INTERNATIONAL SYMPOSIUM ON POLYMERS FROM RENEWABLE …polychem15.boun.edu.tr/POLYCHEM-2015-Abstract-Book.pdf · INTERNATIONAL SYMPOSIUM ON POLYMERS FROM RENEWABLE RESOURCES . May

INTERNATIONAL SYMPOSIUM ON

POLYMERS FROM RENEWABLE RESOURCES

May 8, 2015

Istanbul

POLYCHEM2015

http://polychem15.boun.edu.tr/





This document is printed by Boğaziçi University, Istanbul

2015

POLYCHEM2015 Özet Kitabı Boğaziçi Üniversitesi Matbaası tarafından basılmıştır.

This symposium is dedicated to Prof. Selim Küsefoğlu

on the occasion of his 40 years in science.

POLYCHEM2015 Organizasyon Komitesi olarak katkılarından dolayı Boğaziçi Üniversitesi Rektörlüğü’ne teşekkür ediyoruz.

Symposium Program May 8, 2015

PROGRAM

9:00-9:30 Registration

9:30-10:00 Prof. Hadi Özbal – Opening Remarks

10:00-10:45 Prof. Lon J. Mathias (IL-1)

10:45-11:00 Coffee Break

11:00-11:45 Prof. Duygu Avcı Semiz (IL-2)

11:45-14:00 Poster Session & Lunch

14:00-14:45 Prof. Jürgen O. Metzger (IL-3)

14:45-15:30 Prof. Yusuf Yağcı (IL-4)

15:30-16:00 Coffee Break

16:00 Prof. Selim Küsefoğlu – Closing Remarks

POLYCHEM2015-International Symposium on Polymers from Renewable Resources 1


INVITED LECTURES

Invited Lectures May 8, 2015

IL-1

Adventures in Hydroxymethylacrylate Chemistry

Lon J. Mathias Department of Polymer Science, University of Southern Mississippi, Hattiesburg, MS 39406-0076

USA

E-mail: [email protected]

Hydroxymethylacrylate and its various esters, derivatives and heteroatom-linked dimers, offer a wealth of properties controlling polymerization and final behaviour. While long known as a natural product, it wasn’t until work in the US and Japan resulted in inexpensive syntheses of the various acrylate ester derivatives that this family of monomers became economically viable. Even the surprising contact dermatitis displayed by the methyl ester could be overcome by use of novel catalysts and conditions. Despite clean, high yield reaction of acrylates with acetaldehyde to give the corresponding ethacrylate derivative (which does not polymerize free radically), use of formaldehyde often results in a mixture of products. Early work in our lab by Professor Kusefoglu (many years ago) led to separation and identification of many products including formal-linked dimers and oligomers and the newly discovered ether dimer. Collaborations with Professor Kusefoglu and his students, and with Professor Duygu Avci Semiz and her students have resulted in dozens of publications based on new derivatives and their properties. Turkish collaborations continued with Professor Ersin Acar and others which extended this work into new areas such as living free radical polymerization to give controlled properties. This talk will provide a brief history of the syntheses and properties of the basic family of ester derivatives of hydroxymethylacrylate. This will be followed by examples of novel mono-, di- and multi-functional derivatives that allow tailoring of virtually any physical or chemical property of the monomers and their polymers. The talk will briefly touch on recent industrial work involving commercialization of a thermally crosslinked and optically clear derivative that displays useful properties in transparent coatings, containers and windows. Finally, new monomer structures are proposed for synthesis and examination that will further extend structure-property behaviour of this valuable family of acrylate/methacrylate based materials.




IL-2

New Adhesives for Longer-lasting Dental Fillings

Duygu Avcı Bogazici University, Chemistry Department, 34342 Istanbul, Turkey


Self-etch adhesives (SEAs) are used in restorative dentistry in order to achieve a strong bond between the dental hard tissues and the restorative material. SEAs are water-based and have several components: an acidic adhesive (AA) monomer, crosslinking monomers, a monofunctional comonomer, an initiator and fillers. These AA monomers usually have dihydrogen phosphates, carboxylic or phophonic acid groups, and it is desired that they have the following properties: (i) ability to partially demineralize the tooth tissues, (ii) ability to form strong bonds with tooth tissue, in particular, hydroxyapatite (HAP), (iii) high rate of homopolymerizability or copolymerizability with the other monomers in the adhesive, (iv) sufficient stability both in storage and in the mouth. The demineralization requirement is satisfied by the acidic nature of the AA monomer. The required strong interaction can occur by a variety of bonding mechanisms, and small differences in the monomer structures can cause significant differences in their adhesive performances, so it is important to understand the effect of structure, sometimes parametrized by variables such as polarity, as much as possible. The third requirement is addressed by using the highly reactive (meth)acrylate- and (meth)acrylamide-based acidic monomers. The main problem limiting the stability is the hydrolysis of the ester groups in (meth)acrylates forming the basis of these monomers; in adhesive mixtures necessarily containing water, or in the aqueous mouth environment; resulting in both inadequate shelf life of adhesives and undesirably short useful lifetime of the dental material. One avenue of addressing this problem, also pursued by us, is using monomers with amide linkages instead of ester bonds. We report on our efforts on the synthesis of new acidic monomers (Figure 1) designed to meet the requirements mentioned above, with the ultimate goal of improving the performance of self-etching adhesives.

NH

O

POH

OOH

NH

O

POH

OOH

NH

O

POH

OOH

NH

O

POH

OOH

NH

O

POH

OOH

C6H13

NH

O

POH

OOH N

H

O

POH

OOH

P OOH

HO

C6H13

Figure 1. Structures of the (bis)phosphonic acid monomers POLYCHEM2015-International Symposium on Polymers from Renewable Resources 6



IL-3

Oils and Fats as Renewable Feedstock for Chemistry

Jürgen O. Metzger University of Oldenburg, Oldenburg, Germany, and abiosus e.V., Oldenburg,

Germany

E mail: [email protected]

Oils and fats of vegetable and animal origin have been the most important renewable feedstock of the chemical industry, and it can be expected that their importance will steadily increase in the future. The fatty acids of bulk oils used in current oleochemistry are rather uniform. Saturated fatty acids with an even number of carbon atoms (C8 – C18) and unsaturated C18-fatty acids such as oleic acid, linoleic acid, and in addition relatively small amounts of linolenic acid and ricinoleic acid, an enantiomerically pure fatty acid, are industrially utilized. Since the eighties of the last century modern organic chemistry has been applied to oils and fats to obtain new oleochemicals with interesting properties.1 Moreover, fatty acids from special plant oils as e.g. petroselinic acid from Coriandrum sativum, calendic acid from Calendula officinalis, α-eleostearic acid from tung (chinese wood) oil, santalbic acid from the seed oil of the sandalwood tree, and vernolic acid from Vernonia galamensis offer fascinating opportunities for organic synthesis.2

References

1. U. Biermann, W. Friedt, S. Lang, W. Lühs, G. Machmüller, J.O. Metzger, M. Rüschgen. Klaas,

H.J. Schäfer, M.P. Schneider, Angewandte Chemie, 2000, 112, 2292-2310; Angewandte Chemie International Edition, 2000, 39, 2206-2224; J. O. Metzger, U. Bornscheuer, Applied Microbiology Biotechnology, 2006, 71, 13-22; M.A.R. Meier, J.O. Metzger, U.S. Schubert, Chemical Society Reviews, 2007, 36, 1788-1802; U. Biermann, U. Bornscheuer, M.A.R. Meier, J.O. Metzger, H.J. Schäfer, Angewandte Chemie, 2011, 123, 3938 – 3956; Angewandte Chemie International Edition, 2011, 50, 3854-387.

2. J.O. Metzger, European Journal of Lipid Science and Technology, 2009, 111, 865-876. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 7



IL-4

New Approaches for Macromolecular Synthesis by Photochemical Methods

Yusuf Yagci Department of Chemistry, Istanbul Technical University, 34469, Maslak, Istanbul, Turkey


Light is a widely available, non-invasive, and environmentally benign reagent that provides opportunities in many applications. In macromolecular chemistry, light induced reactions have been the basis of the polymerization processes which find application in coatings, adhesives, inks, printing plates, optical waveguides, and microelectronics.1 In this presentation, recent studies conducted in author’s laboratory on light induced polymerization processes involving free radical, cationic2 and step-growth modes will be described.1 Particular emphasize will be devoted to the visible light initiating systems using meso and micro porous materials, and semiconducting nanoparticles will be addressed.3 Besides conventional polymerizations, the photochemical methods also facilitate preparation of more complex structures such as block and graft copolymers, and hyper branched polymers.4 Finally, the two new methods developed in the author’s laboratory, namely photoinduced Atom Transfer Radical Polymerization5 and Click Chemistry will be presented.6-8

References

1. Y. Yagci, S. Jockusch, N.J. Turro, Macromolecules, 2010, 43, 6245-6260. 2. S. Erdur, G. Yilmaz, D.G. Colak, I. Cianga, Y. Yagci, Macromolecules, 2014, 47, 7296-7302. 3. S. Dadashi-Silab, M.A. Tasdelen, B. Kiskan, X. Wang, M. Antonietti, Y. Yagci,

Macromolecular Chemistry and Physics, 2014, 215, 675-681. 4. S. Bektas, M. Ciftci, Y. Yagci, Macromolecules, 2013, 46, 6751-6757. 5. S. Dadashi-Silab, M.A. Tasdelen, Y. Yagci, Journal of Polymer Science: Polymer Chemistry,

2014, 52, 2878-2888. 6. M.A. Tasdelen, Y. Yagci, Angewandte Chemie International Edition, 2013, 52, 5930-5938. 7. M.A. Tasdelen, G. Yilmaz, B. Iskin, Y. Yagci, Macromolecules, 2012, 45, 56-61. 8. G. Yilmaz, B. Iskin, Y. Yagci, Macromolecular Chemistry and Physics, 2014, 215, 662-668.



