螺杆结构对轮胎胶粉超声波脱硫工艺及性能的影响

采用负载超声波发生装置的同向旋转双螺杆挤出机对40目废旧轮胎胶粉（GTR）进行超声波脱硫,考察了两种不同结构螺杆对脱硫过程中的口型压力和功率消耗、脱硫GTR（DGTR）的外观形貌、流变性能、硫化特性及DGTR硫化胶力学性能的影响。结果表明,在13 μm超声波振幅和含较多捏合块部件螺杆的作用下得到的DGTR的凝胶含量、黏度及储能模量较低,说明含捏合元件的螺杆剪切作用更强,能使GTR获得更高程度的脱硫。该条件下所制得的DGTR硫化胶的拉伸强度和100%定伸应力较低,扯断伸长率较高。     

亚临界流体挤出法对天然橡胶基轮胎胶粉脱硫化反应的影响

采用亚临界流体挤出法对天然橡胶基轮胎胶粉(GTR)与三元乙丙橡胶(EPDM)进行熔融共混脱硫,得到脱硫轮胎胶粉(DGTR)/EPDM共混物,然后与丁苯橡胶(SBR)共混制备了再硫化材料,考察了亚临界流体品种和双螺杆挤出机螺杆转速、挤出温度对GTR脱硫效果与再硫化材料物理机械性能的影响,并通过傅里叶变换红外光谱和扫描电子显微镜表征了脱硫共混物和再硫化材料。结果表明,在相同挤出温度和螺杆转速条件下,采用亚临界水挤出制得的DGTR/EPDM共混物的凝胶含量和门尼黏度较采用其他亚临界流体挤出共混物低;在3种亚临界醇状态下,采用亚临界甲醇挤出DGTR/EPDM共混物的凝胶含量较低,门尼黏度最高;采用亚临界醇所得DGTR/EPDM/SBR再硫化材料的拉伸性能均明显优于采用亚临界水所得的再硫化材料,其中,采用亚临界乙醇且在挤出温度为180℃、螺杆转速为500 r/min、反应压力为2.0 MPa的条件下,所制得DGTR/EPDM/SBR再硫化材料的拉伸强度和扯断伸长率分别达到19.4 MPa和456%;采用不同亚临界流体脱硫后制得再硫化材料中未熔融凝胶粒子尺寸大小不等,其中采用亚临界水时最小,小于1μm,分别采用亚临界甲醇、乙醇时较小,约为1μm,而采用亚临界丙醇时较大;随着反应温度的升高或螺杆转速的增加,再硫化材料中凝胶粒子的数目及尺寸均明显减小。     

亚临界流体挤出法复合诱导丁苯橡胶基轮胎胶粉脱硫及再硫化材料的性能研究

将丁苯橡胶（SBR）基轮胎胶粉（GTR）与三元乙丙橡胶（EPDM）混合物在双螺杆挤出机中熔融挤出,通过亚临界流体与高剪切应力相结合复合诱导SBR基GTR脱硫,研究亚临界流体品种、螺杆转速、促进剂450以及挤出反应温度对脱硫共混物［脱硫GTR（DGTR）/EPDM］凝胶质量分数、门尼粘度、溶胶红外光谱以及SBR/DGTR/EPDM再硫化材料拉伸性能和断面形貌的影响。结果表明：亚临界水、乙醇和丙醇均能很好地促进脱硫反应,提高交联键断裂的选择性,降低DGTR/EPDM的凝胶质量分数和凝胶颗粒尺寸,明显提高SBR/DGTR/EPDM再硫化材料的拉伸性能,其中亚临界乙醇的作用最显著;添加促进剂450能促进脱硫反应;200 ℃时亚临界丙醇脱硫效果较佳。     

亚临界流体挤出法复合诱导SBR基轮胎胶脱硫化及 再硫化材料力学性能

在SBR基轮胎胶(GTR)与三元乙丙橡胶（EPDM）混合物的熔融挤出过程中,采用改变亚临界流体品种和提高螺杆转速的方法,研究了亚临界流体（水,乙醇,丙醇）、螺杆转速、烷基酚多硫化物促进剂（450）以及温度对脱硫共混物（DGTR/EPDM）凝胶含量、门尼粘度、溶胶红外光谱及脱硫共混物共混丁苯橡胶（SBR）再硫化材料（SBR/(DGTR/EPDM)）力学性能的影响,对再硫化材料的试样断面形貌也进行了SEM观察。实验结果表明：亚临界流体（水,乙醇,丙醇）作为一种溶胀剂和反应性介质能够很好地促进脱硫反应,提高交联键断裂的选择性,降低脱硫产物的凝胶含量和凝胶颗粒尺寸并明显提高脱硫共混物共混丁苯橡胶再硫化材料的力学性能,其中亚临界乙醇的作用最显著。当450作为一种脱硫促进剂,在最优亚临界乙醇挤出反应条件（200℃,1.6 MPa,600 rpm）下,脱硫共混物共混丁苯橡胶分别达到丁苯生胶混炼硫化材料拉伸强度（24.0MPa）和断裂伸长率（356%）的99.6%和209%。     

