Autoritatea contractanta Unitatea Executiva pentru Finantarea Invatamantului Superior

Autoritatea contractanta: Unitatea Executiva pentru Finantarea Invatamantului Superior si a Cercetarii Stiintifice Universitare Cercetari avansate privitoare la comportarea polimerilor sub actiunea factorilor de mediu Program IDEI-Proiect de cercetare exploratorie Contract nr. PN-II-ID-PCE-2011 -3 -0187 Contractor: Institutul de Chimie Macromoleculara "Petru Poni" Iasi Durata proiect: 2011 – 2014

ECHIPA PROIECTULUI Director proiect: Dr. Dan Rosu Institutul de Chimie Macromoleculara "Petru Poni" Iasi Tel. : 0232 -260332 E-mail: drosu@icmpp. ro Membrii echipei de cercetare: ¨ Dr. Liliana Rosu ¨ Dr. Carmen-Alice Teaca ¨ Dr. Ruxanda Bodirlau ¨ Drd. Cristian-Dragos Varganici ¨ Drd. Oana Maria Paduraru ¨ Drd. Manuela Tatiana Nistor ¨ Masterand Elena Marlica

REZUMAT Imbatranirea sistemelor polimere implica diferiti factori: naturali (lumina, caldura, umiditate), structurali si accidentali (impuritati, procese de oxidare produse in timpul fabricatiei), toti acestia fiind capabili sa reduca semnificativ durata de viata a materialelor. Mecanismele degradarii polimerilor sunt foarte complexe. Astfel, ei pot initia reactii de fotoreticulare sau reactii foto-oxidative insotite de descresterea gradului de polimerizare, cresterea polidispersitatii si formarea structurilor chimice capabile sa modifice proprietatile polimerilor. Prezentul proiect vizeaza cresterea nivelului cunostintelor in investigarea efectului factorilor externi asupra stabilitatii sistemelor polimerice multicomponente. Se urmareste sa se creeze un grup de cercetare (format din 4 cercetatori cu experienta si 3 doctoranzi) focalizat pe achizitia de date experimentale si elaborarea de teorii originale pentru a explica pierderea performantelor sistemelor polimerice in timpul expunerii la factori de mediu controlati si prezicerea duratei de viata. Se considera ca rezultatele stiintifice obtinute, vor fi comparabile cu cele deja existente la nivel mondial, si vor contribui la cresterea vizibilitatii internationale a activitatii cercetarii romanesti. Rezultatele preconizate vor contribui la finalizareatezelor de doctorat de catre tinerii doctoranzi inclusi in echipa de cercetare.

OBIECTIVE n n n In prezentul proiect sunt urmarite transformarile suferite de catre polimeri cu diferite structuri sub actiunea principalilor factori agresivi din mediul inconjurator si sub actiunea luminii in special. In realizarea acestui obiectiv general se iau in considerare urmatoarele obiective specifice: imobilizarea pe polimeri naturali si/sau sintetici de coloranti cu diferite structuri si in diferite concentratii realizarea de sisteme polimere multicomponente continand polizaharide obtinere de retele polimerice interpenetrate pe baza de colagen sau poli(acid aspartic) studiul actiunii factorilor de mediu (lumina, caldura, umiditate asupra polimerilor colorati) studiul stabilitatii sistemelor multicomponente la actiunea factorilor de mediu

Directii de cercetare Obiectivele prezentate se vor orienta spre urmatoarele directii: Cunoasterea implicarii unor coloranti reactivi imobilizati pe polimeri si determinarea efectelor biologice in corelatie cu proprietatile fizico-chimice ¨ Caracterizarea si evaluarea stabilitatii la conditiile de mediu a sistemelor polimere multicomponente continand polizaharide ¨ Studiul polimerilor naturali sub actiunea radiatiilor UV ¨

BUGETUL PROIECTULUI Etapa 2011: 120. 000 lei Etapa 2012: 500. 000 lei Etapa 2013: 203. 171 lei Etapa 2014: 596. 829 lei Buget total: 1. 420. 000 lei

Etapele proiectului Etapa 2011 Obiective: n Analiza comparativa a stadiului actual privind comportarea polimerilor sub actiunea factorilor de mediu n Documentare in domeniul tehnicilor si metodelor instrumentale moderne

