Photocrosslinking of styrene–isoprene–styrene; effect of benzoin and ethylene glycol dimethacrylate on physical properties

Crosslinking reaction of polymer by ultraviolet (UV) irradiation has been important in industries. In this work, photocrosslinking of styrene–isoprene–styrene (SIS) triblock copolymer in the presence of benzoin photoinitiator and a dimethacrylate monomer as crosslinking agent was investigated. Curing of samples was initiated under UV irradiation. Benzoin was used as photoinitiator because it contains chromophore group that could absorb UV irradiation. Ethylene glycol dimethacrylate (EGDMA) was used as crosslinking agent, since it has alkene functional groups that could react with the alkene group of SIS. ATR-FTIR spectra of samples show that absorption band of double bond at 1500–1600?cm^?1 decreases after UV exposure. Increasing the concentration of benzoin (0.1–1?phr) and EGDMA (1–10?phr) leads to an increase in gel content and hardness, while swelling ratio decreases. After 5?min heating at 150?°C, about 20%wt of the unirradiated compound became insoluble, because heating of compound at 150?°C causes crosslinking reaction without any irradiation.     

Preparation and properties of high viscosity and elasticity asphalt by styrene–butadiene–styrene/polyurethane prepolymer composite modification

The porous asphalt pavements is often used in important occasion for its special properties and performance which can be to a great extent attributed to the binder—high viscosity and elasticity asphalt (HVEA). To prepare high demanding binder for porous asphalt pavements, the polyurethane prepolymer (PUP) and styrene–butadiene–styrene (SBS) were used to modify the matrix asphalt compositely. First, based on a series of physical tests, the effects of binder composition on performance of SBS/PUP HVEA binder (SBS/PUP-HVEA) were investigated. Then the Fourier transform infrared (FTIR) test was conducted to investigate the reaction mechanism of SBS/PUP-HVEA binder. Last, the fluorescence microscopy, stability tests, multiple stress creep recovery test, and differential scanning calorimetry test were carried out to evaluate and compare the phase structure, storage, high-temperature performance, thermostability characteristics of several HVEA binders. It is found that the composite modification of SBS and PUP can produce high quality binder which possesses high viscosity and high elasticity. And the composition of SBS/PUP-HVEA were recommended as follows: Shell-70# can be chosen as matrix asphalt, the contents of SBS modifier (SBS1301:SBS4303 = 1:2), H2122A PUP, chain extender M-OEA, and crosslinker sulfur were suggested 4%, 5%, 0.5%, and 1‰, respectively. The new functional groups observed in FTIR confirmed the existence of physical and chemical reactions in the modification process, which were beneficial to improve the high temperature performance and storage stability of the binder. SBS/PUP-HVEA had good phase structure, storage stability, high temperature performance, and thermostability compared to other HVEA binders. This study demonstrated that the SBS/PUP compositely modified asphalt possessed high viscosity and high elasticity, which can be used in the porous asphalt mixture and other highly demanding working environment as well.     

Chemical modification of styrene–butadiene–styrene co-polymer by grafting of N-carbamyl maleamic acid

A styrene–butadiene–styrene (SBS) block co-polymer was functionalized using different amounts of N-carbamyl maleamic acid (NCMA) and benzoyl peroxide as initiator. NCMA, which is a bifunctional monomer, was synthesized in our laboratories. The concentration of NCMA used in the functionalization of SBS ranged from 0.5 to 3% (w/w) based on the co-polymer mass. Benzoyloxy radicals generated from the thermal decomposition of benzoyl peroxide initiated the grafting reaction. The concentration of the initiator was kept constant at 0.076% (w/w). FT-IR spectroscopy was used to determine the amount of NCMA effectively grafted onto the SBS. The maximum amount of monomer grafted was about 0.3% (w/w) when the SBS was modified with 1% (w/w) NCMA. The effect of grafting on the surface properties and the adhesion to polyurethane adhesive of the modified SBS were evaluated. Contact angle values were obtained using liquid droplets. When the concentration of the NCMA used in the grafting reaction was 1% (w/w), the contact angles with water on original and modified SBS were 95° and 77°, respectively. Adhesion properties were evaluated by standard peel tests employing a commercial polyurethane adhesive. The modified SBS having the largest amount of NCMA displayed a T-peel strength value 5-times higher than the corresponding value measured with the original SBS.     

