selim kusefoglu | Bogazici University, Istanbul, Turkey (original) (raw)
Papers by selim kusefoglu
Journal of Supercritical Fluids, Aug 1, 2006
The aim of this research is to hydroxybrominate and hydroxychlorinate the double bonds of methyl ... more The aim of this research is to hydroxybrominate and hydroxychlorinate the double bonds of methyl oleate and soybean oil in dense CO 2. The hydroxychlorination reactions of vegetable oils in dense CO 2 are the first such report in literature. Experiments were performed at the reaction conditions of 8, 25 and 40 • C and 60, 100, 120 and 150 bar. Effects of temperature, pressure, reaction time and the reactant amounts on the extent of reaction are studied. Hydroxybromination and hydroxychlorination reactions are conducted using sodium hypobromite (NaOBr) and sodium hypochlorite (NaOCl) solutions, respectively. The polymerization of the product is performed by urethane formation with toluenediisocyanate at 40 • C. The products were analyzed by NMR and IR spectrometry. Fifty percent consumption of the double bonds was observed in the hydroxybromination reaction of methyl oleate, but no OH addition was determined. In hydroxychlorination reactions of methyl oleate the consumption of double bonds ranges from 40 to 95%, and the introduction of OH groups ranges from 14 to 30%. Best yields were observed when the mole ratio of NaOCl to methyl oleate double bonds is 5 to 1. The consumption of soybean triglyceride double bonds, in the hydroxychlorination reactions, are observed to range from 18 to 75% and the formation of OH groups ranges from 8 to 33%. The highest conversion for one-step hydroxychlorination of soybean is obtained at 25 • C and 120 bar for a reaction time of 6 h, with 10/1 ratio of NaOCl to double bonds. Better results were obtained when the product of the reaction was reintroduced to the reactor and retreated with NaOCl and 75% consumption of double bonds and 33% formation of OH groups were observed.
Journal of Applied Polymer Science, Jan 15, 2010
Single fiber fragmentation test (SFFT) was used to investigate the interfacial adhesion in glass ... more Single fiber fragmentation test (SFFT) was used to investigate the interfacial adhesion in glass fiber‐unsaturated polyester composites. A simplified approach was developed for SFFT based on determination of the maximum number of fragments on the fiber at the end of the test. This approach does not involve length measurements and shortens the experiment time to a few minutes. By using a digital camera attached to the microscope, photographs of the coupon were taken during the test, and the number of fragments within the gauge length were counted later. This method allows quick, quantitative comparison of different fibers and matrices. The test samples were prepared by using commercial polyester resin and E‐glass fibers having different commercial sizings. SFFT results were in excellent agreement with the macromechanical test done on samples prepared with the same glass fiber and same polyester. The crack modes and debonding phenomena were examined from the microscopic images. Atomic force microscopic (AFM) images of the fiber were examined to get detailed topographic information about fiber surfaces. To improve interfacial adhesion, commercial unsaturated polyester was reacted with 3‐aminopropyltriethoxy silane via Michael Addition reaction on the maleate double bonds of the polyester. The resulting silylated polyester was characterized by H1 NMR spectroscopy. The results of SFFT showed that the maximum numbers of fragments increased 23% on using silylated polyester. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
Journal of Applied Polymer Science, Oct 11, 2010
In this study, maleinized soybean oil triglycerides (SOMA) were reacted with epoxidized soybean o... more In this study, maleinized soybean oil triglycerides (SOMA) were reacted with epoxidized soybean oil triglycerides (ESO) to give plant oil-based thermoset polymers. To increase fracture toughness of the product, different amounts of SOMA was replaced by maleic anhydride grafted polypropylene (MMPP) (Epolene E43, maleate content 2.9%, M n ¼ 3900 and Polybond 3200, maleate content 1%, M n ¼ 1,10,000). The improvement in mechanical properties was monitored. The characterizations of the products were done by DMA, DSC, TGA, and IR spectroscopy. ESO-SOMA and ESO-SOMA-MMPP polymers are crosslinked rigid infusible polymers. ESO-SOMA-MMPP(E43) and ESO-SOMA-MMPP(PB3200) showed a phase change at 146 and 169 C, respectively, probably due to the melting transition of the MMPP backbone. Storage moduli of the two polymers at 35 C were 54.6 and 246.1 MPa, respectively. Storage moduli and the impact strength of the polymers increased with MMPP content and with MMPP molecular weight.
Korean Journal of Chemical Engineering, Sep 1, 2006
Journal of Applied Polymer Science, Jul 21, 2003
Epoxidized soybean oil was reacted with cinnamic acid with triphenyl phosphine as a catalyst. Cin... more Epoxidized soybean oil was reacted with cinnamic acid with triphenyl phosphine as a catalyst. Cinnamic acid reacted with 79% of the available epoxy groups, and this yielded cinnamate esters of epoxidized soybean oil (ESOCA). 1 H-NMR, IR, and mass spectra of the new cinnamate derivatives confirmed the proposed structure. The mass spectra revealed that the average number of cinnamate groups per triglyceride molecule was 3.33. ESOCA could be photopolymerized with UV light. ESOCA could also be homopolymerized into a soft and insoluble polymer by freeradical initiation and copolymerized with styrene, vinyl acetate, and methyl methacrylate. A mixture of ESOCA with 25 wt % styrene had a viscosity of 410 cP and could be free-radically polymerized with benzoyl tert-butyl peroxide at elevated temperatures. Differential scanning calorimetry confirmed the formation of copolymers. The ESOCA homopolymer and its copolymers all showed a first-order transition by differential scanning calorimetry around Ϫ1.5°C that was attributable to side-chain relaxations of the triglyceride fatty acids. The styrene copolymer of ESOCA showed a tan ␦ peak at 66.6°C.
