Interfacially modified LDPE/GTR composites with non-polar elastomers: From microstructure to macro-behavior

This paper provides some new insights into the mechanism of interaction and modifications in thermoplastic composites based on low density polyethylene (LDPE), ground tire rubber (GTR) and non-polar elastomer. The composites were prepared using a co-rotating twin-screw extruder at variable LDPE/GTR ratio and constant elastomer content. Two types of commercial elastomer were applied: styrene-butadiene-styrene (SBS) block copolymers (Kraton^®) with different topologies (linear/branched) and partially cross-linked butyl rubbers (Kalar^®) with different Mooney viscosities. Processing characteristics, static mechanical properties (tensile strength, elongation at break, hardness), dynamic mechanical properties, thermal properties and morphology of the resulting thermoplastic composites were investigated. Microstructure analysis shows that modification of LDPE/GTR composites with non-polar elastomers caused encapsulation of GTR particles within the elastomer phase. This phenomenon has significant influence on macro-behavior of thermoplastic composites based on LDPE/GTR blends. The results indicate that SBS copolymer improves interfacial interactions between GTR and LDPE, which enhances mechanical and thermal properties of the composites. On the other hand, cross-linked butyl rubber showed partial compatibility with LDPE and low compatibility with GTR particles.     

Chemical modification of butyl rubber. II. Structure and properties of poly(ethylene oxide)-grafted butyl rubber

Poly(ethylene oxide)-grafted butyl rubbers (IIR-g-PEOs), which were synthesized from potassium salt of polyethylene glycol monomethyl ether (PEGM) and chlorinated butyl rubber, were found to behave like thermoplastic elastomers. The poly(ethylene oxide) (PEO) content of these amphiphilic polymers was ca. 10 wt %, and their PEO lengths were 750, 2000, and 5000, respectively. The grafted segments of PEO in butyl rubber (IIR) aggregated to form the PEO domains in IIR matrix. At constant PEO content, the longer the PEO segment length, the larger the size and the crystallinity of PEO domains became. This PEO domain worked as a cross-linking site and a reinforcing filler. The degree of swelling in water of IIR-g-PEO film that was prepared from PEGM-5000 was largest, but its emulsification ability was smallest among them. © 1995 John Wiley & Sons, Inc.     

硫酸铁铵催化合成肉桂酸酯

利用十二水合硫酸铁铵为催化剂,使肉桂酸与醇类发生酯化反应合成了肉桂酸甲酯、肉桂酸乙酯、肉桂酸正丙酯、肉桂酸正丁酯、肉桂酸异丁酯、肉桂酸正戊酯和肉桂酸异戊酯,测定了各种酯的沸点（或熔点）折光率、元素组成和IR。     

Green biocomposites of chitosan dispersed in natural rubber matrices,and their urea controlled-release application

A green biocomposite comprising chitosan dispersed in partially cross-linked natural rubber matricesd was prepared. The starting materials and biocomposites were characterized by means of Fourier transform–infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. Chitosan was found well dispersed in partially cross-linked natural rubber matrices indicating that natural rubber latex is successfully stabilized by sodium dodecyl sulfate. The swelling study of the biocomposites was carried out in several solvents. The biocomposites were used for the controlled-release of urea. The release behavior was found consistent, controlled, and prolonged over a period of 72 h. The Korsmeyer–Peppas model was applied to the experimental data and the possible release mechanism was found Fickian diffusion, which indicates that the polymer relaxation time is much greater than the characteristic solvent diffusion time.     

