技术领域technical field
本发明涉及纳米复合材料领域，具体讲，涉及一种埃洛石纳米管/环氧树脂纳米复合材料。The invention relates to the field of nanocomposite materials, in particular to a halloysite nanotube/epoxy resin nanocomposite material.
背景技术Background technique
埃洛石纳米管是一种价格低廉的天然纳米管，由高岭石的片层在特定气候条件下卷曲而成。一般管外径40～100nm，长度约为0.2～2μm。HNTs是双层1:1型铝硅酸盐，其分子式为Al2SiO5(OH)4·nH2O(n＝0或2)，由内层铝氧八面体和外层的硅氧四面体晶格错位卷曲而成，其层间存在结晶水。HNTs的外表面主要是由Si-O-Si键组成，内壁则主要是铝羟基。在HNTs的结晶边缘或管的端面上存在硅/铝羟基，而在结晶结构的内壁也存在少量的包埋羟基。由于HNTs具有较长的长径比，单根纳米管的弹性模量可达140GPa，是制备高性能聚合物纳米复合材料的新型廉价纳米填料。Halloysite nanotubes are inexpensive natural nanotubes formed from sheets of kaolinite that curl under certain climatic conditions. Generally, the outer diameter of the tube is 40-100 nm, and the length is about 0.2-2 μm. HNTs is a double-layer 1:1 type aluminosilicate, its molecular formula is Al2 SiO5 (OH)4 ·nH2 O (n=0 or 2), which consists of an inner layer of aluminum-oxygen octahedra and an outer layer of silicon-oxygen tetrahedrons. The bulk crystal lattice is dislocated and curled, and there is crystal water between the layers. The outer surface of HNTs is mainly composed of Si-O-Si bonds, and the inner wall is mainly composed of aluminum hydroxyl groups. There are silicon/aluminum hydroxyl groups on the crystalline edges of HNTs or the end faces of the tubes, while a small amount of embedded hydroxyl groups are also present on the inner walls of the crystalline structure. Due to the long aspect ratio of HNTs, the elastic modulus of a single nanotube can reach 140GPa, which is a new and cheap nanofiller for the preparation of high-performance polymer nanocomposites.
环氧树脂是一种应用广泛的热固性聚合物，这主要得益于它在固化时低的收缩率，优异的尺寸稳定性，良好的耐腐蚀性和突出的粘附性。但是，环氧树脂的脆性是将它用作结构材料，特别是用在电子、航空航天工业中的主要缺点。用HNTs来增韧增强环氧是一种新的选择。HNTs与环氧树脂的相容性较好，但复合后也不可避免出现5～10μm的HNTs团聚体。合理克服HNTs之间的团聚，对获得优异性能的复合材料十分关键。通常可以对HNTs表面改性或添加HNTs与聚合物的界面改性剂，其中共价接枝硅烷偶联剂是纳米粒子改性中简单通用的方法。Epoxy resin is a widely used thermosetting polymer, which is mainly due to its low shrinkage during curing, excellent dimensional stability, good corrosion resistance and outstanding adhesion. However, the brittleness of epoxy resin is the main disadvantage of its use as a structural material, especially in the electronics and aerospace industries. Toughening and reinforcing epoxy with HNTs is a new option. The compatibility between HNTs and epoxy resin is good, but HNTs aggregates of 5-10 μm are unavoidable after compounding. Reasonably overcoming the agglomeration between HNTs is critical to obtain composites with excellent properties. Usually, the surface of HNTs can be modified or an interfacial modifier between HNTs and polymers can be added, among which covalently grafted silane coupling agent is a simple and general method in nanoparticle modification.
硅烷偶联剂改性HNTs和环氧树脂制备的纳米复合材料，团聚问题并没有明显改善。Mingxian Liu等(M Liu,et al.Journal of Polymer Research,2008,15:205–212)用环氧基偶联剂γ-缩水甘油醚氧丙基三甲氧基硅烷(Z-6040)改性HNTs，与环氧树脂/异氰酸酯共固化体系进行复合。但在加入较多含量改性HNTs后，团聚体的出现导致复合材料的弯曲强度减小。Shiqiang Deng等(S Deng,et al.Composites Science and Technology,2009,69:2497–2505)用偶联剂N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷(Z-6020)对HNTs进行接枝改性，并与环氧树脂通过球磨机混合。复合材料并没有表现出比纯环氧树脂体系优异多少的力学性能，且埃洛石纳米管仍然存在一定量的团聚。硅烷偶联剂虽可在一定程度上改善纳米粒子和基体的相容性，但偶联剂毕竟是小分子，难以在渗透进入纳米粒子团聚体的内部后将团聚体充分解开。同时，埃洛石纳米管表面的羟基含量少，接枝在埃洛石纳米管表面的有机硅烷分子也相对较少，纳米管与树脂基体之间的界面也不能得到很好的提高。为了要尽量增加埃洛石纳米管表面的活性基团(氨基、环氧基、异氰酸酯等)，可以接枝含有大量的这种基团的物质。超支化聚乙烯亚胺就是这样的一种物质，若将超支化聚乙烯亚胺接枝到HNTs表面，接枝物表面大量的伯胺和仲胺基团可提高与基体之间的界面结合力。另外，支化聚合物本身的结构特点利于减少接枝链的相互缠结，进一步改善纳米粒子在基体中的分散。The nanocomposites prepared by silane coupling agent modified HNTs and epoxy resin did not significantly improve the agglomeration problem. Mingxian Liu et al. (M Liu, et al. Journal of Polymer Research, 2008, 15:205–212) modified HNTs with epoxy-based coupling agent γ-glycidyl etheroxypropyltrimethoxysilane (Z-6040) , compounded with epoxy resin/isocyanate co-curing system. However, after adding a large amount of modified HNTs, the appearance of aggregates leads to a decrease in the flexural strength of the composite. Shiqiang Deng et al. (S Deng, et al.Composites Science and Technology, 2009,69:2497-2505) used coupling agent N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (Z-6020 ) to graft-modify HNTs and mix them with epoxy resin through a ball mill. The composites did not show much better mechanical properties than the pure epoxy system, and there was still a certain amount of agglomeration of the halloysite nanotubes. Although the silane coupling agent can improve the compatibility between the nanoparticles and the matrix to a certain extent, the coupling agent is a small molecule after all, and it is difficult to fully untie the aggregate after penetrating into the interior of the nanoparticle aggregate. At the same time, the hydroxyl content on the surface of the halloysite nanotubes is small, and the organosilane molecules grafted on the surface of the halloysite nanotubes are relatively small, and the interface between the nanotubes and the resin matrix cannot be well improved. In order to increase the active groups (amino group, epoxy group, isocyanate, etc.) on the surface of halloysite nanotubes as much as possible, substances containing a large amount of such groups can be grafted. Hyperbranched polyethyleneimine is such a substance. If hyperbranched polyethyleneimine is grafted onto the surface of HNTs, a large number of primary and secondary amine groups on the surface of the graft can improve the interfacial binding force with the matrix. . In addition, the structural characteristics of the branched polymer itself are conducive to reducing the intertanglement of the grafted chains and further improving the dispersion of nanoparticles in the matrix.
目前，支化型聚乙烯亚胺接枝改性埃洛石纳米管用于增韧增强环氧树脂还未见介绍，但聚乙烯亚胺对其它纳米粒子的表面修饰已经有报道。公开号为“CN103831089A”的发明专利使用γ-氯丙基三甲氧基硅烷改性酸化的凹凸棒土，然后将硅烷化的凹凸棒土加入聚乙烯亚胺水溶液中制得聚乙烯亚胺-凹凸棒土吸附剂。Hodna Kassab等(H Kassab,etal.RSC Advances,2012,2,2508–2516)利用偶联剂Z-6040的环氧基和PEI的氨基进行反应，成功将超支化结构接枝到介孔SiO2表面，所得的产物是优异的CO2吸附剂。黄寅峰等(高分子学报，2012，3，250-255)利用3-缩水甘油氧基丙基三甲氧基硅烷接枝SiO2的环氧基与超支化聚乙烯亚胺分子中的氨基进行反应，得到SiO2接枝超支化聚乙烯亚胺的纳米粒子。少量这种改性粒子加入到PP/PP-g-MAH中，PP的冲击强度和拉伸强度获得了显著的提高。LeiLiu等(L Liu,et al.Macromol.Rapid Commun.2009，30，627–632)根据超支化聚乙烯亚胺表面的氨基与碳纳米管表面的羧基进行反应，得到表面修饰有大量氨基基团的碳纳米管。改性碳纳米管在环氧树脂中分散性优于未改性碳纳米管。含超支化聚乙烯亚胺改性碳纳米管的环氧树脂纳米复合材料，比相同含量未改性碳纳米管的复合材料有更高的储能模量和更低的导电性。At present, the use of branched polyethyleneimine to graft modified halloysite nanotubes for toughening and reinforcing epoxy resin has not been introduced, but the surface modification of polyethyleneimine to other nanoparticles has been reported. The invention patent with the publication number "CN103831089A" uses γ-chloropropyltrimethoxysilane to modify acidified attapulgite, and then adds silanized attapulgite to polyethyleneimine aqueous solution to obtain polyethyleneimine-attapulgite stick clay adsorbent. Hodna Kassab et al. (H Kassab, etal.RSC Advances, 2012, 2, 2508–2516) used the epoxy group of the coupling agent Z-6040 to react with the amino group of PEI, and successfully grafted the hyperbranched structure onto the mesoporous SiO2 On the surface, the resulting product is an excellentCO2 sorbent. Huang Yinfeng et al. (Acta Polymer Sinica, 2012, 3, 250-255) used 3-glycidyloxypropyltrimethoxysilane to graft the epoxy group ofSiO2 to react with the amino group in the hyperbranched polyethyleneimine molecule, Nanoparticles ofSiO2 grafted hyperbranched polyethyleneimine were obtained. When a small amount of these modified particles are added to PP/PP-g-MAH, the impact strength and tensile strength of PP are significantly improved. LeiLiu et al. (L Liu, et al. Macromol. Rapid Commun. 2009, 30, 627–632) reacted the amino groups on the surface of hyperbranched polyethyleneimine with the carboxyl groups on the surface of carbon nanotubes to obtain a surface modified with a large number of amino groups of carbon nanotubes. The dispersibility of modified carbon nanotubes in epoxy resin is better than that of unmodified carbon nanotubes. Epoxy resin nanocomposites containing hyperbranched polyethyleneimine modified carbon nanotubes have higher storage modulus and lower electrical conductivity than composites with the same content of unmodified carbon nanotubes.
综上所述，为了发挥埃洛石纳米管的优异力学性能，提高埃洛石纳米管在环氧树脂中的分散性及与基体的界面结合质量，特提出本发明。In summary, in order to bring into play the excellent mechanical properties of the halloysite nanotubes, improve the dispersion of the halloysite nanotubes in the epoxy resin and the interface bonding quality with the matrix, the present invention is proposed.
发明内容Contents of the invention
本发明的首要发明目的在于提出了一种埃洛石纳米管/环氧树脂复合材料。The primary purpose of the present invention is to propose a halloysite nanotube/epoxy resin composite material.
