Influences of the grafting percentage of natural rubber‐graft‐poly(2‐hydroxyethyl acrylate) on properties of its vulcanizates

The graft copolymerization of 2‐hydroxyethyl acrylate (HEA) monomer onto natural rubber (NR) latex was successful using cumene hydroperoxide and tetraethylene pentamine as redox initiators. The grafting of poly(2‐hydroxyethyl acrylate) (PHEA) on the NR particles was confirmed by Fourier transform infrared spectroscopy, ¹H NMR spectroscopy and TEM. The NR‐g‐PHEA with various grafting percentages (0%, 8.7%, 14.3% and 18.7%) was compounded on a two‐roll mill with a sulfur vulcanization system. The effects of grafting percentage on the cure characteristics, dielectric properties, thermal properties and physical properties of NR‐g‐PHEA vulcanizates were investigated. It was found that increased grafting caused NR‐g‐PHEA vulcanizates to have reduced water contact angle, scorch time and cure time, while the dielectric constant and dissipation factor increased. The NR‐g‐PHEA vulcanizate with 8.7% grafting exhibited the highest delta torque (M_H ? M_L), crosslink density, tensile strength, moduli at 100%, 200% and 300% strains, and hardness, with insignificant loss of elongation at break in comparison to the other cases. © 2018 Society of Chemical Industry     

Preparation of electrorheological active ionomers from poly(2‐hydroxyethyl methacrylate)‐co‐poly(4‐vinyl pyridine)

In this study, synthesis, characterization, partial hydrolysis, and salt formation of poly(2‐hydroxyethyl methacrylate)‐co‐poly(4‐vinyl pyridine), (poly(HEMA)‐co‐poly‐(4‐VP)) copolymers were investigated. The copolymers were synthesized by free radical polymerization using K₂S₂O₈ as an initiator. By varying the monomer/initiator ratio, chain lengths of the copolymers were changed. The copolymers were characterized by gel permeation chromatography (GPC), viscosity measurements, ¹H and ¹³C NMR and FTIR spectroscopies, elemental analysis, and end group analysis methods. The copolymers were partially hydrolyzed by p‐toluene sulfonic acid monohydrate (PTSA·H₂O) and washed with LiOH_(aq) solution to prepare electrorheological (ER) active ionomers, poly(Li‐HEMA)‐co‐poly(4‐VP). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3540–3548, 2006     

Pervaporation separation of water/dimethylformamide mixtures using poly(vinyl alcohol)‐g‐polyacrylamide copolymeric membranes

Grafted copolymeric membranes of poly(vinyl alcohol) with acrylamide (PVA‐g‐AAm) were developed and used in the pervaporation separation of water–dimethylformamide mixtures by varying the amount of water in the feed from 0 to 100%. From these data, the permeation flux, pervaporation separation index, diffusion coefficient, swelling index, and separation selectivity were calculated at 25, 35, and 45°C. The Arrhenius activation parameters for permeation flux ranged between 22 and 63 kJ/mol, while the activation energy for diffusion ranged between 23 and 67 kJ/mol. Separation selectivity was between 15 and 22. The highest permeation flux of 0.459 kg m^?2 h^?1 was obtained for the 93% grafted membrane at 90% of water in the feed mixture. The results are discussed using the principles of the solution–diffusion model. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 273–282, 2002     

Preparation of collagen‐immobilized poly(ethylene glycol)/poly(2‐hydroxyethyl methacrylate) interpenetrating network hydrogels for potential application of artificial cornea

To enhance the mechanical strength of poly(ethylene glycol)(PEG) gels and to provide functional groups for surface modification, we prepared interpenetrating (IPN) hydrogels by incorporating poly(2‐hydroxyethyl methacrylate)(PHEMA) inside PEG hydrogels. Formation of IPN hydrogels was confirmed by measuring the weight percent gain of the hydrogels after incorporation of PHEMA, as well as by ATR/FTIR analysis. Synthesis of IPN hydrogels with a high PHEMA content resulted in optically transparent and extensively crosslinked hydrogels with a lower water content and a 6 ～ 8‐fold improvement in mechanical properties than PEG hydrogels. Incorporation of less than 90 wt % PHEMA resulted in opaque hydrogels due to phase separation between water and PHEMA. To overcome the poor cell adhesion properties of the IPN hydrogels, collagen was covalently grafted to the surface of IPN hydrogels via carbamate linkages to hydroxyl groups in PHEMA. Resultant IPN hydrogels were proven to be noncytotoxic and cell adhesion study revealed that collagen immobilization resulted in a significant improvement of cell adhesion and spreading on the IPN hydrogel surfaces. The resultant IPN hydrogels were noncytotoxic, and a cell adhesion study revealed that collagen immobilization improved cell adhesion and spreading on the IPN hydrogel surfaces significantly. These results indicate that PEG/PHEMA IPN hydrogels are highly promising biomaterials that can be used in artificial corneas and a variety of other load‐bearing tissue engineering applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical characteristics of poly(2‐hydroxyethyl methacrylate) hydrogels crosslinked with various difunctional compounds

