硫化剂对陶瓷化耐火硅橡胶性能的影响

研究了2,5-二甲基-2,5-二（叔丁基过氧基）己烷（俗称双二五）、2,4-二氯过氧化苯甲酰（俗称双二四）、过氧化二异丙苯（DCP）3种硫化剂对陶瓷化耐火硅橡胶力学性能和烧结性能的影响。结果表明,一次硫化和二次硫化后,使用DCP做硫化剂的硅橡胶的硬度都是最大,使用双二五做硫化剂的硅橡胶的拉断伸长率都是最高,采用双二四做硫化剂的硅橡胶拉伸强度都是最大;使用双二四做硫化剂的硅橡胶烧结硬度最高。综合来看,使用双二四作硫化剂时陶瓷化耐火硅橡胶的力学性能最好,其最佳用量为1.25份。     

The effect of curing system on the properties of the thermoplastic elastomer foams of ethylene‐vinyl acetate copolymer and styrene‐butadiene and ethylene‐propylene‐diene monomer rubbers

Thermoplastic elastomer (TPE) foams have important application in electrical, toys, and other industries. Several foams were prepared by ethylene‐vinyl acetate copolymer (EVA) lonely, and in combination with styrene‐butadiene and ethylene‐propylene‐diene monomer rubbers (SBR and EPDM). The effects of crosslinking and foaming agents and EVA type on density and mechanical properties of the cured foams with two curing systems, peroxide and sulfur‐peroxide with potential use in automotive applications, were studied. The results showed that proposed compounds formulations were foamed properly. The viscosity of the EVA was a key factor for the density values of the formed foams. The densities of the cured foams with peroxide system with various SBR contents were higher when compared with cured foams with sulfur‐peroxide system. With increasing foaming agent, the densities of the foams were reduced for studied curing systems. The densities of the EVA–EPDM foams were lower than those of the EVA–SBR foams in the same studied conditions. Increasing rubber in foam formulation had adverse effect on tensile properties of the foams. The existence of the talc powder in foam formulation had important role on the shape and type of the formed cells and resulted in foams with mostly closed cells. The results of this study help the automotive article designer to produce suitable TPE foam. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45357.     

Systematic investigation on the effect of crosslinking agent type and dosage on the performance of TPU/MVQ based thermoplastic vulcanizates

Dynamic vulcanized thermoplastic polyurethane (TPU)/methyl vinyl silicone rubber (MVQ) thermoplastic vulcanizates (TPVs) were prepared in torque rheometer. The influence of the type and amount of peroxide crosslinking agent on the mechanical properties, thermal stability, micromorphology and melt flowability was systematically investigated. The results showed that the mechanical properties of the TPVs vulcanized by 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane (DBPH) first increased and then decreased with increasing the peroxide amount, while for dicumyl peroxide (DCP) vulcanizing system the mechanical properties slowly increased. Besides, the comprehensive mechanical properties vulcanized by DBPH were better than those of DCP group. The results of the thermogravimetric analysis showed that the TPVs vulcanized by DBPH had better heat stability, corresponding to the excellent thermo-oxidative aging performance and the 38% increase in tensile strength after aging. In addition, the MVQ rubber particles showed better dispersing performance for DBPH vulcanizing system. The melt flow rate of the TPVs showed a linear relationship with increasing DBPH dosage and became worse after the amount of crosslinking agent exceeded 1.5 phr. By comprehensive comparison, the TPVs have better performance when use peroxide DBPH as the crosslinking agent and the dosage is 1.5 phr.     