Journal of Applied Polymer Science, Sep 20, 1989
Copolyesters containing pendent vinylidine groups were prepared in a one-step synthesis by reacti... more Copolyesters containing pendent vinylidine groups were prepared in a one-step synthesis by reacting either chloroor bromoacetic acid with 2-(bromomethyl)acrylc acid and triethylamine in diethyl ether. Polymers were characterized by IR, 'H-and 13C-NMR, DSC, and TGA. Copolymer formation supports a mechanism involving a triethylammonium carboxylate salt acting as an active nucleophilic species in a manner analogous to that seen in phase transfer catalysis involving carboxylate anions. Comparison of I3C-NMR spectra intensities indicates that 2-(bromomethy1)acrylic acid is much more reactive than the haloacetic acids leading to higher copolymer incorporation than in the monomer feed. Unsaturation in the copolymers provides a site for crosslinking during radical polymerization with an added vinyl monomer, similar to the way unsaturated polyesters function in commercial fiberglass formulations. This was confirmed by polymerization of both styrene and methyl methacrylate in the presence of an unsaturated copolymer giving insoluble semi-interpenetrating networks. These unsaturated copolymers are the first examples of soluble biodegradable glycolic acid polyesters containing such reactive functionality.
Journal of Applied Polymer Science, 2009
In this study, styrene maleic anhydride copolymer (SMA2000, Styrene : Maleic Anhydride 2 : 1) is ... more In this study, styrene maleic anhydride copolymer (SMA2000, Styrene : Maleic Anhydride 2 : 1) is grafted and/or crosslinked with epoxidized methyl oleate, epoxidized soybean oil, methyl ricinoleate (MR), castor oil (CO), and soybean oil diglyceride. Base catalyzed epoxy-anhydride and alcohol-anhydride polyesters were synthesized by using the anhydride on SMA, the epoxy or secondary alcohol groups on the triglyceride based monomers. The characterizations of the products were done by DMA, TGA, and IR spectroscopy. SMA-epoxidized soy oil and SMA-CO polymers are crosslinked rigid infusible polymers. SMA-epoxidized soy oil and SMA-CO showed T g 's at 70 and 66 C, respectively. Dynamic moduli of the two polymers were 11.73 and 3.34 Mpa respectively. SMA-epoxidized methyl oleate, poly[styrene-co-(maleic anhydride)]-graft-(methyl ricinoleate), and SMA-soy oil diglyceride polymers were soluble and thermoplastic polymers and were characterized by TGA, GPC, DSC, NMR, and IR spectroscopy.
Journal of Polymer Science Part A, Nov 1, 1993
Ethyl-a-hydroxymethylacrylate (EHMA) was esterified with hexanoyl chloride in 80% yield. The homo... more Ethyl-a-hydroxymethylacrylate (EHMA) was esterified with hexanoyl chloride in 80% yield. The homopolymer of the hexanoate ester was found to be a glassy thermoplastic and soluble polymer. Copolymerization of the hexanoate ester with EHMA in varying ratios gave polymers that were thermoplastic and more soluble as a result of internal lubrication of the long alkyl pendant groups. Copolymers with styrene were synthesized with relatively high conversion. Reaction of EHMA with adipoyl chloride gave a bis-ester which served as crosslinking agent when copolymerized with different monomers including EHMA itself. In a separate synthesis EHMA was reacted with toluenediisocyanate (T D I). In the absence of catalyst a monourethane was formed. This monomer still contains one isocyanate function and is capable of further reactions subsequent to double bond addition polymerization. This reaction was also carried out on poly-EHMA, with or without catalyst. The products were the mono and the crosslinked bisurethanes as expected. Thus, acyl chlorides and isocyanates were found to be excellent reagents for derivatization of EHMA.
![Research paper thumbnail of A convenient synthesis of [3.3]paracyclophane](https://attachments.academia-assets.com/109046893/thumbnails/1.jpg)
](Journal of Organic Chemistry, Aug 1, 1977
Figure 1. Composition during initial stages of a 30 O C reaction of HCHO with 1 in methanol, K2C0... more Figure 1. Composition during initial stages of a 30 O C reaction of HCHO with 1 in methanol, K2C03 catalysis (as in Experimental Section). Data taken from 13C NMR methyl signal intensities. (@-@) 1; (A-A) 2; (x-x) 4. Methacrylophenone (3), present at a low (ca. 10-15%) equilibrium concentration, is not shown. mmol) of propiophenone, and 750 mg (5.4 mmol) of potassium carbonate was stirred in 39 mL of methanol for 6 days at room temperature. Proton NMR (60 MHZ) showed a mixture which could be integrated for 10-15 mol % of 3. Carbon NMR spectroscopy showed 2 and 4 to be present in the ratio of 1:15 compared to 1:4 after only 3 days. The solvent was removed in vacuo without applied heat, and the residual oil was taken up in benzene, washed with water, and dried over sodium sulfate. Fractional distillation gave 6.1 g (55%) of pure 8: bp 75 O C (0.1 mm); 60-MHz lH NMR (CDC13) 6 1.
