CN110713719A - Silicon rubber composition and preparation method thereof - Google Patents
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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Abstract
本发明公开了一种硅橡胶组合物及其制备方法，该组合物包括复合绝缘子硅橡胶胶粉和室温固化硅橡胶，其中，复合绝缘子硅橡胶胶粉为退役复合绝缘子硅橡胶经处理得到，优选地，复合绝缘子硅橡胶胶粉为偶联剂改性的退役复合绝缘子硅橡胶胶粉，该组合物具有良好的力学性能。本发明还提供了一种硅橡胶组合物的制备方法，该制备方法原料易得、工艺简单、条件温和、易于实现，实现了退役复合绝缘子硅橡胶的循环利用，从而降低了材料成本、节约资源、保护环境。The invention discloses a silicone rubber composition and a preparation method thereof. The composition comprises a compound insulator silicone rubber powder and a room temperature curing silicone rubber, wherein the compound insulator silicone rubber powder is obtained by processing decommissioned compound insulator silicone rubber, preferably The composite insulator silicone rubber powder is a decommissioned composite insulator silicone rubber powder modified by a coupling agent, and the composition has good mechanical properties. The invention also provides a preparation method of the silicone rubber composition, the preparation method has easy-to-obtain raw materials, simple process, mild conditions and easy realization, and realizes the recycling of decommissioned composite insulator silicone rubber, thereby reducing material cost and saving resources ,protect environment.
Description
技术领域technical field
本发明属于复合绝缘子技术领域，涉及退役复合绝缘子硅橡胶制品的循环利用方法，具体涉及一种硅橡胶组合物及其制备方法。The invention belongs to the technical field of composite insulators, and relates to a recycling method for decommissioned composite insulator silicone rubber products, in particular to a silicone rubber composition and a preparation method thereof.
背景技术Background technique
随着社会的进步，电力作为主要能源得到迅速发展。遍布各地的输电线路随处可见，其中，在各电压等级交流运行线路及新建线路工程中，复合绝缘子得到大批量甚至全线路使用，性能优异的硅橡胶复合绝缘子更是得到了广泛应用。With the progress of society, electricity has developed rapidly as the main energy source. Transmission lines all over the place can be seen everywhere. Among them, in AC operation lines of various voltage levels and new line projects, composite insulators are used in large quantities or even in all lines, and silicone rubber composite insulators with excellent performance are widely used.
但是，随着硅橡胶复合绝缘子的大批量生产和消费，相应也会产生大量的复合绝缘子生产废料、加工废品和边角料等。此外，随着复合绝缘子的退役，大量的退役复合绝缘子占用大量厂房，由于没有更好的处理办法而被遗弃，造成环境的污染和资源的浪费。However, with the mass production and consumption of silicone rubber composite insulators, a large amount of composite insulator production waste, processing waste and leftovers will also be produced accordingly. In addition, with the decommissioning of composite insulators, a large number of decommissioned composite insulators occupy a large number of workshops and are abandoned because there is no better disposal method, resulting in environmental pollution and waste of resources.
硅橡胶复合绝缘子中的硅橡胶具有优异的性能，如高热稳定性、高疏水性等特点，具有较高的回收利用价值，因此，对退役复合绝缘子和其边角料的回收利用对于减少环境污染，提高产品经济效益具有重要的现实意义。The silicone rubber in the silicone rubber composite insulator has excellent properties, such as high thermal stability, high hydrophobicity, etc., and has a high recycling value. Therefore, the recycling of decommissioned composite insulators and their leftovers is important for reducing environmental pollution and improving. Product economic benefits have important practical significance.
退役复合绝缘子的回收利用主要面临的是其中硅橡胶的回收处理问题。复合绝缘子中的硅橡胶具有耐腐蚀性、抗氧化性和抗紫外等性能，在自然环境下难以降解。目前，对退役复合绝缘子中硅橡胶的处理方法主要通过化学裂解或热裂解的方法实现有机硅氧烷化合物的循环回收，但是化学裂解法裂解产物中D4含量高，产生大量废液，容易造成二次污染；热裂解法所需温度高，副反应多，收率低。并且复合绝缘子硅橡胶为特殊环境下使用橡胶材料，经过特殊的高温硫化，辐射交联等工艺处理，采用常规处理方法不适合，所以需要寻求其他简便易行的处理复合绝缘子硅橡胶的方法。The recycling and utilization of decommissioned composite insulators is mainly faced with the recycling and disposal of silicone rubber. The silicone rubber in the composite insulator has properties such as corrosion resistance, oxidation resistance and UV resistance, and is difficult to degrade in the natural environment. At present, the treatment method of silicone rubber in decommissioned composite insulators mainly realizes the recycling and recovery of organosiloxane compounds by chemical cracking or thermal cracking. Secondary pollution; thermal cracking requires high temperature, many side reactions and low yield. In addition, the composite insulator silicone rubber is a rubber material used in special environments. After special high-temperature vulcanization, radiation cross-linking and other processes, the conventional treatment method is not suitable, so it is necessary to find other simple and feasible methods for the treatment of composite insulator silicone rubber.
国内报道了利用硅橡胶复合绝缘子胶粉作为EPDM的填料，但是降低了所得产物的性能，缺乏实际使用价值[孙斌,曹宏伟,杜琳娟,等.改性废旧硅橡胶复合绝缘子胶粉与三元乙丙橡胶(EPDM)共混物的性能研究[J].北京化工大学学报(自然科学版),2017,44(3):33-38.]。The use of silicone rubber composite insulator rubber powder as a filler for EPDM has been reported in China, but the performance of the obtained product is reduced and the actual use value is lacking [Sun Bin, Cao Hongwei, Du Linjuan, et al. Modified waste silicone rubber composite insulator rubber powder and ternary Properties of Ethylene Propylene Rubber (EPDM) Blends[J].Journal of Beijing University of Chemical Technology(Natural Science Edition),2017,44(3):33-38.].
国内有人通过采用酸化、硅氢化等处理方式，将废弃绝缘子硅橡胶进行改性，与聚磷酸铵进行复配应用于阻燃聚乳酸(PLA)，加入改性后的退役复合绝缘子胶粉对PLA的具有更好的阻燃效果，这对退役复合绝缘子硅橡胶胶粉的回收利用具有比较大的意义[曹宏伟,张艳,李晓楠,等.废弃绝缘子硅橡胶的改性及在阻燃聚乳酸中的应用[J].高分子材料科学与工程,2017,33(11):119-124.]。Some people in China have modified waste insulator silicone rubber by using acidification, hydrosilation and other treatment methods, compounded it with ammonium polyphosphate and applied it to flame retardant polylactic acid (PLA), and added the modified decommissioned composite insulator rubber powder to PLA. It has better flame retardant effect, which is of great significance for the recycling of decommissioned composite insulator silicone rubber powder [Cao Hongwei, Zhang Yan, Li Xiaonan, et al. Modification of waste insulator silicone rubber and its application in flame retardant polylactic acid Application in [J]. Polymer Materials Science and Engineering, 2017, 33(11):119-124.].
因此，寻求退役复合绝缘子硅橡胶的处理方法，并将退役复合绝缘子硅橡胶胶粉作为填料对合适的基体进行填充改性，是实现硅橡胶绝缘子循环利用的简便易行的方案，同时也是复合绝缘子领域的重要发展方向。Therefore, seeking a treatment method for decommissioned composite insulator silicone rubber and filling and modifying a suitable matrix with decommissioned composite insulator silicone rubber powder as a filler is a simple and feasible solution to realize the recycling of silicone rubber insulators, and it is also a composite insulator. important development directions in the field.