亚临界水挤出法复合诱导丁苯橡胶基轮胎胶脱硫化及其对热塑性弹性体性能的影响

在亚临界水挤出反应条件下,研究了双螺杆挤出机的螺杆转速、亚临界水温度、压力及脱硫促进剂种类对丁苯橡胶(SBR)基轮胎脱硫胶(DGTR)/高密度聚乙烯(PE-HD)共混物性能的影响。结果表明,挤出机螺杆的高剪切应力解交联作用与亚临界水分解、降解的解交联作用能产生协同解交联反应,提高脱硫反应效果;正丁胺具有明显促进脱硫反应和保护产物分子双键的功能;在正丁胺作为脱硫促进剂的最佳脱硫反应条件(亚临界水温220℃,螺杆转速1000r/min,水压2.4MPa)下,亚临界水挤出法所得脱硫共混物制备的DGTR/PE-HD/三元乙丙橡胶(EPDM)热塑性弹性体的拉伸强度和断裂伸长率分别达到12.8MPa和614.6%。     

亚临界水挤出法应力诱导挤出条件对废轮胎胶粉脱硫共混物及其热塑性弹性体性能的影响

采用亚临界水挤出法应力诱导废轮胎胶粉解交联反应,研究挤出条件对废轮胎胶粉脱硫共混物[脱硫废轮胎胶粉(DGTR)/高密度聚乙烯(HDPE)共混物]凝胶含量和熔体流动速率以及脱硫共混物/HDPE/三元乙丙橡胶动态硫化热塑性弹性体性能的影响。结果表明:采用亚临界水挤出法应力诱导废轮胎胶粉脱硫,随着螺杆转速增大,挤出反应温度升高和压力增大,脱硫共混物凝胶含量下降和熔体流动速率上升,动态硫化热塑性弹性体拉伸强度提高;在正丁胺作脱硫促进剂、挤出反应温度为220℃、挤出反应压力为2.4 MPa、螺杆转速为1 000 r·min~(-1)的优化条件下,亚临界水挤出法制得的脱硫共混物/HDPE/EPDM热塑性弹性体的拉伸强度和拉断伸长率分别达到12.8 MPa和615%。     

挤出反应温度与剪切应力对动态硫化PP/EPDM性能的影响

采用动态硫化的方法,在双螺杆挤出机中制备了聚丙烯(PP)/三元乙丙橡胶(EPDM)热塑性弹性体,研究了挤出反应温度与螺杆转速提供的剪切应力对动态硫化PP/EPDM热塑性弹性体性能的影响。结果表明,适当提高挤出反应温度或螺杆转速可提高PP/EPDM热塑性弹性体的拉伸强度、拉断伸长率和凝胶含量,当挤出反应温度为200℃、螺杆转速为600 r/min时,热塑性弹性体的综合拉伸性能最好,拉伸强度为19.87 MPa,拉断伸长率为527.3%,凝胶含量为54.69%。高螺杆转速提供的高剪切应力可在一定程度上提高PP/EPDM热塑性弹性体的熔融温度。     

酚硫化物/醇复合促进剂对废轮胎胶应力诱导脱硫反应的影响

在废轮胎胶(GTR)与三元乙丙橡胶(EPDM)熔融挤出过程中添加多烷基苯酚二硫化物(简称420)或/和仲丁醇作为脱硫促进剂,考察了在不同螺杆转速和挤出反应温度下脱硫促进剂对GTR与EPDM脱硫共混物(DGTR/EPDM)凝胶含量和溶胶分子链结构的影响,研究了DGTR/EPDM/丁苯橡胶(SBR)再硫化胶的相态结构及物理...     

