Co-reporter:Lei Meng, Mark D. Soucek, Zhen Li, Toshikazu Miyoshi
Polymer 2017 Volume 119(Volume 119) pp:
Publication Date(Web):16 June 2017
DOI:10.1016/j.polymer.2017.05.006
•Hydrogen bonding from carbamate acrylate monomer increased both elongation and tensile modulus for latexes.•Compositional drift occurs in batch latexes using the carbamate monomer.•The carbamate monomer can be located cleanly either in the core or shell in a core-shell latex.A urethane methacrylate monomer, 2-[(butylcarbamoyl)oxy]ethyl methacrylate (BEM), methyl methacrylate (MMA), and butyl acrylate (BA) were used to prepare latexes. The effects of polymer process (batch versus semi-batch), polymer composition, and the locus (core-shell) of urethane functionality in the latex particles were studied. Urethane functional latexes were evaluated by FT-IR, solid state nuclear magnetic resonance (SS-NMR), dynamic light scattering (DLS), gas chromatography (GC), differential scanning calorimetry (DSC), tensile and dynamic mechanical thermal analysis (DMTA). A compositional drift was observed for the batch polymerization which resulted in early formed polymers rich in MMA and BEM. This accounted for the higher modulus and tensile strength in latexes derived from batch polymerization. Both homogeneous and core-shell structures were prepared. The tensile modulus, tensile strength and elongation-at-break were all dependent on BEM content.Download high-res image (173KB)Download full-size image
Co-reporter:Lei Meng, Xiaojiang Wang, Martin Ocepek, Mark D. Soucek
Polymer 2017 Volume 109() pp:146-159
Publication Date(Web):27 January 2017
DOI:10.1016/j.polymer.2016.12.022
•New class of urethane acrylic monomers for emulsion polymerization.•Carbamate groups have beneficial effects on film formation and latex performance.•Carbamate groups increase both tensile strength and elongation.A series of new urethane methacrylate (UMA) monomers were synthesized with the reaction of ethylene carbonate and aliphatic amines, followed by the reaction with methacrylic anhydride. The monomers were characterized by 1H, 13C nuclear magnetic resonance (NMR), mass (MS), and Fourier transform infrared (FTIR) spectroscopies. Urethane latexes were prepared by monomer-starved semibatch polymerization of the new urethane methacrylates with methyl methacrylate (MMA) and butyl acrylate (BA). A uniform morphology and a unimodal particle distribution were observed by a combination of dynamic light scattering (DLS), ultrasound acoustic attenuation spectroscopy (UAAS), and transmission electron microscopy (TEM). The thermal stability, minimum film formation temperature (MFFT) and thermo-mechanical properties of the urethane latexes were also studied. The inclusion of urethane monomers appeared to have lowered the MFFT via a water plasticization effect, while enhancing the Tg of the final film properties.
Co-reporter:Tongzhai Gao;Enrique Maya-Visuet;Zhouying He;Homero Castaneda-Lopez;Irina J. Zvonkina
Journal of Applied Polymer Science 2016 Volume 133( Issue 5) pp:
Publication Date(Web):
DOI:10.1002/app.42947
ABSTRACT
Rutile TiO2 was formulated into polyurethane/polysiloxane hybrid coatings in order to investigate the influence of pigmentation on the inorganic phase of the hybrid coatings. Two urethanes were prepared from the isocyanurate of hexane diisocyanate (HDI), alkoxysilane modified HDI, and tetraethyl orthosilicate (TEOS) oligomers, with oligoesters derived from either cyclohexane diacids (CHDA) and 2-butyl-2-ethyl-1,3-propanediol (BEPD) or adipic acid (AA), isophthalic acid (IPA), 1,6-hexanediol (HD), and trimethylol propane (TMP). The oligoesters were spectroscopically characterized using GPC, FT-IR, and NMR. Chemical interaction between the TiO2 and the sol–gel precursor was investigated using solid-state 29Si NMR and XPS. The morphology, mechanical, viscoelastic, thermal properties of the pigmented coatings are evaluated as a function of pigmentation volume concentration (PVC). Using AFM and SEM, the pigment was observed to be well dispersed in the polymer binder. The thermal stability, the tensile modulus, and strength of the coatings were enhanced with increasing PVC, whereas the pull-off adhesion and flexibility (elongation-at-break) were reduced with increasing PVC. Finally, the pigmented coatings were evaluated by electrochemical impedance spectroscopy (EIS) and the results showed that 10 wt % of the pigment improved the corrosion resistance of the entire coating system. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42947.
Co-reporter:Mayela Ramirez-Huerta;Irina J. Zvonkina
Journal of Coatings Technology and Research 2016 Volume 13( Issue 5) pp:781-793
Publication Date(Web):2016 September
DOI:10.1007/s11998-016-9798-0
A series of hydroxyl-terminated oligoesters were synthesized to determine the structural effects on the relative rates of hydrolysis in both acidic and alkaline media. Model compounds consisting of one diol and one dibasic acid were used because the simplicity of the chemical structure allowed for the analysis of individual effects. Linear, cycloaliphatic, and aromatic dibasic acids were used. The diacids were reacted with a series of linear and bulky diols. All hydroxyl-terminated oligoesters were end-capped with phenyl isocyanate. Three different stages were distinguished in the case of aliphatic oligoesters, while more bulky structures (cycloaliphatic and aromatics) only presented one or two stages. Hydrolysis rates showed a complex behavior where steric and anchimeric effects play a mutual role on initial hydrolysis rates.
Co-reporter:K. R. Miller and M. D. Soucek
Journal of Materials Chemistry A 2015 vol. 3(Issue 35) pp:9175-9190
Publication Date(Web):10 Aug 2015
DOI:10.1039/C5TC01376C
Macro-initiators were prepared using three magnetic nanoparticles, Fe3O4, FeCo, or Co. Azo free radical initiators were grafted onto the magnetic particles in a two-step reaction utilizing alkoxysilane and ambient temperature esterification reactions. The magnetic initiators (MI) were characterized using IR, DSC, TGA, SEM with EDAX, and DLS. An alternating gradient magnetometer gave saturation magnetization (Ms) values of 42.1, 178.3, and 36.1 A m2 kg−1 for Fe3O4, FeCo, and Co MIs respectively. Bulk polymerization of styrene was used to assess the effectiveness of MIs in free radical polymerization. Molecular dynamic (MD) simulations were performed on the magnetic macro initiators to determine the feasibility of initiating free radical polymerization by application of an external AC MF. The MD simulations showed that magnetically induced polymerization is possible with a minimum force of 62 kcal mol−1 Å−1 required to be applied to the core of the MI in order to decompose the C–N bond of the azo group, producing free radicals.
Co-reporter:Martin Ocepek;Peter Berce;Tina Razbor&x161;ek;Jo&x17e;efa Zabret;Lei Meng
Journal of Applied Polymer Science 2015 Volume 132( Issue 24) pp:
Publication Date(Web):
DOI:10.1002/app.42062
ABSTRACT
Semibatch, power feed, and shot-addition feeding strategies were employed to synthesize carboxylated latex under acidic conditions, using emulsion polymerization. As a source of carboxyl groups, acrylic (AA) or methacrylic acid (MAA) was used. The distribution of carboxyl groups between feeding strategies were investigated using rheology, potentiometric/conductometric titrations, transmission electron microscopy, and FT-IR spectroscopy. Upon alkalization, particle swelling was observed using dynamic light scattering. With increasing pH, both the AA- and MAA-based latexes showed significant increase in hydrodynamic diameter as a consequence of the dissociation state of carboxyl groups. However, only MAA-based latexes exhibit very pronounced increase in viscosity and storage modulus, and were therefore characterized as gels. The effect of feeding strategies was found to be more pronounced with the MAA functionalized latexes. By employing mentioned three procedures, significant differences in the rheological behavior of the neutralized dispersions were detected. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42062.
Co-reporter:Martin Ocepek;Peter Berce;Lei Meng
Macromolecular Chemistry and Physics 2015 Volume 216( Issue 4) pp:400-416
Publication Date(Web):
DOI:10.1002/macp.201400476
Co-reporter:Priyanka P. Nalawade
Journal of Coatings Technology and Research 2015 Volume 12( Issue 6) pp:1005-1021
Publication Date(Web):2015 November
DOI:10.1007/s11998-015-9691-2
A long oil alkyd was formulated with three soybean oil-based reactive diluents. Coatings properties were evaluated as a function of concentration of reactive diluent in the formulation. The tensile, thermomechanical, and general coating properties were evaluated. General coatings properties
included crosshatch adhesion, pencil hardness, impact resistance, and solvent resistance. The siloxane and allyl ether-functionalized soybean oil enhanced the tensile modulus and crosslink density by 20% and 70%, respectively. Coatings with fluorine-functionalized soybean oil showed enhanced contact angle and solvent resistance, compared to alkyd coatings alone. The incorporation of reactive diluents in the formulation improved pencil hardness, while other general coating properties were not significantly affected.
Co-reporter:Mayela Ramirez;Kent R. Miller
Journal of Applied Polymer Science 2014 Volume 131( Issue 9) pp:
Publication Date(Web):
DOI:10.1002/app.40198
Abstract
The hydrolytic stability of a series of oligoesters comprised of three and four different monomers was evaluated. The hydroxyl terminal oligoesters were prepared from adipic acid (AA) and isophthalic acid (IPA), with six different diols and one triol, which included: 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, trimethylolpropane, and 2-butene-1,4-diol. The hydroxyl terminated oligoesters were reacted with phenyl isocyanate to form telechelic urethane groups. Hydrolysis rate constants were obtained from plots of acid number vs. time. It was observed that ternary oligoester systems had lower hydrolysis rates than quaternary systems. In addition to investigating the hydrolytic stability of the synthesized oligoesters, polyurethane coatings were produced by reacting the hydroxyl-terminated oligoesters with an aliphatic polyisocyanate (1,6-hexanediisocyanate trimer). Model oliogester hydrolysis was then correlated to the weatherability of a crosslinked polyurethane film. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40198.
Co-reporter:Kent R. Miller
Journal of Applied Polymer Science 2014 Volume 131( Issue 13) pp:
Publication Date(Web):
DOI:10.1002/app.40475
ABSTRACT
A series of acrylic poly(lactic acid) (PLA) films were produced via photopolymerization. Enzymatic degradation of the films was investigated by submerging or spraying the films with a solution of proteinase K, Chromobacterium viscosum (CvL), Rhizomucor miehei (RmL), or Candida cylindracea (CcL). Degradation was monitored by titration of the carboxylic acid groups, MS, and MS/MS. It was found that the degradation rate of the films was dependent on the water uptake of the film and enzyme solution used. The highest degradation rates, for both systems, were obtained by use of a proteinase K solution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40475.
