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Method for preparing aging-resistance rubber by utilization of halloysite slow-release anti-aging agent

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CN104877178A
CN104877178A CN 201510128852 CN201510128852A CN104877178A CN 104877178 A CN104877178 A CN 104877178A CN 201510128852 CN201510128852 CN 201510128852 CN 201510128852 A CN201510128852 A CN 201510128852A CN 104877178 A CN104877178 A CN 104877178A
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aging
method
halloysite
anti
resistance
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CN 201510128852
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CN104877178B (en )
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王文才
张立群
付烨
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北京化工大学
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Abstract

The invention discloses a method for preparing aging-resistance rubber by the utilization of a halloysite slow-release anti-aging agent. According to the method, a natural nanotube structure of halloysite is used as a carrier, and an anti-aging agent preparation functional filler is loaded inside the halloysite tube by a vacuum physical absorption method, and the functional filler and rubber are compounded to prepare an aging-resistance rubber composite material with excellent mechanical property. By slow release of the halloysite nanotube by the anti-aging agent, functional long-acting performance and controllability of the composite material are realized. The method provided by the invention is simple to operate and has low time consumption. The prepared composite material has excellent mechanical performance and ageing resistance.

Description

一种利用埃洛石缓释防老剂制备耐老化橡胶的方法 Anti-aging preparation utilizing rubber antioxidant release method halloysite

技术领域 FIELD

[0001] 本发明属于制备功能复合材料领域,具体涉及一种利用埃洛石缓释防老剂制备耐老化橡胶的方法,尤其通过真空物理吸附制备负载防老剂的埃洛石纳米管的方法。 [0001] The present invention belongs to the field of making a composite function, particularly to a method of using the antioxidant preparation of sustained release halloysite aging of rubber, in particular, a method of adsorbing halloysite nanotube prepared by vacuum antioxidant physical load.

背景技术 Background technique

[0002] 弹性体材料在加工,贮存和使用过程中,由于受内外因素的综合作用老化而引起其物理化学性质和机械性能的逐步变坏,最后丧失使用价值。 [0002] elastomeric material during processing, storage and use, due to the combined effect of aging by external factors cause gradual deterioration of its physico-chemical and mechanical properties, and finally the loss of value. 主要表现为龟裂、发粘、硬化、 软化、粉化、变色、长霉等。 Mainly for cracking, sticky, hardening and softening, chalking, discoloration, mildew and the like. 弹性体材料老化方式中最主要的是热氧老化,针对热氧老化通常采用在复合材料中添加抗氧化剂与氧气/臭氧发生反应从而减缓弹性体材料的老化。 Aging manner the elastomeric material is the most important thermal aging, aging usually the addition of antioxidants and oxygen / ozone reacts to slow the aging of the elastomeric material in the composite material for the hot oxygen. 然而小分子的防老剂能够在弹性体大分子交联网络间移动并富集在弹性体制品表面产生"喷霜"现象,因此弹性体配方中防老剂的份数有严格的限定,不同种防老剂的最高添加份数不同。 However antioxidant small molecules can move between the elastomer and enriched macromolecular crosslinked network have a "blooming" phenomenon in the surface of elastomer products, so elastomer formulations in parts antioxidant strictly limited, and various kinds of old age the highest number of parts of different agents. 本专利将具体涉及一种可在将防老剂等功能制剂负载在天然埃洛石纳米管管腔内以及对其进行有效改性用以制备具备耐老化等性能的功能弹性体的方法,主要以防老剂4010NA 为实例。 This patent is particularly directed to a method for tube cavity can be modified and its effective antioxidant in the formulation functions supported halloysite nano natural elastomer prepared for function includes the aging resistance, mainly antioxidant 4010NA as an example.

