Kinetic analysis of the swelling behavior of poly(n‐butylacrylate‐1,6‐hexanedioldiacrylate) networks in 4‐cyano‐4′‐n‐pentyl‐biphenyl (5CB)

The dynamic swelling behavior of chemically crosslinked poly(n‐butylacrylate/1,6‐hexanedioldiacrylate) [poly(Abu‐HDDA)] networks, immersed in an nematogenic and two isotropic solvents, was experimentally analyzed. These networks were elaborated by ultraviolet (UV)–visible light‐induced radical polymerization/crosslinking reactions of Abu/HDDA mixtures, to yield poly(Abu/0.5 wt % HDDA) and poly(Abu/5 wt % HDDA) networks corresponding to weakly and strongly crosslinked systems, respectively. The swelling behavior of these poly(Abu‐HDDA) networks was investigated by immersion in excess solvent, followed by subsequent measurements of the variation of the sample size by means of optical microscopy, depending on temperature and immersion time. Methanol and toluene were employed as isotropic solvents and the nematic liquid crystal molecule 4‐cyano‐4 ′ ‐n‐pentyl‐biphenyl, was considered as anisotropic medium. Swelling ratios were calculated by taking into account diameter sizes as function of immersion time compared to the dry state. Experimental data were analyzed using the Komori–Sakamoto approach and the results of this model were found to be in good agreement with the obtained data. The plateau values of the swelling curves at equilibrium were used to establish phase diagrams as function of temperature and solvent concentration. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45452.     

Pervaporation separation of 1,1,2‐trichloroethane–water mixture through crosslinked acrylate copolymer composite membranes

The separation of a chlorinated hydrocarbon from a dilute aqueous solution through a crosslinked acrylate copolymer–porous substrate composite membrane by pervaporation was investigated. Poly(n‐butyl acrylate‐co‐acrylic acid) and poly(n‐butyl acrylate‐co‐2‐hydroxyethyl acrylate) were synthesized and composite membranes were prepared, which were made from the crosslinked polymer and a porous substrate. Pervaporation measurement was carried out for a dilute aqueous solution of 1,1,2‐trichloroethane at 25°C and under a vacuum on the permeate side (below 10 mmHg). The separation factor, overall flux, 1,1,2‐trichloroethane concentration in the membrane, and the degree of swelling decreased with increase in the acrylic acid or 2‐hydroxyethyl acrylate content of the acrylate copolymer. The influence of the crosslinking agent content on the pervaporation performance was small, and the separation factor and the overall flux showed a convex curve. The structure of the crosslinking agent had no effect on the separation. The influence of the pore size of the substrate and the thickness of the polymer layer on the separation of 1,1,2‐trichloroethane was observed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 983–994, 1999     

Influence of structural parameters on the degradation of ultrahigh‐molecular‐weight vinyl‐type network‐polymer precursors during elution through size exclusion chromatography columns

Network‐polymer precursors obtained in various crosslinking monovinyl/divinyl copolymerization systems, including benzyl methacrylate/1,6‐hexanediol dimethacrylate, benzyl acrylate (BzA)/1,6‐hexanediol diacrylate (HDDA), and vinyl benzoate/divinyl adipate, were subjected to degradation during elution through size exclusion chromatography (SEC) columns, although the copolymerizations were conducted under specified conditions where the factors for the greatly delayed gelation from the Flory–Stockmayer gelation theory were reduced. The most remarkable degradation was observed for the BzA/HDDA copolymerization, which provided prepolymers with the most flexible backbone chains. Thus, the BzA/HDDA precopolymers were chosen, and their degradation behavior during elution through SEC columns was explored in detail as one of the representatives of vinyl‐type network‐polymer precursors. The results were correlated with the structural parameters of network‐polymer precursors, including primary polymer chain length, branched structure, and multiple crosslink or network structure. The degradation became more remarkable with decreased primary polymer chain length, that is, the increment of branching, whereas reduced degradation was observed with the incorporation of loop and network structures into the prepolymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 577–582, 2003     

Polymer hybrids from self‐emulsified PU anionomer and water‐reducible acrylate copolymer via a postcuring reaction