POSTER PRESENTATIONS (alphabetical order according to the last name)

Poster Presentations May 8, 2015

LIST OF POSTER PRESENTATIONS

PP-1: Investigation of Adsorption Isotherms of Basic Blue 3 onto New

Polymeric Sorbent - Gizem Akdut

PP-2: Adsorption of Basic Yellow 28 onto Ternary Polymer Nanocomposite

- Gizem Akdut

PP-3: Cyclodextrin Mediated Polymer Coupling via Thiol-maleimide

Conjugation: Facile Access to Functionalizable Hydrogels - Mehmet

Arslan

PP-4: Synthesis and Characterization of Cyclodextrin Modified

Montmorillonite Clay - Mustafa Arslan

PP-5: Synthesis and Characterization of Polymers of Aromatic Aldehydes

with 4-Aminoquinaldine via Oxidative Polycondensation - Feyza

Atadinç Kolcu

PP-6: Polyacrylonitrile/Hexagonal Boron Nitride Nanocomposite Polymer

Electrolytes for Lithium Ion Battery Application - Hamide Aydın

PP-7: Nanocomposite, PVA-graft-PEGME/TiO2, Polymer Electrolytes for

Rechargeable Lithium Batteries- Hamide Aydın

PP-8: Polymerization Reactions of Epoxidized Soybean Oil and Maleate

Esters of Oil-Soluble Resoles - Jesmi Çavuşoğlu

PP-9: Molecularly Imprinted Polymers for the Recognition of Bioactive Plant

Extracts - Pınar Çakır

PP-10: Polymerization of Epoxidized Soybean Oil (ESO) with Tri Salicyl

Borate - Gökhan Çaylı

PP-11: Synthesis of Block Copolymers Based on Polyethylene by Thermally

Induced Controlled Radical Polymerization Using Mn2(CO)10 -

Mustafa Çiftçi

PP-12: Copper(II)-thioxanthone: A Photoswitchable Catalyst for the

Copper(I)-catalyzed Azide-alkyne Cycloaddition - Sajjad Dadashi-

Silab




PP-13: Antimicrobial Properties of Phoshonium Based ROMP Polymers -

Ceren Demir

PP-14: Characterization and Cu (II) Ion-Binding Properties of Porous

Hydrogels Synthesized from Different Types of Jeffamine Molecules -

Ahmet Erdem

PP-15: Utilization of Renewable and Lichen Based Filler Material with LDPE

- Hüseyin Esen

PP-16: Drug Release of Newly Synthesized Copolymer Derived from

Salicylic Acid and Acrylate - Parisa Golshaei

PP-17: A Stimuli-Responsive Hybrid Sol-Gel Molecularly Imprinted Polymer

as a Potential Delivery System for Controlled Release - Orhan Güney

PP-18: ROMP Based Boron Nitride Composites - Keziban Hüner

PP-19: Polymers in Organic Photo-Electronics - Sıddık İçli

PP-20: UV and Thermal Curable, Bromo-methacryl Functionalized

Methyloleate - Gizem Kahraman

PP-21: Synthesis and Characterization of Ion-imprinted Sol-gel Derived

Fluorescent Polymer for Selective Determination of Mercury(II) Ion -

Fehmi Karagöz

PP-22: Dispersion and Characterization of Copper Nanoparticles into

Chitosan/ Silica Matrix - Selcan Karakuş

PP-23: Synthesis and Characterization of Novel Vinyl Ester Resins Based on

Cardanol - Emre Kınacı

PP-24: Synthesis and Characterization of Epoxidized Soybean Oil /

Diisocyanate Based Thermoset Polymers - Gizem Kırevliyası

PP-25: Thioxanthone Modified Poly(Vinyl Alcohol) as a Macro-initiator for

Photoinduced Radical Polymerization - Senem Körk

PP-26: Novel Difunctional Monomeric and Polymeric Photoinitiators with

Both Type I and Type II Side Chains - Fulya Köylü


http://www.sciencedirect.com/science/article/pii/S0268005X14004688




PP-27: Effect of Catalysts on the Stereoregularity of Acrylamide Derivatives:

a Computational Approach - Berkehan Kura

PP-28: Sustainable, Efficient Approaches to Renewable Platform Chemicals

and Polymers - Hatice Mutlu

PP-29: Synthesis and Characterization of Side Chain Primary Amine

Functionalized Polysulfones - Serhat Oran

PP-30: Modeling Non-covalent Interactions in Polymers - Alimet S. Özen

PP-31: Synthesis and Characterization of Poly(MA-alt-NVP) Copolymers and

Conjugation with Fluorouracil (5-FU) - Shahed Parvizi Khosroshahi

PP-32: Investigation of Proton Conductivity of Poly(vinyl phosphonic acid) /

Hexagonal Boron Nitride Based Composite Membranes - Deniz

Sinirlioğlu

PP-33: Preparation of Biopolymer/Fe-Silica Bio-nanocomposite via Sol-gel

Method - Ezgi Tan

PP-34: Polymer/POSS Nanocomposites by Photochemical Routes - Mehmet

Atilla Taşdelen

PP-35: Click Reaction of Azide-Alkyne Cycloaddition using Solid Supported

Microporous Heterogeneous Copper (I)-Catalyst - Omer S. Taskin

PP-36: Synthesis, Characterization and Antibacterial Activity of a Novel Bio-

nanocomposite: CMC-Chitosan/Fe-Sepiolite - Öykü Ürk

PP-37: Visible Light-induced Copper(I)-catalyzed Azide-alkyne

Cycloaddition with Zinc Oxide Semiconductor Nanoparticles - Özde

Yetişkin

PP-38: Novel Poly(arylene ether sulphone) Based Polymer Electrolyte

Membranes for Direct Methanol Fuel Cell (DMFC) Applications - Esra

Yılmaz Sincan




PP-1

Investigation of Adsorption Isotherms of Basic Blue 3 onto New Polymeric Sorbent

Erdem Yavuz2, Gizem Akdut1, Fatih Bildik2, Filiz Şenkal2, Tuba Şişmanoğlu1

1Istanbul University, Engineering Faculty, Department of Chemistry, Avcılar, İstanbul, Turkey 2Istanbul Technical University , Faculty of Science, Department of Chemistry, Maslak, Istanbul,

Turkey


Among the different pollutants of aquatic ecosystem, dyes are a large and important group of chemicals.1 Dyes are widely used in the industry, such as textile, leather, plastics and paper one, to color the final products.2 These dyes include different compounds with unknown environmental behavior. Many dyes are toxic and some of them, such as those based on benzidine or arylamine are well known for their carcinogenicity. Dye producers and users are interested in dye stability therefore dyestuffs always more difficult to degrade after use are being produced. Since many synthetic dye compounds are harmful to human beings, it is important to encourage industries to implement the color removal from wastewater before to discharge it. Among several chemical and physical methods, the adsorption process, either on activated carbon, fly ash or chitin, is one of the most effective method to remove dyes from wastewater. Basic Blue 3 is cationic dye. It is commercial product and used without purification.3 In this study, polystyrene resin with cross-linked chlorosulphonated (CSPS) has been modified with aminosulfonic acid (ASA), as seen in Sheme1. The new polymeric sorbent (NPS) has been used to adsorption of basic blue 3 (BB3). The adsorption of BB3 on new polymeric sorbent has been investigated at 25oC aqueous solutions. The uptake of basic blue 3 from aqueous solutions has been determined by UV-vis spectroscopy. For different concentrations of basic blue 3, Freundlich, Langmuir, Temkin, Dubinin-Radushkevich (D-R), and Flory-Huggins Isotherm (F-H) isotherms have been applied.

P SO

O

Cl + P S

O

NH-CH2-SO3HO

H2N-CH2-SO3H

CSPS ASA NPS

Scheme1. Polymeric sorbent molecules structures References 1. F.K. Bangash, A. Manaf, Journal of Chemical Society Pakistan, 2004, 26, 111-115. 2. L. Pietrellia, I. Francolinib, A. Piozzib, Separation Science and Technology, DOI:

10.1080/01496395.2014.964632, 2014. 3. G. Crini, F. Gimbert, C. Robert, B. Martel, O. Adam, N. Morin-Crini, F. De Giorgi, P.M. Badot,

Journal of Hazardous Materials, 2008, 153, 96–106. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 15

mailto:[email protected]



PP-2

Adsorption of Basic Yellow 28 onto Ternary Polymer Nanocomposite

Selcan Karakuş1, Gizem Akdut1, Sedef Şişmanoğlu2, Öykü Ürk1, Tuba Şişmanoğlu1, Ayben Kilislioğlu1

1Istanbul University, Engineering Faculty, Department of Chemistry, Avcılar, İstanbul, Turkey 2Karabuk University, Engineering Faculty, Metallurgical and Materials Engineering,

Karabuk,Turkey


Water pollution is one of the environment problems which will cause severe impact to living organisms. Some of these dyes are toxic and carcinogenic, therefore the necessity of dye wastewater undergo pretreatment prior of disposal is important. Nanocomposites consist with nano-size distribution of multiple materials. Especially, several binary studies of polymer-clay have been made for nanomaterial. Using crosslinkers, the polymer/clay or polymer/polymer mixtures are obtained nanomaterials.1 Both Gum Arabic and Alginate are content polysaccharides and glycoproteins groups. Polysaccharides and glycoproteins have alcohol and carboxyl groups. When extra carboxyl groups formed by matching these groups, the cationic dyes having cationic groups are easily adsorbed. So, Gum/PVA/Alginate was preferred for adsorption of Basic Yellow 28 (BY28).

Basic Yellow 28 (BY28)

In this study, the adsorption of BY28 from aqueous solutions has been determined by UV-vis spectroscopy. The adsorption isotherms models of BY28 were studied at 25oC for Langmuir, Freundlich and BET. The adsorption kinetic studies of BY28 were investigated at temperature between 25°C and 45°C and different concentrations. Also, the swelling behaviour of the ternary nanocomposite was characterized by gravimetrically for the different pH medium. References 1. K. Bon-Cheol, F. Danielle, S. Diane, K. Dong Wook, A. Heejoon, R. Jo Ann, B. Alexandre, K.

Jayant, A.S. Lynne, Journal of Macromolecular Science Part A: Pure and Applied Chemistry, 2004, 41, 1401-1410.




PP-3

Cyclodextrin Mediated Polymer Coupling via Thiol-maleimide Conjugation: Facile Access to Functionalizable Hydrogels

Mehmet Arslan, Amitav Sanyal, Rana Sanyal Boğaziçi University Department of Chemistry, Istanbul, 34342, Turkey


The excellent biocompatibility, ability of absorbing large amount of water and rubbery state similar to soft body tissues make hydrogels applicable in designing controlled release systems for drug delivery, biomolecular immobilization, contact lens applications and wound healing dressings.1 Many different covalent strategies including “click” methodologies2, Diels-Alder reactions3, and UV- cross-linking4 are widely used to obtain various kinds of hydrogel systems. Besides, demands in industrial and research settings still continue to necessitate hydrogel systems to be prepared with more controlled and well defined architectures. In this study, fabrication of well-defined chemically cross-linked poly(ethylene glycol) (PEG)-based hydrogels using the thiol-maleimide addition reaction is reported. Maleimide containing homobifunctional PEGs with different molecular weights were synthesized and reacted with thiol functionalized β-cyclodextrin-based crosslinker to yield hydrogels with high efficiency under mild conditions. The resulting hydrogels were characterized by their water uptake properties, surface morphologies and rheological behaviors. In order to introduce reactive functional groups into the hydrogels, the stoichiometry of the thiol and maleimide groups was varied to obtain either thiol or maleimide functionalized hydrogels. Efficient functionalization of these reactive hydrogels in a tailored fashion was demonstrated through conjugation of appropriately functionalized fluorescent dye molecules. References 1. A. Jones, D. Vaughan, Journal of Orthopaedic Nursing, 2005, 9, 1-11. 2. H. Altin, I. Kosif, R. Sanyal, Macromolecules, 2010, 43, 3801–3808. 3. H. Tan, J.P. Rubin, K.G. Marra, Macromolecular Rapid Communications, 2011, 32, 905–911. 4. X. Zhu, P. Lu, W. Chen, J. Dong, Polymer, 2010, 51, 3054-3063.




