不同辅助生物凝固剂用量对天然橡胶性能的影响

通过改变不同辅助生物凝固剂的用量,讨论不同用量对天然橡胶性能的影响。结果表明,在理化性能方面微生物凝固胶的性能优于酸对照样;在力学性能方面,酸凝固胶明显差于微生物凝固胶;微生物凝固胶的硫化特性和热分析优于酸对照样;相对分子质量及相对分子质量分布与酸对照样差异不显著。     

微生物凝固天然橡胶与酸凝固天然橡胶的性能差异

为揭示微生物凝固天然橡胶(NR-w)和酸凝固天然橡胶(NR-a)的性能差别,制备了3个系列的NR,并对其性能进行了全面的研究.结果发现,在生胶性能方面,NR-w凝胶含量和塑性初值均高于NR-a,而分子量低于NR-a.对于硫化胶,NR-w纯胶硫化胶的力学性能远高于NR-a纯胶,而NR-w炭黑胶的力学强度与NR-a炭黑胶很接近;此外,NR-a纯胶的抗老化性能远高于NR-w,其炭黑胶的抗老化性能也高于NR-w,在硫化性能方面,NR-w的转矩增大速率快于NR-a,强度也比NR-a高.在动态性能方面,NR-w的抗湿滑性能和滚动阻力均高于NR-a.     

凝固方法对天然橡胶性能的影响

本文研究了凝固方法对天然橡胶性能的影响。结果表明:不同凝固方法制备的天然橡胶都达到5号标准橡胶的质量指标,生物凝固的天然橡胶硫化时间较短、硫化胶力学性能较好、而抗老化性能较差,HAc凝固的天然橡胶的硫化时间较长,硫化胶力学性能较差,而抗老化性能较好。     

几种不同凝固方法对天然橡胶性能的影响

对6种不同的凝固方法与酸对照样的性能进行对比,探讨不同凝固方法对天然橡胶性能的影响。结果表明,辅助生物凝固剂凝固胶理化性能优于其它方法;酸对照样的力学性能低于微生物凝固胶;硫化特性和热分析的微生物凝固胶也优于酸对照样;不同的凝固方法对相对分子质量及其分布影响不显著。     

使用核磁共振交联密度仪测试不同方法凝固天然橡胶的交联密度和性能的关系

用核磁共振(NMR)法测定不同方法凝固天然橡胶的交联密度,研究其与性能之间的关系。结果表明,硫化胶的交联密度不仅影响其核磁共振的横向弛豫时间(T1),而且影响其纵向弛豫时间(T2)。随着交联密度大,硫化胶的核磁共振弛豫时间缩短。另外,微生物凝固天然橡胶硫化胶的交联密度、正硫化时刻扭矩和拉伸强度均大于酸凝固天然橡胶硫化胶的。     

溶菌酶凝固天然橡胶加工性能和力学性能的研究

采用溶菌酶凝固天然胶乳,对凝固后天然橡胶的理化性能、加工性能及力学性能等进行研究,并与酸凝固天然橡胶对照。研究表明,溶菌酶凝固天然橡胶综合性能优异。溶菌酶凝固天然橡胶混炼胶与酸凝固天然橡胶混炼胶相比,弹性模量G’高,损耗因子tanδ小。与酸凝固天然橡胶相比,溶菌酶凝固天然橡胶蛋白质含量高,耐氧老化性能好,硫化速率快,硫化胶交联密度高,力学性能好。     

溶菌酶凝固天然橡胶加工性能和力学性能的研究

采用溶菌酶凝固天然胶乳,对凝固后天然橡胶的理化性能、加工性能及力学性能等进行研究,并与酸凝固天然橡胶对照。研究表明,溶菌酶凝固天然橡胶综合性能优异。溶菌酶凝固天然橡胶混炼胶与酸凝固天然橡胶混炼胶相比,弹性模量G’高,损耗因子tanδ小。与酸凝固天然橡胶相比,溶菌酶凝固天然橡胶蛋白质含量高,耐氧老化性能好,硫化速率快,硫化胶交联密度高,力学性能好。     