Water‐reducible acrylate copolymer is obtained from a free‐radical copolymerization of n‐butyl acrylate, acrylic acid, and methacrylic acid. Self‐emulsified aqueous‐based polyurethane (PU) anionomer is prepared by the conventional method. The latent curing agents (di‐ and triaziridinyl compounds, HDDA‐AZ and TMPTA‐AZ) are synthesized from the reaction of aziridine with hexandiol diacrylate and trimethylolpropane triacrylate, respectively. These two polymers and the latent curing agent are miscible in each other and become a single component and self‐curable polymer dispersion. The carboxyl ions of polymers not only stabilize the aqueous polymer dispersions but also serve the curing site toward latent curing agent in the drying process. These two polymers blend with a curing agent, which results in new polymer hybrid formation. These polymer hybrids have the improvements on performance properties and the cost/performance benefits. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3578–3587, 2003     

Study on synthesis and morphology control of poly(4‐vinylpyridine‐co‐butyl acrylate)/poly(styrene‐co‐butyl acrylate) composite microspheres

Monodispersed crosslinked cationic poly(4‐vinylpyridine‐co‐butyl acrylate) [P(4VP‐BA)] seed latexes were prepared by soapless emulsion polymerization, using 2,2′‐azobismethyl(propionamidine)dihydrochloride (V₅₀) as an initiator and divinylbenzene (DVB) or ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The optimum condition to obtain monodispersed stable latex was investigated. It was found that the colloidal stability of the P4VP latex can be improved by adding an adequate amount of BA (BA/4VP = 1/4, w/w), and adopting a semicontinuous monomer feed mode. Subsequently, poly(4‐vinylpyridine‐co‐butyl acrylate)/Poly(styrene‐co‐butyl acrylate) [P(4VP‐BA)/P(ST‐BA)] composite microspheres were synthesized by seeded polymerization, using the above latex as a seed and a mixture of ST and BA as the second‐stage monomers. The effects of the type of crosslinker, the degree of crosslinking, and the initiators (AIBN and V₅₀) on the morphology of final composite particles are discussed in detail. It was found that P(4VP‐BA)/P(ST‐BA) composite microspheres were always surrounded by a PST‐rich shell when V₅₀ was used as initiator, while sandwich‐like or popcorn‐like composite particles were produced when AIBN was employed. This is because the polarity of the polymer chains with AIBN fragments is lower than for the polymer with V₅₀ fragments, hence leading to higher interfacial tension between the second‐stage PST‐rich polymer and the aqueous phase, and between PST‐rich polymer and P4VP‐rich seed polymer. As a result, the seed cannot be engulfed by the PST‐rich polymer. Furthermore, the decrease of T_g of the second‐stage polymer promoted phase separation between the seeds and the PST‐rich polymer: sandwich‐like particles formed more preferably than popcorn‐like particles. It is important knowledge that various morphologies different from PST‐rich core/P4VP‐rich shell morphology, can be obtained only by changing the initiator, considering P4VP is much more hydrophilic than PST. The zeta potential of composite particles initiated by AIBN in seeded polymerization shifted from a positive to a negative charge. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1190–1203, 2002     

Phase Behavior of Poly(butyl acrylate) Networks in Nematic Liquid Crystal Solvents

Summary: This paper reports the phase behavior of photochemically crosslinked poly(butyl acrylate) networks in nematic liquid crystal (LC) solvents. The swelling properties are studied as a function of temperature for two low molecular weight nematic LCs, 4‐cyano‐4′‐pentylbiphenyl (5CB) and the eutectic mixture of cyanoparaphenylenes (E7). Chemically crosslinked polymer networks were formed by the UV radiation of initial solutions of the reactive monomer, butyl acrylate, a crosslinker (hexanediol diacrylate), and a photoinitiator. To obtain different network densities, the ratio of butyl acrylate to hexanediol diacrylate was varied prior to polymerization/crosslinking reactions. Immersion in an excess of the LC solvent allowed for the measurement of size increase by polarized optical microscopy in terms of temperature. Length, width, and diagonal ratios were calculated considering swollen to dry network states of the samples. In general, swelling leads to an increase in the network size by increasing the temperature with a significant dependence on the degree of crosslinking. A large shift in the swelling ratio was found in the vicinity of the nematic to isotropic transition temperatures of the LCs.

