Modification of a nitrile-phenolic bonding agent by addition of an interfacial agent: effect on the practical adhesion between nitrile rubber and metal

—The mechanism of vulcanization bonding of a nitrile rubber (NBR) elastomer to metal with a single-coat nitrile-phenolic bonding agent is discussed. A nitrile-phenolic bonding agent consisting of NBR, phenol formaldehyde (PF) resin, and vulcanizing agents was modified with an interfacial agent (p-cresol formaldehyde resin) and the effect of interfacial agent addition on the practical adhesion between metal and the NBR elastomer after vulcanization was investigated. The adhesion strength was measured in terms of the metal-to-NBR elastomer peel strength using the bonding agent. The addition of p-cresol formaldehyde (PCF) resin to the bonding agent with a proportionate reduction of PF resin initially improved the peel strength; a maximum was reached at about 20% PCF content and then decreased with a further increase in the PCF content. The improvement in peel strength produced by the addition of PCF resin is attributed to the increased chemical bonding between NBR and the phenolic resin. The drop in peel strength above 20% PCF content is explained by the increased diffusion of the bonding agent into the NBR elastomer, away from the bond line, leading to a starved glue line. The mechanism for the optimum performance at about 20% PCF resin content is believed to be due to the balance of diffusion and chemical crosslinking.     

Effect of partial replacement of di(2‐ethyl hexyl)phthalate,by a polymeric plasticizer,on the permeability and leaching properties of poly(vinyl chloride)

Acrylonitrile butadiene rubber (NBR) was used as a polymeric plasticizer in poly(vinyl chloride) (PVC) for the partial replacement of di(2‐ethyl hexyl)phthalate (DEHP). The effect of this partial replacement on DEHP leaching from the PVC was evaluated at 10, 25, and 40°C. The study shows that the incorporation of NBR reduces the rate of DEHP leaching, the reduction being prominent at lower temperatures. Gas permeability of the NBR‐modified samples was also evaluated at the above temperatures using oxygen and carbon dioxide. A reduction in gas permeability is observed in NBR‐modified samples compared to the PVC plasticized with DEHP alone particularly in the case of carbon dioxide. Water vapor transmission rates of the NBR‐modified samples are higher than that of the control sample. The NBR‐modified PVC sample was found to be noncytotoxic in the in vitro cytotoxic evaluation both by direct contact and test on extract methods. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4720–4727, 2006     

三元共聚尼龙/聚氯乙烯/丁腈橡胶三元共混弹性体研究

选择三元共聚尼龙（PA），聚氯乙烯（PVC）和丁腈橡胶（NBR）为主体材料，采用高温机械共混，化学交联工艺制得了PA／PVC／NBR三元共混弹性体，探讨了PA／NBR，POM／NBR，PVC／NBR，HMWPVC／NBR三元共混体系性能，重点讨论了PA／PVC／NBR共混比，不同硫化体系，有机过氧物DCP用量等因素对PA／PVC／NBR三元共混弹性体性能的影响，实验结果表明：选择适宜配方制得力学性能和耐油耐溶剂性能较好的PA／PVC／NBR三元共混弹性体，扫描电镜的实验结果证实m(PA):m(PVC):m(NBR)=10:30:60和m(PA):m(PVC):m(NBR)=30:10:60两个体系的三元共混弹性体均具有较好的相容性，且前者的相容性更好。     

Crosslinking of PVC and NBR blends

The purpose of our work is to control the interfacial bonds between PVC and NBR using the ammonium salts of triazine thiols and dithiodimorpholine (DTDM) and thereby reveal the relation between the interfacial bonds and the final mechanical properties of products. In the experimental work a two-stage process was used. At first, an NBR/PVC blend was mixed with a mono-tetra-n-butylammonium salt of triazine trithiol at a temperature of 100°C on a two-roll mill to give the branching structure of triazine thiols into PVC. In the second stage branched NBR/PVC reacted with DTDM to afford the branched PVC containing trithiomorphonyl groups. In the presence of ZnO at 160°C trithiomorphonyl groups react with NBR to form a crosslinking structure between NBR and PVC. The mechanical properties of cured NBR/PVC blends were markedly improved by the treatment process and after addition of tetramethylthiuram monosulphide also. The mechanical properties were not improved by increasing the concentration of TT-TBA (tetrabutylammonium salt of 1,3,5-triazine-2,4,6-trithiol) over 4.2 phr.     