射流凝固制备的天然橡胶性能的研究

利用射流凝固(NR-j)的方法制备天然橡胶,研究了天然橡胶的性能。分析结果可得:射流凝固天然橡胶的溶胶含量较低,杂质含量、灰分含量、氮含量和塑性初值比酸凝固天然橡胶的大,而挥发分和塑性保持率较小。在硫化性能上,射流凝固天然橡胶的硫化速率比酸凝固天然橡胶的速率稍大,硫化胶的强度也大于酸凝固天然橡胶的强度,但其老化后的强度保持率小于酸凝固天然橡胶。     

酸凝固天然橡胶和微生物凝固天然橡胶硫化特性研究

采用硫化仪分析2种天然橡胶的硫化过程,探讨了炭黑和硫化温度对硫化诱导期、正硫化时间和最大转矩的影响。研究结果发现：微生物凝固胶和酸凝固胶的硫化诱导期和正硫化时间随硫化温度的上升显著下降,且都能很好符合阿仑尼乌斯方程;胶样的最大转矩与硫化温度呈很好的线性关系,且随着硫化温度的升高,逐渐降低;当采用纯胶配方时,微生物凝固胶的MH0显著高于酸凝固胶,而加入炭黑后．2种胶样的MH0均显著提高。但微生物凝固胶的MH0稍低于酸凝固胶。     

天然橡胶硫化动力学研究

采用硫化仪测定了2种不同凝固工艺的天然橡胶（NR）的硫化过程,探讨了制胶工艺、配方和温度对硫化动力学参数的影响。研究结果发现,随着温度的上升,硫化速率常数迅速上升。在纯胶体系中,微生物凝固胶的活化能高于酸凝固胶。当加入炭黑后,酸凝固胶的活化能升高,而微生物凝固胶的活化能下降。     

微生物凝固天然橡胶加工性能的研究

使用橡胶加工分析仪和流变仪,研究了微生物凝固天然橡胶的加工性能。结果表明,与5#标准天然橡胶相比,微生物凝固的天然橡胶具有较低弹性模量和损耗因子以及较短应力松弛时间和较快硫化速度。     

Novel thermoplastic natural rubber based on thermoplastic polyurethane blends: influence of modified natural rubbers on properties of the blends

Three different forms of natural rubber: maleated natural rubber (MNR), epoxidized natural rubber (ENR) and natural rubber-graft-poly(methyl methacrylate) (NR-g-PMMA) were prepared. Degree of functional groups in rubber molecules was quantified using the integrated peak areas of ¹H NMR. It was found that the modified rubbers with similar level of functionality had been successfully prepared. Thermoplastic natural rubber (TPNR) based on blending of thermoplastic polyurethane (TPU) and various forms of rubber were then prepared using melt blending method. The properties of the blends were studied and compared together in relation to different types of natural rubbers prepared (i.e., unmodified NR, MNR, ENR and NR-g-PMMA). It was found that the blends with modified NR exhibited superior stiffness, entropy effect and damping factor compared to other blends with unmodified NR. This is attributed to the chemical interaction between the functional groups of modified NR molecules and polar functional groups in TPU molecules which facilitated higher interfacial adhesion between both phases. The chemical interaction was verified by ATR-FTIR and TSSR techniques. It was also found that the MNR/TPU blend showed the highest tensile modulus, mechanical and elastic properties with smallest and finer grain dispersion of co-continuous phase compared to ENR/TPU, NR-g-PMMA/TPU and unmodified NR/TPU blends, respectively. This might be due to higher chemical interactions between MNR and TPU phases. Furthermore, the incorporation of rubber did reduce hardness (i.e., <60 Shore A) with improvement of elasticity of the blends compared with the original TPU (i.e., ~85 Shore A).     