PP-4

Synthesis and Characterization of Cyclodextrin Modified Montmorillonite Clay

Mustafa Arslan1,3,*, Mehmet Atilla Tasdelen2, Yusuf Yagci1 1Department of Chemistry, Istanbul Technical University, Maslak, Istanbul, 34469, Turkey

2Department of Polymer Engineering, Faculty of Engineering, Yalova University, 77100 Yalova,Turkey

3Department of Chemistry, Kirklareli University, Kirklareli, 39000, Turkey


Since integrating at nanoscale, an organic and inorganic structure in one single material is one of the most effective approaches for modern polymer science and it has reached a very high level of sophistication. During the last two decades, the introduction of welldispersed clay layers such as montmorillonite (MMT) into a polymer matrix has been attracted great interest because of their tremendously improved properties such as high dimensional stability, gas barrier performance, flame retardancy, and mechanical strength that cannot be achieved by pure polymer or conventional composites. In the present study, a cyclodextrin modified clay was synthesized and characterized. For this purpose, first the carboxylic acid functionalized clay (MMT–(CH2CH2OH)2–COOH) was prepared by treating the organo-modified clay, Cloisite 30B (MMT–(CH2CH2OH)2) with succinic anhydride in dichloromethane at room temperature. Then, esterification reaction of β-cyclodextrin (CD) with MMT–(CH2CH2OH)2–COOH at 70 ̊ C resulted in the formation of MMT–(CH2CH2OH)2–CD with an intercalated clay structure. The structure and characteristics of the resulting products were confirmed by FT-IR, TGA and XRD analysis.

Figure 1. Modification of MMT-(CH2CH2OH)2 with succinic anhydride and β-cyclodextrin. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 18



PP-5

Synthesis and Characterization of Polymers of Aromatic Aldehydes with 4-Aminoquinaldine via Oxidative Polycondensation

Feyza Atadinç Kolcu1,2, İsmet Kaya2 1Çanakkale Onsekiz Mart University, Lapseki Vocational School, Department of Chemistry and

Chemical Processing Technologies, 17020, Çanakkale, Turkey 2Çanakkale Onsekiz Mart University, Faculty of Sciences and Arts, Department of Chemistry,

Polymer Synthesis and Analysis Lab.17020, Çanakkale, Turkey


The synthesis of polyazomethines is of great international interest because of their useful properties and wide application fields such as electrical conductivity, electrochemical cell, and resisting to high energy.1 In this study, the Schiff base monomers were synthesized from condensation reactions of 4-aminoquinaldine with aromatic aldehydes, such as 4-hydroxybenzaldehyde, salicylaldehyde, and o-vanillin. Then, these monomers were converted to poly(azomethine)s by oxidative condensation (OP) reactions by using NaOCl oxidant in an aqueous alkaline medium at the various temperatures. The structural characterizations of the synthesized polymers were carried out by FT-IR, NMR, and UV-Vis measurements. These polymers were studied with their thermal, optical, electrical end electrochemical properties. Optical properties of polymers were investigated by UV-Vis and fluorescence analyses. The HOMO-LUMO energy levels, electrochemical (E′g) and optical (Eg) band gaps of polymers were calculated from cyclic voltammetry, (CV) and UV-Vis measurements, respectively. Cyclic voltammetry (CV) technique was used to determine the electrochemical oxidation-reduction characteristics of the polymers. Thermal characterizations of compounds were made by TG-DTA and DSC techniques. Morphological properties of polymers were obtained by Atomic Force Microscopy and Scanning Electron Microscopy techniques. Molecular weight distributions of polymers were determined from size exclusion chromatography.

References 1. X.Y. Deng, International Journal of Molecular Sciences, 2011, 12, 1575-1594. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 19



PP-6

Polyacrylonitrile/Hexagonal Boron Nitride Nanocomposite Polymer Electrolytes for Lithium Ion Battery Application

Hamide Aydın*, Mehmet Kaynak, Sevim Ünügür Çelik, Ayhan Bozkurt

Department of Chemistry, Fatih University, 34500 Büyükçekmece, Istanbul, Turkey


Li-ion batteries have important place in the market of small electronic devices due to their advantages such as being compact, lightweight, high average discharge rate (~3.7 V) and performing the highest energy density among all current systems.1 A typical Li-ion battery contains a current collector, positive electrode, negative electrode and separator. The separator is essential in determining battery performance providing the electrical insulation between anode and cathode and allowing ionic conduction during the charge and discharge process.2 There are several factors affecting the performance of the separator in a lithium-ion battery such as permeability, porosity, electrolyte absorption and retention, chemical, mechanical and thermal stability.3 Hexagonal boron nitride (hBN) is structurally similar to graphite and is the most investigated polymorph among other boron nitrides. It naturally contains hexagonal layers and the adjacent layers are held together by van der Waals forces, with an interlayer spacing of ∼0.33 nm.4 Herein, we have prepared polyacrylonitrile/hBN/CF3SO3Li and LiBF4 composite electrolytes for lithium ion battery applications. The materials were characterized by using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC). The materials are thermally stable up to 250 oC. The ionic conductivity of these novel polymer electrolytes were studied by dielectric-impedance spectroscopy. Li-ion conductivity of these polymer electrolytes depends on the length of Li-salt content as well as the hBN content. The important result of the study is hBN does not block the ionic conduction but enhances it a little. The nanocomposite polymer electrolytes illustrated a satisfactory ionic conductivity of 10−3 − 10−2 S/cm at 100 oC. References 1. J.K. Park, Principles and Applications of Lithium Secondary Batteries, Wiley, 2012. 2. J. Nunes-Pereira, C.M. Costa, S. Lanceros-Mendez, Journal of Power Sources, 2015, 281, 378-

398. 3. P. Arora, Z. Zhang, Chemical Reviews, 2004, 104, 4419-4462. 4. R.S. Pease, Acta Crystallographica, 1952, 5, 356–361. This work was supported by Scientific and Technological Research Council of Turkey (TÜBİTAK) with project number 112M488. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 20



PP-7

Nanocomposite, PVA-graft-PEGME/TiO2, Polymer Electrolytes for Rechargeable Lithium Batteries

Hamide Aydın1,*, Ayhan Bozkurt2

1BioNanoTechnology R&D Center, Fatih University, 34500 Büyükçekmece-İstanbul, Turkey 2Department of Chemistry, Fatih University, 34500 Büyükçekmece-İstanbul, Turkey


Energy storage has become more important in this century due to world's increasing energy demand and energy supply ratio. Lithium polymer batteries are acquiring an important role as energy storage devices in various important markets, in particular, consumer electronics as well as electric or hybrid cars.1 Nanostructured materials are currently of interest for lithium-ion storage devices because of their high surface area, porosity, etc. Ceramic fillers such as SiO2, Al2O3, TiO2 and ZrO2 have also been incorporated along with the host polymer to obtain composite PEs. They improved the ionic conductivity as well as enhanced the mechanical strength and stability of the materials.2 The present work investigates inorganic-organic nanocomposite polymer electrolytes (NCPEs) for lithium-ion battery applications. Nanoscale TiO2 particles were dispersed into boron comprising poly(vinyl alcohol) (PVA)-g-poly(ethylene glycol) methyl ether (PEGME) host polymer at several percentages. They were doped with lithium salt (CF3SO3Li) at several molar ratios, with respect to EO/Li ratios and homogeneous soft solid materials were obtained. The EO units of the polymer are capable of forming donor:acceptor type bonds by complexing with the lithium ion. These PEs were characterized using FTIR, SEM, TGA, DSC, and dielectric-impedance spectroscopy. FTIR spectroscopy confirmed both the formation of graft copolymer and the existence of complexation between the nano-TiO2 and host polymer matrix. The samples are thermally stable up to 250 °C. DSC results showed that nanocomposite electrolyte showed more crystalline behaviour with increasing PEGME molecular weight. Also the increase in lithium salt contents lead to an amorphous character. The conductivity studies illustrate that the ionic conductivity of these NCPEs was found to be dependent on side chain length, the TiO2 and Li+ content. The electrolyte PVA1PEGME350-20-3 illustrated a satisfactory ionic conductivity of 1.58x10-4 S/cm at 30 °C. These materials have high ion conductivity and can be suggested for application to lithium-ion batteries. References 1. A.S. Arico, P. Bruce, B. Scrosati, J-M. Tarascon, W. Van Schalkwijk, Nature Materials, 2005,

4, 366–377. 2. J. Zhou, D. Gao, Z. Li, G. Lei, T. Zhao, X. Yi, Pure and Applied Chemistry, 2010, 82, 2167–

2174. This work was supported by National Boron Research Institute (BOREN) with Project Number 2014.Ç0424. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 21



PP-8

Polymerization Reactions of Epoxidized Soybean Oil and Maleate Esters of Oil-Soluble Resoles

Jesmi Çavuşoğlu1, Gökhan Çaylı2 1Boğaziçi University, Department of Chemistry, İstanbul, Turkey 2İstanbul University, Department of Chemistry, İstanbul, Turkey


Petroleum is one of the most important resources in today’s world. Unfortunately, because of the depletion of petroleum reserves and environmental concerns, too much effort has been spent to develop new materials that can be manufactured in environmentally acceptable ways that involve a minimum consumption of energy and petroleum-based raw materials and still maintain as favourable an ecological balance as possible.1 For these reasons, vegetable oils seem to be one of the most important renewable feedstock for industry.2 A wide variety of chemicals and polymers can be synthesized from plant oils, and mechanical properties of the synthesized materials can be adjusted with different types of plant oils and petroleum-based compounds.3 In this study, the polymerization reaction of the maleate half esters of oil-soluble resoles with epoxidized soybean oil (ESO) was demonstrated. The aim of this study was to synthesize industrially applicable thermoset polymers from cheap starting materials with a minimum amount of petroleum-based chemicals. The maleate half-esters of the dimeric oil-soluble resoles were obtained by the esterification reaction of maleic anhydride with a p-tertiary butyl phenol (p-TBP) resole and p-nonyl phenol resole resins in the first step. The monomers synthesized were characterized by IR and 1H-NMR techniques. The oil-soluble resole maleates were polymerized with ESO to obtain tough and load-bearing thermoset materials. The thermal and mechanical properties of the materials were determined by dynamic mechanical analysis, differential scanning calorimetry, thermogravimetric analysis, and tensile strength testing. References 1. G.I.P. Lligadas, Ph.D. dissertation, Universitat Rovira I Virgili, 2006. 2. J.O. Metzger, U. Bornscheuer, Applied Microbiology and Biotechnology, 2006, 71, 13-22. 3. A. Shabeer, Ph.D. dissertation, University of Missouri-Rolla, 2006.




PP-9

Molecularly Imprinted Polymers for the Recognition of Bioactive Plant Extracts

Pınar Çakır1, Elif Çepni Yüzbaşıoğlu2 1Department of Biomedical Engineering, Istanbul Arel University, Istanbul, Turkey

2Department of Molecular Biology and Genetics, Istanbul University, İstanbul, Turkey


Molecularly imprinted polymers (MIPs) are synthetic materials with specific recognition properties for target molecules.1 MIPs are considered as alternatives to biomolecules and are characterized by a higher chemical and physical stability, as well as better availability and lower cost. The principle of the molecular imprinting is based on intermolecular interactions formed between functional monomers and the target molecule surrounded by cross-linked polymer network. Following the removal of the target molecule, polymer network becomes a rigid biomimetic system with molecular memory. Due to the specific recognition characteristics of imprinted polymers, MIPs have been applied to chiral separation, solid extraction, drug delivery, sensor and catalyst. Recent studies show that catechin and its derivatives extracted from green tea and oleuropein extracted from olive leaf have great beneficial effects on health.2 Encapsulation of bioactive plant extracts, which is used to protect antioxidant activity of the extracts from environmental conditions such as light, pH and ionic strength, attracts an increasing interest by researchers.3 Additionally, it's well known that industrial applications often require spherical monodisperse micro/nanostructures. In the literature, there are a number of studies regarding encapsulation of bioactive plant extracts and molecular imprinting of plant extracts, however to the best of our knowledge no study has been conducted concerning monodisperse imprinted polymer particles for the recognition of catechin and oleuropein molecules. The aim of our study is to synthesize monodisperse MIP micro/nanoparticles for specific recognition of the bioactive plant extracts catechin and oleuropein and to employ the MIP micro/nanoparticles as extracting phase for separation purposes and as bioactive molecule-loaded particles for cosmetotextile applications. References 1. K. Haupt, K. Mosbach, Chemical Reviews, 2000, 100, 2495-2504. 2. D. C. Christodouleas, C. F. K. Papadopoulos, A. C. Calokerinos, Talanta, 2014, 130, 233–240. 3. A. Munin, F. Edwards-Lévy, Pharmaceutics, 2011, 3, 793-829.




