PERCIT

Cellular materials with thermal insulation and fire resistance properties, via energetic efficient
recycling process of PET wastes, for minimizing heat loss in civil and industrial buildings (PERCIT)
UEFISCDI, PNII-PT-PCCA-2013-4-1388, no 61/2014

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.
Thus:
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.
Thus:
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: 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:
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.
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:
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.
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:
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:
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:

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.