Synthesis and thiol–ene photopolymerization of (meth)allyl‐terminated polysulfides

Thiol‐terminated polysulfides (PS) are cured by mixing with an oxidant, resulting in limited shelf‐ and/or pot‐life, depending on whether formulated as a one‐ or two‐component system. Mixtures of thiol‐ and alkene‐terminated polysulfides offer the potential for an on‐demand curing process through thiol–ene photopolymerization. Thiol end groups of commercial polysulfides, PS‐1 (1000 g/mol) and PS‐2 (3000 g/mol), were converted to alkene by reaction with (meth)allyl bromide. Photopolymerizations were performed by irradiating films of equimolar thiol:ene mixtures at 320–500 nm (30 mW/cm²) in the presence of 5 wt % 2,2‐dimethoxy‐2‐phenyl‐acetophenone (DMPA). Reaction kinetics were measured using real‐time FTIR by monitoring absorbances at 3075 cm^?1 (alkene) or 2550 cm^?1 (thiol). In the absence of any reactive diluent, mixtures of thiol and alkene polysulfides failed to gel notwithstanding high reaction conversion (>90%). Partial or total replacement of the thiol polysulfide component with pentaerythritol tetrakis(3‐mercaptopropionate) (PETMP) yielded solid elastomeric films and ultimate reaction conversions of 80–96% after 5 min irradiation. Crosshatch adhesion measured on glass, aluminum, and steel was very poor (0B) for (meth)allyl PS‐1/PETMP and poor (2B) for (meth)allyl PS‐2/PETMP without adhesion promoters. (3‐Mercaptopropyl)trimethoxysilane (1 wt %) significantly improved adhesion of (meth)allyl PS‐2/PETMP on all substrates (4B) but yielded no improvement for (meth)allyl‐terminated PS‐1/PETMP. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45523.     

Swelling behavior of semi‐interpenetrating polymer network hydrogels composed of poly(vinyl alcohol) and poly(acrylamide‐co‐sodium methacrylate)

Interpenetrating polymer network (IPN) hydrogels based on poly(vinyl alcohol) (PVA) and poly(acrylamide‐co‐sodium methacrylate) poly(AAm‐co‐SMA) were prepared by the semi IPN method. These IPN hydrogels were prepared by polymerizing aqueous solution of acrylamide and sodium methacrylate, using ammonium persulphate/N,N,N¹,N¹‐tetramethylethylenediamine (APS/TMEDA) initiating system and N,N¹‐methylene‐bisacrylamide (MBA) as a crosslinker in the presence of a host polymer, poly(vinyl alcohol). The influence of reaction conditions, such as the concentration of PVA, sodium methacrylate, crosslinker, initiator, and reaction temperature, on the swelling behavior of these IPNs was investigated in detail. The results showed that the IPN hydrogels exhibited different swelling behavior as the reaction conditions varied. To verify the structural difference in the IPN hydrogels, scanning electron microscopy (SEM) was used to identify the morphological changes in the IPN as the concentration of crosslinker varied. In addition to MBA, two other crosslinkers were also employed in the preparation of IPNs to illustrate the difference in their swelling phenomena. The swelling kinetics, equilibrium water content, and water transport mechanism of all the IPN hydrogels were investigated. IPN hydrogels being ionic in nature, the swelling behavior was significantly affected by environmental conditions, such as temperature, ionic strength, and pH of the swelling medium. Further, their swelling behavior was also examined in different physiological bio‐fluids. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 302–314, 2005     

Novel thermal curing of cycloaliphatic resins by thiol–epoxy click process with several multifunctional thiols

Novel thermosets were prepared by the base‐catalysed reaction between a cycloaliphatic resin (ECC) and various thiol crosslinkers. 4‐(N,N‐Dimethylaminopyridine) (DMAP) was used as base catalyst for the thiol–epoxy reaction. A commercial tetrathiol (PETMP) and three different thiols synthesized by us, 6SH‐SQ, 3SH‐EU and 3SH‐ISO, were tested. 6SH‐SQ and 3SH‐EU were prepared from vinyl or allyl compounds from renewable resources such as squalene and eugenol, respectively. Thiol 3SH‐ISO was prepared starting from commercially available triallyl isocyanurate. A kinetic study of the mixtures was performed using differential scanning calorimetry. Stoichiometric ECC/thiol/DMAP formulations were cured at 120 °C for 1 h, at 150 °C for 1 h and post‐cured for 30 min at 200 °C. The materials were characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis and dynamic mechanical thermal analysis. The results revealed that the materials obtained from the synthesized thiols had higher thermal stability and glass transition temperatures than those obtained from the commercial PETMP. In addition, all the materials obtained exhibited very good transparency. This study proves the ability of multifunctional thiols to crosslink cycloaliphatic epoxy resins, leading to more flexible materials than those obtained by cationic homopolymerization of ECC or base‐catalysed ECC–anhydride copolymerization. © 2017 Society of Chemical Industry     

