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。     

复合促进剂对双螺杆诱导废轮胎胶粉力化学脱硫反应的影响

利用自行组装的双螺杆挤出机对废轮胎胶粉进行力化学剪切脱硫,考察了过氧化物、烷基酚多硫化物及其复合促进剂对脱硫产物门尼黏度、凝胶含量以及共混天然橡胶硫化胶力学性能的影响。结果表明,过氧化物或烷基酚多硫化物均可促进力化学脱硫反应,当以过氧化物/烷基酚多硫化物为复合促进剂时可产生协同效应,起到共同促进力化学脱硫反应和保护产物双键的作用。在主机转速100 r/min、喂料与主机螺杆转速比1.4和180℃的脱硫条件下,以过氧化二异丙苯-烷基酚多硫化物480为复合促进剂时,二者的协同作用可使产物的门尼黏度和凝胶质量分数分别达到29.9和68.1%,脱硫产物共混天然橡胶硫化胶的拉伸强度和扯断伸长率分别达到19.3 MPa和588%。此外,根据红外光谱的表征结果推测了复合促进剂对废轮胎胶粉脱硫反应的可能机理。     

异戊橡胶与三元乙丙橡胶并用胶料及其硫化胶的结构与性能

研究了三元乙丙橡胶的化学组成和物理结构对其性能的影响、不同品种三元乙丙橡胶与异戊橡胶并用胶及其共硫化胶结构与性能的关系。线型高乙烯含量的三元乙丙橡胶(乙烯／丙烯70：30)具有较好的物理性能。并用胶的性能与两胶的比例有关，也与三元乙丙胶的类型有关。异戊橡胶与三元乙丙胶(组成比为70：30)的并用胶具有良好的物理机械性能和耐热性。     

HNBR/EPDM共混硫化胶的性能

研究了HNBR／EPDM共混硫化胶的性能与EPDM质量分数的关系。结果表明，EPDM的加入对HNBR的硬度影响不大，但对HNBR胶料的粘度及硫化性能产生影响，当EPDM质量分数不大于15％时，在改善HNBR低温顺性能的同时，保持其较高的拉伸强度和优异的耐油性能。     

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。     

氯化聚乙烯对三元乙丙橡胶与丁腈橡胶并用胶物理机械性能的影响

研究了氯化聚乙烯对EPDM／NBR并用胶物理机械性能的影响。结果发现，加入氯化聚乙烯后，并用胶的混合平衡扭矩降低，达到平衡扭矩所需的时间缩短，且无论用硫黄硫化还是用过氧化物硫化，硫化胶的物理机械性能都提高，表明氯化聚乙烯对EPDM／NBR并用胶有一定的增容作用。同时也发现用过氧化物硫化的EPDM／NBR并用胶物理机械性能优于硫黄硫化的并用胶物理机械性能。     

用于变压器的丁腈橡胶/三元乙丙橡胶并用胶

为了实现丁腈橡胶(NBR)与三元乙丙橡胶(EPDM)并用作为变压器密封材料,研究了并用比、增容剂及硫化体系种类对NBR/EPDM并用胶的影响。结果表明,NBR/EPDM(质量比)为70/30时并用胶具有良好的耐臭氧性能与最佳的综合物理机械性能;在并用胶中加入增容剂乙华平8784可以改善其物理机械性能;使用过氧化物硫化体系硫化并用胶的物理机械性能比使用硫黄/促进剂硫化体系者更好。     

氟橡胶/三元乙丙橡胶并用胶的性能

研究了不同并用比(质量比)时氟橡胶(FKM)/三元乙丙橡胶(EPDM)并用胶动态硫化和静态硫化后的低温性能、物理机械性能、耐老化性能和热稳定性,并用扫描电子显微镜表征了并用胶.结果表明,当并用比为30/70时,并用胶有较好的相容性;EPDM可以改善FKM的低温性能;随着EPDM用量的增加,并用胶的拉伸强度及邵尔A硬度降低;动态硫化FKM/EPDM并用胶比静态硫化FKM/EPDM并用胶具有更好的耐老化性能,但老化前前者的拉伸强度稍低于后者;FKM/EPDM并用胶的热稳定性优于纯EPDM;静态硫化FKM/EPDM并用胶中片层现象严重,动态硫化FKM/EPDM并用胶的EPDM包覆在FKM中,但相畴偏大.     

