Dendrimers in thiol‐ene crosslinked networks and the effect of subsequent generations on thermoset properties

A series of well‐defined allyl‐ether functionalized polyester dendrimers has been synthesized via the divergent approach using traditional esterification reactions. Two commercially available trifunctional thiols, trimethylolpropane tri(3‐mercaptopropanoate) (TRIS) and ethoxylated trimethylolpropane tri(3‐mercaptopropanoate) (ETTMP), were incorporated with the dendrimers into the thiol‐ene polymer networks. The thiol‐ene reactions were conducted at room temperature and cured by UV light without the addition of photoinitiatior. Highly crosslinked films were obtained and characterized with respect to mechanical (DMA) and thermal (DSC and TGA) properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 589–601, 2009     

Photopolymerization of ternary thiol–ene/acrylate systems: Film and network properties

Photocurable, ternary‐component mixtures of a 1:1 molar multifunctional thiol–ene (trithiol and triallyl ether) blend and a 16‐functional acrylate based monomer have been photopolymerized, and the final film properties of the ternary crosslinked networks have been measured. The photopolymerization kinetics, morphology, and mechanical and physical properties of the films have been investigated with real‐time infrared, atomic force microscopy, and dynamic mechanical analysis. The photopolymerization process is a combination of acrylate homopolymerization and copolymerizations of thiol with allyl ether and acrylate functionalities. The tan δ peaks of the photopolymerized ternary systems are relatively narrow and tunable over a large temperature range. The morphology is characterized by a distinct phase‐separated nanostructure. The photocured thiol–ene/acrylate ternary systems can be made to exhibit good mechanical properties with enhanced energy absorption at room temperature by the appropriate selection of each component concentration. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 822–829, 2007.     

Ester‐ and amide‐terminated dendrimers with alternating amide and ether generations

Ester‐terminated polyamide dendrimers up to the third generation and amide‐terminated polyamide dendrimers of the first generation were synthesized by convergent growth. The Williamson ether synthesis and diphenylphosphoryl azide (DPPA) coupling of amines to carboxylic acids were used for the construction of the dendrimers, having alternate ether and amide generations. The methyl ester‐ and N,N‐diethylamide‐terminated dendrimers were readily soluble in common organic solvents while the N‐methylamide‐ and N‐benzylamide‐terminated dendrimers were soluble only in DMF and DMSO. Both the end and internal amide groups of the N,N‐diethylamide‐terminated dendrimer were reduced by LiAlH₄ to form a polyamine dendrimer. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1533–1543, 2000     

Controlled synthesis of polyepichlorohydrin with pendant cyclic carbonate functions for isocyanate‐free polyurethane networks

Poly(allyl glycidyl ether) and poly(allyl glycidyl ether‐co‐epichlorohydrin) were prepared by monomer‐activated anionic polymerization. Quantitative and controlled polymerization of allyl glycidyl ether (AGE) giving high molar mass polyether was achieved in a few hours at room temperature in toluene using tetraoctylammonium salt as initiator in presence of an excess of triisobutylaluminum ([i‐Bu₃Al]/[NOct₄Br] = 2?4). Following the same polymerization route, the copolymerization of AGE and epichlorohydrin yields in a living‐like manner gradient‐type copolymers with controlled molar masses. Chemical modification of the pendant allyl group into cyclic carbonate was then investigated and the corresponding polymers were used as precursors for the isocyanate‐free synthesis of polyurethane networks in presence of a diamine. Formation of crosslinked materials was followed and characterized by infrared and differential scanning calorimetry. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

One‐pot enzymatic route to tetraallyl ether functional oligoesters: Synthesis,UV curing,and characterization

An enzymatic one‐pot route in bulk was used to synthesize tetraallyl ether (tAE) functional oligomers based on divinyl adipate, 1,4‐butanediol and trimethylolpropane diallyl ether. By using lipase B from Candida antarctica as catalyst and varying the stoichiometric ratio of monomers, it was possible to reach targeted molecular weights (from 1300 to 3300 g mol^?1) of allyl‐ether functional polyesters. The enzyme catalyzed reaction reached completion (>98% conversion based on all monomers) within 24 h at 60 °C, under reduced pressure (72 mbar) resulting in ～90% yield after filtration. The tAE‐functional oligoesters were photopolymerized, without any purification other than removal of the enzyme by filtration, with thiol functional monomers (dithiol, tetrathiol) in a 1:1 ratio thiol‐ene reaction. The photo‐initiator, 2,2‐dimethoxy‐2‐phenylacetophenone, was used to improve the rate of reaction under UV light. High conversions (96–99% within detection limits) were found for all thiol‐ene films as determined by FT‐Raman spectroscopy. The tAE‐functional oligoesters were characterized by NMR, MALDI, and SEC. The UV‐cured homopolymerized films and the thiol‐ene films properties were characterized utilizing DSC and DMTA. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Minimally adhesive polymer surfaces prepared from star oligosiloxanes and star oligofluorosiloxanes

