Stage I: “Development of laboratory experimental models"
involved the achievement of three activities, by the four partners, in cooperation:
Act 1.1 "Systematic investigations and preliminary experiments on identifying potential catalytic systems and procedures of synthesis, allowing the preparation of oligoester polyols with tuned chemical structures from PET and renewable materials, with minimum energy consumption. The “Development of of laboratory experimental models" aimed formulating the scientific program of the project. After a comprehensive investigation of the correlation of prior art with the specific objectives of the project, and some preliminary experiments, the partners planned, through the development of experimental models (Stage planned results – deliverables, presented in summary form in The scientific and technical report), on theoretical principles and a common approach to the subject, the steps to be followed in order to achieve the project objectives.
- An assessment of commercial organic catalysts and their potential chemical modification and the possibility of achieving and testing new structures, likely to present catalytic activity for de-polymerization of PET in the presence of chemical agents derived from renewable materials, under reaction conditions allowing the minimization of energy consumption and a theoretical investigation (quantum computing) on the activity of a versatile catalyst in the presence of a diol selected from biomass were achieved, which allowed the development of The experimental model on the synthesis of modified organic catalysts;
- The main correlations between the designed chemical structures of the oligoester polyols resulting from PET de-polymerization in the presence of renewable materials and their physico - chemical properties, required for obtaining rigid polyurethane foams with thermo-insulating properties, were formulated and analyzed, and The experimental model on the synthesis of oligoester polyols was developed;
- The most appropriate techniques for oligoester polyols characterization, in order to relieve their characteristics necessary for the pursued applications, and for polyurethane foams characterization, in order to verify the proposed properties, were identified, and The experimental model for the characterization of oligoester polyols and cellular materials was developed;
- Main correlations between the physico-chemical properties of the oligoester polyols, the formulation of foam systems and the physico-chemical and physical-mechanical properties of polyurethane insulating materials were evaluated, and The experimental laboratory model for the formulation of polyurethane materials was developed.
Act 1.2 "Starting the experimental model on the synthesis of organic catalysts and the experimental model on the synthesis of oligoester polyols“ consisted in conducting laboratory experiments to provide scientific experimental information for achieving studies regarding structure - selectivity of organic catalysts correlation, obtaining appropriate chemical structures of oligoester polyols from PET waste and renewable materials, identifying the optimal parameters of synthesis reactions and establishing of appropriate formulations for sprayed polyurethane foams.
- Experiments of PET depolymerization in the presence of organic selected catalysts were performed, monitoring the correlations between catalytic activity (type and amount of catalyst), the parameters of the synthesis reactions (type and ratio of reagents, temperature, reaction time) and structural characteristics of the reaction products;
- Synthesis experiments of oligoester polyols with various chemical structures from PET waste and renewable materials in the presence of organic catalysts selected were acheived, monitoring the interdependencies between the reaction parameters (type and ratio of raw materials, temperature, reaction time) and physical -chemical characteristics and structural properties of the products;
- The oligoester polyols showing the most suitable properties, were tested in polyurethane foam preparation, monitoring the effect of the polyols chemical structures and physical-chemical properties on the physical-chemical properties of the foaming systems and the physical-chemical and physical -mechanical properties of the polyurethane foams.
- A Research report on the results of experiments (planned result of the stage –deliverable, presented in summary form in The scientific and technical report) was drawn.
Act 1.3: "Dissemination of results", aimed drafting and submitting for publication of a scientific article in a ISI indexed scientific journal and / or achieving and presenting of two communications in national and international scientific events (Planned results of the stage - deliverables).
The scientific data obtained were subject to:
- A scientific article drafted and submitted for publication in a scientific Romanian journal (Revista de chimie –Chemistry magazine);
- An oral scientific communication was presented in a national conference of chemistry (The XXXIII-nd Romanian Chemistry Conference – Caciulata 2014);
- Two posters were presented at an international symposium held in Romania (International Symposium PRIOCHEM, 10-th edition, 2014).
