Lianshi Wang

The synthesis and characterization of supramolecular elastomers based on linear carboxyl-terminated polydimethylsiloxane oligomers

Supramolecular elastomers obtained through a two-step reaction of linear carboxyl-terminated polydimethylsiloxane oligomers (PDMS–COOH2) with diethylenetriamine (DETA) and urea show reasonable hysteresis and acceptable self-healing properties. The results of temperature-dependent infrared analysis suggest the existence of hydrogen bonding interactions with good thermal reversibility in the matrix. Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses demonstrate that the supramolecular network structure is totally amorphous at room temperature. The rheological, mechanical and self-healing properties are closely related to the PDMS chain length, whereas the stability seems to be independent of the PDMS chain length. The viscoelastic properties of these materials are believed to be the result of entangled chains in the amorphous matrix. Only the hydrogen bonds formed by 1,1-dialkylurea groups and imidazolidone derivatives serve as effective crosslinks for contributing to the stability of the supramolecular network.

Properties of Natural Rubber Vulcanizates/Nanosilica Composites Prepared Based on the Method of In-situ Generation and Coagulation

Using the characteristics of silica sol dispersing well in water and easy formation of silica gel when the silica sol is heated, by mixing a system of concentrated natural rubber latex and silica sol, the silica sol can in-situ generate SiO2 particles when heated. After coagulation of the mixed system, natural rubber/nanosilica composites C(NR/nSiO2) were obtained. The composites C(NR/nSiO2) and their vulcanizates were studied using a rubber processing analyzer (RPA), dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). The influence of silica contents on the C(NR/nSiO2) vulcanizates mechanical properties, cross-linking degree, Payne effect, dissipation factor (tanδ), and the particle size and dispersion of SiO2 in NR were investigated. The results obtained were compared with the NR/SiO2 composites based on traditional dry mixing of bale natural rubber and precipitated silica (white carbon black). The results showed that when using a sulfur curing system with a silica coupling agent ...

Reaction mechanism of suspension graft copolymerization of styrene and acrylonitrile in the presence of ethylene propylene diene terpolymer

A sequential synthesis of ethylene propylene diene terpolymer-g-poly (styrene-co-acrylonitrile) (EPDM-g-SAN) graft copolymers was carried out via suspension graft copolymerization using benzoyl peroxide (BPO) as an initiator. After the synthesis, the final product was separated by Soxhlet extraction to obtain the styrene-acrylonitrile free copolymer (SANf), non-grafted EPDM and EPDM-g-SAN, which were subsequently characterized by 1H-NMR and FTIR analyses to verify their purity. The dependence of the reaction behaviors on the reaction time was systematically investigated. When the reaction time was varied from 20 min to 100 min, the GPC analysis of the obtained SANf showed a bimodal profile, due to the co-existence of SANL and SANH free copolymers, of low and high molecular weights, which were respectively formed by chain transfer termination and bi-radical termination of the free polymeric radicals. These results revealed that the graft site initiation was dominated by free polymeric radicals attacking the EPDM backbones at the beginning of the grafting process, accompanied by non-grafting copolymerization reactions. On the other hand, the GPC analysis of non-grafted EPDM and EPDM-g-SAN revealed that the reaction mechanism also involved the chain scission of the EPDM molecules which were partly incorporated into the backbone of EPDM-g-SAN and the incorporation of SANf into the grafted chains (g-SAN), resulting in added grafted EPDM and grafting ratio. Furthermore, a novel and effective method was developed to determine the number of g-SAN, and thus the number-average molecular weight of g-SAN was estimated.

Carbon Black Filled Powdered Natural Rubber

Carbon black (CB) filled powdered natural rubber [P(NR/N234)] was prepared using a patented method of latex/CB coagulation technology. The influence of curing recipes and CB contents on the curing, mechanical, and dynamic properties were studied in depth, and the results were compared with that of NR/N234 compounds based on traditional dry mixing of bale NR and CB. The results showed that, compared with NR/N234, P(NR/N234) showed higher tensile strength, tear strength, rebound elasticity and flexibilities, and the antiabrasion properties were similar, while the dynamic temperature-build-up and dynamic compression permanent set were about 50% of that of NR/N234. The analysis based on scanning electron micrographs (SEM) and the Payne effect showed that the fine dispersion of CB in the rubber and the enhanced interaction between CB and rubber contributed to the excellent properties of P(NR/N234), sufficient that they make P(NR/N234) a potential material for the tread compounds of heavy-duty all-steel cord radial tires.

