CN108102160A - 一种钢边止水带及其制备方法 - Google Patents
一种钢边止水带及其制备方法 Download PDFInfo
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- CN108102160A CN108102160A CN201711500885.1A CN201711500885A CN108102160A CN 108102160 A CN108102160 A CN 108102160A CN 201711500885 A CN201711500885 A CN 201711500885A CN 108102160 A CN108102160 A CN 108102160A
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Abstract
本发明属于密封技术领域,具体涉及一种高性能钢边止水带及其制备方法,该高性能钢边止水带,由中间基体和两侧与中间基体硫化粘结的镀锌钢板组成,镀锌钢板上下表面有间隔的肋条,中间基体由橡胶基体和橡胶基体排水孔表面覆盖的特氟龙薄膜组成,橡胶基体包括天然橡胶、硫磺、氧化锌、功能填料、阻燃剂、促进剂和防老剂。
Description
技术领域
本发明涉及密封技术领域,具体涉及一种高性能钢边止水带及其制备方法。
背景技术
随着经济的快速发展,我国的交通建设事业也取得了极大的成就,尤其是隧道勘察设计、施工和运营管理水平都有了很大的提高。由于不能连续浇筑或地基变形,温度变化引起的混凝土构件热胀冷缩等原因,需要预留施工缝、沉降缝、变形缝。在这些接缝处必须安装止水带以防止水的渗漏问题。
止水带密封材料能阻塞介质透过渗透通道,起到水密、气密性作用的材料。目前止水带根据材质可分为:橡胶止水带、塑料止水带、金属止水带和复合止水带。止水带的性能直接影响到了隧道的安全形成以及公路的营运效率。
在申请号201611112918.0的发明专利中介绍了一种聚氨酯组合物、一种聚氨酯止水条及包括该止水条的钢边止水带,该聚氨酯组合物遇水可以反复膨胀,使得该新型止水带能够与混凝土紧密粘结,防水性能优异,耐久性好,从而解决现有隧道二衬止水带不能根治渗漏水的问题,膨胀止水条能在其膨胀倍率范围内起到防水的作用,然而在枯水期,膨胀止水条会失水收缩,在止水条反复膨胀与收缩的复杂工作环境下,遇水膨胀止水条很难有效的发挥作用,最终势必导致止水条与衬砌环向施工缝两侧混凝土间出现间隙,使渗水沿此间隙渗出,从而引发施工缝的渗漏。在申请号20140636333.3的发明专利中介绍了一种钢边止水带及其制备方法,该止水带由三元乙丙橡胶、氯丁橡胶、复合补强剂、硫化剂、硫化促进剂和镀锌钢板组成,其具有耐腐蚀、可承受高水压、变形大的施工缝、变形缝等特点,然而其使用寿命短、耐老化性能不佳,严重影响了钢边止水带的实际应用。如果橡胶止水带因质量问题使隧道出现漏水、窜水问题,则会给铁路运营安全带来极大的安全隐患。止水带的质量好坏对隧道的养护成本关系重大。同时,防水材料的使用增加了建筑外立面的火灾风险,一旦发生火灾,很有可能引燃整栋建筑。止水带排水区的橡胶容易被渗漏水或酸雨等腐蚀,有些止水带往往因为排水区橡胶的损坏而导致再次漏水,现有技术鲜有介绍对其防护。促进剂的使用也有一定的要求,根据期刊China Rubber,2002,18:25的报道现用二硫代氨基甲酸盐类促进剂是仲胺的衍生物,这种仲胺类促进剂已经证实能够在硫化过程中产生致癌性物质——亚硝胺,受到了严格的限制。因此,制备环保、阻燃、耐老化性能优异、使用寿命长且力学性能优异的高性能钢边止水带对于止水带的实际应用具有重要意义。