Journal of Applied Polymer Science, 2005
ABSTRACT
Journal of Applied Polymer Science, 2003
Simultaneous addition of bromine and acrylate to the double bonds of fatty acids in triglycerides... more Simultaneous addition of bromine and acrylate to the double bonds of fatty acids in triglycerides was achieved. In the first part of the study, methyl oleate was bromoacrylated in the presence of acrylic acid and N-bromosuccinimide as a model compound for the application of the reaction to the triglycerides. Next, soybean oil and high oleic sunflower oil were bromoacrylated by using the same procedure. The products were characterized by GC, IR, 1 H-NMR, 13 C-NMR, and mass spectrometry. The bromoacrylation yields for soybean oil and sunflower oil were 75 and 55%, respectively. A rigid thermoset polymer was prepared from the radical copolymerization of bromoacrylated soybean oil with styrene. The bromoacrylated sunflower oilstyrene copolymer showed semirigid properties. The crosslinked network structure of the copolymers was examined by their swelling behavior in different solvents. Glass-transition temperatures were also determined and soybean oil-based polymer and sunflower oil-based polymer showed a glass transition at 55-65 and 20-30°C, respectively. The storage moduli of the soybean-based and sunflower-based polymers at room temperature were approximately 1.0 ϫ 10 10 and 1.1 ϫ 10 8 Pa, respectively. Photopolymerization was also carried out by using 2,2-dimethoxy-2-phenyl-acetophenone as initiator. The response of the cured polymers to the thermal energy produced by a small flame was also tested by the ignition respond index method according to ASTM D 3713-78 and was found to be 5 B at 2.00 mm.
Journal of Applied Polymer Science, Jul 25, 2003
In this study soybean oil triglycerides were reacted with maleic anhydride in an ene reaction to ... more In this study soybean oil triglycerides were reacted with maleic anhydride in an ene reaction to introduce more than two maleate residues per triglycerides. The maleinized soybean oil (SOMA) was then polymerized with diols to the half-ester stage only. Two different types of alcohols was used in this work: (1) short-chain polyhydroxy linear or cyclic alcohols having 2, 3, 4, or 6 hydroxyl groups; and (2) long-chain dihydroxy alcohols. The aim was to determine the effect of functionality and chain length by choosing alcohols with increasing number of hydroxyl groups and different chain lengths. The reaction of alcohols with anhydride functionalized soybean oil to give a polymeric halfester is a reaction that proceeds without the formation of byproducts and is different from complete polyesterification of maleinized oils, which are well known. To improve the reaction yields, different catalysts and different reaction conditions were examined. The structural analysis of the products was done with 1 H-NMR and IR spectroscopy. All of the new polymers obtained were resilient and soft rubbers at room temperature. Castor oil polymer mixed with 60% CaCO 3 and 12% cork powder gave a resilient and nontacky linoleum composition.
Journal of polymer science, Nov 1, 1987
ABSTRACT
Journal of Applied Polymer Science, Sep 1, 2010
In this study, maleinized (SOMAP) and isocyanated soybean oil (SONCO) triglycerides have been suc... more In this study, maleinized (SOMAP) and isocyanated soybean oil (SONCO) triglycerides have been successfully grafted onto one surface of poly(vinyl alcohol)(PVA) films to give films that are hydrophilic on one side and hydrophobic on the other. The surface grafting was accomplished by the reaction of succinic anhydride or isocyanate functionalities of soybean oil derivatives and the hydroxyl groups of PVA films. The reaction was run in toluene, using PVA films on glass slides so that only one side of the film was accessible. After grafting, the films were rinsed with hot toluene to remove ungrafted triglycerides from the surface. The reaction on the surface was confirmed by ATR‐FTIR and 1H‐NMR spectroscopic techniques. A series of films were prepared at different concentrations of SOMAP or SONCO in toluene. The increase in hydrophobicity with an increase in SOMAP or SONCO concentrations was observed by water contact angle measurements. The contact angles on the grafted side of the film reach their maximum value of 88° and 94° for 26 and 2.5% SOMAP and SONCO concentrations in toluene, respectively, while the ungrafted side gives contact angle of 48°. Surface morphologies of PVA‐g‐SOMAP and PVA‐g‐SONCO films were investigated by atomic force microscopy, whereas optical microscopy and staining was used to determine the homogeneity of the films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011
Macromolecules, Mar 1, 1994
Introduction. Monomers based on a-(hydroxymethy-1)acrylate offer great versatility for functional... more Introduction. Monomers based on a-(hydroxymethy-1)acrylate offer great versatility for functionalization and polymer formation. Earlier work in this area involved complicated or low-yield monomer Insertion of formaldehyde at the cy-position of acrylic esters catalyzed by DABCO (1,4-diazabicyclo[2.2.2loctane) produces alkyl
European Journal of Lipid Science and Technology, 2004
Soft, stratified, amphiphilic systems are recurrent motifs in nature, e.g., in myelin sheaths or ... more Soft, stratified, amphiphilic systems are recurrent motifs in nature, e.g., in myelin sheaths or thylakoid stacks, and synthetic analogues are increasingly being exploited in the areas of biocatalysis, biosensing, and drug delivery. The synthesis of such complex multilayered systems usually requires lengthy preparation protocols. Here, we demonstrate the formation of multilayered fatty acid/polysaccharide thin films prepared via a single step protocol, which exploits the spontaneous self-assembly of the components into vesicular systems in aqueous solution. The solutions are characterized by light and neutron scattering experiments and the thin films by neutron reflectometry, optical ellipsometry, atomic force microscopy, and x-ray diffraction. The thin films exhibit structural features with sub-10 nm dimensions, stemming from the ordered sequence of hydrophilic and hydrophobic layers and respond strongly to changes in ambient humidity. Using this approach, films with a total thickness varying from tens to hundreds of nanometers can be easily prepared.