     

Super‐macroporous dextran cryogels via UV‐induced crosslinking: synthesis and characterization

Cryogenic treatment and UV irradiation were exploited for the preparation of super‐macroporous cryogels from non‐modified high‐molar‐mass dextran. The photo‐crosslinking process was initiated by (4‐benzoylbenzyl)trimethylammonium chloride and N,N′‐methylenebisacrylamide (BAAm) was used as a crosslinking agent. Gel fraction yield and degree of swelling of the dextran cryogels were determined gravimetrically. Cryogel morphology and mechanical properties were studied using environmental scanning electron microscopy and dynamic rheological measurements, respectively. The effects of dextran concentration in the initial polymer solution, polymer molar mass and BAAm content on the crosslinking efficacy, physico‐mechanical properties and morphology of the cryogels were evaluated. The dextran cryogels were assessed as carriers of the model water‐soluble drug metoprolol. © 2017 Society of Chemical Industry     

Poly(N‐isopropylacrylamide‐co‐sodium acrylate) hydrogels: Interactions with surfactants

Poly(N‐isopropylacrylamide‐co‐sodium acrylate) [poly(NIPAM‐co‐SA)] hydrogels were modified with three different kind of surfactants (cationic, anionic, and nonionic) to study the effect on the swelling properties. The structural variation of the surfactant‐modified hydrogels was investigated in detail. The interaction between the surfactants and the hydrogel varies and strictly depends on the surfactant type. The variation in thermal stability of the modified surfactant hydrogels was investigated and compared with unmodified hydrogel. Further, the hydrogel swelling/diffusion kinetic parameters were investigated and diffusion of water into hydrogel was found to be of the non‐Fickian transport mechanism. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3423–3430, 2007     

Synthesis and characterization of photo‐crosslinkable polyfluorene with acrylate side‐chains

A photo‐crosslinkable polymer, poly[2,7‐(9,9‐dioctylfluorene)‐co‐2,7‐(9‐hexyl‐9‐(2‐acrylate ethyl)‐9H‐fluorene)] (P3), was synthesized and the photo‐crosslinkable acrylate groups were introduced into the side‐chains of the polyfluorene derivative after its polymerization. This method avoids the possible crosslinkage of the crosslinkable groups on the monomers during polymerization in the traditional synthesis route by the polymerization of the monomers with the crosslinkable side‐chains. The soluble and processable polymer P3 could be crosslinked via the acrylate groups in its side‐chains upon exposure to UV light in nitrogen atmosphere. The crosslinking was confirmed by IR spectroscopy: the IR peak of C?C bond at 1635 cm^?1 decreased and that of the vinyl C? H bond at 742 cm^?1 disappeared after the UV exposure. The absorption spectra of P3 remain unchanged after crosslinking, but a longer wavelength emission at 517 nm appeared in the photoluminescent and electroluminescent spectra of the crosslinked P3, which could be attributed to the formation of keto defects during the photo crosslinking. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2336–2342, 2006     

n‐Butyl acrylate based latex interpenetrating polymer networks used as processing modifiers and impact modifiers of poly(vinyl chloride)

A latex interpenetrating polymer network (LIPN), consisting of poly(n‐butyl acrylate), poly(n‐butyl acrylate‐co‐ethylhexyl acrylate), and poly(methyl methacrylate‐co‐ethyl acrylate) and labeled PBEM, with 1,4‐butanediol diacrylate as a crosslinking agent was synthesized by three‐stage emulsion polymerization. The initial poly(n‐butyl acrylate) latex was agglomerated by a polymer latex containing an acrylic acid residue and then was encapsulated by poly(n‐butyl acrylate‐co‐ethylhexyl acrylate) and poly(methyl methacrylate‐co‐ethyl acrylate). A polyblend of poly(vinyl chloride) (PVC) and PBEM was prepared through the blending of PVC and PBEM. The morphology and properties of the polyblend were studied. The experimental results showed that the processability and impact resistance of PVC could be enhanced considerably by the blending of 6–10 phr PBEM. This three‐stage LIPN PBEM is a promising modifier for manufacturing rigid PVC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1168–1173, 2004     

