Synthesis and solution properties of temperature‐sensitive copolymers based on NIPAM

A kind of temperature‐sensitive water‐soluble polymers P(NIPAM‐HEMA‐AM) of N‐isopropylacrylamide (NIPAM), hydroxyethyl methacrylate (HEMA) and acrylamide (AM) were synthesized by free radical aqueous solution copolymerization. The polymers were characterized by Fourier transform infrared spectrum (FTIR) method. Solution properties, such as the influences of monomer ratios and additives on the low critical soluble temperature (LCST) of the polymer solutions as well as the viscosity‐temperature properties were studied. The results show that the polymer concentrations have no significant influence on the LCST of polymer solutions. The incorporation of HEMA units leads to a lower LCST, while AM units to a higher LCST. The additions of small molecules such as salt and surfactant also have significant effect on the LCST, the addition of NaCl decreases the LCST, while the addition of sodium dodecylbenzenesulfonate (SDBS) increases the LCST. The apparent viscosity of polymer solutions depends on temperature. The 1.5 wt % aqueous solutions of P(NIPAM‐HEMA‐AM) exhibits good thermo‐thickening behavior over 55°C, whereas the 0.8 wt % aqueous solutions do not show this behavior during the heating process. The aqueous solutions of P(NIPAM‐HEMA‐AM) are viscoelastic fluids, and the viscoelasticities mainly depend on temperature. Both the storage modulus (G') and loss modulus (G'') of 1.5 wt % polymer solutions increase with temperature. Over 55°C, G' exceeds G'', and the polymer solutions are elasticity‐dominated. In contrast, below 55°C, G'' is larger than G', and the polymer solutions are viscosity‐dominated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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 temperature‐responsive copolymers based on N‐vinylcaprolactam and their grafting on fibres

BACKGROUND: Responsive materials are able to respond reversibly to an environmental stimulus. When the stimulus is temperature in the physiological range, the responsive material is particularly interesting for textile applications. We describe here the synthesis and characterization of reactive temperature‐responsive copolymers and their subsequent grafting on cotton fabrics. RESULTS: Copolymers of N‐vinylcaprolactam and various reactive monomers were synthesized via free radical polymerization in solution. The copolymers were characterized in terms of chemical structure, molecular weight and temperature‐responsive properties. The copolymer of N‐vinylcaprolactam and methacrylic acid (11 or 22 wt%) and the hydrolysed copolymer of N‐vinylcaprolactam and acryloyl chloride were found to be temperature responsive. They were subsequently grafted on cotton fabrics. The grafting was studied using X‐ray photoelectron spectroscopy and scanning electron microscopy measurements and was found to be effective. Finally, the modified cotton fabrics were found to exhibit temperature‐responsive water regain and water vapour transmission rates. CONCLUSION: Temperature‐responsive copolymers were synthesized, characterized and successfully grafted on cotton fabrics, yielding responsive fabrics. Such fabrics can hence be used to modulate the skin microclimate under textiles. Copyright © 2009 Society of Chemical Industry     

Preparation,characterization, and drug‐release properties of pH/temperature‐responsive poly(N‐isopropylacrylamide)/chitosan semi‐IPN hydrogel particles

Novel poly(N‐isopropylacrylamide) (PNIPAAm)/chitosan (CS) semi‐interpenetrating polymer network hydrogel particles were prepared by inverse suspension polymerization. The prepared particles were sensitive to both temperature and pH, and they had good reversibility in solution at different temperatures and pH values. The swelling ratios of PNIPAAm/CS hydrogel particles decreased slightly with the addition of CS, which did not shift the lower critical solution temperature. The drug‐release behavior of the particles was investigated using cyclic adenosine 3′,5′‐monophosphate (cAMP) as a model drug. The release of cAMP from the hydrogel particles was affected by temperature, pH, and the CS content in the particles. These results showed that semi‐IPN hydrogel particles appeared to be of great promise in pH‐ and temperature‐sensitive oral drug release. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of pH and temperature dual‐sensitive molecularly imprinted polymers based on chitosan and N‐isopropylacrylamide for recognition of bovine serum albumin

