Refining natural rubber matrix for electrically stimulated transdermal drug delivery

This work focuses on the enhancement of transdermal delivery of indomethacin (IN) from natural rubber matrix by deproteinization, the addition of ethylene glycol (EG) as a plasticizer, and the enlarged matrix size under electrical field. The starting double-centrifuge natural rubber (DCNR) was deproteinized to produce the deproteinized natural rubber (DPNR). Both DCNR and DPNR patches were fabricated by the UV curing method, and blended with EG to enhance the IN loading and release–permeation. Using a pig skin to simulate the human skin, the IN release–permeation was found to increase with increasing plasticizer, removed protein, and applied electrical potential.     

国产脱蛋白天然橡胶的性能及应用

研究国产脱蛋白天然橡胶（DPNR）的性能及其在减震橡胶制品中的应用。结果表明：与普通天然橡胶（NR）相比,DPNR的氮含量较小,压缩生热较低,压缩永久变形较小,弹性和电绝缘性能较好,拉伸强度和拉断伸长率略低,耐老化性能稍差;用国产DPNR为主体材料试制的机车弹性旁承的强化疲劳性能、尺寸稳定性和弹性好,压缩永久变形小。     

Comparative d.s.c. studies of the crystallization of natural rubber and its synthetic analogues

A comparative d.s.c. crystallization study has shown that deproteinized natural rubber (DPNR) undergoes crystallization much more readily than synthetic analogues of 99% cis-1,4 purity. Acetone extracted DPNR is closer in behaviour to the synthetic materials whereas, the latter, when doped with 1% w/w stearic acid or rubber extract approach the crystallization character of DPNR. The differences in crystallization behaviour are thus largely, but not entirely, due to the presence of nucleating impurities in the natural product. Secondary rate effects may also be caused by slight differences in polymer microstructure or variation in molecular weight distribution. The maximum extent of crystallinity observed under the most favourable conditions approaches 40% for the DPNR samples as determined from the observed heat of fusion of the crystalline regions.     

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.     

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     

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.     

Polymer electrolyte membrane with nanomatrix channel prepared by sulfonation of natural rubber grafted with polystyrene

High‐proton‐conductive polymer electrolyte with a nanomatrix channel was prepared by graft copolymerization of styrene onto deproteinized natural rubber followed by sulfonation with chlorosulfonic acid. First, natural rubber latex was purified with urea in the presence of surfactant to remove almost all proteins present in the rubber. Second, graft copolymerization of styrene onto deproteinized natural rubber was carried out with tert‐butyl hydroperoxide/tetraethylenepentamine as an initiator at 30°C in latex stage. The graft‐copolymerized natural rubber (DPNR‐graft‐PS) was sulfonated with chlorosulfonic acid in chloroform solution at an ambient temperature. The resulting sulfonated DPNR‐graft‐PS was characterized by FTIR spectroscopy, solid state ¹³C CP/MAS NMR spectroscopy, elemental analysis, and transmission electron microscopy. High proton conductivity of about 0.1 S/cm, less water uptake of 24 wt % and comparatively good stress at break of 9 MPa were accomplished at suitable contents of styrene units and sulfur, i.e., 32 wt % and 75 mol %, respectively. The high proton conductivity, excellent stability, and good mechanical properties were associated with not only the formation of the nanomatrix channel but also a specific concentration of sulfuric acid group. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

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     

The role of linked phospholipids in the rubber-filler interaction in carbon nanotube (CNT) filled natural rubber (NR) composites

The aim of the present work is to evidence the role of the linked phospholipids of natural rubber (NR) in the rubber-carbon nanotube (CNT) interactions in rubber composites. Three rubbers namely NR, deproteinized NR (DPNR) and a synthetic rubber isoprene (IR) were used as matrix for CNTs. The selective wetting of CNTs in miscible NR/IR and DPNR/IR blends was investigated by means of the modified wetting concept based on Fourier transformed infrared (FTIR) analysis of the rubber-filler gel of blends. It revealed that the surface of CNTs is entirely wetted by NR or DPNR molecules, respectively, but not by IR. This result emphasizes that proteins do not influence the affinity between NR and CNTs, while the linked phospholipids interact with CNT surface through cation-π linkage. This linkage acts as anchor point supporting NR molecules to wet CNT surface effectively. The modified wetting concept can be used for characterization of selective wetting of different fillers in blends consisting of miscible rubber components.     

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.     