Hydrogels composite of poly(acrylamide‐co‐acrylate) and rice husk ash. I. Synthesis and characterization

Composite hydrogels of poly(acrylamide‐co‐acrylate) with rice husk ash (RHA) were synthesized and studies of the swelling variables were accomplished comparatively with commercial polyacrylamide gel and PAMACRYL, a poly(acrylamide‐co‐acrylate) hydrogel without RHA. FT‐IR and WAXS were the techniques employed for characterizing a series of hydrogel obtained by varying the percentage of RHA (1, 2, 5, 10, and 20 wt %) and the amount of crosslinking agent (0.05, 0.1, and 0.2 mol %) relative to sum of AAm and AAc. Superabsorbent hydrogel with W_eq > 800 g H₂O/g gel was obtained with percentage of 10 wt % of RHA and 0.1 of crosslinking agent mol %. The hydrogel showed to be sensitive to the pH variation and to the presence of salts. The hydrogels, even though submitted through cycles of drying and swelling, preserved their superabsorbent characteristics and demonstrated better water absorbance properties when compared with commercial polyacrylamide gel. The composite hydrogels of poly(acrylamide‐co‐acrylate) with RHA presented good characteristics to be applied as soil conditioner for using in agriculture. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of nonmesogenic crosslinking units on the mesogenic properties of side‐chain cholesteric liquid crystalline elastomers

A series of cyclosiloxane‐based cholesteric liquid crystalline elastomers were synthesized by using cholest‐5‐en‐3‐ol(3β)‐4‐(2‐propenyloxy)benzoate and a soft nonmesogenic crosslinking agent, acryloyl‐hexyl acrylate. The polymers were prepared in a one‐step reaction with the crosslinking contents ranging between 0 and 5.6 weight %. The effective crosslink density (M_c) was determined by swelling experiments employing Flory–Rehner models. All the polymers exhibited thermotropic LC properties and revealed a cholesteric phase. With increase of the crosslinking component in the polymers, the melting behavior disappeared and the enthalpy of transition decreased. But the temperature of glass transition and clear point changed little and did not show uptrend or downtrend. Reflection spectra of the cholesteric mesophase of the polymers showed that the reflected wavelength became broad and shifted to long wavelength with increase of the soft crosslinking component in the polymer systems. All these results originate from the effect of the soft nonmesogenic chemical crosslinking. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 625–631, 2005     

Hydroxyethyl chitosan‐g‐poly(acrylic acid‐co‐sodium acrylate) superabsorbent polymers

A novel hydroxyethyl chitosan‐g‐poly(acrylic acid‐co‐Sodium Acrylate) (HECTS‐g‐(PAA‐co‐PSA)) superabsorbent polymer was prepared through graft copolymerization of acrylic acid and sodium acrylate onto the chain of hydroxyethyl chitosan. The structure of the polymer was characterized by FTIR. By studying the water absorption of the polymer synthesized under different conditions, the optimal conditions for synthesizing the polymer with the highest swelling ratio was defined. This superabsorbent polymer was further treated by the solvent precipitation method and by the freeze‐drying method. We found that the water absorption rate of the treated polymer was greatly increased and the microstructure of the treated polymer was changed from small pores to loose macro pores. The swelling processes of the polymers before and after modification fit first‐order dynamic processes. The amount of the residual acrylic acid was greatly decreased after treatments. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fast responsive and strong swelling hydrogels based on N‐isopropylacrylamide with sodium acrylate

Poly(N‐isopropylacrylamide‐co‐sodium acrylate) gels with N,N‐methylene bisacrylamde (BIS) as crosslinker were prepared by free radical polymerization method at the temperature of 35°C, which was just around the lower critical solution temperature (LSCT) of the hydrogels. The gels synthesized at 35°C demonstrated strong swellability and fast responseability when compared with the gels synthesized at the temperature of 0 and 18°C (below the LCST) and 50 and 80°C (above the LSCT). The response rate and swelling behavior of poly(N‐isopropylacrylamide‐co‐sodium acrylate) gels was investigated and characterized by the temperature‐dependent swelling ratio and swelling and deswelling kinetics. The swelling behavior of the gels indicated that the synthesis temperature was the main factor when the swellability concerned and also had effect on the responseability of the resulting hydrogels. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and network parameters of hydrophobic poly(N‐[3‐(dimethylaminopropyl)]methacrylamide‐co‐lauryl acrylate) hydrogels

