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An overview of the methodologies to elucidate the microstructure of copolymers of ethylene and cyclic olefins through 13C Nuclear magnetic resonance (NMR) analysis is given. 13C NMR spectra of these copolymers are quite complex because of the presence of stereogenic carbons in the monomer unit and of the fact that chemical shifts of these copolymers do not obey straightforward additive rules. We illustrate how it is possible to assign 13C NMR spectra of cyclic olefin-based copolymers by selecting the proper tools, which include synthesis of copolymers with different comonomer content and by catalysts with different symmetries, the use of one- or two-dimensional NMR techniques. The consideration of conformational characteristics of copolymer chain, as well as the exploitation of all the peak areas of the spectra by accounting for the stoichoimetric requirements of the copolymer chain and the best fitting of a set of linear equation was obtained. The examples presented include the assignments of the complex spectra of poly(ethylene-co-norbornene (E-co-N), poly(propylene-co-norbornene (P-co-N) copolymers, poly(ethylene-co-4-Me-cyclohexane)s, poly(ethylene-co-1-Me-cyclopentane)s, and poly(E-ter-N-ter-1,4-hexadiene) and the elucidation of their microstructures.

cited By 2; International audience; Based on the heterogeneous nature of semi-crystalline terpolymer and the important role that interface polarization plays for dielectric and electromechanical response, small molecular plasticizer bis(2-ethylhexyl) phthalate (DEHP) was introduced into electrostrictive terpolymer to improve electromechanical performances of electrostrictive terpolymer P(VDF-TrFE-CTFE). As expected, the introduced DEHP contributes to greatly increased dielectric permittivity at low frequency, decreased Young's modulus and moderately reduced dielectric breakdown strength of terpolymers, which are closely related with the increased mobility of polymer chains caused by DEHP. Consequently, DEHP modified terpolymers exhibit well improved electromechanical performance in contrast with pure terpolymer. The evolution of electromechanical performances of modified terpolymer with DEHP loading, electric field and frequency was well investigated for actuator applications. © 2016 Elsevier Ltd. All rights reserved.

The development and availability of new protecting groups are vital for all branches of synthetic chemistry. Equally vital is the facile and selective removal of these groups, leaving intact other protecting groups which are to be cleaved later. Herein we demonstrate this concept of orthogonal deprotection by combining three different forms of protected methacrylic acid (MAA) in the same terpolymers. One of these protected monomers was 2-(pyridin-2-yl)ethyl methacrylate (PyEMA), recently developed by us, whose units can be readily converted to MAA units either under alkaline hydrolysis conditions or thermally. The second monomer was tetrahydro-2H-pyran-2-yl methacrylate (THPMA) which can be cleaved either via acidic hydrolysis or by thermolysis. The third form of protected MAA was benzyl methacrylate (BzMA) which can be subjected to hydrogenolysis. Two ABC triblock terpolymers based on all three of these monomers were successfully synthesized-one by reversible addition-fragmentation chain transfer (RAFT) polymerization and the other by group transfer polymerization (GTP)-thus proving the feasibility of these demanding three-stage syntheses via both polymerization methods. The molecular weight characteristics and compositions of the terpolymers were determined by gel permeation chromatography and proton nuclear magnetic resonance spectroscopy (1H NMR), respectively. Subsequently, the ABC triblock terpolymers were sequentially subjected to conditions of alkaline hydrolysis, acidic hydrolysis, and hydrogenolysis, leading to the selective cleavage of the PyEMA, the THPMA and the BzMA units, respectively, without affecting the remaining types of protecting groups, according to analysis using 1H NMR spectroscopy. Similarly selective was the acidic hydrolysis followed by alkaline hydrolysis. Thermal treatment at 130 °C of the terpolymers led to the conversion of both the PyEMA and the THPMA units to MAA units, without affecting the BzMA units, yielding amphiphilic diblock copolymers whose self-assembly properties in water were investigated. © 2015 American Chemical Society. 48 20 7503 7512 Cited By :8

International audience; Electro-active polymers (EAPs) such as P(VDF-TrFE-CTFE) was demonstrated to be greatly promising in the field of flexible sensors and actuators[1], but their low dielectric strength driven by ionic conductivity is main concern for achieving high electrostrictive performance. The well-known quadratic dependence of applied electric field on strain response as well as mechanical energy density highlights the importance of improving EAPs electrical breakdown while reducing the leakage current. This paper demonstrates that by controlling processing parameters of polymer synthesis and fabrication procedure, it is possible to drastically increase the electrical breakdown and decrease the ionic conductivity, giving rise to an enhancement in breakdown voltage of around 64% and a reduction in leakage current intensity of 73% at 30V/mu m. Effect of polymer crystallinity, molecular mass, as well as crystallization temperature on leakage current were also investigated.

This work describes the important effects of microstructural features on crystalline structure, mechanical behavior and molten state response for poly (propylene-co-1-pentene-co-1-heptene) terpolymers. The study was carried out in a wide range of compositions, varying the 1-pentene/1-heptene ratio and the thermal history applied. Molecular features, as propylene sequences and compositional triads, allow predicting the material behavior. Moreover, rheological response has demonstrated the influence of molecular weight, comonomer content and short-chain branches on the properties. The flow activation energy can justify the importance of the material density over the whole spectrum of properties., The financial support from project MAT2016-79869-C2-1-P (AEI/ FEDER, UE) is greatly acknowledged. Finally, we thank Ms. Mürüvvet Begüm Özen for her valuable experimental advices and Dr. Mahdi Abbasi for his helpful discussion

The mechanical response and crystalline structure have been analyzed in several propylene-co-1-pentene-co-1-hexene terpolymers. Different polymorphs are developed in these terpolymers depending on global comonomer content, 1-pentene:1-hexene ratio and thermal history. The trigonal δ crystal modification is observed in addition to monoclinic and orthorhombic crystallites and mesomorphic entities. For the terpolymers with higher comonomers contents, the mesophase and even the totally amorphous samples can be readily obtained at easily accessible cooling rates. Intensity and location of relaxation processes, values for storage and indentation modulus and hardness as well are found to be related to the type of crystallites and to the crystallinity. The variation of crystallinity upon the comonomer content is rather unusual when trigonal lattice is able to be developed if compared with that exhibited by other copolymers/terpolymers based on propylene. Because of the important effect of this variable on mechanical response and mobility within amorphous regions, relationships found in other mechanical parameters and in the relaxation associated with glass transition (location and intensity) are also uncommon. The presence of trigonal polymorph exerts a key role in those atypical dependences., The financial support from projects MAT2013-47972-C2-1-P and MAT2013-47972-C2-2-P (MINECO) and from project MAT2016-79869-C2-1-P (AEI/FEDER, UE) is greatly acknowledged. The synchrotron experiments were performed at beamline BL11-NCD at ALBA Synchrotron Light Facility with the collaboration of ALBA staff

