F. Rodríguez. Activities of octoate salts as novel catalysts for the transesterification of flexible polyurethane foams with diethylene glycol. Polymer Degradation and Stability. 2009. 94, 533-539.  

– C. Molero, A. de Lucas, F. Romero, J. F. Rodríguez. Influence of the use of recycled polyols obtained by glycolysis on the preparation and physical properties of flexible polyurethane. Journal of Applied Polymer Science. 2008. 109, 617-626.  

– C. Molero, A. de Lucas, J. F. Rodríguez. Recovery of polyols from flexible polyurethane foam by “split phase” glycolysis: Study on the influence of reaction parameters Polymer Degradation and Stability. 2008. 93, 353-361.  

– C. Molero, A. de Lucas, J. F. Rodríguez. Recovery of polyols from flexible polyurethane foam by “split phase” glycolysis: glycol influence. Polymer Degradation and Stability. 2006. 91, 221-228.  

– C. Molero, A. de Lucas, J. F. Rodríguez. Recovery of polyols from flexible polyurethane foam by “split phase” glycolysis with new catalyst. Polymer Degradation and Stability. 2006. 91, 894-901.  

– C. Molero, A. de Lucas, J. F. Rodríguez. Purification by liquid extraction of recovered polyols. Solvent Extraction Ion Exchange. 2006. 24, 719-730. 

 

DEVELOPMENT OF MICROCAPSULES THAT CONTAIN EXTRACTION AGENTS FOR THE RECOVERY AND SELECTIVE SEPARATION OF HEAVY METALS FROM CONTAMINATED WATERS  

The contamination and environmental impact caused by heavy metals due to their toxicity and a growing interest in their intrinsic value, motivates the development of new techniques for their recovery or elimination, further encouraged by the control exercised by the current legislation.  

Solvent extraction and ion exchange are the most commonly used techniques for industrial separation and recovery of heavy metals. However, these have several drawbacks. Among them, in the case of solvent extraction, the problem of extraction agent losses, with the consequent contamination of the aqueous phase and difficulties in phase separation, should be highlighted. In the ionic exchange, the conventional resins are not very selective and in the case of the chelanting, of greater selectivity, they present very slow kinetics.  

The main objective of this research is the microencapsulate extraction agents in a functionalized shell (with sulphonic groups as active centers). This novel material combines the advantages of the conventional methods discussed above and improves the selective separation of the heavy metals from contaminated aqueous phases.  

Research staff: Ángela Alcázar Román, Manuel Carmona Franco, Ángel Pérez Martínez, Antonio de Lucas Martínez, Juan Francisco Rodríguez Romero.  

Publications:  

– Á. Alcázar, A.M, Borreguero, A. de Lucas, F.J. Rodríguez, M. Carmona. Microencapsulation of TOMAC by suspensión polymerisation: Process optimisation. Chemical Engineering Research and Desing. 2017.117, 1-10.  

– Á. Alcázar, C. Gutiérrez, A. de Lucas, M. Carmona, J.F. Rodríguez. Equilibrium treatment for highly selective sulfonated microcapsules containing Di(2-ethylhexyl)phophoric Acid. Industrial and Engineering Chemistry Research. 2016. 55(4), 1033-1042.  

– Á. Alcázar, I. Garrido, E.M. García, A. de Lucas, M. Carmona, J.F. Rodríguez. New type of highly selective microcapsules for the removal of mercury from Surface polluted waters. Separation and Purification Techonology. 2015. 154, 255-262.  

– Á. Alcázar, M. Carmona, A.M. Borreguero, A. de Lucas, J.F. Rodríguez. Synthesis of microcapsules containing different extractant agents. Journal of Microencapsulation. 2015. 32(7), 642-649.  

– L. Sánchez-Silva, Á. Alcázar, A. de Lucas, M. Carmona, J.F. Rodríguez. Functionalization of microcapsules for the removal of heavy metal ions. Journal of Chemical Technology & Biotechnology 2011. 86(3), 437−446.  

