Modification of deproteinized natural rubber via grafting polymerization with maleic anhydride

Modification of natural rubber (NR) via grafting polymerization with maleic anhydride (MA) has received wide attention as it could improve the hydrophilicity of NR and extend its application to a wider application field. However, the grafting efficiency of MA onto NR in either the molten state or solution state is low and is accompanied with undesired high gel content in the grafts. In this work a novel technical route was developed in that a deproteinization operation was conducted before carrying out the grafting process and a differential microemulsion polymerization technique was applied for the grafting reaction. The effects of initiator and monomer concentration, reaction temperature, and reaction time on the grafting efficiency and gel fraction were investigated, and a comparison of the reaction performance was conducted for deproteinized NR (DPNR) and NR. The results indicated that the deproteinization operation could significantly improve the grafting efficiency and reduce the gel content, and a 29% yield of MA grafted onto the rubber backbone could be achieved at a condition of a DPNR:MA:initiator ratio of 85:9:6 (wt%) at 60 °C for 8 h.     

Cation exchange membranes by pre-irradiation grafting of styrene into FEP films. II. Properties of copolymer membranes

The structure and some physico-chemical properties of radiation grafted FEP-g-polystyrenesulfonic acid proton exchange membranes were studied as a function of the degree of grafting. The distribution of grafted polymer across the membrane thickness was obtained from microprobe measurements. It was found that for low levels of grafting (ca. 3%), polystyrene chains are located near the membrane surface only, and the interior of the membrane remains ungrafted. With the increasing degree of grafting, polystyrene chains were incorporated into the interior of the membrane as well. An almost homogeneous distribution of grafts in the membrane was obtained at a graft level of > 13%. The influence of the degree of grafting on membrane properties, such as ion exchange capacity, swelling, and specific resistivity was studied. Three different states of water, viz., freezing free, freezing bound, and nonfreezing water have been identified in noncrosslinked membranes. However, the nature and the amount of crosslinker had a profound influence on the states of water in a membrane. © 1996 John Wiley & Sons, Inc.     

Introduction of O-butyrylchitosan with a photosensitive hetero-bifunctional crosslinking reagent to silicone rubber film by radiation grafting and its blood compatibility

Based on an in vitro test for an improvement of the blood compatibility of silicone rubber (SR) films by grafting O-butyrylchitosan (OBCS), OBCS was covalently immobilized onto SR film surface using the photosensitive hetero-bifunctional crosslinking reagent, 4-azidobenzoic acid, which was previously bonded to OBCS by reaction between an acid group of the crosslinking reagent and a free amino group of OBCS. Surface properties of SR film were investigated by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), electron spectroscopy for chemical analysis (ESCA) and the water contact angle measurements. The blood compatibility of SR film was evaluated by platelet rich plasma (PRP) contacting experiments and the results were observed by scanning electron microscopy (SEM). The state of platelet adhesion was described. The suitable modifications could be carried out to tailor SR films biomaterial to meet the specific needs of different biomedical applications. These results suggest that the blood compatible of SR films/OBCS films show their suitability as potential biomaterials.     

Influence of different functionality degree grafting monomers on polypropylene melt radical branching reaction and their structure

Long‐chain–branched polypropylene (LCBPP) is one of polypropylenes (PPs) with high melt strength and good melt elasticity. Recently, due to its outstanding properties, LCBPP have been attracted increasingly attention in the field of development and characterization by the researchers all over the world. In this study, LCBPP was prepared by the melt radical branching reaction in a torque rheometer. The influences of various acrylate monomers with different functionality degrees on the structure and melt performance of PP products were investigated. The results indicated that grafting monomers with different functionality degrees made diverse influences on the branching density and branching chain length of branching PP products. With the increase of the functionality degree of grafting monomers, the branching level of PP products increased gradually and the “multiplicity” of branches became increasingly obvious. Besides, a higher reactivity of pentaerythritol triacrylate with hydroxyl than the similar molecular structured pentaerythritol tetraacrylate was confirmed. Furthermore, due to the high reactivity of dipentaerythritol penta(hexa)acrylate, branching and crosslinking reaction occurred simultaneously during the reaction process. As a result, the gel content increased and finally formed highly star branching structures with a shape of “dense and short.”     

