环氧化天然橡胶的研究与应用

环氧化天然橡胶（ENR）是由NR化学改性而成,笔者阐述了环氧化天然橡胶制备原理和方法、环氧化天然橡胶性能及应用研究、环氧化天然橡胶共混改性研究,其中包括ENR与PVC共混体系的研究、ENR其它共混体系的研究和ENR改性的研究.     

环氧化天然橡胶的性能及应用

天然胶乳在严格控制的条件下与过氧化物反应,在橡胶主分子链双键上引入环氧基团,从而改变了原来的分子结构,使其一系列性能发生变化。这种经过环氧化改性的天然橡胶称为环氧化天然橡胶（简称ENR）。ENR的透气性比天然橡胶（NR）显著低,对非极性油类的耐油性及其与多种工业材料的粘着力显著提高,可代替一些专用橡胶,用于气密性、耐油性橡胶制品及胶粘剂。近几年国内已有不少院校、科研所和厂家开展ENR用于内胎、印刷胶辊、耐油胶管、胶板、胶粘剂、球服、无内胎轮胎内村层和ENR胶乳作玻纤、化纤橡胶基布表面浸胶处理及ENR与多种…     

ENR改性陶土和填充NR硫化胶结构与性能的研究

采用环氧化天然橡胶（ENR25和ENR45）改性陶土,通过对混炼胶结合胶质量分数、硫化胶表观交联密度、补强性能和力学性能的测定,研究了ENR与陶土的相互作用,ENR的环氧化程度及ENR的用量对陶土和填充NR硫化胶结构与性能的影响。结果表明,ENR可提高陶土与NR间界面的作用强度,提高混炼胶的结合胶质量分数,增大硫化胶的表观交联密度,改善硫化胶的网络结构,提高陶土填充NR硫化胶的力学性能,其中ENR25对陶土的改性效果优于ENR45。     

环氧化天然橡胶共交联改性EPDM/NR共混物的性能

将三元乙丙橡胶(EPDM)与环氧化天然橡胶(ENR)共交联改性后,再与天然橡胶(NR)共混,考察了ENR共交联改性EPDM/NR共混胶的硫化特性、硫化胶的物理机械性能、溶胀指数和耐热空气老化性能,并对该硫化胶进行了差示扫描量热分析。结果表明,EPDM经过ENR共交联改性后与NR共混,ENR共交联改性EPDM/NR共混胶的交联程度明显提高,各相达到了同步交联,硫化胶的综合性能得到了显著改善。     

环氧化天然橡胶及其应用研究进展

介绍环氧化天然橡胶(ENR)的制备方法、性能及其对聚合物基复合材料的改性效果.ENR在保留天然橡胶(NR)的结构和性能的基础上,可进一步提高NR的气密性能和耐油性能等.不同硫化体系硫化ENR的性能不同,ENR的环氧度越高,其玻璃化温度越高,气密性能和耐溶剂性能越好.ENR可作为相容剂对NR和其他橡胶及白炭黑进行改性,提高胶料的性能和白炭黑在胶料中的分散性.     

环氧化液体对天然橡胶对丁腈橡胶胶料性能的影响

天然橡胶（NR）中顺式－异戊二烯上存在的活性双键使NR分子可通过加成或产生小官能团的方式进行化学改性。通过改性，改变了NR的化学性质的一般物理性能，从而使其适用于一些新的应用场合。例如，氧与双键反应形成的环氧化天然橡胶（ENR）对烃类油和溶剂有很好的抗耐性，有较高的极性和玻璃化转变温度，但气透性降低了。     

环氧化天然橡胶对累托石/炭黑/天然橡胶纳米复合材料性能的影响

研究环氧化天然橡胶（ENR）对累托石（REC）/炭黑/天然橡胶（NR）纳米复合材料性能的影响。结果表明：REC/炭黑/NR纳米复合材料中填料分散均匀,REC片层呈纳米级分散;ENR改善了REC与橡胶基体间的界面相互作用,增大了复合材料交联密度,从而显著提高了复合材料的力学性能、抗切割性能和耐磨性能,且各性能增幅随ENR用量的增大而增大。     

一种环氧化天然橡胶包覆改性白炭黑及其制备方法以及橡胶材料

授权公告号:CN 105330899B授权公告日:2018年8月7日专利权人:中国热带农业科学院农产品加工研究所、中国热带农业科学院橡胶研究所发明人:廖禄生、李一民、钟杰平等本发明公开了一种环氧化天然橡胶(ENR)包覆改性白炭黑的方法及改性效果。将白炭黑分散液与ENR混合,经剪切处理、固液分离和高温处理,环氧基与硅羟基发生化学反应,得到ENR包覆改性白炭黑。ENR包覆改性白炭黑填充的橡胶材料与     

