CN101168600A - 一种废旧轮胎胶高剪切应力诱导脱硫及改性方法 - Google Patents
一种废旧轮胎胶高剪切应力诱导脱硫及改性方法 Download PDFInfo
- Publication number
- CN101168600A CN101168600A CNA2007101329355A CN200710132935A CN101168600A CN 101168600 A CN101168600 A CN 101168600A CN A2007101329355 A CNA2007101329355 A CN A2007101329355A CN 200710132935 A CN200710132935 A CN 200710132935A CN 101168600 A CN101168600 A CN 101168600A
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- rubber
- desulfurization
- reaction
- product
- ethylene
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Links
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Abstract
本发明涉及一种废旧轮胎胶高剪切应力诱导脱硫及改性方法,将占反应物总重量百分含量为5%~50%的线性高分子物质、占反应物总重量百分含量为49%~94%的废旧轮胎胶粉和占反应物总重量百分含量为0.01%~1.8%的稳定化助剂相混合;混合物一并加入高转速、高剪切型同向旋转双螺杆挤出机中,熔融挤出脱硫反应;反应产物经水冷、切粒、干燥或经辊筒压延冷却、成片,即获得脱硫改性的再生胶产物。本发明将脱硫反应及反应产物的粗炼、精炼和滤胶过程集成为一体,脱硫过程效率高、产率高、能量消耗低,易于大型化、规模化;脱硫反应易于控制;反应过程对环境污染小,脱硫产物再硫化材料的力学性能好。
Description
技术领域:
本发明涉及一种废旧轮胎胶脱硫再生新技术,属于聚合物材料的改性领域。
技术背景:
随着世界经济和科学技术的不断发展,橡胶材料已越来越成为人们无法离开的重要物资。根据国际橡胶研究组织(IRSG)统计,2003年全球橡胶消耗量已达1897万吨,2004年达1930万吨,同比增长5%左右。预计2020年将达2600万吨。我国是橡胶工业大国,生胶的消耗量年均递增10%以上,2003年为364万吨,2004年达420万吨,2006年达540万吨,已跃居世界第一,成为全球最大的橡胶消费国和第一大橡胶进口国。根据国际橡胶研究组织预测,2020年我国橡胶消耗量将有可能超过750万吨,由现在占世界消耗量的17%提高到29%。
轮胎制造是橡胶消费的主流走向,占到橡胶消费总量的70%左右。根据资料统计,目前全球每年汽车轮胎的产量在10亿至15亿条之间,与每年报废的废旧轮胎数量相当。我国又是轮胎生产和消费大国。2004年我国轮胎总产量约1.9亿至2亿条,进出口相抵后,国内需求量1.4亿至1.5亿条,按平均70%用于更新旧胎计算,当年更换下来的废旧轮胎约为1亿条左右。据此我国废旧轮胎的产量仅次于美国,居世界第二。废胎堆积侵占耕地面积、污染环境,存在火灾隐患,威胁人们的生命、财产安全。如何综合利用这数量巨大的废旧轮胎,治理环境污染、循环使用废旧橡胶资源是全社会都应重视解决的重大课题。
目前世界各国对废旧轮胎处理利用的途径和重点各不相同,大体可区分为四个方面:(1)原形利用,即旧胎翻新、或作为护航鱼礁鱼具,路标墙屏等;(2)粉粹加工制备细微胶粉,用作橡胶、塑料和建材工业中的掺混材料;(3)脱硫再生,继续用作制备轮胎等橡胶制品的生胶替代材料;(4)热能利用,即高温裂解制备燃油或直接作为燃料使用。国外一般以热能利用为主,用作热电厂、造纸厂等工厂锅炉的燃料,用量占到一半以上。原形利用约占15%至20%,其余则用于制备胶粉、胶粒,掺混使用。我国是橡胶资源短缺国家,目前仍以脱硫再生为主,再生比例约占利用总量的90%左右。
废旧轮胎是由高质量的橡胶、碳黑、有机纤维和钢丝等所组成的高度强韧复合材料,具有巨大的内在经济价值,将其作为热能材料利用,易产生大量有害气体污染环境,且循环经济价值很低,资源浪费很大。制备成细微胶粉用作掺混材料,其所利用的经济价值也不高,不能充分发挥出其应具备的再生潜值。而原形利用的用量有限,不能及时消化掉这数量巨大的废胶资源。其中只有高效率的逆硫化反应——脱硫再生,继续将其作为制备轮胎等橡胶制品的生胶替代材料,循环使用废旧橡胶资源,才是真正有效的解决途径。