Poly(2‐hydroxyethyl methacrylate) hydrogels were prepared in the presence of 30 wt% water using two series of crosslinking agents including divinylic (ethyleneglycol dimethacrylate, 1,4‐butanediol dimethacrylate, 2,3‐dihydroxybutanediol 1,4‐dimethacrylate) and diallylic (1,5‐hexadiene‐3,4‐diol and 1,5‐hexadiene) compounds, over a concentration range between 0.1 and 5 mol%. The resulting polymers were swollen in water to yield homogeneous transparent hydrogels. These hydrogels were characterised in terms of equilibrium swelling in water, tensile properties and compression stress–strain measurements. The influences of the nature and the concentration of crosslinking agent on the swelling behaviour and the mechanical properties of these hydrogels were investigated. The crosslinking efficiency of two representative agents (ethyleneglycol dimethacrylate and 1,5‐hexadiene‐3,4‐diol) was quantified by compression experiments. A much lower crosslinking efficiency (0.013) was observed for 1,5‐hexadiene‐3,4‐diol than for ethyleneglycol dimethacrylate (0.336). It is suggested that the low crosslinking efficiency of diallylic agents is responsible for a trend in properties different from that displayed by the gels crosslinked with dimethacrylates. A comparison was made to the similar effect observed previously in heterogeneous PHEMA hydrogels. © 2001 Society of Chemical Industry     

Comparison of viscoelastic properties of polydimethylsiloxane/poly(2‐hydroxyethyl methacrylate) IPNs with their physical blends

Interpenetrating polymer networks (IPNs) of polydimethylsiloxane (PDMS) and poly(2‐hydroxyethyl methacrylate) (PHEMA) were prepared by sequential method. The dynamic mechanical parameters of obtained IPNs and their variations with the structural composition were evaluated. The results for the IPNs were compared with corresponding physically blended systems. The tensile properties and damping factor (tan δ) were assessed by stress–strain measurement and dynamic mechanical thermal analysis (DMTA), respectively. The glass–rubber transition temperature (T_g) was assessed by DMTA and differential scanning calorimetry (DSC). The results showed higher tensile strength and elongation at break for IPNs than those for physical blends. The shifts of T_g for that two components that make up the IPNs were greater than those for corresponding blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3480–3485, 2002     

Rheological,thermal, and curing properties of natural rubber‐g‐poly(methyl methacrylate)

Graft copolymers of NR and PMMA (i.e., NR‐g‐PMMA) were prepared with the bipolar redox initiation system, using various percentages of molar ratios of NR/MMA at 95/5, 90/10, 80/20, 70/30, and 60/40. It was found that the Mooney viscosity, shear stress, and shear viscosity of the NR‐g‐PMMA increased with an increase in the molar ratio of MMA used in the graft copolymerization. This may be attributed to an increasing trend of the chemical interaction between polar functional groups within the grafted PMMA molecules. Furthermore, a decreasing trend of storage moduli was observed with increasing molar ratios of MMA. The glass transition temperature was obtained from the tan δ curves. We found a slightly increasing trend of the T_g's with an increase in molar ratios of MMA used in the grafting reaction. The NR‐g‐PMMA was later compounded using TBBS as an accelerator. With an increase in molar ratios of MMA in the grafting reaction, we observed an increasing trend of minimum torque, maximum torque, cure time, and scorch time, but quite similar levels of torque difference and crosslink density. Furthermore, the tensile strength of the NR‐g‐PMMA gum vulcanizate increased with an increase in molar ratios of MMA, whereas the elongation at break decreased. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1600–1614, 2006     