Hydrophobic poly(N‐[3‐(dimethylaminopropyl)]methacrylamide‐co‐lauryl acrylate) [P(DMAPMA‐co‐LA)] hydrogels with different LA content were synthesized by free‐radical crosslinking copolymerization of corresponding monomers in water by using N,N‐methylenebis(acrylamide) as the crosslinker, ammonium persulfate as the initiator, and N,N,N′,N′‐tetramethylethylenediamine as the activator. The swelling equilibrium of the hydrogels was investigated as a function of temperature and hydrophobic comonomer content in pure water. An interesting feature of the swelling behavior of the P(DMAPMA‐co‐LA) hydrogels with low LA content was the reshrinking phase transition where the hydrogels swell once and collapse as temperature was varied in the range of 30–40°C. The average molecular mass between crosslinks (M?_c) and polymer–solvent interaction parameter (χ) of the hydrogels were calculated from equilibrium swelling values. The enthalpy (ΔH) and entropy (ΔS) changes appearing in the χ parameter for the hydrogels were determined by using the Flory–Rehner theory based on the phantom network model of swelling equilibrium. The positive values for ΔH and ΔS indicated that the hydrogels had a positive temperature‐sensitive property in water, that is, swelling at a higher temperature and shrinking at a lower temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4159–4166, 2006     

pH‐responsive core crosslinked polycarbonate micelles via thiol‐acrylate Michael addition reaction

A facile method for the construction of pH‐responsive core crosslinked micelles (CCLMs) based on polycarbonate was developed. Biodegradable amphiphilic block copolymer monomethoxy poly(ethylene glycol)‐b‐Poly(AC) (mPEG‐b‐poly(AC)) with pendant acrylate group was synthesized by means of ring opening polymerization of acryloyl carbonate (AC). Then CCLMs were obtained via thiol‐acrylate Michael addition reaction between the pendant acrylate group in the hydrophobic block and the crosslinker 1,6‐hexanedithiol. DLS results showed that the CCLMs prepared from mPEG‐b‐poly(AC)₂₅ were more stable than uncrosslinked micelles (UCLMs) upon dilution by 10‐fold DMF. Model drug Coumarin 102 was then encapsulated into the micelles. The pH‐responsive release of coumarin 102 from the CCLMs was demonstrated by fluorescence spectroscopy. The core crosslinked polycarbonate micelles have a potential as efficient intracellular smart drug delivery platforms. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44421.     

Electro‐optic properties of CO2 fixed‐polymer/nematic LC composite films

Bis(cyclic carbonate) was obtained from the epoxide and CO₂ reaction with a quaternary ammonium halide salt catalyst. Cyclic carbonate derivatives were then reacted with amine to obtain quantitatively poly(hydroxy)urethanes that were reacted with isophorone diisocyanate (IPDI) and end capped with acrylate to form prepolymers. These prepolymers were mixed with reactive diluents and nematic LCs, and subjected to UV cure to form polymer/LC composite films in a transparent cell. Three types of diglycidyl ether [poly(propyleneglycol), cyclohexane, bisphenol A], three types of end‐capping acrylates [2‐hydroxyethyl acrylate (HEA), 2‐hydroxypropyl acrylate (HPA), and 2‐hydroxyethyl methacrylate (HEMA)], three types of multyfunctional diluents [tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), dipentaerythritol hydroxy penta/hexa acrylate (DPHPA)], and three types of photoinitiators (Irgacure‐651, Irgacure‐184, Darocure‐1173) were incorporated to control the morphology, and hence, the electro‐optic properties of the polymer/nematic LC composite films. Poly(propylene glycol) diglycidyl ether segment of polyurethane acrylate (PUA) showed lower viscosity and gave larger domain size resulting in lower threshold (V₁₀) and driving (V₉₀) voltages, together with larger nematic–isotropic transition temperature depression. HEA end‐capped PUA gave larger polymer–LC phase separation and smaller V₁₀ as well as V₉₀. TPGDA‐based PUA showed the lowest V₁₀ and V₉₀ and the shortest response time. Among the three types of photoinitiators used Irgacure‐651 showed the larger LC domain, and smaller V₁₀ and V₉₀. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2744–2753, 2001     