Copolymers of acrylic acid with N‐vinylpyrrolidinone and 2‐hydroxyethyl methacrylate as pH‐responsive hydrogels synthesized through a photoinitiator‐free photopolymerization technique

pH‐sensitive hydrogels for biomedical applications were synthesized using a photoinitiator‐free technique involving the initiation of photopolymerization by donor/acceptor pairs. The differential photocalorimetric technique indicated a high polymerization rate for the N‐vinylpyrrolidinone (NVP, donor)/acrylic acid (AA, acceptor) pair at a 1:1 molar ratio. However, photopolymerization of larger quantities of these monomers (1:1 molar ratio) produced a water‐soluble polymer. Nevertheless, an anionic hydrogel was successfully formed when a small quantity of 2‐hydroxyethyl methacrylate (HEMA) was included in the NVP/AA formulation. A mixture of HEMA and AA, although both are classified as acceptors, photopolymerized to produce a copolymer which functioned as an anionic hydrogel. The swelling and drug release of these hydrogels were investigated in acidic, neutral and basic pH environments. Their biocompatibility with HaCaT human epidermal keratinocyte cells was tested and a positive cell growth as evidenced by the 3‐[4,5‐dimethylthiazol‐2‐yl]‐2,5‐diphenyl tetrazolium bromide (MTT) cell proliferation assay indicated that these hydrogels have no toxic effect on HaCaT. Copyright © 2006 Society of Chemical Industry     

Synthesis and properties of radiation‐induced acrylamide–acrylic acid hydrogels

Acrylamide (AAm)/acrylic acid (AAc) hydrogels in the cylindirical form were prepared by γ‐irradiating binary systems of AAm/AAc with 2.6–20.0 kGy γ‐rays. The effect of the dose and relative amounts of AAc and pH on the swelling properties, diffusion behavior of water, diffusion coefficients, and network properties of hydrogel systems was investigated. The swelling capacities of AAm/AAc hydrogels were in the range of 1000–3000%, while poly(acrylamide) (PAAm) hydrogels swelled in the range of 450–700%. Water diffusion into hydrogels was found to be non‐Fickian‐type diffusion. Diffusion coefficients of AAm/AAc hydrogels were found between 0.79 × 10^?5 and 2.78 × 10^?5 cm² min^?1. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3570–3580, 2002     

Synthesis and characterization of poly(N‐vinyl imidazole) hydrogels crosslinked by gamma irradiation

Crosslinked poly(N‐vinyl imidazole) (PVIm) hydrogels in the form of rods have been prepared by ⁶⁰Co γ‐radiation initiated simultaneous polymerization and crosslinking of N‐vinyl imidazole in bulk and water. In binary aqueous systems, the percentage gelation decreased with increasing water content. The PVIm hydrogels synthesized were further protonated in HCl solutions of different concentration. PVIm and protonated PVIm (H‐PVIm) hydrogels have been characterized using spectroscopic and thermal methods, and the swelling behaviour of these two types of hydrogel has been investigated. PVIm hydrogels originally swelled to 600% (by volume) but in their protonated form at pH 7.0 reached 4000% swelling. © 2002 Society of Chemical Industry     

Radiation synthesis and characterization of 2‐hydroxyethyl‐methacrylate‐based hydrogels containing di‐ and tri‐protic acid and its application on wastewater treatment