Water uptake and pore volume determination of porous styrene–divinylbenzene copolymers

The relationship of water uptake and pore volume has been investigated for porous styrene–divinylbenzene (St–DVB) copolymers prepared in the presence of different inert diluents. It was found that the copolymers prepared in some conditions significantly increased their volume on taking up the water (swelling), and thus the use of water to measure the pore volume of porous St–DVB copolymers could hardly be recommended because the water uptake measurement does not always give a true value of the pore volume in dry state.     

Recycling by injection and chrome plating of acrylonitrile–butadiene–styrene parts pickled in hydrochloric and nitric acids

Chrome-plated acrylonitrile–butadiene–styrene ( ABS) parts with defects in the metal layer were submitted to pickling with hydrochloric and nitric acids and recycled by injection in different proportions with neat ABS. For comparison, samples with neat ABS (ABSn) and ABS submitted to pickling (ABSp) were also injected. The influence of the pickled material on the samples properties was evaluated by chemical, thermal, and mechanical analysis. The injected samples were chrome by conventional process and evaluated by visual inspection, adhesion test, resistance to corrosion, and accelerated aging test, to evaluate the quality of the chrome finish. A gradual darkening of samples and formation of carbonyl groups with the increase in the pickled ABS concentration and little influence on the melt flow index were observed. The samples exhibited one thermal degradation stage similar to ABSn. The increase in the pickled ABS percentage caused a slight increase in glass-transition temperature of polybutadiene phase, and did not influence the tensile properties and hardness of samples, but decreased the impact resistance. After chrome plating, all samples were approved for visual inspection and metal layer adhesion test. Only the sample injected with pickled ABS was reproved in corrosion test, due to the oxidation of the chrome layer. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48372.     

Chemical modification of styrene–butadiene–styrene (SBS) rubber by reactive grafting with maleic anhydride

A procedure to increase the adhesion of block styrene-butadiene-styrene (SBS) rubber consisting of the reactive grafting with maleic anhydride (MA) in the presence of an organic peroxide radical initiator is proposed. The influence of the reactive grafting on the surface properties of SBS has been studied with special emphasis on the improvement of the adhesion to polyurethane adhesive. The grafting of MA onto SBS was carried out in the presence of different concentrations of 2,5-dimethyl-2,5-di(tertbutyl peroxy) hexane (DBPH) as initiator to generate oxygen radicals by thermal decomposition, which induce the grafting reaction. The modification process was performed in the molten state using a Brabender mixer to premix the reactants and a hot press to initiate the functionalizing reaction. ATR-IR and XPS spectroscopies were employed to verify the grafting of MA on SBS. The changes in wettability on the modified SBS rubber were determined by contact angle measurements. Adhesion properties were evaluated from T-peel tests of SBS rubber/polyurethane adhesive joints. Reasonable extents of MA grafting on SBS were obtained (evidenced by the presence of a weak carbonyl vibration at 1700 cm^-1 in the ATR-IR spectra and by the carbon- oxygen band at a binding energy of 287.0 eV in the XPS spectra). The higher the DBPH amount, the higher the MA amount grafted onto the SBS surface. The maximum grafting level was obtained using 2 wt% MA. Grafted species seemed to be mainly concentrated on the surface of the SBS-molded sheets. The wettability of the modified rubber increased with respect to the original polymer, new carbon-oxygen moieties were created and the C/O ratio increased. A noticeable enhancement in peel strength values was observed, which was ascribed to the creation of interfacial interactions between the polyurethane and the SBS rubber surfaces.     