Grafting of N‐carbamyl maleamic acid onto a styrene–butadiene–styrene copolymer

A styrene–butadiene–styrene block copolymer (SBS) was functionalized with N‐carbamyl maleamic acid (NCMA) using two peroxide initiators with the aim of grafting polar groups onto the molecular chains of the polymer. The influence of the concentration of benzoyl peroxide (BPO) and 2,5‐dimethyl, 2,5‐diterbuthylperoxihexane (DBPH) was studied. The concentration of peroxy groups ranged between 0.75 and 6 × 10^?4 mol % while the concentration of NCMA was constant at 1 wt %. The reaction temperature was chosen according to the type of peroxide employed, being 140°C for BPO and 190°C for DBPH. FTIR spectra confirmed that NCMA was grafted onto the SBS macromolecules. It was found that the highest grafting level was achieved at a concentration of peroxy groups of about 3 × 10^?4 mol %. Contact angle measurements were used to characterize the surface of the SBS and modified polymers. The contact angle of water drops decreased with the amount of NCMA grafted from 95°, the one corresponding to the SBS, to about 73°. T‐peel strength of polymer/polyurethane adhesive/polymer joints made with the modified polymers was larger than those prepared with the original SBS. The peel strength of SBS modified with 1.5 and 3 × 10^?4 mol % of peroxy groups from BPO were five times larger than that of the original SBS. The materials modified using BPO showed peel strengths higher than the ones obtained with DBPH. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4468–4477, 2006     

Physicomechanical,friction, and abrasion properties of EVA/PU blend foams foamed by supercritical nitrogen

Elastomer foams based on EVA, PU, and EVA/PU blends formulated for shoe‐sole applications were prepared by a supercritical N₂ batch foaming process and characterized for physicomechanical, friction and abrasion properties. The blending of EVA with PU was aimed for improving the friction and wear characteristics of the EVA based foams. All of the foams prepared showed spherical cells with closed‐cell morphology and the cell sizes varied with varying the EVA/PU blend ratio and CaCO₃ content of the foams. The properties such as hardness and resilience, friction coefficients and abrasion resistance improved for the EVA/PU blend foams compared to the EVA foam, but their compression set, tensile strength, and tear strength were inferior to the EVA foam. The incorporation of CaCO₃ filler increased density, hardness, tensile strength, and tear strength of the EVA/PU blend foams but decreased resilience, compression set, friction coefficients, and abrasion resistance. The improvement in friction coefficients and wear resistance obtained in the EVA/PU blend foams was significant for shoe‐sole applications. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

New polyol for production of rigid polyurethane‐polyisocyanurate foams,Part 2: Preparation of rigid polyurethane‐polyisocyanurate foams with the new polyol

The method of preparation, determination of foaming parameters, and methods for the determination of physicochemical properties of polyurethane‐polyisocyanurate (PUR‐PIR) foams prepared with the use of N,N′‐di(methyleneoxy‐2‐hydroxyethyl)urea and boric acid derivatives are presented in this paper. It was found that application of the borate as a polyol component and simultaneously as a flame retardant in the recipe for production of PUR‐PIR foams was very favorable. The foams prepared were characterized by reduced brittleness, higher compressive strength and content of closed cells, as well as considerably lower flammability in comparison with standard foam. The results show that the new polyol prepared on the basis of N,N′‐di(methyleneoxy‐2‐hydroxyethyl)urea and boric acid can be applied for production of rigid PUR‐PIR foams, and it improves their physicochemical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

NR/PP thermoplastic vulcanizates: Selection of optimal peroxide type and concentration in relation to mixing conditions

Thermoplastic vulcanizates (TPVs) from natural rubber (NR) and polypropylene (PP) were studied, prepared by dynamic vulcanization during melt mixing, using various peroxides to crosslink the rubber phase. The objective was to find a proper balance between degree of crosslinking of the rubber and degradation of the PP‐phase, and the tendency of the peroxide to form smelly by‐products, in particular acetophenone. Four types of peroxides were investigated: 2,5‐dimethyl‐2,5‐di(tert‐butyl‐peroxy) hexyne‐3 (DTBPHY), 2,5‐dimethyl‐2,5‐di(tert‐butyl‐peroxy) hexane (DTBPH), di(tert‐butylperoxyisopropyl) benzene (DTBPIB), and dicumyl peroxide (DCP), at two mixing temperatures: 160 and 180°C for a 60/40 NR/PP TPV. The maximum and final mixing torques are clearly related to the intrinsic decomposition temperature of the particular peroxide used, where DCP and DTBPIB turn out to be effective at 160°C, whereas the other two require a higher temperature of 180°C. The best mechanical properties, tensile strength, elongation at break and compression set are obtained at lower mixing temperature with DCP and DTBPIB, presumably due to less degradation of the NR and PP. Unfortunately, these two peroxides form more smelly by‐products than DTBPHY and DTBPH. Dependent on the requirements of the pertinent application, a balanced selection needs to be made between the various factors involved to obtain an optimal product performance of these NR/PP TPVs. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Mechanical Properties of Silicone Rubber Enhanced Microcellular EPDM Foams Based on Supercritical CO2 Foaming Technology

