环氧化反式-1,4-聚异戊二烯的硫化及硫化胶性能

研究了4种不同环氧基摩尔分数化反式－1，4－聚异戊二烯（ETPI）的硫化及硫化胶性能，并对其在轮胎胶料中的应用进行了探讨，结果表明，ETPI可用传统的硫黄－促进剂体系进行硫化，在3类常用促进剂（M，CZ，TMTD）中，以CZ为硫化促进剂时的硫化曲线最为理想，随着环氧基摩尔分数的增加，ETPI硫化胶的弹性变差，耐磨性，耐油性，与轮胎帘线的粘接性和抗湿滑性较未硫化反式－1，4－聚异戊二烯（TPI）均有大幅度提高，但生热和滚动损失有所增加。在100℃下热空气老化结果表明，ETPI硫化胶属于交联反应为主的老化历程。环氧基摩尔分数为17％－25％的ETPI综合性能最好，ETPI与丁苯橡胶并用于胎面胶中可显著地提高其抗湿滑性能和耐油性，并用于天然橡胶帘布层胶中能显著地提高其与钢丝或尼龙帘线的粘接性。     

一种新型无毒性偶联剂

业已开发成功一种新型的炭黑－橡胶偶联剂，这就是对氨基苯磺酰叠氮化物，将这种化合物添加到胶料中，可提高硫化胶的回弹性和模量，同时使磨耗降低，通过测定硫化胶的动态物理机械特性，验证了对氨基苯磺酰叠氮化物偶联剂上述特性，受试硫化胶的玻璃化温度（Ｔｇ）已被调整的较高水平，含有氨基苯磺酰叠氮化物偶联剂的胶料可和作轮胎胎面，藉此达到降低轮胎滚动阻力，提高湿路面耐滑性的目的。通过动态性能测定，我们对氨基苯磺酰叠     

轮胎胶粉（GTR）的再生：生胶／再生GTR的（再）硫化

热化学部分脱硫的GTR（GTR^D）与不同生胶混合后进行了再硫化，用含／不合操作油的两种脱硫剂（软化剂的混合物）分别对GTR进行了脱硫处理。选用丁苯胶（SBR）、异戊橡胶（IR）、顺丁胶（BR）或它们的共混物，并通过硫黄、二硫化四甲基秋兰姆（TMTD）或过氧化物对其进行了硫化。对GTR^D含量为20-80％的橡胶／（再）硫化胶进行了制备和研究。对于IR／GTR^D体系，用硫黄体系硫化较好，而TMTD硫化体系可使BR／GTR^D和SBR／GTR^D硫化胶达到最佳性能。GTR^D粒子与橡胶基体间界面相的共硫化提高了所得（再）硫化胶的机械性能。所研究的再生GTR^D已可成功地应用到标准的轮胎生产配方中，起部分替代生胶的作用。     

采用以硝基醇为基础的粘合增进体系提高轮胎的耐久性

本研究的目的是当胶料中使用以硝基醇为基础的粘合体系时，对胶料实验室粘合试验观测到的粘合性能的提高与轮胎耐久性能的提高进行对比。在硫化过程中２－硝基－２－甲基－１－丙醇（ＮＭＰ）和间苯二酚化合生成一种增粘树脂。在以前的研究中已证明ＮＭＰ提高了典型帘布胶与帘布骨架材料之间的粘合性能。另外还证明了ＮＭＰ体系和钴并用也可以提高典型的带束层胶料与镀黄铜钢丝帘线之间的粘合性能。本文继续研究用镀黄铜钢丝和聚酯帘线增强的轮胎胶料粘合性能的改善。实验室粘合试验表明，硫化胶老化前后的粘合性能均有所提高。还测定了硫化特性曲线和物理性能。粘合性能的改善预示着轮胎耐久性会提高。当ＮＭＰ－ＰＬＵＳＴＭ（６０％活化的白炭黑）在轻型载重轮胎（１８５ＳＲ１４ＬＴ）中试验时，试验结果表明轮胎耐久性能大幅度提高。对轮胎试验数据、轮胎样品的粘合性能试验以及胶料性能作了评述。     

硫化胶中橡胶种类的定性和定量分析

采用裂解-气相色谱/质谱（Py-GC/MS）法研究子午线轮胎常用的4种橡胶天然橡胶（NR）、丁苯橡胶（SBR）、顺丁橡胶（BR）和溴化丁基橡胶（BIIR）及其并用胶NR/SBR,SBR/BR,NR/BR和NR/BIIR,确定4种橡胶的特征裂解产物,建立Py-GC/MS法定性定量分析未知硫化胶中并用橡胶的方法。结果表明,本方法在未知硫化胶分析时定性分析非常准确,可做半定量分析,重复性良好,相对标准偏差为0.01%。     