发明内容
本发明的一个目的是提供一种高性能钢边止水带,由中间基体和两侧与中间基体硫化粘结的镀锌钢板组成,镀锌钢板上下表面有间隔的肋条,其特征在于,中间基体由橡胶基体和橡胶基体排水孔表面覆盖的特氟龙薄膜组成,橡胶基体包括天然橡胶、硫磺、氧化锌、功能填料、阻燃剂、促进剂和防老剂。
所述橡胶基体的成分按重量份计为:天然橡胶100-120重量份、硫磺0.5-2重量份、氧化锌2-5重量份、功能填料2-15重量份、阻燃剂0-10重量份、促进剂0.5-2重量份和防老剂0.5-1重量份。优选的,所述阻燃剂5-10重量份。
优选地,所述橡胶基体的成分按重量份计为:天然橡胶120重量份、硫磺1重量份、氧化锌3重量份、功能填料10重量份、阻燃剂5重量份、促进剂1重量份和防老剂1重量份。
优选地,所述防老剂为MMB(2-硫醇基甲基苯并咪唑)、MBZ(2-硫醇基苯并咪唑锌盐)和MB(2-巯基苯并咪唑)中的一种或两种以上混合。
优选地,所述促进剂为二硫化四苄基秋兰姆、二硫化四异丁基秋兰姆和一硫化四异丁基秋兰姆中的一种或两种以上混合。
优选地,所述阻燃剂为氢氧化铝和氢氧化镁中的一种或两种混合。
优选地,所述功能填料为聚离子液体包覆纳米二氧化硅微粒。
本发明的另一个目的是提供聚离子液体包覆纳米二氧化硅微粒的制备方法,所述聚离子液体包覆纳米二氧化硅微粒通过通过离子液体单体1-乙烯基-3甲基咪唑溴盐的无皂乳液聚合法制备,具体制备方法如下:
(1)将纳米二氧化硅和去离子水混合配制成质量分数为6-10%的水悬浮,在1500-2000r/min条件下搅拌分散10-30min;
(2)将悬浊液在500-1500r/min条件下搅拌加热升温至60-85℃后稳定5-20min后加入引发剂过硫酸钾,其加入量占离子液体单体质量的0.5-2%;
(3)向步骤(2)所得的悬浮液中滴加离子液体单体反应8-24h,停止反应,其中离子液体单体的加入量占二氧化硅质量的50-80%;
(4)将步骤(3)所得反应液冷却至室温后真空抽滤,将滤饼置于干燥箱中于50-80℃条件下干燥6-24h,将干燥后的滤饼粉碎得到功能填料;
上述步骤(1)至(4)中的反应在N2气氛下进行。
功能填料对橡胶基体的制备起了促进作用。所述功能填料原料中的纳米二氧化硅在悬浮液中均匀分散,引发剂在热作用下分解生成自由基,溶在水中的离子液体单体分子被引发聚合形成一端带有亲水基团的自由基活性链。纳米粒子表面带正电,易与带负电的自由基活性链结合,从而使其表面疏水性增强,有利于剩余单体在纳米二氧化硅表面聚合包覆,从而形成纳米二氧化硅/聚离子液体复合微粒。
本发明的另一个目的是提供一种高性能钢边止水带的制备方法,其步骤如下:
(1)设置哈克流变仪的起始温度40-60℃,转速为40-50r/min,将天然橡胶加入到哈克流变仪中,待转矩平稳后,加入硫磺、氧化锌、促进剂、阻燃剂、防老剂以及功能填料,胶料温度达到105-120℃时排出胶料;
(2)将在哈克流变仪中混炼好的胶料在开炼机上进一步的混炼均匀,得到薄片;
(3)将薄片放入两端装有镀锌钢板的模具中,在平板硫化机上硫化得到橡胶基体,硫化压力为10-25MPa,硫化温度160-180℃,硫化时间为5-20min;
(4)使用无水乙醇清洗特氟龙薄膜表面,接着在室温下,用萘钠处理液处理其表面5-10min,然后用去离子水漂洗,并在干燥箱中于50-80℃条件下干燥6-12h;
(5)将粘结剂均匀地涂到橡胶基体排水孔表面,然后将表面处理过的特氟龙覆盖于橡胶基体排水孔表面,即得到高性能钢边止水带。
优选地,粘结剂为MDI、LQI、JQ-6的一种或两种以上混合。