Enhanced properties of poly(styrene–b–ethylene–co–butylene–b–styrene) nanocomposites with in situ construction of interconnected graphene network

In this work, such elastomeric nanocomposites were fabricated with graphene (GE) sheets selectively distributing between polymer matrices and forming three-dimensional networks. The solvent evaporation process was first introduced to produce poly(styrene–ethylene–co–butadiene–b–styrene) (SEBS) microspheres and then reduced GE oxide attached to the surface of SEBS microspheres via electrostatic interaction and sonication-assisted reduction. The microstructure of nanocomposites, prepared by compression molding using SEBS/GE microspheres, was investigated using scanning electron microscopy and transmission electron microscopy. The results showed that interconnected GE networks formed in heat-pressing composite and was destroyed after twin-roll mixing. The SEBS/GE nanocomposites showed enhanced electrical, thermal, and mechanical properties. The electrical resistivity of nanocomposites obtained via heat-pressing reached to 1.1 × 10³ Ω m at a 2.5 wt % (1.07 vol %) content of GE. The thermal and mechanical properties were also characterized. It was found that the initial degradation temperature increased by nearly 40 °C and the mechanical properties continued to rise with GE content below 0.5 wt %. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47118.     

Ultra-stretchable thermoplastic elastomeric materials based on styrene–isoprene–styrene triblock copolymer: Influence of calcium copper titanate on mechanical and dielectric properties

Conventional charge storage devices made of ceramic materials have limited deformability and configurability due to their extreme stiffness. The high demand for compliant dielectrics has led researchers to look beyond conventional ceramics, despite their very high dielectric properties. In this work, a mechanically robust, highly-flexible and ultra-stretchable thermoplastic elastomeric material with dielectric characteristics has been fabricated by introducing calcium copper titanate [CaCu₃Ti₄O₁₂] (CCTO) dielectric material onto macromolecular chains of styrene–isoprene–styrene (SIS) triblock copolymer via a solution-based polymer processing technique. CCTO powders have been synthesized using sol–gel technique. The resulting composite is ultra-stretchable with strain at break of ~3200% and has high dielectric permittivity of ~10. High dielectric property is attributed to the well-dispersed dielectric CCTO fillers within the SIS matrix, which provide sites for interfacial polarization and space charge accumulation. The influence of CCTO on dielectric properties has also been validated using the modified Cole–Cole model.     

Melting and crystallization behaviors of compatibilized poly(trimethylene terephthalate)/acrylonitrile–butadiene–styrene blends

The melting and crystallization behaviors of poly(trimethylene terephthalate) (PTT)/acrylonitrile–butadiene–styrene (ABS) blends were investigated with and without epoxy or styrene–butadiene–maleic anhydride copolymer (SBM) as a reactive compatibilizer. The existence of two separate composition-dependent glass-transition temperatures (T_g's) indicated that PTT was partially miscible with ABS over the entire composition range. The melting temperature of the PTT phase in the blends was also composition dependent and shifted to lower temperatures with increasing ABS content. Both the cold crystallization temperature and T_g of the PTT phase moved to higher temperatures in the presence of compatibilizers, which indicated their compatibilization effects on the blends. A crystallization exotherm of the PTT phase was noticed for all of the PTT/ABS blends. The crystallization behaviors were completely different at low and high ABS contents. When ABS was 0–50 wt %, the crystallization process of PTT shifted slightly to higher temperatures as the ABS content was increased. When ABS was 60 wt % or greater, PTT showed fractionated crystallization. The effects of both the epoxy and SBM compatibilizers on the crystallization of PTT were content dependent. At a lower contents of 1–3 wt % epoxy or 1 wt % SBM, the crystallization was retarded, whereas at a higher content of 5 wt %, the crystallization was accelerated. The crystallization kinetics were analyzed with a modified Avrami equation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal and mechanical enhancement of styrene–butadiene rubber by filling with modified anthracite coal