[0003] 埃洛石(Al2O3 *2Si02 ·2Η20)是一种天然纳米管状材料,其结构可视为由高岭土卷曲而成的15-20层的多壁管,内径为l〇-15nm,外径为50-70nm,长度为1-1. 5 μπι。 [0003] halloysite (Al2O3 * 2Si02 · 2Η20) nanotube material is a natural, visible by the kaolin structure from crimped multi-walled tube 15-20 layers, an inner diameter of l〇-15nm, an outer diameter It is 50-70nm, a length of 1-1. 5 μπι. 埃洛石纳米管外表面为SiO2,管腔内部为Al2O3,密度为2. 53g/cm3,比表面积为60-70m2/g。 Halloysite nano-tube outer surface of SiO2, within the lumen of Al2O3, a density of 2. 53g / cm3, specific surface area of ​​60-70m2 / g. 不同于蒙脱土、高岭土、膨润土等片状粘土材料,埃洛石的一大优点为无需剥离便能很好地分散于水和极性聚合物中,同时它在低极性聚合物乃至熔融聚丙烯中的分散性也很好。 Unlike montmorillonite, a big advantage as kaolin, bentonite clay sheet-like material, without release of halloysite able well dispersed in water and a polar polymer, even while it is melted in a low polar polymer dispersion of polypropylene is also very good. 但是为了使埃洛石在橡胶中仍能良好分散需要对其进行表面改性,例如表面硅烷偶联剂改性。 However, in order to make halloysite still good dispersion in the rubber needs to be surface modified, for example surface-modified silane coupling agent. 由于其较高的长径比,埃洛石纳米管用作填料制备复合材料时添加份数远远低于粒状填料。 Because of its high aspect ratio, halloysite nanotube as far below the number of parts of the particulate filler preparing a composite filler. 在埃洛石纳米管管腔内负载功能制剂,如防腐剂、阻燃剂、抗生素等赋予埃洛石功能性,使其能够用于制备功能性复合材料。 Halloysite nano tube cavity in function of load formulations, such as preservatives, flame retardants, halloysite antibiotics imparting functionality, it can be used for preparing functional composite. 埃洛石纳米管的负载容积为l〇_15wt%,溶液中负载制剂的释放时间为几小时到几天不等,聚合物基体中为几个月到数年不等。 The load capacity of the halloysite nanotube l〇_15wt% solution formulations release the load time ranging hours to days, the polymer matrix ranging from several months to several years.

[0004] 近两百年来,人们致力于研宄填料增强弹性体复合材料,一方面可以提高橡胶的模量和强度,另一方面能够降低成本。 [0004] The last two centuries, people committed study based filler reinforced elastomer composite, one can improve the modulus and strength of the rubber, on the other hand the cost can be reduced. 由于天然粘土纳米粒子的高增强效率和低填充率,使天然粘土纳米粒子作为填料的研宄引起了极大关注,其中棒状和管状粘土纳米粒子如坡缕石、凹凸棒石、埃洛石用于增强橡胶无需剥离可直接复合。 Due to the high reinforcement efficiency of natural clay nanoparticles and the filling rate is low, so that natural clay nanoparticles as a filler in a Subsidiary caused great concern, and where the tubular rod-shaped particles such as nano clays palygorskite, attapulgite, halloysite with the reinforcing rubber can be peeled off without direct recombination. 因此,在埃洛石纳米管中负载功能制剂利用其缓释作用使其作为功能性填料用以增强橡胶等复合材料是极具创新性的。 Thus, the halloysite nanotube-loads its sustained release formulation using it as a functional filler for rubber reinforced composite materials is a very innovative.

发明内容 SUMMARY

[0005] 本发明的目的在于解决现有制备橡胶复合材料技术中存在的不足,而提供利用埃洛石缓释防老剂制备耐老化橡胶的方法。 [0005] The object of the present invention is to solve shortcomings of the prior art prepared rubber composite present in the sustained release provides a method of using the antioxidant preparation halloysite aging rubber. 本发明所提供的方法操作简便、耗时短,所制备的耐老化橡胶机械性能以及耐老化性能好。 The method of the present invention provides a simple, short time-consuming, aging-resistant rubber produced mechanical properties and anti-aging properties.

[0006] 本发明采用埃洛石纳米管作为基体,利用真空吸附将功能制剂负载在埃洛石纳米管腔内之后,将负载功能制剂的埃洛石纳米管与聚合物基体复合,制备机械性能良好的功能性聚合物/埃洛石复合材料,具体步骤如下: [0006] The present invention employs the halloysite nanotube as a substrate, with a vacuum suction function of the load in the preparation of nano lumen halloysite, halloysite nanotube and the polymer-matrix function of load formulation, the preparation of the mechanical properties good functional polymer / halloysite composite material, the following steps:

[0007] 1)将埃洛石纳米管基体在丙酮溶液中超声波分散后,将其置于浓度为2~50g/L 的防老剂溶液中,在真空室保持真空5~60min,再在常压下保持5~30min,重复该循环三次以上后,用去离子水洗涤样品,在50°C烘箱烘干后,得到负载防老剂的埃洛石纳米管; [0007] 1) After halloysite nanotube matrix to ultrasonic dispersion in an acetone solution, which was placed in a concentration of 2 ~ 50g / L of the antioxidant solution, 5 ~ 60min maintaining a vacuum in a vacuum chamber, at atmospheric pressure and then after holding at 5 ~ 30min, the cycle is repeated more than three times, samples were washed with deionized water, at 50 ° C after oven drying, to obtain a load antioxidant halloysite nano tubes;

[0008] 2)将步骤1)制备的负载防老剂的埃洛石纳米管以20~IOOphr的比例与橡胶复合制备混炼胶,而后硫化成型,制得负载防老剂的埃洛石纳米管填充的橡胶复合材料。 [0008] 2) the load antioxidant Step 1) Preparation of the halloysite nanotube in a ratio of 20 to prepare a rubber compound and IOOphr the mix, and then vulcanizing, antioxidant load obtained halloysite nanotube filled the rubber composite.