PP-10

Polymerization of Epoxidized Soybean Oil (ESO) with Tri Salicyl Borate

Gökhan Çaylı1, Hüseyin Esen2 1Faculty of Engineering, Department of Engineering Sciences, Istanbul University, Istanbul,

Turkey 2Polymer Engineering Department, Engineering Faculty, Yalova, Turkey


The world largest boron reserves is found in Turkey.1 Thus, it has a vital importance to synthesis boron derivatives and boron based polymers. In this study, boric acid (BA) was reacted with salicylic acid (SA) in order to obtain trisalicyl borate (TSB) ester. TSB monomer was characterized by FTIR and 1H NMR techniques. In the presence of free –COOH and -OH groups, Boric acid reacts only with –OH groups and corresponding boric acid ester forms. This results are congruent with the literature.2,3 Then TSB was polymerized with ESO at 90oC under nitrogen atmosphere. The TSB-ESO polymer was a rubbery material that showed 0.1 MPa stress at break value with 300 % elongation at break value. Thermal properties were analyzed with DSC and TGA methods. TSB-ESA rubber showed one Tg at -2 oC and a melting peak at 100 oC. TGA plot showed 4 segmental lost and 5 % weight loss temperature was measured as 105 oC.

References

1. C. Helvacı, R.N. Alonso, Turkish Journal of Earth Sciences, 2000, 9, 1-27. 2. N. Alemdar, A.T. Erciyes, N. Bicak, Polymer, 2010, 51(22), 5044–5050. 3. D. Gunes, B. Karagoz, N. Bicak, Designed Monomers and Polymers, 2009, 12(5), 445-454.


http://www.sciencedirect.com/science/article/pii/S0032386110007676



http://www.sciencedirect.com/science/journal/00323861

http://www.sciencedirect.com/science/journal/00323861/51/22

http://www.tandfonline.com/loi/tdmp20?open=12%23vol_12



PP-11

Synthesis of Block Copolymers Based on Polyethylene by Thermally Induced Controlled Radical Polymerization Using Mn2(CO)10

Mustafa Ciftci1, Sébastien Norsic2, Christophe Boisson2, Franck D’Agosto2, Yusuf Yagci1

1Department of Chemistry, Istanbul Technical University, Maslak, TR-34469, Istanbul, Turkey 2C2P2 (Chemistry, Catalysis, Polymers & Processes), Team LCPP Bat 308F, Universitéde Lyon, Univ Lyon 1, CPE Lyon, CNRS, UMR 5265, 43 Bd du 11 Novembre 1918, 69616 Villeurbanne,

France


Iodo functionalized polyethylene (PE-I), prepared by the addition of iodine after catalyzed polyethylene chain growth on magnesium,1 is demonstrated to be an efficient macroinitiator for thermally induced controlled free radical polymerization using dimanganese decacarbonyl (Mn2(CO)10). The free radical polymerization of methyl methacrylate was initiated by thermal homolysis of (Mn2(CO)10) at 80 oC forming reactive manganese pentacarbonyl radical species [•Mn(CO)5] capable of activating C-I bond of PE-I. The metal catalyzed radical generation and degenerative iodine processes yielded polyethylene-b-poly(methyl methacrylate) (PE-b-PMMA) block copolymers with relatively low dispersities. The end group functionality of the block copolymer was confirmed by the successful thermal polymerization of styrene by using PE-b-PMMA as a macroinitiator in the described process. This work conclusively provides a new approach for combining polyethylene with vinyl polymers via manganese chemistry in a simple and efficient pathway of importance in synthetic polymer chemistry and other related applications.2

Mn2(CO)10

: methyl methacrylate

: I

: polyethylene

: styrene

80 0C

Mn2(CO)1080

0C

References 1. I. German, W. Kelhifi, S. Norsic, C. Boisson, F. D'Agosto, Angewandte Chemie International

Edition, 2013, 52, 3438-3441. 2. M. Ciftci, S. Norsic, C. Boisson, F. D'Agosto, Y. Yagci, Macromolecular Chemistry and

Physics, 2015, DOI: 10.1002/macp.201500016.




PP-12

Copper(II)-thioxanthone: A Photoswitchable Catalyst for the Copper(I)-catalyzed Azide-alkyne Cycloaddition

Sajjad Dadashi-Silab, Yusuf Yagci Department of Chemistry, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey


Merging photochemistry with copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) has opened new possibilities of gaining spatiotemporal control over the click reaction as well as softening the reaction conditions.1-4 In this study, an efficient one-component copper photocatalyst is reported to photochemically induce the CuAAC reaction without the need of additional ligands. Combination of thioxanthone carboxylate as the counter anion to copper(II) ions stimulated intramolecular photoinduced electron transfer reactions to form copper(I) species to catalyze the click reaction with the ability of gaining temporal control over the process. Figure 1 illustrates the synthesis of copper(II)-thioxanthone photocatalyst and its use in the photoinduced CuAAC reaction under soft irradiation conditions.

Figure 1. Photoinduced CuAAC by copper(II)-thioxanthone photocatalyst: (a) synthesis of the photocatalyst, (b) schematically representation of the photoinduced CuAAC in a model reaction, and (c) evidence of temporal control over the click reaction by Light On/Off experiments. References 1. M.A. Tasdelen, Y. Yagci, Angewandte Chemie International Edition, 2013, 52, 5930-5938. 2. M.A. Tasdelen, Y. Yagci, Tetrahedron Letters, 2010, 51, 6945-6947. 3. M.A. Tasdelen, G. Yilmaz, B. Iskin, Y. Yagci, Macromolecules 2012, 45, 56. 4. S. Dadashi-Silab, B. Kiskan, M. Antonietti, Y. Yagci, RSC Advances, 2014, 4, 52170-52173. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 26



PP-13

Antimicrobial Properties of Phoshonium Based ROMP Polymers

Tarık Eren1, Ceren Demir1, Naime Ceren Süer1, Tanıl Kocagöz2, Nihan Aytekin Ünübol2

1Yildiz Technical University, Chemistry Deparment, Istanbul, Turkey 2Acıbadem University, Medical Microbiology Department, Istanbul, Turkey


Infectious disease is a critically important global healthcare issue. The rate of bacterial resistance, to even most powerful antibiotics, is increasing at an alarming rate. For example, two million nosocomial infections occur in hospitals in the United States annually and add 5 billion dollars to healthcare costs.1 Polymeric antibacterial agents represent new developing direction in this field and offer great promise for enhancing activity and selectivity. In this study, we synthesized and investigated the properties of phosphonium salts containing “well-defined” ROMP based polymers. Mainly ROMP based polymerization was studied, after synthesizing norbornene monomers Grubbs’ catalyst was used for metathesis polymerization. Molecular weights of these polymers were assigned by GPC and NMR techniques. Cationic charge density of polymer coated glasses was measured with colorimetric method based on fluorescent complexation and UV-Vis spectroscopy. Antimicrobial properties of the polymers were investigated in solution and on the glass coated surface. Structure-activity relationship of the synthesized polymers has been investigated with cell data, bacteria Staphylococcus aureus (ATCC 25923), Escherichia coli (ATCC 25922), Pseudomonas aeruginosa (ATCC 27853) and Mycobacterium tuberculosis (H37Ra).

O

NO O

PhCH CH2

m

PR R

RBr

Homopolymer

1. R=-CH32. R=-CH2CH33. R=-

(CH2)2CH34. R=-C(CH3)35. R=-C6H56. R=-C6H5OCH3

References 1. R.P. Wenzel, Journal of Hospital Infection, 1995, 31, 79-87.




PP-14

Characterization and Cu (II) Ion-Binding Properties of Porous Hydrogels Synthesized from Different Types of Jeffamine Molecules

Ahmet Erdem, Ufuk Yildiz Kocaeli University, Department of Chemistry, Faculty of Science, Umuttepe Campus 41380-

Kocaeli


Polyether amines with a wide range of applications varying from use as coatings, ink resins, adhesives, elastomers, hot melt adhesives, sealants, engineering plastics and composites. Notwithstanding these compounds do demonstrate bonding affinity towards heavy metals such as copper, a chelating agent.1 In this study, Jeffamine a commercial polyether amine based on ethylene oxide (EO), propylene oxide (PO), and EO/PO mix were used to synthesize hydrogels of varying molecular weight (600, 900, 2000) Jeffamines and glutaraldehyde in water via the lyophilization process with jeffamine T-400 as crosslinker. Reduction of cross-linked gel with NaBH4 is then achieved to increase the number of free amines.2 Characterization by FT-IR and swelling analysis were performed for the synthesized hydrogels. Investigations on copper removal at varying parameters of pH, temperature demonstrated the role of Jeffamine molecular weight with percentage removal increasing with decrease molecular weight and a maximum adsorption capacity of porous material was attained. Based on these experimental analyses, this novel synthesized hydrogel shows a potential eco-friendly alternative for jeffamine based hydrogels for copper and other heavy metals removal from aqueous solution. References 1. B.P. Annamaria, Z. Kiraly, A. Mastalir, J. Dudas, S. Puskas, A. Vago, Journal of Physical

Chemistry B, 2008, 112, 15320-15326. 2. J.H. Billman, A.C. Diesing, Journal of Organic Chemistry, 1957, 22, 1068-1070. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 28



PP-15

Utilization of Renewable and Lichen Based Filler Material with LDPE

Musa Gültekin, Hüseyin Esen Polymer Engineering Department, Engineering Faculty, Yalova, Turkey


Fillers are generally used in order to lower the cost of polymeric materials. Besides these, they have the ability to affect the processability, transparency, thermal, electrical, mechanical, rheological properties. Recycling of polymers filled with organic fillers is difficult and their wastes have ecologically negative effects. These make natural-organic fillers interesting. These fillers have some advantages compared to mineral fillers. They are cheapness, low density, high specific strength and modulus, lightness, relative nonabrasiveness to processing equipment, wide availability, renewability, biodegradability, energy recovery (when incinerated), low health hazards and eco-friendly properties. In addition polymers filled with organic fillers have some advantages too. They are low cost, eco-friendly properties, good chemical and mechanical properties, good processability, creep and thermal stability, more resistant to insects compared to wood products and nice aesthetic appearance. Lichens can be considered as small ecosystems consisting of at least two or more organisms. These organisms are fungi called mycobiont with photosynthetic partner called photobiont. Lichens are found use in perfume, paint and food industry together with medicine and bioremediation. However, neither of these application areas is noteworthy in terms of commercial applications. Thus, utilization of lichen not only will find a new application area but also could be represented as a new alternative to common fillers. In this work, it is aimed to obtain lichen in its powder form and to characterize it with FTIR, TGA, dissolution test and density measurements. Later on it is planned to obtain compounds with LDPE with three different load ratios, %5, %10 and %15 followed molding test pieces with injection molding. The next step will consist of physical, mechanical and thermal analysis of the LDPE filled lichen with density measurements, tensile test, impact strength test, abrassive wear test, hardness test, MFI test, vicat-softening point test, TGA and DSC test and commenting on the results. These results will be compared with the literature values and give us a clue about the possibility to use this filler in polymeric systems.