废旧轮胎胶具有三维网络状的分子结构,不熔化、不溶解。这也是废旧轮胎胶区别于废旧塑料,难以真正再生利用的关键所在。发展一种有效的逆硫化(即脱硫)反应技术,使其分子恢复到硫化前的一维线性结构,一直是各国化学家们努力追求的目标,并为此发展出了一系列的脱硫再生方法及工艺。其中较为重要的方法及工艺有:早期的水油法、油法,高温、高压动态脱硫法,DE-LINK低温脱硫再生工艺等。但由于这些方法存在工艺流程长、生产能耗大、操作工人劳动强度大或脱硫过程易产生大量废水或废气,难以制理,污染环境和所得再生胶产品的质量较差等技术难题,故现在国外已基本被摈弃。目前我国仍以高温、高压动态脱硫法生产再生胶为主,虽然比一般的水油法、油法有所改进,但仍然不可避免的具有大量废水、废气产生,严重污染和破坏了工厂周围的生态和环境。而微波脱硫法,超声波脱硫法,微生物技术脱硫法和超临界CO2溶胀脱硫法等近代技术,由于存在需要屏蔽辐射、放大困难、或能量消耗较大、不易较大规模工业化实施等技术难题,目前尚处于研究、开发之中。
因此在目前废旧轮胎胶工业脱硫再生技术取得一定发展的基础上,继续探索、寻找一种高效率、高质量、无污染且易于工业化实施的脱硫再生新技术,具有十分重要的意义。
发明内容:
本发明的目的是为了改进以往废旧轮胎脱硫再生方法中所存在的不足而提出一种废旧轮胎胶高剪切应力诱导脱硫及改性的新方法。
本发明所采取的技术方案是:根据机械剪切应力具有大小和方向性的特征,当作用于聚合物交联网络的剪切应力超过其临界值时,即会诱发垂直于剪切应力方向聚合物分子链的断链反应,而平行于剪切应力方向的聚合物分子链却不受影响;并根据废旧轮胎胶中的硫-硫键键能和碳-硫键键能均比碳-碳键键能低,较易发生断裂的特征;通过添加线形高分子物质和改变螺杆转速、挤出反应温度来调控反应体系中的剪切应力大小和热能作用的强弱,从而达到对轮胎胶粒中交联网络的选择性断裂,实现废旧轮胎胶脱硫反应的目的。同时利用脱硫过程中轮胎胶分子主链和线性高分子物质主链断裂而产生的接枝或嵌段反应,对轮胎胶分子主链进行相容性性质的改性,以有利于脱硫轮胎胶与其它聚合物材料的共混改性。
本发明所采取的具体技术方案是:一种废旧轮胎胶高剪切应力诱导脱硫及改性方法,将占反应物总重量百分含量为5%~50%的线性高分子物质、占反应物总重量百分含量为49%~94%的废旧轮胎胶粉和占反应物总重量百分含量为0.01%~1.8%的稳定化助剂相混合;混合物一并加入高转速、高剪切型同向旋转双螺杆挤出机中,熔融挤出脱硫反应;反应产物经水冷、切粒、干燥或经辊筒压延冷却、成片,即获得脱硫改性的再生胶产物。
其中所述的线性高分子物质为聚乙烯(PE)、聚丙烯(PP)、乙烯-丙烯嵌段共聚物(共聚PP)、乙烯-丙烯共聚物(EPR)、乙烯-丁烯共聚物(LLDPE)、乙烯-醋酸乙烯共聚物(EVA)、乙烯-辛烯共聚物(POE)、乙烯-丙烯-二烯类三元共聚物(EPDM)、氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS),或未硫化的丁苯橡胶(SBR)、顺丁橡胶(BR)或天然橡胶(NR)的混炼胶中的任意一种。
其中所述废旧轮胎胶粉为8目至80目的汽车子午线轮胎胶粉、汽车斜胶胎胶粉、自行车轮胎胶粉或硫化的橡胶板、传送带胶粉中的任意一种。
其中所述稳定化助剂为酚类抗氧剂与金属皂类热稳定剂的混合物;其中酚类抗氧剂和金属皂类热稳定剂的质量比为1∶1至1∶5。所述的酚类抗氧剂至少为四[3-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(抗氧剂1010)、β-(4-羟基-3,5-二叔丁基苯基)丙酸正十八碳醇酯(抗氧剂1076)、4,4’-硫代双(2-甲基-6-叔丁基苯酚)(抗氧剂736)或1,3,5-三(3,5-二叔丁基-4-羟基卞基)均三嗪-2,4,6-(1H,3H,5H)-三酮(抗氧剂3114)中的一种,金属皂类热稳定剂至少为硬脂酸钙、硬脂酸钡或硬脂酸锌的混合物中的一种。
其中上述熔融挤出脱硫反应中挤出温度控制在150℃~320℃;所述高转速、高剪切型同向旋转双螺杆挤出机为螺杆转速为300r/min至1600r/min的二阶至四阶的同向旋转双螺杆挤出机,螺杆长径比可以为24至60,由输送螺纹元件、捏合螺纹元件、压缩螺纹元件和反螺纹元件混合组成。
