Preparation and graft‐copolymerization of hydrogenated natural rubber in latex stage

Preparation and graft‐copolymerization of hydrogenated natural rubber are performed in latex stage after removal of proteins from the rubber with urea and surfactant. Hydrogenation of deproteinized natural rubber (DPNR) latex is carried out with palladium catalyst under hydrogen atmosphere. The hydrogenated DPNR (HDPNR) is crosslinked with a peroxide followed by graft‐copolymerization of styrene (Sty) and acrylonitrile (AN) in latex stage in order to prepare a graft‐copolymer of crosslinked HDPNR with poly(Sty‐co‐AN) (HDPNR‐graft‐PSAN). Characterization of the products is performed by nuclear magnetic resonance spectroscopy. The conversion of hydrogenation is investigated with respect to the catalyst feed, acidity (pH), and dry rubber content. In the resulting HDPNR‐graft‐PSAN, mole fraction of AN and Sty is 1.4 and 5.8 mol %, respectively. The graft‐copolymer is used to improve properties of PSAN as an impact modifier. The Charpy impact strength of crosslinked HDPNR‐graft‐PSAN/PSAN is about eight times as high as that of PSAN. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42435.     

Studies on the curing behaviour and mechanical properties of styrene/methyl methacrylate grafted deproteinized natural rubber latex

The graft copolymerization of styrene/methyl methacrylate (MMA) onto deproteinized natural rubber (DPNR) latex was carried out using ammonium peroxy disulfate (N₂H₈O₈S₂) as the initiator. The presence of the grafted polystyrene (PS) and polymethyl methacrylate (PMMA) on the rubber backbone was confirmed by FTIR spectroscopy. The effects of monomer concentrations on curing characteristics and mechanical properties were studied. It was found that the cure time and scorch time were increased with increasing monomer concentration whereas the torque_max–min value was slightly decreased. It was also noted that the increase in the monomer concentration resulted in stiffer rubber with increased modulus and reduced elongation at break.     

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     

Removal of proteins from natural rubber with urea and its application to continuous processes

The removal of proteins from natural rubber through a batch process was studied by the incubation of the rubber latex with urea in the presence of sodium dodecyl sulfate. Under suitable conditions, the total nitrogen content of deproteinized natural rubber (DPNR) decreased from 0.38 to 0.02 wt % after incubation for 10 min; this was similar to that of the rubber deproteinized with a proteolytic enzyme for 12 h. For applications, continuous incubation and centrifugation were individually investigated by the use of a semicircular channel and a continuous centrifuge, respectively, to scale up DPNR preparation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Cationic cyclization of purified natural rubber in latex form with a trimethylsilyl triflate as a novel catalyst

Cyclization of deproteinized natural rubber (DPNR) or purified natural rubber latex was effectively performed in latex phase by using trimethylsilyl‐trifluoromethane sulfonate or trimethylsilyl triflate (TMSOTF) as a novel catalyst, which is still not reported in the case of natural rubber latex. Various cyclization conditions affecting the degree of cyclization were studied, such as dry rubber contents, temperature, TMSOTF concentrations, and time. The cyclized products were characterized by FTIR, Raman, ¹H‐, and ¹³C‐NMR spectroscopies, as well as DSC and TGA. The degree of cyclization was estimated by ¹H‐NMR spectrum. It was found that the degree of cyclization in NR was a function of cyclization conditions. The thermal stability of cyclized DPNR increased with the degree of cyclization. Solubility of the obtained rubber was good in chloroform, toluene, cyclohexanone, and cyclohexane, and bad in tetrahydrofuran. The average number molecular weight of cyclized DPNR with 76% degree of cyclization was about 4.2 × 10⁴ g/mol. On the basis of FTIR, Raman, ¹H‐, and ¹³C‐NMR, the C?C of cyclized DPNR dramatically decreased after prolonged reaction time. In addition, the topology of cyclization DPNR particles was rough on its rubber particle as analyzed by TEM. The mechanism for this reaction will also be discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007.     