pH and temperature dual‐sensitive protein imprinted microspheres with high absorption capacity have been successfully synthesized on the surface of SiO₂ using chitosan grafted N‐isopropylacrylamide (CS‐g‐NIPAM) as the pH and temperature sensitive monomer, with acrylamide as comonomer, N,N′‐methylenebisacrylamide as the crosslinking agent and bovine serum albumin (BSA) as the template protein. The pH and temperature dual‐sensitivity was also investigated. The results showed that the adsorption capacity and imprinting factor improved slowly with increasing incubation pH from 4.6 to 7.0, and then decreased sharply in alkaline conditions due to the reduction of non‐specific binding from electrostatic and hydrogen bonding interactions. Fourier transform infrared spectroscopy, thermogravimetric analysis and transmission electron microscopy were used to characterize the polymers. The as‐prepared SiO₂@BSA molecularly imprinted polymers were also found to have high adsorption capacity (119.88 mg g^?1) within 2 h, an excellent imprinting factor (α = 2.25), specific selectivity and good reusability. © 2019 Society of Chemical Industry     

Uses of electron‐beam irradiation to prepare pH‐ and temperature‐sensitive hydrogels from reactive poly(vinyl alcohol) grafts

Thermosensitive poly(vinyl alcohol)‐graft‐(maleic anhydride), PVA‐MA, and poly(vinyl alcohol)‐graft‐(N‐isopropylacrylamide maleic anhydride) (PVA‐MA‐NIPAAm) copolymers containing carboxyl groups were prepared using electron beam irradiation at dose 80 kGy. The swelling ratios of the cross‐linked gels were measured at various temperatures. The LCST values were measured using DSC technique. The temperature dependence of the swelling ratios of the cross‐linked copolymers and terpolymers were measured at different temperatures. The swelling ratios of copolymers increased with increasing temperature up to 25–38°C, then decreased. The swelling behavior of both copolymers and terpolymers was referred to formation of hydrogen bonds between amide group of NIPAAm moieties and carboxyl group in MA moieties and to hydrophobic interaction due to methyl groups of NIPAAm. The swelling behaviors of these gels were analyzed in buffer solution at various pH. Swelling ratios of all gels were relatively high and they showed reasonable sensitive to pH. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology and water vapor permeability of temperature‐sensitive polyurethanes

A series of segmented polyurethanes (PUs) were prepared, in which five different polyols and hexamethylene diisocyanate were used as soft segments, and 4,4′‐diphenylmethane diisocyanate, hydrophilic segment poly (ethylene glycol) 200 (PEG 200), and chain extender 1,4‐butanediol were used as hard segment. Morphology of the PUs was investigated using differential scanning calorimetry, wide angle X‐ray diffraction, polarizing microscopy, and transmission electron microscopy. Water vapor permeability of the membranes as a function of temperature was tested accordingly. Results show that the presence of PEG200 interferes the crystallization of hard segment in these PUs, and at the same time, increases phase compatibility between soft and hard segment in the PET‐PU. It leads to a lower crystal melting temperature and degree of crystallinity of soft segment in the segmented PU than those of pure polyols, and no crystallization existing in hard segment. A morphological model is proposed, that is, aggregated soft‐segment‐rich domains can be observed clearly in the PUs with high crystallinity in soft segment, while identifiable hard domains are well‐distributed in the soft segment domains in the PU with low crystallinity. Within the temperature range of crystal melting, water vapor permeability of the PU membranes increases significantly with increase of temperature. Such temperature‐sensitive property is triggered by crystal melting of soft segment. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of molecular weight of poly(N‐isopropyl acrylamide) temperature‐sensitive flocculants on dewatering