Radiation‐crosslinked 2‐hydroxyethylmethacrylate/citric acid (HEMA/CAc), 2‐hydroxyethylmethacrylate/tartaric acid (HEMA/TA), and 2‐hydroxyethylmethacrylate/succinic acid (HEMA/Sc) copolymers were prepared by using ⁶⁰Co γ‐rays. The gel fraction yield and the swelling behavior of the prepared hydrogels were studied. It was shown that increasing irradiation doses was accompanied by an increase in yield of gel fraction and a decrease in swelling degree. The parameters of equilibrium swelling, maximum swelling, initial swelling rate, swelling exponent, and diffusion coefficient of the hydrogels were determined by studying the swelling behavior of the hydrogels prepared. It was seen that the equilibrium swelling degree increases as the content of acid increases, as a result of introducing more hydrophilic groups. When the hydrophilic polymer (acids) varies in the content range of 40–80 mg, swelling exponents (n) decreases, thereby indicating a shift in the water‐transport mechanism from the anomalous (non‐Fickian)‐type to the Fickian‐type. Characterization and some selected properties of the prepared hydrogels were studied, and accordingly the possibility of its practical use in the treatment of industrial wastes such as dyes and heavy metals (Fe, Ni, Co, and Cu) were also studied. The effect of treatment time, pH of feed solution, initial feed concentration, and temperature on the dye and heavy metals uptake was determined. The uptake order for a given metal was HEMA/TA hydrogel > HEMA/CAc > HEMA/Sc hydrogel. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

pH/temperature‐responsive semi‐IPN hydrogels composed of alginate and poly(N‐isopropylacrylamide)

Amino semitelechelic poly(N‐isopropylacrylamide) (PNIPAAm) was prepared by radical polymerization with aminoethanethiol hydrochloride as a chain‐transfer agent. Semi‐interpenetrating polymer network (semi‐IPN) hydrogels, composed of alginate and amine‐terminated PNIPAAm, were prepared by crosslinking with calcium chloride. From the swelling behaviors of semi‐IPNs at various pH's and Fourier transform infrared spectra at high temperatures, the formation of a polyelectrolyte complex was confirmed from the reaction between carboxyl groups in alginate and amino groups in modified PNIPAAm. Semi‐IPN hydrogels reached an equilibrium swelling state within 24 h. The water state in hydrogels, investigated by differential scanning calorimetry, showed that sample CAN55 [alginate/PNIPAAm (w/w) = 50/50] exhibited the lowest equilibrium water content and free water content among the hydrogels tested, which was attributed to its more compact structure compared to other samples and the high content of interchain bonding within the hydrogels. Alginate/PNIPAAm semi‐IPN hydrogels exhibited a reasonable sensitivity to the temperature, pH, and ionic strength of swelling medium. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1128–1139, 2002     

Synthesis and characterization of novel pH‐sensitive chitosan‐poly(acrylamide‐co‐itaconic acid) hydrogels

Novel pH‐sensitive chitosan‐poly(acrylamide‐co‐itaconic acid) hydrogels were prepared by free radical copolymerization of acrylamide and itaconic acid (IA) in chitosan solution. The hydrogels were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry and the swelling ratios of the hydrogels in water (pH 6.8) and pH 1.2. The influence of composition on the thermal properties of the hydrogels was assessed. The glass transition temperatures of the samples increased with IA content, ranging from 110 to 136 °C. Swelling of the hydrogels was found to obey second‐order kinetics with respect to the remnant swelling, indicating that diffusion is controlled by the relaxation of chains. The equilibrium swelling degree was strongly dependent on pH and composition. At both pH values the highest water uptake was obtained for the IA‐free sample M1. From the equilibrium swelling results the average molar mass between crosslinks, M_c, and the crosslink density of the chitosan‐poly(acrylamide‐co‐itaconic acid) samples were calculated. The results evidenced the reinforcing effect of IA on the hydrogel structure. It is concluded that these highly swellable pH‐sensitive hydrogels can be useful for applications in biomedicine and pharmacy. © 2013 Society of Chemical Industry     

Properties of polythiourethanes prepared by thiol–isocyanate click reaction

Polythiourethane networks with systematic compositional variations of thiol [ethoxylated trimethylol‐propane tri(3‐mercapto‐propionate), ETTMP1300 and pentaerythritol tetra(3‐mercapto‐propionate), PETMP] and isophorone diisocyanate (IPDI), i.e., IPDI/ETTMP1300/PETMP = 100/100/0, 100/80/20, 100/60/40, 100/40/60, 100/20/80, and 100/0/100, were prepared by base catalyzed thiol–isocyanate click type reaction where the base catalyst (tributylamine, TBA) was photolytically generated using photolatent amine (TBA·tetraphenylborate salt, TBA·HBPh₄). The kinetics of the polythiourethane network formation investigated using real‐time infrared indicates that the thiol–isocyanate coupling reaction was successfully triggered photolytically and the conversion of both thiol and isocyanate reached near 100% in a matter of minutes. The T_g of the polythiourethane networks progressively increases (–8 to 143 °C by DMTA) as a function of the PETMP content due to the higher extent of crosslinks, also resulting in enhanced rubbery modulus. Very narrow full width at half maximum (15–28 °C) of tan δ peak was obtained for all six sets of polythiourethane networks, which is induced by the highly uniform and dense structures of thiol‐based polymeric network. Energy damping performance of polythiourethane networks measured by nondestructive impact testing exhibited remarkably high (～95%) and the relationship with temperature was in accordance with tan δ peak. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46070.     