The effects of the surface energy, storage modulus (G′), and glass‐transition temperature (T_g) on the biofouling behavior of siloxane and fluorosiloxane polymer surfaces (films) were studied. Irregular Si? H‐terminated tetrabranched star oligosiloxanes and star oligofluorosiloxanes were prepared by the acid‐catalyzed equilibration of octamethylcyclotetrasiloxane or 1,3,5‐trimethyl‐1,3,5‐tris(3′,3′,3′‐trifluoropropyl)cyclotrisiloxane with tetrakis(dimethylsiloxy)silane, respectively. Terminal epoxy groups were introduced via Pt‐catalyzed hydrosilylation with allyl glycidyl ether to yield compounds that were subsequently crosslinked with α,ω‐bis(3‐aminopropyl)poly(dimethylsiloxane). The resulting films were characterized by goniometry, dynamic mechanical thermal analysis, and thermogravimetric analysis. The foul‐release behavior was studied by the measurement of how strongly sporelings (young plants) of the green seaweed Ulva adhered. The corrosion protection of aluminum was evaluated by electrochemical impedance spectroscopy. Fluorosiloxane films displayed higher G′ and T_g values, decreased contact angles (with water), and more effectively released Ulva sporelings in comparison with siloxane films. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2551–2566, 2006     

Anionic alternating copolymerization of 3,4‐dihydrocoumarin and glycidyl ethers: A new approach to polyester synthesis

Anionic copolymerizations of 3,4‐dihydrocoumarin (DHCM) and a series of glycidyl ethers (n‐butyl glycidyl ether, tert‐butyl glycidyl ether, and allyl glycidyl ether) with 2‐ethyl‐4‐methylimidazole as an initiator proceeded in a 1:1 alternating manner to give the corresponding polyesters, whose structures were confirmed by spectroscopic analyses and reductive scission of the ester bonds in the main chain with lithium aluminum hydride, followed by detailed analyses of the resulting fragments. The polyester obtained by the copolymerization of DHCM and allyl glycidyl ether inherited the allyl groups in the side chain, whose applicability to chemical modifications of the polyester was successfully demonstrated by a platinum‐catalyzed hydrosilylation reaction. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4092–4102, 2008     

Synthesis of new fluorinated allyl ethers for the surface modification of thiol–ene ultraviolet‐curable formulations

Thiol–ene photocurable systems based on a trifunctional thiol [trimethylolpropane tris‐(3‐mercaptopropanoate)] and two different multifunctional allyl ethers (trimethylolpropane triallyl ether and Boltorn U2, an allyl functional dendritic polyester) were examined. To these systems, small amounts (<1 wt %) of fluorinated allyl ethers were added for the modification of their surface properties. Two new fluorinated allyl ethers, 1H,1H‐perfluoro‐1‐heptylallyl ether and 1H,1H‐perfluoro‐1‐decylallyl ether, were synthesized for this purpose by allylation of the corresponding 1H,1H‐perfluoro alcohols. The fluorinated monomers, despite their very low concentrations, caused sharp changes in the surface properties of the films and in the solvent resistance without any changes in the curing conditions and bulk properties. Completely hydrophobic surfaces were obtained (as a result of the selective enrichment of the fluorinated monomers on the film surfaces) that depended on the monomer structure and its concentration. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2583–2590, 2002     

Syntheses,characterization, optical properties,and charge‐transfer complexation study of fluorescent poly(aryl‐ether‐urea) dendrimers

