Tailoring the swelling and glass‐transition temperature of acrylonitrile/hydroxyethyl acrylate copolymers

Novel polyacrylonitrile (PAN)‐co‐poly(hydroxyethyl acrylate) (PHEA) copolymers at three different compositions (8, 12, and 16 mol % PHEA) and their homopolymers were synthesized systematically by emulsion polymerization. Their chemical structures and compositions were elucidated by Fourier transform infrared, ¹H‐NMR, and ¹³C‐NMR spectroscopy. Intrinsic viscosity measurements revealed that the molecular weights of the copolymers were quite enough to form ductile films. The influence of the molar fraction of hydroxyethyl acrylate on the glass‐transition temperature (T_g) and mechanical properties was demonstrated by differential scanning calorimetry and tensile test results, respectively. Additionally, thermogravimetric analysis of copolymers was performed to investigate the degradation mechanism. The swelling behaviors and densities of the free‐standing copolymer films were also evaluated. This study showed that one can tailor the hydrogel properties, mechanical properties, and T_g's of copolymers by changing the monomer feed ratios. On the basis of our findings, PAN‐co‐PHEA copolymer films could be useful for various biomaterial applications requiring good mechanical properties, such as ophthalmic and tissue engineering and also drug and hormone delivery. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of poly(styrene‐b‐2‐hydroxyethyl acrylate) block copolymer using reverse iodine transfer polymerization

Reverse iodine transfer polymerizations (RITP) of 2‐h‐ydroxyethyl acrylate (HEA) were performed in N,N‐dimethylformamide at 75°C using AIBN as initiator. Poly(2‐hydroxyethyl acrylate) (PHEA) with M_n = 3300 g mol^?1 and M_w/M_n <1.5 were obtained. Homopolymerization of styrene in RITP was also carried out under similar conditions using toluene as solvent. The resulting iodo‐polystyrene (PS‐I) with (M_{n, SEC} = 607 g mol^?1, polydispersity index (PDI) = 1.31) was used as a macroinitiator for the synthesis of amphiphilic block copolymers based on HEA with controlled well‐defined structure. Poly(styrene‐b‐2‐hydroxyethyl acrylate) (PS‐b‐PHEA) with M_n = 13,000 g mol^?1 and polydispersity index (M_w/M_n) = 1.4 was obtained, copolymer composition was characterized using ¹H‐NMR and FTIR, whereas SEC and gradient HPLC were used to confirm the formation of block copolymer and the living character of polymer chains. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Amelioration of acrylonitrile–butadiene copolymer properties using natural rubber graft p‐aminophenol

A two‐roll mill machine was used for the grafting of p‐aminophenol (pAP) onto natural rubber (NR). The prepared NR graft p‐aminphenol (NR‐g‐pAP) was characterized by ¹H NMR and IR spectroscopy techniques. The goal of this article is to study the effect of commercial antioxidants, N‐phenyl‐N′‐(1,3‐dimethylbutyl)‐p‐phenylenediamine (6PPD) and N‐phenyl‐N′‐isopropyl‐p‐phenylenediamine (IPPD), and the prepared NR‐g‐pAP, on the mechanical properties of acrylonitrile–butadiene (NBR) vulcanizates, the fluid compatibility of NBR vulcanizates, the hydraulic brake and clutch fluid dot, the diffusion out for NBR vulcanizate components, and the compression recovery of NBR vulcanizates. This study indicates that the NBR copolymer vulcanizate which contains the prepared NR‐g‐pAP has good protection against mechanical stress and the diffusion out of NBR vulcanizate components. The 6PPD and the prepared NR‐g‐pAP ameliorates the fluid compatibility of the oil seals, which is based on NBR as elastomer, and the hydraulic brake and clutch fluid dot. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis,characterization, and evaluation of natural rubber‐graft‐N‐(4‐aminodiphenyl methane) acrylamide as an antioxidant