Improving the mechanical properties of short pineapple leaf fiber reinforced natural rubber by blending with acrylonitrile butadiene rubber

This work proposes a simple method for improving the rubber to filler stress transfer in short pineapple leaf fiber-reinforced natural rubber (NR). This was achieved by replacing some of the non-polar NR by polar acrylonitrile butadiene rubber (NBR). The amount replaced was varied from 0% to 20% by weight. The mixing sequence was designed so that the fiber would be coated with polar NBR before being dispersed in the NR matrix. A comparison system in which the mixing was carried out in a single step was also examined. Despite the fact that the two rubbers are immiscible, it was found that significant improvement of the stress transfer in the low strain region can be obtained. The mixing sequence affected the mechanical properties of the resulting composites. It is concluded that frictional stress transfer between the immiscible rubbers contributes more to the total stress transfer than does the frictional stress transfer between non-polar NR and polar cellulose fiber.     

Modification of epoxidised natural rubber film surface by polymerisation of methyl methacrylate

Epoxidised natural rubber (ENR) latex, having 25% of epoxide content, was prepared by in situ epoxidation reaction using performic acid. The ENR latex film surface was modified by immersing into methyl methacrylate (MMA) emulsion and then alkaline aqueous solution of ferrous ion/fructose for redox-initiated polymerisation. Increasing polymerisation time caused an increase in percent conversion of MMA swelled in ENR sheet. The presence of poly(methyl methacrylate) on the ENR surface was examined by attenuated total reflection-Fourier transform infrared spectroscopy. The nano-scale indentation experiment performed on the cross-section of the modified ENR sheet indicated that MMA polymerisation occurred mainly near the rubber’s surface. The surface morphology observed under scanning electron microscopy and atomic force microscopy revealed a pronounced roughness which, consequently, decreased the friction coefficient of ENR surface.     

Improving thermal and ozone stability of skim natural rubber by diimide reduction

The physical, chemical and thermal properties of diene-based polymers are improved by a chemical modification method such as hydrogenation. Skim natural rubber (SNR) which is mainly comprised of cis-1,4-polyisoprene was hydrogenated by diimide reduction in latex form, using hydrazine and hydrogen peroxide with copper sulfate as catalyst. The effect of various parameters on the level of hydrogenation calculated from proton nuclear magnetic resonance spectroscopy (¹H NMR) was investigated. The kinetic results indicated that the diimide hydrogenation of skim natural rubber latex (SNRL) exhibited a first order behavior with respect to the CC concentration. The apparent activation energy of the catalytic and non-catalytic hydrogenation of SNRL was calculated as 9.5 and 21.1 kJ/mol, respectively. From the TEM micrograph of hydrogenated SNRL particles, non-hydrogenated rubber core and hydrogenated rubber layer were observed according to a layer model. The results from thermal analysis confirmed that thermal stability of hydrogenated SNR was improved compared with the starting SNR. In addition, the thermal aging and ozone resistance of vulcanized hydrogenated SNR blends were also investigated.     

Influences of different dimensional carbon-based nanofillers on fracture and fatigue resistance of natural rubber composites

The dimensions of reinforcing filler is a key factor in influencing the fracture and fatigue of rubbers. Here, the fracture and fatigue resistance of natural rubber (NR) filled with different dimensional carbon-based fillers including zero-dimensional spherical carbon black (CB), one-dimensional fibrous carbon nanotubes (CNTs) and two-dimensional planar graphene oxide (GO) were explored. To obtain equal hardness, a control indicator in the rubber industry, the amounts of CB, CNTs, and GO were 10.7 vol%, 1.2 vol%, and 1.6 vol%, respectively. J-integral and dynamic fatigue tests revealed that NR filled with CB exhibited the best quasi-static fracture resistance and dynamic crack growth resistance. The much higher hysteresis loss of NR filled with CNTs weakened its fatigue resistance. The planar GO played a limited role in preventing crack growth. Furthermore, digital image correlation revealed that NR filled with CB had the highest strain amplification level and area at the crack tip, which dissipated the most local input energy and then improved the fracture and fatigue performance.     

