基于X射线衍射法研究改性脱硫灰基生态橡胶的制备过程及机理

脱硫灰作为半干法脱硫技术主要副产品,其利用难度大且成本高,导致大量脱硫灰以直接堆放和填埋的方式处理,不但造成环境污染,而且浪费潜在资源。橡胶作为广泛应用的聚合物材料,在橡胶制备加工过程中需大量使用填料改善其力学性能、加工性能和填充增容。炭黑与白炭黑作为常用的橡胶填料,其不仅生产工艺繁杂,而且对能源和资源消耗量大,导致成本较高。面对上述问题,如何利用脱硫灰开发一种价格低廉的无机橡胶填料,既是固体废弃物高附加值利用又是资源可持续发展的重要途径之一,也是橡胶企业大幅降低填料成本提高经济效益的重要途径之一。由于脱硫灰属于无机材料,橡胶属于有机材料,为了更好的降低脱硫灰界面与橡胶界面(无机界面/有机界面)的不相容性,需要对脱硫灰进行化学改性处理。以该课题组前期取得的研究成果为基础,创新性以改性脱硫灰取代部分炭黑制备改性脱硫灰基生态橡胶。利用XRD对改性脱硫灰基生态橡胶制备过程各阶段的生产物质进行测试,即丁苯橡胶密炼胶制备阶段、改性脱硫灰基生态橡胶密炼胶制备阶段和改性脱硫灰基生态橡胶制备阶段,从微观层面揭示丁苯橡胶密炼胶制备过程、改性脱硫灰基生态橡胶密炼胶制备过程和改性脱硫灰基生态橡胶制备过程,阐明硫化过程中丁苯橡胶密炼胶与改性脱硫灰的结合机理。同时采用SEM对丁苯橡胶密炼胶与改性脱硫灰基生态橡胶密炼胶的微观形貌进行测试,以进一步佐证所获得的相关机理。结果表明:改性脱硫灰加入丁苯橡胶密炼胶后,改性脱硫灰基生态橡胶密炼胶的最大转矩F max大幅下降、最小转矩F L保持稳定、ΔF=F max-F L显著下降,同时焦烧时间t 10与正硫化时间t 90均缩短。硫化诱导期为0~387 s、硫化反应期为387~1586 s和硫化平坦期为1586~1800 s。在硫化诱导期形成非交联网络结构、硫化反应期前期形成基本交联网络结构、硫化反应期后期完善交联网络结构和硫化平坦期保持交联网络结构。以期为高附加值的脱硫灰资源化利用提供一定理论依据和技术支持。

Study on Preparation Stage and Mechanism of Modified Desulfurization Ash-Based Eco Rubber by X-Ray Diffraction

As main by-product of semi-dry desulfurization technology,desulfurization ash is very difficult to be utilized and there is a high-cost for its utilization.It cannot be disposed through direct stacking and landfill,otherwise it will cause environmental pollution and waste of potential resources.Rubber is a kind of widely used polymer material,of which the mechanical properties,machining properties and filling capacity can be improved by using large amounts of fillers during preparation.Carbon black and white carbon black,as the commonly used rubber packing,can only be prepared by complicated process,which always leads to large consumption of energy and resources,resulting in higher costs.Thus,the development of desulfurization ash into low-cost inorganic rubber fillers has become one of the main methods to achieve resource sustainable development and enhance economic performance by high value-added utilization of solid wastes and cost reduction of fillers in rubber industry to a great extent,respectively.The desulfurization ash is organic while rubber is inorganic.Therefore,chemical modification is necessary to be conducted for desulfurization ash to weaken incompatibility of interface(organic/inorganic)between them.Based on the research results obtained in the early stage of this research group,in this paper,modified desulfurization ash was innovatively used to replace part of carbon black to prepare modified desulfurization ash-based eco rubber.Production materials in every stage of preparation process of modified desulfurization ash-based eco rubber were measured by XRD,such as preparation stage of styrene butadiene rubber mixer glue,preparation stage of modified desulfurization ash-based eco rubber mixer glue and preparation stage of modified desulfurization ash-based eco rubber.The preparation process of styrene butadiene rubber mixer glue,preparation process of modified desulfurization ash-based eco rubber mixer glue and preparation process of modified desulfurization ash-based eco rubber were revealed at the microscopic level,respectively,in order to explain the bonding mechanism of styrene butadiene rubber mixer glue and modified desulfurization ash in vulcanization process.Meanwhile,microstructures of styrene butadiene rubber mixer glue and modified desulfurization ash-based eco rubber mixer glue were tested by SEM so as to further support the obtained mechanism.The results showed that after adding modified desulphurizing ash to styrene butadiene rubber,modified desulfurization ash-based eco rubber’maximum torque F max drops dramatically,minimum torque F L remains stable,△F=F max-F L is significantly reduced,meanwhile scorch time and optimum cure time are shortened.Vulcanization induction stage is 0~387 s,vulcanization reaction stage is 387~1586 s and vulcanization flat stage is 1586~1800 s.Form the non-crosslinking network structure in vulcanization induction stage,form the basic crosslinking network structure in early of vulcanization reaction stage,improve the crosslinking network structure in later of vulcanization reaction stage and maintain the crosslinking network structure in vulcanization flat stage.It aims to provide some theoretical basis and technical support for high value-added desulphurization ash resource utilization.