Adsorption of surfactant by hydrophobically modified poly[2‐(diethylamino)ethylmethacrylate‐co‐N‐vinyl‐2‐pyrrolidone/octadecyl acrylate)] hydrogels and effect of surfactant adsorption on the volume phase transition

Hydrophobically modified poly[2‐(diethylamino)ethylmethacrylate‐co‐N‐vinyl‐2‐pyrrolidone/octadecyl acrylate) [P(DEAEMA‐co‐NVP/OA)] hydrogels were synthesized by free‐radical crosslinking copolymerization of 2‐(diethylamino)ethylmethacrylate (DEAEMA), N‐vinyl‐2‐pyrrolidone (NVP) with different amounts of hydrophobic comonomer octadecyl acrylate (OA) in tert‐butanol with ethylene glycole dimethacrylate (EGDMA) as a crosslinker. The swelling equilibrium of the hydrogels was investigated as a function of temperature and hydrophobic comonomer content in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). The results indicated that the swelling behavior and temperature sensitivity of the hydrogels were affected by the type and concentration of surfactant solutions. Additionally, the amount of the adsorbed SDS and DTAB molecules onto the hydrogels was determined by fluorescence measurements. An increase of OA content in the hydrogel caused an increase in the amount of adsorbed surfactant molecules in both media. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3771–3775, 2007     

Synthesis and characterization of crosslinking waterborne fluorinated polyurethane‐acrylate with core‐shell structure

Crosslinking core‐shell emulsions of waterborne fluorinated polyurethane‐acrylate (WFPUA) were successfully synthesized using a solvent‐free method. The crosslinkers of diacetone acrylamide and adipic dihydrazide were introduced into the WFPUA emulsions. The physical properties of hybrid emulsions such as the average particle size, stability, and viscosity were characterized. The core‐shell of crosslinking WFPUA emulsion synthesized in this study was observed by transmission electron microscopy. Then, the results of Fourier transform infrared spectroscopy, atomic force microscopy, and X‐ray photoelectron spectroscopy indicated that the fluorinated monomer (FA) had been polymerized into the crosslinking waterborne polyurethane‐acrylate polymer, and the fluorinated groups have evident enrichment on the film‐air surface with the increase of FA content. At the same time, the thermal properties, water repellent/antifouling properties, and mechanical properties were measured. Moreover, the thermal properties and the elongation are raised but tensile stress and shore hardness are decreased with the increase of FA content. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40970.     

Partially constrained recovery of (meth)acrylate shape‐memory polymer networks

The purpose of this study was to characterize the partial strain recovery of a thermoset shape‐memory polymer under a constraining stress. Three polymer networks were synthesized from tert‐butyl acrylate and poly(ethylene glycol) dimethacrylate (PEGDMA) solutions. The molecular weight and the weight fraction of the PEGDMA crosslinking monomer was altered systematically to maintain a constant glass transition temperature (T_g = 54°C) but tailorable rubbery moduli, which varied by almost an order of magnitude for the three polymer networks (E = 1.8–11.3°MPa). The shape‐recovery behavior of the polymers under a constraining stress was characterized for programming temperature below (20°C) and above (70°C) the T_g. The experiments revealed a peak in the recovered strain for samples programmed at 20°C. Recovered strain scaled linearly with the constraining stress by the rubbery modulus. The work performed by the shape‐memory polymer networks was observed to be primarily a function of constraining stress and crosslinking density, while programming temperature had a relatively mild influence; however, the efficiency of the shape‐memory effect was shown to be a function of constraining stress and programming temperature, but was independent of crosslinking density. Maximum work efficiencies (up to 45%) were observed for programming temperature of 70°C. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012