DNA adsorption on a poly‐L‐lysine‐immobilized poly(2‐hydroxyethyl methacrylate) membrane

The DNA adsorption properties of poly‐L ‐lysine‐immobilized poly(2‐hydroxyethyl methacrylate) (pHEMA) membrane were investigated. The pHEMA membrane was prepared by UV‐initiated photopolymerization and activated with epichlorohydrin. Poly‐L ‐lysine was then immobilized on the activated pHEMA membrane by covalent bonding, via a direct chemical reaction between the amino group of poly‐L ‐lysine and the epoxy group of pHEMA. The poly‐L ‐lysine content of the membrane was determined as 1537 mg m^?2. The poly‐L ‐lysine‐immobilized membrane was utilized as an adsorbent in DNA adsorption experiments. The maximum adsorption of DNA on the poly‐L ‐lysine‐immobilized pHEMA membrane was observed at 4 °C from phosphate‐buffered salt solution (pH 7.4, 0.1 M; NaCl 0.5 M) containing different amounts of DNA. The non‐specific adsorption of DNA on the plain pHEMA membrane was low (about 263 mg m^?2). Higher DNA adsorption values (up to 5849 mg m^?2) were obtained in which the poly‐L ‐lysine‐immobilized pHEMA membrane was used. Copyright © 2003 Society of Chemical Industry     

HEMA接枝改性天然胶乳的制备及其粘接性能研究

以甲基丙烯酸羟乙酯(HEMA)作为天然胶乳(NRL)的接枝改性剂,采用乳液聚合法制备了NR-g-HEMA[HEMA接枝NR(天然橡胶)]胶乳;然后以此为基体,并以水溶性松香树脂为增黏树脂、邻苯二甲酸二丁酯(DBP)为增塑剂等,制备相应的NR-g-HEMA胶粘剂;最后,用该胶粘剂压制胶合板,并对胶合板的粘接性能进行了测定。结果表明:采用单因素试验法优选出制备NR-g-HEMA胶乳的最佳工艺条件为m(干态单体)∶m(NRL)∶m(引发剂)∶m(活化剂)∶m(交联剂)=20∶100∶0.2∶0.2∶0.1、反应时间为8 h和反应温度为16℃,此时相应胶合板的剪切强度(1.88 MPa)符合Ⅲ类胶合板的指标要求。     

A novel route for the synthesis of poly(2‐hydroxyethyl methacrylate) grafted TiO2 nanoparticles via surface thiol‐lactam initiated radical polymerization

Hybrid nanocomposites of poly(2‐hydroxyethyl methacrylate) (PHEMA) and TiO₂ nanoparticles were synthesized via surface thiol‐lactam initiated radical polymerization by following the grafting from strategy. Initially, TiO₂ nanoparticles were modified by 3‐mercaptopropyl trimethoxysilane to prepare thiol functionalized TiO₂ nanoparticles (TiO₂? SH). Subsequently, surface initiated polymerization of 2‐hydroxyethyl methacrylate was conducted by using TiO₂? SH and butyrolactam as an initiating system. The anchoring of PHEMA onto the surface of TiO₂ nanoparticles was investigated by FTIR, ¹H‐NMR, XPS, TGA, and XRD analyses. The experimental results indicated a strong interaction between PHEMA and TiO₂ nanoparticles owing to covalent bonding. The TEM and SEM images of PHEMA‐g‐TiO₂ showed that the agglomeration propensity of TiO₂ nanoparticles was significantly reduced upon the PHEMA functionalization. The molecular weight and polydispersity index of the cleaved PHEMA from the surface of TiO₂ nanocomposites were estimated by GPC analysis. An improved thermal property of the nanocomposites was observed from TGA analysis. PHEMA‐g‐TiO₂ nanocomposites were found to be highly dispersible in organic solvents. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Poly(Li‐2‐hydroxyethyl methacrylate)‐co‐poly(4‐vinyl pyridine): Molar mass effects on strong electrorheological response