为了实现本发明的目的，采用的技术方案为：In order to realize the purpose of the present invention, the technical scheme adopted is:
本发明涉及一种埃洛石纳米管/环氧树脂纳米复合材料，该埃洛石纳米管为支化型聚乙烯亚胺接枝的埃洛石纳米管，支化型聚乙烯亚胺接枝的埃洛石纳米管与环氧树脂的重量比为0.2～20：100；优选0.5～5：100；所述复合材料的制备方法包括以下步骤：方法示意图如图1所示：The invention relates to a halloysite nanotube/epoxy resin nanocomposite material, the halloysite nanotube is a halloysite nanotube grafted with branched polyethyleneimine, and the branched polyethyleneimine grafted The weight ratio of the halloysite nanotubes to the epoxy resin is 0.2 to 20:100; preferably 0.5 to 5:100; the preparation method of the composite material comprises the following steps: the schematic diagram of the method is shown in Figure 1:
(1)埃洛石纳米管的酸化：将埃洛石纳米管粒子与酸性试剂按照1:5～1:100的质量比混合，充分反应，洗涤、干燥得到酸活化埃洛石纳米管；本发明的该步骤的目的主要是为去除伴生矿物杂质，改变表面电荷，增加活性中心点数，活化表面的作用。根据选用酸性试剂的强弱来控制处理时间，强酸处理的时间短，弱酸处理的时间长。(1) Acidification of halloysite nanotubes: mix halloysite nanotube particles and acidic reagents in a mass ratio of 1:5 to 1:100, fully react, wash and dry to obtain acid-activated halloysite nanotubes; The purpose of this step of the invention is mainly to remove the accompanying mineral impurities, change the surface charge, increase the number of active centers, and activate the surface. The treatment time is controlled according to the strength of the selected acid reagent, the time for strong acid treatment is short, and the time for weak acid treatment is long.
(2)硅烷偶联剂改性的埃洛石纳米管的制备：将酸化埃洛石纳米管悬浮于有机溶剂，然后加入环氧基硅烷偶联剂，充分反应，洗涤、干燥得到硅烷偶联剂改性的埃洛石纳米管：(2) Preparation of halloysite nanotubes modified by silane coupling agent: suspend acidified halloysite nanotubes in organic solvent, then add epoxy silane coupling agent, fully react, wash and dry to obtain silane coupling Agent-modified halloysite nanotubes:
(3)超支化聚乙烯亚胺接枝改性的埃洛石纳米管的制备：将步骤⑴得到的硅烷偶联剂改性的埃洛石纳米管悬浮于有机溶剂充分分散，加入催化剂分散后加入支化型聚乙烯亚胺，在惰性气体的保护下，加热搅拌反应；洗涤、干燥得到超支化聚乙烯亚胺接枝改性的埃洛石纳米管；(3) Preparation of the halloysite nanotubes modified by hyperbranched polyethyleneimine grafting: the halloysite nanotubes modified by the silane coupling agent obtained in step (1) are suspended in an organic solvent to fully disperse them, and after adding a catalyst for dispersion Adding branched polyethyleneimine, under the protection of inert gas, heating and stirring to react; washing and drying to obtain halloysite nanotubes grafted with hyperbranched polyethyleneimine;
(4)将支化型聚乙烯亚胺接枝改性的埃洛石纳米管在有机溶剂悬浮于有机溶剂充分分散后，加入环氧树脂，混合后除尽有机溶剂；再加入固化剂混合，固化得到埃洛石纳米管/环氧树脂复合材料。(4) After the halloysite nanotubes of the branched polyethyleneimine graft modification are suspended in the organic solvent and fully dispersed in the organic solvent, epoxy resin is added, and the organic solvent is removed after mixing; then the curing agent is added and mixed, After curing, the halloysite nanotube/epoxy resin composite material is obtained.
本发明的第一优选技术方案为：在步骤(1)中，埃洛石纳米管粒子与酸性试剂的反应时间为1～48小时，优选2～24小时，更优选2～12小时；并优选先进行超声分散后再进行反应。The first preferred technical solution of the present invention is: in step (1), the reaction time of the halloysite nanotube particles and the acidic reagent is 1 to 48 hours, preferably 2 to 24 hours, more preferably 2 to 12 hours; and preferably Ultrasonic dispersion is carried out first and then the reaction is carried out.
本发明的第二优选技术方案为：所述的酸性试剂选自高氯酸、盐酸、硫酸、甲磺酸、硝酸、磷酸、醋酸、草酸或双氧水中的至少一种；作为优选使用盐酸、硫酸和双氧水混合酸、双氧水。The second preferred technical solution of the present invention is: the acid reagent is selected from at least one of perchloric acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, nitric acid, phosphoric acid, acetic acid, oxalic acid or hydrogen peroxide; as preferably use hydrochloric acid, sulfuric acid Mix acid and hydrogen peroxide with hydrogen peroxide.
本发明的第三优选技术方案为：在步骤(2)中，酸化埃洛石纳米管与有机溶剂按照质量比为1:10～1:100配成悬浮液，并优选采用超声分散，时间为5～60分钟；酸化埃洛石纳米管与环氧基硅烷偶联剂的质量比为1：0.1～3，优选1：0.2～1；酸化埃洛石纳米管与环氧基硅烷偶联剂的反应温度为25～150℃，优选50～100℃；反应时间为2～48小时，优选2～24小时。The third preferred technical solution of the present invention is: in step (2), acidified halloysite nanotubes and organic solvent are made into suspension according to the mass ratio of 1:10～1:100, and preferably adopt ultrasonic dispersion, the time is 5 to 60 minutes; the mass ratio of acidified halloysite nanotubes to epoxy silane coupling agent is 1:0.1 to 3, preferably 1:0.2 to 1; acidified halloysite nanotubes to epoxy silane coupling agent The reaction temperature is 25-150°C, preferably 50-100°C; the reaction time is 2-48 hours, preferably 2-24 hours.
本发明的第四优选技术方案为：所述环氧基硅烷偶联剂选自偶联剂Rn-Si-X(4-n)中的一种，其中：n选自1、2或3；末端可水解基团X选自三乙氧基、三甲氧基、甲基二甲氧基、甲基二乙氧基或二甲基乙氧基中的一种；R选自γ-缩水甘油醚氧丙基、β-(3,4-环氧环己基)乙基中的一种；优选γ-缩水甘油醚氧丙基三甲氧基硅烷；硅烷偶联剂的添加方式为搅拌混合条件下滴加。The fourth preferred technical solution of the present invention is: the epoxy silane coupling agent is selected from one of the coupling agentsRn -Si-X(4-n) , wherein: n is selected from 1, 2 or 3 ; The terminal hydrolyzable group X is selected from one of triethoxy, trimethoxy, methyldimethoxy, methyldiethoxy or dimethylethoxy; R is selected from γ-glycidol One of etheroxypropyl and β-(3,4-epoxycyclohexyl)ethyl; preferably γ-glycidyloxypropyltrimethoxysilane; the addition method of silane coupling agent is under the condition of stirring and mixing Add dropwise.
本发明的第五优选技术方案为：在步骤(3)中，将步骤⑴得到硅烷偶联剂改性的埃洛石纳米管的分散采用超声分散，时间为5～60分钟，优选15～45分钟；并在加入催化剂后超声分散；加入聚乙烯亚胺后，在惰性气体的保护下，加热跟所用的溶剂有关系，最高温一般不能超溶剂沸点太多。如甲苯作溶剂，温度限定在120℃；反应2～72h，优选4～24h；因为埃洛石难以改性，所用改性的时间稍长。The fifth preferred technical solution of the present invention is: in step (3), the dispersion of the halloysite nanotubes modified by the silane coupling agent obtained in step (1) adopts ultrasonic dispersion, and the time is 5 to 60 minutes, preferably 15 to 45 minutes. Minutes; and ultrasonic dispersion after adding the catalyst; after adding polyethyleneimine, under the protection of inert gas, the heating is related to the solvent used, the highest temperature generally cannot exceed the boiling point of the solvent too much. If toluene is used as a solvent, the temperature is limited to 120°C; the reaction time is 2 to 72 hours, preferably 4 to 24 hours; because halloysite is difficult to modify, the modification time is slightly longer.
本发明的第五优选技术方案为：所述催化剂选自三乙胺、乙二胺、KOH水溶液；所述惰性气体优选为氮气和氩气；干燥过程采用真空干燥或冷冻干燥，并优选冷冻干燥。The fifth preferred technical solution of the present invention is: the catalyst is selected from triethylamine, ethylenediamine, KOH aqueous solution; the inert gas is preferably nitrogen and argon; the drying process adopts vacuum drying or freeze drying, and preferably freeze drying .
本发明的第五优选技术方案为：所述支化型聚乙烯亚胺的重均分子量为600～60000。The fifth preferred technical solution of the present invention is: the weight average molecular weight of the branched polyethyleneimine is 600-60000.
本发明的第五优选技术方案为：在步骤(4)中，将支化型聚乙烯亚胺接枝改性的埃洛石纳米管在有机溶剂中的分散采用机械混合或超声分散，并优选超声分散；时间为10～60分钟；加入环氧树脂后，优选采用真空条件除尽有机溶剂，真空条件优选0.1MPa～0.5MPa；溶剂除尽后，优选使用研磨和高速搅拌的方法进一步打碎团聚体；加入固化剂后的混合优选机械搅拌混合。The fifth preferred technical solution of the present invention is: in step (4), the dispersion of the halloysite nanotubes grafted with branched polyethyleneimine in an organic solvent is mechanically mixed or ultrasonically dispersed, and preferably Ultrasonic dispersion; the time is 10 to 60 minutes; after adding epoxy resin, it is preferable to use vacuum conditions to remove the organic solvent, and the vacuum condition is preferably 0.1MPa to 0.5MPa; after the solvent is removed, it is preferable to use grinding and high-speed stirring for further crushing Agglomerates; the mixing after adding the curing agent is preferably mechanical stirring and mixing.
本发明的第五优选技术方案为：所述环氧树脂选自双酚A系环氧树脂、双酚F系环氧树脂、双酚S系环氧树脂、氢化双酚A环氧树脂、酚醛环氧树脂、脂肪族缩水甘油醚树脂、溴代环氧树脂、缩水甘油酯类树脂、氨基环氧树脂、脂环族环氧树脂、环氧化聚烯烃、有机硅环氧树脂或丙烯酸类环氧树脂中的至少一种，优选使用双酚A型环氧、酚醛环氧或多官能度环氧。The fifth preferred technical solution of the present invention is: the epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydrogenated bisphenol A epoxy resin, phenolic Epoxy resins, aliphatic glycidyl ether resins, brominated epoxy resins, glycidyl ester resins, amino epoxy resins, cycloaliphatic epoxy resins, epoxidized polyolefins, silicone epoxy resins, or acrylic rings At least one of epoxy resins, preferably bisphenol A epoxy, novolak epoxy or multifunctional epoxy.
本发明的第五优选技术方案为：在步骤(4)中，所述固化剂选自脂肪族胺类固化剂、脂环族胺类固化剂、芳香胺类固化剂、叔胺类固化剂、酸酐类固化剂、咪唑类固化剂、聚酰胺类固化剂、聚醚胺类固化剂、双氰胺固化剂中的一种；还添加有固化促进剂，选自叔胺类、咪唑类、季铵盐类、有机磷类、取代脲类及三氟化硼胺络合物等中的一种，并优选N,N-二甲基苄胺或DMP-30。The fifth preferred technical solution of the present invention is: in step (4), the curing agent is selected from the group consisting of aliphatic amine curing agents, alicyclic amine curing agents, aromatic amine curing agents, tertiary amine curing agents, One of acid anhydride curing agent, imidazole curing agent, polyamide curing agent, polyether amine curing agent, dicyandiamide curing agent; curing accelerator is also added, selected from tertiary amines, imidazoles, quaternary One of ammonium salts, organophosphorus, substituted urea and boron trifluoride amine complex, and preferably N,N-dimethylbenzylamine or DMP-30.