Surface modification of natural rubber film by polymerisation of methyl methacrylate in water-based system

Polymerisation of methyl methacrylate (MMA) on the surface of natural rubber (NR) film was studied in order to increase the surface hardness, roughness and, hence, to decrease the friction coefficient of rubber. We used the two-step process: (i) swelling of MMA and tert-butyl hydroperoxide, emulsified in an aqueous solution of sodium dodecyl sulphate, onto the NR film surface, and (ii) subsequently immersing the swollen rubber strip into an alkaline aqueous solution of ferrous ion/fructose for redox initiation. The presence of PMMA on the NR surface was examined by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR). Increasing the concentration of ferrous ion caused an increase in MMA conversion. The surface morphology observed by scanning electron microscopy (SEM) and atomic force microscopy (AFM) in tapping mode revealed the aggregation of micronmetre-scale nodules on the modified surface. The surface hardness and roughness increased with increasing PMMA content.     

Degradation of polychloroprene/natural rubber (PCP/NR) blends by photo-Fenton process

The effect of light and FeCl₃·6H₂O on polychloroprene (PCP)/natural rubber (NR) blends in toluene solution were investigated to demonstrate the influence of each polymer on the degradation process. The contributions of total polymer concentration (C_p), temperature (T) and polychromatic light exposure (L) on the degradation process were investigated through a 2³ factorial design approach. Degradation kinetics was examined by solution viscosity time data. FTIR spectroscopy and TGA were used to characterize the degradation. The exposure of the PCP/NR blend solution containing FeCl₃·6H₂O to light induces degradation in the polymers. A decrease of up to 70% in solution efflux time at constant temperature and without aggregation or phase separation was observed. PCP degradation by-products amplify the degradation of NR, as evidenced by the decrease in the PCP/NR 1:99 (w/w) solution efflux time, which was larger than that of the pure NR solution. The film cast from the solution exposed to light was thermally less stable than the one which was cast without FeCl₃·6H₂O.     

The sensitizing effect of acrylates on radiation vulcanization of natural rubber latex

The sensitizing effect of acrylates on radiation vulcanization of natural rubber latex was studied. The results indicate that Gc value of crosslinking (Gc) will be higher at the same radiation dose when a sensitizer exists, and Gc value decreases with the increase of radiation dose (D) conforming to the formula Gc=KD^-α, where K and α are constants depending on sensitizers. The more sensitizers added, the greater the Gc value. However, the viscosity of the natural rubber latex also increases rapidly along with the increase of sensitizers added.Some sensitizers, such as TMPTA, can decrease the optimum dose from about 200 kGy to approximately 20 kGy according to our experiment. The tensile strength of the film can reach round 20 MPa. Other physical properties are comparable to those of unsensitized.     

Radical grafting from glass fiber surface: Graft polymerization of vinyl monomers initiated by azo groups introduced onto the surface

This paper describes the radical graft polymerization of vinyl monomers from glass fiber surface initiated by alkylazo groups introduced onto the fiber surface. The introduction of azo groups onto the glass fiber surface was achieved by reaction of isocyanate groups which were previously attached onto the surface with two kinds of azo initiators, 4,4′-azobis(4-cyanopentanoic acid) (ACPA) and 2,2′-azobis(2-cyanopropanol) (ACP). The amounts of surface azo groups introduced by ACPA and ACP were both determined to be 1.3 × 10⁻⁵ mol g⁻¹ by nitrogen analysis. The radical graft polymerization of methyl methacrylate (MMA) was found to be initiated in the presence of the glass fiber having surface azo groups. During the polymerization, part of resultant poly(MMA) grafted onto the fiber surface through propagation of the polymer from the surface radicals produced by the decomposition of the azo groups. The percentage of grafting of poly(MMA) reached 48.1% after 24 h. The graft polymerizations of other monomers, such as styrene, N-vinylcarbazole, and acrylic acid, were also initiated by the surface azo groups, and the corresponding polymer effectively grafted onto the surface. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2121–2128, 1999     