Microcellular ethylene-propylene-diene monomer (EPDM) foams derived from miniaturizing the cellular structure can improve mechanical properties of traditional EPDM foams. It is a current challenge that microcellular EPDM foams prepared by supercritical CO₂ foaming technology cannot undergo the post-crosslinking process due to the disappearance of cellular structure, which strongly restricts the development of the mechanical properties of EPDM foams. Hence, a scalable and blending route by selecting the silicone rubber (SR) with different crosslinking temperature compared to EPDM is developed to improve mechanical properties of EPDM foams. During the pre-crosslinking process of EPDM, SR forms a complete crosslinking network, which can make up for the strength of EPDM without the post-crosslinking. Meanwhile, the silica can reduce the domain size of SR and enhance the compatibility between EPDM and SR. As expected, the addition of SR improves the storage modulus, viscosity and matrix strength of EPDM, which shows enhanced mechanical properties of EPDM foams. When the foam density is basically the same, the tensile strength and compressive strength of SR/EPDM foam are increased by 461% and 283% respectively compared with that of EPDM foam. Finally, the maximum tensile strength and compressive strength (40% strain) of SR/EPDM foam achieves 3.58 MPa and 0.59 MPa, respectively.     

Mechanical and dynamic mechanical properties of epoxy syntactic foams reinforced by short carbon fiber

Epoxy syntactic foams were prepared with diglycidyl ether of bisphenol‐A (DGEBA) epoxy resin, 2.4.6‐tri(dimethylaminomethyl)phenol (DMP‐30), coupling treated microsphere and short carbon fiber. The density of the foam was maintained between 0.56 and 0.91 g/cm³ for all compositions. Compressive, flexural, tensile and dynamic mechanical properties of the foams were investigated with respect to hollow glass microsphere (HGM) and carbon fiber (CF) content. A considerable improvement in the mechanical properties viz. compressive, flexural and tensile strengths was observed for the foams on incorporation of a small quantity of CF. The storage modulus were higher for the foam composites containing CF. The presence of HGM has significant influence on T_g of the syntactic foams, spherical filler diminished the T_g of the syntactic foams due to the plasticizing effect of the coupling treatment of HGM, that is helpful for enhancing damping properties of syntactic foams. POLYM. COMPOS., 37:1960–1970, 2016. © 2015 Society of Plastics Engineers     

Cure and scorch in the processing of ethylene‐propylene‐diene terpolymer (EPDM)

The objective of this work is to ascertain the characteristics of desirable (cure) and especially undesirable (scorch) crosslinking when carbon black filled ethylene propylene diene terpolymer (EPDM) is processed using different peroxide initiators. The mixing temperature and the nature of the peroxide initiator are crucial parameters affecting scorch (undesirably premature crosslinking) in this rubber. Processability and properties of EPDM prepared using various mixer set temperatures have been investigated. Dicumyl peroxide (Luperox DC), di(t‐butylperoxy) diisopropylbenzene (Luperox F), and 2,5‐dimethyl‐2,5‐di(t‐butylperoxy) hexane (Luperox 101) were used as crosslinking initiators. Higher mixing temperatures give shorter scorch times, greater scorch magnitudes, greater heterogeneities in crosslink spatial distribution and poorer tensile properties. However, extreme localization of the unwanted crosslinking at the rubber‐filler interface does have a beneficial effect. Luperox DC offers poorer processability and poorer resulting properties than do Luperox F and Luperox 101, due to its shorter half‐life and greater solubility in the rubber phase. This is the first time that the spatial heterogeneity of crosslinking and scorch has been related to the basic thermodynamics of 3‐component 2‐phase systems. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44523.     