高分子力学阻尼材料的研究——Ⅰ.填料对氯化丁基橡胶的力学阻尼行为的影响

本文研究了填料对氯化丁基橡胶在玻璃化转变温度以上的温度范围里的力学阻尼行为的影响。在T_g-36℃的范围里,通过测定填料表面吸附的结合橡胶和填料的表面积,用填料-橡胶界面积函数和单位重量橡胶在填料表面占据的表面积等参数,研究了填料-橡胶相互作用对氯化丁基橡胶的力学阻尼行为的影响;用界面积函数和填充胶中填料的体积份数之积研究填料-填料相互摩擦对它的力学阻尼行为的影响。发现在填料浓度低时,氯化丁基橡胶的力学阻尼行为主要受填料-橡胶相互作用的影响,高浓度时,填料-填料相互摩擦显著地改善了它的力学阻尼行为。     

pH-Sensitive micelles with cross-linked cores formed from polyaspartamide derivatives for drug delivery

A series of polyaspartamide derivatives were synthesized by grafting O-(2-aminoethyl)-O'-methylpoly(ethylene glycol) 5000 (MPEG), 1-(3-aminopropyl) imidazole (API), and cinnamate onto polysuccinimide (PSI) with the respective degrees of substitution adjusted by the feed molar ratio. The chemical structure of the prepared polymer was confirmed using FT-IR and (1)H NMR spectroscopy. A new pH-sensitive polymeric micelle based on the synthesized polymer was prepared and characterized, and its pH-sensitive properties were characterized by the measurement of light transmittance and particle sizes at varying pH values. pH-dependent aggregation and deaggregation behavior was clearly observed in the polymer aqueous dispersion system. Photo-cross-linking of the cinnamate branches cross-linked the core of the micelles. The core cross-linked micelles showed high stability over a wider pH range and displayed obvious pH-dependent swelling-shrinking behavior instead of micelle-unimer transition behavior. This micelle system overcame the drawback of the facile disintegration of normal polymeric micelles and showed obvious delayed paclitaxel release in in vitro drug delivery experiments.     

The influence of physical ageing on the electrical and swelling behaviour of ternary rubber vulcanizates

The effects of pre-annealing ageing time at 70 °C on the electrical properties and swelling behaviour in kerosene of a new tri-block rubber based on blends of natural rubber (NR) and different concentration ratios of both styrene-butadiene rubber (SBR) and butyl rubber (IIR), all incorporating 40 phr (parts per hundred parts of rubber by weight) of high abrasion furnace (HAF) carbon black, were investigated.

It was found that the interspacing distance, d, between carbon particles or aggregates is greatly affected by physical ageing and also by the rubber ratios in the test specimens.

Moreover, the degree of swelling, Q (%), in kerosene was found to decrease with both physical ageing and IIR content of the specimen.     

Application of the acid-base approach to explain adhesive properties of modified rubber coatings

The influence of the content and composition of polymeric petroleum resins (PPRs) on the properties of incongealable sealants based on butyl rubber was studied. It was shown that the introduction of PPR B grade increases the adhesion ability of these sealants to duralumin. It was concluded that use of the acid-base approach is a good tool for explaining the nature of adhesive relationships.     

The Effect of Hollow Corundum Microspheres on the Properties of Materials Based on Carbon-Chain Rubbers

The effect of hollow corundum microspheres on the properties of a rubber mixture based on a combination of carbon-chain rubbers was studied. Owing to the formation of a cross-linked structure of microspheres with a rubber matrix and its additional structuring with Hexol KhPI adhesion modifier, it was shown that it is possible to increase the physicomechanical characteristics and the heat and fire resistance of rubber by establishing the optimal microsphere content in it.     

Reaction of chlorine-containing polymers with living polymers

A graft polymer was prepared by means of the coupling reaction of chlorinated ethylene–propylene terpolymer with living polystyrene, obtained with a sodium–naphthalene complex as initiator, under various conditions; the grafting efficiency and the percentage of grafting are discussed. Poly(chloroprene), chlorinated butyl rubber, poly(vinyl chloride), poly(epichlorohydrin), and epichlorohydrin–ethylene oxide copolymer were also used as chlorine-containing polymers. The grafting efficiencies were found to be in the following order: chlorinated butyl rubber > poly(epichlorohydrin) > epichlorohydrin-ethylene oxide copolymer > chlorinated ethylene-propylene terpolymer > poly(chloroprene) > poly(vinyl chloride). A graft polymer was obtained from the reaction between chlorinated ethylene–propylene terpolymer and living poly(isoprene), with butyllithium in benzene. The undesirable metal–halogen interchange reaction was considerable.     

