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。     

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。     

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...     

Sulfuric acid treatment of ground tire rubber and its effect on the mechanical and thermal properties of polypropylene composites

Ground tire rubber (GTR) was modified by sulfuric acid in order to improve its compatibility with and reinforcement of a polypropylene (PP) matrix. Polymer composites PP/GTR were prepared by melt mixing at different concentrations, with a maximum of 50 wt % of GTR. Studies by Fourier transform infrared spectroscopy (FTIR), surface specific area by BET (Brunauer, Emmett, and Teller), and scanning electron microscopy were used to characterize the untreated GTR and treated GTR, while the mechanical and thermal properties of the PP/GTR composites were assessed to understand how the surface treatment of GTR affected the mechanical and thermal properties of the composite PP/GTR. FTIR revealed the presence of sulfonic groups on the surface of sulfuric acid–treated GTR, and BET analyses showed an increase of about 625% in the specific surface area as a result of the high porosity produced by the treatment. In all composites containing treated GTR, a higher Young's modulus was obtained than for composites containing untreated GTR. Particularly, an increase of about 275% in the Young's modulus was obtained in composites with treated GTR (40 wt %) against that containing untreated GTR. However, a more significant reduction of the elongation at break was observed in composites containing treated GTR than in those containing untreated GTR. Also, an increase of the crystallization temperature of PP as a function of GTR was observed by differential scanning calorimetry, but the crystallinity of the composites was reduced by the addition of both untreated and treated GTR. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44858.     

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。     

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%.     

Thermoplastic elastomeric composition based on maleic anhydride–grafted ground rubber tire

Ground rubber tire (GRT) powder was maleated in an internal mixer using maleic anhydride and dicumyl peroxide at 160°C. Maleated GRT was characterized by using X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, wettability, and differential scanning calorimetry. The physical properties of the dynamically vulcanized 60 : 40, rubber : plastic composition based on acrylated high‐density polyethylene as the plastic phase and ethylene propylene diene rubber containing maleated GRT as the rubber phase were found to be greater than the corresponding composition containing nonmaleated GRT. The blend was found to be reprocessable, like themoplastic elastomers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 370–378, 2002; DOI 10.1002/app.10348     

单螺杆挤出机连续脱硫制备再生胶的结构与性能

利用本课题组研制的单螺杆挤出机,对废旧轮胎胶(GTR)粉进行连续脱硫制备再生胶(DGTR),并对DGTR进行再硫化制成DGTR硫化试样.结果显示,随螺杆转速增加,DGTR凝胶含量和DGTR硫化试样交联密度逐渐降低,DGTR硫化试样的拉伸强度和拉断伸长率有所提高;螺杆转速设定为40 r·min^-1时,在205℃脱硫温度下取得了最好的脱硫效果,DGTR硫化试样的拉伸强度和拉断伸长率分别约为11 MPa和386%.从红外光谱和光电子能谱的分析结果推测,在单螺杆挤出机的剪切和热等的共同作用下,GTR粉中部分S-S键和C-S键发生了断裂.     

New applications for foam composites of polyurethane and recycled rubber

In Portugal, most end‐of‐life tires are recycled through a process involving a cryogenic grinding technology. The purpose of this work was to envisage new applications for recycling rubber from end‐of‐life tires. In this work, rubber was supported in a polyurethane matrix generating two new products of distinct characteristics and properties. The choice of these products was ruled by the requests of potential clients: (a) Floating trays to withstand the load of plants capable of cleansing polluted water from lagoons, ponds, or basins; (b) Compression‐absorbing buoys to dampen the shocks and the compressive stresses between ships and docks. The polyurethane formulations developed herein were based on methylene diphenyl diisocyanate and a trifunctional polyol such that the final foam would be flexible. As the floating trays' density should be lower than the water density, the best formulation found comprised 150% of rubber, 4% of water (relative to the polyol mass), with an isocyanate index of 105% and a density of 89 kg m^?3. The foam that presented the optimal compression behavior to be applied in compression absorbing buoys, comprised 200% of rubber, 3% of water, with an isocyanate index of 105% and a density of 121 kg m^?3. In both cases, the composite foam materials obtained showed final properties compatible with the envisaged applications, pointing out that the implied methodology may be used in the future to recycle rubber from end‐of‐life tires. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

胶粉/聚烯烃类热塑性硫化胶共混材料的研究

研究胶粉/聚烯烃类热塑性硫化胶(TPV)共混材料的力学性能、耐油性、热稳定性、动态力学性能及材料的界面増容,并采用扫描电镜对共混材料的断面微观形貌进行了表征分析。研究结果表明:TPV/胶粉共混材料的力学性能随着胶粉粒径的减小而提高;增容剂PP-g-MAH可有效地改善胶粉与TPV的相容性,提高共混材料的力学性能;同时,胶粉和增容剂的加入增强了TPV的耐油性。     

Full factorial experimental design to study the devulcanization of ground tire rubber in supercritical carbon dioxide

In this study a 2⁴ factorial design was employed to investigate the supercritical CO₂ devulcanization process of ground tire rubber from end of life tires performed using diphenyl disulfide (DD) as devulcanizing reagent.The aim of the experimental design was to investigate the influence on the process of temperature, pressure, amount of devulcanizing reagent, treatment time and their interactions.The crosslink density, sol fraction, gel fraction and sulfur content were chosen as experimental responses. Multiple linear regression was used for modeling the relationship between each response and the process variables. Reduced regression models were obtained for each response, considering only the significant variables and interactions. The predicted results from these reduced models showed good agreement with the experimental values.Temperature, amount of DD and DD–temperature interaction resulted the relevant parameters for the process. On the contrary, the influence of treatment time, pressure and all other interactions proved to be negligible.These results have an important outcome since this devulcanization process can be carried out in a short time and at relatively low pressure, with subsequent energy saving.     