The synthesis of N‐(4‐aminodiphenylmethane) acrylamide (ADPMA) was performed through the reaction of 4,4′‐diaminodiphenyl methane and acryloyl chloride in the presence of triethyl amine. The grafting of ADPMA onto natural rubber was executed with UV radiation. Benzoyl peroxide was used to initiate the free‐radical grafting copolymerization. Natural rubber‐graft‐N‐(4‐aminodiphenyl methane) acrylamide (NR‐g‐ADPMA) was characterized with an IR technique. We studied the effect of aging on the mechanical properties and the swelling and extraction phenomena for acrylonitrile–butadiene copolymer (NBR) vulcanizates, which contained the prepared NR‐g‐ADPMA and a commercial antioxidant, N‐isopropyl‐N′‐phenyl‐p‐phenylenediamine. The prepared antioxidant enhanced both the mechanical properties of the NBR vulcanizates and the permanence of the ingredients in these vulcanizates. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 843–849, 2006     

Upgrading of acrylonitrile–butadiene copolymer properties using natural rubber–graft–N‐(4‐aminodiphenylether) acrylamide

The grafting of ADPEA onto natural rubber was executed with UV radiation. Benzoyl peroxide was used to initiate the free‐radical grafting copolymerization. Natural rubber‐graft‐N‐(4‐aminodiphenylether) acrylamide (NR‐g‐ADPEA) was characterized with an IR technique. The ultrasonic velocities of both longitudinal and shear waves were measured in thermoplastic discs of NBR vulcanizates as a function of aging time. Ultrasonic velocity measurements were taken at 2 MHz ultrasonic frequency using the pulse echo method. We studied the effect of aging on the mechanical properties and the swelling and extraction phenomena for acrylonitrile–butadiene copolymer (NBR) vulcanizates, which contained the prepared NR‐g‐ADPEA and a commercial antioxidant, N‐isopropyl‐N′‐phenyl‐p‐phenylenediamine. The prepared antioxidant enhanced both the mechanical properties of the NBR vulcanizates and the permanence of the ingredients in these vulcanizates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Improving the properties of polylactic acid by blending with low molecular weight polylactic acid‐g‐natural rubber

The low molecular weight (M_w) polylactic acid‐g‐natural rubber (PLA‐g‐NR) was synthesized by grafting the maleated natural rubber (MNR) with low molecular weight PLA at a weight ratio of 1:1 in toluene at 80°C. Two types of MNR (MNR10 and MNR20) having anhydride moieties of 10 and 20 wt%, respectively, were prepared. The reaction was followed by IR analysis. Next, the obtained PLA‐g‐NR was blended with pristine PLA using a twin‐screw extruder at PLA to PLA‐g‐NR weight ratios of 90:10, 80:20, 70:30, and 60:40 followed by compression to obtain specimens for testing. In case of 10 wt% PLA‐g‐NR having MNR10, it was found that blending of PLA with PLA‐g‐NR resulted in a 200% improvement in impact strength and twofold percent elongation at break (flexibility). Further SEM analysis confirmed that PLA‐g‐NR was compatible with PLA matrix. In contrast, NR was present as disperse particles which exhibited poor adhesion to PLA. From these findings, it was also found that PLA‐g‐NR was capable of improving the properties of PLA more than NR due to the fact that it exhibited higher compatibility. POLYM. ENG. SCI., 54:2770–2776, 2014. © 2013 Society of Plastics Engineers     

Analysis of unbound materials in carbon‐black‐filled NR vulcanizates

Extraction of unbound materials from carbon‐black‐filled natural rubber (NR) vulcanizates with different cure systems was studied using various solvents with different dielectric constants of n‐hexane, toluene, THF, acetone, and acetonitrile. The extraction was performed at room temperature and 40°C for 2 days and in the boiling solvent for 8 h. Amounts of extracted materials from the NR vulcanizates increase by increasing the temperature. Amounts of extracted materials from the NR vulcanizates with n‐hexane, toluene, and THF are more than those with acetone and acetonitrile. Amounts of extracted materials from the NR vulcanizate with a high crosslink density are less than those from the NR vulcanizate with a low one. Thermogravimetric analysis of the NR vulcanizates before and after the extraction were carried out to investigate components of the extracted materials. It was found that there were polymer components and metal complexes, as well as organic matters with a low molecular weight in the extracted materials. Abilities of the solvents to extract unbound materials from the NR vulcanizates were discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1995–2005, 1999     

Functionalization of styrene–butadiene rubber with meta‐pentadecenyl phenol for better processing: A multifunctional additive and renewable resource