用双螺杆挤出机脱硫制备再生胶的工艺及性能

利用改进的双螺杆挤出机对废旧轮胎橡胶胶粉进行剪切脱硫,讨论了螺杆转速和反应温度对脱硫效果及再生胶力学性能的影响,通过扫描电镜分析了胶粉脱硫前后形貌的变化及再生胶硫化试样的界面结合状况。结果表明,废旧轮胎橡胶胶粉的凝胶含量和交联密度随着螺杆转速和反应温度的升高明显下降,脱硫胶粉恢复了塑性,再生胶硫化试样的界面结合紧密。将螺杆转速控制在50～120 r/min、反应温度控制在190/180/170～210/190/200℃时脱硫效果最佳,此时再生胶的拉伸强度由未脱硫前的3.1 MPa提高到了12.4 MPa,扯断伸长率由75%提高到452%。     

酵母菌生物脱硫胎面胶粉及其填充天然橡胶的力学性能

用酵母菌对胎面胶粉(GTR)进行了生物脱硫实验,考察了酵母菌与GTR共培养脱硫过程中酵母菌的生长情况,对比了GTR和脱硫GTR(DGTR)填充天然橡胶(NR)硫化胶的交联密度、表面元素含量和力学性能.结果表明,在共培养脱硫过程中酵母菌依然可以保持较高的生物量,脱硫6 d后可获得生物脱硫的GTR.随着胶粉用量的增加,填充NR硫化胶的交联密度和力学性能逐渐降低.相比较GTR/NR硫化胶,DGTR/NR硫化胶的表面硫元素含量和交联密度更低,力学性能明显提高.     

Balancing mechanical properties and processability for devulcanized ground tire rubber using industrially sized single‐screw extruder

Devulcanized ground tire rubber (DGTR) samples were produced using an independently developed industrially sized single‐screw extruder. The DGTR was further revulcanized to produce revulcanized DGTR (RDGTR) samples. The structure and properties of the produced samples were investigated via tests and characterization of sol fraction, crosslink density, Fourier transform infrared spectroscopy spectra, X‐ray photoelectron spectroscopy spectra, Mooney viscosity, curing characteristics, dynamic rheology, tensile properties, and surface morphology. The results demonstrate that the extruder can effectively break up crosslinked structure of ground tire rubber to achieve high devulcanization level (characterized by sol fraction and crosslink density), which is mainly associated with its moderate shear strength. The balance between mechanical properties and processability for the DGTR samples was analyzed. Lower ratios of main‐chain to crosslink scission and good processability (mainly characterized by modest Mooney viscosity) for the DGTR samples, and high tensile strengths and elongations at break for the RDGTR samples are obtained via appropriately combining the barrel temperature and screw speed. High quality DGTR sample with tensile strength and elongations at break of up to 11 MPa and 370%, respectively, is prepared under the conditions used in this work. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43761.     

Effects of shear stress and subcritical water on devulcanization of styrene–butadiene rubber based ground tire rubber in a twin‐screw extruder

The devulcanization reaction of styrene–butadiene rubber (SBR) based ground tire rubber (GTR) in GTR/ethylene–propylene–diene monomer rubber (EPDM) blend was investigated through a compound‐induced reaction by increasing screw rotation speed and being in the presence of subcritical water. The effects of temperature, pressure, screw rotation speed, or promoting agents on the gel content, Mooney viscosity, and Fourier transform infrared spectra of the sol of the devulcanized blends (devulcanized ground tire rubber (DGTR)/EPDM) were measured, and the mechanical properties and microstructures of the revulcanized blend ((DGTR/EPDM)/SBR) were characterized. The results show that subcritical water as a swelling agent and reaction medium promotes the devulcanization reaction, increases the selectivity of the crosslink breakage, keeps the extrusion material from oxidative degradation, reduces the gel particle size of the devulcanized blends, and significantly improves the mechanical properties of the revulcanized SBR/(DGTR/EPDM) blends. In subcritical water, the suitable promoting agents (alkylphenol polysulfide 450, hydrogen peroxide H₂O₂, or 450/H₂O₂) accelerate the devulcanization reaction, keep the double bond content, and lead to further decrease of the gel content and Mooney viscosity of the devulcanized blends and further increase of the mechanical properties of the revulcanized SBR/(DGTR/EPDM) blends. Especially the compound promoting agent (450/H₂O₂) improves the selectivity of the crosslink breakage in devulcanization of SBR‐based GTR. When 450/H₂O₂ is added as a compound promoting agent at the best reaction condition in subcritical water (200°C, 1.6 MPa and 1000 rpm), the tensile strength and elongation at break of the revulcanized SBR/(DGTR/EPDM) blends reach to 85.4% and 201% of vulcanized SBR (24.0 MPa, 356%), respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1845–1854, 2013     

Effects of processing parameters on the properties of microwave‐devulcanized ground tire rubber/polyethylene dynamically revulcanized blends

This work aimed to evaluate the effects of processing parameters on properties of dynamically revulcanized blends based on 60 wt % of devulcanized ground tire rubber (GTR) and 40 wt % of high density polyethylene (HDPE). Devulcanization of the GTR was carried out in a system comprised of a conventional microwave oven adapted with a motorized stirring system with speed control. The resulting devulcanized GTR contained 26 wt % soluble in toluene. It was processed with HDPE in a twin screw extruder to produce a dynamically revulcanized blend. Processing parameters such as screw speed and feeding mode were varied. Their effects were evaluated based on tensile, dynamic mechanical, thermal and rheological properties, as well as on morphology. The results show the importance of the processing parameters involved in the production of blends with dynamically revulcanized rubber phase in the extruder, and good match between the residence time of the rubber and its revulcanization kinetics. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43503.     