[0009] 进一步,步骤1)中的埃洛石纳米管的基体为天然埃洛石纳米管。 [0009] Further, the substrate in step 1) of the halloysite nanotube natural halloysite nanotube.

[0010] 步骤2)中橡胶基体可替换为其他聚合物,包括塑料、树脂、涂料以及粘合剂等。 In [0010] Step 2) the rubber substrate may be replaced with another polymers, including plastics, resins, coatings and adhesives.

[0011] 其中,步骤1)中所述的方法对于所有的功能制剂都适用,包括但不限于药物、蛋白质、金属及其氧化物粒子等。 [0011] wherein method step 1) for all of said functions are applicable to formulations, including but not limited to drugs, proteins, and metal oxide particles. 分散埃洛石的溶剂与配制功能制剂溶液的溶剂一致即可,不限于丙酮,可替换为水、乙醇、乙酸乙酯或甲苯,防老剂替换药物、蛋白质、金属或金属氧化物粒子。 Dispersing solvent solution formulation formulated function halloysite same solvent can be, not limited to acetone, water may be replaced, ethanol, ethyl acetate or toluene, an antioxidant replacement drugs, proteins, metal or metal oxide particles.

[0012] 本发明的原理在于:利用真空吸附作用使防老剂溶液充满埃洛石纳米管内部,通过洗涤干燥过程,溶液中的防老剂负载在埃洛石纳米管腔内,得到功能化的埃洛石纳米管。 [0012] The principles of the present invention is characterized: by a vacuum adsorption so antioxidant solution is filled inside halloysite nanotube by washing and drying process, the antioxidant is in the loading solution halloysite nano lumen, resulting functionalized Å Los stone nanotubes. 将负载防老剂的埃洛石纳米管与橡胶基体复合,防老剂从埃洛石纳米管两端缓慢释放至橡胶基体中,实现提高防老剂用量又不引起喷霜的目的,同时埃洛石纳米管又对橡胶基体起到增强的作用。 The load antioxidant halloysite nanotube and the rubber matrix composite, antioxidant slowly released from both ends of the halloysite nanotube to the rubber matrix, the amount of antioxidant be improved without causing blooming purpose, while halloysite nano tube and acts on the rubber matrix reinforced.

[0013] 与现有制备耐老化橡胶技术相比较,本发明方法具有以下有益效果: [0013] Compared with the prior art rubber anti-aging preparation, the method of the present invention has the following advantages:

[0014] 1)本发明可制备负载各种功能制剂的埃洛石纳米管用做功能填料,且操作简便, 耗时短,成本低。 [0014] 1) The present invention may be prepared a variety of functions supported formulation halloysite nanotubes do the functional filler, and the operation is simple, less time consuming, and low cost.

[0015] 2)本发明所制备的负载功能制剂的埃洛石纳米管用于聚合物增强无需像片状粘土一样进行剥离,而且较粒状纳米填料所需的添加份数要小得多可以保持产品的胶感。 [0015] 2) Load function formulation prepared according to the present invention is halloysite nanotube reinforced polymer used as the sheet-like clay as without peeling, and nano-particulate filler than the desired number of parts of the product can be kept much smaller the glue sense.

[0016] 3)本发明所制备的负载功能制剂的埃洛石纳米管的可控缓释作用能够在不引起喷霜的前提下增大橡胶配方中的功能制剂用量进而提高橡胶的功能性。 [0016] 3) function of the load acting controlled release formulation of the present invention is prepared halloysite nanotube can increase the functionality of the formulation amount of the rubber formulation without causing blooming further increase the functionality of the rubber.

[0017] 4)本发明对功能制剂的成分没有限制,功能制剂的负载不会影响埃洛石的物理机械性能。 [0017] 4) The present invention is not limited to the function of components of the formulation, the formulation does not affect the function of the load physical and mechanical properties halloysite.

附图说明 BRIEF DESCRIPTION

[0018] 图1制备负载功能制剂埃洛石纳米管流程图。 [0018] Preparation of 1-loads formulation flowchart of FIG halloysite nano tube.

[0019] 图2实施例1负载防老剂4010NA的埃洛石纳米管的热重分析(TGA)曲线。 Thermogravimetric analysis 4010NA halloysite nanotube (TGA) curve of Example 1 Antioxidant load [0019] FIG. 2 embodiment.