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     

Preparation of high-performance deproteinized natural rubber/chitosan composite films via a green and sulfur-free method

To solve the environment and health issues arose from the sulfur vulcanization, a facile and completely eco-friendly method of latex-assembly and in situ cross-linking is developed to prepare fully bio-based and high-performance rubber films. The films are featured by a “reinforced concrete” structure composed of dynamically cross-linked chitosan framework and unvulcanized deproteinized natural rubber (DPNR) matrix. The self-assembly of DPNR latex particles and chitosan, as well as the in situ cross-linking of chitosan in the film forming process are confirmed by transmission electron microscope and dynamic light scattering. As green rubbers without vulcanization, the as-designed composite films possess excellent mechanic properties comparable to those of the sulfur vulcanized DPNR film, whose tensile strength and toughness reach 15.2 MPa and 77.6 MJ m⁻³ respectively. Moreover, the films exhibited appropriate permeability to moisture and achievable reprocessing, which have potential applications in wearable devices.     

Mechanical properties of deproteinized natural rubber in comparison with synthetic cis‐1, 4 polyisoprene vulcanizates: Gum and black‐filled vulcanizates

Gum and black‐filled vulcanizates having various crosslink densities were prepared from 2 types of rubber, namely, deproteinized natural rubber (DPNR) and synthetic cis‐1, 4 polyisoprene vulcanizates (IR). Their mechanical properties, such as tensile strength, tear strength, abrasion loss, and heat buildup resistance, at various crosslink densities as well as at similar optimum crosslink density were compared. For both gum and black‐filled systems, IR possessed a higher crosslink density than that of DPNR at a fixed curative content. Tensile and tear strength of all vulcanizates passed through a maximum with increasing crosslink density. For gum vulcanizates, tensile and tear strengths of DPNR and IR below the maximum were not much different. However, IR had a narrower tear strength peak relative to DPNR. At a comparable optimum crosslink density, DPNR exhibited higher tensile strength and crack growth resistance than IR. For black‐filled vulcanizates, tensile and tear strengths, and heat buildup resistance of DPNR and IR at a given crosslink density were similar. The results revealed that the properties of gum samples were more dependent upon crosslink density than the black‐filled ones because the reinforcement by carbon black overshadowed the intrinsic properties of the rubbers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1139–1144, 2005     

Reducing and stabilizing the viscosity of natural rubber by using sugars: Interference of the Maillard reaction between proteins and sugars

This work is an extension of previous work elucidating the reduction and stabilization of solid natural rubber (NR) viscosity by using sugars. Various amounts of glucose, fructose, sucrose, and maltose were incorporated into fresh NR (FNR), deproteinized NR (DPNR), and synthetic polyisoprene (IR) latexes. The results revealed that all sugars cannot decrease the Mooney viscosity of FNR, while only monosaccharides, that is, glucose and fructose, can significantly decrease the Mooney viscosity of both DPNR and IR by way of a lubrication mechanism. The proteins in FNR can diminish the capability of glucose and fructose to decrease the Mooney viscosity. Furthermore, glucose was found to reduce the occurrence of storage hardening in DPNR by interacting with polar groups of phospholipids at the rubber chain ends. Measurements of browning intensity as well as analysis of Maillard reaction products together with the NR protein–glucose model compound were utilized to confirm that the reduction and stabilization of the viscosity of NR using monosaccharides were interfered by the Maillard reaction between the proteins in NR and the monosaccharides.     

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.     

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.     

Effect of natural and synthetic tackifiers on viscosities,adhesion properties and thermal stability of SNR and DPNR solution adhesives

Styrene-grafted natural rubber (SNR) and deproteinized natural rubber (DPNR) latexes were formulated with coumarone-indene (CI), gum rosin and petro resin (PR) tackifiers into solution adhesives with toluene as a solvent. The solution viscosities were evaluated by a Brookfield viscometer DV-II Plus with spindle No. 3. Pressure sensitive adhesives (PSAs) films were made and the adhesion properties were evaluated with loop tack, peel strength and shear strength tests. Thermal stability of the film was evaluated via Perkin-Elmer Pyris 6^TM thermogravimetric analysis at temperatures ranging from 30 to 600?°C at a heating rate of 10?°C per minute in nitrogen environment. Results indicate that as the tackifiers content increased, the solution viscosities increased with SNR/PR and DPNR/PR formulations showing the highest viscosities. Adhesion test also indicates that loop tack and peel strength of the adhesive solution increased but their shear strength decreased; increase of CI tackifier loadings conferred the highest peel strength for both SNR- and DPNR-based PSAs. Thermal analyses show that the addition of 40 phr CI tackifiers improved thermal stability of SNR adhesives based on their higher T_max and integral procedural decomposition temperature properties.     

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.     

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