影响废旧轮胎胶粉热-机械剪切脱硫再生效果的因素

利用自行研制的长径比为60/1的强剪切型双螺杆挤出机对废旧轮胎胶粉进行热-机械剪切脱硫,用傅里叶变换红外光谱对脱硫胶粉进行了表征,考察了胶粉粒径和喂料螺杆转速与主机转速之比对脱硫胶粉凝胶含量、交联密度及再生胶力学性能的影响,以及脱硫过程中胶粉相对分子质量及其分布的变化。结果表明,随着胶粉粒径的增大,胶粉所受到的剪切力增强,脱硫效果也越好。随着转速比的增加,胶粉的脱硫程度提高;脱硫过程的第1个阶段是交联网络的破坏,第2个阶段除交联网络的破坏外分子主链也发生降解,再生胶的力学性能先增大后减小;当转速比为1.4时再生胶的扯断伸长率和弹性最好,拉伸强度也相对较高。     

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%。     

Recycling of tire‐curing bladder by ultrasonic devulcanization

The recycling of butyl rubber‐based tire‐curing bladder was carried out by means of a grooved barrel ultrasonic extruder. Die pressure and ultrasonic power consumption were measured as a function of flow rate and ultrasonic amplitude. Gel fraction and crosslink density of the ultrasonically devulcanized rubber were substantially reduced. In turn, this led to some reduction in gel fraction and crosslink density in the revulcanized rubber. These findings were correlated with dynamic properties and the cure behavior of the devulcanized rubber. The mechanical properties of the revulcanized rubber, dependent on processing conditions during devulcanization, were compared with that of the virgin vulcanizate. Good mechanical properties of revulcanized rubber was achieved with 86 and 71% retention of the tensile strength and the elongation at break respectively, and with modulus increased by 44%. The devulcanized rubber was found to contain tiny gel particles of a wide size distribution with a predominant size of <4 μm. POLYM. ENG. SCI., 46:8–18, 2006. © 2005 Society of Plastics Engineers     

Properties of natural rubber vulcanizates containing mechanochemically devulcanized ground tire rubber

The devulcanization of ground tire rubber (GTR) was carried out with a self-designed pan-mill type mechanochemical reactor. Gel fraction and crosslink density measurements confirmed the occurrence of stress induced mechanochemical devulcanization of GTR. The partially devulcanized GTR (dGTR) was blended with virgin natural rubber (NR) at different ratios. The curing characteristics and mechanical properties of these composites were investigated and compared with those composites of raw ground tire rubber (rGTR) and NR. The results showed that the tensile properties of the dGTR/NR vulcanizates were much better than those of the rGTR/NR vulcanizates, which are comparable to or even better than the virgin vulcanizate, indicating the significant benefit of mechanochemical devulcanization. At the GTR content of 10%, the tensile strength of the dGTR/NR blends increased to 23.2 MPa from 13.7 MPa of the rGTR/NR blends, enhanced by 69% through partial devulcanization of GTR, and the elongation at break increased by 47%.     

Preparation of rubber composites from ground tire rubber reinforced with waste‐tire fiber through mechanical milling

Composites made from ground tire rubber (GTR) and waste fiber produced in tire reclamation were prepared by mechanical milling. The effects of the fiber content, pan milling, and fiber orientation on the mechanical properties of the composites were investigated. The results showed that the stress‐induced mechanochemical devulcanization of waste rubber and the reinforcement of devulcanized waste rubber with waste‐tire fibers could be achieved through comilling. For a comilled system, the tensile strength and elongation at break of revulcanized GTR/fiber composites reached maximum values of 9.6 MPa and 215.9%, respectively, with 5 wt % fiber. Compared with those of a composite prepared in a conventional mixing manner, the mechanical properties were greatly improved by comilling. Oxygen‐containing groups on the surface of GTR particles, which were produced during pan milling, increased interfacial interactions between GTR and waste fibers. The fiber‐filled composites showed anisotropy in the stress–strain properties because of preferential orientation of the short fibers along the roll‐milling direction (longitudinal), and the adhesion between the fiber and rubber matrix was improved by the comilling of the fiber with waste rubber. The proposed process provides an economical and ecologically sound method for tire‐rubber recycling. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4087–4094, 2007