Anthracite is the highest rank of coal with a layered structure similar to that of graphite. Here, styrene–butadiene rubber/modified anthracite (MA) composites were prepared and analyzed. The microstructure and dispersion of the anthracite were improved by ball milling with the modifier bis-(γ-triethoxysilylpropyl)-tetrasulfide (KH-Si69). The particle size of the modified coal was decreased significantly to ~3 μm, while surface interactions with the modifier yielded enhanced lamellar morphology and hydrophobic surfaces. The anthracite lamellae were well dispersed in the rubber matrix, providing good reinforcement; the tensile strength of the composite exceeded that of a composite with carbon black (CB) N660 filler (16.65 vs. 14.68 MPa). Moreover, low-level CB or silica compositing further promoted the dispersion of coal particles in the rubber, effectively enhancing the mechanical reinforcement behavior of the coal particles as well as the thermal stability of the rubber composite. Notably, it led to a 10.63% improvement in tensile strength and a 9.96 °C increase in the 5% mass loss temperature compared to the composite with a single MA filler. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48203.     

Study of the styrene–acrylic emulsion modified by hydroxyl-phosphate ester and its stoving varnish

A styrene–acrylic copolymer emulsion containing hydroxyl-phosphate as flash-rust functional monomer and hydroxypropyl acrylate as cross-linking monomer was synthesized. The effects of the hydroxyl phosphate dosage, the hydroxypropyl acrylate dosage as well as the ratio of soft to hard monomer on the emulsion and coating film were investigated. The results showed that the emulsion of 4% hydroxyl phosphate function monomer and 3% hydroxypropyl acrylate with soft and hard monomer ratio of 1:1.6 and modified emulsion and amino resin ratio of 6:1 resulted in a coating film with the best performance.     

Effects of styrene–acrylic emulsion on bond performance and interface microstructure of repair mortar of ternary cementitious system

This study investigates the effects of styrene–acrylic emulsion (SAE) as a modifier and interfacial agent on the interfacial bond performance of ordinary Portland cement–aluminate cement–gypsum (PAG) repair mortar. The hydration products and interfacial microstructure are analyzed via x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM). The results demonstrate that the addition of SAE can effectively enhance the tensile bond strength and flexural bond strength of the PAG repair mortar, and the optimal addition amount of SAE is 10 wt%. The tensile and flexural bond strengths of the PAG repair mortar with SAE interfacial agent at 40% concentration are 1.38 and 1.34 times than those of the mortar without the interfacial agent, respectively. XPS and FTIR analyses reveal that the carboxyl groups in SAE and Ca²⁺ generated from cement hydration form Ca²⁺–carboxyl complexes. The SEM and XRD analyses indicate that SAE can alter the distribution and size of crystals at the bond interface and considerably reduce the thickness of the bond interface; however, SAE cannot change the type of hydration products at the bond interface.     

Preparation and characterization of natural rubber/ultrafine full-vulcanized powdered styrene–butadiene rubber blends

In this paper, natural rubber (NR)/ultrafine full-vulcanized styrene–butadiene powdered rubber (UFPSBR) blends were prepared and studied for the first time. Scanning electron microscopy and thermogravimetric analysis were employed to characterize UFPSBR. Equilibrium swelling method was used to determine the crosslink density of NR/UFPSBR vulcanizates. The results on mechanical properties showed that when NR/UFPSBR ratio was 100/5, the formulation exhibited favorable performances compared to pure NR vulcanizates. The heat build-up temperature also decreased after adding UFPSBR into the NR formulation. In dynamic mechanical analysis, in the temperature range of ?10 to ?5 °C, loss factor (tanδ) values of NR/UFPSBR vulcanizates showed an increasing trend over the given temperature range and exhibited a peak value at approximate ?5 °C. This indicates that wet traction and rolling resistance of samples were improved after UFPSBR was added in NR. This research demonstrates that UFPSBR can be incorporated into a conventional NR formula to successfully improve the comprehensive performances and dynamic mechanical properties of NR formula.     