Radical-Initiated Reaction of Methyl Linoleate with Dialkyl Phosphites

The addition of dialkyl phosphite (methyl, ethyl and n‐butyl) to methyl linoleate (MeLin) double bonds was investigated. The reaction proved to be more challenging than the analogous reaction with methyl oleate (MeOl), due to inhibition of the radical reaction by the bis‐allylic hydrogens of MeLin and the lower reactivity of MeLin double bonds. However, we demonstrated that this self‐inhibition problem can be solved by simply keeping the MeLin reagent at low concentrations, while keeping the dialkyl phosphite at high concentrations. For optimization of the reaction, four different radical initiators were investigated: dilauroyl peroxide (LP), 2,2′‐azobis(2‐methylpropionitrile) (AIBN), tert‐butyl perbenzoate (t‐BP), and tert‐butyl peroxide (TOOT). The initiators were used at temperatures that provided a half‐life of 10 h: 64, 64, 104, and 125 °C respectively for LP, AIBN, t‐BP, and TOOT. The tests showed the reaction to be faster at higher temperatures, but transesterification of the ester groups was also observed at elevated temperatures. t‐BP was chosen as an optimal initiator for carrying the reaction. The apparent order of reactivity of the dimethyl, diethyl and di‐n‐butyl phosphites (Me >Et >n‐Bu) towards MeLin was due to differences in their molar volumes. When the concentrations of dialkyl phosphite were kept the same, the order reversed (n‐Bu > Et~Me). GC–MS spectra of the resulting phosphonates are reported and the main fragments assigned.     

Isobutylaluminum aryloxides as metallocene activators in Homo‐ and copolymerization of olefins

The article describes that sterically hindered isobutylaluminum aryloxides with bulky ^tBu substituents at 2,6‐ positions of aryl fragment, i.e. (2,6‐di‐^tBu,4‐R‐C₆H₂O)AlⁱBu₂ (R = H ( 1‐DTBP ), Me ( 1‐BHT ), ^tBu ( 1‐TTBP )) and (2,6‐di‐^tBu,4‐R‐C₆H₂O)₂AlⁱBu (R=H( 2‐DTBP ), Me( 2‐BHT )) can serve as cocatalysts for metallocene complexes. Isobutylaluminum aryloxides have been applied for activation of rac‐Et(2‐MeInd)₂ZrMe₂ in homopolymerization of ethylene, propylene, copolymerization of ethylene and propylene, and terpolymerization of ethylene, propylene, and 5‐ethylidene‐2‐norbornene at Al/Zr = 300 mol/mol. The type of R substituent at 4‐position has a significant effect on catalyst activity. The catalytic system with 1‐TTBP showed the highest activity in all homo‐ and copolymerization processes. Diisobutylaluminum aryloxides provide much higher activity to the systems in all polymerization processes and stronger ability for propylene incorporation in copolymer than diaryloxides. The activities of the systems with isobutylaluminum aryloxides are similar or exceed that of the system with MAO as activator as have shown for propylene polymerization. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43276.     

Extruded foams prepared from high amylose starch with sodium stearate to form amylose inclusion complexes*

Extruded starch foams were prepared from high amylose corn starch with and without sodium stearate and poly(vinyl alcohol) (PVOH) to determine how the formation of amylose–sodium stearate inclusion complexes and PVOH addition would affect foam properties. X‐ray diffraction and Differential Scanning Calorimetry (DSC) showed that amylose–sodium stearate inclusion complexes were formed by low temperature extrusion and did not dissociate during foam formation by a second extrusion at higher temperatures. In the absence of PVOH, water absorption, and foam shrinkage at 95% RH were decreased because of the hydrophobicity of the complex. PVOH addition increased both the expansion ratio and the shrinkage of the foam, although shrinkage at 95% RH was still less than that observed with uncomplexed amylose. The structural integrity and some tensile properties of stearate‐containing foams were improved by PVOH addition. These results provide the manufacturer of biodegradable starch foams with an inexpensive method for tailoring foam properties for specific end‐use applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43251.     