Co-reporter:Jinping Wu, ;Mukerrem Cakmak
Polymer Engineering & Science 2014 Volume 54( Issue 12) pp:2979-2988
Publication Date(Web):
DOI:10.1002/pen.23859
The effect of electron beam (E-beam) radiation on a series of styrenic block copolymers (SBCs) was investigated. These SBCs included newly developed poly(styrene-block-isoprene/butadiene-block-styrene) (SIBS), poly(styrene-block-butadiene-block-styrene) (SBS), and poly(styrene-block-isoprene-block-styrene) (SIS). The tensile properties, stress relaxation, molecular weight, and dynamical mechanical properties were studied. Generally, the crosslink density and tensile moduli of SBCs increased with increasing of E-beam radiation dose. The tensile strength of SIBS and SIS was shown to first decrease at lower E-beam radiation dose (<120 kGy) and then increase at higher radiation dose (>190 kGy). The tensile strength of SBS was significantly decreased at high E-beam radiation dose (>190 kGy). This was attributed to the differences between entanglement before E-beam radiation and the homogeneity of the crosslink network after exposure. POLYM. ENG. SCI., 54:2979–2988, 2014. © 2014 Society of Plastics Engineers
Co-reporter:Priyanka P. Nalawade;Brinda Mehta;Coleen Pugh
Journal of Polymer Science Part A: Polymer Chemistry 2014 Volume 52( Issue 21) pp:3045-3059
Publication Date(Web):
DOI:10.1002/pola.27352
ABSTRACT
Soybean oil was modified in two steps: (1) conjugation of soybean oil and (2) Diels-Alder addition with 3-(trimethoxysilyl)propyl methacrylate, 2,2,2-trifluoroethyl methacrylate and triallyl ether acrylate. The structures were characterized using 1H NMR, 13C NMR, 13C-1H gradient heteronuclear single quantum coherence (gHSQC) NMR spectroscopy, and MALDI-TOF mass spectrometry. The 13C-1H gHSQC NMR spectra helped confirm the formation of a cyclohexene ring in all reactions, indicating a Diels-Alder addition. The diluent efficiency of modified soybean oil was evaluated in long oil alkyd formulation. Triallyl ether functionalized soybean oil resulted in the highest reduction in the viscosity of the alkyd formulations. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 3045–3059
Co-reporter:Elif Alyamac;Hua Gu
Journal of Coatings Technology and Research 2014 Volume 11( Issue 5) pp:665-683
Publication Date(Web):2014 September
DOI:10.1007/s11998-014-9591-x
A homogeneous mixture of two polymers dissolved in a common solvent or a mixture of solvents was applied as a thin film. The first component was a bisphenol-A based epoxide derivative modified with tetraethoxysilane (TEOS) oligomer and the second component was a high-solids fluorinated acrylic copolymer. The thin films were coated on steel substrates and were thermally crosslinked using a methylated melamine formaldehyde and/or a polyamide-amine curing agent. The films were evaluated via x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) with integrated energy dispersive spectroscopy (EDS). It was found that the molecular weight of the resins, fluorine content, epoxide inorganic modification, and curing agent affected the degree of stratification.
Co-reporter:Xiaojiang Wang, Mark D. Soucek
Progress in Organic Coatings 2013 Volume 76(7–8) pp:1057-1067
Publication Date(Web):July–August 2013
DOI:10.1016/j.porgcoat.2013.03.001
•Three urethane dimethacrylates were synthesized via a non-isocyanate method.•PU coatings showed improvements in impact resistance and elongation-at-break.•The coatings properties were dependent on the reactive diluents type and content.Three non-isocyanate urethane dimethacrylate reactive diluents 2-(methacryloyloxy)ethyl 2-(methacryloyloxy)ethylcarbamate (EOAED), 2-(methacryloyloxy)ethyl 3-(methacryloyloxy)propylcarbamate (POAED), and 1-(methacryloyloxy)propan-2-yl 3-(methacryloyloxy)propylcarbamate (POAPD) were synthesized by the reaction of a cyclic carbonate with an amino alcohol followed by a second reaction with the methacrylic anhydride. These reactive diluents were formulated with an acrylated polyester (APE) oligomer and free radical photoinitiator to prepare UV-curable polyurethane coatings. For comparison with urethane dimethacrylate reactive diluents, ethylene glycol dimethacrylate (EGDMA) was also used. The effect of reactive diluent type and content on the viscosity of the APE oligomer was measured. After UV curing, the viscoelastic, tensile, and thermal properties of the cured films were evaluated as a function of the reactive diluent using dynamic mechanical thermal analysis (DMTA), tensile, differential scanning calorimeter (DSC), and thermal gravimetric analysis (TGA). In addition, coating properties such as pencil hardness, chemical resistance, impact resistance, and gloss were also investigated. It was found that crosslink density, storage and tensile modulus, pencil hardness, chemical resistance, gel content, total water absorption, and glass transition temperature (Tg) were directly proportional to the amount of the reactive diluent. The urethane dimethacrylate reactive diluents show significant improvements in impact resistance and elongation-at-break properties compared to the EGDMA. It was found that the optimum level of the urethane dimethacrylate reactive diluents concentration is between 10 and 20 wt%.
Co-reporter:Serkan Bas, Mark D. Soucek
Reactive and Functional Polymers 2013 73(2) pp: 291-302
Publication Date(Web):1 February 2013
DOI:10.1016/j.reactfunctpolym.2012.05.005
Thermosetting acrylic latexes were synthesized using butyl acrylate (BA), methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (HEMA), and methacrylic acid (MAA) via seeded two-stage process. A 2-level factorial experimental design was employed to investigate the effect of hydroxyl (core phase), carboxylate (shell phase) groups, and type of surfactant (Triton X200, Tergitol XJ) on the mechanical properties of thermosetting latexes. Eight latexes with varying concentration of HEMA, MAA and two types of surfactants were synthesized and crosslinked with three crosslinkers. Latex functionality for crosslinking was located in the core only, the shell only, and both the core–shell with varying concentrations. Melamine-formaldehyde (hexamethoxymethyl melamine) resin was employed to crosslink hydroxyl functionalities in the core. Carboxylic acid groups in the shell were crosslinked with zinc ammonium carbonate. HDI isocyanurate (Desmodur N3300A) were used to crosslink with hydroxyl or carboxyl functional groups in core and shell. The mechanical properties of coatings were evaluated in terms of tensile properties, cross-hatch adhesion, pencil hardness, and impact resistance. Design of experiment (DOE) was utilized to investigate the effect of variables on mechanical properties of crosslinked thermoset films.
Co-reporter:Serkan Bas
Silicon 2013 Volume 5( Issue 2) pp:139-159
Publication Date(Web):2013 April
DOI:10.1007/s12633-012-9135-x
Three methods were used to prepare polysiloxane-functionalized acrylic latexes via emulsion polymerization. Ethyl acrylate and 2-ethylhexyl acrylate were used in all three methods as the acrylic phase. In the first method, an acrylic core was prepared with addition of a coupling agent, 3-(trimethoxysilyl) propyl methacrylate, after which a cyclic siloxane monomer (octamethylcyclotetrasiloxane) was reacted with the coupling agent. In the second method, a silane-terminated polysiloxane (H-PDMS) was reacted with ethylene glycol dimethacrylate, and then copolymerized with ethyl acrylate and 2-ethylhexyl acrylate in a batch emulsion polymerization. In the third method, cyclic siloxane monomer was added during emulsion polymerization of ethyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl methacrylate. Particle size distribution and particle morphology were evaluated using dynamic light scattering (DLS) and transmission electron microscopy (TEM), respectively. A core-shell morphology was observed in TEM for the first preparation method as proposed. After film formation, surface tension, morphology and dynamic mechanical properties were investigated. Stratification was also examined by Fourier-transform infrared spectroscopy (FT-IR) and energy dispersive X-ray (EDX). Microphase separation was observed by atomic force microscopy (AFM) after polysiloxane modification. Energy dispersive X-ray data indicated that only the second preparation method had a higher silicon content at the film-air interface than film-substrate interface. In all methods, the storage modulus and surface energy of latex films decreased after polysiloxane modification.
Co-reporter:Y. Cao;M. Cakmak ;M.D. Soucek
Polymer Engineering & Science 2013 Volume 53( Issue 10) pp:2228-2241
Publication Date(Web):
DOI:10.1002/pen.23477
Antireflective (AR) coatings were prepared using a polyimide and two types of organically modified silica colloids via a solution casting method. The optically transparent polyimide was prepared from 2,2′-Bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) and 4,4′-oxydianiline (ODA). The silica colloids were driven to the coating-air interface by either the fluorinated alkyl group or PDMS (Polydimethylsiloxane) segment tethered onto the silica colloids. The amount of fluorinated alkyl groups and the molecular weight of the siloxane grafted on the silica colloid were varied. The PDMS-silica and fluorosilica colloids were characterized by TEM (Transmission Electron Microscopy), DLS (Dynamic Light Scattering), FTIR (Fourier Transform Infrared Spectroscopy), solid-state 13C NMR (Nuclear Magnetic Resonance) and solid-state 29Si NMR. The AR coatings were characterized by UV–vis (Ultraviolet–Visible Spectroscopy) transmittance spectra, AFM (Atomic Force Microscope), and SEM (Scanning Electron Microscope). The effects of modified silica loading and type of solvent on AR properties were studied. An enhancement in AR activity was observed for 1 wt% PDMS-modified (low molecular weight) silica coatings and 3 wt.% fluorosilica-10 in dimethylacetamide (DMAc). In comparison with cyclopentanone (CPT), DMAc favors migration of silica particles toward coating-air interface giving higher transmittance. The migration of particles to the surface and consequently increased surface roughness was observed by SEM. POLYM. ENG. SCI., 53:2228–2241, 2013. © 2013 Society of Plastics Engineers
Co-reporter:M.D. Soucek, T. Khattab, J. Wu
Progress in Organic Coatings 2012 Volume 73(Issue 4) pp:435-454
Publication Date(Web):April 2012
DOI:10.1016/j.porgcoat.2011.08.021
This article is an overview of the chemistry and driers used in autoxidatively cured coatings and in particular alkyds. The drying process for alkyds and other unsaturated fatty acid materials is based on a series of chemical reactions known as autoxidation. The autoxidative process is usually catalyzed by metal salts known as driers. Numerous of investigations have elucidated the catalytic activity and reaction mechanism of the drying process. Spectroscopic techniques, especially mass spectrometry, have been used to study the autoxidation process and its products. Recent investigations on the oxidative drying of alkyd coating films are presented with a focus on both metal based and more environmental friendly means of catalysis.Highlights► Synthesis of autoxidative mechanism. ► Review of new driers. ► Review of drier chemistry.
Co-reporter:Elif Alyamac, Hua Gu, Mark D. Soucek, Shuyan Qiu, Rudolph G. Buchheit
Progress in Organic Coatings 2012 Volume 74(Issue 1) pp:67-81
Publication Date(Web):May 2012
DOI:10.1016/j.porgcoat.2011.11.012
Telechelic resins with reactive end groups (epoxy phosphate and epoxy ester) were synthesized using bisphenol-A (BPA) epoxide. The bisphenol-A based epoxide, the epoxy phosphate, and the epoxy ester were all modified with tetraethylorthosilicate (TEOS) oligomers, which were prepared through the hydrolysis and condensation of TEOS monomer with water under acidic condition. The epoxide/polysilicate (organic/inorganic) hybrid systems were characterized systematically, using FTIR, 1H, 13C, 31P, and 29Si NMR, and MALDI-TOF. The modified epoxides were thermally cured with a melamine-formaldehyde resin, cast on steel substrates. The coating performance of the modified epoxides was evaluated by pencil hardness, crosshatch adhesion, reverse and direct impact resistance, mandrel bending, and pull-off adhesion. Viscoelastic properties of the hybrid systems were also evaluated as a function of polysilicate content. Corrosion performance was evaluated via salt spray (fog) test for 264 h. Salt spray analysis revealed that inorganically modified epoxides provided improvement over the unmodified epoxide resins with respect to both corrosion resistance and adhesion to steel substrates.