Journal of Applied Polymer Science, Jul 14, 2010
In this study, maleinized soybean oil triglycerides (SOMA) were reacted with epoxidized soybean o... more In this study, maleinized soybean oil triglycerides (SOMA) were reacted with epoxidized soybean oil triglycerides (ESO) to give plant oil-based thermoset polymers. To increase fracture toughness of the product, different amounts of SOMA was replaced by maleic anhydride grafted polypropylene (MMPP) (Epolene E43, maleate content 2.9%, M n ¼ 3900 and Polybond 3200, maleate content 1%, M n ¼ 1,10,000). The improvement in mechanical properties was monitored. The characterizations of the products were done by DMA, DSC, TGA, and IR spectroscopy. ESO-SOMA and ESO-SOMA-MMPP polymers are crosslinked rigid infusible polymers. ESO-SOMA-MMPP(E43) and ESO-SOMA-MMPP(PB3200) showed a phase change at 146 and 169 C, respectively, probably due to the melting transition of the MMPP backbone. Storage moduli of the two polymers at 35 C were 54.6 and 246.1 MPa, respectively. Storage moduli and the impact strength of the polymers increased with MMPP content and with MMPP molecular weight.
Journal of Applied Polymer Science, 2004
The ene reaction between plant oil triglycerides (such as soybean and sunflower oils) and parafor... more The ene reaction between plant oil triglycerides (such as soybean and sunflower oils) and paraformaldehyde was used to introduce a homoallylic hydroxyl functionality on the triglyceride. Paraformaldehyde and triglyceride were reacted in the presence of a Lewis acid catalyst, ethylaluminum dichloride, and hydroxymethyl derivatives were obtained at yields of 42 and 55% for sunflower oil and soybean oil, respectively. In the next step, hydroxymethyl products were reacted with maleic anhydride at 100°C to produce the maleate half esters. The average number of maleate groups per triglycerides was found to be 1.7 for soybean oil and 1.3 for sunflower oil. In the final step, the free-radical-initiated copolymerization of the maleinized triglycerides with styrene produced rigid polymers. Characterization of new monomers and polymers was done by 1 H-NMR, 13 C-NMR, and infrared and mass spectrometries. The swelling behavior of the crosslinked network polymers was determined in different solvents. The glass-transition temperature of the cured resin was also determined by differential scanning calorimetry to be 40°C for soybeanbased polymer and 30°C for sunflower-based polymer.
Journal of Applied Polymer Science, Aug 5, 2009
In this study, rubbery, bio‐based thermoset polymers were synthesized from soybean oil (SO) and p... more In this study, rubbery, bio‐based thermoset polymers were synthesized from soybean oil (SO) and p‐dinitrosobenzene (DNB) via an ene reaction. Polymeric p‐dinitrosobenzene (PDNB) was synthesized from p‐quinone dioxime and was thermally depolymerized in the presence of SO. SO/PDNB polymers were synthesized by a two‐stage polymerization. During the reaction, the role of different parameters such as mol ratio of SO and PDNB, preheating temperature of SO, polymerization time, and temperature were examined. Polymerization was followed by IR spectroscopy, and the polymers obtained were characterized by dynamic mechanical analysis, thermogravimetric analysis, and differential scanning calorimetry. The polymers have glass transition temperature ranging from −51.5°C to −46.3°C, whereas their storage moduli are between 430 and 210 MPa at −60°C. Thermogravimetric analysis reveals that all of the polymers have temperatures of maximum degradation around 500°C. The crosslinked network structure of the polymers was investigated by swelling behavior and surface hardness test. Methyl oleate was used as a model compound to examine the chemical structure of the products. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009
Macromolecules, Feb 1, 1988
... for one of us (SHK), and the Department of Defense through the Office of Naval Re-search for ... more ... for one of us (SHK), and the Department of Defense through the Office of Naval Re-search for the instrumentation grant used to ... Lon J. Mathias,* Selim H. Kusefoglu,l and Jim E. Ingram Department of Polymer Science University of Southern Mississippi Hattiesburg, Mississippi ...