本发明的第五优选技术方案为：所述有机溶剂选自乙醇、甲醇、异丙醇、正丁醇、乙二醇、丙酮、氯仿、二氯甲烷、四氢呋喃、苯、甲苯、二甲苯、正己烷、二氧六环、N,N-二甲基甲酰胺或N,N-二甲基乙酰胺中的至少一种，优选乙醇、甲苯或甲苯/甲醇混合溶剂等。The fifth preferred technical solution of the present invention is: the organic solvent is selected from the group consisting of ethanol, methanol, isopropanol, n-butanol, ethylene glycol, acetone, chloroform, dichloromethane, tetrahydrofuran, benzene, toluene, xylene, n-hexyl At least one of alkane, dioxane, N,N-dimethylformamide or N,N-dimethylacetamide, preferably ethanol, toluene or toluene/methanol mixed solvent, etc.
下面对本发明的技术方案做进一步的解释和说明。The technical solution of the present invention will be further explained and illustrated below.
本发明提出了一种用超支化聚乙烯亚胺接枝改性的埃洛石纳米管，本发明的制备过程简单，实验易于操作。本发明通过聚乙烯亚胺接枝后，HNTs表面含有大量的伯胺和仲胺基团，可以进一步功能化HNTs。本发明采用“graft to”的方法，将超支化聚乙烯亚胺接枝到环氧化HNTs上。支化结构具有丰富的氨基基团，使埃洛石纳米管与环氧树脂基体间生成更强的化学键或氢键作用，增强界面作用。与未经支化结构修饰的HNTs相比，改性处理后的HNTs可以提高环氧树脂的力学性能。将接枝支化结构的产物作为填充剂用于环氧树脂复合材料，可以更好的改善HNTs在环氧树脂中的分散及与环氧树脂的界面结合，能明显提高环氧树脂的力学和热学性能，具有很好的实用价值。The invention proposes a halloysite nanotube grafted and modified with hyperbranched polyethyleneimine. The preparation process of the invention is simple, and the experiment is easy to operate. After the polyethyleneimine is grafted in the present invention, the surface of the HNTs contains a large number of primary and secondary amine groups, which can further functionalize the HNTs. The present invention uses a "graft to" method to graft hyperbranched polyethyleneimine onto epoxidized HNTs. The branched structure has abundant amino groups, so that stronger chemical bonds or hydrogen bonds are formed between the halloysite nanotubes and the epoxy resin matrix, and the interface interaction is enhanced. Compared with HNTs without branched structure modification, the modified HNTs can improve the mechanical properties of epoxy resin. The product of grafted branched structure is used as a filler in epoxy resin composites, which can better improve the dispersion of HNTs in epoxy resin and the interface bonding with epoxy resin, and can significantly improve the mechanical properties of epoxy resin. Thermal performance, has very good practical value.
本发明的支化型聚乙烯亚胺(PEI)改性埃洛石纳米管的制备方法包括以下步骤：The preparation method of branched polyethyleneimine (PEI) modified halloysite nanotube of the present invention comprises the following steps:
(1)埃洛石纳米管粒子与酸性试剂按照1:5～1:100的质量比混合，超声分散5～60分钟后搅拌1～48小时，离心、过滤、水洗至中性，干燥后即得酸化埃洛石纳米管。本发明通过酸化，可以除去原料埃洛石纳米管粒子中的杂质，作用请补充。酸化可以进一步除去伴生的矿物杂质，疏通内孔孔道，改变其结构电荷和表面电荷，从而增加吸附中心的点数，起到提高比表面积、活化内外表面的作用。(1) Halloysite nanotube particles and acidic reagents are mixed according to the mass ratio of 1:5 to 1:100, ultrasonically dispersed for 5 to 60 minutes, stirred for 1 to 48 hours, centrifuged, filtered, washed until neutral, and dried acidified halloysite nanotubes. The present invention can remove the impurities in the halloysite nanotube particles through acidification, please add the effect. Acidification can further remove associated mineral impurities, dredge the inner pore channel, change its structural charge and surface charge, thereby increasing the number of adsorption centers, increasing the specific surface area, and activating the inner and outer surfaces.
(2)将酸化埃洛石纳米管与有机溶剂按照质量比为1:10～1:100配成均匀的悬浮液，并继续超声处理5～60分钟。将酸化埃洛石纳米管质量10～300％的环氧基硅烷偶联剂加入悬浮液中，25～150℃下搅拌反应2～48小时。过滤、洗涤、干燥后，得到表面修饰有环氧基团的埃洛石纳米管。对埃洛石纳米管表面进行环氧基团修饰，其主要目的是为了进一步接枝支化型聚乙烯亚胺；相对于现有技术中常用的胺基、丙烯酰氧基等修饰基团来说，表面修饰环氧基团，埃洛石纳米管与基体之间的相容性增加。本发明通过研究发现，使用胺基硅烷修饰的团聚现象会相对严重，因此本发明选用了采用环氧基团进行修饰。(2) Prepare the acidified halloysite nanotubes and the organic solvent in a mass ratio of 1:10-1:100 to form a uniform suspension, and continue ultrasonic treatment for 5-60 minutes. Add epoxy silane coupling agent with 10-300% mass of acidified halloysite nanotubes into the suspension, and stir and react at 25-150° C. for 2-48 hours. After filtering, washing and drying, halloysite nanotubes with epoxy groups modified on the surface are obtained. The main purpose of modifying the surface of halloysite nanotubes with epoxy groups is to further graft branched polyethyleneimine; Said that the surface modification of epoxy groups increases the compatibility between halloysite nanotubes and the matrix. The present invention finds through research that the agglomeration phenomenon modified by aminosilane will be relatively serious, so the present invention chooses to use epoxy group for modification.
(3)支化型聚乙烯亚胺接枝埃洛石纳米管：将步骤(2)中的环氧基团修饰的埃洛石纳米管在溶剂中超声分散5～60分钟，优选15～45分钟；加入催化剂并继续超声分散。向体系中加入定量的支化型聚乙烯亚胺，在惰性气体的保护下，加热搅拌反应2～72h后。将所得产物经过抽滤、洗涤、干燥得到超支化聚乙烯亚胺改性的埃洛石纳米管。制备支化型聚乙烯亚胺改性埃洛石纳米管(PEI-HNTs)的过程如附图1所示；(3) branched polyethyleneimine grafted halloysite nanotubes: the halloysite nanotubes modified by the epoxy group in step (2) are ultrasonically dispersed in a solvent for 5 to 60 minutes, preferably 15 to 45 minutes; add catalyst and continue ultrasonic dispersion. Adding a certain amount of branched polyethyleneimine to the system, under the protection of inert gas, heating and stirring for 2-72 hours. The obtained product is subjected to suction filtration, washing and drying to obtain halloysite nanotubes modified by hyperbranched polyethyleneimine. The process of preparing branched polyethyleneimine modified halloysite nanotubes (PEI-HNTs) is shown in Figure 1;
其中，为了使环氧化HNTs和支化型PEI接枝HNTs在有机溶剂中分散良好而又不严重破坏结构和所带活性基团，优选的，超声处理时间为15～45分钟；催化剂选自三乙胺、乙二胺、KOH水溶液；惰性气体优选为氮气和氩气；干燥过程采用真空干燥或冷冻干燥；对于在水中有优异分散性的埃洛石纳米管，优选冷冻干燥。Among them, in order to disperse the epoxidized HNTs and branched PEI grafted HNTs well in the organic solvent without seriously damaging the structure and the active groups, preferably, the ultrasonic treatment time is 15 to 45 minutes; the catalyst is selected from Triethylamine, ethylenediamine, KOH aqueous solution; the inert gas is preferably nitrogen and argon; the drying process adopts vacuum drying or freeze drying; for halloysite nanotubes with excellent dispersibility in water, freeze drying is preferred.
本发明采用“graft to”的方法，将超支化聚乙烯亚胺接枝到环氧化HNTs上。支化结构具有丰富的氨基基团，使埃洛石纳米管与环氧树脂基体间生成更强的化学键或氢键作用，增强界面作用。与未经支化结构修饰的HNTs相比，改性处理后的HNT可以提高环氧树脂的力学性能。The present invention uses a "graft to" method to graft hyperbranched polyethyleneimine onto epoxidized HNTs. The branched structure has abundant amino groups, so that stronger chemical bonds or hydrogen bonds are formed between the halloysite nanotubes and the epoxy resin matrix, and the interface interaction is enhanced. Compared with unmodified HNTs, the modified HNTs can improve the mechanical properties of epoxy resins.
(4)将支化型聚乙烯亚胺接枝改性的埃洛石纳米管在有机溶剂中先超声分散10～60分钟，然后加入环氧树脂，混合后除去有机溶剂；真空条件下(0.1MPa～0.5MPa)，进一步除尽有机溶剂。再加入固化剂混合，固化得到功能化埃洛石纳米管/环氧树脂纳米复合材料。(4) The halloysite nanotubes grafted and modified by branched polyethyleneimine were ultrasonically dispersed in an organic solvent for 10 to 60 minutes, then epoxy resin was added, and the organic solvent was removed after mixing; under vacuum conditions (0.1 MPa～0.5MPa), further remove the organic solvent. A curing agent is then added and mixed, and cured to obtain a functionalized halloysite nanotube/epoxy resin nanocomposite material.
作为优选，在有机溶剂中加入环氧树脂后，采用机械混合和超声的方法将其混合均匀。机械混合法为高速搅拌、行星球磨法和乳化剪切分散；超声法选用超声波细胞破碎机混合。作为优选，溶剂除尽后，可以使用三辊研磨和高速搅拌(2000rpm)的方法进一步打碎团聚体。作为优选，加入固化剂后采用机械搅拌使其混合均匀，在30～100℃下真空脱气。将混合物浇注到已经预热的模具中，在程序升温的烘箱中进行固化，得到改性HNTs/环氧树脂纳米复合材料。Preferably, after the epoxy resin is added into the organic solvent, it is uniformly mixed by means of mechanical mixing and ultrasound. The mechanical mixing method is high-speed stirring, planetary ball milling and emulsification shear dispersion; the ultrasonic method uses ultrasonic cell crusher for mixing. Preferably, after the solvent is removed, the agglomerates can be further broken up by three-roll milling and high-speed stirring (2000 rpm). As a preference, after adding the curing agent, use mechanical stirring to mix evenly, and vacuum degas at 30-100°C. The mixture is poured into a preheated mold and cured in a temperature-programmed oven to obtain a modified HNTs/epoxy resin nanocomposite.
本发明将将接枝支化结构的产物作为填充剂用于环氧树脂复合材料，可以更好的改善HNTs在环氧树脂中的分散及与环氧树脂的界面结合，能明显提高环氧树脂的力学和热学性能，具有很好的实用价值。In the present invention, the product of the grafted branched structure is used as a filler in the epoxy resin composite material, which can better improve the dispersion of HNTs in the epoxy resin and the interface combination with the epoxy resin, and can obviously improve the performance of the epoxy resin. Excellent mechanical and thermal properties, with good practical value.