Co-reporter:Serkan Bas
Macromolecular Materials and Engineering 2012 Volume 297( Issue 11) pp:1081-1090
Publication Date(Web):
DOI:10.1002/mame.201100372
Co-reporter:Kent R. Miller, Mark D. Soucek
European Polymer Journal 2012 Volume 48(Issue 12) pp:2107-2116
Publication Date(Web):December 2012
DOI:10.1016/j.eurpolymj.2012.08.006
Telechelic acrylic poly(lactic acid) (PLA) oligomers were synthesized from the transesterification of PLA with ethylene glycol diacrylate. The oligoesters were characterized by 1H NMR and GPC. The telechelic acrylic PLA oligomers were then formulated with four different reactive diluents and photopolymerized into films with photoinitiator Irgacure 2959. Films were formulated to contain either 1,4-butanediol dimethacrylate (BDDM) or triethylene glycol dimethacrylate (TEGDMA) and for each set of formulations the concentration of PLA was varied from 0 to 70 wt.%. The kinetics of the photopolymerizable material was studied by photo-differential scanning calorimeter (DSC). Physical properties were evaluated using pencil hardness, reverse impact resistance, pull off adhesion, solvent resistance, and dynamic mechanical thermal analysis (DMTA) properties. The Photo-DSC results showed that the reaction rate decreased as the PLA concentration increased. Films containing lower concentrations of PLA were harder and less flexible.Graphical abstractHighlights► Telechelic acrylic PLA oligomers photopolymerized with reactive diluents. ► Film properties dependent on concentration and choice of reactive diluent. ► Change of reactive diluent is simple method to achieve a wide range of properties.
Co-reporter:Jamie Dziczkowski, Uma Chatterjee, Mark Soucek
Progress in Organic Coatings 2012 Volume 73(Issue 4) pp:355-365
Publication Date(Web):April 2012
DOI:10.1016/j.porgcoat.2011.03.003
Acrylic modified alkyds were achieved from sequential polymerization of acrylic monomers in the presence of alkyd macro-RAFT agents. Macro-RAFT agents were reached by end-capping a soya-based alkyd with a carboxy-functional trithiocarbonate. The resulting material was then utilized as the RAFT chain transfer agent to affix acrylic blocks onto the alkyd backbone. Butyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate were the acrylic monomers used to achieve the acrylic blocks both individually and in combination. The resulting materials were characterized by various analytical techniques including size-exclusion chromatography (SEC), Fourier transform infrared (FTIR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. Size exclusion chromatography confirms the controlled nature of this approach to acrylated-alkyds and corroborates the NMR spectra that distinctly show the presence of acrylic blocks. Side reactions with the pendant fatty acids and the formation of homopolyacrylate are also distinguished from the analytical results, however, they are suppressed. Pseudo-first-order kinetics behavior and conversion versus molecular weight plots show that the RAFT-mediated reaction afforded a more controlled free radical process for the synthesis of acrylated-alkyd materials. Use of the alkyd macro-RAFT agent provided a new path to acrylated-alkyds that affords a more controlled way to tailor specific material properties.Highlights► Acrylic modified alkyds were achieved from RAFT agents and acrylic monomers. ► Pseudo-first-order kinetics behavior indicate a more controlled process. ► Use of the alkyd macro-RAFT agent provided a new path to acrylated-alkyds.
Co-reporter:Narin Thanamongkollit, Mark D. Soucek
Progress in Organic Coatings 2012 Volume 73(Issue 4) pp:382-391
Publication Date(Web):April 2012
DOI:10.1016/j.porgcoat.2011.02.004
The α-eleosterate pendent fatty acid of a tung oil based alkyd was functionalized via a Diels–Alder reaction with three different acrylate groups: (1) 2,2,2-trifluoroethyl methacrylate, (2) 3-methacryloxypropyl trimethoxysilane, and (3) triallyl ether acrylate. The modified alkyds were characterized by using 1H NMR, 13C NMR, and gel permeation chromatography (GPC). The drying time was measured at ambient temperature. The viscoelastic properties of the alkyd-modified films were measured using dynamic mechanical thermal analysis. The viscoelastic and drying time results show that the alkyd modified with siloxane and triallyl group affords a faster drying time, higher crosslink density, and higher glass transition temperature compared to the unmodified alkyd, whereas the fluorinated alkyd possesses surface active properties, but suffers in terms of drying and crosslinking density.
Co-reporter:P. Chittavanich, K. Miller, M.D. Soucek
Progress in Organic Coatings 2012 Volume 73(Issue 4) pp:392-400
Publication Date(Web):April 2012
DOI:10.1016/j.porgcoat.2011.02.005
The photo-curing of a pigmented UV-curable tung oil alkyd system (UVTA) was investigated. The UV-curable alkyd was a Diels–Alder Adduct of trimethylolpropane trimethacrylate with a tung oil-based alkyd. A mixture of yellow iron oxide, red iron oxide, titanium dioxide and lamp black pigments were chosen to obtain an observed yellow color. The pigment mixture, UV-curable alkyd and a reactive diluent were formulated together and photo-cured via a free radical mechanism. The through and surface cure was assessed by thumb twist, blocking resistance and MEK single rub. The through cure and surface cure assessment showed that optimum cure was achieved using UV-A as a source with two photoinitiators: phenylbis(2,4,6-trimethylbenzoyl-phosphine oxide) at 2 wt% and 1-hydroxy-cyclohexyl-phenyl-ketone at 4 wt%. The effect of reactive diluent was also investigated. Ten different reactive diluents were used. After curing, pencil hardness, conical mandrel, impact resistance, cross cut adhesion and gloss were measured. In addition, dynamic mechanical thermal analysis (DMTA) was used to evaluate selected systems. The coatings tests showed that the use of long chain linear structure diluents, such as isodecyl methacrylate, provided UV-curable paint films with better impact resistance, flexibility, and adhesion over other reactive diluents.
Co-reporter:Jamie Dziczkowski, Venkat Dudipala, Mark D. Soucek
Progress in Organic Coatings 2012 Volume 73(Issue 4) pp:308-320
Publication Date(Web):April 2012
DOI:10.1016/j.porgcoat.2010.12.006
Acrylic groups were grafted onto alkyds via free radical chemistry. The alkyd comprised soybean oil, glycerol, phthalic anhydride, and tetrahydrophthalic anhydride. To closely model acrylated-alkyds, a mixture of four acrylic monomers were copolymerized with the alkyd including: methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), and vinyltrimethyoxysilane (VTMS). Two different initiator systems were used, benzoyl peroxide (BPO) and 2,2′-azobisisobutyronitrile (AIBN), for comparison. To elucidate the grafting sites, 1D NMR spectroscopy and 2D NMR spectroscopy were used. Gradient heteronuclear multiple quantum correlation (gHMQC) was needed to assign the chemical shifts of the 1D carbon and proton NMR spectra. The gHMQC spectra provided evidence of acrylic–alkyd grafted structures formed at doubly allylic hydrogens located on the fatty acid chains. As a side reaction, acrylic groups were grafted into the polyester backbone of the alkyd via hydrogen abstraction of the glycerol. The gHMQC spectra show no evidence of grafting across double bonds on either the fatty acid side chains or the THPA backbone. It was also determined that choice of initiator has no effect on graft location. However, the system initiated with BPO provided spectral evidence of the formation of benzoic acid, which shows that the peroxide initiator can directly abstract the doubly allylic hydrogen. The side product, isobutyronitrile did not appear in the spectra obtained from the AIBN initiated system.
Co-reporter:Jamie Dziczkowski, Mark D. Soucek
Progress in Organic Coatings 2012 Volume 73(Issue 4) pp:330-343
Publication Date(Web):April 2012
DOI:10.1016/j.porgcoat.2011.03.005
Acrylic-grafted-alkyd resins were prepared by free radical chemistry. Long, medium, and short oil alkyds were prepared using soybean oil, glycerol, phthalic anhydride (PA), and tetrahydrophthalic anhydride (THPA) and used as the alkyd phase. Acrylic co-monomer formulas containing methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), and vinyl trimethoxysilane (VTMS) were polymerized in the presence of the different alkyds using 2,2′-azobisisobutyronitrile (AIBN) as the initiator to obtain the final grafted structures. Design of experiments was used to understand how different variables in the synthesis of the acrylated-alkyds affect the film performance. A Box–Behnkin design was used, varying the oil length of the alkyd phase, the degree of unsaturation in the polyester backbone, and acrylic to alkyd ratio. Acrylic–alkyd hybrid resins were reduced with an amine/water mixture. The hydrolytic stability of hybrid alkyd dispersed in water was evaluated. Cured films were prepared and basic coatings properties were also evaluated. It was found that the oil length of the alkyd is the most dominant factor for final coatings properties of the resins. The hydrolytic stability was dependent on the acrylic to alkyd ratio. The oil length of the alkyd backbone had a minimal effect on stability of the resin and film performance.Highlights► Water-reducible acrylated alkyds were evaluated by a design of experiment statistical technique. ► A number of pertinent properties including pot-life stability, hardness, impact resistance, flexibility, adhesion, and chemical resistance were reported. ► The factor of oil length dominated the properties of the acrylated alkyds when the alkyds were <50 wt% acrylate. ► Also, the hydrolytic stability of the alkyd was enhanced by the protective acrylate colloid.
Co-reporter:Kosin Wutticharoenwong, Jamie Dziczkowski, Mark D. Soucek
Progress in Organic Coatings 2012 Volume 73(Issue 4) pp:283-290
Publication Date(Web):April 2012
DOI:10.1016/j.porgcoat.2011.03.017
Reactive diluents were prepared from tung oil via a Diels–Alder reaction with three different dienophiles: methacryloxypropyl trimethoxysilane (TOMAS), 2,2,2-trifluoroethyl methacrylate (TOF) and triallyl ether acrylate (TOTAE). The reactive diluents were mixed with a long oil soya alkyd, a metal drier package, and a wetting agent; and then cured. Formulations were prepared as a function of reactive diluent type and wt%. Tensile, thermomechanical, and coatings properties were evaluated after curing the films. The addition of two reactive diluents, TOMAS and TOTAE, improved the tensile strength and tensile modulus of the alkyd. The addition of the diluents, however, did not significantly change the elongation at break compared to the alkyd in any of the systems. Also, the addition of TOMAS and TOTAE increased both the crosslink density and glass transition temperature of the alkyd. Basic film properties including hardness, solvent resistance, impact resistance, adhesion, and gloss were not adversely affected by the introduction of any of the tung oil based diluents.Highlights► New reactive diluents were prepared from tung oil. ► Formulations were prepared as a function of reactive diluent and an alkyd. ► Both viscosity and coatings properties were improved.
Co-reporter:Jamie Dziczkowski, Venkat Dudipala, Mark D. Soucek
Progress in Organic Coatings 2012 Volume 73(Issue 4) pp:294-307
Publication Date(Web):April 2012
DOI:10.1016/j.porgcoat.2010.12.005
Acrylic monomers were grafted onto alkyds via free radical chemistry. The alkyd was a medium oil soya-based alkyd with glycerol, phthalic anhydride, and tetrahydrophthalic anhydride (THPA) as the other components. To identify the specific graft locations, 1D and 2D NMR spectroscopy techniques were utilized. Gradient heteronuclear multiple quantum coherence (gHMQC) 2D NMR was required to assign the chemical shifts of the 1D carbon and proton NMR spectra. Three acrylic monomers, methyl methacrylate (MMA), butyl acrylate (BA), and methacrylic acid (MAA) were grafted to the alkyd, resulting in either MMA, BA, or MAA modified alkyds. Two-dimensional gHMQC spectra for each system confirm grafting at doubly allylic hydrogens located on the fatty acid chains and the polyol segment of the alkyd backbone. The gHMQC spectra show no evidence of grafting across double bonds on either pendant fatty acid groups or THPA unsaturation sites for any of the monomer choices.