有益效果:
1.不使用硫醇类、硫酚类脱硫助剂和小分子软化剂进行脱硫反应,脱硫反应过程对环境污染小,脱硫产物再硫化材料的力学性能好。
2.少量废气可经真空脱除、水吸收处理,水吸收处理的少量废水易于净化重复使用。
3.脱硫反应易于控制,脱硫反应程度可以根据螺杆转速、螺杆长径比、螺纹组合形式和反应温度进行调整。
4.通过改变线性高分子添加材料的品种,利用脱硫过程中的接枝或嵌段反应,可以改性脱硫轮胎胶的相容性性质,以方便脱硫轮胎胶的不同应用。
5.脱硫过程连续化、易于自动化,操作环境好,操作工人劳动强度小、接触污染少。
6.将脱硫反应及反应产物的粗炼、精炼和滤胶过程集成为一体,脱硫过程效率高、产率高、能量消耗低,易于大型化、规模化。
附图说明:
图1为本发明的工艺流程图;
图2为本发明的主设备之一-20双螺杆挤出机螺杆组合图;其中A-第二排气口,B-第一排气口,C-加料口。
图3为本发明的主设备之二-35双螺杆挤出机螺杆组合图;其中A-第二排气口,B-第一排气口,C-加料口。
具体实施方式:
下面通过实施例对本发明进行具体描述,有必要指出的是以下实施例只用于对本发明进行进一步的说明,不能理解为对本发明保护范围的限制。本领域的技术熟练人员可以根据上述本发明内容进行一些非本质的改进和调整。
实施例1(子午线轮胎胶粉共混EPDM热塑性弹性体脱硫反应及掺混SBR橡胶性能):子午线轮胎胶粉(GTR)20目,江苏通江塑胶有限公司提供,经热失重分析得:橡胶含量为57.3%,碳黑含量为30.1%,灰份含量为6.2%,挥发份含量为6.4%。
将上述轮胎胶粉800克与200克EPDM(NDR3745美国杜邦-淘氏公司产品)、0.15克抗氧剂1010及0.3克硬脂酸钙相混合;混合物一并加入螺杆直径为35mm,长径比为45的三阶同向旋转双螺杆挤出机中(南京科亚机械设备有限公司产,挤出工艺及挤出装置螺杆组合图参见附图1和附图3);控制挤出反应温度为250℃,控制螺杆转速为1000r/min;在挤出反应的同时开动水环式真空泵,真空脱除脱硫反应时产生的挥发性气体;挤出产物经水冷、干燥即获得脱硫轮胎胶产物(DGTR/EPDM)。
脱硫轮胎胶产物经150目铜网包扎、二甲苯抽提得产物凝胶含量为34%;抽提过程中溶于二甲苯的溶胶经丙酮沉析、干燥、称重得到产物溶胶;以环己烷为溶剂,25℃下以稀释外推法测得产物溶胶的特性粘数为0.217。
将上述脱硫轮胎胶产物30份、丁苯橡胶(1502吉林化学工业公司产)70份和碳黑(N330,无锡市苏新精细炭黑厂)35份一并加入双辊混炼机中共混合,同时加入硫磺2份、促进剂1.3份、氧化锌5份、硬脂酸2份和防老剂2份,混合均匀并出片。所得的混炼胶片放置24小时后,以160℃平板硫化机压片,硫化时间为6分钟,得到硫化橡胶片;硫化橡胶片放置24小时后测定力学性能。
参照相应国家标准测得此硫化橡胶片的拉伸强度为19.5MPa、断裂伸长率为385%、撕裂强度为38.2kN/m、邵氏A型硬度为69。
通过改变螺杆转速可得不同螺杆转速条件下实施例1的对比数据如下:
表1螺杆转速对DGTR/EPDM性能及SBR/DGTR/EPDM硫化共混物力学性能的影响*
序号 | 螺杆转速r/min | 凝胶含量% | 溶胶特性粘数 | 拉伸强度MPa | 断裂伸长率% | 撕裂强度kN/m | 邵氏硬度A |
1-11-21-31-41-5 | 40060080010001200 | 43.534.332.734.030.4 | 0.240.220.270.220.23 | 17.218.319.019.518.7 | 360386415383434 | 36.139.338.638.239.5 | 6868676967 |
*脱硫反应温度为250℃
通过改变挤出反应温度可得不同反应温度条件下实施例1的对比数据如下:
表2挤出反应温度对DGTR/EPDM性能及SBR/DGTR/EPDM硫化共混物力学性能影响*
序号 | 挤出反应温度℃ | 凝胶含量% | 溶胶特性粘数 | 拉伸强度MPa | 断裂伸长率% | 撕裂强度kN/m | 邵氏硬度A |
1-61-71-81-91-10 | 190210230250270 | 48.646.440.334.035.0 | 0.260.230.220.220.21 | 17.318.318.819.517.2 | 352356366383376 | 36.139.338.638.239.5 | 6868676967 |