发明内容SUMMARY OF THE INVENTION
为了克服上述问题，本发明人进行了锐意研究，结果发现：对退役复合绝缘子硅橡胶进行处理，并将得到的退役复合绝缘子硅橡胶胶粉与室温固化硅橡胶进行混合、固化，制得硅橡胶组合物，进一步提升了硅橡胶组合物的力学性能，同时实现了退役复合绝缘子硅橡胶的回收利用，降低了材料成本、节约资源、保护环境，从而完成本发明。In order to overcome the above-mentioned problems, the inventors have carried out keen research and found that: the decommissioned composite insulator silicone rubber is treated, and the obtained decommissioned composite insulator silicone rubber powder is mixed and cured with room temperature curing silicone rubber to obtain silicone rubber. The composition further improves the mechanical properties of the silicone rubber composition, and at the same time realizes the recycling of decommissioned composite insulator silicone rubber, reduces material costs, saves resources, and protects the environment, thereby completing the present invention.
本发明的目的一方面在于提供一种硅橡胶组合物，该硅橡胶组合物包括室温固化硅橡胶和复合绝缘子硅橡胶胶粉，其中，复合绝缘子硅橡胶胶粉为退役复合绝缘子硅橡胶经处理得到。One aspect of the object of the present invention is to provide a silicone rubber composition comprising room temperature curing silicone rubber and composite insulator silicone rubber powder, wherein the composite insulator silicone rubber powder is obtained by processing decommissioned composite insulator silicone rubber .
本发明的目的另一方面在于提供一种硅橡胶组合物的制备方法，其中，该方法包括以下步骤：Another aspect of the object of the present invention is to provide a method for preparing a silicone rubber composition, wherein the method comprises the following steps:
步骤1、回收退役复合绝缘子硅橡胶，处理后得到退役复合绝缘子硅橡胶胶粉；Step 1. Recycle the decommissioned composite insulator silicone rubber, and obtain the decommissioned composite insulator silicone rubber powder after processing;
步骤2、将退役复合绝缘子硅橡胶胶粉与室温固化硅橡胶混合；Step 2. Mix the decommissioned composite insulator silicone rubber powder with room temperature curing silicone rubber;
步骤3、将步骤2所得混合物浇注到模具中，固化。Step 3. The mixture obtained in step 2 is poured into a mold and cured.
本发明具有的有益效果为：The beneficial effects that the present invention has are:
(1)本发明中，通过将退役复合绝缘子硅橡胶胶粉加入到室温固化硅橡胶中，得到退役复合绝缘子硅橡胶胶粉/室温固化硅橡胶组合物，提升了硅橡胶组合物的力学性能。(1) In the present invention, the retired composite insulator silicone rubber powder/room temperature cured silicone rubber composition is obtained by adding the retired composite insulator silicone rubber powder to the room temperature curing silicone rubber, which improves the mechanical properties of the silicone rubber composition.
(2)本发明通过将改性的退役复合绝缘子硅橡胶胶粉作为填料加入到室温固化硅橡胶中，制备得到硅橡胶组合物，改性的退役复合绝缘子硅橡胶胶粉与室温固化硅橡胶之间形成化学键，使得二者之间具有良好的界面结合力和相容性，进一步提升了硅橡胶组合物的力学性能，并且硅橡胶组合物中胶粉分布均匀、热稳定性好、储能模量高(例如当添加30gYDH-151改性处理的胶粉时，硅橡胶组合物的杨氏模量比未添加胶粉的室温固化硅橡胶提高85％以上)。(2) The present invention prepares a silicone rubber composition by adding the modified decommissioned composite insulator silicone rubber powder as a filler to the room temperature curing silicone rubber, and the modified decommissioned composite insulator silicone rubber powder and the room temperature curing silicone rubber are combined A chemical bond is formed between the two, so that the two have good interfacial bonding force and compatibility, which further improves the mechanical properties of the silicone rubber composition. The amount is high (for example, when 30 g of YDH-151 modified rubber powder is added, the Young's modulus of the silicone rubber composition is increased by more than 85% compared with the room temperature curing silicone rubber without rubber powder).
(3)本发明提供的室温固化硅橡胶/退役复合绝缘子硅橡胶胶粉组合物的制备方法，原料易得、工艺简单、条件温和、易于实现、节能环保；(3) The preparation method of the room temperature curing silicone rubber/decommissioned composite insulator silicone rubber powder composition provided by the present invention has the advantages of easily available raw materials, simple process, mild conditions, easy realization, energy saving and environmental protection;
(4)本发明实现了退役复合绝缘子硅橡胶的回收利用，使得废弃物循环利用，降低材料成本、节约资源、保护环境，符合绿色发展的要求。(4) The present invention realizes the recycling and utilization of decommissioned composite insulator silicone rubber, enables the recycling of waste, reduces material cost, saves resources, protects the environment, and meets the requirements of green development.
附图说明Description of drawings
图1示出本发明对比例1所得最终产物的SEM图；Fig. 1 shows the SEM image of the final product obtained in Comparative Example 1 of the present invention;
图2示出本发明实施例9所得最终产物的SEM图；Fig. 2 shows the SEM image of the final product obtained in Example 9 of the present invention;
图3示出本发明实施例10所得最终产物的SEM图；Fig. 3 shows the SEM image of the final product obtained in Example 10 of the present invention;
图4示出本发明实施例11所得最终产物的SEM图；Figure 4 shows the SEM image of the final product obtained in Example 11 of the present invention;
图5示出本发明实施例5所得最终产物的SEM图；Figure 5 shows the SEM image of the final product obtained in Example 5 of the present invention;
图6示出本发明实施例12所得最终产物的SEM图；Figure 6 shows the SEM image of the final product obtained in Example 12 of the present invention;
具体实施方式Detailed ways
下面通过附图和优选实施方式对本发明进一步详细说明。通过这些说明，本发明的特点和优点将变得更为清楚明确。The present invention will be further described in detail below through the accompanying drawings and preferred embodiments. The features and advantages of the present invention will become more apparent from these descriptions.
本发明一方面提供一种硅橡胶组合物，该硅橡胶组合物包括室温固化硅橡胶和复合绝缘子硅橡胶胶粉，其中，复合绝缘子硅橡胶胶粉为退役复合绝缘子硅橡胶经处理得到。One aspect of the present invention provides a silicone rubber composition comprising room temperature curing silicone rubber and composite insulator silicone rubber powder, wherein the composite insulator silicone rubber powder is obtained by processing decommissioned composite insulator silicone rubber.
根据本发明，在硅橡胶组合物中，复合绝缘子硅橡胶胶粉的含量为5％～40％，优选为5％～35％，更优选为5％～10％，其中，以室温固化硅橡胶的重量为100％计。According to the present invention, in the silicone rubber composition, the content of the composite insulator silicone rubber powder is 5%-40%, preferably 5%-35%, more preferably 5%-10%, wherein the silicone rubber is cured at room temperature The weight is 100%.
在本发明中，复合绝缘子硅橡胶胶粉是作为填料加入到基体材料室温固化硅橡胶中得到的硅橡胶组合物。In the present invention, the composite insulator silicone rubber powder is a silicone rubber composition obtained by adding as a filler to the room temperature curing silicone rubber of the matrix material.
