Effect of butyl rubber type on properties of polyamide and butyl rubber blends

Polyamide‐12 was blended with butyl rubber, bromobutyl rubber, and chlorobutyl rubber with and without a sulfur curing system. Mechanical properties for dynamically vulcanized blends generally exceed those made with no vulcanization. Chlorobutyl‐containing blends prepared by dynamic vulcanization have higher tensile strength and elongation at break values in comparison to those made from other butyl rubbers. For a variety of polyamide/rubber blends made by dynamic vulcanization, there is very little effect of rubber percentage unsaturation and Mooney viscosity on the mechanical properties of the blends. In chlorobutyl‐containing blends prepared by dynamic vulcanization, the swelling index values attributed to the rubber portion decrease as rubber content decreases, and it is likely that the polyamide phase completely surrounds the rubber particles at compositions exceeding approximately 25% polyamide. Swelling index results can be correlated with elongation at break values for similar blends. The results of differential scanning calorimetry suggest that the polyamide phase is not a neutral component in high shear mixing with butyl rubbers with or without curing agents. Rheological studies indicate strong non‐Newtonian behavior for all blends of polyamide‐12 with butyl rubbers. Scanning electron microscopy on polyamide‐12/butyl rubber blends indicates compatibility for butyl rubbers in the order of chlorobutyl > bromobutyl > butyl rubber. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1423–1435, 2004     

IIR/CIIR共混胶硫化特性的研究

研究了影响丁基橡胶／氯化丁基橡胶(IIR／CIIR)共混胶硫化特性的因素．包括并用比、硫化体系、补强剂和硅炕偶联剂。研究结果表明：随着IIR／CIIR共混胶中CIIR含量的增加，硫化速度加快，是大转矩值减小：用硫磺硫化的共混胶硫化速度比用树脂硫化的快，且共混胶起始转矩值也较高。在选用的几种补强剂中，添加N220补强的共混胶硫化速度较快，T90时间较短，添加活性沉淀白炭黑(WCB)补强的共混胶最大转矩值较高。加入硅烷偶联剂会使共混胶的T90时间延长，最大转矩值变高。     

Thermoplastic natural rubber based on polyamide‐12: Influence of blending technique and type of rubber on temperature scanning stress relaxation and other related properties

Thermoplastic natural rubber based on polyamide‐12 (PA‐12) blend was prepared by melt blending technique. Influence of blending techniques (i.e., simple blend and dynamic vulcanization) and types of natural rubber (i.e., unmodified natural rubber (NR) and epoxidized natural rubber (ENR)) on properties of the blends were investigated. It was found that the simple blends with the proportion of rubber ～ 60 wt % exhibited cocontinuous phase structure while the dynamically cured blends showed dispersed morphology. Furthermore, the blend of ENR exhibited superior mechanical properties, stress relaxation behavior, and fine grain morphology than those of the blend of the unmodified NR. This is attributed to chemical interaction between oxirane groups in ENR molecules and polar functional groups in PA‐12 molecules which caused higher interfacial adhesion. It was also found that the dynamic vulcanization caused enhancement of strength and hardness properties. Temperature scanning stress relaxation measurement revealed improvement of stress relaxation properties and thermal resistance of the dynamically cured ENR/PA‐12 blend. This is attributed to synergistic effects of dynamic vulcanization of ENR and chemical reaction of the ENR and PA‐12 molecules. Furthermore, the dynamically cured ENR/PA‐12 blend exhibited smaller rubber particles dispersed in the PA‐12 matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dynamically vulcanized polypropylene/styrene–butadiene rubber blends: The effect of a peroxide/bismaleimide curing system and composition

Polypropylene (PP)/styrene–butadiene rubber blends were studied with special attention given to the effects of the blend ratio and dynamic vulcanization. Dicumyl peroxide (DCP) was used as the curing agent in combination with N,N′‐m‐phenylene bismaleimide (BMI) as the coagent for the curing process. Outstanding mechanical performance, especially with regard to the elongation at break, and better resistance to compression set were achieved with the dynamic vulcanization; this indicated that the DCP/BMI system also acted as a compatibilizing agent. This phenomenon was also confirmed by Fourier transform infrared spectroscopy of the insoluble material, the crystallinity degree of the PP phase (as investigated by X‐ray diffractometry), and scanning electron microscopy. The dynamic mechanical properties of the nonvulcanized and vulcanized blends were also investigated. The aging resistance of the blends was also evaluated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of dicumyl peroxide and phenolic resin as a mixed curing system on the mechanical properties and morphology of TPVs based on HDPE/ground tire rubber