The influence of molecular weight (MW) and dose of Poly(N‐isopropyl acrylamide) (PNIPAM) (temperature‐sensitive flocculant) on sedimentation rate, sediment density, and supernatant clarity of silica suspensions was investigated. The addition of PNIPAM resulted in rapid sedimentation (T > critical solution temperature, CST) and low sediment moisture (T < CST). Higher MW polymers resulted in more effective flocculation and sediment consolidation. At 10 ppm, PNIPAM (3.6 million Da) produced 20 m/h settling rate and 48 vol % solids sediment density, whereas 0.23 million Da polymer produced 0.1 m/h settling rate. PNIPAM produces effective flocculation and consolidation by cycling the interparticle interactions between repulsion and attraction as temperature is cycled around the CST. The change in temperature produces a hydrophilic/hydrophobic transition of the polymer, influencing adsorption onto the surface and the inter‐particle forces. Conventional polyacrylamide flocculants (not influenced by temperature), cannot be used to produce both rapid sedimentation and dense sediments. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Filled temperature‐sensitive poly(vinyl methyl ether) hydrogels

Temperature‐sensitive hydrogels based on poly(vinyl methyl ether) (PVME) with ferroelectric or ferromagnetic properties were synthesized by high‐energy irradiation. Barium titanate and poly(vinylidene fluoride) (PVDF) were used as ferroelectric filler and Ni as ferromagnetic filler. The filled PVME hydrogels were synthesized by electron beam or γ‐ray irradiation (of a suspension with 5–50 wt % of filler (with respect to polymer mass) in a 20 wt % aqueous PVME solution). Filling of the gel reduces the absolute swelling degree at low temperatures, but do not influence the phase‐transition temperature of the gel. The particle distribution of the fillers inside the gel was visualized by field emission scanning electron microscopy. The fillers were incorporated in the PVME network and fixed because of their size (inorganic particles), as well as by chemical bonds (PVDF). The ferroelectric or ferromagnetic properties of the filled gels were proved. Measurements in a corresponding alternating field provide the hysteresis loop, for both the ferromagnetic and ferroelectric gel. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2253–2265, 2005     

Preparation of temperature‐ and pH‐sensitive,stimuli‐responsive poly(N‐isopropylacrylamide‐co‐methacrylic acid) nanoparticles

The effects of the monomer ratio, surfactant, and crosslinker contents on the particle size and phase‐transition behavior of the copolymer poly(N‐isopropylacrylamide‐co‐methacrylic acid) (PNIPAAm–MAA) were investigated with Fourier transform infrared, differential scanning calorimetry, and dynamic laser scattering techniques. In addition to the thermoresponsive property of poly(N‐isopropylacrylamide), ionized methacrylic acid groups brought pH sensitivity to the PNIPAAm–MAA copolymer particles. The polymer particle size varied with the amounts of the monomer ratio, surfactant, and crosslinker. As the monomer ratio and crosslinker content increased and the amount of the surfactants decreased, the particle size increased. The influence of the crosslinker content on the particle size was less significant than the effect of the monomer ratio and surfactants. When the temperature increased, the particles tended to shrink and decreased in size to near or below 100 nm. Particle sizes at 20°C decreased to less than 100 nm with increased surfactant content. The control of the particle size within the 100‐nm range makes PNIPAAm–MAA copolymer particles useful for biomedical and heavy‐metal‐ion adsorption applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Stimuli sensitive copolymer poly(N‐tert‐butylacrylamide‐ran‐acrylamide): Synthesis and characterization

Temperature sensitive random linear and crosslinked copolymers of N‐tert‐butylacrylamide (NTBA) and acrylamide (Am) were synthesized by the solution polymerization method, using regulated dosing of comonomer Am having a higher reactivity ratio (r_Am = 1.5) than NTBA (r_NTBA = 0.5). Copolymers with varying feed ratios of NTBA and Am (80 : 20 to 20 : 80 mol %) were synthesized and characterized. For the synthesis of copolymer hydrogels, N′, N‐methylene bisacrylamide (MBA) (1.13 mol %) was used along with monomers. The effect of composition on transition properties was evaluated for the linear copolymers and their hydrogels. A definite trend was observed. The incorporation of a higher percentage of the hydrophilic comonomer Am in the structure resulted in the shifting of the transition temperature towards a higher value. The transition temperatures of the copolymers synthesized with feed compositions of 80 : 20, 70 : 30, 60 : 40, 50 : 50, 40 : 60, 30 : 70, and 20 : 80 mol % were found to be 2, 10, 19, 27, 37, 45, and 58°C, respectively. Differential scanning calorimetry (DSC) studies confirmed the formation of random copolymers. The copolymers synthesized with a monomer feed ratio of 50 : 50 with regulated dosing showed a single glass transition temperature (T_g) at 168°C, while the copolymer synthesized with full dosing of Am at the beginning of the reaction showed two T_gs, at 134 and 189°C. The copolymer samples were analyzed by Fourier transform infrared spectroscopy (FTIR) for ascertaining the composition. The composition of the copolymers followed the trend of the feed ratio, but the incorporation of NTBA in the copolymers was found to be lower than the feed ratio because of lower than quantitative yields of the reactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 672–680, 2005     