Cross-linked polyvinylpyrrolidones with increased affinity and specificity for methyl orange and its homologs

Polyvinylpyrrolidones of various degrees of cross-linkage have been prepared by radical polymerization of N-vinylpyrrolidone with methylenebisacrylamide to regulate the fraction of cross-linkage. The insoluble polymers obtained were examined for their ability to bind methyl orange and its homologs, methyl orange, ethyl orange, propyl orange, and butyl orange at 5, 15, 25, and 35°C, respectively, in an aqueous solution. The first binding constants and the thermodynamic parameters that accompanied the binding were calculated. For any particular dye the extent of binding, the absolute magnitude of ΔF°, and the value of ΔS° increased as the degree of cross-linkage increased, starting with water-soluble polyvinylpyrrolidone (zero cross-linkage) and proceeding to the polymer with high cross-linking density. This behavior can be accounted for in terms of more extensive hydrophobic domains in the cross-linked polymeric matrix that enhances hydrophobic interactions in the binding process. Moreover, the cross-linked macromolecule polymerized in the presence of methyl orange and then stripped of the bound methyl orange shows substantially stronger binding for this small molecule than the polymer cross-linked in the absence of methyl orange. In contrast, the cross-linked polymer prepared similarly in the presence of the larger molecule, butyl orange, exhibits decreased affinity toward the smaller consolute, methyl orange, than either of the other polymers described. It seems, therefore, that the polymeric matrix provides favorable binding sites or pockets that can accommodate a specific small molecule. The preparative procedure, which uses a small-molecule template, molds into the polymer some structural specificity in the binding of small molecules.     

Raman investigation of thermoplastic vulcanizates based on hydrogenated natural rubber/polypropylene blends

Raman spectroscopy including mapping technique appears as a powerful technique for the characterization of polymer blends like thermoplastic elastomers (TPEs) and thermoplastic vulcanizates (TPVs). The Raman spectra of polymers blends such as natural rubber/polypropylene (NR/PP) and 65% hydrogenated natural rubber/polypropylene (65%HNR/PP) were identified and the phase distribution was determined. The study was driven for the same type of blends in TPEs state and TPVs state obtained after to 2 different processes, either peroxide cure or sulfur cure. The morphology of TPEs and TPVs obtained by Raman spectroscopy were compared and confirmed using scanning electronic microscopy.Raman mapping shows that the phase morphology of NR/PP, 65%HNR/PP, were characterized as continuous rubber phase morphology of the thermoplastic elastomers (TPEs) and a fine dispersion of cross-linked rubber phase in a continuous matrix of the thermoplastic vulcanizates (TPVs). Raman spectroscopy is demonstrated to be a reference to determine the content ratio of each component in the TPVs. Moreover, Raman mapping could be used to calculate the phase size of cross-linked rubber phase dispersed in the thermoplastic vulcanizates (TPVs).     

Bromination of butyl rubber with a sodium bromide-tert-butyl hypochlorite system

The kinetics of bromination of butyl rubber by a sodium bromide-tert-butyl hypochlorite system is studied. The orders of reaction with respect to reactants are determined, the empirical dependence of the reaction-rate constant on temperature is found, and the activation parameters of reaction are estimated. It is shown that the bromination of isoprenyl units of butyl rubber results in substitution products of a predominantly exomethylene structure that provides a high rate of rubber vulcanization by zinc oxide.     