Study of the phase morphology and toughness in poly (vinyl chloride)/acrylonitrile–styrene-acrylic/styrene–butadiene–styrene ternary blends influenced by interfacial/surface tension

The effect of interfacial interaction on the phase morphology and toughness of poly (vinyl chloride) (PVC)/acrylonitrile–styrene-acrylic (ASA) terpolymer/styrene–butadiene–styrene (SBS) block copolymer ternary blends has been investigated. Water and diiodomethane liquids were used for static contact angle measurements to get surface tension and calculate interfacial tension. A dispersed phase morphology of ASA and SBS in the PVC matrix was predicted by the spreading coefficient theory, which was calculated through interfacial tensions between different polymer pairs. Extraction experiment and scanning electron microscopy were combined to verify this morphology. When the volume fraction of SBS was small, SBS was dispersed in the matrix as droplets and the strong PVC/styrene–acrylonitrile interfacial interaction made up for the poor interfacial adhesion between SBS and PVC. Herein, SBS showed an effective toughening effect on PVC/ASA blends. With the addition of 2.5- and 5-phr SBS, the blends had the highest impact strength of 88.75 kJ/m² at 23 °C and 9.98 kJ/m² at 0 °C, respectively. With the further increase of the SBS content, the diameter of the SBS drops increased largely and the poor interfacial adhesion between SBS and PVC played a leading role, resulting in a sharp decrease in toughness and a sharp ductile–brittle transition. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47721.     

Preparation and properties of soapless poly(styrene–butyl acrylate–acrylic acid)/SiO2 composite emulsion

Soapless emulsion polymerization of styrene-butyl acrylate-acrylic acid was carried out using single or combined polymerizable emulsifiers, such as hydroxypropyl methacrylate sodium sulfate (HPMAS), sodium vinyl sulfate, and vinyl alkylphenol polyether sulfates (NRS-10), in the presence of colloidal nano-SiO₂ solution in order to obtain films with high degree of hardness and water-resistance. Monomer conversion, formation of coagulum, viscosity, particle size, size distribution, and surface tension of the emulsions, as well as the film properties, were determined and compared with those of an emulsion prepared with the conventional emulsifier sodium dodecyl sulfate and polyoxyethylene octylphenol ether. Emulsions prepared from a mixture of two polymerizable emulsifiers NRS-10 and HPMAS (1:1, weight ratio) have presented high monomer conversion, low coagulum, and small particle sizes. When the emulsifier level increased within a certain level, the monomer conversion increased but particles size decreased. Increased amounts of reactive emulsifiers led to low monomer conversion, large amount of coagulum and small particle sizes. With the increase of nano-SiO₂ the particle sizes and the viscosity of the emulsion also increased. The introduction of reactive emulsifiers improved the water-resistance of the resulting films, and the addition of nano-SiO₂ increased the hardness of the coatings. Under optimal conditions, the coatings made from emulsions produced from a combination of reactive emulsifiers such as NRS-10 and HPMAS (1:1, weight ratio) at 2?% level (based on monomer weight) exhibited remarkable hardness, adhesion force and water-resistance.     

Mechanical properties and morphology of coal gasification fine slag glass bead-filled acrylonitrile–butadiene–styrene (ABS) composites

Coal gasification fine slag glass beads (CGFSGBs) were processed via an efficient pneumatic separation technique. CGFSGB products (CGFSGB-S1, CGFSGB-S2, and CGFSGB-S3) with different sizes were acquired. The heavy calcium carbonate (CaCO₃) was used as comparative filler. Effects of particle size and geometric shape on mechanical strengths, flow properties, and solid density of filled acrylonitrile–butadiene–styrene (ABS) were investigated. The mechanical strengths of composites decreased with increasing CGFSGB weight fraction, while MFR and solid density increased. The mechanical strengths were found to increase with decreasing CGFSGB size, and spherical surface of the CGFSGB is more beneficial to improve interface adhesion strength than square surface of the CaCO₃. The flow property analysis showed that the ABS/CaCO₃ composites have better fluidity and the advantages in the processing energy consumption. However, the incorporation of CaCO₃ resulted in the higher solid-state density. In summary, CGFSGBs have the potential to replace CaCO₃ in the ABS market. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48601.     