本发明同现有技术相比,具有以下优点和有益效果:
(1)本发明制备的高性能钢边止水带采用天然橡胶和带有间隔肋条的镀锌钢板为原材料,具有绿色环保、阻燃、耐老化性能优异、使用寿命长以及力学性能优异等特点,其制备工艺简单、易操作,适合于工业化生产;
(2)本发明采用的功能填料为聚离子液体包覆纳米二氧化硅微粒,聚合物增强了二氧化硅与橡胶基体间的相容性,另一方面在橡胶基体与填料之间形成了一个柔性的变形层,它能松弛界面应力,防止界面裂缝的拓展,改善了界面结合强度,提高了橡胶基体的力学性能,延长止水带的使用寿命;
(3)本发明橡胶基体排水孔表面覆盖了特氟龙薄膜,利用特氟龙优异的耐老化、耐酸耐碱和耐溶剂的性能防止排水区被渗漏水或酸雨等腐蚀,进一步延长了整个止水带的寿命;
(4)常用的促进剂TMTD等易形成致癌性物质亚硝胺,从而危害工作人员或其他人的身体健康,而本发明采用的促进剂不会形成亚硝胺,是目前常用促进剂的优良替代品;
(5)本发明采用无机金属化合物作为阻燃剂,其阻燃效果明显、稳定性能好、不挥发、无毒、腐蚀性小且价格低廉。
具体实施方式
为了进一步理解本发明,下面结合实施例对本发明提供的技术方案进行详细说明,本发明的保护范围不受以下实施例的限制。
本发明实施例采用的化学试剂均为市购:
硫磺购自青岛莱茵化学公司;
二氧化硅购自四川锌鸿科技有限公司;
氢氧化铝和氢氧化镁购自于上海佳铄贸易有限公司;
促进剂二硫化四苄基秋兰姆、二硫化四异丁基秋兰姆和一硫化四异丁基秋兰姆、防老剂MMB、MBZ和RD购自河南龙基化工有限公司;
粘结剂为MDI、LQI和JQ-6购自于济南顺鑫化工有限公司;
萘钠处理液购自于镇江市森鑫聚氨脂材料有限公司;
特氟龙薄膜购自宁波登越新材料科技有限公司。
实施例1
功能填料的具体制备方法如下:
(1)将纳米二氧化硅和去离子水混合配制成质量分数为6%的水悬浮,在1500r/min条件下搅拌分散30min;
(2)将悬浊液在500r/min条件下搅拌加热升温至60℃后稳定20min后加入引发剂过硫酸钾,其加入量占离子液体单体质量的0.5%;
(3)向步骤(2)所得的悬浮液中滴加离子液体单体反应8h,停止反应,其中离子液体单体的加入量占二氧化硅质量的50%;
(4)将步骤(3)所得反应液冷却至室温后真空抽滤,将滤饼置于干燥箱中于50℃条件下干燥24h,将干燥后的滤饼粉碎得到功能填料,备用;
上述步骤(1)至(4)中的反应在N2气氛下进行。
高性能钢边止水带的制备方法如下:
(1)设置哈克流变仪的起始温度40℃,转速为40r/min,将100重量份天然橡胶加入到哈克流变仪中,待转矩平稳后,加入0.5重量份硫磺、2重量份氧化锌、0.5重量份促进剂二硫化四苄基秋兰姆、5重量份阻燃剂氢氧化铝、0.5重量份防老剂MMB以及2重量份功能填料,胶料温度达到105℃时排出胶料;
(2)将在哈克流变仪中混炼好的胶料在开炼机上进一步的混炼均匀,得到薄片;
(3)将薄片放入两端装有镀锌钢板的模具中,在平板硫化机上硫化得到橡胶基体,硫化压力为10MPa,硫化温度160℃,硫化时间为20min;
(4)使用无水乙醇清洗特氟龙薄膜表面,接着在室温下,用萘钠处理液处理其表面10min,然后用去离子水漂洗,并在干燥箱中于50℃条件下干燥12h;
(5)将粘结剂MDI均匀地涂到橡胶基体排水孔表面,然后将表面处理过的特氟龙覆盖于橡胶基体排水孔表面,即得到高性能钢边止水带。
实施例2
功能填料的具体制备方法如下:
(1)将纳米二氧化硅和去离子水混合配制成质量分数为10%的水悬浮,在2000r/min条件下搅拌分散10min;
