CN112280511B - 一种智能缓粘结预应力钢绞线及其制备方法 - Google Patents
一种智能缓粘结预应力钢绞线及其制备方法 Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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- C08G59/423—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof containing an atom other than oxygen belonging to a functional groups to C08G59/42, carbon and hydrogen
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- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/24—Measuring force or stress, in general by measuring variations of optical properties of material when it is stressed, e.g. by photoelastic stress analysis using infrared, visible light, ultraviolet
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- G01L5/00—Apparatus for, or methods of, measuring force, work, mechanical power, or torque, specially adapted for specific purposes
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Abstract
本发明提供一种智能缓粘结预应力钢绞线及其制备方法,所述智能缓粘结预应力钢绞线包括:光纤传感器的纤维增强复合智能筋、边丝、缓粘结型粘结剂和护套,所述边丝扭结在智能筋的外周形成智能型预应力钢绞线,缓粘结型粘结剂涂覆在智能型预应力钢绞线的外周,使得智能型预应力钢绞线与护套粘结;所述缓粘结型粘结剂的制备原料包括:环氧树脂、固化剂、稀释剂和填料。所述缓粘结型粘结剂采用含氟聚酰胺、低分子量聚酰胺及羧基官能化的有机硅三者的复配物作为固化剂对主体树脂进行固化,利用羧基和环氧基的固化反应将有机硅引入到缓粘结型粘结剂中,得到具有良好耐热性能和耐高温老化性能的缓粘结型粘结剂。
Description
技术领域
本发明属于工程技术领域,具体涉及一种智能缓粘结预应力钢绞线及其制备方法。
背景技术
智能缓粘结预应力钢绞线是一种将缓粘结预应力钢绞线和光纤光栅传感器结合起来的技术,该技术能随时对缓粘结预应力钢绞线在适用期、固化期、施工期、服役期的受力状态进行监测,该技术避免了传统检测手段存在的精度低、可操作性差、受干扰影响大、稳定性差等缺点,对了解掌握构件的工作性能、指导预应力张拉以及后期的维护有很大的帮助。
智能缓粘结预应力钢绞线中的关键部分-缓粘结预应力钢绞线是利用缓慢凝固的粘结剂包裹在预应力钢绞线上,外面再包裹一层护套制成。粘结剂的凝固比较缓慢,需要3个月以上,一般在固化过程的初期进行张拉,张拉时缓粘结预应力钢绞线与预应力钢绞线性能接近,施工过程简单、布筋方便、质量可靠。待粘结剂完全固化后,粘结剂与预应力钢绞线及外包的塑料护套牢固地粘结在一起,受外部护套的定型,内部的粘结剂亦成护套的肋状结构,成肋状结构的护套和内部粘结剂与周围混凝土咬合,达到共同受力的目的。