– Á. Alcázar, A. de Lucas, M. Carmona, J.F. Rodríguez. Synthesis of sulphonated microcapsules of P(St-DVB) containing di(2-ethylhexyl)phosphoric acid. Reactive & Functional Polymers 2011. 71(8), 891−898. 

 

DEVELOPMENT AND PRODUCTION OF MICROCAPSULES CONTAINING PCM´S AND THEIR INTEGRATION IN INTELLIGENT INSULATING MATERIALS WITH IMPROVED THERMAL PROPERTIES  

The contamination and environmental impact caused by the fossil fuels, together with the increasing price of energy motivates the development of new materials that allow their accumulation and storage. The incorporation of microcapsules containing PCMs in building materials is a recent technology and it is receiving great acceptance for the economic and environmental advantages that presents. Furthermore, by encapsulation, problems such as the formation of flammable mixtures or the loss of mechanical resistance are avoided.  

The main objective of this line of research is the development of microcapsules containing phase change materials for their incorporation into low cost insulation materials in buildings. Two different techniques have been used for the encapsulation of PCM in a polymeric shell, as chemical technique the suspension-like polymerization, in which the Chemical Engineering Group of the UCLM has great experience and as physical technique, the encapsulation by Spray Drying, that a patent has been obtained. In addition, the microcapsules of phase change material are improved with the incorporation of nanomaterials with high thermal conductivity in the capsule, which will provide a better thermal transfer to the organic substance in the interior. The temperatura drops below the PCM melting point.

 

 

Research staff: Anna Mª Szczotok, Mª Luisa Tordesillas Moraga, Ana María Borreguero Simón, María Luz Sánchez Silva, Manuel Carmona Franco, Paula Sánchez Paredes, Antonio de Lucas Martínez, Juan Francisco Rodríguez Romero, José Luis Valverde Palomino  

Publications:  

– A. M. Szczotok, M. Carmona, A.-L. Kjøniksen, J. F. Rodríguez. Equilibrium adsorption of polyvinylpyrrolidone and its role on thermoregulating microcapsules synthesis process. Colloid and Polymer Science. 2017. 295(5), 783-792.  

– V. D. Cao, S. Pilehvar, C. Salas-Bringas, A. M. Szczotok, J. F. Rodríguez, M. Carmona, N. Al-Manasir, A.-L. Kjøniksen. Microencapsulated phase change materials for enhancing the thermal performance of Portland cement concrete and geopolymer concrete for passive building applications. Energy Conversion and Management. 2017. 133, 56-66.  

– D. Simon, J. F. Rodríguez, P. Sanchez, Sanchez-Silva, L. The effect of the dry glass transition temperatura on the synthesis of paraffin microcapsules obtained by suspension-like polymerization. Polymer Engineering and Science. 2014. 54(1), 208-214.  

– A. M. Borreguero, I. Garrido, J. L. Valverde, J. F. Rodríguez, M. Carmona. Development of smart gypsum composites by incorporating thermoregulating microcapsules. Energy and Buildings. 2014. 76, 631-639.  

– A. M. Borreguero, A. Serrano, I. Garrido, J. F. Rodríguez, M. Carmona. Polymeric-SiO2-PCM s for improving the termal properties of gypsum applied in energy efficient buildings. Energy Conversion and Management. 2014. 87, 138-144.  

– A. M. Borreguero, B. Talavera, J. F. Rodríguez, J. L. Valverde, J. L. González, M. Carmona. Enhancing the thermal contort of Smart fabrics for the footwear industry. Textile Research Journal. 2013. 83(16), 1756-1763.  

– C. Barreneche, A. de Gracia, S. Serrano, M. Elena Navarro, A. M. Borreguero, A. Ines Fernández, M. Carmona, J. F. Rodríguez, L. F. Cabeza. Comparison of three different devices available in Spain to test thermal properties of building materials including phase change materials. Applied Energy. 2013. 109, 544-552.  

– A. M. Borreguero, J. F. Rodríguez, J. L. Valverde, T. Peijs, M. Carmona. Characterization of rigid polyurethane foams containing microencapsulated phase change materials: Microcapsules type effect. Applied Polymer Science. 2013. 128. 582-590.  