Electrorheological (ER) fluids display remarkable rheological behavior, being able to convert rapidly and repeatedly from a fluid to a solid‐like when an external electric field (E) is applied or removed. In this study, electrical and ER properties of poly(Li‐2‐hydroxyethyl methacrylate)‐co‐poly(4‐vinyl pyridine), poly(Li‐HEMA)‐co‐poly(4‐VP), copolymeric salts (ionomers) were investigated. For this purpose six ionomers were synthesized with different molar masses. They were then ground‐milled for a few hours to obtain micron size ionomers. The particle sizes of the ionomers were determined by dynamic light scattering. Suspensions of ionomers were prepared in silicone oil (SO), at a series of concentrations (c = 5–30%, m/m). The gravitational stability of suspensions against sedimentation was determined at constant temperature (T = 25°C). Flow times of the suspensions were measured under no electric field (E = 0 kV/mm), and under an external applied electric field (E ≠ 0 kV/mm) strengths and a strong ER activities were observed for all the poly(Li‐HEMA)‐co‐poly(4‐VP)/SO suspensions. Further, the effects of suspension concentration, mole ratios of poly(HEMA) and poly(4‐VP), and the overall molar mass of the copolymers, shear rate, electric field strength, frequency, promoter, and temperature onto ER activities of ionomer suspensions were investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1065–1074, 2006     

Natural rubber‐g‐methyl methacrylate/poly(methyl methacrylate) blends

The grafting of the methyl methacrylate (MMA) monomer onto natural rubber using potassium persulfate as an initiator was carried out by emulsion polymerization. The rubber macroradicals reacted with MMA to form graft copolymers. The morphology of grafted natural rubber (GNR) was determined by transmission electron microscopy and it was confirmed that the graft copolymerization was a surface‐controlled process. The effects of the initiator concentration, reaction temperature, monomer concentration, and reaction time on the monomer conversion and grafting efficiency were investigated. The grafting efficiency of the GNR was determined by a solvent‐extraction technique. The natural rubber‐g‐methyl methacrylate/poly(methyl methacrylate) (NR‐g‐MMA/PMMA) blends were prepared by a melt‐mixing system. The mechanical properties and the fracture behavior of GNR/PMMA blends were evaluated as a function of the graft copolymer composition and the blend ratio. The tensile strength, tear strength, and hardness increased with an increase in PMMA content. The tensile fracture surface examined by scanning electron microscopy disclosed that the graft copolymer acted as an interfacial agent and gave a good adhesion between the two phases of the compatibilized blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 428–439, 2001     

Surface treatment of phosphate glass fibers using 2‐hydroxyethyl methacrylate: Fabrication of poly(caprolactone)‐based composites

2‐Hydroxyethyl methacrylate (HEMA) solution (1–10 wt %) was prepared in methanol and phosphate glass fibers were immersed in that solution for 5 min before being cured (irradiation time: 30 min) under UV radiation. Maximum polymer loading (HEMA content) was found for the 5 wt % HEMA solution. Degradation tests of the fibers in aqueous medium at 37°C suggested that the degradation of the HEMA‐treated fibers was lower than that of the untreated fibers. X‐ray photoelectron spectroscopy revealed that HEMA was present on the surface of the fibers. Using 5 wt % HEMA‐treated fibers, poly(caprolactone) matrix unidirectional composites were fabricated by in situ polymerization and compression molding. For in situ polymerization, it was found that 5 wt % HEMA‐treated fiber‐based composites had higher bending strength (13.8% greater) and modulus (14.0% greater) than those of the control composites. For compression molded composites, the bending strength and modulus values for the HEMA‐treated samples were found to be 27.0 and 31.5% higher, respectively, than the control samples. The tensile strength, tensile modulus, and impact strength of the HEMA composites found significant improvement than that of the untreated composites. The composites were investigated by scanning electron microscopy after 6 weeks of degradation in water at 37°C. It was found that HEMA‐treated fibers inside the composite retained much of their original integrity while the control samples degraded significantly. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Shape memory properties and unusual optical behaviour of an interpenetrating network of poly(ethylene oxide) and poly(2‐hydroxyethyl methacrylate)

An interpenetrating polymer network (IPN) with shape memory properties was prepared by using poly(2‐hydroxyethyl methacrylate) (PHEMA) and poly(ethylene oxide) (PEO). PHEMA acts as a fixed phase and PEO as a switching phase. The switching action of PEO is due to the reversible process of melting and crystallization. It was observed that the shape recovery of the IPN increases with increasing crosslinker concentration up to an optimum value and decreases thereafter. In addition to the shape memory property, the IPNs show a reversible change in optical properties from translucent to opaque. The change in optical properties is quite different from that observed in a semicrystalline polymer system where the transparency increases as a result of the melting of crystals. This behaviour of the IPN is explained in terms of H‐bonding of PEO with PHEMA. Fourier transform infrared spectroscopy was used to study the H‐bonding between PEO and PHEMA. © 2019 Society of Chemical Industry     