缓粘结预应力钢绞线作为一种新型的预应力建筑材料,广泛地运用于桥梁、水利、工业建筑、民用建筑等室外工程,而正常工作时这些室外工程往往要面临长时间的高温曝晒,这时若要缓粘结预应力钢绞线保持持久有效的作用,就需要缓粘结预应力钢绞线中的关键的部分-缓凝粘结剂具有良好的耐热稳定性和耐高温老化性能。公开的缓粘结预应力钢绞线现有技术如专利CN201510187551.8公开了一种缓粘结预应力钢绞线用缓凝粘合剂及其制备方法,该缓凝粘合剂具有以下组成:环氧树脂30-35重量份、聚酰胺树脂0.5-2重量份、有机油脂1-8重量份、N,N-二甲基乙醇胺0.1-1重量份、邻苯二甲酸二丁酯2-8重量份、丙酮1-5重量份、矿渣微粉58-62重量份,这种缓凝粘结剂的固化时间处于6-24个月之间,并且不同的组成能够适应不同的生产与使用环境的温度,有效保证该产品在各种季节与地域环境下应用的性能稳定性;专利CN201911141250.6公开了一种改性缓凝粘结剂及其制备方法,包括如下重量份的原料:双酚A型环氧树脂100份、稀释剂5-15份、低分子量聚酰胺10-20份、改性气相二氧化硅1-5份及水泥15-30份,所述改性气相二氧化硅是气相二氧化硅经高分子表面活性剂改性所得,通过使用高分子表面活性剂丙烯酸或马来酸酐与烯基酰胺的共聚物对气相二氧化硅进行改性,提高了缓凝粘结剂的触变指数保持率,解决缓凝粘结剂低温粘度低,高温粘度高易流淌的问题,还降低了填料水泥的用量,提高了缓凝胶黏剂的韧性。
上述专利公开的缓凝胶黏剂仅能够将钢筋与外包护套结合,使钢筋内的空隙填充并紧密封裹,待固化后获得一定的力学性能,却不具有良好的耐热稳定性,耐高温老化性能也不佳,因而,对这方面进行改进研究将有助于扩大缓粘结预应力钢绞线的应用,进而使智能缓粘结预应力钢绞线得到进一步推广。
有机硅材料的主链主要由Si-O键构成,Si-O键柔顺性好,且其键能比C-C键和C-O键的键能大,因此有机硅材料具有良好的耐热性能和耐候性。中国专利CN201810274595.8公开了羧基官能化的有机硅源及其制备方法和用途、羧基官能化的杂化硅材料及其制备方法,本发明应用上述专利中羧基官能化的有机硅源固化缓粘结型粘结剂的主体树脂以解决上述存在的技术问题。
发明内容
本发明的目的在于克服上述技术问题,提供一种智能缓粘结预应力钢绞线及其制备方法,所述智能缓粘结预应力钢绞线中的缓粘结型粘结剂采用含氟聚酰胺、低分子量聚酰胺及羧基官能化的有机硅三者的复配物作为固化剂对主体树脂进行固化,利用羧基和环氧基的固化反应将有机硅引入到缓粘结型粘结剂中,得到具有良好耐热性能和耐高温老化性能的缓粘结型粘结剂。
为实现上述目的,本发明采取的具体的技术方案如下:
一种智能缓粘结预应力钢绞线,所述智能缓粘结预应力钢绞线包括:光纤传感器的纤维增强复合智能筋、边丝、缓粘结型粘结剂和护套,所述边丝扭结在智能筋的外周形成智能型预应力钢绞线,缓粘结型粘结剂涂覆在智能型预应力钢绞线的外周,使得智能型预应力钢绞线与护套粘结。
所述缓粘结型粘结剂包括以下原料:环氧树脂、固化剂、稀释剂、填料;所述固化剂为含氟聚酰胺、低分子量聚酰胺及羧基官能化的有机硅三者的复配物;
所述含氟聚酰胺由包括含氟二酸、多元伯胺的原料反应而得;
所述羧基官能化的有机硅的结构式为:
所述缓粘结型粘结剂包括以下重量份的原料:100份环氧树脂、15-40份固化剂、5-15份稀释剂、30-80份填料;
所述固化剂中含氟聚酰胺、低分子量聚酰胺及羧基官能化的有机硅三者的复配物中三者的重量比为1-3:1:0.1-0.2。