Modification of natural rubber: A study by H NMR to assess the degree of graftization of polyDMAEMA or polyMMA onto rubber particles under latex form in the presence of a redox couple initiator

On the basis of the proposal that cumene hydroperoxide (CHP) in the presence of the base tetraethylenepentamine (TEPA) can form radicals by the abstraction reaction over addition to allylic double bonds, the efficiency of grafting monomers of methyl methacrylate (MMA) and dimethylaminoethylmethacrylate (DMAEMA) on to natural rubber (NR) has been studied. Seeded emulsion polymerization was used to graft such monomers. Different concentrations of each monomer have been examined. The effects of the concentrations of the monomers were evaluated by ¹H NMR spectroscopy and Transmission Electron Microscopy (TEM). There is good evidence for the formation of graft copolymers of modified NR under the core-shell morphology as well as satisfactory efficiency of grafting in the presence of high concentrations of both monomers. At lower concentrations the grafting were not significant. The images of the morphology was obtained by Transmission Electron Microscopy after the preparation of the samples by cryo-sectioning and chemical fixation techniques.     

Study on degrees of mesomorphic zone of polymerII. Determination of the degree of mesomorphic zone of eucommia ulmoides gum and natural rubber by dynamic mechanical thermal analysis and differential scanning calorimetry

In a foregoing article, a new method based on dynamic mechanical thermal analysis(DMTA)for determining the degrees of crystallinity of the natural rubber (NR) and the eucommia ulmoides (EU) gum, with different crosslink densities, has been established. In order to verify the effectiveness of this method, in the present paper, the degrees of crystallinity of NR and EU gum with different crosslink densities will be determined by differential scanning calorimetry (DSC). The results indicate that the degrees of crystallinity determined by DMTA are much higher than those of DSC. This is because the degree of crystallinity determined by DMTA involves not only the ratio of the crystalline zone, but also the ratio of the mesomorphic zone, while the degree of crystallinity tested by DSC includes only the ratio of the crystalline zone. So, the degree of crystallinity, the degree of mesomorphic zone and the degree of amorphous zone of NR and EU gums with different crosslink densities can be quantitatively determined by the combination of DMTA and DSC. The results show that the degree of crystallinity, the degree of mesomorphic zone and the degree of amorphous zone of NR (crystallized at −25 °C for 12 h) and EU gum are 33%, 53%, 14% and 34%, 54%, 13%, respectively. For NR, increasing the crosslink density or decreasing the induced time will decrease the degree of crystallinity and the degree of mesomorphic zone simultaneously, but will increase the degree of amorphous zones. For EU gum, increasing the crosslink density will decrease the degree of crystallinity and increase the degree of amorphous zone, but keep the degree of mesomorphic zone invariably consistent within the critical crystallization point, which is approximately 55%. At the end of the paper, the impact of crystallization on the mechanical properties of EU gum and NR is discussed as well.     

Experimental determining the mechanical and stiffness properties of natural rubber FRT triangle elastic joint composite reinforcement by glass fibers and micro/nano particles

Rubber is a type of material widely used in industries for waterproofing, storing and transporting fluids, energy shock dampers, thermal insulation, and corrosion protection. Natural Rubber (NR) polymer is a material that is extensively used in the automotive industries because of its unique properties such as high strength, low weight, and excellent corrosion resistance. In this study, the mechanical properties of NR based car bumpers were investigated by adding reinforcing particles to it. The used reinforcing materials include SiC, MgO, Fe₂O₃ particles and Glass fibers, which were added to the base material at different sizes and weight percentages including 4% and 8%. Composite samples were made by mixing NR with reinforcement using special rollers and then vulcanized in the furnace at a specific temperature, to achieve standard torque, for each individual sample. To better characterize produced samples and recognizing of elements and their bonds, FT-IR, TGA, and XRD analysis were done. All specimens were subjected to hardness and tensile tests; their axial and radial stiffness, as well as their component durability tests, were investigated and compared with the base material. The maximum results were obtained from the mechanical property tests belonged to the reinforced specimen with 8%w.t. Glass fibers, that the ultimate tensile strength, hardness, and durability were 57%, 32%, and 33% higher than that of the non-reinforced NR sample, respectively. The SEM and SEM-MAP images of the fracture cross-section showed a crack growth inhibition effect in the samples by adding glass fibers.     