室温固化硅橡胶(RTV)是指室温条件下分子链两端的活性官能团在水分子或一定催化剂作用下，发生交联反应生成三维网状结构的一类硅橡胶。室温固化硅橡胶的强度较低，其力学性能有待进一步提升。Room temperature curing silicone rubber (RTV) refers to a type of silicone rubber in which the active functional groups at both ends of the molecular chain undergo cross-linking reaction under the action of water molecules or a certain catalyst at room temperature to form a three-dimensional network structure. The strength of room temperature cured silicone rubber is low, and its mechanical properties need to be further improved.
在本发明中，采用室温固化硅橡胶作为基体材料，在室温条件下即可固化完成，得到硅橡胶组合物，原料和产物方便易得、节能环保。In the present invention, the room temperature curing silicone rubber is used as the matrix material, and the curing can be completed at room temperature to obtain the silicone rubber composition, the raw materials and products are convenient and easy to obtain, energy saving and environmental protection.
本发明中，退役复合绝缘子硅橡胶包括生产复合绝缘子硅橡胶过程中的生产废料、加工废品、边角料及退役的复合绝缘子中的硅橡胶。In the present invention, the decommissioned composite insulator silicone rubber includes production wastes, processing wastes, scraps and silicon rubber in the decommissioned composite insulators in the process of producing the composite insulator silicone rubber.
根据本发明，退役复合绝缘子硅橡胶的处理方法包括：回收退役复合绝缘子硅橡胶，清洗、粉碎得到退役复合绝缘子硅橡胶胶粉。According to the present invention, the processing method of the retired composite insulator silicone rubber includes: recovering the retired composite insulator silicone rubber, cleaning and pulverizing to obtain the retired composite insulator silicone rubber powder.
本发明中，退役复合绝缘子硅橡胶为废旧复合绝缘子硅橡胶，对退役复合绝缘子硅橡胶回收，并作为填料添加到基体材料制备组合物，需对退役复合绝缘子硅橡胶进行处理，获得退役复合绝缘子硅橡胶胶粉，以更好的与基体材料混合。In the present invention, the decommissioned composite insulator silicone rubber is waste composite insulator silicone rubber, and the decommissioned composite insulator silicone rubber is recovered and added to the matrix material as a filler to prepare a composition. Rubber powder for better mixing with the base material.
本发明中，回收的退役复合绝缘子硅橡胶表面存在很多杂质，需要对其进行清洗以除去表层杂质。In the present invention, there are many impurities on the surface of the recovered decommissioned composite insulator silicone rubber, which needs to be cleaned to remove surface impurities.
根据本发明，对退役复合绝缘子硅橡胶进行清洗的介质为水或有机溶剂。According to the present invention, the medium for cleaning the retired composite insulator silicone rubber is water or an organic solvent.
根据本发明，有机溶剂选自甲醇、乙醇、丙酮、四氢呋喃、醋酸酯类和二醇衍生物中的一种或几种，优选为甲醇、乙醇、丙酮和四氢呋喃中的一种或几种，更优选为甲醇或乙醇，例如乙醇。低沸点有机溶剂可以使得清洗后在较短时间和较低温度下进行干燥，达到节能的目的。According to the present invention, the organic solvent is selected from one or more of methanol, ethanol, acetone, tetrahydrofuran, acetate and glycol derivatives, preferably one or more of methanol, ethanol, acetone and tetrahydrofuran, more Preferably methanol or ethanol, eg ethanol. The low-boiling organic solvent can make drying in a shorter time and at a lower temperature after cleaning, so as to achieve the purpose of energy saving.
根据本发明，清洗方式可采用超声波清洗和/或机械震荡清洗方式。清洗时间根据需要进行选择。According to the present invention, the cleaning method can be ultrasonic cleaning and/or mechanical vibration cleaning. The cleaning time is selected as required.
在本发明中，对退役复合绝缘子硅橡胶进行清洗后需要粉碎处理得到退役复合绝缘子硅橡胶胶粉，以实现对退役复合绝缘子硅橡胶的回收利用，所得到的硅橡胶胶粉作为胶粉填料添加到基体材料中制备组合物。In the present invention, after cleaning the retired composite insulator silicone rubber, it needs to be crushed to obtain the retired composite insulator silicone rubber powder, so as to realize the recycling of the retired composite insulator silicone rubber, and the obtained silicone rubber powder is added as a rubber powder filler. The composition is prepared into a matrix material.
根据本发明，对退役复合绝缘子硅橡胶粉碎处理首先将清洗后的硅橡胶在切片机和/或造粒机上进行预处理，制成预制品，然后再在橡胶破碎机和/或粉碎机中进行粉碎，获得退役复合绝缘子硅橡胶胶粉。According to the present invention, for the crushing treatment of decommissioned composite insulator silicone rubber, the cleaned silicone rubber is firstly pretreated on a slicer and/or a granulator to make a pre-product, and then it is processed in a rubber crusher and/or a pulverizer. Pulverize to obtain decommissioned composite insulator silicone rubber powder.
本发明人发现，可将退役复合绝缘子硅橡胶胶粉作为填料加入到基体材料中制备组合物，从而实现退役复合绝缘子硅橡胶的回收利用，但是在制备组合物过程中，对于有的基体材料来说，退役复合绝缘子硅橡胶胶粉作为填料添加到基体材料中后，胶粉与基体材料不能很好的相容，二者之间存在明显的界面，从而导致所得到的组合物的力学性能较差，为提高二者的界面相容性和结合力，可对退役复合绝缘子硅橡胶胶粉进行表面改性处理。The inventors found that the decommissioned composite insulator silicone rubber powder can be added as a filler to the matrix material to prepare a composition, so as to realize the recycling of decommissioned composite insulator silicone rubber. However, in the process of preparing the composition, for some matrix materials It is said that after the decommissioned composite insulator silicone rubber powder is added as a filler to the matrix material, the rubber powder and the matrix material are not well compatible, and there is an obvious interface between the two, which leads to the resultant composition with poor mechanical properties. In order to improve the interfacial compatibility and bonding force of the two, the surface modification treatment of the retired composite insulator silicone rubber powder can be carried out.
本发明人发现，对退役复合绝缘子硅橡胶胶粉进行表面处理，与基体材料键合，使得胶粉与基体的相容性增强，从而增强二者之间的界面结合力，提高组合物的性能。The inventors found that the surface treatment of the decommissioned composite insulator silicone rubber powder and bonding with the matrix material enhances the compatibility between the rubber powder and the matrix, thereby enhancing the interfacial bonding force between the two and improving the performance of the composition. .
根据本发明，退役复合绝缘子硅橡胶的处理步骤还包括：对所得退役复合绝缘子硅橡胶胶粉进行表面改性。According to the present invention, the processing step of the decommissioned composite insulator silicone rubber further includes: performing surface modification on the obtained decommissioned composite insulator silicone rubber powder.
根据本发明，采用偶联剂对退役复合绝缘子硅橡胶胶粉进行表面改性处理，偶联剂上的基团与退役复合绝缘子键合。According to the present invention, a coupling agent is used to perform surface modification treatment on the decommissioned composite insulator silicone rubber powder, and the groups on the coupling agent are bonded to the decommissioned composite insulator.
在本发明中，通过采用偶联剂对退役复合绝缘子硅橡胶胶粉进行表面改性处理，通过偶联剂使得胶粉与基体材料界面形成化学键，从而增强了二者间的界面结合强度，提高组合物的性能。In the present invention, the surface modification treatment of the decommissioned composite insulator silicone rubber powder is carried out by using a coupling agent, and the interface between the rubber powder and the base material forms a chemical bond through the coupling agent, thereby enhancing the interface bonding strength between the two and improving the properties of the composition.