Several Ziegler-Natta copolymers of iPP with ethylene or 1-butene, and terpolymers with both counits have been characterized, devoting special attention to the effect of composition and processing conditions on the crystal structure and final properties. DSC and X-ray diffraction were used to study the polymorphism of copolymers and terpolymers. Comonomer insertion interrupts the isotactic sequences, acting as a structural defect, and the formation of g form is enhanced. Moreover, crystallinity decreases and crystal structure is modified. Comonomer type and concentration determine the extent of these modifications, resulting in important changes in macroscopic properties. In particular, the excellent optical properties of the analyzed terpolymers make them very attractive for applications such as transparent film or packaging, The financial support of MINECO (projects CYTED 311RT0417 and MAT2016-79869-C2-1-P (AEI/FEDER, UE)), is gratefully acknowledged

High-molecular-weight (MW) symmetrical multiblock copolymers, based on the hydrophobic monomers styrene (Sty) and methyl methacrylate (MMA), and the more polar monomer, 2-vinyl pyridine (2VPy), were prepared using stepwise reversible addition-fragmentation chain transfer polymerization. All copolymers shared a common poly(ethylene glycol) (PEG) midblock, introduced as a bifunctional macromolecular chain transfer agent. In total, five ABA triblock copolymers, five ABCBA pentablock terpolymers, and two ABCDCBA heptablock quaterpolymers (comprising four different monomer types) were synthesized. The MWs of the multiblock polymers were determined using gel permeation chromatography (GPC) and proton nuclear magnetic resonance (1H NMR) spectroscopy, with the latter values being closer to the theoretically expected, whereas GPC MW distributions were relatively narrow, broadening with the number of blocks. The compositions of the synthesized polymers, as determined by 1H NMR spectroscopy, were also close to the expected values. Finally, films cast from chloroform solutions of the pentablock terpolymers P2VPy-b-PSty-b-PEG-b-PSty-b-P2VPy, PSty-b-PMMA-b-PEG-b-PMMA-b-PSty, and P2VPy-b-PMMA-b-PEG-b-PMMA-b-P2VPy examined using transmission electron microscopy exhibited PSty and PMMA cylinders (first two) and lamellae (third terpolymer). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4957–4965

In this study, seven thermoresponsive methacrylate terpolymers with the same molar mass (MM) and composition but various architectures were successfully synthesized using group transfer polymerization (GTP). These terpolymers were based on tri(ethylene glycol) methyl ether methacrylate (TEGMA, A unit), n-butyl methacrylate (BuMA, B unit), and 2-(dimethylamino)ethyl methacrylate (DMAEMA, C unit). Along with the more common ABC, ACB, BAC, and statistical architectures, three diblock terpolymers were also synthesized and investigated for the first time, namely (AB)C, A(BC), and B(AC); where the units in the brackets are randomly copolymerized. Two BC diblock copolymers were also synthesized for comparison. Their hydrodynamic diameters and their effective pKas were determined by dynamic light scattering (DLS) and hydrogen ion titrations, respectively. The self-assembly behavior of the copolymers was also visualized by transmission electron microscopy (TEM). Both dilute and concentrated aqueous copolymer solutions were extensively studied by visual tests and their cloud points (CP) and gel points were determined. It is proven that the aqueous solution properties of the copolymers, with specific interest in their thermoresponsive properties, are influenced by the architecture, with the ABC and A(BC) ones to show clear sol-gel transition.

o -Cresol–thiourea–formaldehyde terpolymer resin was synthesized through the condensation of o -cresol and thiourea with formaldehyde in the mole ratio 1:3:5 in the presence of 2 M hydrochloric acid as a catalyst. The resulting copolymer was characterized with IR and 1 H NMR spectral data. The average molecular weight of the resin was determined by Gel permeation chromatography. Thermal study of the resin was carried out to calculate the activation energy (Ea), enthalpy of activation (H ‡ ), entropy of activation (S ‡ ), free energy of activation (G ‡ ), and pre-exponential factor (A) of various steps of thermal decomposition of the terpolymer. The Dharwadkar and Kharkhanavala method has been used to calculate thermal activation energy and thermal stability. The chelation ion-exchange properties were also studied with the batch equilibrium method. The chelation ion-exchange properties of the copolymer was studied for Fe 3+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , Pb 2+ and Cd 2+ ions. The resin was proved to be selective chelating ion-exchange copolymer for certain metals. The study was carried out over a wide pH range and in media of various ionic strengths.

WOS: 000325096400099, Maleic anhydride-styrene-vinyl acetate (MA-S-VA) terpolymer was prepared. It was modified by ethylenediamine (EDA) and diethylenetriamine (DETA) in order to get cross-linked polymers bearing carboxyl and amine groups. They were shown as MA-S-VA-EDA and MA-S-VA-DETA, and used as an adsorbent for the removal of UO22+ from water. The characterizations of structures of all the polymers were performed by Fourier transform infrared. The adsorptive features of adsorbents were then investigated for UO22+ in view of dependency on ion concentration, temperature and kinetics. Experimentally obtained isotherms were evaluated with reference to Langmuir, Freundlich and Dubinin-Radushkevich models. The maximum monolayer adsorption capacity for UO22+ was found to be 0.58 and 2.56 mol kg(-1) for MA-S-VA-EDA and MA-S-VA-DETA, respectively. It is suggested that the new modified polymers prepared in our laboratory as new adsorbents for uranyl ions., Research Fund of Cumhuriyet University [F290], This work was supported by The Research Fund of Cumhuriyet University (Project No. F290).