所述填料选自石英粉、碳酸钙、水泥、硅灰石、膨润土、硅微粉中的至少一种,所述填料的粒径为20-60μm。
优选的,所述填料为硅微粉,硅微粉又名硅灰(主要成分是二氧化硅,杂质里有氧化钠、氧化钙、氧化镁、氧化铁、氧化铝等)。硅微粉中含有碱性物质,可以起到防腐蚀的作用;硅灰的主要成分为二氧化硅,与前述固化剂相容性好,特别是固化剂羧基官能化的有机硅,有利于强度性能的增强。硅灰中含有微量的碱性杂质,一个个硅灰颗粒相当于一个个硅灰的微球,其中部分碱性物质被包裹在微球中,控制硅灰的粒度,可以起到碱性物质缓慢释放的作用,从而长期防腐蚀,并通过部分地与固化剂中的羧基反应起到调节反应速率的作用。
优选的,所述硅微粉的粒径为20-40μm。
所述含氟酰胺原料中含氟二酸的羧基和多元伯胺中的伯胺基的摩尔比为1:1.1-1.3,得到的含氟聚酰胺为胺基封端聚合物。
所述含氟二酸选自四氟丁二酸、六氟戊二酸、2,2-二氟丙二酸、2,2,3,3,4,4,5,5-八氟己二酸中的至少一种。
所述多元伯胺选自二亚乙基三胺、三亚乙基四胺、四亚乙基五胺中的至少一种。
所述含氟聚酰胺的制备方法,包括如下步骤:
1.将含氟二酸、多元伯胺加至氮气氛围的反应釜内,加压,搅拌,升温,并恒温恒压反应;
2.将反应釜泄压至常压,恒温反应;再抽真空恒温反应,最后将反应釜加压至常压并降温,继续搅拌并恒温反应;
3.将反应釜冷却,停止搅拌,出料,即得含氟聚酰胺。
步骤1所述加压至0.2-0.4MPa,所述升温至130-200℃,所述升温时间为1-2h,所述恒压反应的压力为0.8-2MPa,所述恒压为通过间断排除生成的水蒸气保持压力恒定;所述恒温恒压反应时间为1-3h。
步骤2所述抽真空为抽至压力为-0.08-(-0.12)MPa;所述降温为降至50-80℃;所述恒温反应时间为1-2h。
步骤3所述冷却为冷却至20-30℃。
所述低分子量聚酰胺的数均分子量为600-2000。
所述低分子量聚酰胺具体可以选自203低分子量聚酰胺、300低分子量聚酰胺、3051低分子量聚酰胺、650低分子量聚酰胺、651低分子量聚酰胺中的至少一种。
所述环氧树脂为环氧值为0.2-0.6mol/100g的双酚A型环氧树脂,优选为E-20、E-44、E-51、E-54、E-56环氧树脂中的至少一种。
所述稀释剂为非活性稀释剂,选自邻苯二甲酸二丁酯、邻苯二甲酸二辛酯中的至少一种。
所述护套的材质为聚乙烯,所述聚乙烯的熔融指数为0.1-1.0g/10min,优选0.4-0.7g/10min。
所述缓凝粘结剂的制备方法,包括如下步骤:
T1.将环氧树脂、固化剂加至反应器内,搅拌均匀;
T2.将稀释剂、填料加至反应器内,搅拌均匀;
T3.将步骤T2所得混合物进行真空脱泡,即得缓凝粘结剂。
本发明还提供一种缓粘结预应力钢绞线的制备方法,包括如下步骤:
步骤一、制备具有光纤传感器的纤维增强复合智能筋;
步骤二、制备边丝和中心丝构成的初级钢绞线;
步骤三、将所述初级钢绞线打散,用所述纤维增强复合智能筋代替所述中心丝,重新扭绞成智能钢绞线;
步骤四、在所述智能钢绞线的外围涂覆缓粘结型粘结剂,然后在粘结剂层外侧施加护套,制得所述带有智能筋的缓粘结预应力钢绞线。
此外,需要说明的是,本发明也提供前述缓粘结型粘结剂及其制备方法。
与现有技术相比本发明的有益效果是:
一、利用羧基官能化的有机硅作为环氧树脂的固化剂,得到具有良好耐热性能和耐高温老化性能的缓粘结型粘结剂。
二、本发明预想不到的发现含氟聚酰胺、低分子量聚酰胺及羧基官能化的有机硅三者具有协同提高缓粘结型粘结剂耐高温老化性能的作用。