根据本发明，偶联剂选自硅烷偶联剂或钛酸酯偶联剂。According to the present invention, the coupling agent is selected from a silane coupling agent or a titanate coupling agent.
根据本发明，硅烷偶联剂选自γ-氨丙基三乙氧基硅烷(KH-550)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)、乙烯基三乙氧硅烷(YDH-151)、γ-(2,3-环氧丙氧)丙基三乙氧基硅烷(KH-560)中的一种或几种，优选为KH-550，KH-570和YDH-151中的一种或几种，更优选为YDH-151；和/或According to the present invention, the silane coupling agent is selected from the group consisting of γ-aminopropyltriethoxysilane (KH-550), γ-methacryloyloxypropyltrimethoxysilane (KH-570), vinyltriethylsilane One or more of oxysilane (YDH-151), γ-(2,3-glycidoxy)propyltriethoxysilane (KH-560), preferably KH-550, KH-570 and One or more of YDH-151, more preferably YDH-151; and/or
钛酸酯偶联剂选自钛酸四异丙酯、钛酸四正丁酯、异丙基三(异硬脂酰基)钛酸酯(KR-TTS)、异丙基三(二辛基焦磷酰基)钛酸酯(KR-38S)、异丙基二(甲基丙烯酰基)异硬脂酰基钛酸酯(KR-7)中一种或两种。The titanate coupling agent is selected from tetraisopropyl titanate, tetra-n-butyl titanate, isopropyl tris(isostearoyl) titanate (KR-TTS), isopropyl tris(dioctyl pyrite) One or both of phosphoryl) titanate (KR-38S) and isopropylbis(methacryloyl)isostearoyl titanate (KR-7).
根据本发明，采用偶联剂处理退役复合绝缘子硅橡胶胶粉的具体过程为：将偶联剂与醇类有机溶剂配制成溶液，利于偶联剂在胶粉表面的分散，然后将溶液分一至多次喷洒到退役复合绝缘子硅橡胶胶粉中，搅拌5～30min，优选10～25min，反应结束后过滤、干燥，得到改性的退役复合绝缘子硅橡胶胶粉。According to the present invention, the specific process of using the coupling agent to treat the decommissioned composite insulator silicone rubber powder is as follows: the coupling agent and the alcohol organic solvent are prepared into a solution, which is conducive to the dispersion of the coupling agent on the surface of the rubber powder, and then the solution is divided into It is sprayed into the decommissioned composite insulator silicone rubber powder for many times, stirred for 5-30 minutes, preferably 10-25 minutes, filtered and dried after the reaction to obtain the modified decommissioned composite insulator silicone rubber powder.
根据本发明，偶联剂的添加量为所需进行表面处理的退役复合绝缘子硅橡胶胶粉质量的0.5％～1.2％，优选为0.8％～1.0％，例如1％，其中，以退役复合绝缘子硅橡胶胶粉的重量为100％计。According to the present invention, the amount of coupling agent added is 0.5% to 1.2%, preferably 0.8% to 1.0%, such as 1%, of the mass of the decommissioned composite insulator silicone rubber powder to be surface-treated, wherein the decommissioned composite insulator is used in an amount of 1%. The weight of silicone rubber powder is 100%.
本发明另一方面提供一种硅橡胶组合物的制备方法，优选制备本发明第一方面所述硅橡胶组合物的方法，该方法包括以下步骤：Another aspect of the present invention provides a method for preparing a silicone rubber composition, preferably a method for preparing the silicone rubber composition described in the first aspect of the present invention, the method comprising the following steps:
步骤1、回收退役复合绝缘子硅橡胶，处理后得到退役复合绝缘子硅橡胶胶粉；Step 1. Recycle the decommissioned composite insulator silicone rubber, and obtain the decommissioned composite insulator silicone rubber powder after processing;
根据本发明，步骤1中，退役复合绝缘子硅橡胶为废旧复合绝缘子硅橡胶，对退役复合绝缘子硅橡胶回收，并作为填料添加到基体材料制备组合物，需对退役复合绝缘子硅橡胶进行处理，获得退役复合绝缘子硅橡胶胶粉，以更好的与基体材料混合。According to the present invention, in step 1, the decommissioned composite insulator silicone rubber is waste composite insulator silicone rubber, and the decommissioned composite insulator silicone rubber is recycled and added to the matrix material as a filler to prepare a composition. The decommissioned composite insulator silicone rubber needs to be treated to obtain Retired composite insulator silicone rubber powder for better mixing with the matrix material.
本发明中，退役复合绝缘子硅橡胶表面存在很多杂质，在应用时需要除去表面杂质以更好的与基体材料混合。In the present invention, there are many impurities on the surface of the decommissioned composite insulator silicone rubber, and the surface impurities need to be removed to better mix with the matrix material during application.
根据本发明，步骤1中，对退役复合绝缘子硅橡胶进行处理包括对退役复合绝缘子硅橡胶进行清洗。According to the present invention, in step 1, the processing of the retired composite insulator silicone rubber includes cleaning the retired composite insulator silicone rubber.
根据本发明，步骤1中，对退役复合绝缘子硅橡胶进行清洗的介质为水或有机溶剂，除去硅橡胶表层的杂质。According to the present invention, in step 1, the medium for cleaning the retired composite insulator silicone rubber is water or an organic solvent to remove impurities on the surface of the silicone rubber.
根据本发明，步骤1中，有机溶剂选自甲醇、乙醇、丙酮、四氢呋喃、醋酸酯类、二醇衍生物中的一种或几种，优选为甲醇、乙醇、丙酮或四氢呋喃，更优选为甲醇或乙醇，例如乙醇。低沸点有机溶剂可以使得清洗后在较短时间和较低温度下进行干燥，达到节能的目的。According to the present invention, in step 1, the organic solvent is selected from one or more of methanol, ethanol, acetone, tetrahydrofuran, acetates, and glycol derivatives, preferably methanol, ethanol, acetone or tetrahydrofuran, more preferably methanol or ethanol, such as ethanol. The low-boiling organic solvent can make drying in a shorter time and at a lower temperature after cleaning, so as to achieve the purpose of energy saving.
根据本发明，清洗方式可采用超声波清洗和/或机械震荡清洗方式。According to the present invention, the cleaning method can be ultrasonic cleaning and/or mechanical vibration cleaning.
在本发明中，对退役复合绝缘子硅橡胶进行清洗后需要粉碎处理得到硅橡胶胶粉，以实现对硅橡胶的回收利用，所得到的硅橡胶胶粉作为胶粉填料添加到基体材料中制备组合物。In the present invention, after the decommissioned composite insulator silicone rubber is cleaned, it needs to be pulverized to obtain silicone rubber powder, so as to realize the recycling of the silicone rubber, and the obtained silicone rubber powder is added as a rubber powder filler to the matrix material to prepare a combination. thing.
根据本发明，对退役复合绝缘子硅橡胶粉碎处理首先将清洗后的硅橡胶在切片机和/或造粒机上进行预处理，制成预制品，然后再在橡胶破碎机和/或粉碎机中进行粉碎，获得退役复合绝缘子硅橡胶胶粉。According to the present invention, for the crushing treatment of decommissioned composite insulator silicone rubber, the cleaned silicone rubber is firstly pretreated on a slicer and/or a granulator to make a pre-product, and then it is processed in a rubber crusher and/or a pulverizer. Pulverize to obtain decommissioned composite insulator silicone rubber powder.