pH‐ and temperature‐responsive IPN hydrogels based on soy protein and poly(N‐isopropylacrylamide‐co‐sodium acrylate)

pH‐ and temperature‐responsive interpenetrating polymer network (IPN) hydrogels based on soy protein and poly(N‐isopropylacrylamide‐co‐sodium acrylate) were successfully prepared. The structure and properties of the hydrogels were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry, and thermogravimetric analyzer. The equilibrium and dynamic swelling/deswelling behaviors and the drug release properties of the hydrogels responding to pH and/or temperature were also studied in detail. The hydrogels have the porous honeycomb structures, good miscibility and thermal stability, and good pH‐ and temperature‐responsivity. The volume phase transition temperature of the hydrogels is ca. 40°C. Changing the soy protein or crosslinker content could be used to control the swelling behavior and water retention, and the hydrogels have the fastest deswelling rate in pH 1.2 buffer solutions at 45°C. Bovine serum albumin release from the hydrogels has the good pH and temperature dependence. The results show that the proposed IPN hydrogels may have potential applications in the field of biomedical materials such as in drug delivery systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39781.     

Preparation of novel amphiphilic copolymer microspheres and their drug‐release and glucose‐sensitive properties

A novel amphiphilic copolymer was prepared by the copolymerization of N‐acryloyl‐3‐aminophenylboronic acid with β‐cyclodextrin containing maleic anhydride. The copolymer was fully characterized with ¹³C‐NMR, ¹H‐NMR, IR, and scanning electron microscopy. The self‐assembling mechanism of the copolymer in H₂O–CH₃OH cosolvents was studied. Gliclazide as a model drug was loaded inside the copolymer microspheres, and the drug‐release behavior of the microspheres was studied. The results of in vitro oscillating release tests indicated that the microspheres responded to glucose rapidly in 30 min, and the microspheres exhibited self‐regulated on–off release behavior four to six times in 6 h between the solution with 3 g/L glucose and the medium without glucose; this met the clinical requirements of multidrug delivery. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of antibacterial temperature‐sensitive silver‐nanocomposite hydrogels from N‐isopropylacrylamide with green tea

This article reports the temperature‐sensitive, green tea (GT)‐based silver‐nanocomposite hydrogels for bacterial growth inactivation. The temperature‐sensitive hydrogels were prepared via free‐radical polymerization using temperature‐sensitive N‐isopropylacrylamide (NIPAM) monomer with GT as the hydrogel matrix. The nanocomposite hydrogels were encapsulated with silver ions via swelling method, which was later reduced to silver nanoparticles using Azadirachta indica leaf extract. The temperature‐sensitive silver nanocomposite hydrogels were analyzed by using Fourier transforms infrared, UV–visible spectroscopy, differential scanning calorimetry–thermogravimetric analysis, X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The prepared hydrogels exhibited higher phase volume transition temperature than the NIPAM. The inhibition zone study of the inactivation of bacteria on the developed hydrogels was carried out against Gram negative (Escherichia coli) and Gram positive (Staphylococcus aureus), which revealed that the prepared hydrogels are helpful for the inactivation of these bacteria due to the high stabilization of antibacterial properties of the silver nanoparticles. The developed hydrogels are promising for biomedical applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45739.     