PP-16

Drug Release of Newly Synthesized Copolymer Derived from Salicylic Acid and Acrylate

Parisa Golshaei Faculty of Science, Department of Chemistry, Division of Polymer Chemistry, Hacettepe

University, 06800 Beytepe, Ankara, Turkey


In the last decades much attention has been directed to speciality polymers for biomedical application. One particular approach towards the improved use of drugs is the design of polymer-drug conjugates or polymeric prodrugs.1 Salicylates are used in medicine as analgesic and antipy retic agents. They also act as non-steroidal anti-inflammatory drugs (NSAIDs) and induces apoptosis in cancer cells. Recent years have witnessed many studies on the synthesis and hydrolysis of polymer-drug conjugates of NSAIDs such as: naproxen indomethacin ibuprofen ketoprofen and fenoprofen.2 This work describes an efficient chemical method to design and in vitro evaluation of new vinyl ester type polymeric pro-drugs of salicylic acid as materials for drug delivery systems. Vinyl salicylate (Vinyl Sal) was first synthesized by reacting salicylic acid and vinyl acetate in the presence of mercuric acetate as a catalyst (Scheme 1). Vinyl Sal was then copolymerized with Acrylic acid (AA) or Methacrylic acid (MAA) in N,N-dimethylformamide solution, utilizing benzoyl peroxide. The compounds were characterized by FT-IR, NMR spectroscopy, elemental analysis and gel permeation chromatography. The hydrolysis of the drug–polymer conjugates were carried out in dialysis bags containing aqueous buffer solutions (pH 1, 7.4 and 10) at 37°C. The drug-release profiles indicated that hydrolytic behaviour of polymeric pro-drugs is strongly based on polymer hydrophilicity and pH of the hydrolysis solution.

OH O

OH HgOAC/H2SO4

Vinyl acetate

OH

CO

CC

O

Scheme 1.The synthesis route of vinyl ester type derivative of salycilic acid (Vinyl sal) References 1. Z. Liu, S. Rimmer, Journal of Controlled Release, 2002, 81, 91-99. 2. S. Davaran, A. Entezami, Journal of Controlled. Release, 1997, 47, 41-49. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 30



PP-17

A Stimuli-Responsive Hybrid Sol-Gel Molecularly Imprinted Polymer as a Potential Delivery System for Controlled Release

Orhan Güney, Erdal Serin Istanbul Technical University, Department of Chemistry, 34469 Istanbul, Turkey


The growing interest in sol-gel science is due to the straightforwardness in tailoring the porosity in these materials, particularly in achieving molecular recognition in different systems such as adsorption or absorption, stationary phases in liquid or gas chromatography and chemical sensing applications. Sol-gels have a porous network which we can control the porosity by controlling the density of cross-links or by changing the swell affinity in the environment. Stimuli-responsive or smart polymers are macromolecules that display a significant physiochemical change in response to small changes in their environment such as temperature, pH, light, magnetic field, ionic factors, etc.1 Molecular imprinting is a technique to synthesize cross-linked polymers with a predetermined selectivity and specificity for a given analyte.2 In molecular imprinting processes, one needs a template, functional monomers, cross-linker(s), initiator, porogenic solvent. Molecular imprinting technique has been widely and successfully used to prepare polymers offering high affinity binding sites for a variety of molecules, including organic, inorganic, biological molecules or ions.3 In this study, a stimuli-responsive hybrid gel system with an improved mechanical stability was developed as a controlled drug delivery carrier that can undergo phase transition by the stimulation of ethanol-water mixture. For this aim, trimethoxysilane terminated poly(propylene glycol) was synthesized by coupling of 3-isocyanatopropyltriethoxysilane with the hydroxyl end groups of poly(propylene glycol) which was introduced as a chain extender. Aminopropyltriethoxysilane was incorporated as a functional precursor into hybrid gel system. Imprinted hybrid gel prepared in the presence of tryptophan was characterized by spectroscopic methods. Solvent uptake of hybrid gels in ethanol-water mixtures with different composition was evaluated depending on time. The solvent release and swelling kinetic of hybrid gels were investigated. The diffusional exponents and diffusion constants of gels were calculated by using the swelling kinetic data. The effect of functional precursor on tryptophan release profile was analyzed. References 1. O. Güney, Journal of Molecular Recognition, 2003, 16, 67-71. 2. C.A. Lorenzo, O. Güney, T. Tanaka, Macromolecules, 2000, 33, 8693-8697. 3. O. Güney, F.Ç. Cebeci, Journal of Applied Polymer Science, 2010, 117, 2373–2379. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 31

mailto:[email protected]



PP-18

ROMP Based Boron Nitride Composites

Keziban Hüner1, Alper Aşçı1, Y. Voynich2, Lina L. Sartinska2, Tarik Eren1

1Yildiz Technical University, Chemistry Department, Istanbul, Turkey 2Frantsevich Institute for Problems of Materials Science, NAS of Ukraine, Kiev, Ukraine


Nowadays, synthesis and development of inorganic-organic hybrid polymer composites play an important role in scientific studies. The mechanical and thermal properties of polymers and composite structures can be altered through the use of various kinds of fillers. In this project one- and two-dimensional nanostructure of boron nitride will be used as a reactive filler in the polymer matrix. Project objective is to develop physical, A new kind of high performance composites with high thermal conductivity, low coefficient of thermal expansion and low dielectric loss was successfully developed based on using amino silane functionalized hexagonal boron nitride (hBN) in situ synthesis of ROMP (Ring Opening Metathesis Polymerization). Carboxylic acid and phosphonic acid containing ROMP polymers are synthesized and mixed with different ratio of hBN. Surface initiated ROMP polymers is also investigated by using bromoocanorbornen monomer with reaction of amino silane containing hBN. The effects of hBN and its content on the thermal conductivity, dielectric properties, and thermal resistance of cured composites, are systematically investigated and discussed.

O

NO O

PhCH

P OHO

OH

O

O O

CH2

m n

A

O

NO O

PhCH

P OHO

OH

m

CH2

n

B

OH HO

NH2

OH

amino silane modif ied boron nitride

C

BN

OH

Norbornene functionalized

boron nitride

BN

O

D

NH

N

O

O

Figure 1. Used monomers in the ROMP based boron nitride composites. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 32



PP-19

Polymers in Organic Photo-Electronics

Sıddık İçli

Solar Energy Institute, Ege University, İzmir 35100, Turkey

E-mail: [email protected], [email protected]

Organic photo-electronic technologies of Organic photovoltaics (OPV, DSSC), organic LEDs (OLED) and organic field effect transistors (OFET) are now the emerging novel technologies, in competition to known Si & Thin Film PV, LED, FET technologies, based on inorganic materials.1-5 Conducting polymers are employed at OPV and DSSCs, for efficient photo-electron transfers, in order to improve the efficiencies. These technologies are targeted as energy efficient in competition to their inorganic rivals. Basic advantage is the employment of organic materials rather than inorganic materials. Endorsements of polymers have been a major concept. Particularly at organic photovoltaics, together with monomolecular dyes, polymers are also employed, such as Porphrines, P3HT, MDMO-PPV and low–band gap polymers of thiophene-indol, by A. J. Heeger (Nobel Prize Winner; 2001);6

Organic photo-electronic technology tools, in their function mechanisms, simulate the organic living species on Earth, such as plants. In order to create the flexibility, organic photo-electronics are produced on polymers also, rather than on glass surfaces, in order to create flexibility. Therefore Printed, Flexible and Organic Photo Electronics are now one of the fastest growing technologies in the world. It is of vital interest to industries as diverse as consumer goods, healthcare, mobility, electronics, media and architecture. The sector comprises of a diverse range of enabling technologies at different stages of commercialization.IDTechEx, Ossila Ltd., ImageExpert, Mercgroup, Toyobo, Hueckfolien, Laytec, Dyesol, 3dMicromac, Flexcell, Southwall Techn. and TeraBarrier, Heliatek are among the companies in the World in production of organic photoelectronic devices.



Poster Presentations May 8, 2015 References 1. B. O’Regan, M. Gratzel, Nature, 1991, 353, 737-739. 2. T. Toyoda et al., Journal of Photochemistry and Photobiology A: Chemistry, 2004, 164, 203-

207. 3. S. Icli et al., Organic Electronics, 2006, 7, 188–194. 4. K. Ocakoglu, C. Zafer, C. Varlikli, S. Icli, Materials Science in Semiconductor Processing,

2013, 16, 1688- 1694. 5. C. Tozlu, S. Erten-Ela, Th. B. Singh, N. S. Sariciftci, S. Icli, Synthetic Metals, 2013, 172, 5-10. 6. N. S. Sariciftci, D. Braun, C. Zhang, V. I. Srdanov, A. J. Heeger, G. Stucky, F. Wudl, Applied

Physics Letters, 1993, 6, 585-587. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 34



PP-20

UV and Thermal Curable, Bromo-methacryl Functionalized Methyloleate

Gizem Kahraman, Demet Karaca Balta, Muhammed Kanat, Tarık Eren Yıldız Technical University, Chemistry Department, İstanbul, Turkey


The purpose of this work is to synthesize new free radically polymerizable monomer based on methyl oleate. The chemistry consist of reaction of the unsaturated fatty ester with N-bromosuccinimide (NBS) in the presence of exces amount of a nuclophile, methacrylic acid. Monomers are the addition products of bromine and the nucleophile to the oleate double bond. New monomer and polymers were characterized by spectroscopic techniques. UV and thermal initiation efficiency of boromo-methacrylated methyl oleate was investigated with flame reterdancy behaviour.