The Effect of Epoxidized Sunflower Oil on the Miscibility of Plasticized PVC/NBR Blends

Blends of plasticized poly(vinyl chloride) (PVC) with several ratios of nitrile rubber (NBR) were studied. The effects of epoxidized sunflower oil (ESO) in combination with di-(2-ethylhexyl)phthalate (DEHP) in the PVC blends on the tensile strength, elongation, hardness, and dynamical mechanical analysis (DMA) were studied. The modulus and hardness results revealed that the addition of ESO to the blend favors the miscibility of PVC and NBR. The PVC/NBR/(DEHP-ESO) blends behave as a compatible system as is evident from the single T _g observed in DMA. The moderate level broadening of the T _g zone in blends is due to the presence of ESO in the plasticizer system. Blends of plasticized PVC and nitrile rubber showed promising properties. The ESO is suitable to partially replace DEHP in PVC/NBR blends.     

Enhancement of the chemical resistance of nitrile rubber by direct fluorination

Nitrile rubber (NBR), poly(acrylonitrile‐co‐butadiene) or NBR packers, are used to seal oil‐well tubing, where they often come into contact with ZnBr₂ brines at high temperatures and pressures. Under these conditions, NBR exhibits accelerated chemical degradation, which results in embrittlement and cracking. Although alternative fluoropolymers exhibit excellent chemical resistance, their strength is less than NBR, and replacement of the usual gasket materials with fluoroelastomers is expensive. We have demonstrated that a fluoropolymer surface on a nitrile elastomer provides the necessary chemical resistance while the elastomer retains strength. This can be achieved by direct fluorination, a rather easy and inexpensive process. Samples of NBR O‐rings were fluorinated by exposure to F₂ and F₂/HF mixtures at various temperatures. Although fluorination by F₂ produced the desired fluoropolymer layer, fluorination by F₂/HF (hydrofluoric acid) mixtures gave a smoother fluorinated layer at lower temperatures and shorter reaction times. Elemental analysis showed that the fluorinated layer eliminated ZnBr₂ diffusion into the NBR polymeric matrix. Surface fluorination also significantly retarded the loss of the mechanical properties of NBR when it was exposed to zinc bromide fluid. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 971–979, 2003     

Irradiation Modification of PVC/NBR Blend

Electron beam initiated cross-linking on the 50/50 poly(vinyl chloride), PVC/acrylonitrile butadiene rubber, NBR blend was studied in the absence and presence of 4 phr trimethylolpropane triacrylate (TMPTA). The 50/50 NBR/PVC blend was prepared by mixing in a Brabender Plasticoder at 170°C. The blend was then irradiated by using a 3.0 MeV electron beam machine at doses ranging from 0 to 200 kGy in air and room temperature. The changes in gel fraction, tensile strength, hardness, impact strength, scanning electron micrographs and dynamic mechanical properties of the samples were investigated. The gel fraction results indicate that under the irradiation conditions employed, the PVC/NBR blend cross-linked by electron beam irradiation. The addition of TMPTA was found to be effective in the acceleration of the radiation-induced cross-linking. Gradual increases in mechanical properties with irradiation dose were observed before exhibiting a decline due to embrittlement as a consequence of excessive cross-linking at higher irradiation doses. The gradual changeover from ductile to brittle fracture due to the irradiation-induced cross-linking was evident from the SEM examination The increase in the storage modulus and T_g as well as the reduction in the damping peak with the increase in irradiation dose reveal that the enhancement in mechanical properties of NBR/PVC blends upon irradiation is due to the irradiation-induced cross-linking, as well as the improved interaction between NBR and PVC.     

Friction and wear properties of NBR/PVC composites

Acrylonitrial butadiene rubber (NBR)/Polyvinyl chloride (PVC) composites with different PVC content were prepared. The effect of PVC content on the mechanical strength and tribological properties of the NBR/PVC composites was investigated. The morphologies of the worn traces and debris of NBR/PVC composites and worn traces of mating ball were observed using a scanning electron microscope (SEM). It was found that the friction and wear of NBR/PVC was lower than that of NBR without PVC. The NBR/PVC composite with 30% PVC content showed the best synthetic mechanical and tribological properties. The inferior elastic properties and the lesser deformation under the applied load of composites with PVC resulted in hysteric force and adhesion force decrease, which leading to a lower friction and wear of NBR/PVC composites. The frictional failure unit of NBR70/PVC30 composite being smaller should be an important reason of the wear of the composite being lowest. The lubricating effect of PVC played an important role in decreasing the friction coefficient and wear of NBR/PVC composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Study on the damping of EVM based blends