Research on rapid preparation and performance of polymethacrylimide foams

A high‐performance polymethacrylimide (PMI) foam was prepared from the reactive monomers of acrylonitrile (AN) and methacrylic acid (MAA) via ultrasonic combined with thermal initiation radical bulk copolymerization and free heat foaming. The reaction progress of cyano and carboxyl groups were tracked by Fourier transform infrared (FTIR) spectroscopy and X‐ray Photoelectron Spectroscopy, and the results indicated that the imide groups were formed and cyano groups gradually decreased during foaming and thermal treatment. The cell morphologies of the PMI foams were characterized by scanning electron microscopy, and the results showed the PMI foams were consisted of the honeycomb structure. The thermostability of the prepared PMI foam was evaluated by thermogravimetric analysis (TGA), and the results revealed that the PMI foam possessed excellent thermal stability and char forming capability. The mechanical properties of PMI foams were measured by tensile, flexural, and compressive strength, and the responding values for the PMI foams with the density of 32.30 kg m^?3 were 0.71, 0.86, and 1.49 MPa, respectively, which demonstrated the obtained PMI foams presented superior mechanical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44959.     

Synthesis and biodegradability evaluation of 2‐methylene‐1,3‐dioxepane and styrene copolymers

Biodegradable copolymers of 2‐methylene‐1,3‐dioxepane (MDO) and styrene (ST) were synthesized by free‐radical copolymerization using di‐t‐butyl peroxide (DTBP) as the initiator. The copolymers containing ester units were characterized by Fourier transform infrared (FTIR), ¹H‐NMR, and ¹³C‐NMR spectroscopy. Their molecular weight and polydispersity index were determined by gel permeation chromatography (GPC). In vitro enzymatic degradation of poly(MDO‐co‐ST) was performed at 37°C in phosphate buffer solution (PBS, pH = 7.4) in the presence of Pseudomonas lipase or crude enzyme extracted from earthworm. The experiment showed that incorporating ester units into C? C backbone chain of polystyrene would result in a biodegradable copolymer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1146–1151, 2007     

Synthesis of hyperbranched organo‐montmorillonite and its application into high‐temperature vulcanizated silicone rubber systems

N,N‐Di(2‐hydroxyethyl)‐N‐dodecyl‐N‐methyl ammonium chloride was used as intercalation agent to treat Na⁺‐montmorillonite and form a type of organic montmorillonite (OMMT). Hyperbranched OMMT (HOMMT) was prepared by condensation reaction between OMMT and the monomer we synthesized. It was then used in the preparation of high‐temperature vulcanizated silicone rubber (HTV‐SR)/HOMMT nanocomposite. Different types of HTV‐SR/HOMMT nanocomposites were prepared with different amounts of HOMMT and compared with the composites directly incorporated with OMMT. Tensile properties such as tensile strength, elongation at break, permanent distortion, and shore A hardness were researched and compared. A combination of Fourier transform infrared spectroscopy, wide angle X‐ray diffraction, and transmission electron microscopy studies showed that HTV‐SR/HOMMT composites were on the nanometer scale, and the structure of HTV‐SR was not interfered by the presence of HOMMT. Results showed that the tensile properties of HTV‐SR/HOMMT systems were better than that of the HTV‐SR/HOMMT and HTV‐SR. This was probably due to the surface effect of the exfoliated silicate layers and anchor effect of HOMMT in the SR matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of Enhanced Poly(butylene succinate) Foams