CH3

O

O

CH3

NBS

CH2OH

O

CH3

O

O

O

CH3

BrO

CH3

CH2

CH3

Figure 1. Mechanism of the bromomethacrylation of olefin in the presence of NBS




PP-21

Synthesis and Characterization of Ion-imprinted Sol-gel Derived Fluorescent Polymer for Selective Determination of Mercury(II) Ion

Fehmi Karagöz, Orhan Güney Department of Chemistry, Istanbul Technical University, Istanbul 34469, Turkey


Ion imprinting technology based on the highly selective ion imprinted polymer networks has widely been exploited as the new sorbents for the selective preconcentration or separation or removal of metal ions. Ion imprinted polymers are prepared by the imprinting technique which is a powerful method for the preparation of materials with the ability to recognize a specific chemical species. Sol–gel processing has shown a high capability of being integrated in production of organized materials while adding new value by unique properties of the synthesis products. In this process, the chemical compositions of the starting material controls porosity by carefully monitoring the reaction parameters. Molecular imprinting is becoming a well-established technique for the preparation of sensing materials that have the ability to recognize a specific chemical species.1 Molecularly-imprinted polymers (MIPs) are materials prepared in the presence of a template that serves as a mold for the formation of a template-complementary binding site.2 MIPs based on a sol-gel polymeric matrix are prepared through condensation of organically modified silanes giving rise to hybrid sol-gel or xerogel materials. In the present work, 9-aminoacridine moiety was appended to the functional precursor, 3-isocyanatopropyl triethoxysilane and hence a fluorescent functionalized silane was obtained. Fluorescent sol-gel polymeric material was then prepared by a conventional one-pot method with the co-condensation of such fluorescent precursor and the cross-linker, tetramethoxysilane. Ion-imprinted polymeric material synthesized in the presence of Hg2+ was characterized by Fourier transform-infrared spectroscopy, scanning electron microscopy, N2 adsorption–desorption analysis and thermogravimetric analysis by comparing with non-imprinted polymeric material which was obtained in the absence of Hg2+. Surface area, pore volume and diameter were analyzed from the profile of nitrogen adsorption. Steady-state fluorescence experiments were performed for spectral characterization of the polymeric films and the advancement of the reaction was defined. The design, synthesis and characterization of such ion imprinted sol-gel materials and their applicability to selective determination of Hg2+were investigated. The corresponding selectivity factors of the imprinted fluorescent polymeric film toward Hg2+ against the other analogues were evaluated. References 1. M.J. Whitcombea, N. Kirschb, I.A. Nichollsb, Journal of Molecular Recognition, 2014, 27,

297–401. 2. O. Güney, F.Ç. Cebeci, Journal of Applied Polymer Science, 2010, 117, 2373–2379.




PP-22

Dispersion and Characterization of Copper Nanoparticles into Chitosan/ Silica Matrix

Selcan Karakuş, Tuba Şişmanoğlu, İsmail Sıtkı Başdemir, Gizem Akdut, Öykü Ürk, Ezgi Tan, Ayben Kilislioğlu*

Department of Chemistry, Engineering Faculty, Istanbul University, Avcilar-Istanbul, Turkey

E-mail: [email protected] The aim of this study is to investigate the dispersion of copper nanoparticles into the biopolymer matrix with and without silica. Copper nanoparticles were prepared in chitosan via reduction of Cu(II) ions with sodium borohydride and than dispersed into chitosan. Dispersion and size of copper nanoparticles are characterized by XRD and SEM techniques. Antibacterial activity of chitosan/Cu-silica is tested by comparing mean diameter of inhibition zone against gram negative bacteria.

Figure 1. Antibacterial activity of chitosan/Cu-silica

References 1. Y. Liu, H.-I. Kim, Carbohydrate Polymers, 2012, 89, 111-116.






PP-23

Synthesis and Characterization of Novel Vinyl Ester Resins Based on Cardanol

Emre Kınacı1, Giuseppe R. Palmese1, Erde Can2 1Department of Chemical and Biological Engineering, Faculty of Engineering

Drexel University, Philadelphia, PA, USA 2Department of Chemical Engineering, Faculty of Engineering and Architecture, Yeditepe

University, Istanbul, Turkey


Polymers which have become indispensable materials of our modern lives are mainly derived from petroleum feedstocks. With the petroleum production facing exhaustion day by day, the use of renewable plant based feed-stocks for making polymers offer both economic and environmental advantages. One such plant based resource for polymers is the Cashew nutshell liquid (CNSL) which is a natural resin found in the honeycomb structure of the cashew nutshell and is a byproduct of processing cashew nuts.1 The main component of thermally treated CNSL is cardanol which is a phenol derivative mainly having a meta substutient of a C15 unsaturated hydrocarbon chain with one to three double bonds.2 The main objective of this study is to obtain new thermosetting materials from cardanol and compare their properties with those of the conventional ones derived from petroleum sources. For this purpose, two commercially available CNSL resins, NC 514 with approximately two epoxies per molecule and LITE 2035 HP with approximately one epoxy per molecule were methacrylated and the methacrylated NC-514 resin (NC514VE) was used as the thermosetting resin and the mono-functional methacrylated LITE monomer (LITEVE) was used as the reactive diluent in both conventional DGEBA vinyl ester resin (DGEBAVE) and in NC514VE resin at changing concentrations. Resin formulations of NC514VE using styrene as the reactive diluent were also prepared. The resins were cured in the presence of Trigonox A initiator and cobalt napthanate catalyst at room temperature and then post-cured at a higher temperature. The methacrylated products were characterized via acid number titration and spectroscopic techniques like GPC, FT-IR and 1H-NMR spectroscopy. The rheological properties of the liquid resin mixtures were evaluated and the cure temperatures were analyzed via Differential Scanning Calorimetry (DSC). The thermo-mechanical properties of the cured resins were determined via Dynamic Mechanical Analysis (DMA), mechanical properties were determined via tensile tests and the thermal stabilities of the resins were examined by thermal gravimetric analysis (TGA) method. References 1. R.L. Quirino, T.F. Garrison, M.R. Kessler, Green Chemistry, 2014, 16, 1700-1715. 2. M. Sultania, J.S.P. Rai, D. Srivastava, Journal of Hazardous Materials, 2011, 185, 1198–1204.


http://apps.webofknowledge.com.lproxy.yeditepe.edu.tr/OneClickSearch.do?product=UA&search_mode=OneClickSearch&excludeEventConfig=ExcludeIfFromFullRecPage&SID=Q28bHjTkm3ZQ2DrDPbl&field=AU&value=Quirino,%20RL

http://apps.webofknowledge.com.lproxy.yeditepe.edu.tr/OneClickSearch.do?product=UA&search_mode=OneClickSearch&excludeEventConfig=ExcludeIfFromFullRecPage&SID=Q28bHjTkm3ZQ2DrDPbl&field=AU&value=Garrison,%20TF

http://apps.webofknowledge.com.lproxy.yeditepe.edu.tr/OneClickSearch.do?product=UA&search_mode=OneClickSearch&excludeEventConfig=ExcludeIfFromFullRecPage&SID=Q28bHjTkm3ZQ2DrDPbl&field=AU&value=Kessler,%20MR



PP-24

Synthesis and Characterization of Epoxidized Soybean Oil / Diisocyanate Based Thermoset Polymers

Gizem Kirevliyasi, Selim Kusefoglu

Department of Chemistry, Bogazici University, Istanbul, Turkey


Approximately 13 % of the fossil fuel resources are consumed to produce the vast majority of polymer products and organic chemicals. Price of fossil fuel based polymers, nondegradability, greenhouse gas emission during combustion and dwindling of fossil fuel sources are the reasons of investigating novel biobased polymers. Research efforts are being made for utilizing green polymerization systems which uses renewable materials.1,2 In this study, novel biobased thermoset poly(oxazolidone/isocyanaurate)s from epoxidized soybean oil and different monomeric diisocyanates such as methylene diphenyl diisocyanate, Toluene diisocyanate, isophorone diisocyanate were synthesized. The polymeric products identified by FTIR spectroscopy. Tertiary amine and Lewis acid catalysts were used to maximize oxazolidone formation. The mechanical properties of the polymer determined by solvent uptake, surface hardness and compression tests. Thermal properties determined by TGA tests.

O

Epoxy group

O C NR

N C O

N O

O

R

N

C

O

N O

O

R

N

O

O

N O

O

R

NN

N

O

OO

OxazolidoneRoute

Oxazolidone / Isocyanurate

Route

Diisocyanate

Oxazolidone

Both of

the routes form thermoset polymers

Figure 1. Main routes of diisocyanate-epoxy reaction.

References 1. M.R. Islam, M.D. Beg, S. Jamari, Journal of Applied Polymer Science, 2014, 131, 40787-

40800. 2. P.A. Wilbon, F. Chu, C. Tang, Macromolecular Rapid Communications, 2013, 34, 8-37.




PP-25

Thioxanthone Modified Poly(Vinyl Alcohol) as a Macro-initiator for Photoinduced Radical Polymerization

Senem Kork*, Gorkem Yilmaz, Yusuf Yagci Department of Chemistry, Istanbul Technical University, Maslak, Istanbul, 34469, Turkey


Photopolymerization is a well-known technique utilized in many technologically important areas. Both free radical and cationic modes have been intensively investigated and numbers of papers reported innovative developments in the field. In this current work, we have incorporated thioxanthone moiety to the side chains of commercially available poly(vinyl alcohol) (PVA) by a simple acetylization reaction. For this purpose, a thioxanthone structure with aldehyde functionality (TX-A) is designed and properly synthesized. Afterwards, the obtained TX-A is linked to the PVA counterpart by a simple addition reaction to yield the desired TX-PVA macroinitiator.

SH

OH

O

+S

O O

yield: 88%

H

O

HH2SO4

OH O

O

n m

S

O O

H+ p-TSA

reflux O

O

a mO OOH

S

b

O

Figure 1. Synthesis of thioxanthone attached poly(vinyl alcohol) macro-photoinitiator




PP-26

Novel Difunctional Monomeric and Polymeric Photoinitiators with Both Type I and Type II Side Chains

Tugce Nur Eren1, Fulya Koylu1, Jacques Lalevée2, Duygu Avcı1 1Department of Chemistry, Bogazici University, 34342 Bebek, Istanbul, Turkey

2Institut de Science des Matériaux de Mulhouse IS2M, UMR CNRS 7361, UHA, 15, rue Jean Starcky, 68057 Mulhouse Cedex, France


A recent trend in the effort to develop high performance photoinitiator systems for photopolymerization is to consider polymerizable or polymeric ones. These have some advantages such as high reactivity, low volatility and low migration in comparison with low-molecular weight nonmonomeric analogues. In this work, the first methacrylate monomers containing both Type I (Irgacure 2959) and Type II (benzophenone or thioxanthone) photoinitiating groups in their structures were synthesized (Figure 1). The photopolymerization efficiencies of the synthesized photoinitiators were investigated in the polymerizations of 1,6-hexanedioldiacrylate and trimethylolpropane trimethacrylate and compared with small molecule photoinitiators they are synthesized from (benzophenone, thioxanthone and Irgacure 2959).

S

OOO

OH

O

OOOO

O

OH

O

O

O

Figure 1. Structures of novel monomeric photoinitiators This work was supported by a grant from the Scientific and Technological Research Council of Turkey (TÜBİTAK) (113Z241).




PP-27

Effect of Catalysts on the Stereoregularity of Acrylamide Derivatives: a Computational Approach

Berkehan Kura, Tuğba Furuncuoğlu Özaltın, Şaron Çatak, Viktorya Aviyente Department of Chemistry, Boğaziçi University, 34342, Bebek, İstanbul, Turkey


Free radical polymerization is used in industry to obtain high molecular weight polymeric materials from a wide variety of vinyl monomers without extensive purification.1 Well-defined polymers with controlled molecular weights can be obtained with living/controlled radical polymerization.2-3 Besides the molecular weight, the tacticity of the growing chain should also be controlled during the free radical polymerization. Tacticity is a measure of stereoregularity of a polymer chain and many of the polymer properties such as tensile strength, melting point, and solubility depend on it.4 There are two fundamental approaches for stereochemical control of polymers during free radical polymerization: catalytic control of the propagating chain end using Lewis acids, solvents, and chiral auxiliaries, and the use of polymerizations in organized and constrained media.5

O

N

Figure 1. DMAM (Dimethylacrylamide).