Co-reporter:Narin Thanamongkollit, Kent R. Miller, Mark D. Soucek
Progress in Organic Coatings 2012 Volume 73(Issue 4) pp:425-434
Publication Date(Web):April 2012
DOI:10.1016/j.porgcoat.2011.02.003
Two UV-curable tung oil-based resins were synthesized via a Diels–Alder cycloaddition. An UV-curable tung oil (UVTO) was prepared from bodied tung oil and trimethylolpropane trimethacrylate (TMPTMA). An inhibitor, phenothiazine, was added to avoid homopolymerization of TMPTMA. The UV-curable tung oil alkyd (UVTA) was prepared from the monoglyceride process and then reacted with TMPTMA via the Diels–Alder reaction similar to the UVTO. The UVTO and UVTA were characterized by 1H NMR, 13C NMR, and MALDI-TOF mass spectroscopy. The UVTO and UVTA were formulated with a free radical reactive diluent, tripropylene glycol diacrylate (TPGDA) and photoinitiator Irgacure 2100. Photo differential scanning calorimeter (Photo-DSC) was used to investigate curing kinetics of the UVTO and the UVTA. Both the UVTO and UVTA were photocurable with the UVTA formula exhibiting a faster curing speed than the UVTO.
Co-reporter:Serkan Bas;Uma Chatterjee
Journal of Applied Polymer Science 2012 Volume 126( Issue 3) pp:998-1007
Publication Date(Web):
DOI:10.1002/app.36844
Abstract
A series of amphiphilic poly(2-hydroxyethyl methacrylate)-b-polydimethylsiloxane-b-poly(2-hydroxyethyl methacrylate) (pHEMA-b-PDMS-b-pHEMA) (A-B-A) triblock copolymers were synthesized from three different carbinol-terminated polydimethylsiloxanes with varying molecular weight. A carbinol-terminated polydimethylsiloxane was modified with 2-bromoisobutyryl bromide to obtain a macroinitiator. The block copolymers were characterized by NMR, GPC, and dynamic light scattering (DLS). Reverse micelles of a copolymer were formed in mixture of benzene/methanol solution which served as nanoreactors for the synthesis of magnesium fluoride (MgF2) nanoparticles. The MgF2 was prepared via chemical precipitation using magnesium chloride and potassium fluoride as reactants. The MgF2-triblock copolymer composites were synthesized as a function of MgF2–weight ratio (0.5, 5, and 10 wt%) in copolymer. The MgF2 colloids were dissolved in three organic solvents: methanol, isopropanol, and tetrahydrofuran. The polymer nanoparticles were characterized by DLS, transmission electron microscopy, thermogravimetric analysis, and X-ray diffraction (XRD) analysis. The formation of MgF2 crystals was observed by XRD. Particle size and particle size distribution showed significant changes in different solvents. The thermal stability of MgF2 colloids increased as the amount of nanoparticle increased in polymeric matrix. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
Co-reporter:Elif Alyamac, Mark D. Soucek
Progress in Organic Coatings 2011 Volume 71(Issue 3) pp:213-224
Publication Date(Web):July 2011
DOI:10.1016/j.porgcoat.2011.02.015
A series of low, medium, and high molecular weight copolymers containing methyl methacrylate, n-butyl acrylate, 2-hydroxyethyl methacrylate, and 2,2,2-trifluoroethyl methacrylate were synthesized by solution polymerization under monomer-starved conditions. The acrylate-based copolymers were characterized by FTIR; 1H, 13C, and 19F NMR, and MALDI-TOF mass spectrometry. The molecular weights and the glass transition temperatures of the copolymers were determined using Gel Permeation Chromatography (GPC) and Differential Scanning Calorimetry (DSC). The copolymers were crosslinked with a methylated melamine formaldehyde resin in order to obtain thermosetting acrylics. Surface, optical, barrier, mechanical, and viscoelastic properties of the acrylic coatings were investigated. An enrichment of fluorinated units at the acrylic surface was directly verified measuring dynamic contact angles. Lower wettability, higher oxygen permeability, and lower refractive index were observed for higher concentrations of fluorinated monomer in the copolymer composition. High number-average hydroxyl functionality of high molecular weight copolymers increased the crosslink density of the acrylic films, resulting in improved tensile strength and tensile modulus.
Co-reporter:Uma Chatterjee;Xiaojiang Wang;Suresh K. Jewrajka
Macromolecular Chemistry and Physics 2011 Volume 212( Issue 17) pp:1879-1890
Publication Date(Web):
DOI:10.1002/macp.201100083
Co-reporter:Kosin Wutticharoenwong
Macromolecular Materials and Engineering 2010 Volume 295( Issue 12) pp:1097-1106
Publication Date(Web):
DOI:10.1002/mame.201000099
Co-reporter:Ruby Chakraborty
Journal of Applied Polymer Science 2010 Volume 115( Issue 1) pp:358-369
Publication Date(Web):
DOI:10.1002/app.29820
Abstract
Telechelic glycidyl epoxide siloxanes substituted with either methyl, cyclopentyl, or cyclohexyl groups were cured thermally with corresponding telechelic aliphatic amine. Also, the three glycidyl epoxide functionalized siloxanes were homopolymerized via a photo-initiated cationic mechanism. Both the UV and thermal curing were performed by formulating with reactive diluents. The mechanical properties, viscoelastic behavior, and coatings properties of the thermally cured siloxanes were studied. In addition, the X-ray measurements were performed. The rate of polymerization increased with the increasing size of substituent on the siloxane backbone. The hardness, adhesion, and solvent resistance increased as the bulk of the substituent increased in the siloxane backbone. The release properties for adhesion and readhesion increased with increase in steric bulk of the backbone substituents. Crosslink density reduced and oxygen permeability increased with increase in siloxane substituent size. There was also an increase in the advancing and the receding contact angles with the increase in substituent size. The inverse dependency of substituent size and free volume was observed in the d-spacing of the X-ray data. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
Co-reporter:Liang Zhou;Hendrik Heinz;Elvin A. Alemán;David A. Modarelli
Silicon 2010 Volume 2( Issue 2) pp:111
Publication Date(Web):2010 April
DOI:10.1007/s12633-010-9048-5
Co-reporter:Liang Zhou;Hendrik Heinz;Elvin A. Alemán;David A. Modarelli
Silicon 2010 Volume 2( Issue 2) pp:95-104
Publication Date(Web):2010 April
DOI:10.1007/s12633-009-9030-2
Metal-oxo-colloids have been prepared using tetraethoxysilane (TEOS) oligomers with titanium tetra-i-propoxide (TIP) or titanium (di-i-propoxide) bis(acetylacetonate) (TIA) precursors. Transmission electron microscopy (TEM), FTIR, UV-Vis, and photoluminescence spectroscopy were used to investigate the composition, the size, and optical properties of the Si/Ti core–shell colloids. The presence of hetero-bonded silicate structure (Si–O–Ti) was indicated by FTIR spectroscopy. The size of Si/TIP system ranged from 55 to 120 nm and Si/TIA system ranged from 220 to 250 nm. The TEM data indicated that the size of colloids can be controlled by the TIP or TIA content. The Si/Ti system exhibited strong absorption in the UV-range, yet had excellent optical transmittance in the visible range. The Si/Ti systems exhibited a photoluminescence emission at 329 nm.
Co-reporter:Jamie Dziczkowski
Journal of Coatings Technology and Research 2010 Volume 7( Issue 5) pp:587-602
Publication Date(Web):2010 September
DOI:10.1007/s11998-009-9237-6
A new class of acrylated alkyds resins has been developed using a modern controlled polymerization approach. The reactive relationship between acrylics and alkyds has been defined by difficulty and an inability to propagate to form suitable grafting during a free-radical-based process. A living free-radical process was employed to provide control of both location and blocks of monomers which were attached to the polyester backbone of the alkyd. Both acrylic monomers and blocks of different monomer were successfully polymerized with control. Although there was some side reaction at the pendent fatty acid unsaturation, overall, the system was well behaved with respect to control of blocks of sequential monomers and living characteristics of the free-radical polymerization. Demonstration of concept was achieved in both high solids and waterborne systems. Representative coating properties are also reported for model alkyd systems.
Co-reporter:Ruby Chakraborty
Silicon 2010 Volume 2( Issue 1) pp:61-69
Publication Date(Web):2010 January
DOI:10.1007/s12633-010-9036-9
Siloxanes with either methyl, cyclopentyl, or cyclohexyl groups were functionalized with methacrylate groups, then UV-cured using a free radical photo-initiator and a reactive diluent. Hexanediol dimethacrylate (0.1 wt%) was used as the reactive diluent. After curing, the mechanical, the viscoelastic, the coating, and the release properties of the cured films were studied. In addition, the oxygen permeability and the X-ray diffraction scans were evaluated. The crosslink density reduced with increase in siloxane substituent size. The oxygen permeability was dependent on crosslink density, and increased with increasing substituent size. The increase in permeability, and thus free volume, was supported by X-ray studies which showed an increase in d-spacing with increasing alkyl size. The hardness, adhesion, and solvent resistance increased as the size of the substituent increased (methyl to cyclopentyl to cyclohexyl) in the siloxane backbone. The adhesion and re-adhesion forces increased with an increase in size of the backbone substituents. There was also an increase in the advancing and the receding contact angles with the increase in substituent size.
Co-reporter:Kosin Wutticharoenwong
Journal of Applied Polymer Science 2009 Volume 113( Issue 4) pp:2173-2185
Publication Date(Web):
DOI:10.1002/app.29796
Abstract
Three 3-mercaptopropionate thiols, 1,6-Hexane bis(3-mercaptopropionate) (HD-SH), trans-1,4-Cyclohexanedimethyl bis(3-mercaptopropionate) (CHDM-SH), and 4,4′-Isopropylidenedicyclohexane bis(3-mercaptopropionate) (HBPA-SH) were formulated with 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATATO) and photoinitiator. The formulations were photopolymerized via thiol-ene photopolymerization. A ternary experimental design was employed to elucidate the influence the three thiols on the thermomechanical and coatings properties of thiol-ene photopolymerizable materials. Tensile strength, tensile modulus, elongation-to-break, glass transition temperature (Tg), and crosslink density (XLD) were investigated. Coating properties including pencil hardness, pull-off adhesion, MEK double rubs, and gloss were also investigated. Relative reaction conversion was determined by photo differential scanning calorimeter (PDSC). Thiol-ene photopolymerizable materials containing HBPA-SH resulted in improving tensile strength, tensile modulus, Tg, and pencil hardness but lowering of crosslink density and relative conversion. This was attributed to steric and rigidity of the double cycloaliphatic structure. The inclusion of CHDM-SH into the systems resulted in the synergistic effect on elongation-to-break and pull-off adhesion. The HD-SH generally resulted in a diminution of thermomechanical and coating properties, but improved the crosslink density. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009
Co-reporter:Ruby Chakraborty;Mrunal Thatte
Journal of Coatings Technology and Research 2009 Volume 6( Issue 4) pp:
Publication Date(Web):2009 December
DOI:10.1007/s11998-008-9155-z
The effect of oil length of alkyds and substitution of siloxane backbone has been studied for alkyd–siloxane hybrids. A series of nine alkyd–siloxane hybrids were synthesized by either varying the oil length of the alkyd or the siloxane backbone substitution. Three linseed oil-based alkyds with either a long, medium, or short oil length were grafted with three hydride-terminated siloxanes substituted with methyl, cyclopentyl, or cyclohexyl groups. A hydrocoupling reaction was used to couple the telechelic siloxane with the hydroxyl functionality of the alkyds using Wilkinson’s catalyst. The reaction was monitored by the disappearance of siloxane hydride signal using Fourier transform infrared. Characterization of siloxane–alkyd hybrids was performed using 1H-NMR, 13C-NMR, and gel permeation chromatography. The hybrids were formulated with a Co, Zr, and Ca drier package and auto-oxidatively cured without using any solvent. The tensile, viscoelastic, and coating properties were evaluated for the cured films. The crosslink density, flexibility, and reverse impact resistance were found to increase as a function of oil length. Tensile modulus, elongation-to-break, glass transition temperature, drying time, and fracture toughness decreased with increase in oil length. For the alkyd–siloxane hybrids, the mechanical and rheological properties were dependant on the size of the substituents. The larger-sized cyclopentyl and cyclohexyl groups resulted in better mechanical and rheological properties than the methyl-containing siloxanes.