Rezultate 2011 Pe baza rezultatelor obtinute in cadrul etapei 2011, urmatoarele lucrari au fost prezentate la manifestari stiintifice: 1. R. Bodirlau, C. -A. Teaca, D. Rosu, L. Rosu; Photo-degradation behaviour of wood after coating with epoxidized soybean oil; Zilele Universitatii „Al. I. Cuza”, Iasi, 28 -29 oct. 2011 2. O. M. Paduraru, N. Tudorachi, A. Chiriac; Thermal analysis of new hydrogels based on natural and synthetic polymers; Zilele Universitatii „Al. I. Cuza”, Iasi, 28 -29 oct. 2011 3. L. Rosu, D. Rosu, C. -D. Varganici; The thermal behaviour of some semiinterpenetrated polymer networks based on epoxy resin and aromatic polyurethane; Zilele Universitatii „Al. I. Cuza”, Iasi, 28 -29 oct. 2011 4. D. Rosu, L. Rosu, F. Mustata; Effect of UV radiation on some semiintepenetrated polymer networks based on epoxy-resin and polyurethane; Zilele Universitatii „Al. I. Cuza”, Iasi, 28 -29 oct. 2011

Etapa 2012 Obiective: n Obtinerea de sisteme polimerice multicomponente n Caracterizarea sistemelor polimerice sintetizate si stabilirea relatiilor structuraproprietati

Lucrari stiintifice: 3 1. 2. 3. D. Rosu, L. Rosu, F. Mustata, C. -D. Varganici; Effect of UV radiation on some semi-interpenetrating polymer networks based on polyurethane and epoxy resin; Polym. Degrad. Stab. 97 1261– 1269 (2012) C. -D. Varganici, A. Durdureanu-Angheluta, D. Rosu, M. Pinteala, B. C. Simionescu; Thermal degradation of magnetite nanoparticles with hyrdrophilic shell; J. Anal. Appl. Pyrol. 96, 63– 68 (2012) O. M. Paduraru, D. Ciolacu, R. N. Darie, C. Vasile; Synthesis and characterization of polyvinyl alcohol/cellulose cryogels and their testing as carriers for a bioactive component; Materials Science and Engineering C. 32, 2508– 2515 (2012)

Lucrari publicate in extenso in volume (10) si prezentate la manifestari stiintifice (comunicari: 11 si postere: 16) COFr. Ro. CA – 2012, Septième Colloque Franco-Roumain de Chimie Appliquée, 27 – 29 Juin 2012, Bacau, Roumanie: 1. D. Rosu, L. Rosu, C. -D. Varganici; Le comportement photochimique et thermique des systèmes polymérique multicomposant; Proceedings Colloque ISSN: 2068 -6382, pg. 123 -124 (COMUNICARE) 2. C. -D. Varganici, O. Ursache, C. Gaina, V. Gaina, B. C. Simionescu; Nouveau matériaux hybride autorenouvelable thermique. Etudes thermiques; Proceedings Colloque ISSN: 20686382, pg. 129 -130 (COMUNICARE) 3. L. Rosu, C. C. Gavat, D. Rosu; Decoloration degradation des textiles colores en presence des rayonnement ultraviolets; Proceedings Colloque ISSN: 2068 -6382, pg. 149 -150 (POSTER) 4. C. -A. Teaca, R. Bodirlau, L. osu, D. Rosu; FTIR analyse thermiques des bois resineux apres modification et traitment avec l’huile de soja epoxydee; Proceedings Colloque ISSN: 20686382, pg. 153 -154 (POSTER) 5. M. T. Nistor, L. E. Nita, A. P. Chiriac, C. vasile, R. Darie; Conception des structures polymeres sensibles avec proprietes controlees. L’influence de l’agent de reticulation; Proceedings Colloque ISSN: 2068 -6382, pg. 145 -146 (POSTER si premiu pentru cel mai bun poster)

Lucrari publicate in extenso in volume (10) si prezentate la manifestari stiintifice (comunicari: 11 si postere: 16) 7 th Mo. De. St Conference, 2 - 6 Sept. , 2012, Prague, Czech Republic, Abstract book, published by the Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Prague 6 – Břevnov, Czech Republic 6. D. Rosu, C. -D. Varganici, L. Rosu; Thermal decomposition study of some polymeric multicomponent systems based on aromatic polyurethane and epoxy resin network; ISBN 978 -80 -85009 -74 -3, pg. 222 -223 (COMUNICARE) 7. L. Rosu, F. Mustata, D. Rosu, C. -D. Varganici; Semi-interpenetrating polymer networks polyurethane-epoxy resin. Study of photochemical stability; ISBN 978 -80 -85009 -74 -3, pg. 278 -279 (POSTER) 8. C. -D. Varganici, A. Durdureanu-Angheluta, D. Rosu, M. Pinteala, B. C. Simionescu, Thermal stability of core-shell hydrophilic nanoparticles for biomedicine; ISBN 978 -80 -85009 -74 -3, pg. 290 -291 (POSTER) 9. R. Bodirlau, C. -A. Teaca; Obtainment and characterization of organic acid modified starch/plasticized corn starch composite films; ISBN 978 -80 -85009 -74 -3, pg. 369 -370 (POSTER) 10. C. -A. Teaca, R. Bodirlau, D. Rosu; Characterization of irradiated wood after chemical modification with organic anhydride and coating with epoxidized vegetable oil; ISBN 978 -8085009 -74 -3, pg. 374 -375 (POSTER)