煤矸石粉填充硫化天然橡胶性能的研究

对废弃煤矸石进行超细粉碎、焙烧,用环氧化天然橡胶(ENR)进行表面处理,然后与硫化天然橡胶(NR)充分混炼,对混炼胶表观交联密度、补强性能、应用性能、动态力学性能等进行了测定。试验结果表明,超细煤矸石粉对NR具有较好的补强性能和分散性。经过ENR改性处理后的煤矸石粉其性能更好,完全可以作为补强填料取代或部分取代炭黑。     

天然橡胶／环氧化天然橡胶共混物的相态及性能研究

本文对天然橡胶（NR）和环氧化天然橡胶（ENR）共混物的相态对共混物性能的影响做了研究。共混物的相态采用动态力学分析法和电子显微摄影法进行分析。动态力学分析法和电子显微摄影的结果表明：不同组成的NR／ENR共混物具有多相结构，而当ENR的体积分数占0．35时出现共连续相的转化。共混物的透气性和耐油性受相的结构影响很大，而共混物的力学性能与相的转化有关。     

Thermoplastic vulcanizates based on epoxidized natural rubber/polypropylene blends: Effect of compatibilizers and reactive blending

Epoxidized natural rubber (ENR) was prepared using the performic epoxidation method. TPVs based on ENR/PP blends were later prepared by melt‐mixing processes via dynamic vulcanization. The effects of blend ratios of ENR/PP, types of compatibilizers, and reactive blending were investigated. Phenolic modified polypropylene (Ph‐PP) and graft copolymer of maleic anhydride on polypropylene molecules (PP‐g‐MA) were prepared and used as blend compatibilizers and reactive blending components of ENR/Ph‐PP and ENR/PP‐g‐MA blends. It was found that the mixing torque, apparent shear stress and apparent shear viscosity increased with increasing levels of ENR. This is attributed to the higher viscosity of the pure ENR than that of the pure PP. Furthermore, there was a higher compatibilizing effect because of the chemical interaction between the polar groups in ENR and PP‐g‐MA or Ph‐PP. Mixing torque, shear flow properties (i.e., shear stress and shear viscosity) and mechanical properties (i.e., tensile strength, elongation at break, and hardness) of the TPVs prepared by reactive blending of ENR/Ph‐PP and ENR/PP‐g‐MA were lower than that of the samples without a compatibilizer. However, the TPVs prepared using Ph‐PP and PP‐g‐MA as compatibilizers exhibited higher values. We observed that the TPVs prepared from ENR/PP with Ph‐PP as a compatibilizer gave the highest rheological and mechanical properties, while the reactive blending of ENR/PP exhibited the lowest values. Trend of the properties corresponds to the morphology of the TPVs. That is, the TPV with Ph‐PP as a blend compatibilizer showed the smallest rubber particles dispersed in the PP matrix, while the reactive blending of ENR/PP‐g‐MA showed the largest particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4729–4740, 2006     

Effect of surface modification of silicon carbide nanoparticles on the properties of nanocomposites based on epoxidized natural rubber/natural rubber blends

Improvement of the properties of rubber nanocomposites is a challenge for the rubber industry because of the need for higher performance materials. Addition of a nanometer‐sized filler such as silicon carbide (SiC) to enhance the mechanical properties of rubber nanocomposites has rarely been attempted. The main problem associated with using SiC nanoparticles as a reinforcing natural rubber (NR) filler compound is poor dispersion of SiC in the NR matrix because of their incompatibility. To solve this problem, rubber nanocomposites were prepared with SiC that had undergone surface modification with azobisisobutyronitrile (AIBN) and used as a filler in blends of epoxidized natural rubber (ENR) and natural rubber. The effect of surface modification and ENR content on the curing characteristics, dynamic mechanical properties, morphology and heat buildup of the blends were investigated. The results showed that modification of SiC with AIBN resulted in successful bonding to the surface of SiC. It was found that modified SiC nanoparticles were well dispersed in the ENR/NR matrix, leading to good filler‐rubber interaction and improved compatibility between the rubber and filler in comparison with unmodified SiC. The mechanical properties and heat buildup when modified SiC was used as filled in ENR/NR blends were improved. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45289.     

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     

Internal mixer studies of poly(vinyl chloride)/epoxidized natural rubber blends

Blends of polyvinyl chloride/epoxidized natural rubber (PVC/ENR) blends were studied. Their rheological properties were studied with a Brabrender Plasticorder. It was found that the rheological properties of any PVC/ENR blends are governed by their blending conditions. To ensure homogenous PVC/ENR blends, adequate and suitable blending conditions must be utilized. PVC thermoplastics phases enhances rigidity while ENR rubbery phases imparts flexibility and processability to the blends. With premixing, Ba/Cd/Zn-based PVC stabilizer is effective in stabilizing the PVC/ENR blends. Their properties are further enhanced by the addition of curatives.     