Radiation polymerization and concentration separation of P(NIPA‐co‐AMPS) hydrogels

Extraction or concentration with temperature‐sensitive hydrogels is a novel separation technology. In this study, N‐isopropylacrylamide (NIPA) was synthesized by acrylonitrile and isopropanol. Poly(N‐isopropylacrylamide) (PNIPA) and copolymer of NIPA and 2‐acrylamide‐2‐methylpropane sulfonate [P(NIPA‐co‐AMPS)] hydrogels were prepared by radiation polymerization. Dependence of their swelling behavior on temperature was studied. Effects of radiation dose on polymerization, feed composition on thermoresponse, electrolyte on relative swelling ratio, and swelling and deswelling kinetics were investigated. The experimental results showed that P(NIPA‐co‐AMPS) hydrogels with low content of AMPS/NIPA (1–5 %), prepared at a radiation dose‐rate of 1 kGy/h and total dose of 30–40 kGy, could enhance the swelling ratio of PNIPA hydrogels significantly and raise the phase‐transition temperatures. P(NIPA‐co‐AMPS) hydrogels produced under optimum conditions were used to concentrate aqueous bovine serum albumin (BSA, M = 69 000 g mol^?1) solution. When aqueous BSA concentration was below 5 %, the separation efficiency was more than 80 % with low cost and low energy consumption. Copyright © 2005 Society of Chemical Industry     

Fast‐responding bulk hydrogels with microstructure

A new method was used for the production of fast‐responding bulk hydrogels with microstructure (BHMs) with a high swelling ratio. These BHMs were synthesized first by the formation of poly(N‐isopropylacrylamide‐co‐acrylic acid) (NIPAAm–AA) microgel particles and then by the crosslinking of the particles with N‐isopropylacrylamide monomer. The polymer obtained had the desired microstructure but was bulk (monolithic), so it could be used in a variety of applications. The NIPAAm–AA microgel particles were characterized with transmission electron microscopy, and the formed BHMs were characterized with scanning electron microscopy. Compared with conventional bulk hydrogels, the BHMs had very high swelling ratios and much faster swelling rates attributable to the collaboration of the ionized microgel particles and bulk hydrogels. An increase in the microgel particles embedded in the BHMs provided faster hydrogel swelling. The number of ionic acrylic acid groups in the hydrogels affected their swelling behavior. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 169–178, 2002     

Swelling characteristics of thermo‐ sensitive poly[(2‐diethylaminoethyl methacrylate)‐co‐(N,N‐dimethylacrylamide)] porous hydrogels

Temperature‐sensitive poly[(2‐diethylaminoethyl methacrylate)‐co‐(N,N‐dimethylacrylamide)] [P(DEAEMA‐co‐DMAAm)] hydrogels with five different DMAAm contents were synthesized with and without the addition of sodium carbonate as porosity generator. The synthesized hydrogels were characterized with dry gel density measurements, scanning electron microscopy observation and the determination of swelling ratio. The influence of the pore‐forming agent and content of DMAAm on swelling ratio and network parameters such as polymer–solvent interaction parameter (χ), average molecular mass between crosslinks (M?_c) and mesh size (ζ) of the cryogels are reported and discussed. The swelling and deswelling rates of the porous hydrogels are much faster than for the same type of hydrogels prepared via conventional methods. At a temperature below the volume phase transition temperature, the macroporous hydrogels also absorbed larger amounts water compared to that of conventional hydrogels and showed obviously higher equilibrated swelling ratios in aqueous medium. In particular, the unique macroporous structure provided numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to the external temperature changes during the deswelling and swelling processes. These properties are attributed to the macroporous and regularly arranged network of the porous hydrogels. Scanning electron micrographs reveal that the macroporous network structure of the hydrogels can be adjusted by applying porosity generation methods during the polymerization reaction. Copyright © 2007 Society of Chemical Industry     