Swelling behavior of pH‐ and temperature‐sensitive copolymers containing 2‐hydroxy‐ethyl methacrylate and N‐vinyl‐2‐pyrrolidone crosslinked with new crosslinkers

Copolymers of 2‐hydroxyethyl methacrylate (HEMA) and N‐vinyl‐2‐pyrrolidone (VP) and homopolymers of HEMA and VP were crosslinked in the presence of different mol% of melamine trimethacrylamide (MMAm) and melamine triacrylamide (MAAm) as crosslinkers by bulk radical polymerization. The resultant xerogels were characterized by extracting the soluble fractions and measuring the equilibrium water content. Lower critical solution transition temperatures (LCST) were measured by DSC. The properties of crosslinked HEMA and VP copolymers, VP and HEMA series were evaluated in terms of compositional drift of polymerization, heterogeneous crosslinking, and chemical structure of the relevant components. Soluble fractions of the crosslinked networks were reduced by varying the MAAm and MMAm concentrations. The influence of environmental conditions such as temperature and pH on the swelling behavior of these polymeric gels was investigated. The swelling behaviors of the resulting gels show pH sensitivity. This behavior is explained on the basis that amide groups of VP or crosslinkers could be hydrolyzed to form negatively charged carboxylate ion groups in the produced networks in response to an external pH variation. Copyright © 2004 Society of Chemical Industry     

Preparation and characterization of a temperature‐sensitive nonwoven poly(propylene) with increased affinity for guest molecules

A temperature‐sensitive hydrogel with the capability of inclusion complex formation with guest molecules was successfully grafted onto the surface of nonwoven polypropylene (nonwoven PP). This was carried out by the use of N‐isopropylacrylamide monomer and a modified cyclodextrin (acrylamidomethyl‐β‐cyclodextrin (β‐CD‐NMA)). Fourier‐transform infra red (FT‐IR) and elemental analyses confirmed the presence of poly(N‐isopropylacrylamide) (PNIPAAm) and β‐CD‐NMA components on the surface of the textile. Equilibrium swelling ratio measurements showed that the grafted hydrogel maintained its temperature‐sensitive property compared to a nongrafted hydrogel. The effect of β‐CD‐NMA and crosslink agent concentrations on the grafting yield was studied. The β‐CD‐NMA content into the PNIPPAM‐ β‐CD‐NMA grafted nonwoven PP (PNIPAAm‐β‐CD‐NMA‐PP) was estimated by FT‐IR through a new procedure. The estimated amounts of β‐CD‐NMA in PNIPAAm‐β‐CD‐NMA‐PP were determined to be 0.9, 1.9 mg g^?1 for 0.019M and 0.049M concentrations of β‐CD‐NMA in monomer solution, respectively. The PNIPAAm‐β‐CD‐NMA‐PP showed a remarkable increase in absorbance affinity of 8‐anilino‐1‐naphthalenesulfonic acid ammonium salt at 20°C from 0.93 to 3.33 µmol g^?1 compared to PNIPAAm‐PP. Furthermore, the results showed a temperature‐sensitive loading affinity for PNIPAAm‐β‐CD‐NMA‐PP in absorbance of guest molecules due to the presence of β‐CD‐NMA. The use of hydrophobic guest molecules such as fragrance oils and antibiotics in modified fabrics can provide new applications in textile and pharmaceutical industry. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40497.     

Salt and pH sensitive semi‐interpenetrating polyelectrolyte hydrogels poly(HEMA‐co‐METAC)/PEG and its BSA adsorption behavior