*脱硫反应螺杆转速为1000r/min
表中数据比较说明,在螺杆转速为1000r/min时和250℃的条件下,所得脱硫轮胎胶产物的凝胶含量较低,而掺混于丁苯橡胶中的材料拉伸强度和断裂伸长率较高。
比较例1(硫化丁苯橡胶力学性能):将丁苯橡胶(1502吉林化学工业公司产)100份和碳黑(N330)40份(控制碳黑含量与实施例1相近)一并加入双辊混炼机中共混合,同时加入硫磺2份、促进剂1.3份、氧化锌5份、硬脂酸2份和防老剂2份,混合均匀并出片。所得的混炼胶片放置24小时后,以160℃平板硫化机压片,硫化时间为6分钟,得到硫化橡胶片。硫化橡胶片放置24小时后测定力学性能,得到拉伸强度为22.0MPa、断裂伸长率为391%、撕裂强度为37.1kN/m、邵尔A型硬度为63。
比较例2(丁苯橡胶/轮胎胶粉硫化物力学性能):将未经脱硫的20目子午线轮胎胶胶粉30份、丁苯橡胶(1502吉林化学工业公司产)70份和碳黑(N330)35份一并加入双辊混炼机中共混合,同时加入硫磺2份、促进剂1.3份、氧化锌5份、硬脂酸2份和防老剂2份,混合均匀并出片。所得的混炼胶片放置24小时后,以160℃平板硫化机压片,硫化时间为6分钟,得到硫化橡胶片。硫化橡胶片放置24小时后测定力学性能,得到拉伸强度为14.3MPa、断裂伸长率为299%、撕裂强度为37.8kN/m、邵尔A型硬度为72。
以上比较例数据表明,采用30份本发明的脱硫轮胎胶产物替代丁苯橡胶时,其所得橡胶材料的拉伸强度达到了原丁苯橡胶材料拉伸强度的88%左右,其它力学性能数据则相近。而采用同样粒度的30份轮胎胶粉替代丁苯橡胶时,其所得橡胶材料的拉伸强度仅达到原丁苯橡胶材料拉伸强度的65%左右,材料的断裂伸长率也较低。
实施例2(子午线轮胎胶粉共混天然橡胶NR脱硫反应及掺混SBR橡胶性能):将实施例1中的EPDM改为含33.3%碳黑(N330)的NR混炼胶,挤出反应温度改为180℃,螺杆转速改为800r/min,其它与实施例1相同。得脱硫产物凝胶含量为65.4%,硫化橡胶片的拉伸强度为17.1MPa、断裂伸长率为330%、撕裂强度为33.7kN/m、邵尔A型硬度为73。
实施例3(子午线轮胎胶粉共混顺丁橡胶BR脱硫反应及掺混SBR橡胶性能):将实施例1中的EPDM改为含33.3%碳黑(N330)的BR混炼胶,挤出反应温度改为180℃,螺杆转速改为800r/min,其它与实施例1相同。得脱硫产物凝胶含量为70.9%,硫化橡胶片的拉伸强度为17.0MPa、断裂伸长率为312%、撕裂强度为31.8kN/m、邵尔A型硬度为72。
实施例4(子午线轮胎胶粉共混SEBS热塑性弹性体脱硫反应及掺混SBR橡胶性能):将实施例1中的EPDM改为SEBS热塑性弹性体,挤出反应温度改为180℃,螺杆转速改为800r/min,其它与实施例1相同。得脱硫产物凝胶含量为52.7%,硫化橡胶片的拉伸强度为18.8MPa、断裂伸长率为368%、撕裂强度为34kN/m、邵尔A型硬度为72。
实施例5(子午线轮胎胶粉共混EPDM脱硫反应及制备PP动态交联热塑性弹性体性能):将颗粒直径在10目左右的子午线轮胎胶粉(扬州市绿环废旧橡胶回收有限公司提供)480克与120克EPDM(NDR3745美国杜邦-淘氏公司产品)、0.12克抗氧剂1076及0.24克硬脂酸钡相混合;混合物一并加入螺杆直径为35mm,长径比为45的三阶同向旋转双螺杆挤出机中(挤出工艺及挤出装置螺杆组合图参见附图1和附图3);控制挤出反应温度为200℃,控制螺杆转速为1000r/min;在挤出反应的同时开动水环式真空泵,真空脱出脱硫反应时产生的挥发性气体;挤出产物经水冷、干燥即获得脱硫轮胎胶产物(DGTR/EPDM)。
脱硫轮胎胶产物经150目铜网包扎、二甲苯抽提得产物凝胶含量为40.5%。
将上述脱硫轮胎胶产物600克、PP(F401,扬子石化公司产)400克及引发剂DCP 20克相混合,一并加入螺杆直径为20mm、长径比为32的同向旋转双螺杆挤出机中(南京科亚机械设备有限公司产,螺杆组合图参见附图2),进行熔融挤出动态硫化反应,控制主螺杆转速150r/min,挤出反应温度185℃,挤出物经水冷、切粒、干燥即获得DGTR/EPDM/PP(48/12/40)动态交联热塑性弹性体。
上述动态交联热塑性弹性体测试得熔体流动速率(230℃,5kg载荷)0.75g/10min。经200℃注塑制样,按相关标准测得拉伸强度16.9MPa,断裂伸长率275%,邵氏A型硬度95.5。