Co-reporter:M. D. Soucek;E. Pedraza
Journal of Coatings Technology and Research 2009 Volume 6( Issue 1) pp:27-36
Publication Date(Web):2009 March
DOI:10.1007/s11998-008-9099-3
The location of hydroxyl functionality was investigated for thermosetting acrylic latexes. Large and small latex particles with and without hydroxyl functionality were also synthesized and characterized. Large and small latex particles with and without hydroxyl functionality were blended together, and the latexes were crosslinked. The location of hydroxyl groups in the small or large latex particles had an effect upon the thermomechanical properties and hence on the ultimate performance of the crosslinked latexes. The packing of the large and small latexes was dependent on small-to-large particle ratio, and in addition had an effect upon the speed of film formation. The higher concentration of hydroxyl groups in the small latex particles contributed more to the tensile properties of the latexes than the functionality of the large particles.
Co-reporter:Kosin Wutticharoenwong
Macromolecular Materials and Engineering 2008 Volume 293( Issue 1) pp:45-56
Publication Date(Web):
DOI:10.1002/mame.200700175
Co-reporter:Erika P. Pedraza, Mark D. Soucek
Progress in Organic Coatings 2008 Volume 62(Issue 4) pp:417-424
Publication Date(Web):June 2008
DOI:10.1016/j.porgcoat.2008.02.009
Co-reporter:Ruby Chakraborty
Macromolecular Chemistry and Physics 2008 Volume 209( Issue 6) pp:604-614
Publication Date(Web):
DOI:10.1002/macp.200700496
Co-reporter:Ahmet Nebioglu
Journal of Applied Polymer Science 2008 Volume 107( Issue 4) pp:2364-2374
Publication Date(Web):
DOI:10.1002/app.27381
Abstract
The effect of internal and terminal unsaturation on the properties of the acrylated polyester films was investigated. Four types of acrylated polyester resin were prepared using adipic acid, maleic anhydride, neopentyl glycol, trimethylolpropane, and acrylic acid. Terminal and internal double bond content as well as branching was adjusted by the molar quantities of trimethylolpropane and maleic anhydride, respectively. A reactive diluent, trimethylolpropane triacrylate (TMPTA), was also used. A three-factor, three-level Box-Behnken design was used to investigate complex nonlinear relationships. Dynamic mechanical, fracture toughness, and tensile properties were evaluated with respect to the amount of terminal and internal unsaturation, and reactive diluent concentration. It was found that microgel formation extensively affects the final UV-cured film properties. Small quantities of microgels function as micro-support units, whereas high extent of microgelation causes phase separation through cluster formation and hence, decreases the mechanical properties. It is essential to control the extent of microgelation and phase separation to optimize product performance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008
Co-reporter:Jianyun He;Liang Zhou;Chrys Wesdemiotis;Kathleen M. Wollyung
Journal of Applied Polymer Science 2007 Volume 105(Issue 4) pp:2376-2386
Publication Date(Web):8 MAY 2007
DOI:10.1002/app.25709
Organic–inorganic hybrid coatings were formulated using multifunctional vinyltrimethoxysilane (VTMS) oligomers and acrylated polyester (AP). A radical photoinitiator was added to the VTMS/AP formulation and the films were crosslinked via UV-radiation. The viscoelastic, thermomechanical, and surface properties of the VTMS/AP films were evaluated as a function of VTMS content, using dynamic mechanical thermal analysis (DMTA), thermal gravimetric analysis (TGA), contact angle, fracture toughness, and tensile properties. In addition, coating properties such as adhesion, scratch resistance, pencil hardness, and impact resistance were also investigated. The tensile and scratch data show that VTMS oligomer dramatically increased hardness and scratch resistance. The VTMS oligomer also increased the contact angle, led to a decrease in surface tension, and improved surface appearance. The VTMS oligomer also increases storage modulus, glass transition temperature, and crosslink density. The morphology of films and the particle size were observed using atomic force microscopy (AFM). The data indicated that the average silica particle size was ∼90 nm and the particles were well-dispersed in the organic phase. It was postulated that the VTMS oligomer functioned effectively as a hyperbranched crosslinker, surface modifier, and reactive diluent. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 105:2376–2386, 2007
Co-reporter:Mark D. Soucek;David P. Dworak
Macromolecular Chemistry and Physics 2007 Volume 208(Issue 23) pp:2502-2509
Publication Date(Web):2 NOV 2007
DOI:10.1002/macp.200700304
Cyclopentyl- and cyclohexyl-substituted polysiloxanes terminated with amino groups were prepared. Initially, the cycloalkene and dichlorosilane were reacted at high pressure (approx. 250 psi) and high temperature (120 °C) to yield the cycloaliphatic dichlorosilane in a two-step process. Both the mono- and disubstituted chlorosilane monomers underwent an oligomerization to produce cyclic oligomers of low molecular weight (≈2 000 g · mol−1). Amine-terminated polysiloxanes were produced via a base-catalyzed ring-opening polymerization of the cyclic oligomers with 1,3-bis(3-aminopropyl)tetramethyldisiloxane to yield low molecular weight polysiloxanes (≈9 000 g · mol−1, amine equivalent weight = ≈4 300 g · equiv.−1). The polysiloxanes were characterized by 1H and 29Si NMR, and Fourier transform-infrared spectroscopy (FT-IR). The amine-terminated polysiloxane was mixed with a cycloaliphatic epoxy-functionalized cycloaliphatic polysiloxane in order to produce crosslinked epoxy–amine films. The mechanical and physical properties of the film were evaluated and afford a glass transition of the material was 29.5 ± 0.7 °C for the cyclopentyl-substituted polysiloxane and 38.6 ± 0.7 °C for the cyclohexyl-substituted polysiloxane. Evaluation of pull-off adhesion indicated that 0.5 MPa of normal force was required to remove the epoxy/amine film from an aluminum substrate.
Co-reporter:Mark D. Soucek;David P. Dworak
Journal of Coatings Technology and Research 2007 Volume 4( Issue 3) pp:263-274
Publication Date(Web):2007/09/01
DOI:10.1007/s11998-007-9044-x
A new class of silicone has been developed for coatings or as coating additives. Cycloaliphatic silane monomers were prepared and reacted into more easily handled cyclic oligomers. These cyclic oligomers were ring-opened into siloxane polymers. The polymers were functionalized with a variety of groups, including: amino, glycidyl epoxide, cyclohexene epoxide, acrylic, and alkoxysilane. The cycloaliphatic silicones have been designed for a number of different curing conditions: (1) ambient temperature-cure (amino and glycidyl epoxide), (2) cationic ultraviolet (UV)-cure (cyclohexene epoxide), (3) radical UV-cure (acrylic), and (4) moisture-cure (alkoxysilane). The end usages thus far have been focused on silicone coatings; however, usage as coating additives will be a focus for future research. The cycloaliphatic silicone has been UV-cured with mixed sol–gel precursors for usage as aerospace coatings. The cycloaliphatic silicones have also been ambient temperature-cured for release coatings, and have application as anti-fouling coatings. The inherent low surface energy makes the cycloaliphatic silicones prime candidates for surface tension additives.
Co-reporter:Ahmet Nebioglu
Journal of Coatings Technology and Research 2007 Volume 4( Issue 4) pp:425-433
Publication Date(Web):2007 December
DOI:10.1007/s11998-007-9035-y
The effect of the extent of internal unsaturation and branching on the properties of the acrylated polyester films was investigated. Polyester acrylate resins were prepared based on adipic acid, maleic anhydride, neopentyl glycol, trimethylolpropane, and acrylic acid. As the reactive diluent, trimethylolpropane triacrylate (TMPTA) was used. Experiments were planned according to the three-factor, three-level Box-Behnken design. Coating film properties were evaluated in terms of the independent variables, amount of branching, internal unsaturation, and reactive diluent.
Co-reporter:David P. Dworak
Macromolecular Chemistry and Physics 2006 Volume 207(Issue 14) pp:1220-1232
Publication Date(Web):17 JUL 2006
DOI:10.1002/macp.200600051
Summary: An inorganic hybrid material was produced using a polysiloxane binder and metal-oxo-clusters which were derived from sol-gel precursors. The continuous phase is composed of an elastomeric polysiloxane functionalized with cycloaliphatic epoxide groups. Pendant alkoxy silane groups serve as a coupling agent to form a network between the metal-oxo-clusters and the crosslinked polysiloxane. Methyl, cyclopentyl, and cyclohexyl substituted polysiloxanes were formulated with a variety of sol-gel precursors (tetraethylorthosilicate oligomers, titanium(IV) iso-propoxide, zirconium(IV) propoxide, and zinc acetate). Phase-modulated FT-IR, X-ray photoelectron spectroscopy, solid state 29Si NMR, and solid state 13C NMR were used to investigate the internal structure of the mixed metal-oxo/silicon-oxo colloids prepared within the cured polysiloxane matrix. Results indicate that the cycloaliphatic groups inhibit the complete hydrolysis and condensation of the pendant triethoxysilane group and reaction of the sol-gel precursors. Analysis also indicated that the metal-oxo-clusters were comprised of mixed species of sol-gel precursors resulting in hetero-bonded (SiOMetal) colloids.