Toughening Effect of Poly(ethene-co-1-butene)-graft-methyl Methacrylate and Acrylonitrile on Styrene-acrylonitrile Copolymer (SAN)

Poly(ethene-co-1-butene)-graft-methyl methacrylate-acrylonitrile (PEB-g-MAN), synthesized by suspension grafting copolymerization of methyl methacrylate and acrylonitrile onto PEB, was blended with styrene-acrylonitrile copolymer (SAN). The mechanical properties, phase structure, toughening mechanism, miscibility, and thermal stability of the SAN/PEB-g-MAN blends were studied using a pendulum impact tester, tension tester, scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TG). The results showed that PEB-g-MAN has an excellent toughening effect on SAN resin. The notched impact strength of the blends (containing 25 wt% PEB) was 63.3 kJ/m2, which was nearly 60 times that of SAN resin. The brittle-ductile transition of SAN/PEB-g-MAN blends occurred when the weight percentage of PEB was between 17.5 and ∼20 wt%. SAN and PEB-g-MAN were partially miscible. The toughening mechanism of the blends changed with the PEB content. When the PEB content was low, the toughening mechanism of the blends was branching and termination of cracks with slight cavitation. As the content of PEB increased, the toughing mechanism gradually changed from branching and termination of crack with slight cavitation to both branching and termination of crack and cavitation, to extensive cavitation, and finally to shear yielding accompanied by cavitation. The phase structure of the blends changed from a “sea-island’’ structure to a cocontinuous structure as the PEB content increased. ATG analysis showed that the thermal properties of the SAN resin in the blends were enhanced by adding the PEB-g-MAN.

Synthesis of EPDM-g-MAN by suspension graft copolymerization and its toughening effect on SAN resin

Suspension graft copolymerization of methyl methacrylate and acrylonitrile onto ethylene–propylene–diene terpolymer (EPDM) was carried out under different reaction conditions. A series of graft products of EPDM-graft-methyl methacrylate and acrylonitrile (EPDM-g-MAN), characterized by Fourier-transform infrared spectroscopy, was blended separately with styrene–acrylonitrile (SAN) resin to investigate their toughening effect on SAN matrix. The relationship between the polarity of EPDM-g-MAN and toughness of EPDM-g-MAN/SAN resin blends (AEMS) was evaluated. The compatibility and morphologies of AEMS were probed by dynamic mechanical analysis, transmission electron microscopy, and scanning electron microscopy to determine the toughing mechanism of the blends. Thermogravimetry results showed that the thermal stability of AEMS was enhanced with the incorporation of EPDM-g-MAN graft copolymer.

Carbon Black–Filled Styrene Butadiene Rubber Masterbatch Based on Simple Mixing of Latex and Carbon Black Suspension: Preparation and Mechanical Properties

An improved process was developed for the production of carbon black (CB)–filled styrene butadiene rubber masterbatch (SBR-CB-MB) using a simple latex/CB mixing technology; the improvement comprised processing the CB as an emulsifier-free aqueous suspension by high-rate shearing. Tensile and tear strength, dynamic compression behaviors, the Payne effect, equilibrium swelling and bound rubber of the SBR-CB-MB and dry mixing CB filled SBR (SBR-CB-DM), covering a wide range of CB loading (45–70 phr), were investigated and compared. It was found that the tensile and tear strength, heat buildup and compression set, abrasion volume loss, and the Payne effect of the SBR-CB-MB were lower than those of the SBR-CB-DM, while the bound rubber content were higher, indicating good CB/rubber interaction in the SBR-CB-MB. SEM analysis showed that no free CB could be found on the surface or inside of the granular SBR-CB-MB particles, indicating good CB dispersion in the rubber matrix.