Natural rubber/poly(acrylic acid) semi‐interpenetrating polymer network membranes for the pervaporation of water–ethanol mixtures

Pervaporation membranes for the dehydration of water–ethanol mixtures were prepared from a semi‐interpenetrating polymer network (semi‐IPN) of natural rubber (NR) and crosslinked poly(acrylic acid) (PAA). The swelling studies revealed that hydrophilic PAA present in the semi‐IPN membranes caused the membranes to swell greatly in water. The swelling degree of the membranes in water was significantly affected by the amount ratio between the hydrophobic NR and the hydrophilic PAA. The sorption experiments of the NR/PAA membranes in various concentrations of water–ethanol mixtures suggested the preferential sorption to water. However, for the membrane with high PAA content, the water sorption selectivity decreased considerably at high water concentration of water–ethanol mixtures because the membrane was in the highly swollen state. Pervaporation separations of water–ethanol mixtures using NR/PAA membranes were performed and it was found that at low water concentrations of feed mixtures, increasing the PAA content of the membrane can enhance both water permeation flux and selectivity. Additionally, under low feed water concentration, increasing the feed temperature would increase the water flux with the decreasing of the ethanol flux. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Rheological and curing behavior of reactive blending. II. Natural rubber‐g‐poly(methyl methacrylate)–cassava starch

Graft copolymers of natural rubber (NR) and methyl methacrylate (MMA) were prepared using cumene hydroperoxide and tetraethylene pentamine as redox initiators via the semibatch emulsion polymerization technique. Various molar percentage ratios of NR/MMA were studied in the grafting reaction (i.e., 95/5, 90/10, 80/20, 70/30, and 60/40). The graft copolymer with a 70/30 molar ratio was selected and used to prepare rubber blends with cassava starch. The starch was used at levels of 0, 20, 40, and 60 phr. Another set of rubber blends was prepared for comparison purposes. The NR‐g‐poly(MMA) (PMMA, 75 phr) was blended with 25 phr of NR air dried sheets (ADS) and a given level of the cassava starch. We found that the Mooney viscosity, shear stress, and shear viscosity increased with an increasing concentration of cassava starch. This may be attributed to the chemical interactions between the polar groups of the NR‐g‐PMMA and the cassava starch. The blends were later compounded using a compounding formulation according to ASTM D 3184‐89. A similar short delay onset of vulcanization (i.e., approximately 1 min) was observed for the whole set of compounds under study. However, different curing characteristics were observed for the blends of NR‐g‐PMMA–cassava starch and NR‐g‐PMMA–ADS–cassava starch. The NR‐g‐PMMA–cassava starch compounds exhibited two‐stage curing characteristics. The curing curve had a slight reversion at a testing time of approximately 8 min. The shear modulus then abruptly increased with an increasing testing time in the range of 20–60 min. The curing curves for NR‐g‐PMMA–ADS–cassava starch blends exhibited a single curing stage with a shear modulus that increased slightly with the testing time was increased from 20 to 60 min. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1453–1463, 2003     

Synthesis and rheological properties of soluble poly(hydroxyethyl methacrylate) and some copolymers

Methods to synthesise soluble poly(2-hydroxyethyl methacrylate) (PHEMA) with varying molar mass were developed. Conversions over 90% were achieved without losing solubility. Steady state tests (range 0.01–590 Pa) and oscillatory tests (range 0.001–40 Hz) were carried out on 40% solutions in dimethyl formamide using a Carri-Med rheometer. Only PHEMA having molar mass over 500000 showed significant shear thinning and viscoelastic properties. The copolymers of 2-hydroxyethyl methacrylate (HEMA) with n-butyl acrylate (BA) and 2-hydroxypropyl acrylate (HPA) showed higher viscosities and viscoelastic properties compared with PHEMA homopolymer prepared under identical conditions. Also, viscosity and viscoelasticity increased with increase in acrylate content in the initial mixture. This was attributed to the higher molar mass of copolymers, which resulted from faster polymerisation rates owing to the inclusion of relatively highly reactive acrylates. However, in the case of HEMA : BA copolymers, first, the viscosity and viscoelasticity increased with increasing BA content and then dropped again, giving a maximum around HEMA : BA 75 : 25. This anomaly was explained by taking the effects of changes in inter-and intra-molecular hydrogen bonding as well as conformational differences caused by inclusion of BA in the PHEMA chain into account.     