The mechanical and damping properties of blends of ethylene‐vinyl acetate rubber(VA content >40 wt %) (EVM)/nitrile butadiene rubber (NBR) and EVM/ethylene‐propylene‐diene copolymer (EPDM), both with 1.4 phr BIPB (bis (tert‐butyl peroxy isopropyl) benzene) as curing agent, were investigated by DMA. The effect of polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), and dicumyl peroxide (DCP) on the damping and mechanical properties of both rubber blends were studied. The results showed that in EVM/EPDM/PVC blends, EPDM was immiscible with EVM and could not expand the damping range of EVM at low temperature. PVC was miscible with EVM and dramatically improved the damping property of EVM at high temperature while keeping good mechanical performance. In EVM/NBR/PVC blends, PVC was partially miscible with EVM/NBR blends and remarkably widened the effective damping temperature range from 41.1°C for EVM/NBR to 62.4°C, while CPVC mixed EVM/NBR blends had an expanded effective damping temperature range of 63.5°C with only one damping peak. Curing agents BIPB and DCP had a similar influence on EVM/EPDM blends. DCP, however, dramatically raised the height of tan δ peak of EVM/NBR = 80/20 and expanded its effective damping temperature range to 64.9°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study on compatibilization-crosslinking synergism in PVC/LDPE blends

Influences of nitrile rubber (NBR, acrylonitrile content 33.5 – 36.5 wt.-%) on the structure and mechanical properties of poly(vinyl chloride) (PVC)/low density polyethylene (LDPE) blends and its synergism with crosslinking agent have been studied. The addition of NBR to the blend is accompanied by a decrease in domain size and improvements in mechanical properties of the blend. When dicumyl peroxide (DCP) is added to the blend together with NBR, good synergism is caused and mechanical properties will improve dramatically. It is concluded that NBR can promote the phase dispersion of PVC and LDPE and their interfacial adhesion. Then, the probability of DCP existing at the interface will increase and more co-crosslinked products will form. Therefore, compatibilization and crosslinking are both exerted sufficiently.     

NBR/PVC乳液共沉合金的制备与性能

丁腈橡胶（NBR）与聚氯乙烯（PVC）共混合金是橡塑共混体系中一类重要的共混体系,NBR和PVC都属于极性聚合物,在共混过程中,相容性较好,因此这种体系被广为研究和应用。但此方法是选用粉末丁腈胶直接加入PVC中进行混炼共混,仍然存在共混不均匀的问题。本实验用乳液共混凝聚法制备了NBR/PVC共沉胶,研究了共沉工艺条件、丁腈胶种类与性能对NBR/PVC合金性能影响。     

Effect of acrylonitrile content of acrylonitrile butadiene rubber on mechanical and thermal properties of dynamically vulcanized poly(lactic acid) blends

We report here the morphology, thermal and tensile properties of poly(lactic acid) (PLA) blends composed of acrylonitrile butadiene rubber (NBR) with different acrylonitrile contents with/without dynamic vulcanization by dicumyl peroxide (DCP). The interfacial tension of PLA and NBR measured by contact angle measurement decreased as the acrylonitrile content of NBR decreased. Likewise, SEM images showed that the rubber particle size reduced with decreasing acrylonitrile content owing to the stronger interfacial adhesion between the PLA matrix and NBR domains. Incorporation of DCP at 1.0 phr for dynamic vulcanization led to higher crosslink density and, in turn, optimal tensile strength and tensile toughness as a result of the action of PLA‐NBR copolymer as a reactive compatibilizer. The dynamic vulcanization of the blends containing low acrylonitrile NBR gave the most improved tensile properties because the free radicals from DCP decomposition preferentially attacked the allylic hydrogen atoms or double bonds of the butadiene backbone. Accordingly, more NBR macroradicals were generated and probably more PLA‐NBR copolymers were produced. Moreover, further addition of DCP at 2.0 phr provided a large amount of crosslinked NBR gel, which significantly degraded the tensile properties. From the DSC results, dynamic vulcanization lowered the cold crystallization temperature, implying an improvement of cold crystallization. Finally, TGA results showed a higher degradation temperature as a function of DCP content, which suggested that thermal stability increased due to stronger interfacial adhesion as well as higher gel content. © 2019 Society of Chemical Industry     

Self‐crosslinking and cocrosslinking with nitrile rubber of poly(vinyl chloride) with pendent N,N‐diethyldithiocarbamate group