Presence of planar, bulky heterocyclic pendant groups, attached to polymer chains, alters the thermal properties and, once gelled, they modify their rheological properties as well. The authors report generation of stiff gels coming from terpolymers containing 1,2,4-oxadiazolic pendant groups, obtained by chemical modification of commercial polyacrylonitrile. The gels formed in basic aqueous solutions were compared and the effect of substituents linked to the heterocycles on thermal stability and viscoelastic properties was also analyzed. The structural modifications were followed by FTIR. The potential use of these terpolymers as workover fluids is discussed. Fil: Vega, Isabel. Empresa de Servicios Especiales San Antonio Pride S.a.; Argentina Fil: Lamanna, Melisa Elsa. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina Fil: Fissore, Eliana Noemi. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Industrias; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: D'accorso, Norma Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina Fil: Rojas, Ana Maria Luisa. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Industrias; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina

The synthesis of new random poly(2,7-fluorenylene-vinylene)s was achieved by a Suzuki–Heck cascade polymerization reaction. The poly(fluorenylene-vinylene) base structure was modified by the regio-random incorporation of 1-cyano-2,5-phenylene as electron withdrawing unit (CN-PFV1) and its properties were compared with terpolymers also embodying 1,4-dioctyloxy-2,5-phenylene (CN-PFV2) or 3,6-N-octylcarbazole (CN-PFV3) as electron-donating moieties. Thermal analysis revealed a high thermal stability (Td > 389 °C) and the absence of glass transitions for all polymers. Cyclic voltammetry indicated a high electron affinity of the materials (2.96–3.21 eV) attributed to the presence of the cyano-containing comonomer. In dilute solutions, the copolymers showed a broad green fluorescence with quantum yields ranging from 0.42 to 0.79, while in the solid state, a relatively narrow emission centered at ∼ 560 nm, governed by the low-energy segments within the π-conjugated backbone, was observed. The electroluminescence properties of the materials were tested in OLED devices of ITO/PEDOT-PSS/CN-PFV1-3/Ca/Al or ITO/PEDOT-PSS/CN-PFV1-3/Alq3/Ca/Al configurations, showing a bright green-yellow emission that, in the case of CN-PFV2, reached 1403 cd/m2 with efficiencies as high as 0.13 cd/A. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6051–6063, 2008

Group transfer polymerization was employed for the preparation of six amphiphilic terpolymer networks comprising the hydrophilic, pH-responsive 2-(dime- thylamino)ethyl methacrylate (DMAEMA), the neutral hydrophilic methoxy hexa (ethylene glycol) methacrylate (HEGMA), and the hydrophobic n-butyl methacrylate (BuMA). 1,4-Bis(methoxytrimethylsiloxymethylene)cyclohexane was used as a bifunc- tional initiator, whereas ethylene glycol dimethacrylate served as the crosslinker to interconnect the linear terpolymer precursors to three-dimensional terpolymer net- work structures. Five of the terpolymer networks were model, with linear chains between crosslinks of precise length. Four of the five model networks were based on ABCBA pentablock terpolymers with theoretical structure DMAEMA5-b-BuMAn/2-b- HEGMA10-b-BuMAn/2-b-DMAEMA5 with n values equal to 5, 10, 20, and 30. The model network based on the equimolar statistical terpolymer and the nonmodel ran- domly crosslinked terpolymer network were also prepared. The molecular weights and compositions of the linear pentablock terpolymer precursors to the networks were found to be close to the theoretically expected, while the network sol fractions were found to be relatively low. The degrees of swelling of the networks in water were found to decrease with increasing the hydrophobic content, whereas those in THF exhibited the opposite trend. Small-angle neutron scattering in deuterium oxide indicated structural organization in the most hydrophobic pentablock terpolymer net- works. V C 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4420-4432, 2008

Polimerlerde oksidasyon ısı, ışık, oksijen, basınç gibi birden çok etkenin varlığında kolaylıkla başlayabilen ve müdahale edilmediği sürece devam ederek polimerlerin kimyasal, fiziksel ve mekanik özelliklerinin bozulmasına yol açan, kullanım ömrünü kısaltan ve okside olmuş polimer ile temas eden canlı hücrelere zarar veren reaksiyonlardır. Bu nedenle polimer endüstrisinde oksidasyon problemleriyle çok sık karşılaşılmaktadır. Günümüz teknolojisinde geliştirilen katkı maddeleri ile oksidasyon kaynaklı problemler en aza indirilmiş olsa da, alternatif kaynaklara yönelim ile birlikte ve doğal kaynaklı antioksidan bileşiklerine olan ilgi de giderek artmaktadır. Düşük Yoğunluklu Polietilen (AYPE) ve Akrilonitril Bütadien Stiren (ABS) terpolimeri, plastik endüstrisinde oldukça yüksek miktarlarda kullanılan hammaddelerdir. Bununla birlikte doğal kaynaklara olan eğilimin artışıyla doğal kaynaklı bir polimer olan Poli(laktik asit)'in (PLA) kullanımı da giderek artmıştır. Poli(laktik asit) son yıllardaki teknolojik gelişmeler ile birlikte sıklıkla kullanılan ve biyomedikal uygulamalarda biyouyumluluk nedeniyle tercih edilen bir polimerdir. AYPE, ABS ve PLA, diğer polimerler gibi oksidasyon etkisi altında kullanım ömürleri azalan malzemelerdir. Antioksidan özellik içeren kimyasallar, serbest radikallerin zararlı etkilerini, yapılarındaki fazla elektronları vererek sönümleyebilen bileşiklerdir. Bu nedenle antioksidanlar hem insanlar için sağlıklı bir besin kaynağı, hem de polimerler için bir katkı maddesi olarak kullanılmaktadır. Bilimsel çalışmalarda alternatif antioksidanlara ve genel eğilime bağlı olarak da biyolojik esaslı antioksidanlara, düşük maliyet ve biyo-uyumluluk özellikleri nedeniyle ilgi artmaktadır. Bu çalışmada laboratuvarda sentezlenen fosfor bileşikleri ile biyo-kaynaklı bileşikler antioksidan katkısı olarak seçildi ve ticari antioksidan bileşikleriyle karşılaştırmalı performans değerlendirmeleri yapıldı.Örneklerin hazırlanması için 16 mm vida çapı ve L/D oranı 35 olan eş yönlü çift vidalı ekstruder, uygun vida hızı ile uygun kovan ve kalıp sıcaklığı ile kullanılmıştır. Hazırlanan örneklerin antioksidan performansları, Diferansiyel Taramalı Kalorimetre (DSC) kullanılarak Oksijen Indükleme Süresi (OIT) analizi ile belirlendi. Ayrıca bileşiklerin mekanik özellikler üzerindeki etkilerini incelemek için uzama ve çekme dayanım testleri de örnekler üzerine uygulandı. Oxidation process is a very powerful chemical reaction presence of heat, light, oxygen and pressure that produce harmful free radicals can damage to the cells in living organism or the chains and can deterioration physical, mechanical and chemical properties in all polymer matrices. Therefore, polymer oxidation problems are being encountered frequently in polymer industry. Low density polyethylene (LDPE) and acrylonitrile butadiene styrene (ABS) terpolymer are the raw materials which used in relatively high amounts in the plastic industry. However, with the increasing trend for using natural recources, it is increasing the use of natural sourced Poly(lactic asit). Polylactic acid (PLA) is often used in conjunction with technological advances in recent years, and it is the preferred polymer due to its biocompatibility in biomedical applications. Life times of LDPE, ABS, and PLA decreases under oxidation effect like other polymers.Polylactic acid (PLA) is a commonly used material in polymer applications recent years. In order to prevent of devastating effect of oxidation reactions, antioxidants were performed a very important role in both living organisms and polymers.Antioxidants can scavenge free radicals by donating electrons to them and changing harmless forms. Hence antioxidants are widely used both in dietary supplements for humans and in additives for polymers. Studies on more effective, economic and bio-based antioxidants were drew interest due to provide desired effects. In this study lab-synthesized various phosphorous compounds and bio-based compounds were investigated as antioxidant. Different commercial type of antioxidants were also used for comparison of performances in polymers. Preparation of samples were achieved by using co-rotating intermeshing twin screw extruder (16 mm, L/D ratio:35) under constant suitable rate at suitable temperature profile according to melting and degradation points of polymers.Antioxidant performances of all compounds were evaluated by determination of oxygen induction times (OIT) of obtained homogenous, well mixed samples with DSC equipment. Mechanical test such as tensile strenght and elongation test were also performed in order to expose of effects of antioxidant additives to mechanical properties. 91