Meta‐pentadecenyl phenol, a nonisoprenoid phenolic lipid, is a renewable agricultural resource and also a byproduct of the cashew industry; it is popularly known as cardanol. This study throws light on the grafting of cardanol, which has been established as a multifunctional additive for natural rubber, onto the main‐chain backbone of styrene–butadiene rubber (SBR), a synthetic polymer used to imbibe the multifunctional properties of the former, such as those of a plasticizer, curing promoter, process aid, and antioxidant, into the latter. The grafting was carried out in the solution stage on a trial basis with a peroxide catalyst, and all of the grafting parameters were optimized with a Taguchi methodology. The grafting of cardanol onto the SBR backbone was successfully confirmed by UV–visible spectroscopy, Fourier transform infrared spectroscopy, and NMR analysis. Thermal analysis of the cardanol‐grafted styrene–butadiene rubber (C‐g‐SBR) revealed a higher thermal stability and better plasticizing effect than that those found in the virgin SBR. The rheological properties of the grafted rubber indicated the improvement of the pseudo‐plastic (shear‐thinning) nature compared to that in gum SBR. The unfilled C‐g‐SBR vulcanizates exhibited physicomechanical properties comparable to 5‐phr processing‐oil‐containing SBR [oil‐plasticized styrene–butadiene rubber (OPSBR)] vulcanizates. The carbon‐black‐filled C‐g‐SBR vulcanizates exhibited improved plasticization, a faster curing rate, easy processability, and better physicomechanical properties compared to the 5‐phr OPSBR vulcanizates. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45150.     

Preparation,structural characterization,and antioxidative behavior in natural rubber of antioxidant GM functionalized nanosilica

To restrain the migration and extractability of the antioxidants and improve the dispersion of nanosilica in natural rubber (NR), antioxidant 2‐tert‐butyl‐6‐(3‐tert‐butyl‐2‐hydroxy‐5‐methylbenzyl)‐4‐methyphenyl acrylate (GM) functionalized nanosilica was prepared using antioxidant coupling agent (KH590‐GM) as functional modifier, which was first synthesized through thiol‐ene reaction between the mercapto group of γ‐mercaptopropyl trimethoxysilane (KH590) and the CC double bonds of antioxidant GM. Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance confirmed the structure of KH590‐GM and GM functionalized nanosilica. Thermogravimetry analysis indicated that the grafting rate of GM functionalized nanosilica reached 13.4%, and the antioxidant had good thermal stability. Scanning electron microscope and mechanical properties measurement showed GM functionalized nanosilica was dispersed uniformly in NR vulcanizates, and helpful for the increase of the tensile strength and tensile stress of NR vulcanizates. Based on the study of the antioxidative behavior and extraction resistance of the NR vulcanizates, it was found that in contrast to NR vulcanizates with GM, the ageing coefficient and oxidation induction time of that with GM functionalized nanosilica increased to 0.66 and 39 min from 0.58 and 30 min, respectively. Furthermore, the NR vulcanizates with GM functionalized nanosilica also exhibited excellent extraction resistance. POLYM. COMPOS., 38:1241–1247, 2017. © 2015 Society of Plastics Engineers     

Properties and morphologies of elastomer blends modified with EPDM‐g‐poly[2‐dimethylamino ethylmethacrylate]

The graft copolymerization of 2‐dimethylamino ethylmethacrylate (DMAEMA) onto ethylene propylene diene mononer rubber (EPDM) was carried out in toluene via solution polymerization technique at 70°C, using dibenzoyl peroxide as initiator. The synthesized EPDM rubber grafted with poly[DMAEMA] (EPDM‐g‐PDMAEMA) was characterized with ¹H‐NMR spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). The EPDM‐g‐PDMAEMA was incorporated into EPDM/butadiene acrylonitrile rubber (EPDM/NBR) blend with different blend ratios, where the homogeneity of such blends was examined with scanning electron microscopy and DSC. The scanning electron micrographs illustrate improvement of the morphology of EPDM/NBR rubber blends as a result of incorporation of EPDM‐g‐PDMAEMA onto that blend. The DSC trace exhibits one glass transition temperature (T_g) for EPDM/NBR blend containing EPDM‐g‐PDMAEMA, indicating improvement of homogeneity. The physico‐mechanical properties after and before accelerated thermal aging of the homogeneous, and inhomogeneous EPDM/NBR vulcanizates with different blend ratios were investigated. The physico‐mechanical properties of all blend vulcanizates were improved after and before accelerated thermal aging, in presence of EPDM‐g‐PDMAEMA. Of all blend ratios under investigation EPDM/NBR (75/25) blend possesses the best physico‐mechanical properties together with the best (least) swelling (%) in brake fluid. Swelling behavior of the rubber blend vulcanizates in motor oil and toluene was also investigated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Effect of crosslink structures on dynamic mechanical properties of natural rubber vulcanizates under different aging conditions