Synthesis of silane monomer-modified styrene–acrylate microemulsion coatings by photopolymerization

A relatively concentrated silane monomer-modified styrene–acrylate microemulsion coating with high monomer to surfactant ratio of 7.5:1 has been prepared by microemulsion photopolymerization. The properties and the structure of the microemulsion coatings were investigated using TEM, FTIR and UV–vis measurements. The microemulsions are transparent with high transmittance in the visible range. The particle sizes of the produced latexes are in the range of 34–52 nm with the number average diameter of 40.9 nm and D_w/D_n of 1.16. FTIR spectrum indicates the possible structure of the silane monomer-modified styrene–acrylate copolymer, and confirms the hydrolysis and condensation resulting in siloxane bonds between polymer particles. The microemulsion coatings show enhanced acid, base and water resistance with decrease of surfactant content and increase of silane coupling agent.     

Structure–property relationships of silica/silane formulations in natural rubber,isoprene rubber and styrene–butadiene rubber composites

The mechanical performance of natural rubber (NR), synthetic poly-isoprene rubber (IR), and styrene–butadiene rubber (SBR) composites filled with various silica/silane systems is investigated. The results are analyzed by referring to micro-mechanical material parameters, which quantify the morphological and structural properties of the polymer and filler network. These are obtained from fits with the dynamic flocculation model (DFM) describing the strongly nonlinear quasi-static stress–strain response of filler-reinforced elastomers as found from multihysteresis measurements of the investigated compounds. We focus on the reinforcement mechanisms of silica compounds with coupling and covering silane, respectively. The fitted material parameters give hints that the coupling silane provides a strong chemical polymer–filler coupling, which is accompanied by improved strength of filler–filler bonds for all three rubbers types. This may result also from the chemical coupling of short chains bridging adjacent silica particles. It implies larger stress values for the coupling silane and, in the case of NR and IR, a more pronounced “Payne effect” compared to the covering silane. In contrast, for SBR, the coupling silane delivers a lower Payne effect, which is explained by differences in the compatibility between rubber type and silane-grafted silica surface. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48435.     

Synthesis of emulsion styrene butadiene rubber by reversible addition–fragmentation chain transfer polymerization and its properties

Emulsion polymerization is generally used to synthesize styrene butadiene rubber (SBR), and the molecular weight of this rubber can be easily increased. However, the broad molecular weight distribution (MWD) of SBR increases energy loss and adversely affects the dynamic viscoelastic properties. To overcome this disadvantage, reversible addition–fragmentation chain transfer (RAFT) polymerization, which is a type of living polymerization, is applied to emulsion polymerization for preparing RAFT emulsion SBR (ESBR). The molecular weight and microstructure of RAFT ESBR are compared to those of commercially available ESBR 1502 by gel permeation chromatography and proton nuclear magnetic resonance spectroscopy. The aforementioned two polymers are used to prepare unfilled ESBR compounds, which are compared in terms of key physical properties (abrasion resistance, mechanical properties, and dynamic viscoelastic properties). It is confirmed that various physical properties of RAFT ESBR are improved due to its narrow MWD. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47069.     

Effects of modified silica on the co-vulcanization kinetics and mechanical performances of natural rubber/styrene–butadiene rubber blends

Rubber blends are widely used for combining the advantages of each rubber component. However, to date, how to determine and distinguish the vulcanization kinetics for each single rubber phase in rubber blends during the co-vulcanization process is still a challenge. Herein, high-resolution pyrolysis gas chromatography–mass spectrometry (HR PyGC-MS) was employed for the first time to investigate the vulcanization kinetics of natural rubber (NR) and styrene–butadiene rubber (SBR) in NR/SBR blends filled with modified silica (SiO₂). The reaction rates of crosslinking of each rubber phase in NR/SBR were calculated, which showed that the crosslinking rates of NR were much lower than those of SBR phase in the unfilled blends and blends filled with unmodified and silane modified silica. Interestingly, the vulcanization rates of NR and SBR phase were approximately same in the vulcanization accelerator modified silica filled blends, showing better co-vulcanization. In addition, the vulcanization accelerator modified silica was uniformly dispersed and endowed rubber blends with higher mechanical strength compared to the untreated silica. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48838.