(2)将悬浊液在1500r/min条件下搅拌加热升温至85℃后稳定5min后加入引发剂过硫酸钾,其加入量占离子液体单体质量的1%;
(3)向步骤(2)所得的悬浮液中滴加离子液体单体反应24h,停止反应,其中离子液体单体的加入量占二氧化硅质量的80%;
(4)将步骤(3)所得反应液冷却至室温后真空抽滤,将滤饼置于干燥箱中于80℃条件下干燥6h,将干燥后的滤饼粉碎得到功能填料,备用;
上述步骤(1)至(4)中的反应在N2气氛下进行。
高性能钢边止水带的制备方法如下:
(1)设置哈克流变仪的起始温度50℃,转速为50r/min;将120重量份天然橡胶加入到哈克流变仪中,待转矩平稳后,加入1重量份硫磺、3重量份氧化锌、1重量份促进剂二硫化四异丁基秋兰姆、5重量份阻燃剂氢氧化镁、1重量份防老剂MMB以及10重量份功能填料,胶料温度达到110℃时排出胶料;
(2)将在哈克流变仪中混炼好的胶料在开炼机上进一步的混炼均匀,得到薄片;
(3)将薄片放入两端装有镀锌钢板的模具中,在平板硫化机上硫化得到橡胶基体,硫化压力为20MPa,硫化温度170℃,硫化时间为10min;
(4)使用无水乙醇清洗特氟龙薄膜表面,接着在室温下,用萘钠处理液处理其表面5min,然后用去离子水漂洗,并在干燥箱中于50℃条件下干燥6h;
(5)将粘结剂JQ-6均匀地涂到橡胶基体排水孔表面,然后将表面处理过的特氟龙覆盖于橡胶基体排水孔表面,即得到高性能钢边止水带。
实施例3
功能填料的具体制备方法如下:
(1)将纳米二氧化硅和去离子水混合配制成质量分数为10%的水悬浮,在2000r/min条件下搅拌分散10min;
(2)将悬浊液在1500r/min条件下搅拌加热升温至85℃后稳定5min后加入引发剂过硫酸钾,其加入量占离子液体单体质量的2%;
(3)向步骤(2)所得的悬浮液中滴加离子液体单体反应8h,停止反应,其中离子液体单体的加入量占二氧化硅质量的80%;
(4)将步骤(3)所得反应液冷却至室温后真空抽滤,将滤饼置于干燥箱中于50℃条件下干燥24h,将干燥后的滤饼粉碎得到功能填料,备用;
上述步骤(1)至(4)中的反应在N2气氛下进行。
高性能钢边止水带的制备方法如下:
(1)设置哈克流变仪的起始温度60℃,转速为50r/min,将100重量份天然橡胶加入到哈克流变仪中,待转矩平稳后,加入2重量份硫磺、5重量份氧化锌、2重量份促进剂一硫化四异丁基秋兰姆、10重量份阻燃剂氢氧化镁、1重量份防老剂MBZ以及15重量份功能填料,胶料温度达到120℃时排出胶料;
(2)将在哈克流变仪中混炼好的胶料在开炼机上进一步的混炼均匀,得到薄片;
(3)将薄片放入两端装有镀锌钢板的模具中,在平板硫化机上硫化得到橡胶基体,硫化压力为25MPa,硫化温度180℃,硫化时间为5min;
(4)使用无水乙醇清洗特氟龙薄膜表面,接着在室温下,用萘钠处理液处理其表面10min,然后用去离子水漂洗,并在干燥箱中于80℃条件下干燥6h;
(5)将粘结剂JQ-6均匀地涂到橡胶基体排水孔表面,然后将表面处理过的特氟龙覆盖于橡胶基体排水孔表面,即得到高性能钢边止水带。
实施例4
高性能钢边止水带的制备方法同实施例2,只是不添加功能填料和特氟龙。
实施例5
高性能钢边止水带的制备方法同实施例2,只是不添加功能填料。
实施例6
高性能钢边止水带的制备方法同实施例2,只是不添加特氟龙。
实施例7
高性能钢边止水带的制备方法同实施例2,功能填料仅为纳米二氧化硅。
实施例8
功能填料和高性能钢边止水带的制备方法同实施例2,只是不添加阻燃剂。
实施例9性能测试