The effects of crosslink structures on the dynamic mechanical properties (DMPs) of unfilled and carbon black N330‐filled natural rubber (NR) vulcanizates cured with conventional (CV), semiefficient (SEV), and efficient (EV) cure systems and having about the same total crosslink densities were investigated before and after aerobic and anaerobic aging at 100°C. The three unfilled NR vulcanizates cured with the CV, SEV, and EV systems had about the same mechanical loss factor (tan δ) values at about 0°C but showed some apparent differences in the tan δ values in the order EV > SEV > CV at relatively high temperatures of 40–80°C before aging. However, N330‐filled NR vulcanizates gave higher tan δ values than the unfilled vulcanizates and showed little effect of the crosslink types on the tan δ at different temperatures over the glass‐transition temperature (T_g) before aging. Aerobic heat aging increased the T_g and tan δ values of the vulcanizates over a wide range of temperatures from ?80 to 90°C that was mainly due to the changes in the total density and types of crosslinks. The unfilled vulcanizates cured with the CV system showed the greatest change in DMP because of their poor resistance to heat aging. Aerobic heat aging of NR vulcanizates caused a more significant change in the DMP than anaerobic heat aging because of the dominant effect of the oxidative degradation during aerobic heat aging on the main‐chain structure, crosslink structures, and DMPs of the vulcanizates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 710–718, 2001     

Poly(2‐hydroxyethyl acrylate) hydrogels reinforced with graphene oxide: Remarkable improvement of water diffusion and mechanical properties

A series of hybrid hydrogels of poly(2‐hydroxyethyl acrylate), PHEA, and graphene oxide, G? O, with G? O content up to 2 wt % has been prepared by in situ polymerization. Because PHEA has been used as biomaterial in various applications, has a side chain with the hydroxyl functional group and its mechanical properties are poor, it is a good candidate for reinforcement with G? O. Fourier transform (infrared) spectroscopy, atomic force microscopy, differential scanning calorimetry, the thermal, mechanical, and water sorption properties of neat PHEA and PHEA/G? O composites have been studied in order to elucidate the dispersion and interaction between both components. An increase in the water diffusion coefficient and dramatic changes in its mechanical properties are the most remarkable results. Thus, at a nanofiller load of 2 wt %, the novel materials present an increased diffusion coefficient higher than 380% and the elastic modulus is enhanced by more than 650% in dry state and by more than 100% in swollen state, both compared to neat PHEA. These results have been attributed to the excellent interaction between the matrix, PHEA, and the reinforcement, G? O, and could open the door to new applications in the field of biomaterials with higher structural requisites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46158.     

Synergic effect of N‐benzylimine aminothioformamide secondary accelerator during sulfur vulcanization of a styrene‐butadiene‐natural rubber blend

In this study we reported synergic activity of a novel secondary accelerator N‐Benzylimine aminothioformamide (BIAT) along with tetramethylthiuram disulfide (TMTD) in improving cure and mechanical properties of gum and filled mixes of Styrene‐Butadiene Rubber (SBR). The feasibility of application of BIAT in sulfur vulcanization of an ideal blend of SBR and natural rubber (NR) has also been investigated. The mechanical properties like t ensile strength, tear resistance, hardness, compression set, and abrasion loss were measured. Swelling values were also determined as a measure of crosslink densities of the vulcanizates. The binary accelerator system BIAT‐TMTD was found very effective in improving cure properties of the mixes of pure SBR and a 50/50 blend of SBR and NR.There was also found simultaneous improvement in mechanical properties of vulcanizates of both pure and blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of NR‐g‐PMMA by “grafting from” method using ATRP process