通过改变脱硫反应的螺杆转速可得不同螺杆转速条件下实施例5的对比数据如下:
表3螺杆转速对DGTR/EPDM性能及DGTR/EPDM/PP热塑性弹性体性能影响*
序号 | 螺杆转速r/mm | 凝胶含量% | 熔体流动速率g/10min | 拉伸强度MPa | 断裂伸长率% | 邵氏硬度A |
6-16-26-36-46-5 | 40060080010001200 | 50.847.340.740.541.4 | 0.220.470.450.750.55 | 18.117.316.716.917.5 | 215252260275220 | 9596.59595.597 |
*脱硫反应温度为200℃
通过改变脱硫反应的温度可得不同反应温度条件下实施例5的对比数据如下:
表4挤出反应温度对DGTR/EPDM性能及DGTR/EPDM/PP热塑性弹性体性能影响*
序号 | 挤出反应温度℃ | 凝胶含量% | 熔体流动速率g/10min | 拉伸强度MPa | 断裂伸长率% | 邵氏硬度A |
6-66-76-86-96-10 | 160180200240260 | 46.446.340.535.432.4 | 0.30.40.751.01.2 | 15.716.216.915.414.3 | 228284275300254 | 929395.59596 |
*脱硫反应螺杆转速为1000r/min
表中数据比较说明,在螺杆转速为1000r/min时和200℃的条件下,所得脱硫轮胎胶产物制备PP动态交联热塑性弹性体的综合力学性能较好。
比较例3(EPDM/PP动态交联热塑性弹性体力学性能):将上述EPDM600克、PP(F401)400克及引发剂DCP 25克相混合,一并加入螺杆直径为20mm、长径比为32的同向旋转双螺杆挤出机中,进行熔融挤出动态硫化反应,控制主螺杆转速150r/min,挤出反应温度185℃,挤出物经水冷、干燥即获得EPDM/PP(60/40)动态交联热塑性弹性体。按标准测试得熔体流动速率(230℃,5kg载荷)为0.02g/10min,经200℃注塑制样,按相关标准测得拉伸强度12.3MPa,断裂伸长率197%,邵氏A型硬度90。
比较例4(子午线轮胎胶粉/EPDM/PP动态交联热塑性弹性体力学性能):将上述粒径在10目左右的子午线轮胎胶轮胎胶粉480克、EPDM120克、PP(F401)400克及引发剂DCP 25克相混合,一并加入螺杆直径为20mm、长径比为32的同向旋转双螺杆挤出机中,进行熔融挤出动态硫化反应,控制主螺杆转速150r/min,挤出反应温度185℃,挤出物经水冷、干燥、切粒即获得GTR/EPDM/PP(48/12/40)动态交联热塑性弹性体。按标准测试得熔体流动速率(230℃,5kg载荷)0.34g/10min,经200℃注塑制样,按相关标准测得拉伸强度12.5MPa,断裂伸长率18%,邵氏A型硬度93,并且试样表面粗糙、不光洁。
以上比较例数据表明,采用本发明方法制得的PP动态交联热塑性弹性体的各项力学性能均明显优于由EPDM新胶制得的同样材料,并且其断裂伸长率也大大优于由相同胶粉制得的材料。
实施例6(斜胶胎胶粉共混EPDM脱硫反应及制备PP动态交联热塑性弹性体性能):将颗粒直径在10目左右的子午线轮胎胶粉改为10目左右的斜胎胶胶粉,其它与实施例5相同。得DGTR/EPDM/PP(48/12/40)动态交联热塑性弹性体的拉伸强度为17.2MPa,断裂伸长率为147%,邵氏A型硬度为97。
实施例7(子午线轮胎胶粉共混HDPE脱硫反应及制备HDPE动态交联热塑性弹性体性能):将约粒径在20目左右的子午线轮胎胶粉(江苏通江塑胶有限公司提供)500克与300克HDPE(5000S,扬子石化公司产品)、0.15克抗氧剂1010及0.3克硬脂酸钙相混合;混合物一并加入螺杆直径为20mm,长径比为32的三阶同向旋转双螺杆挤出机中(南京科亚机械设备有限公司产,挤出工艺及挤出装置螺杆组合图参见附图1和附图2);控制挤出反应温度为200℃,控制螺杆转速为600r/min;在挤出反应的同时开动水环式真空泵,真空脱出脱硫反应时产生的挥发性气体;挤出产物经水冷、干燥即获得脱硫轮胎胶产物(DGTR/HDPE(50/30))。
脱硫轮胎胶产物经150目铜网包扎、二甲苯抽提得产物凝胶含量为44.9%。按标准测试得熔体流动速率(230℃,5kg载荷)为0.8g/10min。