Fast‐swelling oxidized starch phosphate–poly(acrylate/acrylamide/2‐acryloylamino‐2‐methyl‐1‐propanesulfonic acid) superabsorbent composite

A fast‐swelling superabsorbent composite was prepared by solution polymerization of acrylate, acrylamide, 2‐acryloylamino‐2‐methyl‐1‐propanesulfonic acid and oxidized starch phosphate. Ethanol, propyl alcohol, butyl alcohol, and sodium bicarbonate were used as foaming agents to produce fast‐swelling characteristics. The structure of the superabsorbent composite was characterized using Fourier transform infrared spectroscopy (FTIR). The influences of the amount of water, acrylamide, 2‐acryloylamino‐2‐methyl‐1‐propanesulfonic acid, oxidized starch phosphate, initiator, and trihydroxymethyl propane glycidol ether, as well as the neutralization degree of acrylic acid on the equilibrium swelling degree and swelling rate of the superabsorbent composite, were investigated. The equilibrium swelling degree of the superabsorbent composite prepared in a 0.9 wt% NaCl aqueous solution was 52 g g^?1, and the swelling rate reached 0.86 mL g^?1 s^?1. The swelling kinetics was also investigated, and the results indicate that swelling of the superabsorbent composites obeys Schott's pseudo second‐order kinetics model. POLYM. ENG. SCI., 56:1267–1274, 2016. © 2016 Society of Plastics Engineers     

Dual‐Crosslinked Human Serum Albumin‐Polymer Hydrogels for Affinity‐Based Drug Delivery

A dual‐crosslinked in situ gelling drug delivery scaffold based on dextran (DEX), thiolated serum albumin, and poly(ethylene glycol) (PEG) is presented. Dextran–vinyl sulfone conjugates with varied molecular weight and degrees of substitution are synthesized by controlling the reaction time and temperature with divinyl sulfone. Dextran–human serum albumin (sHSA) hydrogels are prepared using a thiol‐vinyl sulfone Michael addition reaction with thiolated albumin as the crosslinker. Poly(ethylene glycol) dithiol is added as a third component to the crosslinked dextran–human serum albumin hydrogel to facilitate additional crosslinking, and reduce gelation time, while modulating the physicochemical properties of the Dex–sHSA–PEG network. The onset of gelation of the modular three‐component dual‐crosslinked hydrogel network ranges from 45 min to 1.5 h depending on gel constituent concentrations and the gelation temperature (25 or 37 °C). All gels remain stable for over a 25 d period under physiological conditions. In vitro drug release assays show that dual‐crosslinked Dex–sHSA–PEG hydrogels can deliver doxorubicin in a sustained manner over 7 d. Finally, a Tetrazolium‐based assay shows the biocompatible nature of the Dex–sHSA–PEG hydrogels and capacity to deliver doxorubicin successfully to MCF‐7 breast cancer cells.     

Hyperbranched polyesters based on hydroxyalkyl‐lactones via thiol‐ene click reaction

The preparation of AB₂ monomers via thiol‐ene click reaction from six‐ and seven‐membered unsaturated lactones is described. The hydroxyl‐functionalized valerolactone was prepared by use of Michael thiol‐ene‐addition reaction starting from 2‐mercaptoethanol and 3‐methylenetetrahydro‐2H‐pyran‐2‐on. The hydroxyl‐functionalized caprolactone was prepared radically from 2‐mercaptoethanol and 7‐allyloxepan‐2‐one. Both AB₂ monomers were polymerized via ring opening in the presence of tin(II)‐2‐ethylhexanoate (Sn(Oct)₂) as a catalyst yielding the hyperbranched polyesters. The new hyperbranched polyesters were analyzed by ¹³C NMR spectra to determine the degree of branching. © 2014 Society of Chemical Industry     

A comparative study of swelling properties of hydrogels based on poly(acrylamide‐co‐methyl methacrylate) containing physical and chemical crosslinks