本发明中，环氧树脂固化体系中加入的支化型聚乙烯亚胺改性埃洛石纳米管的质量分数为0.2～20wt％，优选0.5～5wt％。固化剂的用量由环氧树脂的环氧值和固化剂的类型及其可反应的活性基团所确定，且应确保环氧树脂能够充分交联。In the present invention, the mass fraction of the branched polyethyleneimine-modified halloysite nanotubes added to the epoxy resin curing system is 0.2-20 wt%, preferably 0.5-5 wt%. The amount of curing agent is determined by the epoxy value of the epoxy resin, the type of curing agent and its reactive active groups, and it should be ensured that the epoxy resin can be fully cross-linked.
本发明在有机溶剂中用环氧基硅烷偶联剂对酸化的埃洛石纳米管进行改性，然后将带环氧基团的埃洛石纳米管与支化型PEI反应，通过环氧基和氨基的反应将支化结构接枝到埃洛石纳米管表面。硅烷化改性埃洛石纳米管的整体工艺简单、可靠，而改性埃洛石纳米管与PEI上氨基的环氧开环反应产率高，易于提纯。同时，傅里叶变换红外光谱(FTIR)、热失重分析(TGA)和光电子能谱(XPS)证实了表面接枝反应的发生。In the present invention, the acidified halloysite nanotubes are modified with an epoxy silane coupling agent in an organic solvent, and then the halloysite nanotubes with epoxy groups are reacted with branched PEI. The reaction with amino groups grafts branched structures onto the surface of halloysite nanotubes. The overall process of silylation modified halloysite nanotubes is simple and reliable, and the epoxy ring-opening reaction between modified halloysite nanotubes and amino groups on PEI has a high yield and is easy to purify. Meanwhile, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and photoelectron spectroscopy (XPS) confirmed the occurrence of surface grafting reaction.
本发明将超支化聚乙烯亚胺修饰的埃洛石纳米管添加到环氧树脂中，通过不同的混合方法成功制得环氧树脂纳米复合材料。本发明充分利用PEI分子表面众多的功能基团，通过共价键修饰到埃洛石纳米管的表面，阻止了埃洛石纳米管之间的团聚，使得埃洛石纳米管在环氧树脂中有良好的分散。利用氨基的反应活性，可以与环氧树脂反应，增强了埃洛石纳米管和环氧树脂之间的界面结合。用扫描电子显微镜(SEM)等表征证明，经过超支化聚乙烯亚胺修饰的埃洛石纳米管在环氧树脂基体中的分散获得明显改善。对所制得的环氧树脂/埃洛石纳米管复合材料进行力学性能测试，结果显示，经过支化聚乙烯亚胺改性的埃洛石纳米管在较低含量下(2.3wt％)就能够将环氧树脂的冲击韧性提高80％。通过电镜观察，PEI改性后的HNTs能均匀分散在环氧树脂中，没有明显的团聚体存在。如图7所示，即为改性后HNTs分散较好。In the invention, halloysite nanotubes modified by hyperbranched polyethyleneimine are added to epoxy resin, and epoxy resin nanocomposite materials are successfully prepared through different mixing methods. The present invention makes full use of numerous functional groups on the surface of PEI molecules to modify the surface of halloysite nanotubes through covalent bonds, preventing the agglomeration between halloysite nanotubes and making halloysite nanotubes in epoxy resin Has good dispersion. Utilizing the reactivity of the amino group, it can react with epoxy resin, which enhances the interfacial bonding between halloysite nanotubes and epoxy resin. Characterization by scanning electron microscopy (SEM) proved that the dispersion of the halloysite nanotubes modified by hyperbranched polyethyleneimine in the epoxy resin matrix was significantly improved. The obtained epoxy resin/halloysite nanotube composite was tested for mechanical properties, and the results showed that the halloysite nanotubes modified by branched polyethyleneimine were at a lower content (2.3wt%). Able to increase the impact toughness of epoxy resin by 80%. Observed by electron microscope, PEI-modified HNTs can be uniformly dispersed in epoxy resin without obvious aggregates. As shown in Figure 7, the HNTs are better dispersed after modification.
与现有技术相比，本发明的有益效果是：本发明制备的改性埃洛石纳米管能有效地提高环氧树脂的抗冲击性能，减少环氧树脂的脆性断裂。本发明的环氧树脂纳米复合材料在汽车、电子、功能材料、航空航天等领域有着广阔的应用前景。当加入2.3wt％的HNTs和PEI接枝改性的HNTs后，冲击强度从纯环氧树脂的1.08kJ/m2分别增加到1.4kJ/m2和1.98kJ/m2，分别提高29.6％和83.3％。Compared with the prior art, the beneficial effect of the present invention is that the modified halloysite nanotube prepared by the present invention can effectively improve the impact resistance of the epoxy resin and reduce the brittle fracture of the epoxy resin. The epoxy resin nanocomposite material of the invention has broad application prospects in the fields of automobiles, electronics, functional materials, aerospace and the like. When 2.3wt% of HNTs and PEI graft-modified HNTs were added, the impact strength increased from 1.08kJ/m2 of pure epoxy resin to 1.4kJ/m2 and 1.98kJ/m2 , increasing by 29.6% and 83.3%.
附图说明Description of drawings
图1为本发明超支化聚乙烯亚胺(PEI)接枝改性埃洛石纳米管(HNTs)方法的示意图；Fig. 1 is the schematic diagram of hyperbranched polyethyleneimine (PEI) graft modification halloysite nanotube (HNTs) method of the present invention;
图2为实施例1的改性和未改性埃洛石纳米管的FTIR光谱图；Fig. 2 is the FTIR spectrogram of the modification of embodiment 1 and unmodified halloysite nanotube;
图3为实施例1的改性和未改性埃洛石纳米管光电子能谱图；Fig. 3 is the modified and unmodified halloysite nanotube photoelectron spectrum figure of embodiment 1;
图4为实施例3的环氧基硅烷改性HNTs、超支化聚乙烯亚胺改性HNTs与未改性HNTs的热失重曲线图。Fig. 4 is the thermal weight loss curve of epoxy silane modified HNTs, hyperbranched polyethyleneimine modified HNTs and unmodified HNTs of Example 3.
图5为实施例3的未改性HNTs和经超支化聚乙烯亚胺改性过的HNTs的SEM图；其中上图为未改性埃洛石纳米管；下图为PEI接枝改性埃洛石纳米管；Fig. 5 is the SEM figure of the unmodified HNTs of embodiment 3 and the HNTs modified by hyperbranched polyethyleneimine; Wherein the upper figure is the unmodified halloysite nanotube; The lower figure is the PEI graft modified angstrom Rocky nanotubes;
图6为对比例1中环氧树脂中加入不同量的未改性和改性HNTs后，复合材料的冲击强度对比图；Fig. 6 is after adding different amounts of unmodified and modified HNTs in the epoxy resin in comparative example 1, the impact strength contrast chart of composite material;
图7为对比例1的未改性和改性HNTs与环氧树脂体系固化后，经过冲击测试后断面的SEM图；Fig. 7 is the SEM image of the section after the impact test after the unmodified and modified HNTs and the epoxy resin system of Comparative Example 1 are cured;
图8为对比例2复合材料的冲击强度对比图；Fig. 8 is the comparison diagram of the impact strength of comparative example 2 composite material;
图9为对比例3复合材料的冲击强度对比图。Fig. 9 is a comparison chart of the impact strength of the composite material of Comparative Example 3.
为了更好地对本发明进行说明，通过下面的实施例来加以进一步的描述，但是本发明并不局限于这些实施例。In order to illustrate the present invention better, the following examples are used for further description, but the present invention is not limited to these examples.
具体实施方式detailed description
实施例1Example 1
(1)埃洛石纳米管的酸化：将埃洛石纳米管粒子与1mol/L的盐酸溶液按照1:20的质量比混合，超声分散60分钟后搅拌4小时，离心、过滤、水洗至中性，110℃干燥2h后即得酸化处理的埃洛石纳米管；(1) Acidification of halloysite nanotubes: mix halloysite nanotube particles with 1mol/L hydrochloric acid solution at a mass ratio of 1:20, ultrasonically disperse for 60 minutes, stir for 4 hours, centrifuge, filter, and wash with water until medium properties, acidified halloysite nanotubes were obtained after drying at 110°C for 2 hours;
(2)硅烷偶联剂表面改性埃洛石纳米管：将酸化埃洛石纳米管与甲苯按照质量比为1:50配成均匀的悬浮液，并继续超声处理30分钟。滴加酸化埃洛石纳米管质量20％的γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)，120℃下搅拌反应4小时；反应结束后，过滤、洗涤、干燥，得到表面修饰有环氧基团的埃洛石纳米管(KH560-HNTs)；(2) Surface modification of halloysite nanotubes by silane coupling agent: prepare a homogeneous suspension with acidified halloysite nanotubes and toluene at a mass ratio of 1:50, and continue ultrasonic treatment for 30 minutes. Add dropwise γ-glycidyl etheroxypropyltrimethoxysilane (KH560) with 20% mass of acidified halloysite nanotubes, and stir and react at 120°C for 4 hours; after the reaction, filter, wash, and dry to obtain surface-modified Halloysite nanotubes with epoxy groups (KH560-HNTs);
(3)支化型聚乙烯亚胺接枝埃洛石纳米管：将步骤(2)得到的环氧基团修饰的埃洛石纳米管在三氯甲烷中超声分散60分钟，得到均匀分散的悬浮液；向体系中加入等质量的支化型聚乙烯亚胺(Mw＝1200)，再滴加适量的催化剂三乙胺。在氮气保护下，加热至60℃下回流，充分搅拌反应24小时后冷却至室温。用三氯甲烷和乙醇洗涤，重复3次，80℃下烘干即得超支化聚乙烯亚胺改性的埃洛石纳米管(PEI-KH560-HNTs)；(3) Branched polyethyleneimine grafted halloysite nanotubes: the epoxy group-modified halloysite nanotubes obtained in step (2) were ultrasonically dispersed in chloroform for 60 minutes to obtain uniformly dispersed Suspension; add an equal mass of branched polyethyleneimine (Mw=1200) to the system, and then add an appropriate amount of catalyst triethylamine dropwise. Under the protection of nitrogen, it was heated to reflux at 60°C, fully stirred and reacted for 24 hours, and then cooled to room temperature. Washing with chloroform and ethanol, repeated 3 times, and drying at 80°C to obtain hyperbranched polyethyleneimine-modified halloysite nanotubes (PEI-KH560-HNTs);
将所得改性埃洛石纳米管进行红外分析，结果如图2所示的FTIR光谱图。表1为实施例1中改性和未改性埃洛石纳米管表面元素相对含量表。The resulting modified halloysite nanotubes were subjected to infrared analysis, and the result is the FTIR spectrum shown in FIG. 2 . Table 1 shows the relative contents of surface elements of modified and unmodified halloysite nanotubes in Example 1.