In order to realize the self‐crosslinking and cocrosslinking of poly(vinyl chloride) (PVC) with nitrile‐butadiene rubber (NBR), PVC with pendent N,N‐diethyldithiocarbamate groups (PVC‐SR) was prepared from the reaction of PVC with sodium SR in butanone. The PVC‐SR was self‐crosslinked and the PVC‐SR/NBR blend was cocrosslinked under heating at 170°C. The effect of the degree of functionality of PVC‐SR on the torque, gel content, glass‐transition temperature, and tensile properties was investigated. The results showed that the crosslinking reaction did not occur for PVC, NBR, or the PVC/NBR blend. Introducing the SR groups into PVC caused the crosslinking reaction to occur and the high gel contents of the crosslinked samples were obtained in 15 min. The degree of crosslinking increased with the degree of functionality of PVC‐SR. The mechanism of the crosslinking reaction was discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 634–638, 2001     

Microwave‐absorbing performance and mechanical properties of poly(vinyl chloride)/acrylonitrile–butadiene rubber thermoplastic elastomers filled with multiwalled carbon nanotubes and silicon carbide

Poly(vinyl chloride) (PVC)/acrylonitrile–butadiene rubber (NBR) were mixed with multiwalled carbon nanotubes (MWCNTs) and silicon carbide (SiC) to prepare microwave‐absorbing composites. The complex permittivity, direct‐current (dc) conductivity, microwave‐absorbing performance, morphology, and mechanical properties of the composites were studied. The real and imaginary parts of the permittivity of the composites increased with increasing MWCNT content. The premixing of the MWCNTs with PVC was more beneficial to the dispersion of MWCNTs; this led to a higher dc conductivity and permittivity and better microwave‐absorbing performance than the premixing of MWCNTs with NBR for the PVC/NBR/MWCNT composites. The PVC/NBR/MWCNT composites had a minimum reflection loss (RL_min) of ?49.5 dB at the optimum thickness of 1.96 mm. The efficient microwave absorption of the PVC/NBR/MWCNT composites was due to a high dielectric loss and moderate permittivity. The incorporation of SiC into the PVC/NBR/MWCNT composites increased the real and imaginary parts of permittivity of the composites. When the SiC content was 70 phr, RL_min decreased to ?34.9 dB at a thickness of 3 mm. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improved properties of molecular composite of nitrile rubber and poly (p-phenylene terephthalamide) by blending with poly (vinyl chloride)

Summary Nitrile rubber (NBR) was reinforced by poly(p-phenylene terephthalamide) (PPTA) with a coprecipitation method from a common solvent of them. PPTA was converted to N-sodium PPTA with sodium hydride in DMSO, forming homogeneous solution. DMF dissolves NBR. Both solutions were blended to form an isotropic solution. The precipitant was NBR reinforced by PPTA which was regenerated from N-sodium PPTA at coagulation as reported previously. The molecular composite thus obtained was mill-blended with poly(vinyl chloride) (PVC) in order to enhance solvent resistant property. The vulcanized composite of NBR/PVC reinforced by PPTA showed higher modulus, higher strength and more improved solvent resistance than the gum stock and the black stock of NBR/PVC. The properties of the molecular composite containing 5phr PPTA found approximately comparable to those of the black stock of NBR/PVC with 30–40phr ISAF carbon black.On Leave from Japan synthetic Rubber Co., Ltd., Higashi-yurigaoka, Assao-ku, Kawasaki 215, Japan     

高岭土增强PVC/橡胶非硫化复合体系的研究

研究了橡胶种类及用量、增塑剂用量、表面处理剂种类及用量对聚氯乙烯／橡胶非硫化复合体系力学性能的影响,并用扫描电镜分析了有机胺类表面处理剂改性高岭土／聚氯乙烯／丁腈橡胶的界面结合状况。结果表明,当丁腈橡胶（NBR）用量为30份,增塑剂DOP用量为60份,表面处理剂1质量分数为3％,并且填有60份的高岭土时,可得到力学性能较佳的高岭土／聚氯乙烯／丁腈橡胶共混物。     

Mechanical and thermo-oxidative properties of blends of poly(vinyl chloride) with epoxidized natural rubber and acrylonitrile butadiene rubber in the presence of an antioxidant and a base