Thermoplastic vulcanizates (TPVs) are a special group of thermoplastic elastomer with the characteristic that consists of rubber elasticity and the processability of thermoplastic polymers. TPVs based on high density polyethylene (HDPE)/ground tire rubber (GTR) with phenolic resin (HY‐2045) and dicumyl peroxide (DCP) as vulcanizing agents are prepared through dynamic vulcanization in this article. The blends consisting of 40/60 HDPE/GTR are melt‐mixed in an internal mixer and then pressed with a compression molding machine. The aim of this experiment is to study the influence of a compound curing agent system on the mechanical properties of the HDPE/GTR composites. The results indicate that the mechanical properties of the HDPE/GTR blends are improved significantly by adding 4 phr HY‐2045 and 0.3 phr DCP than those of TPVs without any vulcanizing agents after dynamic vulcanization. The X‐ray photoelectron spectroscopy study and the FTIR‐ATR analysis confirmed that the crosslinking phenomenon occurred in the preparation of TPVs; and the gel fraction analysis indicates that the GTR components and the HDPE components of the HDPE/GTR blends are all moderately crosslinked. In addition, the morphology of the HDPE/GTR blends has been investigated by scanning electron microscopy. POLYM. COMPOS., 36:1907–1916, 2015. © 2014 Society of Plastics Engineers     

AS/NBR/HSB三元共混体系的动态硫化

采用动态硫化方法制备了丙烯腈-丁二烯共聚物/丁腈橡胶/高苯乙烯树脂（AS/NBR/HSB）三元共混热塑性弹性体，研究了NBR中丙烯腈质量分数，橡塑比和硫化剂对共混体系性能的影响。结果表明，动态硫化显著提高了共混材料的拉伸强度和扯断伸长率，酚醛树脂是AS/NBR，HSB共混体系比较理想的动态硫化交联剂；采用HSB，NBR，AS三元共混，共混材料的拉伸强度和扯断伸长率得到良好的平衡；差示扫描量热分析表明，该三元共混材料具有NBR和AS两相的玻璃化转变温度，说明该体系是典型的不相容体系。     

On the Mechanical Properties of EPDM/CIIR Blends Cured with Reactive Phenolic Resin

Blends of ethylene propylene diene monomer rubber (EPDM) and chlorinated isobutylene isoprene rubber (chlorobutyl, CIIR) with a reactive phenolic resin as the curing agent have been prepared through conventional two-roll mill mixing. The effect of resin curing on the mechanical properties of EPDM/CIIR blends was investigated and compared with conventional curing systems. The morphology of the blends as well as their thermal and steam aging resistance has also been reported. It was found that blends with a phenolic curing system exhibited superior mechanical and thermal aging properties and have potential applications in high-temperature engineered products.     

Effect of dynamic vulcanization on properties and morphology of nylon/SAN/NBR blends: A new compatibilization method of nylon/ABS blends

Dynamically vulcanized blends of nylon, styrene–acrylonitrile copolymer (SAN), and nitrile–butadiene rubber (NBR) were examined for mechanical properties, Shore D hardness, Vicat softening temperature, impact process, and phase morphology. The effect of a curing system such as phenolic formaldehyde resins (PF), dicumylperoxide (DCP), and a sulfur system on the mechanical properties of the nylon/SAN/NBR blends was studied, and dynamic vulcanization with a PF system was found to lead to outstanding toughness of the blends. The effect of PF content on the mechanical properties, Shore D hardness, and heat resistance of the nylon/SAN/NBR blends was also investigated. With increasing PF content the notched‐impact strength and Vicat softening temperature (VST) of the nylon/SAN/NBR (50/25/25) blends evidently improved, but tensile strength and Shore D hardness of the blends changed slightly. It can be concluded that the nylon/SAN/NBR (50/25/25) blends dynamically vulcanized by high‐content PF can attain excellent comprehensive mechanical properties, especially supertoughness, at room temperature. SEM was used to investigate the effect of dynamic vulcanization on disperse‐phase particle size, particle size distribution, and phase morphology. It was obvious that disperse‐phase particle size decreased with an increasing PF content. Thermal behavior and miscibility of dynamically vulcanized nylon/SAN/NBR with PF were investigated by DMTA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2057–2062, 2003     