马来酸酐接枝天然橡胶对纤维素纤维增强天然橡胶复合材料的增容作用

在无引发剂的熔融状态下,利用剪切力将马来酸酐接枝于天然橡胶分子链上,并将马来酸酐接枝天然橡胶(MNR)作为增容剂添加到纤维素纤维增强天然橡胶复合材料中,研究其对复合材料性能的影响.结果表明,在熔融状态下利用剪切力能够发生自由基反应或Diels-Alder反应,将马来酸酐接枝于天然橡胶分子链上而制得MNR.添加了MNR的纤维增强天然橡胶硫化胶的物理机械性能,尤其是定伸强度比未添加MNR的硫化胶有明显提高,应力弛豫程度减小;扫描电镜分析也说明添加MNR使填料与橡胶基质之间有了更强的界面黏合力.     

Reinforcement of maleated natural rubber by precipitated silica

Graft copolymers of maleic anhydride and natural rubber or so‐called maleated natural rubbers (MNRs) were prepared in a molten state with varying maleic anhydride contents from 4 to 10 phr. In this work, the filler–filler and filler–rubber interactions of the MNR and precipitated silica were investigated. The MNR compounds containing 40 phr of silica both with and without 9 wt % of silane coupling agent were prepared. By increasing the maleic anhydride contents, the Mooney viscosity and cure times were increased, but the torque differences and cure rate indices were decreased. Bound rubber was increased with increasing maleic anhydride content, indicating an increase of filler–rubber interaction. In case of the compounds without silane, the MNR with 6 phr of maleic anhydride showed the lowest filler–filler interaction as indicated by a decrease of storage modulus upon an increase of strain in the filled compound i.e., Payne effect. This MNR compound also yielded the optimum mechanical properties. It has been demonstrated that a use of MNR with appropriate maleic anhydride content can reduce filler–filler interaction dramatically and hence improve a silica dispersion, as confirmed by SEM micrographs, resulting in an enhancement of the mechanical and dynamical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Maleated natural rubber prepared through mechanochemistry and its coupling effects on natural rubber/cotton fiber composites

Maleated natural rubber (MNR) was prepared by blending natural rubber (NR) and maleic anhydride (MA) in an internal mixer at 150 °C through mechanochemistry. The graft reaction of MA onto NR and the hydrogen bonding formed between fiber and MA were confirmed by Fourier transformation infrared spectrometer (FTIR). The quantity of grafted MA increased with increasing MA content. The composites showed better mechanical properties with MNR that contains higher MA content. The MNR with 20 phr MA was used as a coupling agent. Kraus equation showed the incorporation of MNR favored the reinforcement of fiber. The composites with MNR showed higher modulus and tensile strength than those without MNR. The coarse surfaces of the pullout fibers and the high storage modulus of composites with MNR implied the enhancement of interfacial adhesion.     

Thermoplastic vulcanizates based on maleated natural rubber/polypropylene blends: Effect of blend ratios on rheological,mechanical, and morphological properties

Maleated natural rubber (MNR) was prepared and used to formulate thermoplastic vulcanizates (TPVs) based on various MNR/PP blends. The influence of mixing methods on the TPVs properties was first studied. We found that mixing all ingredients in an internal mixer provided the TPVs with better mechanical properties. The final mixing torque, shear stress, and shear viscosity of the TPVs prepared with various blend ratios of MNR/PP increased with increasing levels of MNR in the blends. This may be attributed to higher shear viscosity of the pure MNR than that of the pure PP. Furthermore, as evidenced in SEM micrographs, the TPVs are two phase morphologies with dispersed small vulcanized rubber domains in the PP matrix. Therefore, the higher content of PP caused the more molten continuous phase of the flow during mixing and rheological characterization. Tensile strength and hardness of the TPVs increased with increasing levels of PP, while the elongation at break decreased. Furthermore, the elastomeric properties, in terms of tension set, increased with increasing levels of MNR in the blends. This may be attributed to decreasing trends in the size of vulcanized rubber particles dispersed in the PP matrix with an increasing concentration of MNR. POLYM. ENG. SCI. 46:594–600, 2006. © 2006 Society of Plastics Engineers.     