NR／EPDM并用胶共硫化的研究

采用了一种新的工艺方法－热处理－动态硫化法，有效地改善了ＮＲ／ＥＰＤＭ并用胶的共硫化性和力学性能。在硫化体系不变的情况下，可用硫化曲线定笥比较并用胶的共硫化程度。通过分析比较认为，粘弹谱仪法是测定并用硫化胶两相交联程度的简便可靠方法。     

水胎胶嘴存在的问题及解决措施

水胎是轮胎硫化的必备工具,其使用寿命直接影响轮胎的成本。水胎一般是因胶嘴部位损坏,无法更换胶嘴而报废的。一条水胎从使用到报废,胶嘴通常可更换３～４次（一次使用寿命为５０～６０次）。本文对胶嘴几个常见问题形成的原因和造成的影响作了简单分析,并提出了相应的解决措施。（１）胶嘴歪斜胶嘴歪斜是水胎成型时组装不正和硫化时装模不正导致的。胶嘴歪斜会造成胶嘴密封性能差（使用中漏水）和轮胎硫化时插嘴歪斜、硫化后胎趾圆角等问题。解决措施是：在水胎制作过程中,严格按照工艺章程操作,防止胶嘴歪斜。（２）胶嘴牙尖损伤水…     

环氧化天然橡胶的湿气硫化及其现场二氧化硅补强作用

环氧化天然橡胶（ＥＮＲ）经常规模压技术，首次用３－氨基丙基三乙氧基硅烷（ＡＰＳ）进行预硫化，获得的预硫化胶在水中浸泡进行湿气硫化（经过水解和缩合反应）．在合适的反应条件下制备的湿气硫化胶与典型的过氧化物硫化胶及硫黄硫化胶不同，具有部分应变－诱导的结晶和适度的拉伸强度。原硅酸四乙基酯（ＴＥＯＳ）作二氧化硅的母体，将ＥＮＲ－ＡＰＳ预硫化胶经溶胶－凝胶工艺进行现场ＳｉＯ_２补强。掺入橡胶中的ＳｉＯ_２重量含量高达３６％，ＴＥＯＳ转化成ＳｉＯ_２的转化率在６０％以上。与经同样的溶胶－凝胶工艺的过氧化物硫化胶进行比较分析表明，在最终的ＥＮＲ－ＡＰＳ溶胶－凝胶硫化胶中的ＳｉＯ_２是化学键结合到橡胶网络上。     

轮胎胶粉的特性及其对天然橡胶胶料性能的影响

聚合物废料的处理是一个世界性问题。一种可行的处理方法是废物的回收利用，把它重新用作部分原始聚合物的替代品。废塑料很容易回收，而回收废橡胶却没那么容易，因为它们是已硫化的和不能被微生物分解的废料。废硫化胶的主要来源是旧轮胎。可以把整个轮胎粉碎，用磁力分离机分离出金属丝，经过进一步研磨可以生产出所需粒径的轮胎胶粉（GRT）。目前已有各种工业方法研磨硫化的橡胶。GRT可用作沥青改性剂、脆性塑料和热固化性材料的增韧剂、橡胶工业用操作助剂（脱硫化以后）以及橡胶胶料的增容剂和填料。Phadke及其同事指出，GRT可作为橡胶和塑料的填充剂。GRT是以一定的粒径范围供应。虽然在橡胶工业中不同粒径碳黑的作用是众所周知的，但不同粒径的GRT的特性及其对橡胶性能的影响也已进行了少量的研究。Baker等发现，GRT的粒子尺寸对线性低密度聚乙烯轮胎胶粉（LLDPE－GRT）胶料的冲击能量有一些影响。本文将介绍关于不同粒子尺寸GRT的特性及其对天然橡胶硫化胶影响的研究结果。特性研究包括粒子尺寸分析、组份分析、聚合物鉴定、总硫含量估算及灰份分析。     

题录精选

１－我国轮胎硫化存在的主要问题与探讨∥现代橡胶工程，［５］，６，７（１９９９）（中文）２－轮胎质量信息反馈、分析处理系统的设计∥现代橡胶工程，［５］，２１～２３（１９９９）（中文）３－应用遗传算法实现轮胎花纹配置最佳化∥自动车技术，５２［３］，２１～２６（１９９８）（日文）４－轮胎包容特性分析及其在汽车振动系统建模中的应用∥汽车工程，２１［２］，６５～７１（１９９９）（中文）５－接地面全溶化条件下冰面轮胎摩擦力的预测∥汽车工程，２１［４］，１９３～１９８（１９９９）（中文）６－未硫化覆胶钢丝帘布…     

Characterization of recycled styrene butadiene rubber ground tire rubber: Combining X‐ray fluorescence,differential scanning calorimetry,and dynamical thermal analysis for quality control