The project website was realized and updated.
Experimental polyurethane rigid foams from PET wastes chemical recycling using reagents from renewable resources, in the presence of some organocatalysts
Stage II: "Development of laboratory technologies for synthesis of modified organic catalysts and oligoester polyols for polyurethane foams with thermal insulating properties"
of the project development involved the achievement of seven activities by the four partners, in cooperation:
Activity 2.1 "Development of the experimental model for synthesis of modified organic catalysts; characterization and testing the catalysts in the synthesis of oligoester polyols” had as objective to obtain modified structures of commercial organic catalysts known in the art for use in PET depolymerization, as well as modified structures of other classes of organic catalysts, characterizing and testing the catalysts obtained and some of their mixtures, likely to have a synergistic effect, in PET chemical cleavage, and selection of the catalyst system used for development of the experimental model for synthesis of oligoester polyols from PET wastes and renewable raw materials:
- CO - conducted experiments for the synthesis of three classes of catalysts: thioureides, TBD monoamide ester derivatives and phosphazenes. The catalysts synthesized were structurally characterized (NMR). One catalyst was selected and the laboratory technology for its synthesis was elaborated (stage planned result -deliverable). oligoester polyols obtained by P1 were characterized, from structural point of view NMR);
- P1 - conducted experiments in order to test the selected catalysts synthesized by CO in oligoester polyols synthesis, the products were characterized in terms of physico-chemical properties and tested in polyurethane rigid foams formation;
- P2 - polyurethane materials characterization, in terms of thermal (TGA) and rheological (DMA) characteristics.
Activity 2.2: "Development of the laboratory experimental model for oligoester polyols synthesis from PET wastes and renewable raw materials, in the presence of organic catalysts“ had as objective the synthesis of various chemical structures of oligoster polyols, testing them in rigid polyurethane foams formation, intermediate products characterization, selection of the optimal variant and determining the optimum parameters of the synthesis reaction.
- CO – obtained the catalysts needed for the development by partner P1 of the experimental model for oligoester polyols synthesis. The oligoester-polyols sinthesized by partner P1 were characterized in terms of structural characteristics (NMR);
- P1 - carried out experiments for the synthesis of three series of oligoester polyols with tailored chemical structures: i) using as a cleaving and modification reagents various conventional linear or branched diols, or mixtures thereof, and mixtures of aromatic and aliphatic dicarboxylic acids, at various mole ratios, ii) using as cleaving and modification reagents mixtures of conventional diols with isosorbide, a cyclic diol which confers special properties to the reaction products (rigidity of the chemical structures), and an aliphatic dicarboxylic acid, iii) using as cleaving and modification reagents mixtures of conventional diols with ethanolamine or aliphatic diamines, when aminolysis reactions of PET occur, besides the glycolysis reactions, and an aliphatic dicarboxylic acid or mixture of aromatic and aliphatic dicarboxylic acids or derivatives, depending on the necessary modifications they provide to the product properties. The products were characterized in terms of physico-chemical properties and tested in a first instance to obtain rigid polyurethane foams. After oligoester polyols complex characterization (by partners CO and P2) the selected optimum variants were submitted to testing for rigid polyurethane foams formation by partner P3. After complex characterization of foams (performed by partners P2 and P3) an optimal oligoester polyol option was selected, for which the laboratory synthesis thechnology was developed (stage planned result - deliverable).
- P2 - performed structural characterization (FTIR) of the oligoester polyols and polyurethane materials characterization in terms of thermal (TGA) and rheological (DMA) characteristics;
- P3 – tested the optimal structures of oligoester- polyols in the process of obtaining rigid polyurethane foams, using appropriate formulations for spray foam formation. Polyol blends were characterized in terms of physicochemical properties and reactivity, while polyurethane foams were characterized in terms of physical and mechanical properties and thermal conductivity.