Synthesis and properties of butyl rubber–poly(ethylene oxide) graft copolymers with high PEO content

Butyl rubber‐poly(ethylene oxide) (PEO) graft copolymers with high PEO content (40–83 wt %) were synthesized by the functionalization and activation of the double bond moiety of butyl rubber containing high (7 mol %) isoprene content and subsequent reaction with PEO of different molecular weights from 750 to 5000 g/mol. The properties of these copolymers, along with other butyl rubber‐PEO graft copolymers were studied in films and in aqueous solution. Despite the high PEO content, films of the copolymers were quite stable in water with respect to mass loss and were capable of releasing an encapsulated probe molecule in a manner that was dependent on the PEO content. At high PEO content they were resistant to the adhesion and growth of C2C12 cells. Despite the resistance of films to dissolution, it was possible to prepare nanosized aqueous assemblies via a THF‐water exchange process and the sizes of the assemblies were tuned by their method of preparation. The assemblies were also able to encapsulate a probe molecule and were found to be nontoxic in vitro. Combined, this set of properties makes these new amphiphilic copolymers promising for a wide range of potential applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3383–3394     

Synthesis and characterization of photosensitive cinnamate-modified cellulose acetate butyrate spin-coated or network derivatives

The photochemical behavior of photosensitive materials obtained by spin-coating or network synthesis of a cellulosic polymer bearing photo-cross-linkable cinnamate groups was investigated. First, cinnamate groups were grafted on a cellulose acetate butyrate polymer, with different grafting densities. The photochemical properties of the polymers were studied in solution by UV–visible and ¹H NMR spectroscopy. Then spin-coated films and networks were prepared and characterized as a function of the number of cinnamate groups per cellulosic unit. The water-wetting properties of both surfaces were studied by dynamic contact angle measurements, before and after photoirradiation, and subsequent heating. The surfaces obtained by the two methods have significantly different behaviors that can be assigned to the distinct photochemical pathways of the cinnamate groups upon irradiation depending on the sample preparation. Indeed, dimerization reaction is evidenced as the main process in the spin-coated films while the expected isomerization is predominant at the surface of the polymer networks.     

Interrelationship between total volatile organic compounds emissions,structure and properties of natural rubber/polycaprolactone bio-blends cross-linked with peroxides

Natural rubber/polycaprolactone (NR/PCL) bio-based blends with different organic peroxides were prepared using an internal batch mixer and subsequently cross-linked at 170 °C. Two types of commonly used organic peroxides, dicumyl peroxide and di(tert-butylperoxyisopropyl)benzene peroxide, were applied as free-radical initiator. Cross-linking efficiency of NR/PCL blends were investigated using oscillating disc rheometer measurements, followed by infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis and tensile testing. Total volatile organic compounds (TVOCs) emissions were determined using headspace analysis integrated with gas chromatography with flame ionization detector. Determined TVOCs emissions varying in range 21.6–52.1 μg/g and generally value of this parameter decreased with increasing content of PCL phase in studied blends or with application of more efficient di(tert-butylperoxyisopropyl)benzene peroxide as cross-linking agent. It was found that increasing of TVOCs parameter indicated deterioration of mechanical properties of NR/PCL blends, which corresponded with the changes in chemical structure and thermal properties of cross-linked NR/PCL. This confirms that evaluation of TVOCs parameter is interesting alternative for “conventional methods” to characterization of the studied bio-based blends.     

Super impact strength of blends prepared from regular HIPS and poly(butyl acrylate)‐block‐poly(styrene) obtained by RAFT polymerization

S‐allyl‐4‐methyldithiobenzoate was synthesized and used as a chain transfer agent for the RAFT polymerization of butyl acrylate to produce a functionalized acrylic rubber. A solution of 8 wt% of this functionalized rubber was prepared in styrene and polymerized to generate a material called acrylic rubber‐modified polystyrene (AMP) constituted by well‐dispersed particles of poly(butyl acrylate)‐block‐poly(styrene) into a polystyrene matrix. Impact strength of injection‐molded samples of AMP was measured and compared with the general purpose polystyrene (GPPS) and the high impact polystyrene (HIPS). AMP itself showed an impact strength value similar to GPPS; however, when AMP was blended with conventional HIPS, the resulting material exhibited an improvement of 76–91% as compared to HIPS by itself, without affecting negatively tensile properties. Transmission electron microscopy analysis revealed both kinds of dispersed phases, i.e. the typical salami particles of polybutadiene coming from HIPS (size: 0.5–2 µ) and small particles from poly(butyl acrylate)‐block‐poly(styrene) (size: ～50 nm). We clearly showed that such a bimodality of the particle size distribution caused the positive synergistic effect on impact strength. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis of Aliphatic Esters of Cinnamic Acid as Potential Lipophilic Antioxidants Catalyzed by Lipase B from Candida antarctica