Grafting poly(methyl methacrylate) or PMMA from natural rubber (NR) using ATRP process, NR has to be transformed into bromoalkyl‐functionalized NR (NRBr) acting as ATRP macroinitiator. The NRBr was prepared by two‐step chemical modification i.e., epoxidation and epoxide ring opening reaction using a nucleophile containing bromine atom such as 2‐bromopropionic acid ( A1 ) and 2‐bromo‐2‐methylpropionic acid ( A2 ). The fixation of A1 and A2 on 4‐methyl‐4‐octene, a model representing one repeat unit of NR, modified by epoxidation was prior studied and it was found that the resulting addition products from A2 using as ATRP initiator for MMA gave a better control of M _n,exp and low PDI of PMMA than that from A1 . Then, the NR was transformed into ATRP rubber macroinitiator via epoxidation, followed by epoxide ring addition with only A2 . ¹H NMR was employed to determine the amount of A2 addition units on NR, which is considered to be the same amount of grafting sites for ATRP of MMA. The grafting of PMMA was then successfully carried out from the NR backbone by ATRP process. The PMMA grafts of the NR‐g‐PMMA were indeed linked to the NR backbone via ester linkage of the A2 unit. The PMMA grafts could be cleaved from the NR backbone by acid hydrolysis, while PMMA grafting by other conventional radical reaction could not be done. Then, the average MW of PMMA grafts after separation using acetone extraction was evaluated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Permanent antistatic polypropylene based on polyethylene wax/polypropylene wax grafting sodium acrylate

Two types of permanent antistatic agents, polyethylene wax grafted with sodium acrylate (PEW‐g‐AAS) and polypropylene (PP) wax grafted with sodium acrylate (PPW‐g‐AAS), were prepared using a solution grafting method and applied to PP for enhancing antistatic properties. The grafting degree was determined using back titration method and structures were confirmed by Fourier transform infrared spectroscopy. The antistatic properties of PEW‐g‐AAS/PP blends and PPW‐g‐AAS/PP blends were characterized by surface resistivities (ρ_s) and volume resistivities (ρ_v), and a combination of contact angle measurements, scanning electron microscope, permittivity, and dielectric loss were used to investigate the surface and inner structures of the blends. Results showed ρ_s and ρ_v of PEW‐g‐AAS/PP blends dropped significantly (4–7 magnitudes) above a critical addition at 10%, where a electrostatic dissipative network formed; PPW‐g‐AAS revealed an inferior antistatic performance than PEW‐g‐AAS due to its better compatibility and smaller dispersed phase in the matrix. Further, the antistatic blends treated in 80°C water, 80°C air, and room temperature were investigated, and the results were interpreted from surface energy. Moreover, the addition of antistatic agent had little impact on tensile strength of the PP matrix. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermomechanical properties and shape memory effect of epoxidized natural rubber crosslinked by 3‐amino‐1,2,4‐triazole

A thermally induced shape memory polymer based on epoxidized natural rubber (ENR) was produced by curing the ENR with 3‐amino‐1,2,4‐triazole as a crosslinker in the presence of bisphenol‐A as a catalyst. Dynamic mechanical and tensile analysis was conducted to examine the variation of glass transition temperature, stiffness, and extensibility of the vulcanizates with the amount of curatives. Shape memory properties of the ENR vulcanizates were characterized by shape retention and shape recovery. It was revealed that the glass transition temperature of the ENR vulcanizates could be tuned well above room temperature by increasing the amount of curing agents. Also, ENR vulcanizates with T_g higher than ambient temperature showed good shape memory effects under 100% elongation, and the response temperatures of the recovery were well matched with T_g of the samples. Copyright © 2006 Society of Chemical Industry     

Utilization of silane functionalized carbon nanotubes‐silica hybrids as novel reinforcing fillers for solution styrene butadiene rubber