Being polar and compatible with poly(vinyl chloride), epoxidized natural rubber (ENR) is similar in behaviour to acrylonitrile butadiene rubber (NBR). To assess the extent of this similarity, the mechanical properties of 50/50 blends of PVC with these two rubbers were compared. Their response to thermo-oxidative ageing in the presence of an antioxidant and a base was also investigated by ageing the blends at 100°C for 7 days. Studies involving mechanical properties and FTIR were used to evaluate the extent of thermal degradation. The results revealed that blends of ENR show mechanical properties which are as good as, and in some instances better than, those of the NBR blends. However, the ENR blends with PVC are very prone to oxidative ageing. This might be attributed to the susceptibility of the oxirane group to ring-opening reactions, particularly in the presence of PVC, which yields HCl as it degrades. The amine-type antioxidant 2,24-trimethyl-1,2-dihydroquinoline (TMQ) improved the oxidative stability of both blends. This was more significant in the ENR blend, which in some cases attained stability comparable with that of NBR. The addition of a base, calcium stearate [Ca(St)₂], did not show any influence in the PVC/ENR blend, even though it was expected to curb acid-catalysed degradation. Ca(St)₂, however, improved the oxidative stability of the PVC/NBR blend. The combination of optimum amounts of TMQ and Ca(St)₂ effectively improved the tensile strength of both unaged blends, without appreciable adverse effect on elongation at break. This combination also imparted stability better than that of TMQ alone.     

Nitrile rubber/sliding graft copolymer damping material with significantly improved strength and damping performance

Nitrile rubber (NBR)/sliding graft copolymer (SGC) composites with significantly improved strength and damping property are successfully prepared. SGC is a novel kind of supramolecular material with sliding crosslink junctions. The micromorphology analyses of NBR/SGC composites indicate that the SGC phase with particle size less than 500 nm is fairly uniformly dispersed in the NBR matrix. As SGC content increases, the loss factors (tan δ) of NBR/SGC composites increase gradually. Specifically, the tan δ of NBR/SGC (100/40) is about 1.2 times higher than that of pristine NBR rubber. The tensile strength and elongation at break of NBR/SGC composites are unexpectedly improved after the addition of SGC. The significantly improved damping performance and tensile strength can be ascribed to the pulley effect of SGC and the strong interfacial hydrogen bonds between SGC and NBR. The high damping performance and good mechanical strength make the NBR/SGC composite a promising high-performance damping material. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47188.     

Synergistic effect of hindered amine light stabilizers/ultraviolet absorbers on the polyvinyl chloride/powder nitrile rubber blends during photodegradation

The photostability of hindered amine light stabilizer (HALS) and ultraviolet absorber (UVA) on the blends of plasticized poly (vinyl chloride) (PVC) and powder nitrile rubber (NBR) has been studied with a Xenon Test Chamber. The digital photos, color differences, attenuated total refection‐Fourier transform infrared (ATR‐FTIR) spectra and mechanical properties of the blends have been determined. HALS combined with UVA effectively protects PVC/NBR blends from yellowing and restrains the decrease of elongation at break of the blends. The synergistic phenomenon is ascribed to the different photostable mechanisms of HALS and UVA at different photo aging stages. The color of PVC/NBR control sample quickly changes into yellow at the first 400 h of irradiation, due to the polyenes structures that induced by the double bonds of butadiene in NBR. From 400 to 800 h, crosslinking dominates and the amount of polyenes decreases, resulting into the decrease of color change. At the early stage of irradiation, chain‐scission of polymer takes the predominant place, and the tensile strength decreases. But during the latter stage, crosslinking takes the predominant place and the tensile strength increases slightly. HALS and UVA have a little effect on the maintaining of elongation at break of PVC/NBR blends. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Mechanical Properties and Thermooxidative Aging of a Ternary Blend,Pvc/Enr/Nbr,Compared with the Binary Blends of Pvc

In the quest to improve the thermooxidative aging of the poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blend, nitrile rubber (NBR) was incorporated into the blend to yield a ternary blend of PVC/ENR/NBR. A Brabender Plasticorder with a mixing attachment was used to perform the melt mixing at 150°C and 50 rpm followed by compression molding. The mechanical properties, dynamic mechanical properties, and thermooxidative aging behavior of the ternary blend were compared with those of the binary blends (i.e., PVC/ENR and PVC/NBR). It was found that the ternary blend exhibits mechanical properties which are superior to those of PVC/ENR. A single glass transition temperature (T _g) obtained from dynamic mechanical analysis coupled with synergism in the modulus and some other mechanical properties indicate that PVC, ENR, and NBR form a single phase (miscible system) in the ternary blend. Di-2-ethyl hexylphthalate (DOP) plasti-cizer improves the aging resistance of the blends generally, whereas the presence of CaCO₃ as a filler only imparts minor influences on the properties and aging resistance of the blends.