Biodegradable poly(butylene succinate) (PBS) foams with high performance are usually difficult to be prepared because of its lower melt viscosity. Herein, high‐melt‐viscosity PBS was firstly prepared by combining the in situ reaction between carboxyl‐ended polyester (CP) and solid epoxy (SE) both as viscosifier and strengthening agent with the presence of crosslinking agent of dicumyl peroxide (DCP) and crosslinking co‐agent of trimethylolpropane trimethacrylate. Then enhanced PBS foams were successfully prepared by the traditional chemical compression‐molding method. Furthermore, the content effects of CP/SE, blowing agent azodicarbonamide, and DCP on the properties and morphologies of enhanced PBS foams were studied in details. Results revealed that the tensile strength of the as‐prepared PBS foams was as high as 32.3 MPa with the density of 0.58 g/cm³, which was higher than that of pure PBS resin (25.6 MPa). POLYM. ENG. SCI., 56:1275–1282, 2016. © 2016 Society of Plastics Engineers     

Mechanical Properties and Antimicrobial Activity of Silicone Rubber Compounds Containing Acrylated Norfloxacin and Its Polymer

Summary: Antibacterial silicone rubbers (SR) were prepared by platinum curing and peroxide curing of a silicone compound containing the synthetic antimicrobial monomer 1‐ethyl‐6‐fluoro‐7‐{4‐[2‐hydroxy‐3‐(2‐methylacryloyloxy)‐propyl]piperazin‐1‐yl}‐4‐oxo‐1,4‐dihyroquinoline‐3‐carboxylic acid (MQ) and its polymer PMQ. The effects of the two curing systems on the mechanical properties were compared. Tensile strength and elongation at break of the platinum‐cured SR decreased with increasing concentrations of MQ and PMQ. For the peroxide curing system, the elongation at break increased with increasing concentrations of the antimicrobial agents. The antibacterial activity of the prepared SR was examined by the shake flask test against Staphylococcus aureus and Escherichia coli, which are representative of Gram‐positive and Gram‐negative bacteria, respectively. All compounds showed excellent antibacterial activities against these two types of bacteria.

Structure of acrylated norfloxacin.     

Grafting itaconic anhydride onto polyethylene using extrusion

Reactive extrusion was employed to graft itaconic anhydride (IA) onto polyethylene, using thermally induced peroxide decomposition. It was found that an increase in IA concentration lead to an increase in the degree of grafting (DOG), but only up to 6 wt % IA. Using di‐cumyl peroxide (DCP) as the initiator resulted in a higher DOG compared to di‐tert‐butyl peroxide (DTBP) and required less reaction time to achieve the same DOG. However, raising the IA concentration also resulted in an increase in cross‐linking. Increasing the initiator concentration from 0.2 to 2 wt % resulted in a higher DOG. However, 5 wt % initiator showed similar results compared to using 0.2 wt % due to termination by disproportionation, which has been shown to be more prevalent at high initiator concentrations. Degradation was clearly observed by the inability to form a continuous extrudate during extrusion as well as discolouration. A residence time of more than 50 seconds, using DCP and 120 s for DTBP didn't offer any further increase in the DOG and also resulted in more pronounced degradation. Optimizing grafting is therefore a trade‐off between maximal DOG and minimizing side reactions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Tensile properties and interfacial adhesion of silicone rubber/polyethylene blends by reactive blending

Two‐phase blends of silicone rubber (SR) and linear low density polyethylene (LLDPE) were prepared by reactive blending using peroxide crosslinking agent of SR. The tensile strength and elastic modulus of the SR were found to be increased by reactive blending with LLDPE without sacrifice of the elongation. The improvement of the tensile properties is attributed to the strong adhesion at the interface between SR matrix and LLDPE domain due to the chemical reaction by peroxide. The observation by polarized optical microscopies revealed that the debonding did not occur at the interface, but the LLDPE domains were elongated to longer one. Despite the elongation of the LLDPE domain, the blends exhibited good deformation recoverability. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46192.