三、本发明制备得到的智能缓粘结预应力钢绞线具有持久的机械性能,并能随时对缓粘结预应力钢绞线的受力状态进行监测,具有精度高、可操作性强、稳定性好的优点。
具体实施方式
下面结合具体实施例对本发明作进一步的说明,但并不局限于说明书上的内容。若无特殊说明,本发明实施例中所述“份”均为重量份。所用试剂均为本领域可商购的试剂。
实施例1
含氟聚酰胺的制备
1.将羧基与伯胺基的摩尔比为1:1.2的四氟丁二酸、四亚乙基五胺,加至氮气氛围的反应釜内,加压至0.3MPa,在1.5h内边搅拌边升温至140℃,此时压力升至1.8MPa,通过间断排除生成的水蒸气保持压力恒定并保持釜内温度为150℃反应2h;
2.将反应釜泄压至常压,140℃恒温反应;再抽真空至-0.08MPa,140℃恒温反应,最后将反应釜加压至常压并降温至60℃,继续搅拌并恒温反应1h;
3.将反应釜冷却至23℃,停止搅拌,出料,即得含氟聚酰胺。
羧基官能化的有机硅的制备
1.将结构式为(C2H5O)3-Si-CH=CH-Si-(OC2H5)3的桥架结构有机硅源、硫代乙酸、二苯酮以摩尔比为1:1:0.15溶解在无水乙醇中,搅拌至均匀混合,制得混合溶液;
2.将步骤1制得的混合溶液放在含有紫外光灯的密闭室温环境中,充分光照12h,制得羧基官能化的有机硅。
缓粘结型粘结剂的制备
T1.将100份环氧树脂E-51、18.75份制备的含氟聚酰胺、9.375份650低分子量聚酰胺、0.9375份羧基官能化的有机硅加至反应器内,以600r/min的转速搅拌45min;
T2.将10份环己酮、50份粒径为40μm的硅微粉加至反应器内,以500r/min的转速搅拌20min;
T3.将步骤T2所得混合物0.1MPa真空脱泡30min,得缓凝粘结剂。
实施例2
其余与实施例1相同,不同之处在于缓粘结型粘结剂的制备过程中,固化剂由13.64份制备的含氟聚酰胺、13.64份650低分子量聚酰胺、2.72份羧基官能化的有机硅复配而成。
实施例3
其余与实施例1相同,不同之处在于缓粘结型粘结剂的制备过程中,固化剂由21.43份制备的含氟聚酰胺、7.14份650低分子量聚酰胺、1.43份羧基官能化的有机硅复配而成。
实施例4
其余与实施例1相同,不同之处在于缓粘结型粘结剂的制备过程中,固化剂由19.35份制备的含氟聚酰胺、9.68份650低分子量聚酰胺、0.97份羧基官能化的有机硅复配而成。
实施例5
其余与实施例1相同,不同之处在于缓粘结型粘结剂的制备过程中,固化剂由12份制备的含氟聚酰胺、6份650低分子量聚酰胺、12份羧基官能化的有机硅复配而成。
实施例6
其余与实施例1相同,不同之处在于缓粘结型粘结剂的制备过程中硅微粉的粒径为20μm。
实施例7
其余与实施例1相同,不同之处在于缓粘结型粘结剂的制备过程中硅微粉的粒径为10μm。
实施例8
其余与实施例1相同,不同之处在于所使用羧基官能化的有机硅由六羟基邻苯二甲酸酐与直链羟基官能性硅烷加成制得:
在一个装有蛇管冷凝器、温度计和滴液漏斗并通有氮气的三颈烧瓶中,将92g六氢邻苯二甲酸酐与908g通式(II)的直链羟基官能性硅氧烷在氮气氛中混合,所述直链羟基官能性硅氧烷的羟值为45mgKOH/g(即a为29)且粘度为85mPa.s。将该溶液加热至120℃,并在该温度下搅拌6小时。冷却至室温后,产物过滤。得到一种酸值为40mg KOH/g、粘度550mPa.s的澄清液体产物。
对比实施例1
其余与实施例1相同,不同之处在于缓粘结型粘结剂的制备过程中,固化剂由20份制备的含氟聚酰胺、10份650低分子量聚酰胺复配而成。
应用例
智能缓粘结预应力钢绞线的制备,包括如下步骤:
步骤一、制备具有光纤传感器的纤维增强复合智能筋;