逆絮凝法制备天然橡胶的研究

本研究使用逆絮凝法制备天然橡胶,分别选用酸凝固剂、无机盐凝固剂、无机盐复合凝固剂进行研究,并探讨了絮凝条件对天然橡胶性能的影响因素。结果表明：酸作为凝固剂时,硫酸的絮胶效果比醋酸、甲酸好,三者物理性能相差不大。无机盐作为凝固剂时,使用氯化钙絮胶效果良好,当氯化钙质量分数为2%时,得到的天然橡胶性能基本与参比样云标、烟片胶性能相当。无机盐复配作为凝固剂时,使用氯化钙/氯化钠凝固剂时絮胶效果良好,得到的天然橡胶性能优越于参比样云标、烟片性能。适当提高温度及搅拌速度,均有利于天然橡胶的絮凝。     

微波辐射凝固天然橡胶的性能研究

采用新型微波辐射凝固法凝固天然橡胶,并与传统天然橡胶凝固方法作比较,对其性能进行了全面研究。通过正交实验探索了实验室微波辐射凝固的适宜工艺条件。对比了微波辐射凝固胶（NR-m）、酸凝固胶（NR-a）和自然凝固胶（NR-n）的性能,结果表明,在理化性能方面,NR-rn的氮含量比NR-a和NR-n高,塑性初值比NR-a高;在物理机械性能方面,NR-m硫化胶老化前的定伸应力和拉伸强度比NR-a高,老化后的拉伸强度保持率比NR-a低,但比NR-n高;在硫化特性方面,NR-m的硫化诱导时间比NR-a和NR-n的短,最大转矩和硫化速度更高。     

Rheological and curing behavior of reactive blending. I. Maleated natural rubber–cassava starch

Maleated natural rubber (MNR) was prepared and used as a blending composition and a compatibilizer for blending of natural rubber (STR 5L) and cassava starch. The melt rheological behavior in terms of Mooney viscosity, apparent shear stress, and shear viscosity at 100°C were quantified. We found that the pure MNR gave the lower apparent shear stress, shear viscosity than did those of the blends with cassava starch. The rheological data of the MNR blends increased with increasing quantity of cassava starch. The highest value was observed for the blend of MNR. The rheological value was as follows: MNR > STR 5L with MNR (as the compatibilizer) > STR 5L compounds. Furthermore, rheological properties increased with increasing the levels of compatibilizer (MNR). The rheological results were described in terms of intermolecular interaction between the polar groups in the natural rubber and cassava starch molecules. Each rubber blend was compounded, and their curing characteristics were studied. The pure MNR compounds exhibited a long delayed onset of vulcanization for approximately 10 min. The retardation was found, because the accelerator (MBT) reacted with the anhydrides in the compound instead of acting as an accelerator. The retardation was not observed for the compound with the cassava starch. The curing curves for all MNRs were not in equilibrium at a maximum torque, while the pure STR 5L compound gave a curing curve with a maximum torque and a slight reversion. The curing curve for the compound with MNR as the compatibilizer was a combination of the curing curves of MNR and STR 5L. That is, the curve was in equilibrium at the maximum torque and the short delayed action. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2803–2813, 2001     

Ionic elastomer blends of zinc salts of maleated natural rubber and carboxylated nitrile rubber: Effect of grafted maleic anhydride

Zinc neutralized maleated natural rubbers (Zn‐MNR) were prepared by solution grafting and neutralization with zinc acetate in one‐step. It was later used for blending with carboxylated nitrile rubber (XNBR) in the composition of 50/50 parts by weight. The effect of grafted anhydride content (1.2, 1.6, 2.0, and 2.5% wt of NR) on the tensile properties of ionic rubber blends (Zn‐MNR/XNBR) was investigated. The tensile strength of the ionic blends was found to be greater than those of pure rubbers. The modulus, tensile, and tear strength of the blends dramatically increased with increasing levels of grafted anhydride. The ionic rubber blends also possessed superior physical properties compared to those of the corresponding nonionic rubber blends (MNR/XNBR). Dynamic mechanical thermal analysis and scanning electron microscopic studies were performed to verify the process of mixing. Fourier transform infrared spectroscopic studies were carried out to characterize the nature of specific intermolecular interactions between Zn‐MNR and XNBR chain segments. The results indicated that the ion‐ion (Zn⁺ ‐COO^?) interactions between Zn‐MNR and XNBR are formed at the interface, which provides the mean of compatibilization in the ionic rubber blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007