在图2中，KH560-HNTs和PEI-KH560-HNTs的红外谱图中均出现了CH2的对称和非对称伸缩振动峰(2930cm-1和2850cm-1)，且PEI-KH560-HNTs的峰强度比KH560-HNTs要强。改性埃洛石纳米管的NH2的剪式运动、CH2的剪式运动和CH2的摇摆振动吸收峰不明显。结合图3和表1中光电子能谱的结果，经过偶联剂KH560改性后，C元素含量增加，Si/Al元素比由1.12增加到1.99，进一步说明了KH560接枝到HNTs的表面。PEI对KH560-HNTs进一步改性后，C元素含量增加更加明显，并出现N元素，说明了PEI已经接枝到HNTs的表面。In Figure 2, both KH560-HNTs and PEI-KH560-HNTs infrared spectra showed CH2 symmetric and asymmetric stretching vibration peaks (2930cm-1 and 2850cm-1 ), and the peak of PEI-KH560-HNTs Stronger than KH560-HNTs. The shear motion of NH2 , the shear motion of CH2 and the rocking vibration absorption peaks of CH2 of the modified halloysite nanotubes are not obvious. Combining the results of photoelectron spectroscopy in Figure 3 and Table 1, after modification by the coupling agent KH560, the content of C element increases, and the ratio of Si/Al element increases from 1.12 to 1.99, which further illustrates that KH560 is grafted to the surface of HNTs. After PEI further modified KH560-HNTs, the content of C element increased more obviously, and N element appeared, indicating that PEI had been grafted to the surface of HNTs.
表1Table 1
(4)改性埃洛石纳米管与环氧树脂混合制备环氧树脂纳米复合材料：将2g支化型聚乙烯亚胺接枝改性的埃洛石纳米管加入到75g丙酮中，搅拌分散30分钟后，再超声处理30分钟，得到均匀分散的悬浮液。在悬浮液中加入50g预热的环氧树脂EPON828，进一步超声分散60分钟得到均匀分散的混合液。将上述混合液在60℃下搅拌处理5小时，真空条件下(0.2MPa)进一步除尽有机溶剂。在得到的混合体系中加入芳香胺类固化剂4,4-二氨基-二苯基甲烷(DDM)共13.5g，于90℃下搅拌混合混匀。将上述混合体系于80℃下真空脱泡除气，然后倒入预热的固化模具中。80℃固化2小时，再于160℃下固化3小时，脱模，即得到含聚乙烯亚胺改性埃洛石纳米管含量为3wt％的环氧树脂基纳米复合材料。而用KH560改性埃洛石纳米管代替支化型聚乙烯亚胺改性埃洛石纳米管，可以制备KH560-HNTs含量为3wt％的环氧树脂基纳米复合材料。(4) Modified halloysite nanotubes are mixed with epoxy resin to prepare epoxy resin nanocomposites: add 2g of branched polyethyleneimine grafted halloysite nanotubes to 75g of acetone, stir and disperse After 30 min, sonicate for another 30 min to obtain a homogeneously dispersed suspension. Add 50 g of preheated epoxy resin EPON828 to the suspension, and further ultrasonically disperse for 60 minutes to obtain a uniformly dispersed mixed liquid. The above mixed solution was stirred at 60° C. for 5 hours, and the organic solvent was further removed under vacuum (0.2 MPa). A total of 13.5 g of aromatic amine curing agent 4,4-diamino-diphenylmethane (DDM) was added to the obtained mixed system, and stirred and mixed at 90°C. The above mixed system was defoamed and degassed in vacuum at 80°C, and then poured into a preheated curing mold. Curing at 80° C. for 2 hours, and then curing at 160° C. for 3 hours, demoulding, and obtaining an epoxy resin-based nanocomposite material containing polyethyleneimine-modified halloysite nanotubes with a content of 3 wt %. The epoxy resin-based nanocomposite with KH560-HNTs content of 3wt% can be prepared by using KH560 modified halloysite nanotubes instead of branched polyethyleneimine modified halloysite nanotubes.
得到复合材料的特性参数：冲击强度1.98kJ/m2。The characteristic parameters of the composite material are obtained: the impact strength is 1.98kJ/m2 .
EP→EP/HNTs→EP/KH560-HNTs→EP/PEI-KH560-HNTs当在环氧树脂中依次添加2.3wt％的改性和未改性的HNTs：EP→EP/HNTs→EP/KH560-HNTs→EP/PEI-KH560-HNTs When sequentially adding 2.3wt% modified and unmodified HNTs in the epoxy resin:
冲击强度由纯环氧树脂的1.25kJ/m2，依次增加至1.67kJ/m2，1.89kJ/m2和2.07kJ/m2；The impact strength increases sequentially from 1.25kJ/m2 of pure epoxy resin to 1.67kJ/m 2, 1.89kJ/m2 and 2.07kJ/m2 ;
弯曲强度由纯环氧树脂的83.6MPa，依次增加至86.7MPa，97.3MPa和101.0MPa；The bending strength increased from 83.6MPa of pure epoxy resin to 86.7MPa, 97.3MPa and 101.0MPa in turn;
弯曲模量由纯环氧树脂的2.44GPa，依次增加至2.54GPa，2.71GPa和2.78GPa。The flexural modulus increased from 2.44GPa of pure epoxy resin to 2.54GPa, 2.71GPa and 2.78GPa in turn.
参照以上步骤可以制备含改性埃洛石纳米管0.2～20wt％的环氧树脂纳米复合材料。The epoxy resin nanocomposite material containing the modified halloysite nanotubes in an amount of 0.2-20wt% can be prepared by referring to the above steps.
实施例2Example 2
(1)埃洛石纳米管的酸化：埃洛石纳米管粒子与2mol/L的硫酸溶液按照1:30的质量比混合，超声分散30分钟后搅拌12小时，离心、过滤、水洗至中性；将洗涤产物导入干净容器中，100℃干燥3小时后即得酸化处理的埃洛石纳米管；(1) Acidification of halloysite nanotubes: Mix halloysite nanotube particles with 2mol/L sulfuric acid solution at a mass ratio of 1:30, ultrasonically disperse for 30 minutes, stir for 12 hours, centrifuge, filter, and wash with water until neutral ; Import the washed product into a clean container, and dry at 100°C for 3 hours to obtain acidified halloysite nanotubes;
(2)硅烷偶联剂表面改性埃洛石纳米管：称取埃洛石纳米管，加入20倍质量的丙酮溶液，超声处理30分钟；滴加酸化埃洛石纳米管质量10％的β-(3,4-环氧环己基)乙基三甲氧基硅烷(A-186)，继续超声搅拌处理30分钟，通过加入氢氧化钠溶液使混合液pH为中性，于70℃下反应5小时；反应结束后，过滤、洗涤、干燥，得到表面修饰有环氧基团的埃洛石纳米管；(2) Surface modification of halloysite nanotubes by silane coupling agent: take halloysite nanotubes by weighing, add 20 times the mass of acetone solution, ultrasonic treatment for 30 minutes; -(3,4-epoxycyclohexyl)ethyltrimethoxysilane (A-186), continue ultrasonic stirring for 30 minutes, add sodium hydroxide solution to make the pH of the mixture neutral, and react at 70°C for 5 hour; after the reaction finishes, filter, wash, dry, obtain the halloysite nanotube that the surface is modified with epoxy group;
(3)支化型聚乙烯亚胺接枝埃洛石纳米管：将步骤(2)中环氧基团修饰的埃洛石纳米管在二氯甲烷中超声分散45分钟，得到均匀分散的悬浮液；向体系中加入环氧基修饰埃洛石纳米管质量1/4的支化型聚乙烯亚胺(Mw＝10000)，再滴加适量的催化剂乙二胺。通氩气保护，于40℃下回流，充分搅拌反应12小时后冷却至室温；用四氢呋喃和甲醇洗涤，重复3次，80℃下烘干即得超支化聚乙烯亚胺改性的埃洛石纳米管；(3) Branched polyethyleneimine grafted halloysite nanotubes: ultrasonically disperse the halloysite nanotubes modified by epoxy groups in step (2) in dichloromethane for 45 minutes to obtain a uniformly dispersed suspension solution; add epoxy-modified halloysite nanotube quality 1/4 branched polyethyleneimine (Mw=10000) to the system, and then add an appropriate amount of catalyst ethylenediamine dropwise. Protected by argon, reflux at 40°C, fully stirred and reacted for 12 hours, then cooled to room temperature; washed with tetrahydrofuran and methanol, repeated 3 times, and dried at 80°C to obtain halloysite modified by hyperbranched polyethyleneimine nanotube;
(4)改性埃洛石纳米管与环氧树脂混合制备环氧树脂纳米复合材料：将0.5g支化型聚乙烯亚胺接枝改性的埃洛石纳米管加入到50g四氢呋喃中，搅拌分散10分钟后，再超声处理40分钟，得到均匀分散的悬浮液。在悬浮液中加入70g预热的环氧树脂EPON828，进一步超声分散50分钟得到均匀分散的混合液。将上述混合液在70℃下搅拌处理3h，真空条件下(0.1MPa)进一步除尽有机溶剂。将得到的混合体系将至室温，加入聚醚胺固化剂T403共计29.4g，于50℃下搅拌混合混匀。将上述混合体系于50℃下真空脱泡除气，然后倒入预热的固化模具中。80℃固化2小时，再于125℃下固化2小时，脱模，即得到含聚乙烯亚胺改性埃洛石纳米管含量为0.5wt％的环氧树脂基纳米复合材料。而用环氧基硅烷改性埃洛石纳米管代替支化型聚乙烯亚胺改性埃洛石纳米管，可以制备环氧基硅烷改性HNTs含量为0.5wt％的环氧树脂基纳米复合材料。(4) Modified halloysite nanotubes are mixed with epoxy resin to prepare epoxy resin nanocomposites: 0.5g branched polyethyleneimine grafted halloysite nanotubes are added to 50g tetrahydrofuran, stirred After dispersing for 10 minutes, sonicate for another 40 minutes to obtain a homogeneously dispersed suspension. Add 70g of preheated epoxy resin EPON828 to the suspension, and further ultrasonically disperse for 50 minutes to obtain a uniformly dispersed mixed solution. The above mixture was stirred at 70° C. for 3 h, and the organic solvent was further removed under vacuum (0.1 MPa). The resulting mixed system was cooled to room temperature, and a total of 29.4 g of polyetheramine curing agent T403 was added, and stirred and mixed at 50°C. The above mixed system was defoamed and degassed in vacuum at 50°C, and then poured into a preheated curing mold. Curing at 80° C. for 2 hours, then curing at 125° C. for 2 hours, demoulding, and obtaining an epoxy resin-based nanocomposite material containing polyethyleneimine-modified halloysite nanotubes with a content of 0.5 wt %. Epoxysilane-modified halloysite nanotubes are used instead of branched polyethyleneimine-modified halloysite nanotubes to prepare epoxy-based nanocomposites with epoxy-silane-modified HNTs content of 0.5wt%. Material.
EP→EP/HNTs→EP/A-186-HNTs→EP/PEI-A-186-HNTs当在环氧树脂中依次添加2.3wt％的改性和未改性的HNTs；EP→EP/HNTs→EP/A-186-HNTs→EP/PEI-A-186-HNTs When sequentially adding 2.3wt% modified and unmodified HNTs to the epoxy resin;
冲击强度由纯环氧树脂的3.75kJ/m2，依次增加至3.97kJ/m2，4.86kJ/m2和5.12kJ/m2；The impact strength increases sequentially from 3.75kJ/m2 of pure epoxy resin to 3.97kJ/m 2, 4.86kJ/m2 and 5.12kJ/m2 ;
拉伸强度由纯环氧树脂的55.6MPa，依次增加至60.7MPa，67.3MPa和70.4MPa；The tensile strength increased from 55.6MPa of pure epoxy resin to 60.7MPa, 67.3MPa and 70.4MPa in turn;
拉伸模量由纯环氧树脂的1.74GPa，依次增加至1.94GPa，2.01GPa和2.18GPa。The tensile modulus increased from 1.74GPa of pure epoxy resin to 1.94GPa, 2.01GPa and 2.18GPa in turn.