[0020] 图3实施例1负载防老剂4010NA的埃洛石的防老剂释放曲线。 Halloysite [0020] Embodiment 1 FIG. 3 embodiment antioxidant antioxidant 4010NA load release profile.

[0021] 图4实施例1埃洛石/ 丁苯胶复合材料的微观形貌,其中(a)埃洛石/ 丁苯胶复合材料的截面扫描电子显微镜(SEM)照片,(b)埃洛石/ 丁苯胶复合材料的超薄切片透射电子显微镜(TEM)照片。 [0021] Embodiment 4 FIG. 1 halloysite microstructure / SBR Composite embodiment, wherein a cross-sectional scan (a) halloysite / SBR Composite electron microscope (SEM) photographs, (b) halloysite ultrathin sections stone / SBR composite transmission electron microscope (TEM) photograph.

[0022] 图5实施例1中埃洛石/ 丁苯胶复合材料(SBR#1)老化前后的机械性能,对比例3~5中埃洛石/ 丁苯胶复合材料(SBR#2~4)老化前后的机械性能。 In halloysite / SBR Composite [0022] 5 Example 1 (SBR # 1) Mechanical properties before and after aging, of the halloysite / SBR composite ratio of 3 ~ 5 (SBR # 2 ~ 4 ) mechanical properties before and after aging.

[0023] 图6实施例1所制备的埃洛石/ 丁苯胶复合材料SBR# 1和对比例6所制备的埃洛石/ 丁苯胶复合材料SBR#5分别在室温条件下静置于白纸上12天和30天,移除样品后白纸的照片(图6 (a))。 [0023] FIG. 6 illustrates an embodiment prepared halloysite / SBR SBR # 1 and the composite of the halloysite prepared in Comparative Example 6 / SBR SBR # 5 Composites were left to stand at room temperature 12 and 30 days on white paper, white paper after removal of the sample photograph (FIG. 6 (a)). 实施例1所制备的埃洛石/ 丁苯胶复合材料SBR#1和对比例6所制备的埃洛石/ 丁苯胶复合材料SBR#5在90°C静置一定时间后的经由表面元素分析(XPS)测得表面氮元素含量结果(图6(b))。 Example 1 Preparation of the halloysite / SBR SBR # 1 and the composite of the halloysite prepared in Comparative Example 6 / SBR composite SBR # 5 was allowed to stand at 90 ° C after a certain time via the surface of the element content analysis results (XPS) surface nitrogen element measured (FIG. 6 (b)).

具体实施方式 detailed description

[0024] 实施例将埃洛石纳米管基体在丙酮溶液中超声波分散后,将其置于浓度为2~ 50g/L的防老剂溶液中,在真空室保持真空5~60min,再在常压下保持5~30min,重复该循环三次后,用去离子水洗涤样品,在50°C烘箱烘干后,得到负载防老剂的埃洛石纳米管; 但本发明不局限于防老剂。 [0024] Example halloysite nanotube after ultrasonic dispersing the matrix in an acetone solution, which was placed in a concentration of 2 ~ 50g / L of the antioxidant solution, 5 ~ 60min maintaining a vacuum in a vacuum chamber, at atmospheric pressure and then after holding at 5 ~ 30min, the cycle is repeated three times, samples were washed with deionized water, at 50 ° C after oven drying load antioxidant obtained halloysite nanotube; but the present invention is not limited antioxidant.

[0025] 实施例1 [0025] Example 1

[0026] 1)按图1所示流程,将等体积的质量分数为5%的埃洛石丙酮分散液与质量分数为10%的防老剂4010NA丙酮溶液混合,埃洛石与防老剂的投料比为1:2,以60转/min的搅拌速率搅拌5min,将混合液在真空室保持真空30min,再在常压下保持15min,重复该过程三次,离心分离得到负载防老剂4010NA的埃洛石,用去离子水洗涤三次,在50°C烘箱干燥。 Antioxidant 4010NA mixed solution of acetone [0026] 1) according to the process shown in FIG. 1, an equal volume of the mass fraction of 5% dispersion of halloysite acetone content of 10%, and halloysite antioxidant feed ratio of 1: 2, at a stirring rate of 60 revolutions / min, stirred 5min, the mixture was kept in a vacuum chamber of the vacuum 30min, 15min maintained at atmospheric pressure, the process is repeated three times and centrifuged to obtain a load of antioxidant 4010NA halloysite stone, washed three times with deionized water, 50 ° C and oven dried.