根据本发明，所得退役复合绝缘子硅橡胶胶粉的粒径或目数为50-300目，优选200-300目。目数为300目以上的胶粉，其制造成本大幅提高。According to the present invention, the particle size or mesh number of the obtained decommissioned composite insulator silicone rubber powder is 50-300 mesh, preferably 200-300 mesh. For rubber powder with a mesh number of 300 or more, the manufacturing cost is greatly increased.
本发明人发现，可将退役复合绝缘子硅橡胶胶粉作为填料加入到基体材料中制备组合物，从而实现退役复合绝缘子硅橡胶的回收利用，但是在制备组合物过程中，对于有的基体材料来说，退役复合绝缘子硅橡胶胶粉作为填料添加到基体材料中后，胶粉与基体材料不能很好的相容，二者之间存在明显的界面，从而导致所得到的组合物的力学性能较差，为提高二者的界面相容性和结合力，可对退役复合绝缘子硅橡胶胶粉进行表面改性处理。The inventors found that the decommissioned composite insulator silicone rubber powder can be added as a filler to the matrix material to prepare a composition, so as to realize the recycling of decommissioned composite insulator silicone rubber. However, in the process of preparing the composition, for some matrix materials It is said that after the decommissioned composite insulator silicone rubber powder is added as a filler to the matrix material, the rubber powder and the matrix material are not well compatible, and there is an obvious interface between the two, which leads to the resultant composition with poor mechanical properties. In order to improve the interfacial compatibility and bonding force of the two, the surface modification treatment of the retired composite insulator silicone rubber powder can be carried out.
本发明人发现，对退役复合绝缘子硅橡胶胶粉进行表面处理，与基体材料键合，使得胶粉与基体的相容性增强，从而增强二者之间的界面结合力，提高组合物的性能。The inventors found that the surface treatment of the decommissioned composite insulator silicone rubber powder and bonding with the matrix material enhances the compatibility between the rubber powder and the matrix, thereby enhancing the interfacial bonding force between the two and improving the performance of the composition. .
根据本发明，步骤1中，对退役复合绝缘子硅橡胶的处理还包括表面改性处理，优选采用偶联剂对退役复合绝缘子硅橡胶胶粉进行表面改性处理，偶联剂上的基团与退役复合绝缘子键合。According to the present invention, in step 1, the treatment of the decommissioned composite insulator silicone rubber also includes surface modification treatment. Preferably, a coupling agent is used to perform surface modification treatment on the decommissioned composite insulator silicone rubber powder, and the groups on the coupling agent and the Decommissioned composite insulator bonding.
根据本发明，偶联剂选自硅烷偶联剂或钛酸酯偶联剂。According to the present invention, the coupling agent is selected from a silane coupling agent or a titanate coupling agent.
在本发明中，通过采用偶联剂对退役复合绝缘子硅橡胶胶粉进行表面改性处理，通过偶联剂使得胶粉与基体材料界面形成化学键，从而增强了二者间的界面结合强度，提高组合物的性能。In the present invention, the surface modification treatment of the decommissioned composite insulator silicone rubber powder is carried out by using a coupling agent, and the interface between the rubber powder and the base material forms a chemical bond through the coupling agent, thereby enhancing the interface bonding strength between the two and improving the properties of the composition.
根据本发明，硅烷偶联剂选自γ-氨丙基三乙氧基硅烷(KH-550)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)、乙烯基三乙氧硅烷(YDH-151)、γ-(2,3-环氧丙氧)丙基三乙氧基硅烷(KH-560)中的一种或几种；和/或According to the present invention, the silane coupling agent is selected from the group consisting of γ-aminopropyltriethoxysilane (KH-550), γ-methacryloyloxypropyltrimethoxysilane (KH-570), vinyltriethylsilane One or more of oxysilane (YDH-151), γ-(2,3-glycidoxy)propyltriethoxysilane (KH-560); and/or
根据本发明，钛酸酯偶联剂选自钛酸四异丙酯、钛酸四正丁酯、异丙基三(异硬脂酰基)钛酸酯(KR-TTS)、异丙基三(二辛基焦磷酰基)钛酸酯(KR-38S)、异丙基二(甲基丙烯酰基)异硬脂酰基钛酸酯(KR-7)中的一种或两种。According to the present invention, the titanate coupling agent is selected from tetraisopropyl titanate, tetra-n-butyl titanate, isopropyl tris(isostearoyl) titanate (KR-TTS), isopropyl tri( One or both of dioctylpyrophosphoryl) titanate (KR-38S) and isopropylbis(methacryloyl)isostearoyl titanate (KR-7).
根据本发明，采用偶联剂处理退役复合绝缘子硅橡胶胶粉的具体过程为：将偶联剂与醇类有机溶剂配制成溶液，利于偶联剂在胶粉表面的分散，然后将溶液分一至多次喷洒到退役复合绝缘子硅橡胶胶粉中，搅拌5～30min，优选10～25min，反应结束后过滤、干燥，得到改性的退役复合绝缘子硅橡胶胶粉。According to the present invention, the specific process of using the coupling agent to treat the decommissioned composite insulator silicone rubber powder is as follows: the coupling agent and the alcohol organic solvent are prepared into a solution, which is conducive to the dispersion of the coupling agent on the surface of the rubber powder, and then the solution is divided into It is sprayed into the decommissioned composite insulator silicone rubber powder for many times, stirred for 5-30 minutes, preferably 10-25 minutes, filtered and dried after the reaction to obtain the modified decommissioned composite insulator silicone rubber powder.
根据本发明，偶联剂的添加量为所需进行表面处理的退役复合绝缘子硅橡胶胶粉质量的0.5％～1.2％，优选为0.8％～1.0％，例如1％，其中，以退役复合绝缘子硅橡胶胶粉的重量为100％计。According to the present invention, the amount of coupling agent added is 0.5% to 1.2%, preferably 0.8% to 1.0%, such as 1%, of the mass of the decommissioned composite insulator silicone rubber powder to be surface-treated, wherein the decommissioned composite insulator is used in an amount of 1%. The weight of silicone rubber powder is 100%.
步骤2、将退役复合绝缘子硅橡胶胶粉与室温固化硅橡胶混合；Step 2. Mix the decommissioned composite insulator silicone rubber powder with room temperature curing silicone rubber;
在本发明中，步骤2中，退役复合绝缘子硅橡胶胶粉为经偶联剂处理的或未经偶联剂处理的。In the present invention, in step 2, the decommissioned composite insulator silicone rubber powder is treated with a coupling agent or not treated with a coupling agent.
本发明中，室温固化硅橡胶(RTV)是指室温条件下分子链两端的活性官能团在水分子或一定催化剂作用下，发生交联反应生成三维网状结构的一类硅橡胶。其作为胶粉填料的基体材料，在室温条件下即可完成固化过程，无需进行加热，达到节能的目的。室温固化硅橡胶的强度较低，其力学性能有待进一步提升，将复合绝缘子硅橡胶胶粉作为填料加入到室温固化硅橡胶中，有望提升室温固化硅橡胶的力学性能。In the present invention, room temperature curing silicone rubber (RTV) refers to a type of silicone rubber in which the active functional groups at both ends of the molecular chain undergo cross-linking reaction under the action of water molecules or a certain catalyst at room temperature to form a three-dimensional network structure. As the base material of the rubber powder filler, the curing process can be completed at room temperature without heating, so as to achieve the purpose of energy saving. The strength of room temperature curing silicone rubber is low, and its mechanical properties need to be further improved. Adding composite insulator silicone rubber powder as a filler to room temperature curing silicone rubber is expected to improve the mechanical properties of room temperature curing silicone rubber.