An inexpensive and highly efficient synthesis of first example of fluorescent aromatic dendrimers having alternative ether and urea linkages without the need for protection and deprotection steps has been developed. Dendrons and dendrimers up to third generation, with amine end‐groups, were prepared by convergent growth approach in high yield. A repetitive synthetic sequence of nucleophilic addition reaction between amine and regenerated isocyanate and reduction of nitro groups into amine are adopted for the synthesis of these dendrimers. The peripheries of the dendrimers contained 6, 12, and 24 amino groups, for the first, second, and third generation, respectively. Materials were characterized by FTIR, NMR, and MALDI‐TOF MS spectrometry. These dendrimers were soluble in amide solvents, THF and acetone and displayed fluorescence maxima in the 440–500 nm range with relatively narrow peak widths indicating that they had pure and intense fluorescence. These dendrimers form charge‐transfer (CT) complexes with electron acceptor molecules such as 7,7,8,8,‐tetracyano‐quino‐dimethane and 1,1,2,2 tetracyanoethane as evidenced by UV‐visible absorption spectra. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 713–724, 2008     

Bioreducible and core‐crosslinked hybrid micelles from trimethoxysilyl‐ended poly(ε‐caprolactone)‐S‐S‐poly(ethylene oxide) block copolymers: Thiol‐ene click synthesis and properties

Bioreducible and core‐crosslinked hybrid micelles were for the first time fabricated from biodegradable and biocompatible trimethoxysilyl‐terminated and disulfide‐bond‐linked block copolymers poly(ε‐caprolactone)‐S‐S‐poly(ethylene oxide), which were prepared by combining thiol‐ene coupling reaction and ring‐opening polymerization. The molecular structures, physicochemical, self‐assembly, and bioreducible properties of these copolymers were thoroughly characterized by means of FTIR, ¹H NMR, gel permeation chromatography, differential scanning calorimetry, wide‐angle X‐ray diffraction, dynamic light scattering (DLS), and transmission electron microscopy. The core‐crosslinking sol‐gel reaction was confirmed by ¹H NMR, and the core‐crosslinked hybrid micelles contained about 3 wt % of silica. The bioreducible property of both uncrosslinked and core‐crosslinked micelles in 10 mM 1,4‐dithiothreitol (DTT) solution was monitored by DLS, which demonstrated that the PEO corona gradually shedded from the PCL core. The anticancer doxorubicin drug‐loaded micelles showed nearly spherical morphology compared with blank micelles, presenting a DTT reduction‐triggered drug‐release profile at 37 °C. Notably, the core‐crosslinked hybrid micelles showed about twofold drug loading capacities and a half drug‐release rate compared with the uncross‐liked counterparts. This work provides a useful platform for the fabrication of bioreducible and core‐crosslinked hybrid micelles potential for anticancer drug delivery system. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Methacrylated dendrimers in thiol‐methacrylate networks and the effect of conversion on the thermoset properties

A series of well‐defined methacrylate‐functionalized polyester dendrimers based on 2,2‐bis(methylol)propionic acid (bis‐MPA) has been synthesized divergently. The thermal properties and conversion of the methacrylate functional dendrimers are investigated along with the structure‐property relationship of networks composed of the methacrylate dendrimers and two commercially available trifunctional thiols, trimethylolpropane tri(3‐mercaptopropanoate) (TRIS) and ethoxylated trimethylolpropane tri(3‐mercaptopropanoate) (ETTMP). The thiol‐methacrylate reactions were conducted at room temperature, under ambient conditions, and triggered by UV light in the presence of a photoinitiator. Crosslinked films were obtained and characterized with respect to conversion (FT‐Raman) and thermal (DSC and TGA) properties. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5815–5826, 2009     

Facile synthesis of core‐shell organic–inorganic hybrid nanoparticles with amphiphilic polymer shell by one‐step sol–gel reactions

Organic–inorganic hybrid core‐shell nanoparticles with diameters ranging from 100 to 1000 nm were prepared by a one‐pot synthesis based on base catalyzed sol–gel reactions using tetraethoxysilane and a triethoxysilane‐terminated polyethylene‐b‐poly(ethylene glycol) as reactants. Data from TEM, TGA, and solid‐state NMR analysis are in agreement with the formation of core‐shell nanoparticles with an inorganic‐rich core and an external shell consisting of an amphiphilic block copolymer monolayer. The influence of the organic–inorganic ratio, solution concentration, and postcuring temperature on core and shell dimensions of the nanospheres were investigated by TEM microscopy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1699–1709, 2008     

Synthesis,morphology, and properties of hydroxyl terminated‐POSS/polyimide low‐k nanocomposite films