Lucrari publicate in extenso in volume (10) si prezentate la manifestari stiintifice (comunicari: 11 si postere: 16) 21 st Symposium on Thermal Analysis and Calorimetry, 17 Feb. 2012, Bucuresti, Romania 11. C. -D. Varganici, O. Ursache, C. Gaina, V. Gaina, B. C. Simionescu; DSC studies on thermoreversible and non-thermoreversible hybrid materials (COMUNICARE) 12. S. Patachia, M. T. Nistor, C. Vasile; Thermal behavior of wood treated with ionic liquid (COMUNICARE) Fifth Cristofor I. Simionescu Symposium “Frontiers in Macromolecular and Supramolecular Science”, 11 – 13 Iunie 2012, Bucuresti, Romania 13. C. -D. Varganici, A. Durdureanu-Angheluta, F. Doroftei, D. Rosu, M. Pinteala, B. C. Simionescu; Core-shell magnetic nanoparticles based on silane compounds and magnetite: Thermal behavior (COMUNICARE) 2 eme Colloque Franco-Roumain de Chimie Medicinale, Co. Fr. Ro. CM 2012, Iasi, Romania, Oct. 3 -5, 2012 14. O. M. Paduraru, A. Bosinceanu, G. Tantaru, C. Vasile; Effect of cyclodextrin on the solubility of an anti-arrhythmic drug (POSTER) Zilele Universitatii "Alexandru Ioan Cuza" Conferinta Facultatii de Chimie, 25 -27 Oct. 2012, Iasi, Romania 15. M. -T. Nistor, C. Vasile; Influence of nanoparticles on thermal decomposition of hybrid nanocomposites based on starch/poly(vinyl alcohol) montmorillonite (COMUNICARE)

Lucrari publicate in extenso in volume (10) si prezentate la manifestari stiintifice (comunicari: 11 si postere: 16) A XXXII-a Conferinta Nationala de Chimie, Calimanesti-Caciulata, Valcea, Romania, 03 -05 octombrie 2012 16. C. -D. Varganici, D. Rosu, L. Rosu; The effect of temperature on thermal stability of some semi-interpenetrated polymer networks based on epoxy resin and aromatic polyurethane (COMUNICARE) 17. D. Rosu, L. Rosu, C. -D. Varganici; Photooxidation behavior of some polyurethane based semi-interpenetrated polymer networks (POSTER) 18. C. -A. Teaca, R. Bodirlau, L. Rosu, D. Rosu, C. -D. Varganici; Wood treatment with organic anhydride and epoxidized vegetable oil – thermal properties investigation (POSTER) 19. L. Rosu, D. Rosu, C. C. Gavat; Effect of radiation UV on textile dyeing (POSTER) 20. F. Mustaţa, I. Bicu, L. Rosu; Formaldehyde resins from hydroxyl esters of resin acids (POSTER) 21. F. Mustata, I. Bicu, D. Rosu; Thermoseting resins obtained via sequential photo and thermal crosslinking of epoxy resins. Curing kinetics, thermal properties and morphology (POSTER)

Lucrari publicate in extenso in volume (10) si prezentate la manifestari stiintifice (comunicari: 11 si postere: 16) Seminar analiza termica: Caracterizarea materialelor cu ajutorul tehnicilor de analiza termica, Iasi, Romania, 24 mai 2012 22. O. M. Paduraru, N. Tudorachi, A. Chiriac; Thermal degradation of carboxymethyl starch-gpoly(lactic acid) copolymer by TG-FTIR-MS analysis (COMUNICARE) 23. C. -D. Varganici, L. Rosu, M. Pinteala, D. Rosu, B. C. Simionescu; Thermal analysis application to some polymeric material micro- and nanoparticles (COMUNICARE) 15 th International Conference Polymeric Materials, Halle, Germany, Sept. 12 -14, 2012 24. O. M. Paduraru, D. Ciolacu, C. Vasile; Polyvinylalcohol/cellulose hydrogels as carriers for a bioactive component (COMUNICARE) 25. O. M. Paduraru, G. Tantaru, C. Vasile; Water soluble complex of hydroxypropyl-βcyclodextrin and aminodarone (POSTER) 4 th Bilateral Symposium on Functional Heterocyclic and Heterochain Polymers for Advanced Materials, Iasi, Romania, Sept. 2 -7, 2012 26. O. M. Paduraru, C. Vasile, D. Ciolacu, R. N. Darie; Evaluation of polyvinylalcohol /cellulose hydrogels as carriers for drug delivery (POSTER)