本发明中，室温固化硅橡胶的来源不受特殊限制，可自制，也可购自市售，优选购自市售，更优选为硅宝科技的室温固化硅橡胶RTV-668。In the present invention, the source of the room temperature curing silicone rubber is not particularly limited, and can be self-made or commercially available, preferably commercially available, more preferably room temperature curing silicone rubber RTV-668 from Silicon Treasure Technology.
本发明人发现，将退役复合绝缘子硅橡胶胶粉作为填料加入到室温固化硅橡胶中，经固化得到退役复合绝缘子硅橡胶胶粉/室温固化硅橡胶组合物，当退役复合绝缘子硅橡胶胶粉添加量在一定范围内时，可改善组合物的力学性能，胶粉的添加量太多，由于胶粉粒子比表面积大，粒子间可能会发生团聚，无法均匀分散在室温固化硅橡胶中，导致所得组合物的力学性能变差。The inventors found that the decommissioned composite insulator silicone rubber powder is added as a filler to the room temperature curing silicone rubber, and after curing, the decommissioned composite insulator silicone rubber powder/room temperature curing silicone rubber composition is obtained. When the decommissioned composite insulator silicone rubber powder is added When the amount is within a certain range, the mechanical properties of the composition can be improved. If the amount of rubber powder added is too large, due to the large specific surface area of the rubber powder particles, agglomeration may occur between the particles, which cannot be uniformly dispersed in the room temperature cured silicone rubber, resulting in the resulting The mechanical properties of the composition deteriorate.
根据本发明，退役复合绝缘子硅橡胶胶粉的添加量为5～40％，更优选为5～35％，更优选为5％～10％，其中，以室温固化硅橡胶的重量为100％计。According to the present invention, the addition amount of the decommissioned composite insulator silicone rubber powder is 5-40%, more preferably 5-35%, more preferably 5-10%, wherein the weight of the room temperature-cured silicone rubber is 100%. .
根据本发明，为保证室温固化硅橡胶和退役复合绝缘子硅橡胶胶粉混合均匀，首先将退役复合绝缘子硅橡胶胶粉和室温固化硅橡胶进行预混合，预混合均匀后，再加入到混合设备中进行高速混合，搅拌均匀，得到混合物。According to the present invention, in order to ensure that the room temperature curing silicone rubber and the decommissioned composite insulator silicone rubber powder are evenly mixed, the decommissioned composite insulator silicone rubber powder and the room temperature curing silicone rubber are first pre-mixed, and then added to the mixing equipment after the pre-mixing is uniform. Mix at high speed and mix well to obtain a mixture.
根据本发明，混合设备选自高速搅拌器和/或双辊混炼机。According to the present invention, the mixing device is selected from high-speed agitators and/or two-roll mixers.
根据本发明，高速搅拌器的搅拌温度为20～30℃，优选为室温25℃，转速为3000-27000r/min，优选为5000～27000r/min，搅拌的时间为5-15min，优选为10～15min。According to the present invention, the stirring temperature of the high-speed stirrer is 20-30°C, preferably 25°C at room temperature, the rotational speed is 3000-27000r/min, preferably 5000-27000r/min, and the stirring time is 5-15min, preferably 10- 15min.
根据本发明，双辊混炼机的混炼温度为20～30℃，优选为室温25℃，转速为100-1000r/min，优选为200～1000r/min，混炼时间为5-50min，优选为15～50min。According to the present invention, the mixing temperature of the twin-roll mixer is 20-30°C, preferably 25°C at room temperature, the rotation speed is 100-1000r/min, preferably 200-1000r/min, and the mixing time is 5-50min, preferably 15 to 50 minutes.
步骤3、将步骤2所得混合物浇注到模具中，固化。Step 3. The mixture obtained in step 2 is poured into a mold and cured.
在本发明中，步骤3包括将步骤2所得混合物浇注到模具中，进行固化。In the present invention, step 3 includes pouring the mixture obtained in step 2 into a mold for curing.
根据本发明，步骤3中，固化温度为15～30℃，湿度为40％～60％，优选固化温度为20～25℃，湿度为45％～55％，例如室温25℃，湿度50％。According to the present invention, in step 3, the curing temperature is 15-30°C, the humidity is 40%-60%, preferably the curing temperature is 20-25°C, and the humidity is 45%-55%, such as room temperature 25°C, humidity 50%.
根据本发明，步骤3中，混合物浇注到模具中，在模具中进行固化，固化时间为12～48h，优选为12～36h，更优选为12～24h，例如24h。According to the present invention, in step 3, the mixture is poured into a mold and cured in the mold, and the curing time is 12-48h, preferably 12-36h, more preferably 12-24h, such as 24h.
根据本发明，步骤3还包括：将模具中的固化产物脱模，继续固化，得到硅橡胶组合物。According to the present invention, step 3 further includes: demoulding the cured product in the mold, and continuing to cure to obtain the silicone rubber composition.
根据本发明，脱模后继续固化的时间为2～10天，优选为2～8天，例如7天。According to the present invention, the time for continued curing after demolding is 2 to 10 days, preferably 2 to 8 days, for example 7 days.
实施例Example
以下通过具体实例进一步描述本发明。不过这些实例仅仅是范例性的，并不对本发明的保护范围构成任何限制。The present invention is further described below through specific examples. However, these examples are only exemplary and do not constitute any limitation to the protection scope of the present invention.
实施例1Example 1
回收退役复合绝缘子硅橡胶，用乙醇清洗，切片粉碎后得到退役复合绝缘子硅橡胶胶粉；Recycle decommissioned composite insulator silicone rubber, wash with ethanol, slice and pulverize to obtain decommissioned composite insulator silicone rubber powder;
称取10g退役复合绝缘子硅橡胶胶粉，加入到100g室温固化硅橡胶中，初步混合后加入到高速搅拌器中，搅拌温度为25℃，转速为27000r/min，搅拌时间为10min，搅拌混合均匀得到混合物；Weigh 10g of decommissioned composite insulator silicone rubber powder, add it to 100g of room temperature cured silicone rubber, add it to a high-speed mixer after preliminary mixing, stir at a temperature of 25°C, rotate at 27000r/min, and stir for 10min, stir and mix evenly get a mixture;
将上述混合物浇注到模具中，置于25℃，湿度50％的环境下固化24h，得到固化中间产物；The above mixture is poured into a mold, and placed in an environment of 25° C. and a humidity of 50% for curing for 24 hours to obtain a cured intermediate product;
将固化中间产物脱模，继续置于25℃，湿度50％的环境下放置7天。The cured intermediate product was demolded, and was further placed in an environment of 25° C. and a humidity of 50% for 7 days.
实施例2Example 2
重复实施例1的制备过程，区别仅在于，称取20g退役复合绝缘子硅橡胶胶粉，其他与实施例1相同。The preparation process of Example 1 was repeated, except that 20 g of decommissioned composite insulator silicone rubber powder was weighed, and the others were the same as those of Example 1.
实施例3Example 3
重复实施例1的制备过程，区别仅在于，称取30g退役复合绝缘子硅橡胶胶粉，其他与实施例1相同。The preparation process of Example 1 was repeated, except that 30 g of decommissioned composite insulator silicone rubber powder was weighed, and the others were the same as in Example 1.
实施例4Example 4
重复实施例1的制备过程，区别仅在于，称取40g退役复合绝缘子硅橡胶胶粉，其他与实施例1相同。The preparation process of Example 1 was repeated, except that 40 g of decommissioned composite insulator silicone rubber powder was weighed, and the rest was the same as Example 1.