Polyhedral oligomeric silsequioxane (POSS), having eight hydroxyl groups for the preparation of nanocomposites with polyimide (PI) was synthesized by the direct hydrosilylation of allyl alcohol with octasilsesquioxane (Q₈M₈^H) with platinum divinyltetramethyl disiloxane Pt(dvs) as a catalyst. The structure of allyl alcohol terminated‐POSS (POSS‐OH) was confirmed by FTIR, NMR, and XRD. A high performance, low‐k PI nanocomposite from pyromellitic dianhydride (PMDA)‐4,4'‐oxydianiline (ODA) polyamic acid cured with POSS‐OH was also successfully synthesized. The incorporation of POSS‐OH into PI matrix reduced dielectric constant of PI without loosing mechanical properties. Furthermore, the effects of POSS‐OH on the morphology and properties of the PI/POSS‐OH nanocomposites were investigated using UV–vis, FTIR, XRD, SEM, AFM, transmission electron microscope (TEM), TGA, and contact angle. The homogeneous dispersion of POSS particles was confirmed by SEM, AFM, and TEM. The nanoindentation showed that the modulus increased upon increasing the concentration of POSS‐OH in PI, whereas the hardness did not increase very much with respect to loading of POSS, due to soft‐interphase around POSS molecules in the resulting nanocomposites. Overall results demonstrated the nanometer‐level integration of the polymer and POSS‐OH. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5887–5896, 2008     

Synthesis of dendrimers through divergent iterative thio‐bromo “Click” chemistry

The development of a novel nucleophilic thio‐bromo “Click” reaction, specifically base‐mediated thioetherification of thioglycerol with α‐bromoesters, is reported. Combination of this thio‐bromo click reaction with subsequent acylation with 2‐bromopropionyl bromide provides an iterative two‐step divergent growth approach to the synthesis of a new class of poly(thioglycerol‐2‐propionate) (PTP) dendrimers. This approach is demonstrated in the rapid preparation of four generation (G1–G4) of PTP dendrimers with high‐structural fidelity. The isolated G1–G4 bromide‐terminated dendrimers can be used directly as dendritic macroinitiators for the synthesis of star‐polymers via SET‐LRP. Additionally, the intermediate hydroxy‐terminated dendrimers are analogs of other water‐soluble polyester and polyether dendrimers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3931–3939, 2009     

Synthesis and properties of waterborne self‐crosslinkable sulfo‐urethane silanol dispersions

A novel type of crosslinkable waterborne polyurethane ionomer was prepared by the acetone process. Two new types of sulfonated diols compatible with this process were synthesized from dimethyl 5‐sodium sulfo isophthalate using a one‐ or two‐stage method. Isocyanate‐terminated polyurethane oligomers were prepared from the sulfonated diols with various combinations of diols and diisocyanates and subsequently reacted with amino silane derivatives. Stable, low‐volatile organic chemical, waterborne dispersions of the sulfo‐urethane silanol polymers spontaneously crosslink upon drying without extra additives or processing steps. Despite the lack of organic coalescing solvents, the dispersions have minimum film‐forming temperatures below 10 °C, regardless of glass‐transition temperature. Tensile strengths up to 6000 psi with elongations between 300 and 600% were obtained for the crosslinked films. The hard‐segment content of the films can be controlled to produce films with a Sward–Rocker hardness value up to 42. Through silane end‐group modification, the crosslinking density of the films can also be modified to produce polyurethanes with a wide range of physical properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3037–3045, 2002     

Photopatternable substrate‐independent poly(glycidyl methacrylate‐ran‐2‐(acryloyloxy) ethyl 2‐methylacrylate) polymer films for immobilization of biomolecules

We report the synthesis and characterization of a photocrosslinkable copolymer containing reactive epoxy groups for binding biomolecules. The epoxide‐containing copolymer poly(glycidyl methacrylate‐ran‐2‐(acryloyloxy) ethyl 2‐methylacrylate) offers distinct advantages such as ease of application to various substrates, enhanced stability of the bound oligonucleotide, low autofluorescence, and the ability to be photopatterned allowing localization of the linkers. The copolymer uses pendant acryloyl groups to control the crosslinking without sacrificing the epoxide groups. The films were characterized using ellipsometry, atomic force microscopy, and fluorescence microscopy. The films on glass, silicon wafer, and stainless steel showed no appreciable degradation in water, tetrahydrofuran, and acetone for ～4 months. The surface topography for a given thickness of crosslinked film was dictated by the deposition conditions. A 16mer oligonucleotide was immobilized on the thin films. A linear relationship between the film thickness and amount of oligonucleotide immobilized was observed with a maximum signal‐to‐background ratio (S/B) of 225 for a 60‐nm‐thick film, a value 50% higher than the S/B for an epoxide monolayer. The crosslinked films maintained a high fluorescence signal following long aqueous washing which is appealing for biological microarrays, immobilizing proteins, and study of slow differentiating cells where stability of the scaffold is relevant. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5826–5838, 2008     