[0027] 2)利用紫外可见光吸收光谱研宄负载防老剂4010NA的埃洛石纳米管防老剂释放过程,将50mg负载防老剂的埃洛石置于ImL去离子水或环己烷中搅拌一定时间,每次经过离心分离溶液后补充新的溶剂,利用紫外可见吸收光谱对上层清液进行分析。 [0027] 2) using a UV-visible absorption spectrum in a Subsidiary load halloysite nanotube antioxidant antioxidant 4010NA release process will load antioxidant 50mg halloysite placed ImL of deionized water was stirred for a certain time or cyclohexane each solution was added after centrifugation fresh solvent, by ultraviolet-visible absorption spectrum of the supernatant was analyzed.

[0028] 3)取20g负载防老剂4010NA的埃洛石纳米管,采用以下配方制备埃洛石/ 丁苯胶复合材料SBR#1。 [0028] 3) Take 20g load antioxidant 4010NA halloysite nanotube, the following formulation was prepared halloysite / SBR composite SBR # 1.

[0029] [0029]

Figure CN104877178AD00051

[0030] 注:硫化条件为15(TC X7min。 [0030] Note: curing conditions were 15 (TC X7min.

[0031] 4)将所制得埃洛石/ 丁苯胶复合材料进行热氧老化,采用的老化条件为90°C和120°C分别老化1天、3天和7天。 [0031] 4) The obtained halloysite / SBR composites thermal aging, aging conditions used are 90 ° C and 120 ° C were aged for 1 day, 3 days and 7 days.

[0032] 本实施例中埃洛石、防老剂4010NA、负载防老剂4010NA的埃洛石的热重分析曲线见图2,负载防老剂4010NA的埃洛石在去离子水中和环己烷中的释放曲线见图3。 [0032] In this example embodiment halloysite, antioxidant 4010NA, antioxidant 4010NA load halloysite thermal analysis curve shown in Figure 2, the load antioxidant 4010NA halloysite in deionized water and cyclohexane release profile shown in Figure 3.

[0033] 本实施例中所制得的埃洛石/ 丁苯胶复合材料断面扫描电子显微镜(SEM)照片和超薄切片透射电子显微镜(TEM)照片分别见图4(a)和图4(b),埃洛石/ 丁苯胶复合材料老化前后的机械性能见图5中SBR#1。 [0033] Examples prepared halloysite / SBR composite material according to the present embodiment sectional scanning electron microscope (SEM) photograph and an ultrathin section transmission electron microscopy (TEM) photographs are shown in Figure 4 (a) and 4 ( b), halloysite / SBR composite mechanical properties before and after aging in Figure 5 SBR # 1.

[0034] 从图2中埃洛石、防老剂4010NA、负载防老剂4010NA的埃洛石的失重量计算得到埃洛石管腔内防老剂的负载量为8. Iwt. %。 [0034] From FIG. 2 halloysite, antioxidant 4010NA, halloysite load loss is calculated by weight of antioxidant 4010NA load within the lumen of the antioxidant is halloysite 8. Iwt.%. 从图3,负载防老剂4010NA的埃洛石在去离子水中和环己烷中的释放曲线可以证明防老剂4010NA从埃洛石管腔内可控缓慢释放出来,如图所示,在环己烷中的释放速度远远高于在去离子水中的释放速度,这是由于防老剂4010NA在环己烷中的高溶解度。 3, the load from FIG antioxidant 4010NA halloysite release profile in deionized water and cyclohexane can be demonstrated antioxidant 4010NA controllable slowly released from the lumen out of the halloysite, as shown in FIG cyclohexyl alkoxy release rate is much higher than the rate of release of deionized water, due to the antioxidant 4010NA high solubility in cyclohexane. 但是在环己烷中较快的释放速度仍是可以接受的,一方面因为抗老化体系需要防老剂具备一定的初始浓度,另一方面在橡胶复合材料中埃洛石纳米管表面被橡胶聚合物高分子包覆大大降低官腔内部防老剂的释放速度。 However, in cyclohexane still faster release rate is acceptable, on the one hand because of aging antioxidant system needs to have some initial concentration, on the other hand the surface of the halloysite nanotube composite rubber is a rubber polymer polymer coating greatly reduces the rate of release of internal bureaucratic antioxidant. 从图4中可以看出,负载防老剂的埃洛石纳米管在橡胶基体中的分散性非常好,基本达到单分散的水平,有效增强橡胶基体,并且在橡胶加工过程中埃洛石纳米管形貌保持良好无破碎现象。 As can be seen from Figure 4, the load antioxidant halloysite nanotube dispersion into the rubber matrix is ​​very good, substantially monodisperse reach levels effective to enhance the rubber matrix, and halloysite nanotube in the rubber processing maintain a good appearance without breaking phenomenon.