Microwave devulcanization of ground tire rubber and applicability in SBR compounds

Rubber recycling is a major environmental challenge, as their covalently crosslinked structure makes it impossible to reprocess via conventional polymer processing technologies. Devulcanization of rubber waste, whereby crosslinks are selectively broken, may provide a solution, as it allows it to be remolded into new shapes. We used two types of ground tire rubbers (GTRs) for this study; mechanically ground and waterjet-milled GTRs with different particle sizes. First, we revealed the effects of GTR particle size on the devulcanization process. We examined the sol content of the samples before and after devulcanization with two different microwave ovens, a power-controlled conventional one, and a temperature-controlled laboratory oven. In the latter one, heating rate and maximum temperature were controlled. We studied the effects of temperature, atmosphere in which the rubber was treated, heating rate, and holding time at maximum temperature. We prepared styrene-butadiene rubber-based rubber compounds containing GTR and optimally devulcanized GTR (dGTR_WJ). The physical and mechanical properties of the samples were assessed. The results indicate that both GTR_WJ and dGTR_WJ have an accelerating and a mildly softening effect on curing and dGTR_WJ has a less significant negative effect on mechanical properties: 15 phr GTR_WJ has the same effect as 45 phr dGTR_WJ. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48351.     

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。     

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     

Thermoplastic elastomers based on recycled high‐density polyethylene,ethylene–propylene–diene monomer rubber,and ground tire rubber

High‐performance thermoplastic elastomers (TPEs), based on recycled high‐density polyethylene (HDPE^R), olefinic type ethylene–propylene–diene monomer rubber (EPDM), and ground tire rubber (GTR) treated with bitumen, were prepared by using dynamic vulcanization technology, and their structure–property relationships were investigated. It was established that special pretreatment of GTR by bitumen confers outstanding mechanical properties on the resulting TPEs. TPEs, containing GTR pretreated by bitumen, exhibit thermal behavior similar to that of the HDPE^R/EPDM basic blend in the temperature region up to about 340°C. Rheological measurements showed that bitumen acts as an effective plasticizer for the GTR‐containing TPEs. SEM, DSC, and DMTA results revealed improved adhesion between the particles of GTR treated by bitumen and the surrounding thermoplastic matrix, compared to that of the untreated GTR particles. It was concluded that bitumen acts as an effective devulcanizing agent in the GTR treatment stage. In the following steps of TPE production, bitumen acts simultaneously as a curing agent for the rubber components (EPDM/GTR) and as a compatibilizer for the blend components. GTR‐containing TPEs, prepared by extrusion technology, were reprocessed (by passing through the extruder six times) without any observable changes in their tensile properties, thermal stability, and melt viscosity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 659–671, 2005     

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     

Preparation and physico‐mechanical,thermal and acoustic properties of flexible polyurethane foams based on hydroxytelechelic natural rubber

Novel flexible polyurethane foams were successfully prepared from a renewable source, hydroxytelechelic natural rubber (HTNR) having different molecular weights (1000–3400 g mol^?1) and variation of epoxide contents (EHTNR, 0–35% epoxidation) by a one‐shot technique. The chemical and cell structures as well as physico‐mechanical, thermal, and acoustic properties were characterized and compared with commercial polyol analogs. The obtained HTNR based foams are open cell structures with cell dimensions between 0.38 and 0.47 mm. The HTNR1000 based foam exhibits better mechanical properties but lower elongation at break than those of commercial polyol analog. However, the HTNR3400 based foam shows the best elastic properties. In a series of EHTNR based foams, the tensile and compressive strengths show a tendency to increase with increasing epoxide content and amount of 1,4‐butanediol (BD). The HTNR based foams demonstrate better low temperature flexibility than that of the foam based on commercial polyol. Moreover, the HTNR based polyurethane foams was found to be an excellent absorber of acoustics. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermomechanical devulcanization of ethylene propylene diene monomer rubber and its application in blends with high-density polyethylene

The recycling of ethylene propylene diene monomer (EPDM) rubber remains a challenge, as its cross-linked structure cannot be broken down reversibly. Devulcanization may offer a breakthrough; however, a 100% decrease in cross-link density (CLD) with no chain degradation has never been reported. In this research, sulfur- and peroxide-cured EPDM rubbers of known compositions were devulcanized on a two-roll mill and in an internal mixer. The CLD of both rubber samples decreased by around 85%, while the sol content of the peroxidic devulcanizate was considerably higher than that of the sulfuric devulcanizate (23% vs. 3%). Horikx's theory revealed that sulfur-cured samples showed excellent selectivity for cross-link scission, while peroxide-cured samples suffered degradation. Uncured, cured, and devulcanized rubber samples were mixed into high-density polyethylene at various compositions. Large EPDM rubber contents impaired the mechanical properties of the blends, indicating insufficient adhesion between the two phases. Compounds containing originally uncured rubber mixtures had the most beneficial mechanical properties.     

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。