Activity 2.3: “Identification and assignment of intellectual property rights” aimed at drafting and submitting a patent application to OSIM. The four partners, in collaboration, filled and submitted to OSIM a patent Application entitled “Aliphatic-aromatic oligoester polyols from PET waste and renewable raw materials and process for producing the same”, registration number: A/00956 / 03.12.2015.
Activity 2.4: “Dissemination of scientific and technical results” had as objective drafting and submitting for publication in an ISI journal one scientific paper and/or presenting two scientific communications in national and international scientific events (stage planned results - deliverables).
Several articles and scientific communications were developed by partners CO, P1 and P2 in cooperation, as follows:
- One scientific article published in a scientific Romanian ISI journal;
- One scientific article published in a scientific Romanian unlisted journal;
- One scientific article accepted for publication in a Romanian scientific ISI journal;
- Four scientific communications (one oral and three poster presentations) presented in international symposia organized in Romania and Moldova.
Activity 2.5: “Demonstration of functioning and reproducibility of laboratory technologies for the synthesis of modified organic catalysts and for the synthesis of oligoester polyols in the presence of the organic catalysts” aimed at improving the lab technologies previously developed.
- CO conducted laboratory experiments for perfecting the technology for the organic catalyst synthesis and verifying its reproducibility;
- P1 -conducted laboratory experiments for perfecting the technology for synthesis of the selected oligoester polyol structure and verifying its reproducibility;
A Demonstration report (stage planned - deliverable) on the results of the research work is contained in The scientific and technical report.
Activity 2.6: “Experiments for creating a “library” of modified organic catalysts and / or combinations thereof with synergistic effect, suitable for selectively depolymerizing PET wastes with various cleavage agents, different from those selected for developing the experimental model for synthesis of oligoester polyols” had the objective of obtaining other structures of organic catalysts suitable for PET depolymerization and testing them as well as mixtures thereof, in degradative transesterification reactions of PET in the presence of various cleavage reagents.
a) CO performed synthesis reactions of four chemical structures belonging to another class of organic catalysts, ie ionic liquids, and developed a research report on the results of the experiments (stage planned result - deliverable), which is contained in The scientific and technical report.
b) P1 tested the organic catalysts activity by performing depolimerization reactions of PET wastes in the presence of various cleavage reagents.
Activity 2.7: “Starting the development of the experimental laboratory model for obtaining polyurethane spray insulating foam”, which began in this stage of the project execution and will continue throughout the next stage, aimed at designing, achieving and testing one polyol mixture formulation, different from those commonly used in polyurethane spray foam, in the process of rigid polyurethane foams formation, in order to achieve the ultimate goal of maximizing the amount of experimental oligoester-polyols integrated into the polyurethane foam.
a) P1 designed, participated in development and testing of polyol mixture formulation and characterized the polyurethane foams in terms of thermal and rheological properties.
b) P3 developed the polyol mixture specific formulations, characterized them in terms of reactivity and physicochemical properties, tested them into rigid polyurethane foams formation and characterized the polyurethane foams in terms of physical and mechanical properties and thermal conductivity.
A research report on the partial results obtained in laboratory during this stage of project development was elaborated (stage planned result - deliverable), which is contained in The scientific and technical report.
Stage III / 2016: "Further development of the experimental model for obtaining polyurethane rigid foams and implementation of the technology for oligoester polyols synthesis on pilot scale"
The project development involved the achievement of 5 activities, the by the 4 partners, in cooperation:
Activity 3.1 "Further experiments for development of the experimental laboratory model for obtaining polyurethane thermal insulating sprayfoams. Characterization of polyurethane foams" had as main objectives: synthesis of oligoester polyols in the optimal version resulting from experiments conducted to date, proceeding the specific formulations of foaming systems using the the optimal version of oligoester polyols obtained by partner P1during the stage, complex characterization (physico-chemical and structural) of the oligoesters, complex characterization (in terms of physico-mechanical, thermal conductivity and fire behavior) of polyurethane rigid (PUR) foams, observing the effect of various formulations of the polyol component on systems reactivity and on the properties of the PUR foams:
- P1 developed experiments for improvement of chemical composition of oligoester polyols, in order to minimize their viscosity, one essential property for obtaining homogeneous polyol component whilst maximizing its content in experimental oligoester polyol, leading to obtaining appropriate PUR foam properties. Several versions of chemical compositions were obtained, which were characterized in terms of physic-chemical properties, and one variant with optimal properties was selected.