[0035] 本实施例中所制得的埃洛石/丁苯胶复合材料老化前后机械性能见图5中SBR#1, 可以看到经过90°C老化7天后,埃洛石/ 丁苯胶的拉伸强度和断裂伸长率基本无变化,硬度(邵A)略微升高,说明该橡胶的耐老化性能具有长效性,这是由于负载防老剂的埃洛石的缓释作用;而经过120°C老化1天、3天后,埃洛石/ 丁苯胶的拉伸强度、断裂伸长率和硬度(邵A)也无明显变化,说明该橡胶的耐老化性能十分优异。 [0035] In the present embodiment, before and after the obtained halloysite / mechanical properties of the SBR Composite aging Figure 5 SBR # 1, 90 ° C can be seen after 7 days of aging, halloysite / SBR tensile strength and elongation at break substantially no change, slight increase in hardness (Shore a), described anti-aging properties of the rubber has a long-acting, sustained action of the load which is due to the antioxidant halloysite; and after 120 ° C aged 1 day, 3 days, the tensile strength halloysite / SBR, the elongation at break, and hardness (Shore a) also no significant change, indicating aging resistance of the rubber is excellent.

[0036] 实施例2 [0036] Example 2

[0037] 过程同实施例1,将步骤1中埃洛石与防老剂的投料比改为4:1、2:1以及1:1,可得到负载防老剂4010NA的埃洛石纳米管。 [0037] The same procedure as in Example 1, step 1 halloysite and feed ratio of the antioxidant to a 4: 2: 1 and 1: 1, the load can be obtained antioxidant 4010NA the halloysite nanotube.

[0038] 本实施例中不同投料比制备的负载防老剂4010NA的埃洛石的热重分析曲线见图2,经计算,投料比4:1、2:1以及1:1的负载防老剂的埃洛石的负载率分别为0. 8wt. %, I. 5wt. %,3. 8wt. % 〇 [0038] The present embodiment is different than the load feed see Ager produced a thermogravimetric analysis profile 4010NA halloysite 2, was calculated feed ratio of 4: 1 load antioxidant: 1,2: 1 and 1 halloysite loading rate was 0. 8wt.%, I. 5wt.%, 3. 8wt.% billion

[0039] 对比例3 [0039] Comparative Example 3

[0040] 1)取20g埃洛石,采用以下配方制备埃洛石/ 丁苯胶复合材料SBR#2。 [0040] 1) Take 20g halloysite, the following formulation was prepared halloysite / SBR composite SBR # 2.

[0041] [0041]

Figure CN104877178AD00061

[0042] 注:硫化条件为150°CX 17min。 [0042] Note: curing conditions were 150 ° CX ​​17min.

[0043] 2)将所制得埃洛石/ 丁苯胶复合材料SBR#2进行热氧老化,采用的老化条件为90°C和120°C分别老化1天、3天和7天。 [0043] 2) The obtained halloysite / SBR SBR # 2 composites for thermal aging, aging conditions used are 90 ° C and 120 ° C were aged for 1 day, 3 days and 7 days.

[0044] 本对比例中所制得的埃洛石/ 丁苯胶复合材料SBR#2老化前后机械性能见图5中SBR#2〇 [0044] In the present Comparative prepared halloysite / SBR SBR # 2 composites mechanical properties before and after aging are shown in Figure 5 SBR # 2〇

[0045] 对比例4 [0045] Comparative Example 4

[0046] 1)采用以下配方制备埃洛石/ 丁苯胶复合材料SBR#3。 [0046] 1) was prepared using the following formulation halloysite / SBR composite SBR # 3.

[0047] [0047]

Figure CN104877178AD00062

[0048] 注:硫化条件为150°CX 15min。 [0048] Note: curing conditions were 150 ° CX ​​15min.

[0049] 2)将所制得埃洛石/ 丁苯胶复合材料SBR#3进行热氧老化,采用的老化条件为90°C和120°C分别老化1天、3天和7天。 [0049] 2) The obtained halloysite / SBR SBR # 3 for composite thermal aging, aging conditions used are 90 ° C and 120 ° C were aged for 1 day, 3 days and 7 days.

[0050] 本对比例中所制得的埃洛石/ 丁苯胶复合材料SBR#3老化前后机械性能见图5中SBR#3〇 [0050] In the present Comparative prepared halloysite / SBR composite SBR # 3 Mechanical properties before and after aging are shown in Figure 5 SBR # 3〇

[0051] 对比例5 [0051] Comparative Example 5

[0052] 1)取负载防老剂4010NA的埃洛石20g,采用以下配方制备埃洛石/ 丁苯胶复合材料SBR#4。 [0052] 1) Take a load antioxidant 4010NA halloysite 20g, the following formulation was prepared halloysite / SBR composite SBR # 4.