Pervaporation of acetone‐chlorinated hydrocarbon mixtures through polymer blend membranes of natural rubber and epoxidized natural rubber

Transparent nonporous membranes were prepared by blending natural rubber (NR) with epoxidized NR (ENR). These blend membranes were evaluated for the selective separation of chlorinated hydrocarbons from acetone. The flux and selectivity of the membranes were determined both as a function of the blend composition and feed mixture composition. Results showed that polymer blending method could be very useful to develop new membranes with improved permselectivity. Pervaporation properties could be optimized by adjusting the blend composition. NR/ENR 70/30 and NR/ENR 30/70 composition showed a decrease in flux and selectivity, whereas the 50/50 composition showed increased flux and increased selectivity. Chlorinated hydrocarbons permeated preferentially through all the tested membranes. The feed mixture composition also strongly influenced the pervaporation characteristics of the blend membranes. Permselectivity was found to depend on the molecular size of the penetrants. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2365–2379, 1999     

Pervaporation separation of MTBE–methanol mixtures using cross‐linked PVA membranes

Poly(vinyl alcohol)(PVA)/poly(acrylic acid)(PAA) and PVA/sulfosuccinic acid (SSA) membrane performances have been studied for the pervaporation separation of methyl tert‐butyl ether (MTBE)/methanol (MeOH) mixtures with varying operating temperatures, amount of cross‐linking agents, and feed compositions. Typically, the separation factor, about 4000, and the permeation rate, 10.1 g/m²/h, were obtained with PVA/PAA = 85/15 membrane for MTBE/MeOH = 80/20 mixtures at 50°C. For PVA/PAA membranes, it could be considered that the flux is affected by the structural changes of the membranes due to the cross‐linking and the free carboxylic acid group also took an important role in the separation characteristics through the hydrogen bonding with PVA and the feed components leading to the increase of flux. The latter membrane of the 5% SSA membrane shows the highest separation factor of 2095 with the flux of 12.79 g/m²/h for MTBE/MeOH = 80/20 mixtures at 30°C. Besides the swelling measurements were carried out for pure MTBE and MeOH, and MTBE/MeOH = 90/10, 80/20 mixtures using PVA/SSA membranes with varying SSA compositions. It has been recognized that there are two factors, the membrane network and the hydrogen bonding in the swelling measurements of PVA/SSA membranes. These two factors act interdependently on the membrane swelling. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1699–1707, 2000     

Poly(N‐isopropylacrylamide‐co‐hydroxyethyl methacrylate) graft copolymers and their application as carriers for drug delivery system

Poly(N‐isopropylacrylamide‐co‐hydroxyethyl methacrylate) [P(NIPAM‐co‐HEMA)] copolymer was synthesized by controlled radical polymerization from respective N‐isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) monomers with a predetermined ratio. To prepare the thermosensitive and biodegradable nanoparticles, new thermosensitive graft copolymer, poly(L ‐lactide)‐graft‐poly(N‐isoporylacrylamide‐co‐hydroxyethyl methacrylate) [PLLA‐g‐P(NIPAM‐co‐HEMA)], with the lower critical solution temperature (LCST) near the normal body temperature, was synthesized by ring opening polymerization of L ‐lactide in the presence of P(NIPAM‐co‐HEMA). The amphiphilic property of the graft copolymers was formed by the grafting of the PLLA hydrophobic chains onto the PNIPAM based hydrophilic backbone. Therefore, the graft copolymers can self‐assemble into uniformly spherical micelles ò about 150–240 nm in diameter as observed by the field emission scanning electron microscope and dynamic light scattering. Dexamethasone can be loaded into these nanostructures during dialysis with a relative high loading capacity and its in vitro release depends on temperature. Above the LCST, most of the drugs were released from the drug‐loaded micelles, whereas a large amount of drugs still remains in the micelles after 48 h below the LCST. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012