- CO performed the structural characterization (NMR) of the oligoester-pololiols obtained in the presence of organic catalysts, enabling elucidation of interdependencies that occur between chemical structure and ratio of reactants and the properties of polyols, thus allowing the achievement of the optimal composition, leading to the expected PUR foams properties;
- P3 together with P1 continued the development of the experimental model for obtaining thermal insulating PUR foams, observing the influence of the content of experimental oligoester polyol into the polyol component, of the type and quantity of catalysts used in foam formulations as well as of the water content of the formulations, on system reactivity and properties of PUR foams, in order to select the formulation that lead to optimal foams properties. PUR foams characterization in terms of mechanical properties, thermal conductivity and fire behavior was also performed;
- P2 performed structural characterization of oligoester polyols (FT-IR) and complex characterization of PUR foams in terms of thermal properties (TGA) and rheology (DMA).
A Research Report on the results obtained during the development of the experimental model for manufacturing thermal-insulating PUR foams - deliverable of the stage- was elaborated.
Activity 3.2 "Continuation of experiments for achieving the" library "of modified organic catalysts and /or combinations thereof with synergistic effect, suitable for selective attack of PET with various cleavage agents " aimed to obtain new chemical structures of catalysts and improve the previously obtained structures, in order to be used for PET chemical cleavage with various agents, and testing the catalytic systems in PET glycolysis reactions and in synthesis reactions of experimental oligoester polyols:
- CO obtained catalysts of five classes of chemical structures: thiourea and derivatives of thiourea (thioureides), derivatized TBD, phosphazene and phosphazenium salts, ionic liquids and carbenes, which were characterized and tested in the cleavage reaction of PET with ethylene glycol; CO also characterized, from structural point of view (NMR), the oligoester polyols synthesized from P1 in order to test the activity of the organic catalyst or their mixtures;
- P1 tested 5 catalytic systems (organic catalysts or mixtures thereof supposed synergistic) in the synthesis reactions of oligoester polyols, characterized the oligoester polyols obtained from physico-chemical point of view, tested the oligoester-polyols in the formation of PUR foams and characterized the foams in terms of mechanical properties, thermal conductivity and fire behavior; the catalysts tested led to oligoesters with high viscosity (with one exception) and did not lower temperatures and reaction times compared to previously selected catalyst version, with one exception. Unfortunately the two positive effects were not obtained for the same catalyst, in conclusion, none of the tested versions of catalytic systems lead to overall results superior to those previously obtained – the selected version;
- P2 performed structural characterization of oligoester polyols (FT-IR) and complex characterization of PUR foams in terms of thermal properties (TGA) and rheology (DMA);
Activity 3.3 "Installation and commissioning of the plants in order to scale-up laboratory technologies for oligoester polyols synthesis and PUR materials formation in pilot plant” had as objectives the preparation and verification in operation of the pilot plant for oligoester polyols synthesis, in order to implement the laboratory synthesis technology on pilot scale, and the preparation and verification in operation of the pilot equipment for obtaining sprayed PUR foams in order to implement the laboratory technology for obtaining PUR foams on pilot scale, during the next stage of the project development. The synthesis plant consists of an esterification-polycondensation stainless steel autoclave with a capacity of 10,000 cm3, and a pressure filter with a capacity of 8,000 cm3. The pilot plant for sprayed PUR foams preparation consists of a PUR rigid foam spraying unit Graco Reactor E10, a power source for spraying equipment, a compressed air source for spraying equipment with built-in air dryer. The pilot plants are presented in the Scientific and technical description of the stage. This activity was attended by partners P1 and P3, in collaboration.