Eight isomeric networks based on equimolar terpolymers were synthesized using group transfer polymerization (GTP) and were characterized in terms of their swelling properties. Two hydrophilic monomers, the nonionic methoxy hexa(ethylene glycol) methacrylate (HEGMA) and the ionizable 2-(dimethylamino)ethyl methacrylate (DMAEMA), and a hydrophobic (nonionic) monomer, methyl methacrylate (MMA), were employed for the syntheses. 1,4-Bis(methoxytrimethylsiloxymethylene)cyclohexane (MTSMC) was used as the bifunctional GTP initiator, while ethylene glycol dimethacrylate (EGDMA) served as the cross-linker. Seven of the networks were model networks, six of which were based on the symmetrical pentablock terpolymers ABCBA, ACBCA, BACAB, BCACB, CBABC, and CABAC, whereas the seventh model network was based on the statistical terpolymer. The eighth network was a randomly cross-linked network based on the statistical terpolymer, prepared by the simultaneous quaterpolymerization of the three monomers and the cross-linker. The molecular weights and molecular weight distributions of the linear pentablock terpolymer precursors, as well as those of their homopolymer and ABA triblock copolymer precursors, were characterized by gel permeation chromatography (GPC in tetrahydrofuran. The sol fraction of each network was measured and found to be relatively low. The aqueous degrees of swelling of all networks were found to increase at acidic pH due to the ionization of the DMAEMA tertiary amine units. The acidic degrees of swelling of the pentablock terpolymer networks were lower than those of their statistical counterparts due to microphase separation in the former type of networks, also confirmed by thermodynamic calculations and small-angle neutron scattering experiments. © 2007 American Chemical Society. 8 5 1615 1623 Cited By :33

Four linear and four star equimolar terpolymers based on non-ionic hydrophilic methoxy hexa(ethylene glycol) methacrylate, ionizable hydrophilic 2-(dimethylamino)ethyl methacrylate and neutral hydrophobic methyl methacrylate were synthesized using group transfer polymerization and investigated in aqueous dilute solutions. It was found that the (ABC)n multi-arm star terpolymers formed unimolecular micelles comprising three centrosymmetric compartments. The position of each compartment could be determined by the block sequence (ABC, ACB or BAC) atwill. On the other hand, the ABC linear counterparts formed loose associates with very low aggregation numbers. It was shown that the polymer architecture (linear versus star) greatly affected the micellization phenomena of the terpolymers in selective media. © 2007 WILEY-VCH Verlag GmbH & Co. KCaA. 28 5 560 566 Cited By :26

The multiarm star-shaped ABC triblock terpolymers of the (ABC)n type and their linear counterparts were synthesized by group transfer polymerization (GTP). The linear and star ABC triblock and statistical terpolymers as well as their homopolymer, diblock and triblock terpolymer precursors were characterized by gas permeation chromatography (GPC) in terms of their molecular weight distributions (MWD). The synthesis was performed using sequential GTP of three monomers and the cross-linker. The synthetic procedure for the preparation of the ABC star terpolymer with structure DMAEMA10-b-HEGMA10-b-MMA10-star was presented. The star terpolymers were soluble in water, exhibiting cloud points from 55 to 77°C. 38 3 1021 1024 Cited By :14

Four isomeric terpolymers based on benzyl methacrylate (BzMA, nonionic hydrophobic), 2-(dimethylamino)ethyl methacrylate (DMAEMA, ionizable hydrophilic), and methoxyhexa(ethylene glycol) methacrylate (HEGMA, nonionic hydrophilic) were synthesized using group transfer polymerization (GTP). The three of the terpolymers were the ABC block sequence isomers, ABC, ACB, and BAC, and the fourth was the statistical terpolymer. Their theoretical molecular weight was 5000 g mol-1, and the theoretical w/w composition was 33% from each monomer. The success of the synthesis was confirmed by gel permeation chromatography (GPC), which showed that the experimental molecular weights were in reasonable agreement with the theoretical ones and the polydispersity indices were low (in most cases Cited By :17