– A. M. Borreguero, J. L. Valverde. J. F. Rodríguez. A. H. Barber. J. J. Cubillo, M. Carmona. Synthesis and characterization of microcapsules containing Rubitherm®RT27 obtained by spray drying. Chemical Engineering Journal. 2011. 166(1), 384-390.  

– A. M. Borreguero, M. L. Sánchez, J. L. Valverde, M. Carmona, J. F. Rodríguez. Thermal testing and numerical simulation of gypsum wallboards incorporated with different PCMs content. Applied Energy. 2011. 88(3), 930-937.  

– A. M. Borreguero, J. F. Rodríguez, J. L. Valverde, R. Arévalo, T. Peijs, M. Carmona. Characterization of rigid polyurethane foams containing microencapsulated Rubitherm®RT27: Catalyst effect. Part II. Journal of Material Science. 2011. 46, 347-356.  

– M. L. Sánchez, J. F. Rodríguez, M. Carmona, A. Romero, A. M. Borreguero, P. Sanchez. Microencapsulation of PCMs with a styrene-methyl methacrylate copolymer Shell by suspension-like polymerization. Chemical Engineering Journal. 2010. 157, 216-222.  

– A. M. Borreguero, J. L. Valverde, T. Peijs, J. F. Rodríguez, M. Carmona. Characterization of rigid polyurethane foams containing microencapsulated Rubitherm®RT27. Part I. Journal of Material Science. 2010. 45, 4462-4469.  

– A. M. Borreguero, M. Carmona, M. L. Sanchez, J. L. Valverde, J. F. Rodríguez. Improvement of the thermal behaviour of gypsum blocks by the incorporation of microcapsules containing PCMs obtained by suspension polymerization with an optimal core/coating mass ratio. Applied Thermal Engineering. 2010. 30, 1164-1169.

– L. Sanchez, P. Sanchez, A. de Lucas, M. Carmona, J. F. Rodríguez. Influence of operation conditions on the microencapsulation of PCMs by means of suspension-like polymerization. Colloid Polymer Science. 2008. 286(8-9), 1019-1027. 

– L. Sanchez, P. Sanchez, A. de Lucas, M. Carmona, J. F. Rodríguez. Microencapsulation of PCMs with a polystyrene shell. Colloid Polymer Science. 2007. 285, 1377-1385. 

Patents:  

J. Gravalos, I. Calvo, J. Mieres, J. Cubillo, A. M. Borreguero, M. Carmona, J. F. Rodríguez, J. L. Valverde. Patent EP2119498 (A1), 2009.  

 

THERMOREGULATING MATERIALS FOR THE IMPROVEMENT OF BUILDING ENERGY EFFICIENCY 

The aim of the project is to obtain phase change materials (PCMs) for incorporation into building elements such as gypsum, rigid polyurethane foam or bricks. The use of these materials in buildings would increase their energy efficiency, due to the passive uptake that these compounds present, reducing energy consumption of houses by at least 30%.  

To achieve these objectives, thermoregulating microcapsules produced in Itquima have been used, as well as the development of new shape-stabilized materials, which allow their incorporation into porous ceramic materials where microcapsules cannot be used.  

Research staff: Ángel Serrano Casero, Manuel Carmona Franco, Juan Francisco Rodríguez Romero.  

Publications:  

– A. Serrano, A.M. Borreguero, I. Garrido, J.F. Rodríguez, M. Carmona. The role of microstructure on the mechanical properties of polyurethane foams containing thermoregulating microcapsules. Polymer Testing. 2017. 60, 274-282.  

– A. Serrano, A.M. Borreguero, I. Garrido, J.F. Rodríguez, M. Carmona. Reducing heat loss through the building envelope by using polyurethane foams containing thermoregulating microcapsules. Applied Thermal Engineering. 2016. 103, 226-232.  

– M.M. Velencoso, M.J. Ramos, A. Serrano, A. de Lucas, J.F. Rodríguez. Fire retardant functionalized polyol by phosphonate monomer insertion. Polymer International. 2015. 62(12), 1706-1714. 