参照以上步骤可以制备含改性埃洛石纳米管0.2～20wt％的环氧树脂纳米复合材料。The epoxy resin nanocomposite material containing the modified halloysite nanotubes in an amount of 0.2-20wt% can be prepared by referring to the above steps.
实施例3Example 3
(1)埃洛石纳米管的酸化：埃洛石纳米管粒子与30％的双氧水按照1:10的质量比混合，超声分散45分钟得到均匀分散的体系；转至80℃下搅拌48小时，离心、过滤、水洗至中性，110℃干燥2.5小时后即得酸化处理的埃洛石纳米管；(1) Acidification of halloysite nanotubes: halloysite nanotube particles are mixed with 30% hydrogen peroxide at a mass ratio of 1:10, ultrasonically dispersed for 45 minutes to obtain a uniformly dispersed system; transferred to 80°C and stirred for 48 hours, Centrifuge, filter, wash with water until neutral, and dry at 110°C for 2.5 hours to obtain acidified halloysite nanotubes;
(2)硅烷偶联剂表面改性埃洛石纳米管：称取酸化埃洛石纳米管，加入10倍质量的乙醇溶液(乙醇和水体积比为95/5)，并继续超声处理45分钟；用稀盐酸调节溶液的pH值为4～5，滴加酸化埃洛石纳米管质量50％的γ-缩水甘油醚氧丙基甲基二甲氧基硅烷(AC-661)，80℃下搅拌反应24小时。待反应结束后，过滤、洗涤、干燥，得到表面修饰有环氧基团的埃洛石纳米管；(2) Surface modification of halloysite nanotubes by silane coupling agent: Weigh acidified halloysite nanotubes, add 10 times the mass of ethanol solution (volume ratio of ethanol to water is 95/5), and continue ultrasonic treatment for 45 minutes The pH value of the solution is adjusted to 4 to 5 with dilute hydrochloric acid, and γ-glycidyl etheroxypropylmethyldimethoxysilane (AC-661) of acidified halloysite nanotube quality 50% is added dropwise, at 80°C The reaction was stirred for 24 hours. After the reaction is finished, filter, wash, and dry to obtain halloysite nanotubes with surface-modified epoxy groups;
(3)支化型聚乙烯亚胺接枝埃洛石纳米管：将步骤(3)中环氧基团修饰的埃洛石纳米管在DMF中超声分散60分钟，得到均匀分散的悬浮液。向体系中加入环氧基团修饰埃洛石纳米管质量1/2的支化型聚乙烯亚胺(Mw＝600)；再滴加适量的催化剂三乙胺。在氮气保护下，加热至80℃下回流，充分搅拌反应20h后冷却至室温；用DMF和乙醇洗涤，重复3次，100℃下烘干即得超支化聚乙烯亚胺改性的埃洛石纳米管；(3) Branched polyethyleneimine grafted halloysite nanotubes: the halloysite nanotubes modified with epoxy groups in step (3) were ultrasonically dispersed in DMF for 60 minutes to obtain a uniformly dispersed suspension. Add branched polyethyleneimine (Mw=600) of epoxy group-modified halloysite nanotube mass 1/2 to the system; then add an appropriate amount of catalyst triethylamine dropwise. Under the protection of nitrogen, heat to reflux at 80°C, fully stir the reaction for 20 hours, then cool to room temperature; wash with DMF and ethanol, repeat 3 times, and dry at 100°C to obtain halloysite modified by hyperbranched polyethyleneimine nanotube;
将所得改性埃洛石纳米管进行热失重分析，热失重分析仪(Pyris 1 TGA)，升温速率为20℃/min，氮气气氛，失重曲线如图4所示。从图4中可以看出，失重曲线可以反映改性埃洛石纳米管的接枝率。改性埃洛石纳米管总的接枝率约为4％，其中PEI的接枝量约为1.1％。图5所示为埃洛石纳米管和PEI改性埃洛石纳米管的扫描电镜照片。未改性埃洛石纳米管表面光滑，轮廓清楚，而经过偶联剂和PEI改性后的埃洛石纳米管表面粗糙，进一步证明PEI可以接枝到埃洛石纳米管表面。The obtained modified halloysite nanotubes were subjected to thermogravimetric analysis with a thermogravimetric analyzer (Pyris 1 TGA) at a heating rate of 20° C./min in a nitrogen atmosphere, and the weight loss curve is shown in FIG. 4 . It can be seen from Figure 4 that the weight loss curve can reflect the grafting rate of the modified halloysite nanotubes. The total grafting rate of the modified halloysite nanotubes is about 4%, and the grafting amount of PEI is about 1.1%. Fig. 5 shows the scanning electron micrographs of halloysite nanotubes and PEI modified halloysite nanotubes. The surface of unmodified halloysite nanotubes is smooth and clear, while the surface of halloysite nanotubes modified by coupling agent and PEI is rough, which further proves that PEI can be grafted onto the surface of halloysite nanotubes.
(4)改性埃洛石纳米管与环氧树脂混合制备环氧树脂纳米复合材料：将5g支化型聚乙烯亚胺接枝改性的埃洛石纳米管加入到120g乙醇中，搅拌分散20分钟后，再超声处理60分钟，得到均匀分散的悬浮液。在悬浮液中加入65.5g预热的环氧树脂四缩水甘油基-4,4’-二氨基二苯甲烷(TGDDM)，进一步超声分散40分钟得到均匀分散的混合液；将上述混合液在90℃下搅拌处理5h，真空条件下(0.1MPa)进一步除尽有机溶剂；在得到的混合体系中加入芳香胺类固化剂4,4-二氨基-二苯砜(DDS)共29.5g，于130℃下边加热边搅拌，待DDS完全熔解。将上述混合体系于100℃下真空脱泡除气，然后倒入预热的固化模具中。130℃固化2小时，再于200℃下固化4小时，脱模，即得到含聚乙烯亚胺改性埃洛石纳米管含量为5wt％的环氧树脂基纳米复合材料；而用AC-661改性埃洛石纳米管代替支化型聚乙烯亚胺改性埃洛石纳米管，可以制备AC-661-HNTs含量为5wt％的环氧树脂基纳米复合材料。(4) Modified halloysite nanotubes are mixed with epoxy resin to prepare epoxy resin nanocomposites: 5g branched polyethyleneimine graft modified halloysite nanotubes are added to 120g ethanol, stirred and dispersed After 20 min, an additional 60 min of sonication was performed to obtain a homogeneously dispersed suspension. Add 65.5g preheated epoxy resin tetraglycidyl-4,4'-diaminodiphenylmethane (TGDDM) to the suspension, and further ultrasonically disperse for 40 minutes to obtain a uniformly dispersed mixed solution; Stir at ℃ for 5 hours, and further remove the organic solvent under vacuum conditions (0.1MPa); Stir while heating at ℃ until the DDS is completely melted. The above mixed system was defoamed and degassed under vacuum at 100°C, and then poured into a preheated curing mold. Cured at 130°C for 2 hours, then cured at 200°C for 4 hours, and demoulded to obtain an epoxy resin-based nanocomposite material containing polyethyleneimine-modified halloysite nanotubes with a content of 5 wt%. The modified halloysite nanotubes can replace the branched polyethyleneimine modified halloysite nanotubes, and the epoxy resin-based nanocomposite with AC-661-HNTs content of 5wt% can be prepared.
EP→EP/HNTs→EP/AC-661-HNTs→EP/PEI-AC-661-HNTs当在环氧树脂中依次添加2.3wt％的改性和未改性的HNTs；EP→EP/HNTs→EP/AC-661-HNTs→EP/PEI-AC-661-HNTs When sequentially adding 2.3wt% modified and unmodified HNTs to the epoxy resin;
拉伸强度由纯环氧树脂的72.6MPa，依次增加至73.7MPa，77.3MPa和81.4MPa；The tensile strength increased from 72.6MPa of pure epoxy resin to 73.7MPa, 77.3MPa and 81.4MPa in turn;
拉伸模量由纯环氧树脂的2.74GPa，依次增加至2.94GPa，3.03GPa和3.22GPa。The tensile modulus increased from 2.74GPa of pure epoxy resin to 2.94GPa, 3.03GPa and 3.22GPa in turn.
参照以上步骤可以制备含改性埃洛石纳米管0.2～20wt％的环氧树脂纳米复合材料。The epoxy resin nanocomposite material containing the modified halloysite nanotubes in an amount of 0.2-20wt% can be prepared by referring to the above steps.