[0053] [0053]

Figure CN104877178AD00071

[0054] 注:硫化条件为150°C X6min。 [0054] Note: curing conditions were 150 ° C X6min.

[0055] 2)将所制得埃洛石/ 丁苯胶复合材料SBR#4进行热氧老化,采用的老化条件为90°C和120°C分别老化1天、3天和7天。 [0055] 2) The obtained halloysite / SBR SBR # 4 composite material for thermal aging, aging conditions used are 90 ° C and 120 ° C were aged for 1 day, 3 days and 7 days.

[0056] 本对比例中所制得的埃洛石/ 丁苯胶复合材料SBR#4老化前后机械性能见图5中SBR#4〇 [0056] In the present Comparative prepared halloysite / SBR SBR # 4 composite mechanical properties before and after aging are shown in Figure 5 SBR # 4〇

[0057] 对比实施例1和对比例3~5,对比例3~5所制备的埃洛石/ 丁苯胶复合材料(SBR#2~SBR#4)经过热氧老化后机械性能都有比较明显的下降,而实施例1所制备的埃洛石/ 丁苯胶复合材料SBR#1的机械性能无明显变化,尤其是经过120°C老化7天,对比例3和对比例4所制备的SBR#2与SBR#3变硬、破裂,而实施例1所制备的SBR#1仍然保持良好的弹性和机械性能,说明埃洛石对丁苯胶的增强作用,负载防老剂的埃洛石的缓释作用能够赋予耐老化作用长效性并且能够通过与游离防老剂的并用在不引起喷霜的前提下大幅度(数倍乃至十数倍)增大防老剂的用量。 [0057] Comparative Example 1 and Comparative Example 3 ~ 5, (2 ~ SBR # 4 SBR #) through the mechanical properties after thermal aging of halloysite / SBR composite material prepared in Comparative Examples 3 to 5 are comparative embodiment significantly decreased, as prepared in Example 1 halloysite / SBR SBR # mechanical properties of the composite material 1 of the embodiment and no significant changes, especially after 7 days aging 120 ° C, and prepared in Comparative Example 3 Comparative Example 4 pairs SBR # 2 with SBR # 3 hardened rupture, and the embodiments prepared in Example 1 SBR # 1 remains good flexibility and mechanical properties, said stone Mingai Luo enhancement of SBR, the load antioxidant halloysite sustained release properties capable of imparting long-term anti-aging effect and antioxidant can be free, and by using substantially (several times or even ten times) the amount of antioxidant increased without causing blooming.

[0058] 对比例6 [0058] Comparative Example 6

[0059] 1)采用以下配方制备埃洛石/ 丁苯胶复合材料SBR#5。 [0059] 1) was prepared using the following formulation halloysite / SBR composite SBR # 5.

[0060] [0060]

Figure CN104877178AD00072

[0061] 注:硫化条件为150 °CX Ilmin。 [0061] Note: curing conditions were 150 ° CX ​​Ilmin.

[0062] 2)将所制得埃洛石/ 丁苯胶复合材料SBR#5分别于室温(25°C )和90°C静置一定时间,与实施例1制得的SBR#1对比喷霜现象。 [0062] 2) The obtained halloysite / SBR SBR # 5 Composites were at room temperature (25 ° C) and 90 ° C was allowed to stand some time, SBR # 1 Comparative Example 1 was spray frost phenomenon.

[0063] 实施例1所制备的埃洛石/ 丁苯胶复合材料SBR#1和对比例6所制备的埃洛石/ 丁苯胶复合材料SBR#5分别在室温条件下静置于白纸上12天和30天,移除样品后白纸的照片见图6 (a)。 Halloysite / SBR composite SBR # [0063] prepared in Example 1 of Embodiment 1 and halloysite prepared in Comparative Example 6 / SBR SBR # 5 Composites were left to stand at room temperature White 12 and 30 days, the sample after removal of the white photograph shown in Figure 6 (a). 实施例1所制备的埃洛石/ 丁苯胶复合材料SBR#1和对比例6所制备的埃洛石/ 丁苯胶复合材料SBR#5在90°C静置一定时间后的经由表面元素分析(XPS)测得表面氮元素含量结果见图6(b)。 Example 1 Preparation of the halloysite / SBR SBR # 1 and the composite of the halloysite prepared in Comparative Example 6 / SBR composite SBR # 5 was allowed to stand at 90 ° C after a certain time via the surface of the element analysis (XPS) the surface of the nitrogen element content was measured results shown in Figure 6 (b).