 

DEVELOPMENT OF SLURRIES BASED ON THERMOREGULATORY MICROCAPSULES FOR RESIDENTIAL APPLICATIONS 

The growth in the world population is generating an increase in global energy demand, causing greenhouse gas emissions to rise as a result of increased consumption of fossil fuels. Therefore, alternative energy sources must be sought for fossil fuels. Solar energy is the main source of renewable energy available in Spain, thanks to the large number of hours of sun obtained throughout the year.  

The main objective is the development of slurries based on thermoregulatory microcapsules for residential applications. The main interest of the research is the possibility of storing energy, which plays a fundamental role in synchronizing supply and demand. The use of solar radiation allows to reduce the dependence of fossil energy homes. In addition, the storage of this energy to be exploited when there is no solar radiation, would allow a great reduction in the consumption of exogenous energy and mitigate the climatological dependence of the system. Being able to have a fluid for thermal accumulation, “slurry”, which exceeds the thermal storage density of the water, maintaining the fluid dynamic properties and improving the thermals of the same, would be a step in the process of getting the building self-sustaining.  

To achieve the above, it is intended to develop stable suspensions of particles with thermal storage capacity commonly known as “slurry or MPCS” and an experimental installation by which the slurry will be circulated to study both its thermal properties as well as its stability and characteristics after different pumping cycles. 

Research staff: Macarena Jiménez Vázquez, Daniel López Pedrajas, Manuel Carmona Franco, Juan Francisco Rodríguez Romero, Ana María Borreguero, Ignacio Garrido Saenz. 

 

DEVELOPMENT OF IMPROVED POLYMER POLYOLS USING A NON-AQUOUS DISPERSANT BASED ON A SILICA GEL 

In this line of research, polymeric polyols are being developed by using different types of monomers, as well as a new non-aqueous dispersant, which consists of a silica gel with hydroxyl and vinyl groups.  

Polymer polyols, with high solids content, will be used for the synthesis of flexible foams and elastomers with improved properties.  

Research staff: Irene Izarra Pérez, Juan Francisco Rodríguez Romero, Manuel Salvador Carmona Franco, Diego Simón Herrero. 

 

AGGLOMERATION OF NANOPARTICLES THROUGH SPRAY-DRYING FOR IMPROVED PROCESS SAFETY

Due to their small size and high reactivity, the handling of nanomaterials in the form of dry dust results in health and safety hazards. Increasing the particle, size through the agglomeration of the nanomaterials, reduces these risks. This is achieved using spray-drying technique, which is developed at two different scales: laboratory and pilot plant scale. Besides, it is being studied the use of the agglomerated nanomaterials as additive for different materials such as polyurethane foams.  

Research staff: Jesús Alberto Martín del Campo Martín-Consuegra, Irene Izarra Pérez, Juan Francisco Rodríguez Romero, Manuel Salvador Carmona Franco, Ana María Borreguero Simón.

 

DEVELOPMENT OF NEW BIODEGRADABLE, BIOCOMPATIBLE AND/OR FLAME RETARDANT POLYURETHANES BASED ON PHOSPHONATES AND NATURAL COMPOUNDS (CTQ2008-06350) 

  • Ministry of Economy and Competitiveness. 
  • January 2009 to December 2013 
  • 396517 € 

MICROENCAPSULATION OF EXTRACTION AGENTS FOR THE SELECTIVE SEPARATION OF HEAVY METALS (CTQ2008-03474/PPQ) 

  • Ministry of Economy and Competitiveness. 
  • January 2009 to December 2011 
  • 184248 € 

SYNTHESIS AND PURIFICATION OF PHARMACEUTICAL ACTIVE INGREDIENTS 

  • Servier Laboratory 
  • September 2009 to August 2010 
  • 72833 € 

MICROCAPSULE PRODUCTION PLANT (ref. PP200905) 