三种不同硫化助剂对MVQ/EPDM共混胶性能的影响

研究了3种硫化助剂对MVQ/EPDM共混胶硫化特性、力学性能、耐热老化性能、高温压缩永久变形性能及动态力学性能的影响。结果表明,添加硫化助剂HVA—2的共混胶焦烧时间和正硫化时间均明显缩短;添加硫化助剂丁羟胶和TAIC的共混胶焦烧时间和正硫化时间均变化不大;添加硫化助剂丁羟胶的共混胶具有最好力学性能、耐热老化性能和压缩永久变形性能,其玻璃化温度也比空白样的低近3℃。     

废旧轮胎胶粉应力诱导脱硫反应影响因素的研究

在废旧轮胎胶粉/EPDM的熔融挤出过程中,以仲丁醇为脱硫反应促进剂,研究螺杆转速和挤出反应温度对脱硫共混物凝胶质量分数(w)、凝胶分子链结构以及SBR/脱硫共混物再硫化材料物理性能的影响。结果表明:在废旧轮胎胶粉/EPDM的熔融挤出过程中,随着螺杆转速和挤出反应温度的升高,废旧轮胎胶粉颗粒所受的机械剪切应力作用增强,引起废旧轮胎胶粉中交联网络的断裂、降解或解交联反应,导致脱硫共混物w显著减小以及SBR/脱硫共混物再硫化材料中凝胶粒子尺寸明显减小;添加仲丁醇有利于脱硫反应的进行,并具有抑制交联副反应和保护脱硫产物中双键的作用,使脱硫共混物的w进一步减小;在螺杆转速为1 000 r.min-1、挤出反应温度为240℃的条件下,SBR/脱硫共混物(添加仲丁醇)再硫化材料的拉伸强度和拉断伸长率分别为19.3 MPa和567%。     

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。     

Dynamic reaction inside co‐rotating twin screw extruder. II. Waste ground rubber tire powder/polypropylene blends

In this article, dynamic reaction of waste ground rubber tire powder/PP blends with compatibilizers is extended to commercially available waste rubber Viz. Ground rubber tire and PP for the possibility of getting recycled material with good mechanical properties. In the first part of the article it was shown that the compatibility of model material/PP blends has greatly improved. In this article, extensive studies have been carried out to study the effect of compatibilizers, in‐situ compatibilization of immiscible waste ground rubber tire (WGRT) powder/polyolefin blends of various concentrations was investigated by means of extrusion process using a co‐rotating twin screw extruder. It was observed that addition of small amounts of compatibilizers like SEBS‐g‐MA to the blends of WGRT and PP‐g‐MA can result in better mechanical properties than the blends with isotactic PP. The blends of WGRT powder and PP‐g‐MA with compatibilizer have better adhesion than those of isotactic PP blends as revealed by the morphological studies using AFM and SEM. The betterment in properties can be attributed to the presence of functional group, maleic anhydride in PP‐g‐MA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Mechanochemical devulcanization of ground tire rubber and its application in acoustic absorbent polyurethane foamed composites

The use of recycled rubber in preparation of acoustic absorbent materials will help to combat the existing environmental problems of both waste disposal and noise pollution. The focus of this work is to investigate the influence of mechanochemical pretreatment of ground tire rubber (GTR) on the acoustic absorption properties of polyurethane (PU)/GTR foamed composites. GTR subjected to pan‐milling could be mechanochemically devulcanized by breaking up the crosslinked structures through inducing fairly strong shearing and compressing forces. The significant increase in sol fraction of GTR confirmed the partial devulcanization during pan‐milling. Moreover, thermal gravimetric analysis indicated that rubber content in the soluble part of GTR was also remarkably increased. The devulcanization increased flexible chains of the GTR particles, which could help to improve damping properties as well as acoustic absorption ability of the PU/GTR foamed composites. Dynamic mechanical analysis and acoustic absorption measurements well confirmed this hypothesis. The loss modulus and sound absorption coefficient of PU/GTR foamed composites were remarkably increased through the mechanochemical pretreatment of GTR. The mechanochemical pretreatment also enhanced foamability of the composites as revealed by cell morphology. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