Poly (acrylamide‐co‐methyl methacrylate) hydrogels of different ratios were prepared by using chemical and physical crosslinks to study the effect of nature of crosslinks on swelling behavior of hydrogels. The chemically crosslinked gels were prepared by using NN′‐methylene bis acrylamide, while physically crosslinked hydrogels were prepared by precipitation polymerization method, using dioxane as solvent. Detailed swelling kinetics such as swelling ratio, transport exponent n, diffusion coefficient D and the effect of pH on equilibrium swelling studies. The study revealed that the nature of crosslinks alter the swelling characteristics of the hydrogel. In chemically crosslinked hydrogels the water transport is Fickian in nature, while in the case of the physically crosslinked hydrogels the water transport mechanism is anomalous indicating major change in relaxation mechanism due to nature of crosslinks. The results also indicate that with increasing acrylamide content the swelling ratio of the hydrogels were also increased, but the transport exponent n remains nearly constant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 779–786, 2003     

The effect of gel composition on the uranyl ions adsorption capacity of poly(N‐vinyl 2‐pyrrolidone‐g‐citric acid) hydrogels prepared by gamma rays

Poly(N‐vinyl 2‐pyrrolidone‐g‐citric acid) (PVP‐g‐CA) hydrogels with varying compositions were prepared from ternary mixtures of N‐vinyl 2‐pyrrolidone–citric acid–water by using ⁶⁰Co γ‐rays. The effect of gel composition on the uranyl ions adsorption capacity of PVP‐g‐CA hydrogels was investigated. Uranyl adsorption capacity of these hydrogels were found to be in the range of 18–144 mg [UO]/g dry gel from the aqueous solution of uranyl nitrate and 22–156 mg [UO]/g dry gel from the aqueous solution of uranyl acetate, depending on the content of citric acid in the hydrogel, while poly(N‐vinyl 2‐pyrrolidone) hydrogel did not sorb any uranyl ion. The swelling of PVP‐g‐CA hydrogel containing 2.7 mol % CA was observed in water (1620%), in uranyl acetate solution (1450%) and in uranyl nitrate solution (1360%), as compared to 700% swelling of pure PVP hydrogels. The diffusion coefficients were varied from 12.57 up to 4.04 • 10⁻⁸ m² s⁻¹. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1037–1043, 2000     

Swelling behaviors of ionic poly(N,N‐dimethylacrylamide‐co‐acrylamide) hydrogels in various media

Polyelectrolyte hydrogels were synthesized from N,N‐dimethylacrylamide, acrylamide, and itaconic acid with ammonium persulfate as a free‐radical initiator in the presence of methylene(bis)acrylamide as a crosslinker. The swelling behavior of the ionic poly(N,N‐dimethylacrylamide‐co‐acrylamide) hydrogels was investigated in pure water, in KSCN solutions with pHs 4 and 9, and in water–acetone mixtures according to the itaconic acid content in the hydrogel. The pulsatile swelling behavior of these hydrogels was studied both in water–acetone and in pH 2–9 buffer solutions. Although the equilibrium swelling ratio of the hydrogels with low concentrations of itaconic acid was almost not affected by changes in the temperature, the equilibrium swelling ratio of the hydrogels with high concentrations of itaconic acid increased in the temperature range of 20–50°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2140–2145, 2007     

Preparation of epoxy‐ended hyperbranched polymers with precisely controllable degree of branching by thiol‐ene Michael addition

Epoxy‐ended hyperbranched polymers (EHPs) have a wide range of applications due to their outstanding performances. Because their microstructures are not positively identified, it is very difficult to ascertain the reinforcing and toughening mechanisms of EHPs and their interface interaction with other matrixes. Controllable synthesis of EHPs with precise degree of branching (DB) remains to be a major challenge. Here, a method for preparing novel nitrogen‐phosphor skeleton epoxy‐ended hyperbranched polymers (NPEHP) with controllable DB by a thiol‐ene Michael addition between thiol‐ended hyperbranched polymers (NPHSH) and glycidyl methacrylate have been firstly reported. NPHSH is synthesized by an esterification between hydroxyl‐ended hyperbranched polymers (NPHOH) and 3‐mercaptopropionic acid. NPHOH is prepared by a thiol‐ene Michael addition between methacrylate group of a monomer and thiol group of linear monomer (AB) and/or branched monomer (AB₂). The molar ratio between the AB and AB₂ monomers controls the DB of the products. The ¹H NMR spectra analysis of NPHOH shows that their experimentally determined DBs are very close to their theoretical values, indicating good controllability of their DBs. The narrow molecular weight distributions of NPHOH, NPHSH, and NPEHP suggest high efficiency of the thiol‐ene Michael addition. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44277.