Bu çalışmada, poli(2,2'–(m-fenilen)-5,5'-bibenzimidazol) (PBI), poli(2,5-benzimidazol) (ABPBI), poli(2,2'-(m-fenol)5,5'-bibenzimidazol) (PBIOH), farklı PBI terpolimerler, ZnO nanopartiküller ve HDTMA ile modifiye edilmiş montmorillonit (OMMT)'in katkı maddesi olarak kullanıldığı polisülfon (PSf) kompozit membranlar hazırlandı. Çeşitli oranlarda katkı içeren bu kompozit membranların yapı, morfoloji, performans ve kirlenme direnci özellikleri, IR, TG, DSC, SEM teknikleri ve çapraz akış ultrafiltrasyon testleri ile incelendi. Kompozit membranların, ham PSf membrana göre daha su sever, daha yüksek akış ve dışlama performansına sahip ve daha yüksek kirlenme dirençli olduğu görüldü.Yüksek oranlarda inorganik katkı içeren membranlar haricindeki tüm kompozit membranların, ham PSf membrana göre, sırası ile %40 ve %12 seviyelerine kadar daha gözenekli ve daha yüksek denge su içeriğine sahip oldukları belirlendi. Ham PSf membran için 69,6° olan temas açısının, PBI, PBIOH, ABPBI, terpolimer, OMMT ve ZnO katkılarının eklenmesi sonrasında, sırasıyla 51, 25, 38, 53, 28 ve 55°'ye düştüğü görüldü. Membranların saf su akışları, PBI, PBIOH ve ABPBI organik katkıları ile sırasıyla yaklaşık 1,6, 2,3 ve 2,0 kat daha yüksek hale geldi. İnorganik katkılı membranların saf su akışları, %0,5 oranına kadar artı, daha yüksek katkı oranlarında ise azaldı. BSA dışlama performansı, ham PSf membran için ~%36, PBI, PBIOH, ABPBI, terpolimer, OMMT ve ZnO katkılı membranlar için ise sırasıyla %69, 78, 59, 83, 62 ve 77 olarak belirlendi. Ayrıca, BSA dışlamasının pH'a bağımlı olduğu belirlendi. %1 PBI katkılı kompozit membranın akış geri kazanım oranı %94'tür ve bu sonuç, ham PSf membrana ait sonuçtan %20 daha yüksektir. In this study, polysulfone composite membranes were prepared by using poly(2,2'-(m-phenylene)-,5'-bibenzimidazole) (PBI), poly(2,5-benzimidazole) (ABPBI), poly(2,2'- (m-phenol)5,5'-bibenzimidazole) (PBIOH), different PBI terpolymers, ZnO nanoparticles and montmorillonite modified with HDTMA (OMMT) as additive. The structure, morphology, performance and fouling resistance of membranes containing additives in various ratios were investigated by using IR, TG, DSC, SEM techniques and cross-flow ultrafiltration tests.It was observed that the composite membranes had higher hydrophilicty, flux, rejection performances and higher fouling resistant than pristine PSf membrane.It was determined that all the composite membranes except for containing large amounts of inorganic additives had higher porosity and equilibrium water content about 40% and 12% respectively. It was observed that the contact angle of pristine PSf membrane which was 69.6°, decreased to 51, 25, 38, 53, 28 and 55° after addition of PBI, PBIOH, ABPBI, terpolymer, OMMT and ZnO, respectively. The pure water fluxes of membranes became higher about 1.6, 2.3 and 2.0 times with PBI, PBIOH and ABPBI additives, respectively. The pure water fluxes of inorganic embedded membranes increased up to the additive amount of 0.5% and then decreased at higher additive ratios. The BSA rejection performances were determined ~36% for pristine PSf membran and 69, 78, 59, 83, 62 and 77% for the PBI, PBIOH, ABPBI, terpolymer, OMMT and ZnO embedded membranes, respectively. Also, pH dependence of BSA rejection was determined. The flux recovery ratio of 1% PBI embedded PSf composite membrane was 94% and it was higher about 20% than pristine PSf membran's result. 157

Various types of ethylene-propylene-diene terpolymers (EPDM) and crosslinking procedures have been investigated with pervaporation, vapor sorption, liquid sorption and gas permeation experiments. The EPDM parameters that have been changed are ethylene content, molecular weight, choice of third monomer, type of branching and various crosslinking procedures. The permeability coefficients were determined from pervaporation experiments and were about 40,000 Barrer for toluene and 700 Barrer for water. However, from vapor sorption measurements, a value of 22,000 Barrer for toluene was obtained which is somewhat lower. It should be realized that these data can only be compared qualitatively; the permeabilities obtained from sorption isotherms are derived data while in case of the pervaporation experiments it is experimentally measured. There is an indication that toluene behaves independently from water but the presence of toluene does influence the water flux during pervaporation. Gas permeation experiments resulted in permeabilities for CO2, O2 and N2 of 120, 24 and 11 Barrer, respectively. No clear differences were found for both EPDM-variation and different crosslinking procedures. © 2001 Published by Elsevier Science B.V.

Ordered planar morphologies in A-b-(B-b-A)(2)-b-C and (B-b-A)(2)-b-C terpolymer melts are studied within the framework of the self-consistent field theory for volume fractions of components A, B, and C in the ratio 1: 1: 2 and the Flory-Huggins interaction parameters satisfying chi(AB) = 2 chi(AC). The stable phases turn out to be the disordered, hexagonal, parallel lamellar-in-lamellar L-parallel to (including the simple lamellar) as well as non-shifted and shifted (L-perpendicular to and SL perpendicular to) perpendicular lamellar-in-lamellar morphologies. Depending on the value of the ratio r = Theta(AB)/Theta(BC), where Theta is a characteristic temperature of the units involved, different sequences of phase transitions are shown to occur. The hexagonal phase is characteristic for r congruent to 1. The L-perpendicular to and SL perpendicular to morphologies occur at weak and intermediate segregations whereas the L-parallel to morphology appears for stronger degrees of segregation. For (B-b-A)(2)-b-C a reduction in r favors the shifted SL perpendicular to phase over the non-shifted L-perpendicular to one, whereas for A-b-(B-b-A)(2)-b-C we find re-entrant phase transitions SL perpendicular to - L-perpendicular to. The physics determining the particular phase behavior is discussed. (C) 2013 AIP Publishing LLC.

We report the design, production and characterization of a biosynthetic asymmetric triblock copolymer which consists of one collagen-like and one cationic block spaced by a hydrophilic random coiled block. The polymer associates into micelles when a polyanion is added due to the electrostatic interaction between the cationic block and the polyanion. The collagen-like block self-assembles into thermo-responsive triple helices upon cooling. When both end blocks are induced to self-assemble, a physical gel is formed via thermo-responsive association of the charge-driven micelles. The self-assembly of both end blocks and the effects of salt and temperature thereon were characterized by light scattering and rheology.

The synthesis and aggregation behaviour in aqueous media of novel amphiphilic poly(ethylene oxide)- block-poly(n-butyl acrylate)-block-poly(acrylic acid) (PEO–PnBA–PAA) triblock terpolymers were studied. Terpolymers composed of two highly asymmetric hydrophilic PEO (113 monomer units) and PAA (10–17 units) blocks, and a longer soft hydrophobic PnBA block (163 or 223 units) were synthesized by atom transfer radical polymerisation (ATRP) of n-butyl acrylate and tert-butyl acrylate (tBA), followed by selective hydrolysis of the PtBA blocks. These terpolymers are not directly soluble in water but form defined spherical micelles by employing the dialysis method as confirmed by dynamic light scattering (DLS) and cryogenic transmission microscopy (cryo-TEM). Based on terpolymer architecture and composition, a three-layered micellar structure comprising a PnBA core, a PEO/PAA middle layer, and a PEO outer layer is suggested. The micelles do not dissociate to very low concentrations and, therefore, are promising candidates for long-circulating drug delivery systems. Further, as evidenced by high-performance liquid chromatography (HPLC), the micelles can load and release, without burst effect, the hydrophobic drug paclitaxel.