Journal of Supercritical Fluids, Aug 1, 2006
The aim of this research is to hydroxybrominate and hydroxychlorinate the double bonds of methyl ... more The aim of this research is to hydroxybrominate and hydroxychlorinate the double bonds of methyl oleate and soybean oil in dense CO 2. The hydroxychlorination reactions of vegetable oils in dense CO 2 are the first such report in literature. Experiments were performed at the reaction conditions of 8, 25 and 40 • C and 60, 100, 120 and 150 bar. Effects of temperature, pressure, reaction time and the reactant amounts on the extent of reaction are studied. Hydroxybromination and hydroxychlorination reactions are conducted using sodium hypobromite (NaOBr) and sodium hypochlorite (NaOCl) solutions, respectively. The polymerization of the product is performed by urethane formation with toluenediisocyanate at 40 • C. The products were analyzed by NMR and IR spectrometry. Fifty percent consumption of the double bonds was observed in the hydroxybromination reaction of methyl oleate, but no OH addition was determined. In hydroxychlorination reactions of methyl oleate the consumption of double bonds ranges from 40 to 95%, and the introduction of OH groups ranges from 14 to 30%. Best yields were observed when the mole ratio of NaOCl to methyl oleate double bonds is 5 to 1. The consumption of soybean triglyceride double bonds, in the hydroxychlorination reactions, are observed to range from 18 to 75% and the formation of OH groups ranges from 8 to 33%. The highest conversion for one-step hydroxychlorination of soybean is obtained at 25 • C and 120 bar for a reaction time of 6 h, with 10/1 ratio of NaOCl to double bonds. Better results were obtained when the product of the reaction was reintroduced to the reactor and retreated with NaOCl and 75% consumption of double bonds and 33% formation of OH groups were observed.
Journal of Applied Polymer Science, Jan 15, 2010
Single fiber fragmentation test (SFFT) was used to investigate the interfacial adhesion in glass ... more Single fiber fragmentation test (SFFT) was used to investigate the interfacial adhesion in glass fiber‐unsaturated polyester composites. A simplified approach was developed for SFFT based on determination of the maximum number of fragments on the fiber at the end of the test. This approach does not involve length measurements and shortens the experiment time to a few minutes. By using a digital camera attached to the microscope, photographs of the coupon were taken during the test, and the number of fragments within the gauge length were counted later. This method allows quick, quantitative comparison of different fibers and matrices. The test samples were prepared by using commercial polyester resin and E‐glass fibers having different commercial sizings. SFFT results were in excellent agreement with the macromechanical test done on samples prepared with the same glass fiber and same polyester. The crack modes and debonding phenomena were examined from the microscopic images. Atomic force microscopic (AFM) images of the fiber were examined to get detailed topographic information about fiber surfaces. To improve interfacial adhesion, commercial unsaturated polyester was reacted with 3‐aminopropyltriethoxy silane via Michael Addition reaction on the maleate double bonds of the polyester. The resulting silylated polyester was characterized by H1 NMR spectroscopy. The results of SFFT showed that the maximum numbers of fragments increased 23% on using silylated polyester. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
Journal of Applied Polymer Science, Oct 11, 2010
In this study, maleinized soybean oil triglycerides (SOMA) were reacted with epoxidized soybean o... more In this study, maleinized soybean oil triglycerides (SOMA) were reacted with epoxidized soybean oil triglycerides (ESO) to give plant oil-based thermoset polymers. To increase fracture toughness of the product, different amounts of SOMA was replaced by maleic anhydride grafted polypropylene (MMPP) (Epolene E43, maleate content 2.9%, M n ¼ 3900 and Polybond 3200, maleate content 1%, M n ¼ 1,10,000). The improvement in mechanical properties was monitored. The characterizations of the products were done by DMA, DSC, TGA, and IR spectroscopy. ESO-SOMA and ESO-SOMA-MMPP polymers are crosslinked rigid infusible polymers. ESO-SOMA-MMPP(E43) and ESO-SOMA-MMPP(PB3200) showed a phase change at 146 and 169 C, respectively, probably due to the melting transition of the MMPP backbone. Storage moduli of the two polymers at 35 C were 54.6 and 246.1 MPa, respectively. Storage moduli and the impact strength of the polymers increased with MMPP content and with MMPP molecular weight.
Korean Journal of Chemical Engineering, Sep 1, 2006
Journal of Applied Polymer Science, Jul 21, 2003
Epoxidized soybean oil was reacted with cinnamic acid with triphenyl phosphine as a catalyst. Cin... more Epoxidized soybean oil was reacted with cinnamic acid with triphenyl phosphine as a catalyst. Cinnamic acid reacted with 79% of the available epoxy groups, and this yielded cinnamate esters of epoxidized soybean oil (ESOCA). 1 H-NMR, IR, and mass spectra of the new cinnamate derivatives confirmed the proposed structure. The mass spectra revealed that the average number of cinnamate groups per triglyceride molecule was 3.33. ESOCA could be photopolymerized with UV light. ESOCA could also be homopolymerized into a soft and insoluble polymer by freeradical initiation and copolymerized with styrene, vinyl acetate, and methyl methacrylate. A mixture of ESOCA with 25 wt % styrene had a viscosity of 410 cP and could be free-radically polymerized with benzoyl tert-butyl peroxide at elevated temperatures. Differential scanning calorimetry confirmed the formation of copolymers. The ESOCA homopolymer and its copolymers all showed a first-order transition by differential scanning calorimetry around Ϫ1.5°C that was attributable to side-chain relaxations of the triglyceride fatty acids. The styrene copolymer of ESOCA showed a tan ␦ peak at 66.6°C.