Co-reporter:Ahmet Nebioglu;Ganghua Teng
Journal of Applied Polymer Science 2006 Volume 99(Issue 1) pp:115-126
Publication Date(Web):11 OCT 2005
DOI:10.1002/app.22461
An unsaturated polyester, based on maleic anhydride, 1,6-hexanediol, and trimethylol propane, was formulated with tetraethylorthosilicate (TEOS) oligomers and a coupling agent to prepare inorganic/organic hybrid films. TEOS oligomers were prepared through the hydrolysis and condensation of TEOS with water, and 3-(triethoxysilyl)propylisocyanate was used as the coupling agent between the organic and inorganic phases. The hybrid materials were cured by moisture via sol–gel chemistry and by the UV curing of unsaturated polyesters. To compare the properties of the moisture-cured inorganic/organic hybrid films, a conventional 2K polyurethane system was also prepared. The tensile, adhesion, abrasion, and fracture toughness properties were investigated as functions of the coupling agent and relative amount of UV cure versus thermal cure. Although no difference could be observed in the tensile properties, the abrasion resistance, fracture toughness, and adhesion were enhanced by the incorporation of TEOS oligomers into polyurethane films. Also, the abrasion resistance, fracture toughness, and tensile properties were increased with both moisture and UV exposure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 115–126, 2006
Co-reporter:D. P. Dworak;H. Lin;B. D. Freeman;M. D. Soucek
Journal of Applied Polymer Science 2006 Volume 102(Issue 3) pp:2343-2351
Publication Date(Web):23 AUG 2006
DOI:10.1002/app.24480
A photo-cured cyclohexyl-substituted polysiloxane (PDCHS) film was prepared and compared with polydimethylsiloxane (PDMS) for the determination of permeability coefficients using various penetrants (H2, N2, O2, CO2, CH4, C3H6, and C3H8). Penetrant sorption isotherms and local effective diffusion coefficients as a function of local penetrant concentration were also determined. The crosslink density of the films was measured via dynamic mechanical thermal analysis and was found to be 6.46 × 104 mol/m3 for PDMS and 1.82 × 103 mol/m3 for PDCHS. Photo-differential scanning calorimetry was used to calculate percent conversion under the conditions used for curing and was found to be (99.6 ± 0.3)% for PDMS and (98.4 ± 0.3)% for PDCHS. When cured, the PDCHS films had a lower crosslink density and lower permeance. It was postulated that the cycloaliphatic substitution along the polysiloxane backbone may not have full rotational ability affording closer intermolecular interactions, thus reducing the available free volume. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:2343–2351, 2006
Co-reporter:Ahmet Nebioglu
Journal of Polymer Science Part A: Polymer Chemistry 2006 Volume 44(Issue 22) pp:6544-6557
Publication Date(Web):9 OCT 2006
DOI:10.1002/pola.21744
The free-radical reaction kinetics and microgel formation of UV-curing unsaturated polyester acrylates were studied in terms of the effects of internal maleic and terminal acrylate unsaturations. A triacrylate-functional monomer, trimethylolpropane triacrylate, was used as the reactive diluent. A time-resolved Fourier transform infrared technique was used to evaluate the consumption of double bonds and showed that internal (maleic) double bonds were involved in microgel formation at a rate similar to that of the more reactive terminal (acrylic) double bonds. Dynamic light scattering was used to measure the microgel particle size. The introduction of internal unsaturations caused smaller microgels, whereas terminal acrylate unsaturations resulted in larger particle sizes. These results were attributed to the higher tendency of the internal maleic double bonds toward intramolecular cyclization reactions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6544–6557, 2006
Co-reporter:Zhengang Zong, Jianyun He, Mark D. Soucek
Progress in Organic Coatings 2005 Volume 53(Issue 2) pp:83-90
Publication Date(Web):1 June 2005
DOI:10.1016/j.porgcoat.2004.08.008
UV-curable organic/inorganic hybrid film based on epoxynorbornene linseed oils (ENLO) was prepared using the in situ method of tetraethylorthosilane (TEOS) oligomers. Three levels of norbornylization of linseed oil (25, 50, and 100%) were utilized in this study. The effects of TEOS oligomers on ENLO film properties such as Young's modulus, tensile strength and elongation and on the coated film properties of pencil hardness, impact resistance, adhesion, chemical resistance, and contact angles were investigated. Fracture toughness and dynamic mechanical properties and thermal properties of the hybrid films were also evaluated. The tensile, dynamic mechanical thermal analyzer (DMTA), and fracture toughness data indicated that after incorporating the TEOS oligomers, the modulus, Tg, crosslink density of the hybrid films were enhanced, while the elongation at break, fracture toughness, and resistance to crack extension decreased. TEOS oligomers improved the hybrid coating properties such as pencil hardness, impact resistance, solvent resistance, and surface tension.
Co-reporter:Mark D. Soucek;Kunrong Zou
Macromolecular Chemistry and Physics 2005 Volume 206(Issue 9) pp:967-975
Publication Date(Web):28 APR 2005
DOI:10.1002/macp.200400390
Summary: Linseed oil was derivitized with 1,3-butadiene via a Diels-Alder reaction. The cycloaddition adduct was then epoxidized using a hydrogen peroxide/quaternary ammonium tetrakis(diperoxotungsto) phosphate system. The cyclohexene derivitized linseed oil (CLO) and the epoxidized cyclohexene derivatized linseed oil (ECLO) were characterized by 1H NMR, 13C NMR, and FT-IR. In addition, 2D NMR measurements (COSY) were performed on CLO and ECLO to identify the cyclohexyl structures. Molecular weight was determined by ESI-MS and GPC. The ECLO was photo-polymerized using UV-light, and the kinetics of the photo-curing reactions was evaluated by real-time FT-IR and photo-DSC. All the characterizations supported the successful introduction of cyclohexyl structure to the backbone of linseed oil directly and indirectly. Real-time FT-IR and photo-DSC indicated the slightly improved reactivity of ECLO.
Co-reporter:Jianyun He;Ahmet Nebioglu;Zhengang Zong;Kathleen M. Wollyung;Chrys Wesdemiotis
Macromolecular Chemistry and Physics 2005 Volume 206(Issue 7) pp:
Publication Date(Web):8 APR 2005
DOI:10.1002/macp.200400391
Summary: A new siloxane colloid was developed, for the use in UV-curable inorganic-organic hybrid films. The UV-crosslinkable silica-colloids were prepared from vinyltrimethoxysilane (VTMS) via a sol-gel method. The structure of silica-colloids was characterized using 1H NMR, 29Si NMR, FT-IR, and matrix-assisted laser desorption/ionization (MALDI-TOF) mass spectrometry (MS). The particle size of the siloxane colloid was evaluated using atomic force microscopy (AFM) and small angle light scattering (SALS). Organic phase was based on an acrylated polyester which was synthesized using 1,4-cyclohexane dimethanol (1,4-CHDM), neopentyl glycol (NPG), 1,6-hexanediol (1,6-HD), maleic anhydride (MA), adipic acid (ADA), and acrylic acid (AA). The acrylated polyester was characterized by gel-permeation chromatography (GPC) and acid titration. A photo-initiator was added to the formulation and the UV-crosslinking reaction of hybrid film was monitored via photo-differential scanning calorimetry (Photo-DSC) and real-time infrared spectroscopy (RT-IR). The effect of the concentration of VTMS colloids, UV-light intensity, and exposure time on the polymerization rate was investigated and compared with an inorganic-organic hybrid film based on TEOS oligomers. Photo-DSC and RT-IR results indicated that VTMS colloids can greatly increase free radical polymerization rate and the VTMS colloids functioned effectively as cross-linker and reactive diluent. AFM and small angle light scattering (SALS) data showed that the silica-colloids were well dispersed in the organic phase.
Co-reporter:Zhengang Zong;Chenchen Xue
Journal of Polymer Science Part A: Polymer Chemistry 2005 Volume 43(Issue 8) pp:1607-1623
Publication Date(Web):1 MAR 2005
DOI:10.1002/pola.20664
Inorganic–organic hybrid materials were prepared with a cycloaliphatic epoxide adduct of linseed oil with tetraethylorthosilicate (TEOS) oligomers via a cationic UV-curing process. The TEOS oligomers were prepared in the presence of water and ethanol with hydrochloric acid as a catalyst. The TEOS oligomers were characterized with 1H and 29Si NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Hybrid films were cured, and the dynamic mechanical and thermal properties of the hybrid films were evaluated as a function of the TEOS oligomer content. The morphology of the hybrid films was examined with atomic force microscopy, transmission electron microscopy, and small-angle light scattering. The microscopy and dynamic mechanical data indicated that the hybrid films were heterogeneous materials with various inorganic particle sizes dispersed within the organic matrix. In addition, 29Si solid-state NMR spectroscopy was used to investigate the coupling between the silicate region and organic regions. A schematic model is proposed to address structural features of hybrid materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1607–1623, 2005
Co-reporter:Mark D. Soucek, Aaron H. Johnson, Jonathan M. Wegner
Progress in Organic Coatings 2004 Volume 51(Issue 4) pp:300-311
Publication Date(Web):20 December 2004
DOI:10.1016/j.porgcoat.2004.07.019
Inorganic/organic hybrid coatings were prepared using epoxidized linseed oil with combinations of the two sol–gel precursors (titanium(IV) isopropoxide, tetraethyl orthosilicate), and a telechelic silicate based on a modified oligomeric caprolactone. The coatings were UV-cured with sulfonium initiators which concomitantly cured the epoxy functional organic phase and the sol–gel inorganic phase to form a co-continuous inorganic/organic system. A ternary experimental design was employed to elucidate the influence of inorganic modifier on the mechanical properties of the inorganic/organic hybrid coatings. Small angle X-ray scattering (SAXS) was used to evaluate radius of gyration of the metal-oxo-cluster. Various coating properties, such as hardness, impact resistance, adhesion, solvent resistance, and surface energy were investigated as a function of sol–gel precursors. Inorganic/organic hybrid coatings containing both tetraethyl orthosilicate and the modified caprolactone resulted in improved hardness and solvent resistance with no loss of impact strength. The inclusion of titanium(IV) isopropoxide in to the systems resulted in a systematic reduction in the coatings properties. This was attributed to inhibition of the organic crosslinking process as a consequence of absorption of ultraviolet light by the titanium-oxo-clusters.
Co-reporter:Mark D. Soucek;Aaron H. Johnson;Leon E. Meemken
Macromolecular Chemistry and Physics 2004 Volume 205(Issue 1) pp:35-41
Publication Date(Web):2 JAN 2004
DOI:10.1002/macp.200350084
Summary: The addition of a trifunctional polyol (trimethylolpropane) to oligoesters comprised of hexahydrophthalic anhydride, cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, neopentyl glycol, and cyclohexane-1,4-dimethanol was investigated via an accelerated hydrolysis environment. The oligoesters were dissolved in an acetone/water solution, and the hydrolysis was evaluated by monitoring carboxylic acid formation and by measurement of the molecular weight shift by size exclusion chromatography. Aliquots of the oligoester solution were evaluated intermittently over a 36-week period. Both the initial rate and the overall rates of hydrolysis were reported as hydrolysis velocities. The influence of hydroxyl concentration is apparent in the initial velocity of hydrolysis. After the induction period, steric effects appear to be the controlling factor for the retardation of main chain scission.
Co-reporter:Kunrong Zou
Macromolecular Chemistry and Physics 2004 Volume 205(Issue 15) pp:
Publication Date(Web):27 SEP 2004
DOI:10.1002/macp.200400115
Summary: Organic-inorganic hybrid films based on epoxidized cyclohexene derivatized linseed oil (ECLO) and tetraethylorthosilicate (TEOS) oligomers were prepared via a UV-curing process. The kinetics of the hybrid materials were studied by photo-differential scanning calorimetry (DSC). In addition to the kinetics, the tensile properties, pencil hardness, pull-off adhesion, reverse impact resistance, solvent resistance and abrasion resistance of the hybrid coatings were evaluated. Both dynamic mechanical thermal analysis (DMTA) and thermogravimetric analysis (TGA) were used to investigate the viscoelastic and thermal properties of the hybrid films. The morphology of the hybrid film was characterized by atomic force microscopy (AFM). Based on the results from the aforementioned evaluation of the coatings, the hybrid films exhibited higher pencil hardness, tensile strength, tensile modulus, fracture toughness, abrasion resistance, cross-link density and thermal stability compared to the ECLO organic film. The Photo-DSC data showed that the photo-curing speed of the hybrid materials increased with TEOS oligomers content. It was postulated that the TEOS oligomers were reactive diluents.