Multifunctional,pH‐responsive graft copolymer prepared from deproteinized natural rubber and 4‐vinylpyridine via emulsion polymerization

We investigated the synthesis of a pH‐responsive graft copolymer of natural rubber and 4‐vinylpyridine. The grafting reaction was carried out using deproteinized natural rubber (DPNR) latex, with potassium persulfate as a free radical initiator. The pH responsiveness of the graft copolymer was investigated using water swelling and contact angle measurements, and was compared with that of pure DPNR. The graft copolymer was found to become responsive in solution at a pH of around 4. Indigo carmine adsorption studies identified the Langmuir isotherm, suggesting monolayer coverage. The adsorbed indigo carmine, a model anionic drug, and carbon dots, an emerging nanosized fluorophore, could be released from the graft copolymer by lowering the pH of the solution. The graft copolymer was tested as a heavy metal adsorbent, and demonstrated selectivity to copper(II) ions. The graft copolymer of 4‐vinylpyridine and DPNR developed in this study is therefore a multifunctional, pH‐responsive material with a wide range of potential applications, including sensing and catalysis, as a biomedical material and as an adsorbent. © 2017 Society of Chemical Industry     

Molecular structure and storage hardening of natural rubber: Insight into the reactions between hydroxylamine and phospholipids linked to natural rubber molecule

The effect of hydroxylamine on the molecular structure and storage hardening of natural rubber (NR) was investigated by the treatment of deproteinized NR (DPNR) latex with hydroxylamine. The hydroxylamine treatment decreased the content of long‐chain fatty acid ester groups in DPNR from about 2–0.7 mol per rubber molecule. The molecular weight and molecular weight distribution changed apparently after treatment with hydroxylamine. The relative intensity of the ¹H NMR signals corresponding to phospholipids at the α‐terminal group decreased after the hydroxylamine treatment. The Huggins ‘k’ constant of hydroxylamine‐treated DPNR showed the liberation of linear rubber molecules caused by decomposition of branch points derived from phospholipids. The absence of storage hardening in hydroxylamine‐treated DPNR was observed to be caused by not only the reaction of hydroxylamine and aldehyde groups but also the removal of phospholipids as well as the breakdown of phospholipid aggregations as a result of hydroxylamime, contributing to the establishment of a newly proposed mechanism of hydroxylamine on the inhibition of storage hardening in NR. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43753.     

New evidence of the surface morphology of deproteinized natural rubber particles

Summary A new evidence of the morphology of deproteinized natural rubber (DPNR) latex particles, i.e., γ-radiation vulcanized-deproteinized NR (RV-DPNR) and deproteinized-γ-radiation vulcanized NR (DP-RVNR), was obtained by transmission electron microscopy (TEM). Micrographs of the rubber particles embedding in polystyrene, prepared by using a phase transfer/ bulk polymerization process, revealed the destruction of membrane layer surrounded the DPNR particles crosslinked by γ-ray (DP-RVNR). Received: 30 July 1998/Revised version: 17 September 1998/Accepted: 14 October 1998     

Synthesis of graft copolymers from natural rubber using cumene hydroperoxide redox initiator

The graft copolymerization of 50/50 (w/w) styrene/methyl methacrylate mixtures onto natural rubber seed latex were carried out by using cumene hydroperoxide/sodium formaldehyde sulfoxylate dihydrate/EDTA‐chelated Fe²⁺ as a redox initiator. The effects of the process factors such as the amount of initiator, emulsifier, and chain‐transfer agent; monomer‐to‐rubber ratio; and temperature on the grafting efficiency (GE) and grafting level (GL) are reported. The mechanism of graft copolymerization was investigated. The synthesized graft copolymers were purified and then characterized by proton nuclear magnetic resonance (¹H‐NMR) analysis. Transmission electron microscopy (TEM) was used to study the morphology of the graft copolymers. It appears that the formation of graft copolymers occurs on the surface of the latex particles through a chain‐transfer process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2993–3001, 2002; DOI 10.1002/app.2328     

A novel pH and temperature-sensitive maleate poly(vinyl alcohol)-<Emphasis Type="Italic">graft</Emphasis>-isopropylacrylamide/natural rubber blend: preparation and properties