Journal of Applied Polymer Science, Sep 20, 1989
Copolyesters containing pendent vinylidine groups were prepared in a one-step synthesis by reacti... more Copolyesters containing pendent vinylidine groups were prepared in a one-step synthesis by reacting either chloroor bromoacetic acid with 2-(bromomethyl)acrylc acid and triethylamine in diethyl ether. Polymers were characterized by IR, 'H-and 13C-NMR, DSC, and TGA. Copolymer formation supports a mechanism involving a triethylammonium carboxylate salt acting as an active nucleophilic species in a manner analogous to that seen in phase transfer catalysis involving carboxylate anions. Comparison of I3C-NMR spectra intensities indicates that 2-(bromomethy1)acrylic acid is much more reactive than the haloacetic acids leading to higher copolymer incorporation than in the monomer feed. Unsaturation in the copolymers provides a site for crosslinking during radical polymerization with an added vinyl monomer, similar to the way unsaturated polyesters function in commercial fiberglass formulations. This was confirmed by polymerization of both styrene and methyl methacrylate in the presence of an unsaturated copolymer giving insoluble semi-interpenetrating networks. These unsaturated copolymers are the first examples of soluble biodegradable glycolic acid polyesters containing such reactive functionality.
Journal of Applied Polymer Science, 2009
In this study, styrene maleic anhydride copolymer (SMA2000, Styrene : Maleic Anhydride 2 : 1) is ... more In this study, styrene maleic anhydride copolymer (SMA2000, Styrene : Maleic Anhydride 2 : 1) is grafted and/or crosslinked with epoxidized methyl oleate, epoxidized soybean oil, methyl ricinoleate (MR), castor oil (CO), and soybean oil diglyceride. Base catalyzed epoxy-anhydride and alcohol-anhydride polyesters were synthesized by using the anhydride on SMA, the epoxy or secondary alcohol groups on the triglyceride based monomers. The characterizations of the products were done by DMA, TGA, and IR spectroscopy. SMA-epoxidized soy oil and SMA-CO polymers are crosslinked rigid infusible polymers. SMA-epoxidized soy oil and SMA-CO showed T g 's at 70 and 66 C, respectively. Dynamic moduli of the two polymers were 11.73 and 3.34 Mpa respectively. SMA-epoxidized methyl oleate, poly[styrene-co-(maleic anhydride)]-graft-(methyl ricinoleate), and SMA-soy oil diglyceride polymers were soluble and thermoplastic polymers and were characterized by TGA, GPC, DSC, NMR, and IR spectroscopy.
Journal of Polymer Science Part A, Nov 1, 1993
Ethyl-a-hydroxymethylacrylate (EHMA) was esterified with hexanoyl chloride in 80% yield. The homo... more Ethyl-a-hydroxymethylacrylate (EHMA) was esterified with hexanoyl chloride in 80% yield. The homopolymer of the hexanoate ester was found to be a glassy thermoplastic and soluble polymer. Copolymerization of the hexanoate ester with EHMA in varying ratios gave polymers that were thermoplastic and more soluble as a result of internal lubrication of the long alkyl pendant groups. Copolymers with styrene were synthesized with relatively high conversion. Reaction of EHMA with adipoyl chloride gave a bis-ester which served as crosslinking agent when copolymerized with different monomers including EHMA itself. In a separate synthesis EHMA was reacted with toluenediisocyanate (T D I). In the absence of catalyst a monourethane was formed. This monomer still contains one isocyanate function and is capable of further reactions subsequent to double bond addition polymerization. This reaction was also carried out on poly-EHMA, with or without catalyst. The products were the mono and the crosslinked bisurethanes as expected. Thus, acyl chlorides and isocyanates were found to be excellent reagents for derivatization of EHMA.
Journal of Organic Chemistry, Aug 1, 1977
Figure 1. Composition during initial stages of a 30 O C reaction of HCHO with 1 in methanol, K2C0... more Figure 1. Composition during initial stages of a 30 O C reaction of HCHO with 1 in methanol, K2C03 catalysis (as in Experimental Section). Data taken from 13C NMR methyl signal intensities. (@-@) 1; (A-A) 2; (x-x) 4. Methacrylophenone (3), present at a low (ca. 10-15%) equilibrium concentration, is not shown. mmol) of propiophenone, and 750 mg (5.4 mmol) of potassium carbonate was stirred in 39 mL of methanol for 6 days at room temperature. Proton NMR (60 MHZ) showed a mixture which could be integrated for 10-15 mol % of 3. Carbon NMR spectroscopy showed 2 and 4 to be present in the ratio of 1:15 compared to 1:4 after only 3 days. The solvent was removed in vacuo without applied heat, and the residual oil was taken up in benzene, washed with water, and dried over sodium sulfate. Fractional distillation gave 6.1 g (55%) of pure 8: bp 75 O C (0.1 mm); 60-MHz lH NMR (CDC13) 6 1.