步骤二、制备边丝和中心丝构成的初级钢绞线;
步骤三、将所述初级钢绞线打散,用所述纤维增强复合智能筋代替所述中心丝,重新扭绞成智能钢绞线;
步骤四、在所述智能钢绞线的外围涂覆缓粘结型粘结剂,然后在粘结剂层外侧施加护套,制得所述带有智能筋的缓粘结预应力钢绞线。所述缓粘结型粘结剂分别通过实施例1-8和对比实施例1的方式制备。
将上述实施例制备而得的缓粘结型粘结剂进行以下性能检测:
耐热性能:
参照标准GB/T 1634-2004《塑料-负荷变形温度的测定》进行测量缓粘结型粘结剂的热变形温度(HDT),固化时间为12个月,结果见表1。
耐高温老化性能:将试样在120℃烘箱中烘200h,再于室温放置24h后参照标准JG/T370-2012《缓粘结预应力钢绞线专用粘合剂》进行拉伸剪切强度保持率的测试,结果见表1。
表1
本发明利用羧基官能化的有机硅作为环氧树脂的固化剂,得到具有良好耐热性能和耐高温老化性能的缓粘结型粘结剂。
本发明预想不到的发现含氟聚酰胺、低分子量聚酰胺及羧基官能化的有机硅三者具有协同提高缓粘结型粘结剂耐高温老化性能的作用。
本发明制备得到的智能缓粘结预应力钢绞线具有持久的机械性能,并能随时对缓粘结预应力钢绞线的受力状态进行监测,具有精度高、可操作性强、稳定性好的优点。
上述详细说明是针对本发明其中之一可行实施例的具体说明,该实施例并非用以限制本发明的专利范围,凡未脱离本发明所为的等效实施或变更,均应包含于本发明技术方案的范围内。
Claims (6)
1.一种智能缓粘结预应力钢绞线,所述智能缓粘结预应力钢绞线包括:光纤传感器的纤维增强复合智能筋、边丝、缓粘结型粘结剂和护套,所述边丝扭结在智能筋的外周形成智能型预应力钢绞线,缓粘结型粘结剂涂覆在智能型预应力钢绞线的外周,使得智能型预应力钢绞线与护套粘结;所述缓粘结型粘结剂的制备原料包括:100份环氧树脂、15-40份固化剂、5-15份稀释剂和30-80份填料;
所述固化剂为含氟聚酰胺、低分子量聚酰胺及羧基官能化的有机硅三者的复配物,氟聚酰胺、低分子量聚酰胺及羧基官能化的有机硅三者的复配物中三者的重量比为1-3:1:0.1-0.2;
所述含氟聚酰胺由包括含氟二酸、多元伯胺的原料反应而得;
所述羧基官能化的有机硅的制备方法是:1)将结构式为(C2H5O)3-Si-CH=CH-Si-(OC2H5)3的桥架结构有机硅源、硫代乙酸、二苯酮以摩尔比为1:1:0.15溶解在无水乙醇中,搅拌至均匀混合,制得混合溶液;
2).将步骤1)制得的混合溶液放在含有紫外光灯的密闭室温环境中,充分光照12h,制得羧基官能化的有机硅。
2.权利要求1所述的智能缓粘结预应力钢绞线,所述填料选自石英粉、碳酸钙、水泥、硅灰石、膨润土、硅微粉中的至少一种,所述填料的粒径为20-60μm。
3.权利要求2所述的智能缓粘结预应力钢绞线,其特征在于,所述填料为硅微粉。
4.权利要求1所述的智能缓粘结预应力钢绞线,所述低分子量聚酰胺的数均分子量为600-2000。
5.权利要求1所述的智能缓粘结预应力钢绞线,所述环氧树脂为环氧值为0.2-0.6mol/100g的双酚A型环氧树脂。
6.权利要求1-5任一项所述智能缓粘结预应力钢绞线的制备方法,包括如下步骤:
步骤一、制备具有光纤传感器的纤维增强复合智能筋;
步骤二、制备边丝和中心丝构成的初级钢绞线;
步骤三、将所述初级钢绞线打散,用所述纤维增强复合智能筋代替所述中心丝,重新扭绞成智能钢绞线;
步骤四、在所述智能钢绞线的外围涂覆缓粘结型粘结剂,然后在粘结剂层外侧施加护套,制得带有智能筋的缓粘结预应力钢绞线。
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