International audience; Thermo Stimulated Current and Dynamic Dielectric Spectroscopy have been applied to investigate dielectric relaxation modes of poly(vinylidene-fluoride trifluoroethylene) copolymer and poly(vinylidene-fluoridetrifluoroethylene-chlorofluoroethylene) terpolymer. The aim of this work is to check the molecular origin of the ferroelectric relaxor behavior of the terpolymer. The combination of data obtained by both dielectricmethods allows us to describe themolecular mobility of the amorphous phase and the cooperativity of the order/disorder dipolar transition in the crystalline phase. The introduction of 1,1-chlorofluoroethylene units in the main chain induces an increase of the Cooperative Rearranging Region size associatedwith less ordered and smaller crystallites. This morphological evolution is responsible of a lack of cooperativity and it explains the dielectric relaxor behavior of the poly(vinylidene-fluoride-trifluoroethylene-chloroethylene) terpolymer.

Bu tez çalışmasında, vinil ferrosen (VFc), metil metakrilat (MMA) ve dimetilaminoetil metakrilat (DMAEMA) monomerlerinin farklı besleme oranlarındaki terpolimerleri, ?,?'-Azoizobutironitril (AIBN) başlatıcısı varlığında, 65?C'de, 1,4-Dioksan çözücüsünde, serbest radikalik polimerizasyonu yöntemi ile hazırlandı. Sentezlenen polimerler 1H-NMR, FT-IR, GPC, DSC, TGA, CV, UV-Vis ve Floresans Spektroskopisi teknikleri ile analiz edildi.Daha sonra, kolloidal, trioktilfosfin oksit (TOPO) liganda sahip CdSe-TOPO kuantum dot (KD) sentezlendi ve hazırlanan polimerlerle ligand değişimi sağlanarak polimer-kuantum dot nanokompozit malzeme elde edildi. CdSe-TOPO ve polimer kaplı CdSe yapılarının yapı ve boyut analizi TEM tekniği ile gerçekleştirildi. UV-Vis, Floresans Spektroskopisi ile optik özellikleri incelendi. KD ve Ferrosen molekülleri arasındaki etkileşim CV tekniği ile araştırıldı. Son olarak, güneş pili uygulamaları gerçekleştirilerek, Ferrosen ve KD arasındaki etkileşim ayrıca ispat edildi. The terpolymers of vinyl ferrocene (VFc), methyl methacrylate (MMA) and dimethylaminoethyl methacrylate (DMAEMA) monomers, with various ratios in feed, were synthesized by free radical polymerization in the presence of ?,?'-Azoisobutyronitrile (AIBN), in 1,4-Dioxane at 65?C. The synthesized polymers were characterized by 1H-NMR, ATR-IR, GPC, DSC, TGA, CV, UV-Vis and Florescence Spectroscopy techniques.Later, colloidal CdSe quantum dot, having trioctylphosphine oxide (TOPO) ligands, was synthesized and polymer-quantum dot nanocomposites were obtained by ligand exchange reaction. The structural and dimensional properties of CdSe-TOPO and polymer coated CdSe were analyzed by TEM technique and its optical properties were examined by means of UV-Vis and Florescence Spectroscopy. The relationship between Quantum dot and ferrocene was investigated by using CV. Finally, the effect of ferrocene on the photovoltaic properties of the nanocomposites was further proved through performing solar cell applications. 60

Vapor–liquid equilibrium data were determined for five polymer + toluene systems at isothermal conditions between 333.15 and 373.15 K. Polymers comprise copolymers and terpolymers of octadecyl acrylate (ODA), acrylic acid (AA), styrene (St), and 1-vinyl-2-pyrrolidone (VP) because of their practical importance as flow improvers for crude oil and/or derivatives. The need to measure these systems has emerged because relevant phase equilibrium data are not available in literature. All-glass micro-ebulliometer with circulation of liquid phase was used for measurement of total pressure over polymer + toluene mixtures, as described in our earlier study.1 To analyze the obtained data, we opted for the prediction of phase behavior, as the data of two experimental points, including concentration end points, could not be reduced with use of the UNIQUAC equation, as is e.g. in the Polymer Solution Data Collection by Hao et al.2 We used two predictive models, the Entropic-FV activity coefficient model3 and the GC-Flory EOS model, 4 to estimate the activity of toluene in a mixture with a polymer. Both models are based on the group contribution method. Two terpolymers, namely poly(ODA0.79–AA0.11–VP0.10) and poly(ODA0.82–St0.05–AA0.13) in mixtures with toluene were chosen as examples of solvent activity predictions, because values of all necessary group parameters for both models were at hand. Figures 1 and 2 show the prediction of toluene activities in both the terpolymer solutions, respectively. It is obvious that the models are mutually comparable and in a good agreement. Moreover, the dependence of solvent activity on concentration provides a qualitative description of particular system behavior over the whole concentration range including activity trends, since the prediction is based on group contributions, which comprises the structure of components involved. It is necessary to point out, that prediction procedures were not used for validation of experimental data, but to give an idea about the trend in activity vs. concentration dependence. As it can be seen, good agreement with experimental data was achieved. Figure 1. Activity of toluene in poly(ODA0.82–St0.05–AA0.13) at 363.15 Figure 2. Activity of toluene in poly(ODA0.79–AA0.11–VP0.10) at 353.15 K. References: 1. J. Pavlíček, G. Bogdanić and I. Wichterle, Fluid Phase Equilib., 2010, 297 (1), 142–148. 2. W. Hao, H. S. Elbro and P. Alessi, Polymer Solution Data Collection. 1: Vapor–liquid Equilibrium, Chemistry Data Series XVI, Part 1, DECHEMA: Frankfurt/M., 1992. 3. G. M. Kontogeorgis, Aa. Fredenslund and D. P. Tassios, Ind. Eng. Chem. Res., 1993, 32 (2), 362–372. 4.G. Bogdanić and Aa. Fredenslund, Ind. Eng. Chem. Res. 1994, 33 (5), 1331–1340.

International audience; The synthesis of poly(VDF-ter-TFMA-ter-HFP) terpolymers (where VDF, TFMA, and HFP stand for vinylidene fluoride, alpha-trifluoromethacrylic acid, and hexafluoropropylene, respectively) and their blends with silica filler for preparing original fluorocomposites are presented. First, the radical terpolymerization of VDF, TFMA, and HFP by iodine transfer polymerization without any surfactant was investigated in the presence of 1,6-diiodoperfluorohexane as the chain transfer agent. TFMA monomer was well incorporated, and the terpolymers were obtained in good yields (>65%). The microstructures of the produced terpolymers were characterized by 1H and 19F NMR spectroscopy to assess the amounts of each comonomer, the molecular weights, and the nature of the end groups of the copolymers. Molar percentages of VDF, TFMA, and HFP were in the 45-80, 12-53, and 1-8 ranges, respectively, whereas the molecular 22 weights of the resulting terpolymers were ca. 5400-12 600 g 3 mol-1. End groups were VDF-I only with a high amount of CH2CF2-I. Then, these poly(VDF-ter-TFMA-ter-HFP) terpolymers were involved in the preparation of the fluorinated polymers/silica nanocomposites by sol-gel reactions in the presence of tetraethoxysilane and silica nanoparticles under alkaline and acidic conditions, respectively. Interestingly, poly(VDF-ter-TFMA-ter-HFP) terpolymer/silica nanocomposites, which were prepared under alkaline conditions, showed exceptional thermal properties because they were found to exhibit almost no weight loss up to 800 C.