The aim of this study is to shed light on the control of stereoregulation by Lewis acids during free radical polymerization by using quantum mechanical tools. This study will be undertaken for the free radical polymerization of dimethylacrylamide (DMAM) (Figure 1) on which we will study the role of Lewis acids.

1. K. Satoh, M. Kamigaito, Chemical Reviews, 2009, 109, 5120-5156. 2. G. Moad, D. H. Solomon, “The chemistry of radical polymerization”, Elsevier: Amsterdam,

Boston, 2006. 3. M. Kamigaito, K. Satoh, Journal of Polymer Science Part A: Polymer Chemistry, 2006, 44,

6147-6158. 4. N. A. Porter, T. R. Allen, R. A. Breyer, Journal of American Chemical Society, 1992, 114,

7676-7683. 5. K. Matyjaszewski, T. P. Davis, “Handbook of radical polymerization”, Wiley-Interscience:

Hoboken, 2002. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 42



PP-28

Sustainable, Efficient Approaches to Renewable Platform Chemicals and Polymers

Hatice Mutlu1, Michael A. R. Meier2 1Institut für Biologische Grenzflächen - Polymeric Materials (IBG III), Lehrstuhl für Präparative Makromolekulare Chemie (Prof. C. Barner-Kowollik), Karlsruhe Institute of Technology (KIT),

Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany 2Laboratory of Applied Chemistry, Institute of Organic Chemistry, Karlsruhe Institute of

Technology (KIT), Fritz-Haber-Weg 6, Building 30.42 76131 Karlsruhe, Germany


Environmental concerns, such as pollution and decreases in natural resources, have led to an increased demand for renewable materials in recent years. Adoption of efficient approaches, like metal-free organocatalysis, olefin metathesis and thiol-ene coupling, both in academic and industrial research, offers the potential of increased sustainability, comparatively lower production costs (besides olefin metathesis), and more environmentally benign processes. Thus, the following work is performed with the attempt to meet both, making use of oils as renewable feedstock, in this case mainly plant oil derived platform chemicals, and using sustainable, efficient approaches as valuable synthetic tools.

References

1. H. Mutlu, M.A.R. Meier, Macromolecular Chemistry and Physics, 2009, 210, 1019-1025.


Plant oils

• easy available & sustainable

• versatile in structure & properties

• relatively low cost


Poster Presentations May 8, 2015 2. H. Mutlu, M.A.R. Meier, Journal of Polymer Science, Part A: Polymer Chemistry, 2010, 48,

5899-5906. 3. H. Mutlu, L. Montero de Espinosa, M.A.R. Meier, Chemical Society Reviews, 2011, 40, 1404–

1445. 4. H. Mutlu, L. Montero de Espinosa, O. Türünc, M.A.R. Meier, Beilstein Journal of Organic

Chemistry, 2010, 6, 1149-1158. 5. C.O. Akintayo, H. Mutlu, M. Kempf, M. Wilhelm, M.A.R. Meier, Macromolecular Chemistry

and Physics, 2011, 213, 87-96. 6. H. Mutlu, A.N. Parvulescu, P.C.A. Bruijnincx, B.M. Weckhuysen, M.A.R. Meier,

Macromolecules, 2012, 45, 1866-1878. 7. H. Mutlu, J. Ruiz, J., S.C. Solleder, M.A.R. Meier, Green Chemistry, 2012, 14, 1728-1735. 8. H. Mutlu, R. Hofsäß, R.E. Montenegro, M.A.R. Meier, RSC Advances, 2013, 3, 4927-4934.




PP-29

Synthesis and Characterization of Side Chain Primary Amine Functionalized Polysulfones

Serhat Oran, Cagatay Altinkok, Mehmet Atilla Tasdelen Department of Polymer Engineering, Faculty of Engineering, Yalova University, TR-77100

Yalova, Turkey


Polysulfones (polysulfones, poly(ether sulfone)s or poly(phenyl sulfone)s) are high performance polymers with excellent chemical and thermal stability, excellent strength and flexibility, transparency, as well as high glass transition temperature and good film forming properties. Due to these properties, polysulfones are used in the field of material science, biology and polymer science and has been the basis of numerous applications. In spite of tremendous progress in their synthesis and applications, these materials have some limitations related to stress cracking with certain solvents, poor tracking resistance and weathering properties. The introduction of functional groups into the polysulfones not only overcomes these limitations but also extends the range of potential applications of these high-performance materials through specific properties gained and thus provides a wider scope. Introduction of functionality to polysulfones has been accomplished by either (i) functional monomer approach allowing modification at the polymerization stage or (ii) the post-functionalization of commercially available polymers. The various functionalities readily attached to the polysulfone backbones, include halides, acids, alcohols, alkyls, amines, phenyls and polymerizable groups. In this study, the polysulfone bearing primary amines at side chain has been prepared via three steps: (i) chloromethylation, (ii) azidation and (iii) reduction to amine. The functionalization steps were followed by FT-IR and 1H-NMR analyses. The results show that the degree of functionalization was determined as 22% by 1H-NMR spectroscopy. Consequently, the selection of a mild and efficient synthetic route is an important issue for the preparation of primary amine functionalized polysulfones. References 1. C. Dizman, M.A. Tasdelen, Y. Yagci, Polymer International, 2013, 62, 991-1007. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 45



PP-30

Modeling Non-covalent Interactions in Polymers

Alimet S. Özen Piri Reis University, Faculty of Arts and Sciences, 34940 Tuzla, Istanbul, Turkey


Non-covalent interactions (hydrogen bonding, heteroatom interactions, π-π stacking) constitute the framework of the structural and environmental factors determining the properties of the functional polymers such as super hydrophobicity, fluorescence or conductivity. In this presentation, computational strategies for defining the intra and intermolecular interactions (structural factors) and interactions with the medium and the solvent molecules (environmental factors) will be discussed for different types of functional polymers.1-6

References 1. A.S. Özen, U. Sen, C. Atilgan, Journal of Chemical Physics, 2006, 124, 064905. 2. A.S. Özen, C. Atilgan, G.Sonmez, Journal of Physical Chemistry C, 2007, 111, 16362-16371. 3. G. Kaçar, C. Atılgan, A.S. Özen, Journal of Physical Chemistry C, 2010, 114, 370-382. 4. A.S. Özen, Journal of Physical Chemistry C, 2011, 115, 25007-25018. 5. B. Dedeoglu, V. Aviyente, T. Etienne, A. Monari, A.S. Ozen, Journal of Physical Chemistry C,

2014, 118, 23946–23953. 6. B. Dedeoglu, V. Aviyente, A.S. Ozen, Journal of Physical Chemistry C, 2014, 118, 6385-6397.




PP-31

Synthesis and Characterization of Poly(MA-alt-NVP) Copolymers and Conjugation with Fluorouracil (5-FU)

Shahed Parvizi Khosroshahi, Hatice Kaplan Can Hacettepe University, Faculty of Science, Department of Chemistry, 06800 Beytepe, Ankara,

Turkey


In recent years developments in the field of material science and biotechnology, feed off each other and the desired functional structure for use in many areas of design, quality of materials, synthesis, characterization and applications of enables cancer caused deregulation of cell growth and normal genes, or a disease caused by diversion of regulatory mechanisms.1 Nowadays treatment of cancers is possible not only with cytotoxic drugs and biological agents, but also via antibodies and some polymer drug conjugates. 5- Fluorouracil (5-FU) with the wide range of usage and is one way the need as well as a single agent administered to the patient intravenously in combination with anticancer drugs. Analog of a fluorinated pyrimidin 5-Fluorouracil (5-FU) with the wide range of usage and is one way the need as well as a single agent administered to the patient intravenously in combination with anticancer drugs. For this purpose, water-soluble polymer drug conjugate systems are obtained of covalently bonded large molecules with the chemotherapy cancer agents.2 The main objective of this study is synthesis of functional alternating poly(MA-alt-NVP) copolymer via charge transfer polymerization complex radical copolymerization by using electron acceptor (MA) and donor (NVP) monomers and preparation of 5FU polymer-drug conjugate. All synthesized polymers, 5-Fluorouracil (5-FU) and poly(MA-alt-NVP)- 5-FU conjugate were characterized by spectroscopic methods such as HR-Raman, ATR-FTIR, 1H and 13C NMR and XRD.

Scheme 1. Chemically conjugation of Poly(NVP-alt-MA) with 5-Fluorouracil (5-FU)

References 1. H. Ringsdorf, Journal of Polymer Science, 1975, 51, 135–153. 2. H. Kaplan Can, G. Karakus, N. Tuzcu, Polymer Bulletin, 2014, 71, 2903-2921.


NNOO

OOOO OO

HHNN NNHH

FFOO

OO

NNOO

OO OOOOHH OO

FF NNHH

NN

OO

OO

TTEEAA,, DDMMFF

7700ooCC,, 44 hh

ppoollyy((NNVVPP--aall tt

--MMAA))//55FFUU

((11::11))



PP-32

Investigation of Proton Conductivity of Poly(vinyl phosphonic acid) / Hexagonal Boron Nitride Based Composite Membranes

Mehmet Sirin Tutgun1, Deniz Sinirlioglu1, Sevim Unugur Celik1,*, Ayhan Bozkurt1,2 1Department of Chemistry, Faculty of Arts and Sciences, Fatih University, 34500, Buyukcekmece-

Istanbul, Turkey 2Bio-nano Technology Center, Fatih University, 34500, Buyukcekmece-Istanbul, Turkey


Hexagonal boron nitride (hBN) particles have attracted increasing interest in the scientific community due to mechanical properties, chemical stability, electrical features, thermal stability and good lubrication property.1-4 In this work, hexagonal boron nitride nanoparticles were used as inorganic fillers which increase the mechanical and thermal stabilities of the membrane. The proton conducting membranes were prepared by blending of poly(vinyl phosphonic acid) (PVPA) and hexagonal boron nitride (hBN). Thermo gravimetric analysis (TGA) showed that the polymer electrolyte membranes are thermally stable up to 200 oC. Scanning electron microscopy (SEM) analysis indicated the homogeneous distribution of hBN nanoparticles in the polymer matrix. Here, PVPA provided high proton conductivity together with boron nitride surface groups. hBN enhanced the membrane formability and thermal property. hBN increased the proton conductivity and the maximum proton conductivity was determined as 6.51x10-3 S/cm at 150 oC for PVPA-15hBN under anhydrous state. References 1. A. Pakdel, Y. Bando, D. Golberg, Chemical Society Reviews, 2014, 43, 934-959. 2. A. Pakdel, Y. Bando, D. Golberg, ACS Nano, 2014, 8, 10631-10639. 3. S. Madakbas, E. Cakmakcı, M.V. Kahraman, Thermochimica Acta, 2013, 552, 1-4. 4. M.S. Tutgun, D. Sinirlioglu, S.U. Celik, A. Bozkurt, Journal of Polymer Research, 2015, 22,

1-11. This work was supported by The Scientific and Technological Research Council of Turkey (TÜBİTAK) under contact number 112M488. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 48