基于1,6-己二醇的哑铃型树状大分子

Novel carbosilane dendrimers based on 1,6-hexanediol were prepared by divergent approach. Using 1,6-hexanediol-based diallyl ether as the core molecule, the dendrimers were prepared to the third generation with 54 allyl groups on the periphery by alternate hydrosilylation-allylation reactions.     

Role of architecture and molecular weight in the formation of tailor‐made ultrathin multilayers using dendritic macromolecules and click chemistry

The high efficiency and mild reaction conditions associated with the Cu(I) catalyzed cycloaddition of azides and alkynes were exploited for the covalent layer‐by‐layer synthesis of dendritic thin films on silicon wafers. The preparation of azide and alkyne‐terminated dendrimers based on bisMPA was accomplished by a divergent strategy; combinations of these monodisperse building blocks from the 2nd to the 5th generation were used for construction of the thin films. The layer‐by‐layer self assembly process proceeds under ambient conditions and was monitored by ellipsometry, XPS, and ATR‐IR, which showed extremely regular growth of the dendritic thin films. Film thickness could be accurately controlled by both the size/generation number of the dendrimers as well as the number of layers. In comparison with linear analogues, the growth of the dendritic films was significantly more controlled and defect‐free with each layer being thinner than the corresponding films prepared from the isomeric linear polymers, demonstrating the well‐defined, three‐dimensional nature of the dendritic architecture. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2835–2846, 2007     

Synthesis and characterization of photocrosslinked poly(ε‐caprolactone)s showing shape‐memory properties

Poly(ε‐caprolactone) (PCL) with a pendent coumarin group was prepared by solution polycondensation from 7‐(3,5‐dicarboxyphenyl) carbonylmethoxycoumarin dichloride and α, ω‐dihydroxy terminated poly(ε‐caprolactone) with molecular weights of 1250, 3000, and 10,000 g/mol. These photosensitive polymers underwent a rapid reversible photocrosslinking upon exposure to irradiation with alternating wavelengths (>280/254 nm) without a photoinitiator. The thermal and mechanical properties of the photocrosslinked films were examined by means of differential scanning calorimetry and stress–strain measurements. The crosslinked films exhibited elastic properties above the melting temperature of the PCL segment along with significant decrease in the ultimate tensile strength and Young's modulus. Shape‐memory properties such as strain fixity ratio (R_f) and strain recovery ratio (R_r) were determined by means of a cyclic thermomechanical tensile experiments under varying maximum strains (ε_m = 100, 300, and 500%). The crosslinked ICM/PCL‐3000 and ‐10,000 films exhibited the excellent shape‐memory properties in which both R_f and R_r values were 88–100% for tensile strain of 100–500%; after the deformation, the films recovered their permanent shapes instantaneously. In vitro degradation was performed in a phosphate buffer saline (pH 7.2) at 37 °C with or without the presence of Pseudomonas cepacia lipase. The presence of the pendent coumarin group and the crosslinking of the polymers pronouncedly decreased the degradation rate. The crosslinked biodegradable PCL showing a good shape‐memory property is promising as a new material for biomedical applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2422–2433, 2009     

Photo‐crosslinked fluorinated thin films from azido‐functionalized random copolymers

Random copolymers of styrene, p‐azidomethylstyrene and 1H,1H,2H,2H‐perfluorodecyl methacrylate were prepared in two steps involving nitroxide‐mediated radical copolymerization and azidation reaction and further characterized by ¹H and ¹⁹F NMR, size exclusion chromatography, differential scanning calorimetry, and thermal gravimetric analysis. Ultrathin films of these azidomethyl‐functionalized fluorinated random copolymers, with thicknesses ranging from 20 to 100 nm, were spin coated onto Si substrates and then crosslinked by ultraviolet irradiation resulting in smooth and insoluble crosslinked fluorinated polymer mats. The surface properties of the supported thin films were investigated by X‐ray photoelectron spectroscopy and water contact angle measurements. These tailored photo‐crosslinked coatings afford a versatile control and homogenization of the wetting properties of different organic and inorganic substrates. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3888–3895, 2010