混炼型聚氨酯橡胶/聚十二内酰胺热塑性硫化胶动态硫化历程与性能

采用动态硫化方法制备了混炼型聚氨酯橡胶（MPU）/聚十二内酰胺（PA 12）热塑性硫化胶（TPV）,通过控制动态硫化时间探究了该TPV的动态硫化历程,同时研究了不同动态硫化阶段共混物的物理机械性能和动态力学性能。结果表明,随着动态硫化时间的延长,MPU/PA 12 TPV逐步完成相转变,在温度和剪切作用下,MPU相由连续相转变为分散相,而PA 12则由分散相转变为连续相;随着动态硫化时间的延长,MPU/PA 12共混物的储能模量升高,损耗模量降低,损耗因子减小。此外,随着动态硫化时间的延长,MPU/PA 12共混物的综合力学性能提高。     

共混橡胶的共硫化研究

探讨了多种共混橡胶的共硫化体系及其对共混橡胶性能的影响。其中采用共硫化剂硫化CO/ECO、CSM/NBR、IIR/EPDM、IIR/CIIR共混胶,采用复合硫化剂硫化PUR/CR、ACM/ECO、ACM/NBR、CR/CIIR、CR/SBR共混胶,研究了硫化体系品种和用量对几种共混胶的硫化特性和力学性能的影响,为共混橡胶的硫化提供研究方案和理论指导。     

Solvent resistance and mechanical properties in thermoplastic elastomer blends prepared by dynamic vulcanization

Dynamic vulcanization was used to prepare thermoplastic elastomer blends of nylon (polyamide), polypropylene (PP) and polybutylene terephthalate thermoplastics with chlorobutyl (CIIR) and nitrile (NBR) rubbers. Mechanical properties of the blends were correlated against composition. Although hardness and tensile strength increase with increasing thermoplastic content for all blends, elongation at break values initially decrease and then increase in the range of 20–40% thermoplastic. For various blend compositions, the swelling behavior was evaluated with solvents that are able to dissolve the uncured rubber portion but not the thermoplastic component of the mixtures. All five systems showed swelling index values that were substantially less than the calculated “theoretical” values of swelling index. This was attributed to a caging effect of the thermoplastic component on the rubber phase, which restricts access of solvent and swelling of the rubber phase. In turn, this affects the solvent resistance of the blend. Some of the blends were evaluated by differential scanning calorimetry to assess the compatibility of the components in the blend. scanning electron microscopy was also used to determine the degree of compatibility of the two phases generated in the mixing process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Enhanced toughening of poly(propylene) with reclaimed‐tire rubber

The dynamic vulcanization of reclaimed‐tire rubber (RTR) and homopolypropylene (PP) was performed by melt‐mixing using either a sulfur crosslinking agent, maleic anhydride (MA), dicumyl peroxide (DCP), or the combination of MA and DCP, in two consecutive machines, first a two‐roll mill and then a counterrotating twin‐screw extruder. In the case of applying a sulfur crosslinking agent, it was demonstrated that the RTR/PP blend at the ratio of 30/70 had the highest impact strength. This could be attributed to the limitation of carbon black in the blend. When the combination of MA and DCP was applied, the result was higher impact strength of the blend at the same ratio. This could be attributed to not only the cohesion between the polymer chains in each phase, PP phase and rubber phase, but also the interfacial adhesion between PP and RTR chains in these two phases. For comparison, the GRT/PP blends with and without sulfur crosslinking agent were prepared as well. All these blends showed low impact strength, which was nearly the same as that of PP. The effects of different crosslinking agents on dispersion and distribution of rubber domain size, viscosity, and percentage crystallinity were also studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 510–515, 2004     

Peroxide cured natural rubber/fluoroelastomer/high‐density polyethylene via dynamic vulcanization

In this work, blends of fluoroelastomer (FKM), natural rubber (NR) along with high‐density polyethylene (HDPE) by dynamic vulcanization using peroxide (DBPH, DCP) as a curing agent were prepared. HDPE was melt‐mixed with NR and FKM at different compositions (HDPE/FKM/NR i.e. 30/60/10, 30/55/15, 30/50/20, and 30/35/35%wt) using an internal mixer at 150°C and 50 rpm rotor speed. The mechanical properties and oil swelling resistances of these blends were analyzed according to ISO 37 (Type 1) and ASTM D471, respectively. The results suggest that DBPH works better as a curing agent for the dynamic vulcanization system than DCP. The optimum mechanical properties and oil resistance were revealed in 30/50/20 and 30/60/10 HDPE/FKM/NR, being dynamic vulcanized with DBPH, respectively. In addition, was found that a dispersed HDPE phase shows the percent crystallinity in the range of 53% to 55% upon increasing the NR content. The SEM micrographs reveal the NR phase is well dispersed in FKM as small particles. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers .     