实施例5Example 5
回收退役复合绝缘子硅橡胶，用乙醇清洗，切片粉碎后得到退役复合绝缘子硅橡胶胶粉，将1g硅烷偶联剂YDH-151加入到9g无水乙醇中配成溶液，将上述溶液分5次喷洒到100g复合绝缘子硅橡胶胶粉中，搅拌10min，得到硅烷偶联剂YDH-151改性的退役复合绝缘子硅橡胶胶粉；Recover decommissioned composite insulator silicone rubber, wash with ethanol, slice and pulverize to obtain decommissioned composite insulator silicone rubber powder, add 1g of silane coupling agent YDH-151 to 9g of absolute ethanol to make a solution, and spray the above solution 5 times Add to 100g of composite insulator silicone rubber powder, stir for 10min to obtain decommissioned composite insulator silicone rubber powder modified by silane coupling agent YDH-151;
称取30g硅烷偶联剂YDH-151改性的退役复合绝缘子硅橡胶胶粉，加入到100g室温固化硅橡胶中，预混合后加入到高速搅拌器中搅拌，搅拌温度为25℃，转速为27000r/min，搅拌时间为10min，混合均匀，得到混合物；Weigh 30g of decommissioned composite insulator silicone rubber powder modified by silane coupling agent YDH-151, add it to 100g room temperature curing silicone rubber, add it to a high-speed stirrer after pre-mixing, and stir at a stirring temperature of 25°C and a rotation speed of 27000r /min, the stirring time is 10min, and the mixture is uniformly mixed to obtain a mixture;
将上述混合物浇注到模具中，置于25℃，湿度50％的环境下固化24h，得到固化中间产物；The above mixture is poured into a mold, and placed in an environment of 25° C. and a humidity of 50% for curing for 24 hours to obtain a cured intermediate product;
将固化中间产物脱模，继续置于25℃，湿度50％的环境下放置7天。The cured intermediate product was demolded, and was further placed in an environment of 25° C. and a humidity of 50% for 7 days.
实施例6Example 6
重复实施例5的制备过程，区别仅在于，所用偶联剂为硅烷偶联剂KH-550，其他与实施例5相同。The preparation process of Example 5 was repeated, except that the coupling agent used was silane coupling agent KH-550, and the others were the same as in Example 5.
实施例7Example 7
重复实施例5的制备过程，区别仅在于，所用偶联剂为硅烷偶联剂KH-570，其他与实施例5相同。The preparation process of Example 5 was repeated, except that the coupling agent used was silane coupling agent KH-570, and the others were the same as in Example 5.
实施例8Example 8
重复实施例5的制备过程，区别仅在于，所用偶联剂为钛酸四异丙酯，其他与实施例5相同。The preparation process of Example 5 was repeated, except that the coupling agent used was tetraisopropyl titanate, and the others were the same as those of Example 5.
实施例9Example 9
重复实施例5的制备过程，区别仅在于，加入5g硅烷偶联剂YDH-151改性的退役复合绝缘子硅橡胶胶粉，其他与实施例5相同。The preparation process of Example 5 was repeated, except that 5 g of decommissioned composite insulator silicone rubber powder modified by the silane coupling agent YDH-151 was added, and the others were the same as those of Example 5.
实施例10Example 10
重复实施例5的制备过程，区别仅在于，加入10g硅烷偶联剂YDH-151改性的退役复合绝缘子硅橡胶胶粉，其他与实施例5相同。The preparation process of Example 5 was repeated, except that 10 g of decommissioned composite insulator silicone rubber powder modified by silane coupling agent YDH-151 was added, and the others were the same as those of Example 5.
实施例11Example 11
重复实施例5的制备过程，区别仅在于，加入20g硅烷偶联剂YDH-151改性的退役复合绝缘子硅橡胶胶粉，其他与实施例5相同。The preparation process of Example 5 was repeated, except that 20 g of decommissioned composite insulator silicone rubber powder modified by silane coupling agent YDH-151 was added, and the others were the same as those of Example 5.
实施例12Example 12
重复实施例5的制备过程，区别仅在于，加入35g硅烷偶联剂YDH-151改性的退役复合绝缘子硅橡胶胶粉，其他与实施例5相同。The preparation process of Example 5 was repeated, except that 35 g of decommissioned composite insulator silicone rubber powder modified by silane coupling agent YDH-151 was added, and the others were the same as those of Example 5.
实施例13Example 13
重复实施例5的制备过程，区别仅在于，加入40g硅烷偶联剂YDH-151改性的退役复合绝缘子硅橡胶胶粉，其他与实施例5相同。The preparation process of Example 5 was repeated, except that 40 g of decommissioned composite insulator silicone rubber powder modified by the silane coupling agent YDH-151 was added, and the others were the same as those of Example 5.
实施例14Example 14
重复实施例5的制备过程，区别在于，加入20g硅烷偶联剂YDH-151改性的退役复合绝缘子硅橡胶胶粉，预混合后加入双辊混炼机混合，混炼温度为25℃，转速为1000r/min，混炼时间为30min，其他与实施例5相同。The preparation process of Example 5 was repeated, except that 20 g of decommissioned composite insulator silicone rubber powder modified by silane coupling agent YDH-151 was added, pre-mixed, and then added to a two-roll mixer for mixing. The mixing temperature was 25 °C, and the rotating speed was is 1000 r/min, the kneading time is 30 min, and the others are the same as in Example 5.
实施例15Example 15
重复实施例5的制备过程，区别在于，加入30g硅烷偶联剂YDH-151改性的退役复合绝缘子硅橡胶胶粉，预混合后加入双辊混炼机混合，混炼温度为25℃，转速为1000r/min，混炼时间为30min，其他与实施例5相同。The preparation process of Example 5 was repeated, except that 30 g of decommissioned composite insulator silicone rubber powder modified by silane coupling agent YDH-151 was added, pre-mixed, and then added to a two-roll mixer for mixing. The mixing temperature was 25 °C, and the rotating speed was is 1000 r/min, the kneading time is 30 min, and the others are the same as in Example 5.
对比例Comparative ratio
对比例1Comparative Example 1
将100g室温固化硅橡胶浇注到模具中，置于25℃，湿度50％的环境下固化24h，得到固化中间产物；100g of room temperature cured silicone rubber was poured into the mold, placed in an environment of 25°C and a humidity of 50% for 24 hours to obtain a cured intermediate product;
将固化中间产物脱模，继续置于25℃，湿度50％的环境下放置7天。The cured intermediate product was demolded, and was further placed in an environment of 25° C. and a humidity of 50% for 7 days.
实验例Experimental example
实验例1Experimental example 1
将实施例1-4和对比例1所得最终产物进行力学性能测试，测试标准按照GB/T13477-2017，拉伸速率500mm/min，测试结果如表1所示。The mechanical properties of the final products obtained in Examples 1-4 and Comparative Example 1 were tested. The test standard was in accordance with GB/T13477-2017, and the tensile rate was 500 mm/min. The test results are shown in Table 1.
表1Table 1
从表1中可以看出，添加胶粉的室温固化硅橡胶组合物的拉伸强度高于未添加胶粉的室温固化硅橡胶，当胶粉添加量为10g时，即胶粉添加量为室温固化硅橡胶的10％时，最终产物的拉伸强度较未添加胶粉的室温固化硅橡胶提高了15.4％。说明添加退役复合绝缘子复合硅橡胶胶粉起到了增强的作用。As can be seen from Table 1, the tensile strength of the room temperature cured silicone rubber composition with rubber powder is higher than that of the room temperature cured silicone rubber without rubber powder. When the amount of rubber powder added is 10g, the amount of rubber powder added is room temperature When curing 10% of the silicone rubber, the tensile strength of the final product is 15.4% higher than that of the room temperature cured silicone rubber without rubber powder. It shows that the addition of decommissioned composite insulator composite silicone rubber powder has played a strengthening role.