A novel semi‐interpenetrating poly(2‐hydroxyethyl methacrylate) (pHEMA) based polyelectrolyte hydrogel [p(HEMA‐co‐METAC)/PEG] was prepared by copolymerizing HEMA with the cationic monomer 2‐methacryloyloxyethyltrimethyl ammonium chloride (METAC) in the presence of polyethylene glycol (PEG) with different content and molecular weight (MW 4000 and 400). The chemical structure of the gels was confirmed by FT‐IR spectroscopy, morphology study was performed by scanning electron microscope (SEM), thermal stability was revealed by thermogravimetric analysis (TGA), and the mechanical properties were determined by electronic universal testing machine. Swelling studies showed introduction of cationic monomer METAC led to high water content, and the obvious salt and pH sensitive properties were observed which proved the smart behavior of the semi‐interpenetrating polymer networks (IPNs) gels. In addition, the effect of temperature and some important biological solution on swelling behavior were reported. Cytotoxicity test demonstrated that synthesized gels owned satisfactory cytocompatibility and were convenient for the application as biomaterials. Finally, the weak bovine serum albumin (BSA) adsorption on semi‐IPNs by introducing METAC and controlling the content of PEG in gels demonstrated that they were of good protein resistance effect in biomedical applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41537.     

Preparation and release behavior of temperature‐ and pH‐responsive chitosan material

BACKGROUND: Chitosan is a polymer with good biocompatibility which makes it promising for potential applications in the field of drug delivery. A novel kind of copolymer, P(CS‐Ma‐graft‐NIPAm), was synthesized with chitosan (CS), maleic anhydride (Ma) and N‐isopropylacrylamide (NIPAm) by grafting and copolymerization. RESULTS: The copolymers were characterized using Fourier transform infrared, ¹H NMR and ultraviolet spectroscopies, and the molecular weight and polydispersity were determined using gel permeation chromatography. The aqueous solution properties of the copolymer and the controlled delivery of coenzyme A from it were also studied. The results showed that the copolymer had temperature and pH sensitivities, and that the release of coenzyme A from the copolymer was dependent on the release medium, namely the concentration of the copolymer, pH and temperature. Higher concentrations of the copolymer absorbed more coenzyme A than lower ones. Increasing temperature accelerated coenzyme A release from the copolymer. Also, the pH of the solution had a significant impact on the release of coenzyme A. CONCLUSION: These results suggest that the novel copolymer could be used in drug delivery systems. Copyright © 2007 Society of Chemical Industry     

Triply‐responsive (thermo/light/pH) copolymeric hydrogel of N‐isopropylacrylamide with an azobenzene‐containing monomer

A series of triply‐responsive copolymer hydrogel was firstly synthesized via free radical polymerization of N‐isopropylacrylamide, 4‐[(4‐(acryloyloxy)ethoxy) phenylazo]benzoic acid (AEPAZA), a water‐soluble azobenzene‐containing comonomer, and crosslinker. The properties of the hydrogel were subsequently investigated by UV‐Vis absorption spectrometry, differential scanning calorimetry, and gravimetry. UV‐Vis spectra showed that the copolymer hydrogel had a reasonable tran–cis photoisomerization rate upon UV irradiation and a relatively slow recovery rate in dark. The critical solution temperature (CST) of the copolymer hydrogel decreased with increasing of AEPAZA content and subsequently shifted higher value after UV irradiation. Meanwhile, the phase transitions profile became slower and broader with the incorporation of AEPAZA, which could be partly counterbalanced by UV irradiation. The CST could also be affected by the pH value of buffer solution. In addition, equilibrium swelling behavior clearly showed that the swelling ratio could be modulated by temperature, light, and pH. These stimuli‐responsive properties should be very important for controlled release delivery system. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Biodegradable and temperature‐responsive thermoset polyesters with renewable monomers

A series of biodegradable thermoset polyesters, poly(1,8‐octanediol–glycerol–dodecanediaote)s (POGDAs), were synthesized with the polycondensation polymerization method without a catalyst and with different monomer molar ratios. Synthesis was confirmed with structural analysis via Fourier transform infrared spectroscopy. The effect of varying the monomer molar ratio on the material properties was illustrated in the gel content and swelling analysis, ultraviolet–visible spectroscopy, differential scanning calorimetry, X‐ray diffraction, and degradation tests. Degradation tests were performed in phosphate‐buffered solution at 37 °C for 60 days. Temperature‐responsive behavior was revealed with POGDA (0.5 glycerol), and bending tests were performed to study the shape‐memory effect. In vitro cytotoxicity tests and cell proliferation tests suggested that these POGDAs have potential applications in biomedical fields such as tissue engineering. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44007.