Co-reporter:Ganghua Teng
Macromolecular Materials and Engineering 2003 Volume 288(Issue 11) pp:844-851
Publication Date(Web):18 NOV 2003
DOI:10.1002/mame.200300118
A series of ceramer coatings were formulated using blown soybean oil as the organic phase, and sol-gel precursors [titanium(IV) isopropoxide, titanium(IV) diisopropoxide bisacetoacetonate, and zirconium propoxide] as the inorganic phase. The corrosion resistance of the ceramer coatings was evaluated using failure-at-scribe and electrochemical impedance spectroscopy (EIS) on aluminium after exposure in a Prohesion Chamber. Scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDXA) were also used to evaluate the coatings after exposure. The ceramer coatings demonstrated higher pull-off adhesion, impedance modulus (after exposure), and lower failure-at-scribe than the blown soybean oil film. It was surmised that the addition of sol-gel precursor enhanced the corrosion protective properties of the ceramer coatings via a self-assembling layer of metal-oxo clusters at the film substrate (aluminium) interface.
Co-reporter:Ganghua Teng;Xiaofan F. Yang;Dennis E. Tallman
Journal of Applied Polymer Science 2003 Volume 88(Issue 2) pp:245-257
Publication Date(Web):4 FEB 2003
DOI:10.1002/app.11682
Core-shell latexes (LAs) designed for crosslinking with cycloaliphatic diepoxide were synthesized. The core contained methyl methacrylate (MMA), butyl acrylate (BA), and 2-hydroxyethyl methacrylate, and the shell was prepared with MMA, BA, and methacrylic acid. The crosslinker was coemulsified with the monomer and added during the LA preparation or after the polymerization either as an emulsion or in an organic solvent. The morphology of the LA was studied with atomic force microscopy and transmission electron microscopy. We used titration to establish the acid distribution. The water absorption and tensile and viscoelastic properties of the LA films were investigated as a function of the addition mode of the cycloaliphatic diepoxide crosslinker. The solution approach generally provided better mechanical properties than the emulsion approach, and the addition of epoxide during the polymerization lowered the water adsorption and hardness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 245–257, 2003
Co-reporter:Jianxia Chen
Journal of Applied Polymer Science 2003 Volume 90(Issue 9) pp:2485-2499
Publication Date(Web):25 SEP 2003
DOI:10.1002/app.12898
The photo-induced curing kinetics of cycloaliphatic epoxide coatings were investigated with real-time Fourier transform infrared spectroscopy with an optical fiber ultraviolet curing system. The consumption of epoxy group as a function of time was obtained by monitoring of the oxirane absorbance in the 789–746-cm−1 region. The effect of the type of epoxide, hydroxyl equivalent weight, ratio of oxirane to hydroxyl groups (R), photoinitiator, and exposure time on the curing reaction was investigated. In general, the rate of curing was dependent on the hydroxyl equivalent weight, R, type of epoxide, and photoinitiator. For formulations without polyol, both initiator concentration and exposure time had minimal effects on the curing reaction. However, for formulations with polyol, the curing a reaction was dependent on the initiator concentration. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2485–2499, 2003
Co-reporter:Zhengang Zong;Yubiao Liu;Jun Hu
Journal of Polymer Science Part A: Polymer Chemistry 2003 Volume 41(Issue 21) pp:3440-3456
Publication Date(Web):24 SEP 2003
DOI:10.1002/pola.10942
New epoxynorbornane linseed oils (ENLOs) were prepared as a function of the norbornene content. The cationic photopolymerization of ENLOs was investigated with real-time infrared spectroscopy and photo-differential scanning calorimetry. The effects of reactive and nonreactive diluents on the polymerization rate were also studied. The diluents reduced the viscosity of the formulations, markedly accelerated the rate of polymerization of ENLOs, and increased their final conversions. The effects of the reactive diluent were compared for ENLOs and epoxidized linseed oil. The relative reactivity of the oxiranes was not as important as the viscosity of the reacting system, and it was proposed that the cationic photopolymerization of ENLOs was controlled by diffusion. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3440–3456, 2003
Co-reporter:Hai Ni, Jeremy L. Daum, Pauline R. Thiltgen, Mark D. Soucek, William J. Simonsick Jr., Wenqing Zhong, Allen D. Skaja
Progress in Organic Coatings 2002 Volume 45(Issue 1) pp:49-58
Publication Date(Web):September 2002
DOI:10.1016/S0300-9440(02)00100-5
Two series of polyesters were synthesized with isomeric cyclohexane diacids. The first series of polyesters was synthesized with 1,4-cyclohexanedimethanol (CHDM) and three cycloaliphatic difunctional acids, 1,4-cyclohexanedicarboxylic acid (1,4-CHDA), 1,3-cyclohexanedicarboxylic acid (1,3-CHDA), or hexahydrophthalic anhydride (HHPA). The second series was prepared with 1,4-CHDA and 1,3-CHDA with CHDM. Control polyesters with adipic, azelaic, and isophthalic acid (AA, AZA, IPA) were prepared for comparison. The solubility and viscosity of polyesters were investigated using the common solvent methyl ethyl ketone (MEK). All the polyesters were cross-linked with hexamethylene diisocyanate (HDI) isocyanurate, forming polyurethane films. General coatings, tensile, and viscoelastic properties were evaluated for the cured polyurethane films. In addition, fracture toughness and the mode of energy dissipation were investigated. The polyesters based on cycloaliphatic diacids have better solubility in MEK compared to the polyesters based on the aromatic or linear aliphatic diacids. The cycloaliphatic diacids based polyurethane coatings had intermediate mechanical and viscoelastic properties compared to polyurethane based on aromatic and linear aliphatic diacids. In addition, the cycloaliphatic diacids afforded polyurethane with a greater adhesion on aluminum substrate compared to the aromatic diacid, IPA.
Co-reporter:Jianxia Chen;William J. Simonsick Jr.;Recep W. Celikay
Macromolecular Chemistry and Physics 2002 Volume 203(Issue 14) pp:2042-2057
Publication Date(Web):14 OCT 2002
DOI:10.1002/1521-3935(200210)203:14<2042::AID-MACP2042>3.0.CO;2-0
A new cycloaliphatic epoxide functionalized monomer was prepared from partially norbornylized linseed oil (Dilulin®). Epoxidation was accomplished using three different approaches: peracetic acid, dioxirane, and hydrogen peroxide. Dioxirane was generated from potassium peroxomonosulfate and acetone. Hydrogen peroxide was used with a quaternary ammonium tetrakis(diperoxotungsto) phosphate(3-) as an epoxidation catalyst. The epoxidation reactions were monitored by FT-IR, and the products were characterized using 1H, 13C NMR, FT-IR, FT-Raman, and electrospray ionization (ESI) mass spectroscopy. For all three approaches, the effect of reaction time, temperature, catalyst concentration, and pH was investigated. Out of the three approaches, the hydrogen peroxide epoxidation was preferred on the basis of yield and ease of purification. The kinetic data were obtained only for the hydrogen peroxide approach. The reaction was found to be first-order with respect to the alkene double bond and 1.4th-order with respect to the catalyst.
Co-reporter:Ganghua Teng
Journal of Polymer Science Part A: Polymer Chemistry 2002 Volume 40(Issue 23) pp:4256-4265
Publication Date(Web):17 OCT 2002
DOI:10.1002/pola.10508
Three series of core-shell hydroxyl-functionalized latexes were synthesized and then crosslinked with a cycloaliphatic diepoxide. The same amount of hydroxyl functional monomer was added during the core stage, shell stage, or partitioned equally between the core and the shell. The morphology of the latexes was examined with transmission electron microscopy and contact-angle measurement. The stress-strain behavior, viscoelastic properties, and water adsorption were evaluated for the latex films as a function of hydroxyl location. The location of hydroxyl groups within latex particles appeared to be dependent on the introduction mode of hydroxyl functional monomers. The introduction of hydroxyl groups during the shell polymerization resulted in a higher crosslinking density but a lower Tukon hardness and tensile properties. Not surprisingly, distribution of hydroxyl groups in both core and shell polymerization provided the lowest water adsorption and impact resistance as well as the highest tensile elongation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4256–4265, 2002
Co-reporter:Heather A. Nash;James G. Worden;Hai Ni
Journal of Polymer Science Part A: Polymer Chemistry 2002 Volume 40(Issue 11) pp:1677-1688
Publication Date(Web):9 APR 2002
DOI:10.1002/pola.10245
The kinetics of the reaction of aliphatic isocyanate with water were investigated with hexyl isocyanate as a model compound. The kinetic study was carried out with a titration method to determine the concentration of the isocyanate group as a function of time. Gas chromatography was used to augment the kinetic data obtained from the titration method. The effects of an organic acid [p-toluene sulfonic acid monohydrate (p-TSA)], a tertiary amine {diazabicyclo[2.2.2]octane (DABCO)}, and an organotin compound [dibutyltin dilaurate (DBTDL)] on the reaction were investigated for the conversion of isocyanate to a urea. Under the reaction conditions in this study, urea was the only product observed. The rate constants indicated that p-TSA had low catalytic activity, DABCO had intermediate catalytic activity, and DBTDL had high catalytic activity. A reaction mechanism was proposed for each of the catalysts. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1677–1688, 2002
Co-reporter:Elif Alyamac, Mark D. Soucek
Progress in Organic Coatings (July 2011) Volume 71(Issue 3) pp:213-224
Publication Date(Web):1 July 2011
DOI:10.1016/j.porgcoat.2011.02.015
A series of low, medium, and high molecular weight copolymers containing methyl methacrylate, n-butyl acrylate, 2-hydroxyethyl methacrylate, and 2,2,2-trifluoroethyl methacrylate were synthesized by solution polymerization under monomer-starved conditions. The acrylate-based copolymers were characterized by FTIR; 1H, 13C, and 19F NMR, and MALDI-TOF mass spectrometry. The molecular weights and the glass transition temperatures of the copolymers were determined using Gel Permeation Chromatography (GPC) and Differential Scanning Calorimetry (DSC). The copolymers were crosslinked with a methylated melamine formaldehyde resin in order to obtain thermosetting acrylics. Surface, optical, barrier, mechanical, and viscoelastic properties of the acrylic coatings were investigated. An enrichment of fluorinated units at the acrylic surface was directly verified measuring dynamic contact angles. Lower wettability, higher oxygen permeability, and lower refractive index were observed for higher concentrations of fluorinated monomer in the copolymer composition. High number-average hydroxyl functionality of high molecular weight copolymers increased the crosslink density of the acrylic films, resulting in improved tensile strength and tensile modulus.
Co-reporter:Jinping Wu, Mark D. Soucek
Radiation Physics and Chemistry (February 2016) Volume 119() pp:55-63
Publication Date(Web):1 February 2016
DOI:10.1016/j.radphyschem.2015.09.012
•Both acrylate and methacrylate additives promoted crosslinking over chain scission.•Acrylate additives were the most effective in promoting crosslinking reactions.•Methacrylate additives were effective in enhancing tensile properties.The effect of multifunctional monomers or oligomers (MFM/O) additives on electron beam (E-beam) radiation induced crosslinking of poly (styrene-block-isoprene/butadiene-block-styrene) (SIBS) was studied. Ten types of MFM/O were investigated, including trimethylolpropane trimethacrylate (TMPTMA), trimethylolpropane triacrylate (TMPTA), triallyl cyanurate (TAC), polybutadiene diacrylate (PB-diacrylate), ethylene glycol dimethylacrylate (EGDMA), butylene glycol dimethacrylate (BGDMA), 1,2-polybutadiene. The effects of MFM/O concentration and E-beam radiation dose on properties of SIBS were studied including tensile strength, elongation-at-break, modulus, gel content, equilibrium swelling and crosslink density. TMPTA significantly improved the tensile modulus and crosslink density of SIBS. SIBS with TMPTMA and TMTPMA with inhibitor showed a 50% increase in tensile strength. The solubility of MFM/O in SIBS was also investigated by a selective swelling method. The MFM/O were found to be soluble in both phases of SIBS. The viscosity of SIBS with methacrylate type MFM/O was stable at 200 °C.