Preparation and Electron Beam Irradiation of PVC/ENR/CNTs Nanocomposites

Poly (vinyl chloride), PVC/epoxidized natural rubber blend, ENR/carbon nanotubes, CNTs nanocomposites were prepared using melt intercalation and solution blending methods. In both preparation methods PVC: ENR: CNTs ratios were fixed at 50:50:2, while the 50/50 PVC/ENR blend without the addition of CNTs was used as control. The PVC/ENR/CNTs nanocomposites were exposed to electron beam (EB) irradiation at doses ranging from 0–200 kGy. The effects of two different preparation methods on the tensile properties, gel fraction and morphology of the PVC/ENR/CNTs nanocomposites were studied. Prior to EB irradiation, the addition of 2 phr of CNTs caused a drop in the tensile strength (Ts) of the 50/50 PVC/ENR blend, implying poor distribution of CNTs in the PVC/ENR blend matrix. However upon EB irradiation, the nanocomposites prepared by the melt blending method exhibited higher values of Ts as compared to the neat PVC/ENR blend due to occurrence of radiation-induced cross-linking in the PVC/ENR blend matrix. Transmission electron microscopy (TEM) images proved that a better dispersion of CNTs in PVC/ENR blend matrix can be achieved by melt intercalation compared to solution blending and the dispersion of CNTs was improved by irradiation. Scanning electron microscopy (SEM) results showed a distinct failure surface with formation of rough structure for the irradiated nanocomposites, which explains the higher values of tensile properties compared to the non-irradiated nanocomposites.     

Rheological and curing properties of reactive blending products of epoxidised natural rubber and cassava starch

Abstract

Epoxidised natural rubber (ENR) has been prepared and used as a blending ingredient together with a compatibiliser for blending of natural rubber (air dry sheet, ADS) and cassava starch. Mooney viscosities of the blends were quantified at 100°C and rheological properties in terms of shear stress and shear viscosity were plotted against shear rates. The results showed that pure ENR gave a lower Mooney viscosity, shear stress, and shear viscosity than blends with cassava starch. Mooney viscosity, shear stress, and shear viscosity for the blends increased with increasing levels of starch. At the same level of cassava starch blended, the highest values of these quantities were observed for the blends with ENR. The blend of ADS with ENR as a compatibiliser showed lower values than those of ENR itself, but higher than those of ADS with the starch. The results are described in terms of the level of chemical interaction between polar groups in ENR and in cassava starch. Curing behaviour for compounds of ENR, ADS, and ADS with ENR as a compatibiliser were studied. The results found that ENR exhibited a long delay (～ 10 min) before the vulcanisation took place compared with 1 min for ADS compounds. In the curing curve for ENR, an equilibrium value at maximum torque was not found indicating that the stiffness of the ENR compounds still increased with increasing testing time until 60 min. Stiffness of the ENR compounds also increased with increasing levels of cassava starch.     

天然橡胶增韧聚氯乙烯的研究

采用未改性的标准天然橡胶(NR)作增韧剂,通过机械共混法制备增韧聚氯乙烯(PVC)复合材料,考察了NR和增容剂用量对PVC增韧效果以及力学性能的影响.结果表明:当NR用量为10份时,材料的冲击强度最高为24.87 kJ/m2;加入增容剂环氧化天然橡胶(ENR)后,材料的冲击强度随其用量的增加而增大,在ENR为5份时其冲击强度为69.86 kJ/m2;氯化聚乙烯(CPE)作增容剂时,其冲击强度先升后降,在4份时达到峰值103.93 kJ/m2;氯化橡胶(CNR)作增容剂在3份时,其冲击强度达到最佳值35.37 kJ/m2;增容增韧后共混物的拉伸强度普遍降低.     

Use of epoxidized natural rubber as a toughening agent in plastics

At present, the rubber toughening of plastics has become an attractive field of study in polymer science and technology because brittleness is known to be a drawback in many engineering plastics; it can cause premature failure during application. Among existing rubber materials, epoxidized natural rubber (ENR) has been widely used as an impact modifier or toughening agent in a large number of engineering plastics; in particular, it enhances the impact strength, which deteriorates with the incorporation of other additives, such as fillers and flame retardants. ENR is a modification product from natural rubber produced via an epoxidation reaction. ENR also has good chemical resistance. In this review, we aim to provide a concise current status in the field of ENR toughening agents for plastics with a brief discussion of their associated problems and potential applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42270.