废聚丙烯/废轮胎胶粉/废尼龙短纤维复合材料Ⅱ.工艺条件

采用反应挤出方法制备了废聚丙烯／废轮胎胶粉／废尼龙短纤维(WPP／GRT／WSF)复合材料,讨论了螺杆转速、机头温度对WPP／GRT／WSF复合材料力学性能的影响。结果表明,当螺杆转速为15r／min,机头温度为185～195℃时,WPP／GRT／WSF复合材料的力学性能达到最佳,拉伸强度为13．6MPa,冲击强度为25．2kJ／m^2。按照最佳配方和工艺挤出管材的拉伸强度为4,6MPa,冲击强度为5．4kJ／m^2,爆破压力为0．69MPa。     

Dynamic reaction inside co‐rotating twin screw extruder. I. Truck tire model material/polypropylene blends

Waste ground rubber tire (WGRT) is a complex composite containing various elastomers, carbon black, zinc oxide, stearic acid, processing oils, and other curatives. Most of the waste ground rubber tire is composed of mainly natural rubber (NR) and styrene butadiene rubber (SBR) in varying proportions. Blending it with other thermoplastic materials is difficult due to the inherent thermodynamic incompatibility. But, the compatibility can be increased by making the reactive sites in WGRT with suitable chemicals under optimum condition of shearing inside a twin screw extruder and it is said to undergo a dynamic reaction inside the extruder. To understand the mechanism of dynamic reaction process of a rubber/polyolefin blend, the blending of a truck tire model material rubber with polyolefin was first tried before it was applied to waste WGRT material. It was observed that the blends of a truck tire model rubber material and PP thermoplastic are physical mixture of two incompatible polymers in which a continuous plastic phase is largely responsible for the tensile properties. The rubber particles are the dispersed phase. The large particle size and the poor adhesion of these rubber particles are believed to be liable for the poor tensile properties. In case of blends of truck tire model material with isotactic polypropylene the tensile properties are found to be lower than that of its PP‐g‐MA counterpart which can be attributed to the reaction of the MA with the carbon black particles. A schematic representation of the possible interactions has been proposed. The effect of addition of compatibilizers such as SEBS and SEBS‐g‐MA has also been studied. The tensile and TGA studies indicate that the polarity of SEBS and SEBS‐g‐MA induces an increase in the performance characteristics for both types of polyolefins but the intensity of this increase is higher in the PP‐g‐MA based blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 106: 3193–3208, 2007     

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。     

热剪切对聚乙烯/胶粉共混物结构演变及性能的影响

研究了聚乙烯(PE)/胶粉(GTR)共混物中GTR在不同热剪切加工条件下结构形态的演变过程及其对共混物力学性能、流变性能和溶胀行为的影响。结果表明,PE/GTR共混物中GTR受到热剪切作用后,体系中会出现大量几微米的小颗粒,且几微米的小颗粒随温度的升高和加工时间的延长而增多,但即使在220℃下连续剪切25 min,仍有100μm以上的大颗粒存在。随着加工温度的升高和加工时间的延长,共混物的力学性能、流变性能略有下降;而溶胀比随温度的升高先减小后增大,随时间的延长则略有减小。     

超声波振幅对轮胎胶粉超声脱硫工艺及性能的影响

以40目废旧轮胎胶粉为原料,采用超声脱硫工艺,使用超声同向旋转双螺杆挤出机制备了脱硫废旧轮胎胶粉（DGTR）,研究了超声波振幅对脱硫工艺过程中口型压力和功率消耗,DGTR的外观形貌、流变性能和硫化特性,以及DGTR硫化胶力学性能的影响。结果表明,随着超声波振幅的增加,DGTR的凝胶含量、黏度及储能模量逐渐降低,损耗因子逐渐增大;当超声波振幅为13 μm时,超声DGTR中交联键断裂数量最多,由此表明此时DGTR的脱硫程度最高。此外,随着超声波振幅的增加,DGTR硫化胶的拉伸强度逐渐降低,扯断伸长率逐渐增加。