Pilot plant for for oligoester polyols synthesis (left) and Pilot plant for sprayed PUR foams preparation (right)
Activity 3.4 "Implementation of laboratory technology for obtaining oligoester polyols from waste PET and renewable materials in mild synthesis conditions, in previously selected version, on pilot scale. Elaboration of pilot technology for oligoester polyols synthesis" aimed to establish the parameters of chemical reactions in pilot scale, in order to lead to the synthesis of oligoester-polyols with appropriate properties for the intended purpose, as well as manufacture the amount of oligoester polyols required for the pilot scale experiments to obtain PUR foams, which are to be done in the next stage of project development:
- P1 and P3, in cooperation, conducted pilot experiments; the recipe established following the experiments for improving technology was used, in order to minimize the viscosity of the product; the other initial reaction parameters (temperature, time) were those established by the laboratory technology. To obtain the pursued physico-chemical properties of the oligoester-poliols slightly longer reaction times than for the standard laboratory version were necessary, but the physic-chemical properties of the oligoester -poliols were almost identical and were exactly reproduced when verifying the reproducibility of the pilot technology. The oligoester polyols were tested, by the partners P1 and P3 in cooperation, in formation of PUR foams, which were characterized in terms of mechanical properties, thermal conductivity and fire behavior;
- CO performed structural characterization (NMR) of the oligoester-pololilor obtained in the presence of organic catalysts in pilot plant, emphasizing that the structural properties of the oligoester polyols were very close to those of standard version, prepared in laboratory;
- P2 performed structural characterization of oligoester- polyols (FT-IR) and complex characterization of PUR foams in terms of thermal properties (TGA) and rheology (DMA).
A "Pilot technology for obtaining oligoester polyols from PET waste and renewable materials" - deliverable of the stage- and a “Data sheet of the pilot technology” - deliverable of the stage- were elaborated.
Oligoester-polyols obtained in pilot plant and PUR foams prepared using the respective oligoester-polyols
Activity 3.5 "Dissemination of scientific and technical results obtained in the 3rd stage" had as objective to elaborate a scientific paper and / or two scientific communications. During this stage one scientific article was published in a Romanian ISI journal, one article was submitted for publication in an international ISI journal and six scientific communications were elaborated and presented in two international events organized in Romania and two scientific conferences organized abroad (Spain and France) - deliverables of the stage. Partners CO, P1 and P2 collaborated for the elaboration of the scientific papers and communications.
Stage IV / 2017: "Elaboration of Laboratory technology for rigid polyurethane foams production and implementation of the laboratory technology on pilot scale"
, of the project PERCIT, Contract 61/2014, involved the achievement of 6 activities, by the four partners, in collaboration.
Activity 4.1 "Completion of experiments planned by the experimental laboratory model for preparation of sprayed polyurethane foam. Characterization of polyurethane foams. Elaboration of laboratory technology for spray polyurethane foams preparation" had as main objectives: obtaining the optimal formulation of foaming system for the production of spray polyurethane foams, the complex characterization of oligoesters and polyurethane foams and the elaboration of laboratory technology for obtaining spray polyurethane foams - P3 and P1 continued the development of the laboratory experimental model for obtaining thermo-insulating polyurethane rigid foams, considering the influence of experimental oligoester-polyols content in the polyol component on the reactivity of the system and the properties of the PUR foams, in order to select the formulation leading to optimal properties. For this purpose the characterization of PUR foams in terms of mechanical properties, thermal conductivity and fire behavior was performed; - CO carried out the structural characterization (NMR) of oligoester-polyols obtained in the presence of organic catalysts; - P2 performed structural characterization of oligo-polyols (FT-IR) and complex characterization of PUR foams (TGA and DMA); The optimal formulation was established in order to elaborate the laboratory technology. A short Research report on the experimental results obtained and the Laboratory technology for the production of rigid polyurethane foams (in order to implement it on pilot scale) - deliverable result of the stage, were elaborated and presented in the Scientific and technical report of the stage.