International audience; Hybrid organic/inorganic membranes that include a functionalized (-SO3H), interconnected silica network, a non-porogenic organic matrix, and a -SO3Hfunctionalized terpolymer are synthesized through a sol–gel-based strategy. The use of a novel crosslinkable poly(vinylidene fluoride-ter-perfluoro(4- methyl-3,6-dioxaoct-7-ene sulfonyl fluoride)-ter-vinyltriethoxysilane) (poly(VDF-ter-PFSVE-ter-VTEOS)) terpolymer allows a multiple tuning of the different interfaces to produce original hybrid membranes with improved properties. The synthesized terpolymer and the composite membranes are characterized, and the proton conductivity of a hybrid membrane in the absence of the terpolymer is promising, since 8mS cm1 is reached at room temperature, immersed in water, with an experimental ion-exchange-capacity (IECexp) value of 0.4 meq g1. Furthermore, when the composite membranes contain the interfaced terpolymer, they exhibit both a higher proton conductivity (43mS cm1 at 65 -C under 100% relative humidity) and better stability than the standard hybrid membrane, arising from the occurrence of a better interface between the inorganic silica and the poly[(vinylidene fluoride)- co-hexafluoropropylene] (poly(VDF-co-HFP)) copolymer network. Accordingly, the hybrid SiO2-SO3H/terpolymer/poly(VDF-co-HFP) copolymer membrane has potential use as an electrolyte in a polymer-electrolytemembrane fuel cell operating at intermediate temperatures.

International audience; Well-defined block copolymers composed of a rigid poly(gamma-benzyl-L-glutamate) (PBLG) sequence and a poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) block were synthesized by Huisgen's 1,3-dipolar cycloaddition (click chemistry) from homopolymers containing azide and alkyne functionalities. These functional groups were introduced in the alpha-position of both PBLG and PDMAEMA precursors using appropriate alpha-omega-functionalized initiators to trigger the living/controlled polymerization of the corresponding monomers. Both alpha-alkyne- and alpha-azido-PBLGs were synthesized by ring-opening polymerization of gamma-benzyl-L-glutamate N-carboxyanhydride at room temperature from amino-containing alpha-alkyne and alpha-azide difunctional initiators, using dimethylformamide as solvent. As for alpha-alkyne-PDMAEMA and alpha-azido-PDMAEMA, they were obtained by copper-mediated atom transfer radical polymerization of 2-(dimethylamino)ethyl methacrylate at 60 degrees C in tetrahydrofuran as solvent. The copper(I)-catalyzed 1,3-dipolar cycloaddition coupling reactions of the alpha-azido-PBLG with the alpha-alkyne-PDMAEMA, in the one hand, and of the alpha-alkyne-PBLG with the alpha-azido-PDMAEMA, on the other hand were conveniently performed in DMF, affording the targeted PBLG-b-PDMAEMA diblock copolymers. Removal of the residual PDMAEMA used in slight excess was facilitated by the retention of this homopolymer onto the stationary phase of the column chromatography. On the basis of size exclusion chromatography, IR and NMR analyses, click chemistry was found to be quantitative, yielding for the first time hybrid diblock copolymers based on a polypeptide and a vinylic polymer.

El objetivo de este trabajo consistió en la modificación sintética de polímeros comerciales para obtener nuevos materiales, con potencial aplicación como fluidos de fractura y/o tapones temporarios. Debido a los usos específicos, estos polímeros deben cumplir con ciertos requisitos de solubilidad, viscosidad y estabilidad térmica. Por lo tanto, la caracterización espectroscópica, térmica y reológica fueron también objetivos importantes. Se sintetizaron a partir de poliacrilonitrilo, terpolímeros con anillos de 1,2,4-oxadiazólicos y 1,3,4-oxadiazólicos como sustituyentes. Se observó que los distintos sustituyentes alteraban las estabilidades térmicas de estos nuevos terpolímeros y su comportamiento reológico en solución. Asimismo, a partir de poliacrilamida se sintetizaron copolímeros, con sustituyentes 1,3-oxazólicos, a diferentes grados de conversión. En este caso, el que mayor viscosidad desarrolló fue el correspondiente a dos horas de conversión y permite suponer que estos geles tienen potencial aplicación como tapones temporarios. Se modificaron poliacrilonitrilo y poliacrilamida por transformación de los productos de su hidrólisis en anillos heterocíclicos para obtener terpolímeros que contuvieran en su estructura grupos sustituyentes 1,3-oxazólicos y benzoimidazólicos. Finalmente, y con el objetivo de desarrollar otro tipo de geles físicos, se entrecruzaron alcohol polivinílico con un colorante azoico como el rojo congo. Se obtuvieron geles cuyas propiedades reológicas resultaron ser muy comparables con la de los geles de goma guar-bórax., sistema más comúnmente utilizado en la industria del petróleo. The main objective of this thesis was the chemical modification of commercial homopolymers, to obtain new materials to be applied as fracturing fluids and temporary blocking gel. Due to the specific uses planned for these new polymers, they must comply with some requirements of solubility, viscosity and thermal stability. Thus, spectroscopical and thermal characterizations as well as rheological properties evaluation were also important objectives sought in this thesis. Terpolymers containing 1,2,4-oxadiazole or 1,3,4-oxadiazole pendant groups in their backbone were synthesized from polyacrylonitrile. Due to the difference in the heteroatoms position, thermal stability as well as their rheological behavior in solution were altered. On the other hand, copolymers obtained from polyacrylamide with 1,3-oxazole pendant groups on the backbone were synthesized. Again, the rheological properties were conversion time dependant. In this case, two hours conversion time copolymer developed the highest viscosity value when it was gelled in basic media. These high viscosities were maintained along extended periods of time having potential application as temporary plug gels. Then, poliacrylamide and polyacrylonitrile were hydrolyzed. The hydrolysis products were modified subsequently to obtain pendant heterocyclic rings in the copolymers. Thus, 1,3-oxazole and benzimidazole pendant groups were synthesized respectively. Finally, we worked on the development of physical gels, similar to those gels traditionally used in the oil field. In this particular case, polyvinyl alcohol was crosslinked with congo red, an azoic dyer, to generate physical gels whose rheological properties resembled to guar gum-borax gels. Fil: Vega, Isabel Natalia. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina.

