I tI I ~f J' j ~~~} c fJ Green Chemistry

and Nallotechnologies in Polymer Chemistry

4-6 Septelnber 2013 - Pisa~ Italy

OrgaJ.íl[sed by

Department of Civil and Industrial Engineering,

Univers~ty of Pisa

bzstitllte for Composite and Bio11ledical Materiais, €NR

Natiollallnterzl1liversity Consortillm of M'aleriais Science aná 'Fecll1lology, INSTM

Conslglo Nozlonole dele Rlcerche

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UNIVEIISITA IH PISA

17.00-19.00 19.00-21.00

8.30-13.00 9.00-9.20

09:20 COOl 09:40 C002

10:00 C003

10:20 C004 10:40 C005

11 :30 C006

11 :50 C007

12:10 C008

12:30 C009

12:50 COlO

15 :00 COII 15:20 C012 15:40 COl3 16:00

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4TH WORKSHOP GREEN CHEMISTRY AND NANOTECHNOLOGIES IN POL YMER CHEMISTRY

4-6 September 2013 - Pisa, Italy

OFFICIAL PROGRAM

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Wednesday, 04.09.2013 .. 1', "!.' . " , .

Registration

Welcome Reception

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.. , " -;:" , T<';' .. Tliursday,05!09.2013 , ,

Registration

Welcome and Opening ~e

Session A - Green Ohemistry -" -'- .. ~.,

Matjaz Kunaver Biomass waste - A source of raw materiaIs Mikelis Kirpluks

,

High Density Rigid Polyurethane Foams from Renewable MateriaIs for Automotive Application Claudia Crestini

'"

Ultrasound assisted praduction of biocompatible lignin core-shell micra/nanocapsules for storage and delivery of hydraphobic molecules Aiga Paberza Flammability and thermal properties of rigid polyurethane foams obtained fram oxypropylated lignin Tomás Vlcek Coatings with enhanced praperties and prolonged lifetime

11.00-11.30 Coffee break .. • i. u. ' ~~" ;7'

Aleksandra Gawelczyk Depolymerization of polycarbonate by castor and rapeseed oils Anda Fridribsone Post curing kinetics of VOC-free, 100 % solids, spray-applied polyurethane coatings fram rapeseed oi!

I polyols Hilda Gómez Bernal Com stover valorization to high energy furan liquids by micrawave assisted autohydrolysis Datta J anusz Thermo dynamical and mechanical characterization of polyurethanes synthesized using glycolysates intermediates M. F ilomena Barreiro Chemical modification as a strategy to modula te properties of oxyprapylated products

13.10-14.00 Luneb

14.00-15.00 Poster session.

.. Session B - Nanotecbnologics

Ivan Kelnar Effect of chitin nanofibrilsl plasticizer combination on mechanical behaviour of chitosan-matrix fiIms PierFrancesco Morganti Chitin nanofibrils: a multifunctional biomaterial of marine origin Jana Mikesováa Rbeological praperties of chitosan solutions fi lled with chitin nanofibrils Galina Tishchenko Biodegradable composite films fram chitosan and chitin nanofibrils

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4TH WORKSHOP GREEN CHEMlSTRY AND NANOTECHNOLOGIES IN POL YMER CHEMISTRY

4-6 September 2013 - Pisa, Italy

ORAL

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4TH WORKSHOP GREEN CHEI\1ISTRV AND NANOTECHNOLOGIES IN POLYMER CHEMlSTRY

4-6 SeptcmIJcr 2013 - Pisa, ltaly

CHEMICAL MODIFICATION AS A STRATEGV TO MODULATE PROPERTIES OF OXYPROPVLATEDPRODUCTS

Mariana Barhosa', Marina Matos", M. Filomena Barreiro"·, and Alessandro Gandini""

" Labora/O/y ofSepara/ion and Reae/ion Engineering (LSRE), Associa/e Labora/OIY LSREILCM, Polyleclmie Ins/itu/e of Bragança, Campus Sallla Apolónia Ap. 1134, 5301·857 Bragança, Por/ugal - b CICECO and

Chemis//y Depar/men/, Universi/)' of Aveira, Campus de Sallliago, 3810·193 Aveira, Por/ugal- 'Presemly a/ Ins/itu/o de Química de São Carlos - São Paulo Unive/'siry, Brasil- *00351273303089, 00351273313951,

barl'eiro@ipb.pt

Concept and objectives Nowadays a great interest is devoted to the production and use of biobased products. The main scope of the oxypropylation process is to obtain polyols, in the form of viscous liquids, which can be interesting co­monomers to produce polyurelhanes and polyesters. Due to the high hydroxyl content of natural polymers (suitable substrates to be oxypropylated), the generated polyols are multifunctional, hence most adequate to be used in rigid polyurethane foam formulations. Additionally, their properties can be modulated through chemical modification, thus opening new avenues for their exploitation. Following that strategy, an oxypropylated producl (lOH of350) used as a model polyol, was modified by reacting it with a mixture containing phenyl isocyanate (PI) and toluene diisocyanate (TDI) at PIITDI molar ratios of 100/0, 80120, 50/50, 20/80 and 0/1 00. This chemical system was chosen in order to guarantee a homogeneous medi um during the course of the reaction. Syntheses were perfonned in dichloromethane solution at room temperature under nitrogen, using DBTDL as catalyst, with a reaction time of 6 hours. Kinetics was followed by FTIR in transmittance mode using a liquid cell equipped with NaCI windows. For that purpose, sample aliquots were taken from the reaction medium at time intervals of 10 minutes during the first hour, 30 minutes during the second hour and at one hour intervals until the end of the reaction. Afier the established reaction time of 6 hours, residual isocyanates were neutralized with methanol and the final product purified, dried and characterized by FTlR and DSC.

Results and Discussioo Figure I shows a typical plot of a FTIR experiment. Quantification of the isocyanate group conversion was

_ _ _ _ _ _ _ _ o estimated from the isocyanate absorption band (2270 em-')

JSOO ~ ~oo 2000 ,,., ''''' "'Qte~\lrrt;e!!= ')

Figure I. Typical FTIR plot.

Aknowledgmeots

'" intensity decay. lt was observed that as the PIITDI molar ratio decreased, i.e, as the content of the difunctional : 1 monomer increased, the final isocyanate conversion (time

! = 360 min) decreased and the polymer Tg shifted towards 00 I- higher values, thus cOIToborating ao increase in the ,'" crosslink density. An increase of crosslinking density

introduces restrictions on the molecular motion lowering NCO conversion and increasing the Tg value. In fact lhe produced polyurethanes changed from a highly viscous liquid (PIITDI= 100/0 and 80/20) to stiff solids (PIITDI=50/50, 20/80 and 011 00). In conclusion, the strategy used in this work demonstrates a way to modulate lhe final properties of the oxypropylated products.

To FCT (project PTDC/CTM/7J49 112006JCOM-0 I-OI 24-FEDER-007 156) and LSRE (strategic project PEst­CIEQBILA0020/20 11).

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