拉伸强度按照GB/T 528-2009测试;邵尔A型硬度按照GB/T 531-2008测试;耐热老化按照GB/T 3512-2001测试,测试条件为温度150℃,时间24h;阻燃性能的测定按照GB/T10707-89氧指数法测试;臭氧老化试验按GB/T7762的规定进行。
表1 实施例1-8所制的高性能钢边止水带的主要性能指标
由上述指标可以看出,本发明的高性能钢边止水带具有环保、阻燃、耐老化性能优异、使用寿命长且力学性能优异的优点。
Claims (7)
1.一种钢边止水带,由中间基体和两侧与中间基体硫化粘结的镀锌钢板组成,镀锌钢板上下表面有间隔的肋条,其特征在于,中间基体由橡胶基体和橡胶基体排水孔表面覆盖的特氟龙薄膜组成,橡胶基体包括天然橡胶、硫磺、氧化锌、功能填料、阻燃剂、促进剂和防老剂。
2.如权利要求1所述的钢边止水带,所述橡胶基体的成分按重量份计为:天然橡胶100-120重量份、硫磺0.5-2重量份、氧化锌2-5重量份、功能填料2-15重量份、阻燃剂0-10重量份、促进剂0.5-2重量份和防老剂0.5-1重量份。
3.如权利要求2所述的钢边止水带,所述橡胶基体的成分按重量份计为:天然橡胶120重量份、硫磺1重量份、氧化锌3重量份、功能填料10重量份、阻燃剂5重量份、促进剂1重量份和防老剂1重量份。
4.如权利要求1所述的钢边止水带,所述功能填料为聚离子液体包覆纳米二氧化硅微粒,所述阻燃剂为氢氧化铝和氢氧化镁中的一种或两种混合,所述促进剂为二硫化四苄基秋兰姆、二硫化四异丁基秋兰姆和一硫化四异丁基秋兰姆中的一种或两种以上混合,所述防老剂为MMB、MBZ和MB中的一种或两种以上混合。
5.如权利要求4所述的钢边止水带,所述聚离子液体包覆纳米二氧化硅微粒通过离子液体单体1-乙烯基-3甲基咪唑溴盐的无皂乳液聚合法制备,具体制备方法如下:
(1)将纳米二氧化硅和去离子水混合配制成质量分数为6-10%的水悬浮,在1500-2000r/min条件下搅拌分散10-30min;
(2)将悬浊液在500-1500r/min条件下搅拌加热升温至60-85℃后稳定5-20min后加入引发剂过硫酸钾,其加入量占离子液体单体质量的0.5-2%;
(3)向步骤(2)所得的悬浮液中滴加离子液体单体反应8-24h,停止反应,其中离子液体单体的加入量占二氧化硅质量的50-80%;
(4)将步骤(3)所得反应液冷却至室温后真空抽滤,将滤饼置于干燥箱中于50-80℃条件下干燥6-24h,将干燥后的滤饼粉碎得到功能填料;
上述步骤(1)至(4)中的反应在N2气氛下进行。
6.权利要求1-4任一项所述的钢边止水带的制备方法,步骤如下:
(1)设置哈克流变仪的起始温度40-60℃,转速为40-50r/min,将天然橡胶加入到哈克流变仪中,待转矩平稳后,加入硫磺、氧化锌、促进剂、阻燃剂、防老剂以及功能填料,胶料温度达到105-120℃时排出胶料;
(2)将在哈克流变仪中混炼好的胶料在开炼机上进一步的混炼均匀,得到薄片;
(3)将薄片放入两端装有镀锌钢板的模具中,在平板硫化机上硫化得到橡胶基体,硫化压力为10-25MPa,硫化温度160-180℃,硫化时间为5-20min;
(4)使用无水乙醇清洗特氟龙薄膜表面,接着在室温下,用萘钠处理液处理其表面5-10min,然后用去离子水漂洗,并在干燥箱中于50-80℃条件下干燥6-12h;
(5)将粘结剂均匀地涂到橡胶基体排水孔表面,然后将表面处理过的特氟龙覆盖于橡胶基体排水孔表面,即得到钢边止水带。
7.如权利要求6所述的钢边止水带的制备方法,所述的粘结剂为MDI、LQI、JQ-6的一种或两种以上混合。
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