A novel pH–temperature-sensitive elastomer was made from maleate poly(vinyl alcohol)-graft-isopropylacrylamide (PVAM-graft-PNIPAM), namely PVNI and deproteinized natural rubber (DPNR) in a water-based system. The swelling ratio in water of PVNI/DPNR hydrogel enhanced as a function of PVNI portion in hydrogel due to increasing of hydrophilic group in the hydrogel. Surprisingly, the percentage of swelling in water of PVNI/DPNR hydrogel 7:3 is 24 times based on pristine DPNR. In addition, the highest tensile strength of PVNI/DPNR hydrogel was found at 7:3 PVNI/DPNR. The highest elongation at break of PVNI/DPNR hydrogel was improved after the addition of DPNR. Moreover, the resulting smart hydrogel showed a good pH–temperature sensitivity. In addition, it yielded a good polymer membrane for encapsulating capsaicin (CSC) in different media. After its use, it also easily decomposed in the natural environment.     

Synthesis and characterization of composites with sulfonated styrene‐divinylbenzene copolymer

In this work light sulfonation was applied to a styrene copolymer crosslinked with divinylbenzene (PS‐co‐DVB). Subsequently the product was incorporated at different concentrations into poly(vinylidene fluoride) (PVDF) and ethylene‐propylene‐diene (EPDM). Also, antimonic acid (HSb) was added. The resulting composites were characterized both microstructurally and electrically. In addition, PVDF/PS‐co‐DVBSH/HSb and EPDM/PS‐co‐DVBSH/HSb membranes were sulfonated, utilizing chlorosulfonic acid as a reagent, and characterized electrically. The membranes obtained by this procedure show good properties from an electric point of view.     

Synthesis of poly(aryl ether sulfone)‐graft‐polystyrene and poly(aryl ether sulfone)‐graft‐[polystyrene‐block‐poly(methyl methacrylate)] through atom transfer radical polymerization

A new graft copolymers poly(aryl ether sulfone)‐graft‐polystyrene (PSF‐g‐PS) and poly(aryl ether sulfone)‐graft‐[polystyrene‐block‐poly(methyl methacrylate)] (PSF‐g‐(PS‐b‐PMMA)) were successfully prepared via atom transfer radical polymerisation (ATRP) catalyzed by FeCl₂/isophthalic acid in N,N‐dimethyl formamide. The products were characterized by GPC, DSC, IR, TGA and NMR. The characterization data indicated that the graft copolymerization was accomplished via conventional ATRP mechanism. The effect of chloride content of the macroinitiator on the graft copolymerization was investigated. Only one glass transition temperature (T_g) was detected by DSC for the graft copolymer PSF‐g‐PS and two glass transition temperatures were observed in the DSC curve of PSF‐g‐(PS‐b‐PMMA). The presence of PSF in PSF‐b‐PS or PSF‐g‐(PS‐b‐PMMA) was found to improve thermal stabilities. © 2002 Society of Chemical Industry     

Synthesis of sub‐micrometer core–shell rubber particles with 1,2‐azobisisobutyronitrile as initiator and deformation mechanisms of modified polystyrene under various conditions

BACKGROUND: Sub‐micrometer core‐shell polybutadiene‐graft‐polystyrene (PB‐g‐PS) copolymers with various ratios of polybutadiene (PB) core to polystyrene (PS) shell were synthesized by emulsion grafting polymerization with 1,2‐azobisisobutyronitrile (AIBN) as initiator. These graft copolymers were blended with PS to prepare PS/PB‐g‐PS with a rubber content of 20 wt%. The mechanical properties, morphologies of the core‐shell rubber particles and deformation mechanisms under various conditions were investigated. RESULTS: Infrared spectroscopic analysis confirmed that PS could be grafted onto the PB rubber particles. The experimental results showed that a specimen with a ‘cluster’ dispersion state of rubber particles in the PS matrix displayed better mechanical properties. Transmission electron micrographs suggested that crazing only occurred from rubber particles and extended in a bridge‐like manner to neighboring rubber particles parallel to the equatorial plane at a high speed for failure specimens, while the interaction between crazing and shear yielding stabilized the growing crazes at a low speed in tensile tests. CONCLUSION: AIBN can be used as an initiator in the graft polymerization of styrene onto PB. The dispersion of rubber particles in a ‘cluster’ state leads to better impact resistance. The deformation mechanism in impact tests was multi‐crazing, and crazing and shear yielding absorbed the energy in tensile experiments. Copyright © 2009 Society of Chemical Industry     