Journal of Applied Polymer Science, 2005
ABSTRACT
Journal of Applied Polymer Science, 2003
Simultaneous addition of bromine and acrylate to the double bonds of fatty acids in triglycerides... more Simultaneous addition of bromine and acrylate to the double bonds of fatty acids in triglycerides was achieved. In the first part of the study, methyl oleate was bromoacrylated in the presence of acrylic acid and N-bromosuccinimide as a model compound for the application of the reaction to the triglycerides. Next, soybean oil and high oleic sunflower oil were bromoacrylated by using the same procedure. The products were characterized by GC, IR, 1 H-NMR, 13 C-NMR, and mass spectrometry. The bromoacrylation yields for soybean oil and sunflower oil were 75 and 55%, respectively. A rigid thermoset polymer was prepared from the radical copolymerization of bromoacrylated soybean oil with styrene. The bromoacrylated sunflower oilstyrene copolymer showed semirigid properties. The crosslinked network structure of the copolymers was examined by their swelling behavior in different solvents. Glass-transition temperatures were also determined and soybean oil-based polymer and sunflower oil-based polymer showed a glass transition at 55-65 and 20-30°C, respectively. The storage moduli of the soybean-based and sunflower-based polymers at room temperature were approximately 1.0 ϫ 10 10 and 1.1 ϫ 10 8 Pa, respectively. Photopolymerization was also carried out by using 2,2-dimethoxy-2-phenyl-acetophenone as initiator. The response of the cured polymers to the thermal energy produced by a small flame was also tested by the ignition respond index method according to ASTM D 3713-78 and was found to be 5 B at 2.00 mm.
Journal of Applied Polymer Science, Jul 25, 2003
In this study soybean oil triglycerides were reacted with maleic anhydride in an ene reaction to ... more In this study soybean oil triglycerides were reacted with maleic anhydride in an ene reaction to introduce more than two maleate residues per triglycerides. The maleinized soybean oil (SOMA) was then polymerized with diols to the half-ester stage only. Two different types of alcohols was used in this work: (1) short-chain polyhydroxy linear or cyclic alcohols having 2, 3, 4, or 6 hydroxyl groups; and (2) long-chain dihydroxy alcohols. The aim was to determine the effect of functionality and chain length by choosing alcohols with increasing number of hydroxyl groups and different chain lengths. The reaction of alcohols with anhydride functionalized soybean oil to give a polymeric halfester is a reaction that proceeds without the formation of byproducts and is different from complete polyesterification of maleinized oils, which are well known. To improve the reaction yields, different catalysts and different reaction conditions were examined. The structural analysis of the products was done with 1 H-NMR and IR spectroscopy. All of the new polymers obtained were resilient and soft rubbers at room temperature. Castor oil polymer mixed with 60% CaCO 3 and 12% cork powder gave a resilient and nontacky linoleum composition.
Journal of polymer science, Nov 1, 1987
ABSTRACT
Journal of Applied Polymer Science, Sep 1, 2010
In this study, maleinized (SOMAP) and isocyanated soybean oil (SONCO) triglycerides have been suc... more In this study, maleinized (SOMAP) and isocyanated soybean oil (SONCO) triglycerides have been successfully grafted onto one surface of poly(vinyl alcohol)(PVA) films to give films that are hydrophilic on one side and hydrophobic on the other. The surface grafting was accomplished by the reaction of succinic anhydride or isocyanate functionalities of soybean oil derivatives and the hydroxyl groups of PVA films. The reaction was run in toluene, using PVA films on glass slides so that only one side of the film was accessible. After grafting, the films were rinsed with hot toluene to remove ungrafted triglycerides from the surface. The reaction on the surface was confirmed by ATR‐FTIR and 1H‐NMR spectroscopic techniques. A series of films were prepared at different concentrations of SOMAP or SONCO in toluene. The increase in hydrophobicity with an increase in SOMAP or SONCO concentrations was observed by water contact angle measurements. The contact angles on the grafted side of the film reach their maximum value of 88° and 94° for 26 and 2.5% SOMAP and SONCO concentrations in toluene, respectively, while the ungrafted side gives contact angle of 48°. Surface morphologies of PVA‐g‐SOMAP and PVA‐g‐SONCO films were investigated by atomic force microscopy, whereas optical microscopy and staining was used to determine the homogeneity of the films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011
Macromolecules, Mar 1, 1994
Introduction. Monomers based on a-(hydroxymethy-1)acrylate offer great versatility for functional... more Introduction. Monomers based on a-(hydroxymethy-1)acrylate offer great versatility for functionalization and polymer formation. Earlier work in this area involved complicated or low-yield monomer Insertion of formaldehyde at the cy-position of acrylic esters catalyzed by DABCO (1,4-diazabicyclo[2.2.2loctane) produces alkyl
European Journal of Lipid Science and Technology, 2004
Soft, stratified, amphiphilic systems are recurrent motifs in nature, e.g., in myelin sheaths or ... more Soft, stratified, amphiphilic systems are recurrent motifs in nature, e.g., in myelin sheaths or thylakoid stacks, and synthetic analogues are increasingly being exploited in the areas of biocatalysis, biosensing, and drug delivery. The synthesis of such complex multilayered systems usually requires lengthy preparation protocols. Here, we demonstrate the formation of multilayered fatty acid/polysaccharide thin films prepared via a single step protocol, which exploits the spontaneous self-assembly of the components into vesicular systems in aqueous solution. The solutions are characterized by light and neutron scattering experiments and the thin films by neutron reflectometry, optical ellipsometry, atomic force microscopy, and x-ray diffraction. The thin films exhibit structural features with sub-10 nm dimensions, stemming from the ordered sequence of hydrophilic and hydrophobic layers and respond strongly to changes in ambient humidity. Using this approach, films with a total thickness varying from tens to hundreds of nanometers can be easily prepared.