International audience; Oligocaprolactone macromonomers functionalized with vinyl ether have been synthesized by polymerization of ε-caprolactone in the presence of hydroxy ethyl or butyl vinyl ether and characterised by NMR and Maldi time-of-flight mass spectroscopy. These macromonomers have been copolymerized with maleic anhydride and N-vinyl pyrrolidone to give terpolymers, which have been used to obtain nanoparticles by the phase-separation-dialysis method. Previously dissolving indomethacin in the terpolymer solution allows one to encapsulate the drug inside the nanoparticles.

The structure of three different ABC triblock star terpolymers in aqueous solution has been investigated by small-angle x-ray scattering (SAXS). The form factor was modeled using an analytical expression for a Gaussian homopolymer star since the SAXS data were not sensitive to the electron density differences between blocks. The interparticle structure factor could be described by the hard sphere model. The radius of gyration of the stars is obtained by modeling of the SAXS data. The overall size of the stars is sensitive to the degree of hydrophobicity of the block located in the center of the star. The dimensions of the starblock terpolymers are compared with those obtained from light-scattering experiments. 43 B 1 43 57 Cited By :2

ÖZET Yüksek Lisans Tezi ALLİL FENİL ETER-MALEİK ANHİDRİT-STİREN TERPOLİMERİ VE EPOKSİ REÇİNESİ TEMELİNDE HAZIRLANAN YAPIŞTIRICILARIN İNCELENMESİ Melike KIROĞLU Cumhuriyet Üniversitesi Fen Bilimleri Enstitüsü Kimya Mühendisliği Ana Bilim Dalı Danışman: Yrd. Doç. Dr. Elçin EKBEROV Bu çalışmada, allil fenil eter-maleik anhidrit-stiren terpolimeri sentezlenmiştir ve (erpolimerin epoksi reçinesinin yapıştırma özelliğine etkileri incelenmiştir. Terpolimer, 1 mol allil fenil eter, 2 mol maleik anhidrit ve 1 mol stirenin polimerleşmesiyle sentezlenmiştir. Terpolimerin limit viskozite sayısı ve anhidrit grupları deneysel yöntemlerle belirlenmiştir. Epoksi reçinesine % 10-30 (m/m) terpolimer eklenmesiyle yapıştırma özelliği artırılmıştır. Hazırlanan yapıştırıcıların dış görünüş, bağıl yoğunluk, ısısal ve mekanik özellikleri farklı deneysel yöntemlerle karakterize edilmiştir. % 10-30 (m/m) terpolimer içeren yapıştırıcılar homojendir. Bu değerin üzerinde ise terpolimer epoksi reçinesinde çözülememiştir. Bağıl yoğunluk ölçümlerine göre terpolimer içeriği ile yapıştırıcının bağıl yoğunluğu artmıştır. DTA yöntemiyle, yapıştırıcının camsı geçiş sıcaklıklarının da terpolimer içeriği ile arttığı belirlenmiştir. TG termogramlarıyla belirlenen epoksi reçinesinin bozunma sıcaklıkları önce azalmış sonra moleküler yapıda çapraz bağların oluşmasıyla artmıştır. % 15-30 terpolimer içeren yapıştırıcı şekillenebilmiştir ve kopma uzaması değerleri terpolimer içeriği ile artmıştır. Alüminyum levhalar, terpolimer içeriği, sıcaklık ve zaman gibi farklı koşullarda hazırlanan yapıştırıcılarla yapıştırılmış ve elde edilen maksimum kopma gerilimleri, % 25 terpolimer, 180 °C ve 2 saat olarak belirlenmiştir. Galvanez, saç ve çelik levhalar bu koşullarda yapıştırılmış ve kopma gerilimleri alüminyum levha ile yaklaşık olarak aynı bulunmuştur. Sonuç olarak, yapıştırıcının ısısal ve mekanik özelliklerinin epoksi reçinesine belirli oranlarda allil fenil eter-maleik anhidrit-stiren terpolimerinin eklenmesiyle iyileştirilebileceği ve bu yapıştırıcının metal levhaları yapıştırmak için kullanılabileceği bulunmuştur. Anahtar Kelimeler: Allil Fenil Eter-Maleik Anhidrit-Stiren terpolimeri, Epoksi Reçinesi ve yapıştırıcı. ABSTRACT M. Sc. Thesis THE INVESTIGATION OF ADHESIVES PREPARED ON THE BASIS OF ALLYL PHENYL ETHER-MALEIC ANHYDRIDE-STYRENE TERPOLYMER AND EPOXY RESIN Melike KIRO?LU Cumhuriyet University Graduate School of Natural and Applied Sciences Department of Chemical Engineering Supervisor: Assis. Prof. Dr. Elçin EKBEROV In this study, allyl phenyl ether-maleic anhydride-styrene terpolymer was synthesized and the effects of terpolymer on to adhesive properties of epoxy resin were investigated. Terpolymer was synthesized by the polymerization of one mole of allyl phenyl ether, two moles of maleic anhydride and one mole of styrene. The number of anhyride groups and the limit viscosity number of terpolymers were determined by experimental methods. 10-30 (w/w) % of terpolymer was added to epoxy resin to increase its adhesion property. External appearance, relative density, thermal and mechanical properties of prepared adhesives were characterized by different experimental methods. Adhesives containing 10-30 (w/w) % terpolymer are homogeneous. Terpolymer could not be dissolved in epoxy resin for the greater values. According to the relative density measurements, the relative densities of adhesives increased with the terpolymer content. Also the glass transition points of adhesives, determined by DTA method increased with the terpolymer content. Disintegration temperatures of epoxy resin determined by TG termograms showed initially a decrease and than an increase due to crosslinking in the molecular structure. The adhesives containing 15-30 (w/w) % terpolymer could be shaped and their fracture elongation values increased with terpolymer content. Aluminum plates were adhered by different adhesives prepared at different conditions such as terpolymer content, temperature and time and the maximum fracture stresses obtained were determined as 25 % terpolymer, 180 °C and 2 hours. Galvanize, sheet iron and steel plates were adhered at these conditions and their fracture stresses were found as around the aluminum plates'. As a result, thermal and mechanical properties of adhesives were improved by the addition of allyl phenyl ether-maleic anhydride-styrene terpolymer to epoxy resin at a certain degree and it was found that this adhesive could be used for the adhesion of metal plates. Key Words: Allyl phenyl ether-maleic anhydride-styrene terpolymer, epoxy resin and adhesive. II 58