实施例4Example 4
(1)埃洛石纳米管的酸化：埃洛石纳米管粒子与2mol/L的硝酸溶液按照1:30的质量比混合，边加热边搅拌；处理10小时后，通过离心处理，加水洗至中性，90℃干燥7小时后即得酸化处理的埃洛石纳米管；(1) Acidification of halloysite nanotubes: the nitric acid solution of halloysite nanotube particles and 2mol/L mixes according to the mass ratio of 1:30, stirs while heating; After processing for 10 hours, by centrifugation, add water washing to Neutral, acidified halloysite nanotubes can be obtained after drying at 90°C for 7 hours;
(2)硅烷偶联剂表面改性埃洛石纳米管：称取酸化埃洛石纳米管，加入70倍质量的环己烷，并继续超声处理45分钟。滴加和酸化埃洛石纳米管质量3倍的γ-缩水甘油醚氧丙基二甲基乙氧基硅烷(AC-662)，80℃下搅拌反应15小时；待反应结束后，过滤、洗涤、干燥，得到表面修饰有环氧基团的埃洛石纳米管；(2) Surface modification of halloysite nanotubes by silane coupling agent: Weigh the acidified halloysite nanotubes, add 70 times the mass of cyclohexane, and continue ultrasonic treatment for 45 minutes. Add dropwise and acidify γ-glycidyl etheroxypropyl dimethylethoxysilane (AC-662) which is 3 times the mass of halloysite nanotubes, and stir and react at 80°C for 15 hours; after the reaction is completed, filter and wash , drying to obtain halloysite nanotubes with epoxy groups on the surface;
(3)支化型聚乙烯亚胺接枝埃洛石纳米管：将步骤(2)中环氧基团修饰的埃洛石纳米管在甲醇中超声分散40分钟，得到均匀分散的悬浮液。向体系中加入环氧基团修饰埃洛石纳米管质量2倍的支化型聚乙烯亚胺(Mw＝1800)，再滴加适量的催化剂KOH溶液。在氩气保护下，加热至70℃下回流，充分搅拌反应36h后冷却至室温；用甲醇重复洗涤6次，85℃下烘干即得支化聚乙烯亚胺改性的埃洛石纳米管；(3) Branched polyethyleneimine grafted halloysite nanotubes: the halloysite nanotubes modified with epoxy groups in step (2) were ultrasonically dispersed in methanol for 40 minutes to obtain a uniformly dispersed suspension. Add branched polyethyleneimine (Mw=1800) twice the mass of halloysite nanotubes modified with epoxy groups to the system, and then add an appropriate amount of catalyst KOH solution dropwise. Under the protection of argon, heat to reflux at 70°C, fully stir the reaction for 36 hours, then cool to room temperature; repeat washing with methanol for 6 times, and dry at 85°C to obtain branched polyethyleneimine-modified halloysite nanotubes ;
(4)改性埃洛石纳米管与环氧树脂混合制备环氧树脂纳米复合材料：将2g支化型聚乙烯亚胺接枝改性的埃洛石纳米管加入到120g三氯甲烷中，搅拌分散15分钟后，再超声处理60分钟，得到均匀分散的悬浮液。在悬浮液中加入57g预热的酚醛环氧树脂F44，行星球磨(250rpm)6小时后得到均匀分散的混合料。将上述混合液在85℃下搅拌处理4h，真空条件下(0.1MPa)进一步除尽有机溶剂。将得到的混合体系将至室温，加入41g酸酐类固化剂(甲基六氢苯酐与N,N-二甲基苄胺的质量比为100:1的混合物)，于85℃下搅拌混合混匀。将上述混合体系于75℃下真空脱泡除气，然后倒入预热的固化模具中。120℃固化1小时，再于160℃下固化2小时。脱模，即得到PEI接枝改性HNTs含量为2wt％的环氧树脂基纳米复合材料。按照上述制备方法，可以制备环氧基改性HNTs含量为2wt％的环氧树脂基纳米复合材料。(4) Modified halloysite nanotubes are mixed with epoxy resin to prepare epoxy resin nanocomposites: 2g branched polyethyleneimine grafted halloysite nanotubes are added to 120g chloroform, After stirring and dispersing for 15 minutes, ultrasonic treatment was performed for 60 minutes to obtain a uniformly dispersed suspension. Add 57g of preheated novolac epoxy resin F44 to the suspension, and obtain a uniformly dispersed mixture after planetary ball milling (250rpm) for 6 hours. The above mixture was stirred at 85° C. for 4 h, and the organic solvent was further removed under vacuum (0.1 MPa). Bring the resulting mixed system to room temperature, add 41g of acid anhydride curing agent (a mixture of methyl hexahydrophthalic anhydride and N,N-dimethylbenzylamine at a mass ratio of 100:1), stir and mix at 85°C . The above mixed system was defoamed and degassed in vacuum at 75°C, and then poured into a preheated curing mold. Cured at 120°C for 1 hour, then cured at 160°C for 2 hours. After demoulding, an epoxy resin-based nanocomposite material with a PEI graft-modified HNTs content of 2 wt % is obtained. According to the above preparation method, an epoxy resin-based nanocomposite material with an epoxy-modified HNTs content of 2 wt % can be prepared.
EP→EP/HNTs→EP/AC-662-HNTs→EP/PEI-AC-662-HNTs当在环氧树脂中依次添加2.3wt％的改性和未改性的HNTs；EP→EP/HNTs→EP/AC-662-HNTs→EP/PEI-AC-662-HNTs When sequentially adding 2.3wt% modified and unmodified HNTs to the epoxy resin;
冲击强度由纯环氧树脂的1.62kJ/m2，依次增加至2.01kJ/m2，2.36kJ/m2和2.52kJ/m2；The impact strength increases from 1.62kJ/m2 of pure epoxy resin to 2.01kJ/m 2, 2.36kJ/m2 and 2.52kJ/m2 in turn;
拉伸强度由纯环氧树脂的67.6MPa，依次增加至70.7MPa，73.5MPa和80.4MPa；The tensile strength increased from 67.6MPa of pure epoxy resin to 70.7MPa, 73.5MPa and 80.4MPa in turn;
拉伸模量由纯环氧树脂的2.94GPa，依次增加至3.14GPa，3.51GPa和3.68GPaThe tensile modulus increased from 2.94GPa of pure epoxy resin to 3.14GPa, 3.51GPa and 3.68GPa in turn
断裂伸长率由2.69％，依次增加至2.62％，2.92％和3.08％。The elongation at break increased from 2.69% to 2.62%, 2.92% and 3.08% in turn.
参照以上步骤可以制备含改性埃洛石纳米管0.2～20wt％的环氧树脂纳米复合材料。The epoxy resin nanocomposite material containing the modified halloysite nanotubes in an amount of 0.2-20wt% can be prepared by referring to the above steps.
实施例5Example 5
(1)埃洛石纳米管的酸化：埃洛石纳米管粒子与食人鱼溶液(浓硫酸和双氧水的体积比7/3)按照1:15的质量比混合，边加热边搅拌。处理1小时后，通过离心处理，加水洗至中性，100℃干燥2小时后即得酸化处理的埃洛石纳米管。(1) Acidification of halloysite nanotubes: halloysite nanotube particles and piranha solution (concentrated sulfuric acid and hydrogen peroxide volume ratio 7/3) were mixed according to the mass ratio of 1:15, and stirred while heating. After being treated for 1 hour, the acidified halloysite nanotubes were obtained by centrifuging, washing with water to neutrality, and drying at 100° C. for 2 hours.
(2)硅烷偶联剂表面改性埃洛石纳米管：称取酸化埃洛石纳米管，加入60倍质量的无水甲苯，并继续超声处理35分钟。滴加和酸化埃洛石纳米管等质量的γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)，120℃下搅拌反应24小时。待反应结束后，过滤、洗涤、干燥，得到表面修饰有环氧基团的埃洛石纳米管(KH560-HNTs)。(2) Surface modification of halloysite nanotubes by silane coupling agent: Weigh the acidified halloysite nanotubes, add 60 times the mass of anhydrous toluene, and continue ultrasonic treatment for 35 minutes. γ-glycidyl etheroxypropyltrimethoxysilane (KH560) was added dropwise and acidified with the same mass of halloysite nanotubes, and stirred at 120° C. for 24 hours. After the reaction is finished, filter, wash, and dry to obtain halloysite nanotubes (KH560-HNTs) with surface-modified epoxy groups.
(3)支化型聚乙烯亚胺接枝埃洛石纳米管：将步骤(2)中环氧基团修饰的埃洛石纳米管在四氢呋喃中超声分散60分钟，得到均匀分散的悬浮液。向体系中加入与环氧基团修饰埃洛石纳米管同质量的支化型聚乙烯亚胺(Mw＝1200)，再滴加适量的催化剂三乙胺。在氮气保护下，加热至75℃下回流，充分搅拌反应24h后冷却至室温。用四氢呋喃和甲醇洗涤，重复3次，80℃下烘干即得支化聚乙烯亚胺改性的埃洛石纳米管((PEI-KH560-HNTs)。(3) Branched polyethyleneimine grafted halloysite nanotubes: ultrasonically disperse the halloysite nanotubes modified with epoxy groups in step (2) in tetrahydrofuran for 60 minutes to obtain a uniformly dispersed suspension. Add branched polyethyleneimine (Mw=1200) of the same mass as the epoxy group-modified halloysite nanotubes into the system, and then add an appropriate amount of catalyst triethylamine dropwise. Under the protection of nitrogen, it was heated to reflux at 75°C, fully stirred for 24 hours and then cooled to room temperature. Washing with tetrahydrofuran and methanol, repeated three times, and drying at 80°C to obtain branched polyethyleneimine-modified halloysite nanotubes ((PEI-KH560-HNTs).
(4)改性埃洛石纳米管与环氧树脂混合制备环氧树脂纳米复合材料：将1g支化型聚乙烯亚胺接枝改性的埃洛石纳米管加入到100g丙酮中，搅拌分散30分钟后，再超声处理60分钟，得到均匀分散的悬浮液。在悬浮液中加入32g预热的环氧树脂EPON828，进一步超声分散60分钟得到均匀分散的混合液。将上述混合液在75℃下搅拌处理3h，真空条件下(0.1MPa)进一步除尽有机溶剂。将得到的混合体系将至室温，加入脂环胺类固化剂3,3-二甲基-4,4-二氨基-二环己基甲烷(DMDC)共计10.6g，于65℃下搅拌混合均匀。将上述混合体系于55℃下真空脱泡除气，然后倒入预热的固化模具中。80℃固化2小时，再于150℃下固化2小时，脱模，即得到PEI-KH560-HNTs含量为2.3wt％的环氧树脂基纳米复合材料。按照上述制备方法，用KH560-HNTs代替PEI-KH560-HNTs，可以制备KH560-HNTs含量为2.3wt％的环氧树脂基纳米复合材料。(4) Modified halloysite nanotubes are mixed with epoxy resin to prepare epoxy resin nanocomposites: add 1 g of branched polyethyleneimine grafted halloysite nanotubes to 100 g of acetone, stir and disperse After 30 min, an additional 60 min of sonication was performed to obtain a homogeneously dispersed suspension. Add 32g of preheated epoxy resin EPON828 to the suspension, and further ultrasonically disperse for 60 minutes to obtain a uniformly dispersed mixed solution. The above mixture was stirred at 75° C. for 3 h, and the organic solvent was further removed under vacuum (0.1 MPa). The resulting mixed system was cooled to room temperature, and a total of 10.6 g of alicyclic amine curing agent 3,3-dimethyl-4,4-diamino-dicyclohexylmethane (DMDC) was added, and stirred and mixed uniformly at 65°C. The above mixed system was defoamed and degassed under vacuum at 55°C, and then poured into a preheated curing mold. Curing at 80° C. for 2 hours, then curing at 150° C. for 2 hours, and demoulding, to obtain an epoxy resin-based nanocomposite material with a PEI-KH560-HNTs content of 2.3 wt%. According to the above preparation method, the epoxy resin-based nanocomposite material with KH560-HNTs content of 2.3 wt% can be prepared by replacing PEI-KH560-HNTs with KH560-HNTs.
参照以上步骤可以制备KH560-HNTs和PEI-KH560-HNTs含量都是5wt％的环氧树脂基纳米复合材料。An epoxy resin-based nanocomposite material with a content of 5 wt% of both KH560-HNTs and PEI-KH560-HNTs can be prepared by referring to the above steps.
实施例6Example 6
(1)埃洛石纳米管的酸化：埃洛石纳米管粒子与3mol/L的硫酸溶液按照1:25的质量比混合，边加热边搅拌。处理20小时后，通过离心处理，加水洗至中性，80℃干燥8小时后即得酸化处理的埃洛石纳米管；(1) Acidification of halloysite nanotubes: Halloysite nanotube particles were mixed with 3mol/L sulfuric acid solution at a mass ratio of 1:25, and stirred while heating. After 20 hours of treatment, centrifuge, wash with water until neutral, and dry at 80°C for 8 hours to obtain acidified halloysite nanotubes;
(2)硅烷偶联剂表面改性埃洛石纳米管：称取酸化埃洛石纳米管，加入25倍质量的乙二醇，并继续超声处理30分钟。滴加和酸化埃洛石纳米管等质量的γ-缩水甘油醚氧丙基甲基二乙氧基硅烷，80℃下搅拌反应48小时。待反应结束后，过滤、洗涤、干燥，得到表面修饰有环氧基团的埃洛石纳米管。(2) Surface modification of halloysite nanotubes by silane coupling agent: Weigh the acidified halloysite nanotubes, add 25 times the mass of ethylene glycol, and continue ultrasonic treatment for 30 minutes. γ-glycidyl etheroxypropylmethyldiethoxysilane of the same mass as the halloysite nanotubes was added dropwise and acidified, and stirred and reacted at 80° C. for 48 hours. After the reaction is finished, filter, wash, and dry to obtain halloysite nanotubes with surface-modified epoxy groups.