Etapa 2013 Obiective: n Influenta factorilor de mediu asupra sistemelor polimerice multicomponente n Cinetica reactiilor de degradare termica n Modificarea proprietatilor in timpul degradarii fotochimice a sistemelor polimere multicomponente

Lucrari stiintifice: 12 n n n D. Rosu, L. Rosu, C. -D. Varganici; The thermal stability of some semi-interpenetrated polymer networks based on epoxy resin and aromatic polyurethane; J. Anal. Appl. Pyrol. 100, 103 -110 (2013) C. -D. Varganici. O. Ursache, C. Gaina, V. Gaina, B. C. Simionescu; Studies on new hybrid materials prepared by both Diels-Alder and Michael addition reactions; J Therm Anal Calorim. 111 (2), 1561 -1570 (2013) C. -A. Teaca, D. Rosu, R. Bodirlau, L. Rosu; Structural changes in wood under artificial UV light irradiation determined by FTIR spectroscopy and color measurements – A brief review; Bio. Resources, 8(1), 1478 -1507 (2013) S. F. Patachia, M. -T. Nistor, C. Vasile; Thermal behavior of some wood species treated with ionic liquid; Ind. Crops and Prod. , 44, 511 -519 (2013) M. -T. Nistor, C. Vasile; TG/FT-IR/MS study on the influence of nanoparticles content on thermal decomposition of the starch/poly(vinyl alcohol) montmorillonite nanocomposites; Iranian Polym. J. , 22 (7), 519 -536 (2013) C. -D. Varganici, L. Rosu, D. Rosu, B. C. Simionescu, Miscibility studies of some semi-interpenetrating polymer networks based on an aromatic polyurethane and epoxy resin, Composites Part B: Eng. , 50, 273 -278 (2013) O. M. Paduraru, A. Bosinceanu, G. Tantaru, C. Vasile, Effect of Hydroxypropyl; -Cyclodextrinon the Solubility of an Antiarrhythmic Agent, Ind. & Eng. Chem. Res. , 52, 2174 -2181 (2013) C. -D. Varganici, O. Ursache, C. Gaina, V. Gaina, D. Rosu, B. C. Simionescu, Synthesis and characterization of a new thermoreversible polyurethane network, Ind, Eng. Chem. Res. , 52(15) 5287 -5295 (2013) R. Bodirlau, C. -A. Teaca, D. Rosu, L. Rosu, C. -D. Varganici, A. Coroaba, Physico-chemical properties investigation of softwood surface after treatment with organic anhydride”, Appl. Surf. Sci, 2013, submitted M. T. Nistor, A. Chiriac, L. Nita, I. Neamtu, C. Vasile, Semi-interpenetrated network with improved sensitivity based on poly(N-isopropylacrylamide) and poly(aspartic acid), Polym. Eng. Sci. , 2013, submitted, DOI: 10. 1002/pen. 23488. O. Ursache, C. Gaina, V. Gaina, C. -D. Varganici, D. Timpu; New hybrid materials obtained by Diels-Alder and Michael addition reactions. A comparative study; Polym. Bull. , 2013, submitted M. T. Nistor, C. Vasile, A. P. Chiriac, Hybrid collagen-based hydrogels with embedded montmorillonite nanoparticles, Applied Clay Science, 2013, submitted

Lucrari prezentate la manifestari stiintifice: 6 (comunicari: 1 si postere: 5) European Polymer Congress – EPF 2013, Pisa, Italy, June 16 -21, 2013 1. L. Rosu, C. -D. Varganici, D. Rosu, Semi-interpenetrating polymer networks based on an aromatic polyurethane and epoxy resin. Surface properties modifications (POSTER) 2. D. Rosu, C. -C. Gavat, L. Rosu, C. -D. Varganici, Cellulose fabrics painted with some reactive azotriazine dyes. Photochemical behaviour (POSTER) 3. C. -D. Varganici, L. Rosu, D. Rosu, B. C. Simionescu, Semi-interpenetrating polymer networks based on an aromatic polyurethane and epoxy resin. Miscibility studies (COMUNICARE) 4. F. Mustata, I. Bicu, Dan Rosu, C. -D. Varganici, Epoxy monomers based on methyl ester of corn oil (POSTER) 5. R. Bodirlau, C. -A. Teaca, D. Rosu, Organic anhydride treatment of softwood to improve its weathering protection (POSTER) 6. C. -A. Teaca, R. Bodirlau, I. Spiridon, N. Tudorachi, Multi-component polymer systems comprising modified starch microparticles and different natural fillers (POSTER)