Journal of Applied Polymer Science, Jul 14, 2010
In this study, maleinized soybean oil triglycerides (SOMA) were reacted with epoxidized soybean o... more In this study, maleinized soybean oil triglycerides (SOMA) were reacted with epoxidized soybean oil triglycerides (ESO) to give plant oil-based thermoset polymers. To increase fracture toughness of the product, different amounts of SOMA was replaced by maleic anhydride grafted polypropylene (MMPP) (Epolene E43, maleate content 2.9%, M n ¼ 3900 and Polybond 3200, maleate content 1%, M n ¼ 1,10,000). The improvement in mechanical properties was monitored. The characterizations of the products were done by DMA, DSC, TGA, and IR spectroscopy. ESO-SOMA and ESO-SOMA-MMPP polymers are crosslinked rigid infusible polymers. ESO-SOMA-MMPP(E43) and ESO-SOMA-MMPP(PB3200) showed a phase change at 146 and 169 C, respectively, probably due to the melting transition of the MMPP backbone. Storage moduli of the two polymers at 35 C were 54.6 and 246.1 MPa, respectively. Storage moduli and the impact strength of the polymers increased with MMPP content and with MMPP molecular weight.
Journal of Applied Polymer Science, 2004
The ene reaction between plant oil triglycerides (such as soybean and sunflower oils) and parafor... more The ene reaction between plant oil triglycerides (such as soybean and sunflower oils) and paraformaldehyde was used to introduce a homoallylic hydroxyl functionality on the triglyceride. Paraformaldehyde and triglyceride were reacted in the presence of a Lewis acid catalyst, ethylaluminum dichloride, and hydroxymethyl derivatives were obtained at yields of 42 and 55% for sunflower oil and soybean oil, respectively. In the next step, hydroxymethyl products were reacted with maleic anhydride at 100°C to produce the maleate half esters. The average number of maleate groups per triglycerides was found to be 1.7 for soybean oil and 1.3 for sunflower oil. In the final step, the free-radical-initiated copolymerization of the maleinized triglycerides with styrene produced rigid polymers. Characterization of new monomers and polymers was done by 1 H-NMR, 13 C-NMR, and infrared and mass spectrometries. The swelling behavior of the crosslinked network polymers was determined in different solvents. The glass-transition temperature of the cured resin was also determined by differential scanning calorimetry to be 40°C for soybeanbased polymer and 30°C for sunflower-based polymer.
Journal of Applied Polymer Science, Aug 5, 2009
In this study, rubbery, bio‐based thermoset polymers were synthesized from soybean oil (SO) and p... more In this study, rubbery, bio‐based thermoset polymers were synthesized from soybean oil (SO) and p‐dinitrosobenzene (DNB) via an ene reaction. Polymeric p‐dinitrosobenzene (PDNB) was synthesized from p‐quinone dioxime and was thermally depolymerized in the presence of SO. SO/PDNB polymers were synthesized by a two‐stage polymerization. During the reaction, the role of different parameters such as mol ratio of SO and PDNB, preheating temperature of SO, polymerization time, and temperature were examined. Polymerization was followed by IR spectroscopy, and the polymers obtained were characterized by dynamic mechanical analysis, thermogravimetric analysis, and differential scanning calorimetry. The polymers have glass transition temperature ranging from −51.5°C to −46.3°C, whereas their storage moduli are between 430 and 210 MPa at −60°C. Thermogravimetric analysis reveals that all of the polymers have temperatures of maximum degradation around 500°C. The crosslinked network structure of the polymers was investigated by swelling behavior and surface hardness test. Methyl oleate was used as a model compound to examine the chemical structure of the products. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009
Macromolecules, Feb 1, 1988
... for one of us (SHK), and the Department of Defense through the Office of Naval Re-search for ... more ... for one of us (SHK), and the Department of Defense through the Office of Naval Re-search for the instrumentation grant used to ... Lon J. Mathias,* Selim H. Kusefoglu,l and Jim E. Ingram Department of Polymer Science University of Southern Mississippi Hattiesburg, Mississippi ...