Co-reporter:IJ Zvonkina, MD Soucek
Current Opinion in Chemical Engineering (February 2016) Volume 11() pp:123-127
Publication Date(Web):1 February 2016
DOI:10.1016/j.coche.2016.01.008
•Compositions of bonded inorganic and organic phases generate new hybrid materials.•Thermal stability and protection functions of hybrid coatings are significantly improved.•The advantages of hybrid coatings lead to expansion of their fields of applications.Development of inorganic–organic hybrid coatings has been fruitful for introducing lots of advantages in performance of coatings, compared to homogenous organic polymer coatings or non-hybrid filled polymer coatings. Considering the benefits of hybrid coatings, the range of different structures and compositions applied in such coatings continuously increases. The current review demonstrates general features of inorganic–organic hybrid coatings, some recent developments in this field, types of hybrid coatings implementing different structures, a brief summary of general characterization techniques and selected applications.
Co-reporter:Jamie Dziczkowski, Uma Chatterjee, Mark Soucek
Progress in Organic Coatings (April 2012) Volume 73(Issue 4) pp:355-365
Publication Date(Web):1 April 2012
DOI:10.1016/j.porgcoat.2011.03.003
Acrylic modified alkyds were achieved from sequential polymerization of acrylic monomers in the presence of alkyd macro-RAFT agents. Macro-RAFT agents were reached by end-capping a soya-based alkyd with a carboxy-functional trithiocarbonate. The resulting material was then utilized as the RAFT chain transfer agent to affix acrylic blocks onto the alkyd backbone. Butyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate were the acrylic monomers used to achieve the acrylic blocks both individually and in combination. The resulting materials were characterized by various analytical techniques including size-exclusion chromatography (SEC), Fourier transform infrared (FTIR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. Size exclusion chromatography confirms the controlled nature of this approach to acrylated-alkyds and corroborates the NMR spectra that distinctly show the presence of acrylic blocks. Side reactions with the pendant fatty acids and the formation of homopolyacrylate are also distinguished from the analytical results, however, they are suppressed. Pseudo-first-order kinetics behavior and conversion versus molecular weight plots show that the RAFT-mediated reaction afforded a more controlled free radical process for the synthesis of acrylated-alkyd materials. Use of the alkyd macro-RAFT agent provided a new path to acrylated-alkyds that affords a more controlled way to tailor specific material properties.Highlights► Acrylic modified alkyds were achieved from RAFT agents and acrylic monomers. ► Pseudo-first-order kinetics behavior indicate a more controlled process. ► Use of the alkyd macro-RAFT agent provided a new path to acrylated-alkyds.
Co-reporter:Jamie Dziczkowski, Mark D. Soucek
Progress in Organic Coatings (April 2012) Volume 73(Issue 4) pp:330-343
Publication Date(Web):1 April 2012
DOI:10.1016/j.porgcoat.2011.03.005
Acrylic-grafted-alkyd resins were prepared by free radical chemistry. Long, medium, and short oil alkyds were prepared using soybean oil, glycerol, phthalic anhydride (PA), and tetrahydrophthalic anhydride (THPA) and used as the alkyd phase. Acrylic co-monomer formulas containing methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), and vinyl trimethoxysilane (VTMS) were polymerized in the presence of the different alkyds using 2,2′-azobisisobutyronitrile (AIBN) as the initiator to obtain the final grafted structures. Design of experiments was used to understand how different variables in the synthesis of the acrylated-alkyds affect the film performance. A Box–Behnkin design was used, varying the oil length of the alkyd phase, the degree of unsaturation in the polyester backbone, and acrylic to alkyd ratio. Acrylic–alkyd hybrid resins were reduced with an amine/water mixture. The hydrolytic stability of hybrid alkyd dispersed in water was evaluated. Cured films were prepared and basic coatings properties were also evaluated. It was found that the oil length of the alkyd is the most dominant factor for final coatings properties of the resins. The hydrolytic stability was dependent on the acrylic to alkyd ratio. The oil length of the alkyd backbone had a minimal effect on stability of the resin and film performance.Highlights► Water-reducible acrylated alkyds were evaluated by a design of experiment statistical technique. ► A number of pertinent properties including pot-life stability, hardness, impact resistance, flexibility, adhesion, and chemical resistance were reported. ► The factor of oil length dominated the properties of the acrylated alkyds when the alkyds were <50 wt% acrylate. ► Also, the hydrolytic stability of the alkyd was enhanced by the protective acrylate colloid.
Co-reporter:Kosin Wutticharoenwong, Jamie Dziczkowski, Mark D. Soucek
Progress in Organic Coatings (April 2012) Volume 73(Issue 4) pp:283-290
Publication Date(Web):1 April 2012
DOI:10.1016/j.porgcoat.2011.03.017
Reactive diluents were prepared from tung oil via a Diels–Alder reaction with three different dienophiles: methacryloxypropyl trimethoxysilane (TOMAS), 2,2,2-trifluoroethyl methacrylate (TOF) and triallyl ether acrylate (TOTAE). The reactive diluents were mixed with a long oil soya alkyd, a metal drier package, and a wetting agent; and then cured. Formulations were prepared as a function of reactive diluent type and wt%. Tensile, thermomechanical, and coatings properties were evaluated after curing the films. The addition of two reactive diluents, TOMAS and TOTAE, improved the tensile strength and tensile modulus of the alkyd. The addition of the diluents, however, did not significantly change the elongation at break compared to the alkyd in any of the systems. Also, the addition of TOMAS and TOTAE increased both the crosslink density and glass transition temperature of the alkyd. Basic film properties including hardness, solvent resistance, impact resistance, adhesion, and gloss were not adversely affected by the introduction of any of the tung oil based diluents.Highlights► New reactive diluents were prepared from tung oil. ► Formulations were prepared as a function of reactive diluent and an alkyd. ► Both viscosity and coatings properties were improved.
Co-reporter:Jamie Dziczkowski, Venkat Dudipala, Mark D. Soucek
Progress in Organic Coatings (April 2012) Volume 73(Issue 4) pp:294-307
Publication Date(Web):1 April 2012
DOI:10.1016/j.porgcoat.2010.12.005
Acrylic monomers were grafted onto alkyds via free radical chemistry. The alkyd was a medium oil soya-based alkyd with glycerol, phthalic anhydride, and tetrahydrophthalic anhydride (THPA) as the other components. To identify the specific graft locations, 1D and 2D NMR spectroscopy techniques were utilized. Gradient heteronuclear multiple quantum coherence (gHMQC) 2D NMR was required to assign the chemical shifts of the 1D carbon and proton NMR spectra. Three acrylic monomers, methyl methacrylate (MMA), butyl acrylate (BA), and methacrylic acid (MAA) were grafted to the alkyd, resulting in either MMA, BA, or MAA modified alkyds. Two-dimensional gHMQC spectra for each system confirm grafting at doubly allylic hydrogens located on the fatty acid chains and the polyol segment of the alkyd backbone. The gHMQC spectra show no evidence of grafting across double bonds on either pendant fatty acid groups or THPA unsaturation sites for any of the monomer choices.
Co-reporter:Narin Thanamongkollit, Mark D. Soucek
Progress in Organic Coatings (April 2012) Volume 73(Issue 4) pp:382-391
Publication Date(Web):1 April 2012
DOI:10.1016/j.porgcoat.2011.02.004
The α-eleosterate pendent fatty acid of a tung oil based alkyd was functionalized via a Diels–Alder reaction with three different acrylate groups: (1) 2,2,2-trifluoroethyl methacrylate, (2) 3-methacryloxypropyl trimethoxysilane, and (3) triallyl ether acrylate. The modified alkyds were characterized by using 1H NMR, 13C NMR, and gel permeation chromatography (GPC). The drying time was measured at ambient temperature. The viscoelastic properties of the alkyd-modified films were measured using dynamic mechanical thermal analysis. The viscoelastic and drying time results show that the alkyd modified with siloxane and triallyl group affords a faster drying time, higher crosslink density, and higher glass transition temperature compared to the unmodified alkyd, whereas the fluorinated alkyd possesses surface active properties, but suffers in terms of drying and crosslinking density.
Co-reporter:Jamie Dziczkowski, Venkat Dudipala, Mark D. Soucek
Progress in Organic Coatings (April 2012) Volume 73(Issue 4) pp:308-320
Publication Date(Web):1 April 2012
DOI:10.1016/j.porgcoat.2010.12.006
Acrylic groups were grafted onto alkyds via free radical chemistry. The alkyd comprised soybean oil, glycerol, phthalic anhydride, and tetrahydrophthalic anhydride. To closely model acrylated-alkyds, a mixture of four acrylic monomers were copolymerized with the alkyd including: methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), and vinyltrimethyoxysilane (VTMS). Two different initiator systems were used, benzoyl peroxide (BPO) and 2,2′-azobisisobutyronitrile (AIBN), for comparison. To elucidate the grafting sites, 1D NMR spectroscopy and 2D NMR spectroscopy were used. Gradient heteronuclear multiple quantum correlation (gHMQC) was needed to assign the chemical shifts of the 1D carbon and proton NMR spectra. The gHMQC spectra provided evidence of acrylic–alkyd grafted structures formed at doubly allylic hydrogens located on the fatty acid chains. As a side reaction, acrylic groups were grafted into the polyester backbone of the alkyd via hydrogen abstraction of the glycerol. The gHMQC spectra show no evidence of grafting across double bonds on either the fatty acid side chains or the THPA backbone. It was also determined that choice of initiator has no effect on graft location. However, the system initiated with BPO provided spectral evidence of the formation of benzoic acid, which shows that the peroxide initiator can directly abstract the doubly allylic hydrogen. The side product, isobutyronitrile did not appear in the spectra obtained from the AIBN initiated system.
Co-reporter:K. R. Miller and M. D. Soucek
Journal of Materials Chemistry A 2015 - vol. 3(Issue 35) pp:NaN9190-9190
Publication Date(Web):2015/08/10
DOI:10.1039/C5TC01376C
Macro-initiators were prepared using three magnetic nanoparticles, Fe3O4, FeCo, or Co. Azo free radical initiators were grafted onto the magnetic particles in a two-step reaction utilizing alkoxysilane and ambient temperature esterification reactions. The magnetic initiators (MI) were characterized using IR, DSC, TGA, SEM with EDAX, and DLS. An alternating gradient magnetometer gave saturation magnetization (Ms) values of 42.1, 178.3, and 36.1 A m2 kg−1 for Fe3O4, FeCo, and Co MIs respectively. Bulk polymerization of styrene was used to assess the effectiveness of MIs in free radical polymerization. Molecular dynamic (MD) simulations were performed on the magnetic macro initiators to determine the feasibility of initiating free radical polymerization by application of an external AC MF. The MD simulations showed that magnetically induced polymerization is possible with a minimum force of 62 kcal mol−1 Å−1 required to be applied to the core of the MI in order to decompose the C–N bond of the azo group, producing free radicals.
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