将上述脱硫轮胎胶产物80份和EPDM 20份一并加入135℃的双辊混炼机中共混合,同时加入DCP 2份、硫磺0.5份、氧化锌4份、硬脂酸1.5份、促进剂DM 1份、CZ 0.5份及防老剂4010 0.5份,混合均匀、动态硫化并出片。所得的动态硫化胶片放置24小时后,在165℃平板硫化机上预热10分钟,保压10分钟,模压成片。得到DGTR/EPDM/HDPE(50/20/30)动态交联热塑性弹性体材料。
上述动态交联热塑性弹性体按相关标准测试,得拉伸强度11.9MPa,断裂伸长率332%,撕裂强度为58.3kN/m,邵氏A型硬度86.0。
通过改变脱硫反应的螺杆转速可得不同螺杆转速下实施例7的对比数据如下:
表5螺杆转速对DGTR/HDPE性能及DGTR/EPDM/HDPE热塑性弹性体性能的影响*
序号 | 螺杆转速r/mm | 凝胶含量% | 熔体流动速率g/10min | 拉伸强度MPa | 断裂伸长率% | 撕裂强度kN/m | 邵氏硬度A |
7-17-27-37-47-57-6 | 20040060080010001200 | 54.450.844.940.739.736.5 | 0.20.30.81.22.23.2 | 9.512.811.910.810.110.4 | 150308332285286289 | 67.261.458.353.160.056.1 | 8887.586898585 |
*脱硫反应温度为200℃
通过改变脱硫反应的温度可得不同反应温度条件下实施例7的对比数据如下:
表6挤出反应温度对DGTR/HDPE性能及DGTR/EPDM/HDPE热塑性弹性体性能的影响*
序号 | 挤出反应温度℃ | 凝胶含量% | 熔体流动速率g/10min | 拉伸强度MPa | 断裂伸长率% | 撕裂强度kN/m | 邵氏硬度A |
7-77-87-97-107-11 | 150170200230260 | 40.440.339.735.231.4 | 0.70.82.22.84.0 | 11.811.710.19.38.4 | 255272286280260 | 61.057.560.059.461.1 | 8585858584 |
*脱硫反应螺杆转速为1000r/min
表中数据比较说明,在螺杆转速为600r/min时和200℃的条件下,所得脱硫轮胎胶产物制备的HDPE动态交联热塑性弹性体的综合力学性能较好。
比较例5(EPDM/HDPE动态交联热塑性弹性体性能):将EPDM 70份和HDPE 30份一并加入135℃的双辊混炼机中共混合,同时加入DCP 2份、硫磺0.5份、氧化锌4份、硬脂酸1.5份、促进剂DM 1份、CZ 0.5份及防老剂40100.5份,混合均匀、动态硫化并出片。所得的动态硫化胶片放置24小时后,在165℃平板硫化机上预热10分钟,保压10分钟,模压成片。得到EPDM/HDPE(70/30)动态交联热塑性弹性体材料。
上述动态交联热塑性弹性体按相关标准测试,得拉伸强度14.0MPa,断裂伸长率580%,撕裂强度为64.2kN/m,邵氏A型硬度85。
比较例6(子午线轮胎胶粉/EPDM/HDPE动态交联热塑性弹性体性能):将上述子午线轮胎胶粉50份、EPDM 20份和HDPE 30份一并加入135℃的双辊混炼机中共混合,同时加入DCP 2份、硫磺0.5份、氧化锌4份、硬脂酸1.5份、促进剂DM 1份、CZ 0.5份及防老剂4010 0.5份,混合均匀、动态硫化并出片。所得的动态硫化胶片放置24小时后,在165℃平板硫化机上预热10分钟,保压10分钟,模压成片。得到GTR/EPDM/HDPE(50/20/30)动态交联热塑性弹性体材料。
上述动态交联热塑性弹性体按相关标准测试,得拉伸强度9.6MPa,断裂伸长率310%,撕裂强度为66.4kN/m,邵氏A型硬度87,并且试样表面粗糙、不光洁。
上述比较例数据表明,采用本发明方法制得的HDPE动态交联热塑性弹性体的拉伸强度和断裂伸长率均略低于由EPDM新胶制得的同样材料,但仍明显优于由轮胎胶粉制得的相同材料。
实施例8(子午线轮胎胶粉共混POE热塑性弹性体脱硫反应及增韧PP材料力学性能):将子午线轮胎胶粉(10目,扬州市绿环废旧橡胶回收有限公司提供)800克与200克POE(美国杜邦-陶氏公司产品)、0.15克抗氧剂1010及0.3克硬脂酸钙相混合;混合物一并加入螺杆直径为35mm,长径比为45的三阶同向旋转双螺杆挤出机中(挤出工艺及挤出装置螺杆组合图参见附图1和附图3);控制挤出反应温度为200℃,控制螺杆转速为1000r/min;在挤出反应的同时开动水环式真空泵,真空脱出脱硫反应时产生的挥发性气体;挤出产物经水冷、切粒、干燥即获得脱硫轮胎胶产物(DGTR/POE)。