Toughening Effect of Ethylene Propylene DieneTerpolymer-Graft-Styrene-Acrylonitrile Copolymer (EPDM-g-SAN) on SAN Resin

The reaction product EPDM-g-SAN, synthesized by suspension graft copolymerization of styrene (St) and acrylonitrile (AN) in the presence of ethylene-propylene-diene terpolymer (EPDM), was blended with a commercial styrene-acrylonitrile copolymer (SAN resin) to prepare AES blends with high impact strength. The effects of AN mass percentage in the St-AN comonomer mixture (f AN), EPDM mass percentage in the feed of EPDM and St-AN (f EPDM) and reaction time on monomer conversion ratio (CR), grafting ratio (GR), and AES notched Izod impact strength were characterized. The notched Izod impact strength of AES containing 15 wt% EPDM reached its maximum with f AN of 40 wt% and f EPDM of 45 wt%; this was attributed to the polarity of the SAN copolymer obtained being appropriate with that of the SAN resin matrix. The dependences of GR and the notched Izod impact strength of AES containing 25 wt% EPDM on the reaction time were in rough agreement. The effect of EPDM content on the AES notched Izod impact strength indicated that the brittle-ductile transition of AES occurred for an EPDM content from 12.5 to 15 wt%. TEM and SEM analysis showed that the phase structure of AES exhibited a “salami” like structure, and the toughening mechanism of AES was shear yielding of the SAN resin matrix, which endowed AES with excellent toughness.

A Study of the Synthesis of EPDM-g-MAN and Toughness of its Blend with SAN (AEMS)

Ethylene–propylene–diene–methyl methacrylate/acrylonitrile terpolymers (EPDM-g-MAN) were synthesized by comonomers methyl methacrylate and acrylonitrile (MMA-AN) grafted on EPDM macromolecules with solution graft copolymerization. The engineering plastics of the blend of EPDM-g-MAN with SAN (AEMS) were prepared by blending EPDM-g-MAN with SAN resin. The effect of AN/MMA-AN weight percentage (f AN) on monomer conversion ratio, grafting ratio, and grafting efficiency of the graft copolymerization and the notched Izod impact strength of AEMS were investigated. The notched Izod impact strength of AEMS, prepared by blending SAN with EPDM-g-MAN, was synthesized under our optimum S2 reaction conditions, with EPDM/MMA-AN weight proportion of 50/50 and f AN of 10 wt%, presenting a peak with the maximum value of 61.0 kJ/m2. The microstructure of AEMS prepared with S2 reaction conditions showed that when the polarity of EPDM-g-MAN was appropriate, the EPDM phase formed a pseudocontinuous phase in the SAN matrix and the interfacial adhesion was strong, which could induce shear yielding of the SAN matrix. Differential scanning calorimetry analysis showed that there was good compatibility between SAN resin and EPDM-g-MAN synthesized with f AN of 10 wt% and a EPDM/MMA-AN weight ratio of 50/50.

Graft Polymerization of Methyl Methacrylate- Acrylonitrile onto Poly(ethene-co-1-butene) and Its Toughening Effect on SAN Resin

Poly(ethene-co-1-butene)-graft-methyl methacrylate-acrylonitrile (PEB-g-MAN) was prepared by suspension grafting copolymerization of methyl methacrylate (MMA) and acrylonitrile(AN) onto PEB. PEB-g-MAN/SAN resin blends (ABMS) were prepared by blending PEB-g-MAN with styrene-acrylonitrile copolymer (SAN resin). The effects of AN/(MMA+AN) feed ratio (fAN), PEB/(PEB+MMA+AN) feed ratio (fPEB) and benzoyl peroxide (BPO) dosage on the monomer conversion ratio (CR), rubbers grafting ratio (GR), grafting efficiency (GE) of the copolymerization and the toughening effect of PEB-g-MAN on the SAN resin were investigated. FTIR quantitative analysis showed that when the weight percent of AN unit in the unextracted product was 21.5 wt% with fAN of 25 wt%, the toughening effect of unextracted PEB-g-MAN on SAN resin was the highest. Gel permeation chromatography (GPC) analysis showed that when fAN was 25 wt%, the grafted copolymer had the lowest molecular weight and ABMS had highest toughness. Transmission electron microscopy (TEM) analysis showed that the highest toughness occurred when the phase structure of ABMS was cocontinuous with fAN of 25 wt%. When fAN was 25 wt% PEB-g-MAN domains have numerous small SAN domains in them, which was occlusion structure. Scanning electron microscopy (SEM) analysis indicated that the ABMS fracture surfaces had plastic flow visible, which looked like a craze fibers morphology, for the sample with highest impact strength (fAN = 25 wt%). Dynamic mechanical thermal analysis (DMA) showed that the miscibility of the PEB phase and SAN phase improved after graft copolymerization of MMA and AN onto PEB.