Carbon nanotubes‐silica (CNTs‐SiO₂) nanohybrid filler was fabricated by coating inorganic silica on multi‐wall CNTs through a sol–gel process. The CNTs‐SiO₂ nanohybrids were then functionalized by 3‐methacryloxypropyltrimethoxysilane (3‐MPTS) followed by compounding to solution styrene butadiene rubber (S‐SBR) through mechanical mixing. The Fourier‐transform infrared spectroscopy showed that the CNTs were coated by inorganic SiO₂, and grafted with 3‐MPTS successfully. The functionalized CNTs‐SiO₂ nanohybrids had a rough surface as revealed by transmission electron microscope images. After hybridization and grafting, the functionalized CNTs‐SiO₂ nanohybrids still maintained the crystal structure of CNTs, which was determined by X‐ray diffraction and Raman spectrum. The addition of nanohybrids accelerated the vulcanization process and improved the crosslinking degree of vulcanizates. With adding 10 phr (parts per hundred of rubber) functionalized CNTs‐SiO₂, the mechanical properties of S‐SBR vulcanizates were improved significantly. The tensile moduli at 100% elongation (M₁₀₀) and tensile strength had 54% and 28% increase, respectively. The incorporation of functionalized CNTs‐SiO₂ nanohybrids also largely enhanced the storage modulus, and slightly increased the thermal conductivity of vulcanizates. POLYM. COMPOS., 00:000–000, 2013. © 2013 Society of Plastics Engineers POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

ABS modified with hydrogenated polystyrene‐grafted‐natural rubber

Natural rubber (NR) latex was grafted by emulsion polymerization with styrene monomer, using cumene hydroperoxide/tetraethylene pentamene as redox initiator system. The polystyrene‐grafted NR (PS‐g‐NR) was hydrogenated by diimide reduction in the latex form using hydrazine and hydrogen peroxide with boric acid as a promoter. At the optimum condition for graft copolymerization, a grafting efficiency of 81.5% was obtained. In addition, the highest hydrogenation level of 47.2% was achieved using a hydrazine:hydrogen peroxide molar ratio of 1:1.1. Hydrogenation of the PS‐g‐NR (H(PS‐g‐NR)) increased the thermal stability. Transmission electron microscopy analysis of the H(PS‐g‐NR) particles revealed a nonhydrogenated rubber core and hydrogenated outer rubber layer, in accordance with the layer model. The addition of H(PS‐g‐NR) at 10 wt % as modifier in an acrylonitrile–butadiene–styrene (ABS) copolymer increased the tensile and impact strengths and the thermal resistance of the ABS blends, and to a greater extent than that provided by blending with NR or PS‐g‐NR. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Retention of activity of urease immobilized on grafted polymer films

Expanded poly(tetrafluoroethylene) (ePTFE) films grafted with 2‐hydroxyethyl methacrylate (HEMA) and 2‐hydroxyethyl acrylate (HEA) were applied to a polymer support for urease immobilization. The HEMA‐ and HEA‐grafted ePTFE (ePTFE‐g‐PHEMA and ePTFE‐g‐PHEA) films prepared by the combined use of the plasma treatment and photografting possessed high water‐absorptivities. Imidazole groups were introduced to grafted PHEMA and PHEA chains with 1,1′‐carbonyldiimidazole (CDI) in acetonitrile. The activity of urease covalently immobilized to the ePTFE‐g‐PHEMA and ePTFE‐g‐PHEA films in a pH 7.0 buffer at 4°C had the maximum value at the optimum pH value of 7.5 for native urease. Urease immobilized on the ePTFE‐g‐PHEMA films with the extent of CDI bonding of about 20% had the maximum activity, and the repeatedly measured activity was kept almost constant. The relative activity of immobilized urease stayed almost constant in the range of the immobilized amounts between 10 and 30 mg/g for both grafted ePTFE films, and decreased at higher immobilized amounts because of the crowding of immobilized urease molecules in the grafted layers. The relative activity of immobilized urease had the maximum values at the grafted amounts of 1.2 and 1.7 mmol/g for the ePTFE‐g‐PHEMA and ePTFE‐g‐PHEA films, respectively, and the further increase in the grafted amount resulted in the decrease in the relative activity. The optimum temperature of the activity for immobilized urease was shifted from 30 to 50°C for native urease by the covalent immobilization on both grafted ePTFE films and immobilized urease was repeatedly usable without a considerable decrease in the activity in the regions of the pH 6.0–9.0 and 10–60°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4886–4896, 2006