脱硫轮胎胶产物经150目铜网包扎、二甲苯抽提得产物凝胶含量为39.6%;按标准测试得产物熔体流动速率(230℃,5kg载荷)为12.0g/10min。
脱硫产物30份与PP(J340,扬子石化公司产)70份混合均匀,一并加入螺杆直径为20mm,长径比为32的三阶同向旋转双螺杆挤出机(螺杆组合图参见附图3)中熔融共混合,主螺杆转速200r/min,挤出共混温度190℃,挤出物经水冷、切粒、干燥即获得弹性体增韧PP材料(PP/DGTR/POE(70/24/6))。
此弹性体增韧PP材料经220℃注塑制样,按相关标准测定材料力学性能得:悬臂梁切口冲击强度47.7kJ/m2,拉伸强度27.9MPa,断裂伸长率180%,弯曲强度16.2,弯曲模量707MPa,熔体流动速率(230℃,2.16kg载荷)1.5g/10min。
通过改变脱硫反应螺杆转速可得不同螺杆转速下实施例8的对比数据如下:
表7螺杆转速对DGTR/POE性能及PP/DGTR/POE共混材料力学性能的影响*
序号 | 螺杆转速r/min | 凝胶含量% | 熔体流动速率g/10min | Izod冲击强度kJ/m2 | 拉伸强度MPa | 断裂伸长率% | 弯曲强度MPa | 弯曲模量MPa |
8-18-28-38-48-5 | 40060080010001200 | 54.244.243.239.639.2 | 4.95.510.012.023.8 | 31.034.942.347.745.2 | 29.531.028.327.927.6 | 81.895.6245180215 | 16.418.116.216.215.5 | 690779690707667 |
*脱硫反应温度为200℃
通过改变脱硫反应的温度可得不同反应温度条件下实施例8的对比数据如下:
表8挤出反应温度对DGTR/POE性能及PP/DGTR/POE共混材料力学性能的影响*
序号 | 挤出反应温度℃ | 凝胶含量% | 熔体流动速率g/10min | Izod冲击强度kJ/m2 | 拉伸强度MPa | 断裂伸长率% | 弯曲强度MPa | 弯曲模量MPa |
8-68-78-88-98-108-11 | 160180200220240260 | 46.244.943.243.846.640.7 | 5.03.910.012.011.820.0 | 41.243.642.344.345.043.0 | 29.627.728.327.728.527.6 | 107263245306311365 | 16.316.416.216.816.916.4 | 716694690728729717 |
*脱硫反应螺杆转速为800r/min
表中数据比较说明,在螺杆转速为1000r/min时和200℃的条件下,本发明所得脱硫轮胎胶产物增韧PP J340材料的缺口冲击强度为最高。其它力学性能也较好。
比较例7(PP J340力学性能):将PPJ340经220℃注塑制样,按相关标准测定材料力学性能得:悬臂梁切口冲击强度10.5kJ/m2,拉伸强度36.8MPa,断裂伸长率138%,弯曲强度33.1MPa,弯曲模量1300MPa,熔体流动速率(230℃,2.16kg载荷)为2.0g/10min。
比较例8(POE增韧PP J340力学性能):将POE 30份与PP(J340,扬子石化公司产)70份混合均匀,一并加入螺杆直径为20mm,长径比为32的三阶同向旋转双螺杆挤出机中熔融共混合,主螺杆转速200r/min,挤出共混温度190℃,挤出物经水冷、切粒、干燥即获得弹性体增韧PP材料(PP/POE/(70/30))。
此弹性体增韧PP材料经220℃注塑制样,按相关标准测定材料力学性能得:悬臂梁切口冲击强度为不断裂,拉伸强度为27.2MPa,断裂伸长率为180%,弯曲强度为16.1MPa,弯曲模量为652MPa,熔体流动速率(230℃,2.16kg载荷)为1.3g/10min。
比较例9(PP/轮胎胶粉/POE共混物力学性能):将上述子午线轮胎胶粉24份、POE 6份与PP(J340,扬子石化公司产)70份混合均匀,一并加入螺杆直径为20mm,长径比为32的三阶同向旋转双螺杆挤出机中熔融共混合,主螺杆转速200r/min,挤出共混温度190℃,挤出物经水冷、切粒、干燥即获得弹性体增韧PP材料(PP/GTR/POE(70/6/24))。