Enhanced wide‐range monotonic piezoresistivity,reliability of Ketjenblack/deproteinized natural rubber nanocomposite,and its biomedical application

Piezoresistive behavior of 6 to 9 wt % Ketjenblack‐reinforced deproteinized natural rubber (KB/DPNR) nanocomposite developed by two‐roll mill was studied under compressive pressure (0 to 12.54 MPa). The 6 wt % KB/DPNR exhibited monotonic piezoresistivity, the highest electrical resistance change (485%), remarkable reversibility and minimal hysteresis. Furthermore, a good sensitivity (S) = 1.1 MPa^?1 for 0.25 to 2.49 MPa, high test–retest reliability (intraclass correlation co‐efficient, ICC = 0.99) under 0 to 2.49 MPa for three repetitions conducted at an interval of 24 h and excellent repeatability (standard deviation, SD = 4.8%) to a swing of 6.25 MPa for 50 cyclic compression were achieved. Homogeneous dispersion and high aspect ratio of KB and higher chemical linkage (due to double crosslinking agents) between KB and DPNR may be responsible for the enhanced piezoresistivity. For practical application, the KB/DPNR was interfaced with the microcontroller through a bridge rectifier via custom‐built Simulink and successfully monitored finger pressure in real time during bone movement on human. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44981.     

Deformation mechanism of polystyrene toughened with sub‐micrometer monodisperse rubber particles

Core–shell polybutadiene‐graft‐polystyrene (PB‐g‐PS) rubber particles with different ratios of polybutadiene to polystyrene were prepared by emulsion polymerization through grafting styrene onto polybutadiene latex. The weight ratio of polybutadiene to polystyrene ranged from 50/50 to 90/10. These core‐shell rubber particles were then blended with polystyrene to prepare PS/PB‐g‐PS blends with a constant rubber content of 20 wt%. PB‐g‐PS particles with a lower PB/PS ratio (≤70/30) form a homogeneous dispersion in the polystyrene matrix, and the Izod notched impact strength of these blends is higher than that of commercial high‐impact polystyrene (HIPS). It is generally accepted that polystyrene can only be toughened effectively by 1–3 µm rubber particles through a toughening mechanism of multiple crazings. However, the experimental results show that polystyrene can actually be toughened by monodisperse sub‐micrometer rubber particles. Scanning electron micrographs of the fracture surface and stress‐whitening zone of blends with a PB/PS ratio of 70/30 in PB‐g‐PS copolymer reveal a novel toughening mechanism of modified polystyrene, which may be shear yielding of the matrix, promoted by cavitation. Subsequently, a compression‐induced activation method was explored to compare the PS/PB‐g‐PS blends with commercial HIPS, and the result show that the toughening mechanisms of the two samples are different. Copyright © 2006 Society of Chemical Industry     

Process variables and their effects on grafting reactions of styrene and methyl methacrylate onto natural rubber

The graft copolymerization of styrene and methyl methacrylate onto natural rubber latex was studied under various reaction conditions using a cumene hydroperoxide redox initiator. The monomer conversion, graft copolymer compositions, and grafting efficiency were determined. The synthesized graft copolymers were purified and then characterized by proton nuclear magnetic resonance (¹H‐NMR) analysis and differential scanning calorimetry (DSC). A 2 fractional factorial experimental design was applied to study the main effects on the grafting. The variables investigated in this work were the amount of the initiator and emulsifier, the presence or absence of a chain‐transfer agent, the styrene‐to‐methyl methacrylate ratio, the monomer‐to‐rubber ratio, and the reaction temperature. The measured response for the experimental design was the grafting efficiency. The analysis of the results from the design showed the sequence of the main effects on the observed response of the grafting of styrene and methyl methacrylate onto natural rubber, in ascending order. The amount of the chain‐transfer agent and the reaction temperature in the range of the test had significant effects and one marginally significant effect was the monomer‐to‐rubber ratio. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 63–74, 2003     