氟橡胶/氯醚橡胶并用胶的加工性能与硫化性能

氟橡胶(FKM)具有耐高温、耐油及耐多种化学药品侵蚀的特点,但加工性能不好,本文通过氟橡胶与氯醚橡胶(CO)并用改性,结果表明,CO的加入改善了FKM的加工性能,当CO并用份数少于40份时,FKM为连续相,CO超过40份时,CO转变为连续相。FKM/CO并用胶需用双硫化体系硫化,当FKM采用AF/BPP硫化时,CO采用NA-22/MgO或TCY/MgO/CaCO3硫化体系,并用胶有较好的硫化效果。     

动态硫化橡胶／橡胶共混物的制备及性能

综述了橡胶／橡胶共混物动态硫化的研究进展，介绍了并用橡胶采用动态硫化技术时，橡胶品种及硫化体系的选择原则，对动态硫化共混橡胶的性能进行了描述。     

氟橡胶/EPDM动态硫化共混物的研究

研究了动态硫化工艺条件和共混比对氟橡胶（ＦＫＭ）／ＥＰＤＭ共混物拉伸性能拉、热油老化性能和应力松弛性能的影响。结果表明：与直接静态硫化相比,动态硫化可避免两种硫化体系的相互影响;静态硫化共混物拉伸强度只有２ＭＰａ,而动态硫化共混物可达１０ＭＰａ以上;工艺条件对动态硫化共混物性能的影响不大;随共混物中ＥＰＤＭ用量的增大,共混物的热空气老化和热油老化性能均有所下降     

Acrylic rubber‐fluorocarbon rubber miscible blends: Effect of curatives and fillers on cure,mechanical, aging,and swelling properties

The cure characteristics and mechanical properties of gum and filled acrylic rubber (ACM), fluorocarbon rubber (FKM), and their blends of varying compositions were studied both under unaged and aged conditions. The rheometric study showed that optimum cure properties were obtained using a mixed curing system of blocked diamine, hexamethylenediamine carbamate (Diak #1), and ammonium benzoate. From varying the curing agents, the optimum levels of Diak #1 and ammonium benzoate were found to be 1.5 and 2.5 phr, respectively. The addition of different fillers and their loading influenced the cure properties, with increased torque and reduced scorch safety. The gum and filled 50:50 (w/w) ACM‐FKM showed overall performance in strength properties. Postcuring improved the strength of all the systems, especially the systems with a higher proportion of FKM. None of the properties changed significantly during aging of the blends. FKM and the blends containing a higher proportion of FKM were affected least by aging. Swelling of the blends was reduced by the addition of fillers. Dynamic mechanical thermal analysis showed a single tan δ peak corresponding to a single phase transition for both cured and filled blends. The storage modulus of the blend increased from the gum blend to the filled blend, indicating the presence of polymer‐filler interaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1442–1452, 2003     

动态硫化制备粉末丁苯橡胶/聚丙烯合金的研究

采用双螺杆动态硫化工艺,用粉末丁苯橡胶(PSBR)改性聚丙烯(PP)制备了PSBR/PP共混物,考察了二者的质量比、软化剂、补强剂和加工工艺对共混物性能的影响,并对体系的耐老化性能进行了初步研究。结果表明,当PSBR与PP质量比为12/88时,使用软化剂可提高共混物的加工流动性;纳米高岭土对共混物有较明显的增强作用;用动态硫化工艺制得共混物的性能优于非动态硫化工艺制得的共混物。     

Polyamide‐reinforced ethylene–propylene–diene rubber compatibilized with chlorinated polyethylene

Vulcanizates of blends of ethylene–propylene–diene rubber and polyamide copolymers were prepared by reactive compatibilization. A reactive route was employed for compatibilizing these blends with the addition of chlorinated polyethylene (CPE). The influence of the compatibilizers, crosslinking agents, blend compositions, and addition modes of the compatibilizers on the mechanical properties of the blends was investigated. The morphologies of the blends were determined with scanning electron microscopy. The addition of CPE was found to reduce the particle size of the dispersed phase remarkably. The stability of the blends with compatibilizers was measured by high‐temperature thermal aging. The mechanical properties were examined by stress–strain measurements and dynamic mechanical thermal measurements; the addition of polyamide copolymers caused significant improvements in the tensile properties of these blends.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1727–1736, 2003