此弹性体增韧PP材料经220℃注塑制样,按相关标准测定材料力学性能得:悬臂梁切口冲击强度为23.7kJ/m2,拉伸强度为26.6MPa,断裂伸长率为34.5%,弯曲强度为18.3MPa,弯曲模量为772MPa,熔体流动速率(230℃,2.16kg载荷)为1.3g/10min,试样表面粗糙、不光洁。
上述比较例数据表明,采用本发明方法制得的脱硫轮胎胶产物可使PP J340的缺口冲击强度提高至原材料4.5倍左右,略低于由纯POE增韧的效果,但明显高于由同样分量的轮胎胶粉的改性效果。
Claims (6)
1.一种废旧轮胎胶高剪切应力诱导脱硫及改性方法,其具体步骤为:
A.将占反应物总重量百分含量为5%~50%的线性高分子物质、占反应物总重量百分含量为49%~94%的废旧轮胎胶粉和占反应物总重量百分含量为0.01%~1.8%的稳定化助剂相混合;
B.将上述的混合物一起加入高转速、高剪切型同向旋转双螺杆挤出机中,熔融挤出脱硫反应;
C.反应产物经水冷、切粒、干燥或经辊筒压延冷却、成片,即获得脱硫改性的再生胶产物。
2.根据权利要求1所述的方法,其特征在于其中所述的线性高分子物质为聚乙烯、聚丙烯、乙烯-丙烯嵌段共聚物、乙烯-丙烯共聚物、乙烯-丁烯共聚物、乙烯-醋酸乙烯共聚物、乙烯-辛烯共聚物、乙烯-丙烯-二烯类三元共聚物、氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物、未硫化的丁苯橡胶、未硫化的顺丁橡胶或天然橡胶的混炼胶中的任意一种。
3.根据权利要求1所述的方法,其特征在于所述的废旧轮胎胶粉为8目至80目的汽车子午线轮胎胶粉、汽车斜胶胎胶粉、自行车轮胎胶粉或硫化的橡胶板、传送带胶粉中的任意一种。
4.根据权利要求1所述的方法,其特征在于所述的稳定化助剂为酚类抗氧剂和金属皂类热稳定剂的混合物;酚类抗氧剂和金属皂类热稳定剂的质量比为1∶1至1∶5。
5.根据权利要求4所述的方法,其特征在于所述的酚类抗氧剂至少为四[3-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、β-(4-羟基-3,5-二叔丁基苯基)丙酸正十八碳醇酯、4,4’-硫代双(2-甲基-6-叔丁基苯酚)或1,3,5-三(3,5-二叔丁基-4-羟基卞基)均三嗪-2,4,6-(1H,3H,5H)-三酮中的一种;金属皂类热稳定剂至少为硬脂酸钙、硬脂酸钡或硬脂酸锌中的一种。
6.根据权利要求1所述的方法,其特征在于步骤B中熔融挤出脱硫反应中挤出温度为150℃~320℃;所述高转速、高剪切型同向旋转双螺杆挤出机为螺杆转速300r/min~1600r/min的二阶至四阶的同向旋转双螺杆挤出机,螺杆长径比为24~60,由输送螺纹元件、捏合螺纹元件、压缩螺纹元件和反螺纹元件混合组成。
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Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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US4833195A (en) * | 1987-07-20 | 1989-05-23 | Bp Performance Polymers, Inc. | High flow drapable polymer compositions |
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CN1313522C (zh) * | 2004-09-28 | 2007-05-02 | 南通回力橡胶有限公司 | 丁基橡胶高温连续再生工艺 |
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2007
- 2007-09-20 CN CN2007101329355A patent/CN101168600B/zh not_active Expired - Fee Related
-
2008
- 2008-09-22 US US12/234,766 patent/US20090082475A1/en not_active Abandoned
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