Appraisal of the main rubber characterization techniques for styrene butadiene rubber (SBR) was performed on standard SBR samples as well as recycled ground tire rubber (GTR) from an industrial tire recycling facility, containing a blend of SBR and natural rubber. The aim of the work was to provide additional information relevant to quality control in the field of rubber recycling. Benchmark characterization of industrial samples by inductively coupled plasma optical emission spectrometry, atomic absorption spectrometry, solid‐state proton nuclear magnetic resonance, and elemental (CHNS) analysis are reported. X‐ray fluorescence spectrometry is shown to be rapid and quantitative for determining the zinc content in an industrial context. Thermogravimetric analysis, already used to determine carbon black and inorganic material content in rubbers and GTR, is recommended for determination of monomer weight ratios of SBR sources not containing other rubbers, but not for GTR. Differential scanning calorimetry (DSC) measurements of the glass‐transition show that changes in monomer ratio affect glass‐transition temperature values, and therefore, DSC can be used to detect changes in rubber composition from batch to batch. These results show that DSC and X‐ray fluorescence spectroscopy characterization techniques can be used for GTR and may lead to more thorough and rapid quality control procedures of these complex samples. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42692.     

Thermoplastic elastomeric composition based on ground rubber tire

Ground rubber tire (GRT) is a particulate vulcanizate consisting mainly of rubber hydrocarbon and fillers. Rubber hydrocarbon of GRT (rGRT) has been used as a partial substitute for EPDM rubber in a dynamically vulcanized EPDM/acrylic‐modified HDPE (A‐HDPE) blend. The blends with higher rubber content show poor processability and physical properties, while the compositions with higher plastic content behave like toughened plastics. However, the 60:40 rubber/plastic blend was found to behave as a thermoplastic elastomer, and it was observed that 50% of EPDM can be replaced by rGRT without deterioration in properties.     

国产原子吸收分光光度计测定硫化橡胶钴含量

硫化橡胶中由于黏合剂的加入带入钴盐,传统的钴测定方法有比色法、滴定法等。探索使用国产原子吸收分光光度计TAS-990进行测定,详细介绍了测试操作过程,通过试验验证结果可见,国产TAS-990原子吸收分光光度计用于测定硫化橡胶中钴含量,操作方便简捷,测试准确度、灵敏度能够达到并满足化学分析试验方法要求。     

炭黑N351填充硫化胶动态性能及生热率的实验研究

借助于动态力学分析技术，对八种胶料配方的动态力学性能及生热特性进行研究，结果表明：SBR和BR是相客的，滚动阻力随炭黑含量的增加而增加，湿抓着性能随炭黑用量的增加而减小．生热率随着温度的升高而升高，随炭黑的增加而增加。本实验结果可以为优化胶料配方和轮胎温度场的研究提供依据。     

无氨保存胶清及胶清胶性能的研究

采用水溶性、不挥发性的广谱抗菌剂——三嗪衍生物(HY)作为鲜胶乳的新型无氨保存剂,研究了HY对胶清凝固总用酸量、胶清胶及胶清胶硫化胶片性能的影响。结果表明,HY保存胶清凝固总用酸量大大减少,除氮含量略微超标外,胶清胶的各项指标均达到1级胶清胶的标准,胶清胶的塑性保持率(PRI)明显提高。HY胶清胶硫化胶片的拉伸强度和耐热氧老化能力均优于氨胶清胶硫化胶片。热解重量分析(TGA)结果表明,HY和氨胶清胶硫化胶片热氧降解均为2步反应,耐热氧降解能力基本相同。     

橡胶反应共混改性沥青的机理

以混入沥青前后的共混物硫化胶模拟反应共混改性沥青,对橡胶／硫化剂／沥青、橡胶／硫化剂2种共混物硫化胶进行了以甲苯为溶剂的抽提,并对抽提物进行了元素分析和红外光谱分析。结果表明,橡胶／硫化剂／沥青共混物硫化胶的抽提物仍呈黑色,其质量保留率小于橡胶／硫化剂共混物硫化胶。SBR／硫化剂／沥青共混物硫化胶的抽提物H／C值小于SBR／硫化剂共混物硫化胶,并且小于纯沥青;且含有沥青组分所特有的N原子。l376cm^-1的甲基对称弯曲振动特征吸收峰可作为共混物硫化胶的抽提物是否存在沥青的依据。含沥青共混物硫化胶中,沥青特别是沥青质与树脂组分参与了橡胶的交联反应。     