Immobilized lipase from Candida antarctica (Novozyme 435) was tested for the synthesis of various phenolic acid esters (ethyl and n-butyl cinnamate, ethyl p-coumarate and n-butyl p-methoxycinnamate). The second-order kinetic model was used to mathematically describe the reaction kinetics and to compare present processes quantitatively. It was found that the model agreed well with the experimental data. Further, the effect of alcohol type on the esterification of cinnamic acid was investigated. The immobilized lipase showed more ability to catalyze the synthesis of butyl cinnamate. Therefore, the process was optimized for the synthesis of butyl cinnamate as a function of solvent polarity (logP) and amount of biocatalyst. The highest ester yield of 60.7 % was obtained for the highest enzyme concentration tested (3 % w/w), but the productivity was for 34 % lower than the corresponding value obtained for the enzyme concentration of 1 % (w/w). The synthesized esters were purified, identified, and screened for antioxidant activities. Both DPPH assay and cyclic voltammetry measurement have shown that cinnamic acid esters have better antioxidant properties than cinnamic acid itself.     

Preparation of high damping elastomer with broad temperature and frequency ranges based on ternary rubber blends

Based on the blends of chlorinated butyl rubber (CIIR), nitrile butadiene rubber (NBR) and chloroprene rubber (CR), a kind of high damping elastomer with broad temperature and frequency ranges is prepared. CIIR/NBR binary blend is prepared to take advantage of the immiscibility and the large difference in cross‐link density of the different phases caused by the curatives and accelerators migration. The dynamic mechanical analysis reveals that the binary blend was immiscible and its loss factor (tanδ) versus temperature curves show two separated and expanded loss peaks when compared with those of pure cured CIIR and NBR. In order to improve its damping properties at room temperature, the third component CR with the polarity between CIIR and NBR was blended into the binary blend. The resulted CIIR/NBR/CR ternary blend has gained effective damping properties (tanδ > 0.3) in the temperature range of ?86.4 to 74.6°C and the frequency range of 10^?2 to more than 10⁹ Hz. Other effects on the damping properties of the ternary rubber were also studied. Copyright © 2013 John Wiley & Sons, Ltd.     

Chemical modification of butyl rubber. III. Butyl rubber with D-maltose derivative as pendant groups

A new type of amphiphilic elastomer was synthesized, which consisted of butyl rubber and a D-maltose derivative as a backbone and side groups, respectively. The synthesis was accomplished by the sequence of the three following reactions: (1) Hydroxyl groups of D-maltonolactone were protected by a trimethylsilyl group. (2) The resulting maltonolactone derivative was subjected to a reaction with chemically modified butyl rubber having pendant amino groups. (3) The protecting trimethylsilyl groups on the maltose residues were removed by treating with tetra-n-butylammonium fluoride. This new amphiphilic elastomer behaved as a thermoplastic elastomer and showed good mechanical properties. The saccharide seg-ments aggregated in the hydrophobic butyl rubber matrix to form a microphase-separated structure, as confirmed by differential scanning calorimetry, transmission electron mi-croscopy, small-angle x-ray scattering, and dynamic mechanical measurements. The ag-gregated saccharide domains are estimated to function both as crosslinking sites and rein-forcing fillers in the rubber matrix. © 1995 John Wiley & Sons, Inc.