Hyperdeproteinized natural rubber prepared with urea

Preparation of hyperdeproteinized natural rubber was made from fresh latex and preserved high‐ammonia latex by treatment with urea in the presence of sodium dodecyl sulfate. Concentration of urea, temperature, and time for the incubation were investigated to remove the proteins effectively. Under the best conditions, the total nitrogen content and amount of allergenic proteins for the deproteinized rubbers were 0.005 wt % and 1.0 μg/ml, respectively, which were less than those of natural rubber deproteinized with proteolytic enzyme. The hyper‐deproteinized natural rubber was proved through FT IR spectroscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 555–559, 2004     

Quantitative analysis for reaction between epoxidized natural rubber and poly (L‐lactide) through 1H‐NMR spectroscopy

Reaction between epoxidized natural rubber and poly(L ‐lactide) (PLLA) was investigated quantitatively in terms of conversion of the epoxidized natural rubber. The epoxidized natural rubber was prepared by epoxidation of high ammonia natural rubber (HA‐NR) or deproteinized natural rubber (DPNR) with peracetic acid followed by depolymerization with ammonium persulfate. The resulting liquid HA‐NR having epoxy group (LENR) or liquid DPNR having epoxy group (LEDPNR) were subjected to heating at 473 K for 20 min, after blending with PLLA. The products were characterized through morphology observation, DSC measurement, and ¹H‐NMR spectroscopy. The conversions of the rubbers were estimated from intensity ratio of signals in ¹H‐NMR spectrum for the products after removing unreacted rubber with toluene. Difference in the estimated conversion between the LENR/PLLA and LEDPNR/PLLA blends was interpreted in relation to proteins present in the rubber. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of polypropylene graft copolymers from a hydroxyl‐groups‐containing polypropylene precursor via atom‐transfer radical polymerization

Isotactic polypropylene graft copolymers, isotactic[polypropylene‐graft‐poly(methyl methacrylate)] (i‐PP‐g‐PMMA) and isotactic[polypropylene‐graft‐polystyrene] (i‐PP‐g‐PS), were prepared by atom‐transfer radical polymerization (ATRP) using a 2‐bromopropionic ester macro‐initiator from functional polypropylene‐containing hydroxyl groups. This kind of functionalized propylene can be obtained by copolymerization of propylene and borane monomer using isospecific MgCl₂‐supported TiCl₄ as catalyst. Both the graft density and the molecular weights of i‐PP‐based graft copolymers were controlled by changing the hydroxyl group contents of functionalized polypropylene and the amount of monomer used in the grafting reaction. The effect of i‐PP‐g‐PS graft copolymer on PP‐PS blends and that of i‐PP‐g‐PMMA graft copolymer on PP‐PMMA blends were studied by scanning electron microscopy. Copyright © 2006 Society of Chemical Industry     

Poly(styrene)‐ and Poly(styrene‐co‐methyl methacrylate)‐graft‐hydrogenated natural rubber latex: Aspect on synthesis,properties, and compatibility

The undesirable properties of natural rubber (NR) can be improved via hydrogenation and graft copolymerization. Hydrogenated NR (HNR) latex was prepared via diimide reduction and then grafted with styrene (ST) or ST/methyl methacrylate (MMA) to form poly(ST)‐graft‐HNR (poly(ST)‐g‐HNR, GHNRS) or poly(ST‐co‐MMA)‐g‐HNR (GHNRSM), respectively. For the grafting of ST monomer onto HNR particles, the %monomer conversion and %grafting efficiency (%GE) were monitored as functions of %hydrogenation, monomer and initiator concentrations, temperature, and time. Under the optimum condition (HNR with 54.3% hydrogenation; 100 phr of ST, 1 phr of initiator at 50°C for 8 h), maximum %conversion and %GE of 44.6% and 36.9%, respectively, were achieved. Thermogravimetric analysis revealed that the HNR grafted with ST or ST/MMA had higher decomposition temperature than an ungrafted one. When these graft products were blended at 10% (w/w) with acrylonitrile‐butadiene‐styrene (ABS) resin, the GHNRS/ABS and GHNRSM/ABS composites exhibited the higher flexural strength and heat aging tolerance compared to the ungrafted HNR/ABS composite. Scanning electron microscopy (SEM) also showed the higher degree of homogeneity at the fractural surface, supporting the higher compatibility between the ABS and the GHNRS or GHNRSM phases in the blends. J. VINYL ADDIT. TECHNOL., 22:100–109, 2016. © 2014 Society of Plastics Engineers