PP-33

Preparation of Biopolymer/Fe-Silica Bio-nanocomposite via Sol-gel Method

Selcan Karakuş1, Tuba Şişmanoğlu1, Gülin Pozan Soylu2, Ezgi Tan1, Öykü Ürk1, Gizem Akdut1, Ayben Kilislioğlu1,*

1Department of Chemistry, Engineering Faculty, Istanbul University, Avcilar-Istanbul, Turkey 2Department of Chemical Engineering, Engineering Faculty, Istanbul University, Avcilar-Istanbul,

Turkey


Because of the huge demand to special properties, developing new nanocomposites are mainly preferred by researchers. Bio-nanocomposites are gained importance where mechanical, barrier and thermal stability is needed at the same time as bio-availability. In order to achieve successfully prepared bio-nanocomposites, type of the biopolymer and inorganic nano-filler are extremely important. In this work, CMC-Chitosan/Fe-Silica bio-nanocomposite has been prepared through the sol-gel method. In the first step silica particles are dispersed in an aqueous medium and than aqueous silica is added into the biopolymer matrix. X-ray diffraction (XRD), Scanning electron microscopy (SEM) and thermogravimetric Analysis (TGA) are used for morphological analysis and thermal stability of the synthesized CMC-Chitosan/Fe-Silica bio-nanocomposite. Finally the antibacterial activity of the new bio-nanocomposite has been studied by inhibition zone method against gram negative bacteria. References 1. H. Bar, D.K. Bhui, G.P. Sahoo, P. Sarkar, S. Pyne, A. Misra, Colloids and Surfaces A:

Physicochemical and Engineering Aspects, 2009, 348, 212–216. 2. S. Pandey, G.K. Goswami, K.K. Nanda, Carbohydrate Polymers, 2013, 94, 229–234. 3. H. Deng, X. Li, B. Ding, Y. Du, G. Li, J. Yang, Carbohydrate Polymers, 2011, 83, 973–978.




PP-34

Polymer/POSS Nanocomposites by Photochemical Routes

Mehmet Atilla Tasdelen, Irem Arslan, Recep Gorkem Sencevik Department of Polymer Engineering, Faculty of Engineering, Yalova University, 77100 Yalova,

Turkey


Nanocomposite materials based on incorporation of nano-sized inorganic particles into polymer matrices have been attracting much attention due to their markedly superior mechanical and thermal properties. Depending on the nanoscale dimension, nano-sized fillers are classified as one-dimensional (clays and graphites), two-dimensional (nanofibers, nanotubes, or whiskers) and three-dimensional (spherical silica, metal particles, polyhedral oligomeric silsesquioxanes (POSS), and semiconductor nanoclusters). Among them, POSS nanoparticles are three-dimensional oligomeric, organosilicon compounds with cage frameworks surrounded by functional groups on the periphery. The incorporation of POSS nanoparticles in a polymeric matrix can dramatically improve its mechanical properties (e.g., strength, modulus, rigidity) as well as reduce its flammability, heat evolution, and viscosity during processing. Photoinitiated polymerizations, which utilize light energy to initiate chain reactions to form polymer materials, offer a number of advantages compared to thermally initiated polymerizations. They can be conducted at room temperature, which is an outstanding advantage for both classical polymerization of monofunctional monomers and modern curing applications of di- and multifunctional monomers. The implementation of photoinitiated polymerization to hybrid network technology offers several significant advantages including ambient temperature cure, rapid cross-linking, direct contact to heat-sensitive substrates, and low or zero volatile organic compounds used during network formation. In this study, tertiary amine or azide functionalized POSS nanoparticles have been used for the preparation of polymer/POSS nanocomposites via photoinitiated polymerization. The effects of POSS nanoparticle concentration on the properties of the nanocomposites, such as thermal and morphological properties have been systematically investigated using transmission electron microscopy, differential scanning calorimeter and thermogravimetric analysis. References 1. R.G. Sencevik, M.A. Tasdelen, Polymer Composites, 2014, 35, 1614-1620. This work was financially supported by TUBITAK (Grant No: 112T528) and Yalova University Research Fund.




PP-35

Click Reaction of Azide-Alkyne Cycloaddition using Solid Supported Microporous Heterogeneous Copper (I)-Catalyst

Omer S. Taskin1,2, Sajjad Dadashi-Silab1, Baris Kiskan1, Yusuf Yagci1,3,* 1Department of Chemistry, Istanbul Technical University, 34469, Maslak, Istanbul, Turkey

2Department of Chemistry, Kirklareli University, Merkez, Kirklareli, Turkey 3Center of Excellence for Advanced Materials Research (CEAMR) and Department of Chemistry,

Faculty of Science, King Abdulaziz University, 21589, Jeddah, Saudi Arabia


A microporous polymer network1 was synthesized as a specific metal template unit and employed as a solid support to stabilize copper(I) ions (Cu(I)). The Cu(I) ions were incorporated into the SNW structure through coordinating with the nitrogen atoms present in the melamine structure. The obtained Cu(I) material showed a highly effective catalytic activity for copper(I)-catalyzed click reaction. Several azide and alkyne groups were used to carry out the click reaction under little catalyst amounts. Leaching tests verified the heterogeneity of the catalyst and more importantly, the material showed reusability under the same conditions without any substantial variation in its activity. All results display that the catalyst system is highly environmentally applicable in view of preparation, stability, selectivity and recovery for copper catalyzed reactions and industrial processes.

Figure 1. General demonstration of the solid supported click system. References 1. M.G. Schwab, B. Fassbender, H.W. Spiess, A. Thomas, X.L. Feng, K. Mullen, Journal of

American Chemical Society, 2009, 131, 7216-7217.




PP-36

Synthesis, Characterization and Antibacterial Activity of a Novel Bio-nanocomposite: CMC-Chitosan/Fe-Sepiolite

Selcan Karakuş1, Tuba Şişmanoğlu1, Gülin Pozan Soylu2, Öykü Ürk1, Ezgi Tan1, Gizem Akdut1, Ayben Kilislioğlu1,*

1Department of Chemistry, Engineering Faculty, Istanbul University, Avcilar-Istanbul, Turkey 2Department of Chemical Engineering, Engineering Faculty, Istanbul University, Avcilar-Istanbul,

Turkey

E-mail: [email protected] Researchers are focused on developing new nanocomposite materials with advanced properties such as antibacterial activity, mechanical, barrier and thermal stability. In order to achieve successfully prepared composite materials, the size of the nanoparticles and their dispersion into the polymer matrix are extremely important1-3. In this work, CMC-Chitosan/Fe-Sepiolite bio-nanocomposite has been synthesized through the well dispersion of inorganic phase within the organic matrix via solution based method. After the fine dispersion of sepiolite micro fibers into the biopolymer matrix the thermal stability of the composite material is reinforced. X-ray diffraction (XRD), Scanning electron microscopy (SEM) and thermogravimetric Analysis (TGA) are used for structural and thermal characterization of the synthesized CMC-Chitosan/Fe-Sepiolite bio-nanocomposite. Finally the antibacterial activity of the new bio-nanocomposite has been studied by inhibition zone method against Escherichia coli. CMC/Chitosan/Sepiolite/Fe demonstrated significant antibacterial effect. References 1. H., Bar, D.K. Bhui, G.P. Sahoo, P. Sarkar, S. Pyne, A. Misra, Colloids and Surfaces A:

Physicochemical and Engineering Aspects, 2009, 348, 212–216. 2. S. Pandey, G.K. Goswami, K.K. Nanda, Carbohydrate Polymers, 2013, 94, 229–234. 3. H. Deng, X. Li, B. Ding, Y. Du, G. Li, J. Yang, Carbohydrate Polymers, 2011, 83, 973–978. POLYCHEM2015-International Symposium on Polymers from Renewable Resources 52



PP-37

Visible Light-induced Copper(I)-catalyzed Azide-alkyne Cycloaddition with Zinc Oxide Semiconductor Nanoparticles

Ozde Yetiskin1,*, Sajjad Dadashi-Silab1, Sher Bahadar Khan2, Abdullah Muhammad Asiri2, Yusuf Yagci1

1Department of Chemistry, Istanbul Technical University, Maslak, Istanbul, 34469, Turkey 2Department of Chemistry and Center of Excellence for Advanced Materials Research

King Abdulaziz University, Jeddah, 21589, Saudi Arabia

E-mail: [email protected] In search of ever-newer and enduring forms of energy which can be obtained, for example, by converting the inexhaustible energy of sunlight to the chemical or electrical energy, semiconductor materials have emerged as potential solution for many energetic issues. In this work, we report a visible light-induced CuAAC strategy benefiting from the electron transfer reactions of ZnO NPs to achieve the required catalyst for CuAAC. We previously reported the use of such photocatalytic system in photoinitiated free radical and atom transfer radical polymerization, which is also similarly catalyzed by Cu(I) species.

Scheme 1. Visible light-induced CuAAC of different of azides and alkynes using zinc oxide nanoparticles as photocatalyst

References 1. C. W. Tornoe, C. Christensen, M. Meldal, Journal of Organic Chemistry, 2002, 67, 3057-3064.




PP-38

Novel Poly(arylene ether sulphone) Based Polymer Electrolyte Membranes for Direct Methanol Fuel Cell (DMFC) Applications

Esra Yılmaz Sincar, Erde Can Department of Chemical Engineering, Faculty of Engineering and Architecture, Yeditepe

University, Istanbul, Turkey


Fuel cells which are electrochemical devices that convert chemical energy to electrical energy are the most promising power sources in the future due to their high energy efficiency and environmental friendship. The most important component of a fuel cell is the proton exchange membrane (PEM). In this study, novel polymer electrolyte membranes based on sulfonated poly(arylene ether sulfone)s were prepared for direct methanol fuel cells (DMFC) which use methanol as the fuel. Common requirements for a polyelectrolyte membrane for DMFC applications include high proton conductivity, high chemical and mechanical durability, low methanol permeability at operation conditions and low cost. Thus in order to fullfill these requirements partially sulfonated poly(arylene ether sulfones) (PESS) (Degree of sulfonation≈ 60%) were prepared via the solution condensation polymerization of 4-fluoro phenyl sulfone, hydroquinone 2-potassium sulfonate and an excess of Bisphenol A. These poly(arylenethersulfone) based polymers were then methacrylated (PESSGMA) via reaction with glycidyl methacrylate and cross-linked and altered via radical polymerization with co-monomers such as styrene and vinyl-phosphonic acid to further reduce methanol permeability and swelling in water and also to improve thermal stability and mechanical properties. Membranes of the synthesized polymers were prepared via solution casting during their thermal cure. The chemical structures of the synthesized polymers were characterized via H1-NMR and FT-IR spectroscopic techniques and the proton conductivity, thermomechanical and thermal properties of the polymers were investigated using impedance spectroscopy, DMA, TGA and DSC methods respectively. Water uptake of the polymers were examined via swelling experiments, ion exchange capacities and methanol permeabilities of the resulting polymer membranes were also determined. Finally the effects of cross-linking and the introduction of the co-monomers on various properties of the polymer membranes were evaluated.



Documents

INTERNATIONAL SYMPOSIUM ON POLYMERS FROM RENEWABLE …polychem15.boun.edu.tr/POLYCHEM-2015-Abstract-Book.pdf · INTERNATIONAL SYMPOSIUM ON POLYMERS FROM RENEWABLE RESOURCES . May