[0064] 实施例1所制备的埃洛石/ 丁苯胶复合材料SBR#1和对比例6所制备的埃洛石/ 丁苯胶复合材料SBR#5分别在室温条件下静置于白纸上12天和30天,移除样品后白纸上残留的为防老剂,颜色的深浅反应了防老剂的喷出量,图6(a)中显示12天后放置SBR#1 样品位置白纸基本无颜色变化而放置SBR#5样品位置白纸变为了棕黄色,而30天后放置SBR#1样品位置白纸仍无明显颜色变化而放置SBR#5样品位置棕黄色加深,说明由于埃洛石的"纳米容器"作用即使添加较高量的防老剂也不会引起喷霜。 Halloysite / SBR composite SBR # [0064] prepared in Example 1 of Embodiment 1 and halloysite prepared in Comparative Example 6 / SBR SBR # 5 Composites were left to stand at room temperature White 12 and 30 days after removal of the sample remaining on the discharge amount of the white reaction antioxidant is antioxidant, color depth, shown in Figure 6 (a) placing the sample position SBR # 1 white 12 days substantially no color change of the sample is placed SBR # 5 becomes a blank position brown, and for 30 days SBR # 1 position of the sample of paper is placed no noticeable color change SBR # 5 sample position deeper brown, due to the described halloysite effect "nano containers" even higher amount of antioxidant added will not cause blooming. 实施例1所制备的埃洛石/ 丁苯胶复合材料SBR#1和对比例6所制备的埃洛石/ 丁苯胶复合材料SBR#5在90°C静置一定时间后的经由表面元素分析(XPS)测得的表面氮元素含量反应了样品表面防老剂的量,由图6(b)可见,样品表面氮元素的含量即防老剂的量逐渐增高并且SBR#5样品表面的氮元素的含量远远高于SBR#1样品表面的,定量地说明了将防老剂负载在埃洛石管腔中有效地控制了喷霜现象。 Example 1 Preparation of the halloysite / SBR SBR # 1 and the composite of the halloysite prepared in Comparative Example 6 / SBR composite SBR # 5 was allowed to stand at 90 ° C after a certain time via the surface of the element analysis (XPS) elemental nitrogen content of the surface reaction measured the amount of the antioxidant sample surface, visible nitrogen content of the sample surface that is gradually increased and the amount of the antioxidant is nitrogen SBR # 5 from the sample surface in FIG. 6 (b) the content of SBR # 1 is much higher than the surface of the sample, the antioxidant described quantitatively supported halloysite lumen to effectively control the blooming phenomenon.

Claims (4)

1. 一种利用埃洛石缓释防老剂制备耐老化橡胶的方法,其特征在于,包括以下步骤: 1) 将埃洛石纳米管基体在丙酮溶液中超声波分散后,将其置于浓度为2~50g/L的防老剂溶液中,在真空室保持真空5~60min,再在常压下保持5~30min,重复该循环三次以上后,用去离子水洗涤样品,在50°C烘箱烘干后,得到负载防老剂的埃洛石纳米管; 2) 将步骤1)制备的负载防老剂的埃洛石纳米管以20~IOOphr的比例与橡胶复合制备混炼胶,而后硫化成型,制得负载防老剂的埃洛石纳米管填充的橡胶复合材料。 CLAIMS 1. A method of using the antioxidant preparation of sustained release halloysite aging of rubber, characterized by comprising the following steps: 1) the halloysite nanotube matrix after acetone ultrasonic dispersion, placed concentration after 2 ~ 50g / L of the antioxidant solution, to maintain the vacuum in the vacuum chamber 5 ~ 60min, and then maintained at atmospheric pressure 5 ~ 30min, the cycle is repeated more than three times, samples were washed with deionized water, drying oven 50 ° C and after drying, the resulting load antioxidant halloysite nanotube; load antioxidant 2) step 1) preparation of the halloysite nanotube in a ratio of 20 ~ IOOphr rubber compound mix was prepared, and then vulcanization molding system load antioxidant obtained halloysite nanotube filled rubber composite materials.
2. 按照权利要求1所述的方法,其特征在于,步骤1)中的埃洛石纳米管的基体为天然埃洛石纳米管。 2. The method according to claim 1, characterized in that the base body in step 1) is halloysite nanotube natural halloysite nanotube.
3. 按照权利要求1所述的方法,其特征在于,步骤2)中橡胶替换为塑料、树脂、涂料或粘合剂。 3. The method according to claim 1, wherein in step 2) is replaced by a rubber plastics, resins, coatings or adhesives.
4. 按照权利要求1所述的方法,其特征在于,丙酮溶液替换为水、乙醇、乙酸乙酯或甲苯,防老剂替换药物、蛋白质、金属或金属氧化物粒子。 4. The method according to claim 1, wherein the water is replaced with acetone, ethanol, ethyl acetate or toluene, an antioxidant replacement drugs, proteins, metal or metal oxide particles.
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