  • FEDER Operative Program 
  • September 2009 to August 2010 
  • 293480 € 

SCALED UP AT THE PILOT PLANT LEVEL OF THE MICROCAPSULE PRODUCTION PROCESS CONTAINING THERMOREGULATORY MATERIALS 

  • Association for the Incorporation of New Technologies to the Company (ASINTEC) 
  • September 2009 to August 2012 
  • 110000 € 

DEVELOPMENT, ANALYSIS AND PREPARATION OF ACTIVE PHARMACEUTICAL AGENT IN LABORATORY AND PILOT PLANT 

  • Servier Laboratory 
  • December 2010 to November 2011 
  • 75148 € 

CHARACTERIZATION OF PCMS FOR ENERGY SAVING IN BUILDINGS AND IN THE IMPROVEMENT OF COMFORT IN CLOTHING OR ON THE SHOES 

  • Secretary of State of Universities – Secretary of State of Research 
  • January 2011 to December 2011 
  • 67800 € 

CALORIMETRY WITH CONTROLLED HIGH PRESSURE CELL FOR THE RECYCLING OF POLYMERIC RESIDUES 

  • Secretary of State of Universities – Secretary of State of Research 
  • January 2011 to December 2011 
  • 100600 € 

ELIMINATION OF MERCURY FROM SURFACE, UNDERGROUND AND DRAINAGE WATERS OF THE ALMADEN MINING AREA THROUGH MICROCAPSULES CONTAINING SELECTIVE EXTRACTION AGENTS (CTQ2011-27085/PPQ) 

  • Ministry of Economy and Competitiveness. 
  • January 2011 to December 2014 
  • 111111 € 

NEW ADVANCED INSULATION AND PHASE CHANGE MATERIALS (CP-CP 260056 NANOPCM) 

  • It funded by the company ACCIONA and the Seventh Framework Program of I+D of the Europe Union FP7-2010-NMP-ENV-ENERGY-ICT-EeB (Grant Agreement: 260056) 
  • June 2010 to May 2013 
  • 304907 € 

MACHINES SERVOIDRAULIC MECHANICAL TESTS OF 100 KN 

  • Ministry of Economy and Competitiveness 
  • January 2013 to December 2015 
  • 198850 € 

AGREEMENT FRAMEWORK OF COLLABORATION FOR RESEARCH IN ADVANCED MATERIALS AND ITS APPLICATION UNDER CONSTRUCTION (CTR-12-0351)

  • ACCIONA
  • January 2013 to December 2013
  • 42000 €

SYNTHESIS OF MICRO AND NANO-PARTICLES OF L-PLYLACTIC DRUG CONTAINING ANTICANCER AGENT USING THE SAS TECHNIQUE AND IMPREGNATION (PEII 11-0180-8491) 

  • Counseling of Education and Science 
  • September 2014 to August 2017 
  • 195000 € 

 

NANOCOMPOSITE FOR BUILDING CONSTRUCTIONS AND CIVIL INFRAESTRUCTURES: EUROPEAN NETWORK PILOT PRODUCTION LINE TO PROMOTE INDUSTRIAL APPLICATION CASES 

  • Europe Union 
  • January 2015 to December 2017 
  • 6878350 € 

 

DEVELOPMENT OF SLURRIES BASED ON THERMOREGULATORY MICROCAPSULES FOR RESIDENTIAL APPLICATIONS (CTQ2015-69299-R) 

  • Ministry of Economy and Competitiveness 
  • January 2016 to December 2018 
  • 220000 € 
  • Antonio de Lucas Martínez 
  • Juan Francisco Rodríguez Romero 
  • Manuel Salvador Carmona Franco 
  • Ignacio Garrido Saenz 
  • Ana María Borreguero Simón 
  • María Jesús Ramos Marcos 
  • Ángel Pérez Martínez 
  • Diego Simón Herrero 
  • Ángel Serrano Casero 
  • Irene Izarra Pérez 
  • Ania Szczotok-Piechaczek 
  • Jesús Alberto Martín del Campo Martín-Consuegra 
  • Macarena Jiménez Vázquez 
  • Daniel López Pedrajas 
  • María del Prado Garrido Martín