实验例2Experimental example 2
对实施例3、实施例5-8和对比例1所得最终产物进行力学性能测试，测试结果如表2所示。The final products obtained in Example 3, Examples 5-8 and Comparative Example 1 were subjected to mechanical property tests, and the test results are shown in Table 2.
表2Table 2
从表2中可以看出，添加经偶联剂改性处理的退役复合绝缘子硅橡胶胶粉的组合物的拉伸强度高于添加未改性处理的胶粉的组合物。说明经偶联剂改性后，退役复合绝缘子硅橡胶胶粉与室温固化硅橡胶之间有很强的界面结合力，进而提高了组合物的力学性能。还可以看出，胶粉经钛酸四异丙酯和YDH-151处理的组合物的拉伸强度比未添加胶粉的室温硅橡胶的拉伸强度大。As can be seen from Table 2, the tensile strength of the composition with the addition of the decommissioned composite insulator silicone rubber powder modified by the coupling agent is higher than that of the composition with the unmodified rubber powder. It shows that after modification by coupling agent, there is a strong interfacial bonding force between the decommissioned composite insulator silicone rubber powder and the room temperature curing silicone rubber, thereby improving the mechanical properties of the composition. It can also be seen that the tensile strength of the rubber powder treated with tetraisopropyl titanate and YDH-151 is higher than that of the room temperature silicone rubber without rubber powder.
实验例3Experimental example 3
对实施例5、实施例9-13和对比例1的最终产物进行力学性能测试，测试结果如表3所示。The mechanical properties of the final products of Example 5, Examples 9-13 and Comparative Example 1 were tested, and the test results are shown in Table 3.
表3table 3
从表3可以看出，当YDH-151改性处理的退役复合绝缘子硅橡胶胶粉的添加量为5％～35％时，组合物的拉伸强度大于未添加胶粉的室温硅橡胶的拉伸强度，当胶粉添加量为35％以上时，组合物的拉伸强度下降。还可看出，添加YDH-151改性处理退役复合绝缘子硅橡胶胶粉的组合物的定伸应力Se(100)和硬度均高于未添加胶粉的组合物。As can be seen from Table 3, when the addition amount of YDH-151 modified decommissioned composite insulator silicone rubber powder is 5% to 35%, the tensile strength of the composition is greater than that of room temperature silicone rubber without rubber powder. Tensile strength, when the amount of rubber powder added is more than 35%, the tensile strength of the composition decreases. It can also be seen that the tensile stress Se(100) and hardness of the composition with YDH-151 modified to treat the retired composite insulator silicone rubber powder are higher than those of the composition without rubber powder.
实验例4Experimental example 4
对实施例5、11、14、15和对比例1所得最终产物进行力学性能测试，测试结果如表4所示。The final products obtained in Examples 5, 11, 14, 15 and Comparative Example 1 were subjected to mechanical property tests, and the test results are shown in Table 4.
表4Table 4
从表4可以看出，经YDH-151改性处理的退役复合硅橡胶胶粉，与室温固化硅橡胶制备组合物时，采用高速搅拌器混合所得组合物的拉伸强度比双辊混炼机混合的组合物的拉伸强度大。As can be seen from Table 4, when the decommissioned composite silicone rubber powder modified by YDH-151 is mixed with room temperature cured silicone rubber to prepare a composition, the tensile strength of the obtained composition is higher than that of the two-roll mixer when mixed with a high-speed agitator. The tensile strength of the blended composition is high.
实验例5Experimental example 5
对实施例5、9-12和对比例1所得最终产物进行热失重分析(TGA)测试，测试结果如表5所示。The final products obtained in Examples 5, 9-12 and Comparative Example 1 were subjected to thermogravimetric analysis (TGA) test, and the test results are shown in Table 5.
表5table 5
从表5中可以看出，不同量YDH-151改性处理的胶粉的硅橡胶的固化样条的失重5％和10％的温度都比不添加胶粉的硅橡胶的固化样条的失重5％和10％的温度低。添加10g，20g，30g，35gYDH-151改性处理的胶粉的固化样条的最大降解速率温度都比不添加胶粉的固化样条的最大降解速率温度高。As can be seen from Table 5, the weight loss of the cured samples of silicone rubber treated with different amounts of YDH-151 modified rubber powder at 5% and 10% is higher than that of the cured samples of silicone rubber without adding rubber powder. 5% and 10% lower temperature. The maximum degradation rate temperature of the cured samples with 10g, 20g, 30g and 35g of YDH-151 modified rubber powder was higher than that of the cured samples without rubber powder.
实验例6Experimental example 6
对实施例5、实施例9-11和对比例1所得最终产物进行动态力学热分析(DMTA)测试，测试结果如表6所示。The final products obtained in Example 5, Examples 9-11 and Comparative Example 1 were subjected to dynamic mechanical thermal analysis (DMTA) test, and the test results are shown in Table 6.
表6Table 6
从表6可以看出，添加YDH-151处理的退役复合绝缘子胶粉的组合物在30℃的储能模量E＇都比未添加退役复合绝缘子胶粉的室温硅橡胶的储能模量E＇大。It can be seen from Table 6 that the storage modulus E' at 30°C of the composition with YDH-151-treated decommissioned composite insulator powder is higher than that of the room temperature silicone rubber without the addition of decommissioned composite insulator powder. 'Big.
实验例7Experimental example 7
对实施例5、9-12和对比例1所得最终产物进行扫描电镜(SEM)测试，测试结果如图1-6所示。Scanning electron microscope (SEM) tests were performed on the final products obtained in Examples 5, 9-12 and Comparative Example 1, and the test results are shown in Figures 1-6.
从图1-6中可以看出，加入YDH-151改性处理的胶粉的固化样条的断裂面比未加胶粉的固化样条的断裂面更加平滑，加入胶粉后，在断裂面上可观察到胶粉颗粒，如图2到图6中的小亮点是胶粉颗粒，可以看出胶粉颗粒分散较均匀。It can be seen from Figure 1-6 that the fracture surface of the cured sample bar with YDH-151 modified rubber powder is smoother than the fracture surface of the cured sample bar without rubber powder. The rubber powder particles can be observed on the top, the small bright spots in Figure 2 to Figure 6 are the rubber powder particles, and it can be seen that the rubber powder particles are relatively uniformly dispersed.
以上结合优选实施方式和范例性实例对本发明进行了详细说明。不过需要声明的是，这些具体实施方式仅是对本发明的阐述性解释，并不对本发明的保护范围构成任何限制。在不超出本发明精神和保护范围的情况下，可以对本发明技术内容及其实施方式进行各种改进、等价替换或修饰，这些均落入本发明的保护范围内。本发明的保护范围以所附权利要求为准。The present invention has been described in detail above with reference to preferred embodiments and exemplary examples. However, it should be stated that these specific embodiments are only illustrative explanations of the present invention, and do not constitute any limitation to the protection scope of the present invention. Various improvements, equivalent replacements or modifications can be made to the technical content of the present invention and its embodiments without departing from the spirit and protection scope of the present invention, which all fall within the protection scope of the present invention. The scope of protection of the present invention is determined by the appended claims.
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