Activity 4.2 “Demonstration of the functionality and reproducibility of the laboratory technology” was aimed at demonstrating the reproducibility of the experimental data in the selected version.
P3 - performed experiments in order to improve and verify the reproducibility of the technology and carried out the characterization of polyurethane foams in terms of physical-mechanical characteristics, thermal insulation and fire resistance properties), P2 performed the complex characterization of oligoester-polyols and of polyurethane materials (TGA, DMA). The experimental results demonstrated the reproducibility of the technology. A Demonstration Report on the results of the experiments performed to verify the reproducibility of the laboratory technology for the production of polyurethane materials - Deliverable result of the stage - was drawn and presented in the Scientific and technical report of the stage.
Activity 4.3 "Defining the library of modified organic catalysts and / or combinations thereof with synergistic effect, suitable for the selective attack of PET with different cleavage agents" aimed at improving the chemical structures of catalysts previously prepared for the chemical destruction of PET with different cleavage agents, their testing in chemical destruction reactions of polyethylene terephthalate (PET) and the systematization of the scientific information obtained on their synthesis, physico-chemical and structural properties and catalytic activity. - CO carried out experiments in order to finalize the chemical structures of the catalysts obtained and delivered a systematic scientific memoir on the synthesis, the physico-chemical and structural properties and the catalytic activity of the said catalysts and catalytic systems ; - P1 tested the catalytic systems in the synthesis of oligoester-polyols and participated in the systematization of scientific information regarding the organic catalytic systems prepared by CO; A "Library of modified organic catalysts and synergistic combinations for the recycling of PET in the presence of (potential) renewable cleavage/chemical modification agents" – Deliverable result of the stage - was developed and presented in the Scientific and technical report of the stage.
Activity 4.4 "Identification and assignment of intellectual property rights" had as objective the elaboration and submission to The Romanian Patent Office OSIM of a Patent application. A Patent application entitled "Oligoester polyols from polyethylene terephthalate waste and renewable materials, process for their preparation and composition for sprayed polyurethane foams incorporating the respective oligoester-polyols" - Deliverable result of the stage - was prepared and registered under the registration number A 2017-00534/31.07.2017; Applicants: ICECHIM (P1), UPB (P2), EUROPLASTIC (P3), Authors: Duldner Monica Mirela; Capitanu Stanca; Cursaru Bogdan; Sarbu Andrei, Apostol Steluta; -ICECHM (P1); Bartha Emeric, Ion Simona Filofteia; -CCO (CO); Garea Sorina Alexandra; - UPB (P2); Ionescu Marcel - SC EUROPLASTIC (P3).
Activity 4.5 "The pilot-scale implementation of the Laboratory technology for spray polyurethane foam using oligoester-polyols from PET wastes and renewable materials" had as objectives: performing experiments in order to transpose the Laboratory technology on pilot scale and elaborating the Pilot Technology of spray polyurethane foams preparation. P3 and P1 participated in setting the process parameters in pilot plant, verifying the reproducibility of the processes and the characteristics of the products at pilot scale and developing the pilot technology; P2 performed the complex characterization of polyurethane cellular materials;
Pictures from the pilot experimentation
A Pilot plant technology for the production of spray polyurethane foams and the Technical Data Sheet – Deliverable results of the stage - were elaborated and presented in the Scientific and technical report of the stage.
Activity 4.6 “Dissemination of the scientific and technical results obtained during the fourth stage” had as objective the elaboration of one article and / or two scientific communications. During this stage, one article was submitted and accepted for publication in a Romanian ISI rated journal, another article is being evaluated for publication in a Romanian ISI rated journal and 6 communications were prepared and presented within international scientific manifestations – Deliverable resuls of the stage. CO, P1 and P2 partners worked together to develop the scientific papers, which are presented in the Scientific and technical report of the stage.