Simple test kit based on colorimetry for quantification of magnesium content in natural rubber latex by miniaturized complexometric titration without using masking agent

A simple, low-cost and portable field test kit based on colorimetry with detection by naked eye was developed for determination of magnesium content in natural rubber latex (NRL). The miniaturized complexometric titration between Mg²⁺ and EDTA without any masking agent was a key reaction in this development, which was designed according to the concept of green chemistry by reduction of waste generation and chemical and time consumption. The system enabled quantification of magnesium content in NRL at low concentration with the detection limit being <50 mg L⁻¹, small sample volume uptake (0.18 g, sampling by a small spoon) and use of <1.5 mL reagent volume which was >70 times less than that applied in the conventional method. Moreover, with the presence of potential interference ions, greater selectivity towards magnesium was observed. Furthermore, the reagents used in our developed test kit were stable for >6 months at room temperature. The results obtained on real samples were in agreement with those obtained from the conventional complexometric titration (ISO 17403: 2014(E)) method. The proposed technique provides a low-cost, rapid, simple, selective and on-site analysis of magnesium content in NRL.     

Curing degree prediction for S-TBBS-DPG natural rubber by means of a simple numerical model accounting for reversion and linear interaction

The paper presents a simple numerical model able to provide directly kinetic constants and reliable numerical rheometer curves for S-TBBS-DPG natural rubber. The approach is suitable to calculate the kinetic constants and maximum torque (MH) at any S-TBBS-DPG concentration, following a 3D mathematical interpolation/extrapolation procedure, when kinetic constants on few grid points of S-TBBS-DPG concentrations are available. In particular, the possibility to estimate with sufficient accuracy the behavior of natural rubber at any intermediate concentration of S-TBBS-DPG having engineering relevance has been proved, calibrating the model by means of simple closed form standard best fitting on few experimental data. The model used is a three kinetic parameters one, derived from the well known Han's and co-workers approach, where constants have been evaluated normalizing experimental rheometers curves following the commonly accepted Sun and Isayev method. The procedure has been validated against experimentally obtained rheometer curves by means of inverse analysis, exhibiting excellent prediction capabilities. The approach may be used for practical purposes in order to avoid expensive and cumbersome experimental investigations.     

Surface treatment of PET fiber by EB-irradiation-induced graft polymerization and its effect on adhesion in natural rubber matrix

Aiming to develop a high performance fiber-reinforced natural rubber (NR) without using resorcinol formaldehyde latex (RFL) adhesives of environmental load substances, a special technique using electron beam (EB) irradiation-induced graft polymerization was applied to high-modulus polyethylene terephthalate (PET) fibers. Although PET is chemically inert, acrylate functional silane could be graft-polymerized onto the PET fiber surface by this special technique. The composite of NR and grafted PET fibers indicated a linear increase in the initial modulus with the fiber content. The fiber reinforced rubber with a good performance was obtained in the system of NR and grafted PET fibers.     

Properties of polymer track membranes modified by grafting with poly(2-methyl-5-vinylpyridine) and poly(N-isopropylacrylamide)

The properties of track membranes (TM) based on poly(ethylene terephthalate) (PETP) and polypropylene (PP) and modified by radiation-induced graft polymerization of 2-methyl-5-vinylpyridine (MVP) andN-isopropylacrylamide (NIPAA) were studied. The rate of grafting and the limiting degree of grafting increase linearly as the pore diameter of TM increases. The gasdynamic and hydrodynamic pore diameters of modified TM were determined. The dependence of water permeability of TM modified by grafting with poly(2-methyl-5-vinylpyridine) (PMVP) on the degree of grafting passes through a maximum, which, according to the data of wetting angle measurements, corresponds to the maximum hydrophilicity. The negative χ-potential of TM changes sign after modification by grafting with PMVP. Thermosensitive TM based on PETP and PP were prepared by radiation-induced graft polymerization of NIPAA. The structure of modified TM was studied by electron microscopy and atomic force microscopy. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 858–864, May, 2000.