Devulcanization of Natural Rubber Vulcanizates by Mechanochemical Process

Using a suitable disulfide-based devulcanizing agent, which cleaved the sulfur cross-links in vulcanized rubber at high temperature, devulcanization of gum natural rubber was carried out. High sulfur and medium sulfur, as well as low sulfur–containing rubber vulcanizates were used to study the cleavage of sulfidic bonds. The cure characteristics and mechanical properties of vulcanized natural rubber and revulcanized natural rubber were studied. Thermal properties of the rubber were analyzed by thermogravimetric analysis (TGA), which indicates that the onset degradation temperature further increased on revulcanization with higher amount of disulfide. The properties of the revulcanized natural rubber increased with increasing disulfide concentration, also the mechanical properties of the devulcanized natural rubber were increased by decreasing the sulfur content in the original rubber vulcanizate. From the rheometric study increases in optimum cure time were observed when ground rubber vulcanizates were treated with higher amounts of disulfide. The scanning electronic microscopy (SEM) study suggested the change in failure mechanism as influenced by the type of cross-linking present and the devulcanizing agent used. From infrared (IR) spectroscopy it was observed that the oxidation of the main polymeric chain did not occur at the time of high temperature milling.     

轮胎胶应力诱导脱硫化及PE-HD动态交联热塑性弹性体制备

采用在废旧轮胎胶粉(GTR)与高密度聚乙烯(PE-HD)的熔融挤出过程中提高双螺杆挤出机螺杆转速的高剪切应力诱导方法,研究了双螺杆挤出机的螺杆转速、挤出反应温度及脱硫促进剂仲丁醇、烷基酚多硫化物(420或450)和正丁胺对轮胎胶脱硫共混物的凝胶含量、熔体流动速率、溶胶红外吸收光谱及轮胎胶脱硫共混物/三元乙丙橡胶(EPDM)动态交联热塑性弹性体力学性能的影响。结果表明:高转速同向双螺杆挤出机的高剪切作用可诱发废旧轮胎胶共混物中交联网络的断链和解交联反应,引起脱硫共混物凝胶含量的下降、未熔融凝胶颗粒尺寸的减小及熔体流动速率的增加;4种促进剂均具有明显促进脱硫反应的作用,其中450或正丁胺的促进脱硫效果较好,并引起脱硫共混物凝胶含量下降、熔体流动速率上升及动态交联热塑性弹性体力学性能的明显改善;当以正丁胺为脱硫促进剂时,最佳脱硫反应条件(240℃和1000r/min)下,脱硫共混物/EPDM动态交联热塑性弹性体的拉伸强度和断裂伸长率分别达到12.5MPa和440.6%。     

Rheology,cure characteristics,physical and mechanical properties of tire tread reclaimed rubber/natural rubber compounds

This work aimed to examine the effect of addition of tire‐tread reclaimed rubber on the properties of two natural rubber (NR) compounds with respect to the reclaimed rubber concentration and mastication time, the properties of interest including rheological and cure characteristics, physical and mechanical properties. The results under the test conditions suggested that Mooney Plasticity and shear viscosity increased with reclaimed rubber content, but decreased with mastication time. The greater the molar mass of the natural rubber the higher the sensitivity to the change in compound viscosity due to mastication and reclaimed rubber content. The die swell was more dependent on the reclaimed rubber than the molar mass of the rubbers. The cure rate and scorch time were found to increase and decrease with reclaimed rubber content, respectively, whereas the cure time was independent of the reclaimed rubber content. For vulcanized rubbers, it was also observed that 100% modulus of the rubber increased with reclaimed rubber content, but this was not the case for tensile stress and elongation at break. The hardness and heat buildup properties of the vulcanizates increased with reclaimed rubber content whereas the tear strength became independent of the reclaimed rubber. The findings in this work suggested that the variations in the rheological and cure characteristics for the unvulcanized rubber were very much dependent on the molar mass of the rubber whereas the mechanical properties for the vulcanized rubber were influenced by crosslink density. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1723–1731, 2003     

The effect of devulcanization level on mechanical properties of reclaimed rubber by thermal‐mechanical shearing devulcanization

Ground tire rubber (GTR) with crosslinked structure has hardly any plasticity and processability, which makes its property very poor. Thermal‐mechanical shearing devulcanization method can effectively destroy the crosslinked structure and restore GTR a certain extent of plasticity and processability. This article investigated the characteristic and reprocessing performance of reclaimed rubber prepared through thermal‐mechanical shearing devulcanization. The relationship between the devulcanization level (indicated by gel fraction and crosslink density) and the mechanical property was analyzed by sufficient experiments. Fourier transform infrared spectroscopy and elemental analyzer studies revealed the chemical structure of GTR changed and many complex reactions occurred after devulcanization. The gel permeation chromatography indicated the specific changes of molecular weight and molecular weight distribution in devulcanization process. The differential scanning calorimetry revealed various vulcanized abilities and vulcanized structures of reclaimed rubber. The scanning electron microscope further confirmed the recovery of plasticity after devulcanization and the distinct vulcanized structures between revulcanizates. The determination of devulcanization level and mechanical properties verified that mechanical properties especially tensile strength reached to the optimum value only at an appropriate devulcanization level. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013