(3)支化型聚乙烯亚胺接枝埃洛石纳米管：将步骤(1)中环氧基团修饰的埃洛石纳米管在环己烷中超声分散45分钟，得到均匀分散的悬浮液。向体系中加入环氧基团修饰埃洛石纳米管质量2/3的支化型聚乙烯亚胺(Mw＝25000)，再滴加适量的催化剂三乙胺。在氮气保护下，加热至90℃下回流，充分搅拌反应18h后冷却至室温。用环己烷和甲醇洗涤，重复3次，100℃下烘干即得支化聚乙烯亚胺改性的埃洛石纳米管。(3) Branched polyethyleneimine grafted halloysite nanotubes: ultrasonically disperse the halloysite nanotubes modified by epoxy groups in step (1) in cyclohexane for 45 minutes to obtain a uniformly dispersed suspension liquid. Add branched polyethyleneimine (Mw=25000) which is 2/3 of the mass of halloysite nanotubes modified by epoxy groups into the system, and then add an appropriate amount of catalyst triethylamine dropwise. Under the protection of nitrogen, it was heated to reflux at 90°C, fully stirred for 18 hours and then cooled to room temperature. Washing with cyclohexane and methanol, repeated three times, and drying at 100°C to obtain branched polyethyleneimine-modified halloysite nanotubes.
(4)改性埃洛石纳米管与环氧树脂混合制备环氧树脂纳米复合材料：将1g支化型聚乙烯亚胺接枝改性的埃洛石纳米管加入到80g三氯甲烷中，搅拌分散40分钟后，再超声处理45分钟，得到均匀分散的悬浮液。在悬浮液中加入62.5g脂肪族环氧树脂聚丙二醇二缩水甘油醚(DER732)，高速搅拌分散60分钟得到均匀分散的混合液。将上述混合液在85℃下搅拌处理3h，真空条件下(0.5MPa)进一步除尽有机溶剂。将得到的混合体系将至室温，经过三辊研磨机进一步混合。加入固化剂2-乙基-4甲基咪唑共计3.2g，室温下搅拌混合均匀。将上述混合体系于45℃下真空脱泡除气，然后倒入预热的固化模具中。75℃固化8小时，脱模，即得到PEI接枝改性HNTs含量为1.5wt％的环氧树脂基纳米复合材料。按照上述制备方法，可以制备环氧基修饰HNTs含量为1.5wt％的环氧树脂基纳米复合材料。(4) Modified halloysite nanotubes were mixed with epoxy resin to prepare epoxy resin nanocomposites: 1g branched polyethyleneimine grafted halloysite nanotubes were added to 80g chloroform, After stirring and dispersing for 40 minutes, ultrasonic treatment was performed for 45 minutes to obtain a uniformly dispersed suspension. Add 62.5g of aliphatic epoxy resin polypropylene glycol diglycidyl ether (DER732) to the suspension, stir and disperse at high speed for 60 minutes to obtain a uniformly dispersed mixed solution. The above mixture was stirred at 85° C. for 3 h, and the organic solvent was further removed under vacuum (0.5 MPa). The resulting mixed system was cooled to room temperature, and further mixed by a three-roll mill. Add a total of 3.2 g of curing agent 2-ethyl-4 methylimidazole, stir and mix evenly at room temperature. The above mixed system was defoamed and degassed under vacuum at 45°C, and then poured into a preheated curing mold. Curing at 75° C. for 8 hours, demoulding, and obtaining an epoxy resin-based nanocomposite material with a PEI graft-modified HNTs content of 1.5 wt %. According to the above preparation method, an epoxy resin-based nanocomposite material with an epoxy-modified HNTs content of 1.5 wt % can be prepared.
参照以上步骤可以制备含改性埃洛石纳米管0.2～20wt％的环氧树脂纳米复合材料。The epoxy resin nanocomposite material containing the modified halloysite nanotubes in an amount of 0.2-20wt% can be prepared by referring to the above steps.
实施例7Example 7
(1)埃洛石纳米管的酸化：埃洛石纳米管粒子与甲磺酸按照1:10的质量比混合，搅拌处理2小时后，通过离心处理，洗至中性，100℃干燥3小时后即得酸化处理的埃洛石纳米管。(1) Acidification of halloysite nanotubes: mix halloysite nanotube particles with methanesulfonic acid at a mass ratio of 1:10, stir for 2 hours, wash to neutral by centrifugation, and dry at 100°C for 3 hours Afterwards, acidified halloysite nanotubes are obtained.
(1)硅烷偶联剂表面改性埃洛石纳米管：称取酸化埃洛石纳米管，加入45倍质量的无水甲苯，并继续超声分散处理30分钟。滴加酸化埃洛石纳米管质量40％的γ-缩水甘油醚氧丙基三乙氧基硅烷，120℃下搅拌反应5小时。待反应结束后，过滤、洗涤、干燥，得到表面修饰有环氧基团的埃洛石纳米管。(1) Surface modification of halloysite nanotubes by silane coupling agent: Weigh the acidified halloysite nanotubes, add 45 times the mass of anhydrous toluene, and continue ultrasonic dispersion treatment for 30 minutes. γ-glycidyl etheroxypropyltriethoxysilane with 40% mass of the acidified halloysite nanotubes was added dropwise, and stirred and reacted at 120° C. for 5 hours. After the reaction is finished, filter, wash, and dry to obtain halloysite nanotubes with surface-modified epoxy groups.
(3)支化型聚乙烯亚胺接枝埃洛石纳米管：将步骤(2)中环氧基团修饰的埃洛石纳米管在乙醇中超声分散55分钟，得到均匀分散的悬浮液。向体系中加入和环氧基团修饰埃洛石纳米管等质量的支化型聚乙烯亚胺(Mw＝1800)，再滴加适量的催化剂乙二胺。在氩气保护下，加热至80℃下回流，充分搅拌反应72h后冷却至室温。用乙醇洗涤，重复6次，90℃下烘干即得支化聚乙烯亚胺改性的埃洛石纳米管。(3) Branched polyethyleneimine grafted halloysite nanotubes: the halloysite nanotubes modified with epoxy groups in step (2) were ultrasonically dispersed in ethanol for 55 minutes to obtain a uniformly dispersed suspension. Add branched polyethyleneimine (Mw=1800) of the same quality as the epoxy group-modified halloysite nanotubes to the system, and then add an appropriate amount of catalyst ethylenediamine dropwise. Under the protection of argon, heat to reflux at 80°C, stir the reaction fully for 72h and then cool to room temperature. Wash with ethanol, repeat 6 times, and dry at 90°C to obtain branched polyethyleneimine-modified halloysite nanotubes.
(4)改性埃洛石纳米管与环氧树脂混合制备环氧树脂纳米复合材料：将15g支化型聚乙烯亚胺接枝改性的埃洛石纳米管加入到150g丙酮中，搅拌分散30分钟后，再超声处理60分钟，得到均匀分散的悬浮液。在悬浮液中加入100g脂环族缩水甘油酯三官能度环氧TDE85与E51混合树脂中(质量比3:1)，乳化剪切分散处理60分钟得到均匀分散的混合液。将上述混合液在75℃下搅拌处理2.5h，真空条件下(0.1MPa)进一步除尽有机溶剂。将得到的混合体系将至室温，经过高速搅拌进一步混合。加入酚醛胺固化剂T31共45g，室温下搅拌混合均匀。将上述混合体系于50℃下真空脱泡除气，然后倒入预热的固化模具中。室温固化1小时，再在温度为140℃下固化7小时，即得到含改性埃洛石纳米管9.4wt％的环氧树脂纳米复合材料。(4) Modified halloysite nanotubes are mixed with epoxy resin to prepare epoxy resin nanocomposites: 15g branched polyethyleneimine graft modified halloysite nanotubes are added to 150g acetone, stirred and dispersed After 30 min, an additional 60 min of sonication was performed to obtain a homogeneously dispersed suspension. Add 100g of cycloaliphatic glycidyl ester trifunctional epoxy TDE85 and E51 mixed resin (mass ratio 3:1) to the suspension, and emulsify, shear and disperse for 60 minutes to obtain a uniformly dispersed mixed solution. The above mixture was stirred at 75° C. for 2.5 h, and the organic solvent was further removed under vacuum (0.1 MPa). The resulting mixed system was cooled to room temperature, and further mixed by high-speed stirring. Add a total of 45g of phenalkamine curing agent T31, stir and mix evenly at room temperature. The above mixed system was defoamed and degassed in vacuum at 50°C, and then poured into a preheated curing mold. Curing at room temperature for 1 hour, and then curing at 140° C. for 7 hours to obtain an epoxy resin nanocomposite material containing 9.4 wt % of modified halloysite nanotubes.
参照以上步骤可以制备含改性埃洛石纳米管0.2～20wt％的环氧树脂纳米复合材料。The epoxy resin nanocomposite material containing the modified halloysite nanotubes in an amount of 0.2-20wt% can be prepared by referring to the above steps.
对比例1：未改性埃洛石纳米管和环氧树脂复合Comparative example 1: Composite of unmodified halloysite nanotubes and epoxy resin
取5.3g纯化埃洛石纳米管加入到150g丙酮中，搅拌30分钟后，再经超声处理30分钟配成均匀悬浮液。在悬浮液中加入经预热的75g双酚A环氧树脂EPON828，室温下搅拌混合30分钟制得均匀混合液。将上述混合液于75℃下500转/分钟的转速搅拌2小时，再经真空条件下(0.1MPa)处理得到环氧树脂/埃洛石纳米管母料。按计量比在混合体系中加入的脂环型固化剂3,3-二甲基-4,4-二氨基-二环己基甲烷(DMDC)计25g，与上述环氧树脂/埃洛石纳米管母料混合均匀。将上述反应物置于真空下脱泡除气，后倒入预热的模具中，80℃固化2小时，再在150℃固化2小时，即制得埃洛石纳米管含量为5wt％的环氧树脂基纳米复合材料。依此方法，可以制得不同埃洛石纳米管含量的环氧基纳米复合材料。5.3 g of purified halloysite nanotubes were added to 150 g of acetone, stirred for 30 minutes, and then subjected to ultrasonic treatment for 30 minutes to form a uniform suspension. Add 75g of preheated bisphenol A epoxy resin EPON828 into the suspension, and stir and mix at room temperature for 30 minutes to prepare a homogeneous mixture. The above mixed solution was stirred at 75° C. at 500 rpm for 2 hours, and then treated under vacuum (0.1 MPa) to obtain an epoxy resin/halloysite nanotube masterbatch. The alicyclic curing agent 3,3-dimethyl-4,4-diamino-dicyclohexylmethane (DMDC) added in the mixed system according to the metering ratio is 25g, and the above-mentioned epoxy resin/halloysite nanotube The masterbatch is mixed evenly. Put the above reactant under vacuum for defoaming and degassing, then pour it into a preheated mold, cure at 80°C for 2 hours, and then cure at 150°C for 2 hours to obtain an epoxy resin with a halloysite nanotube content of 5wt%. resin-based nanocomposites. According to this method, epoxy-based nanocomposites with different halloysite nanotube contents can be prepared.
将制得的含有不同含量的改性埃洛石纳米管的环氧树脂纳米复合材料样条进行抛光处理，铣制缺口。简支梁冲击性能测试根据ASTM5942标准，冲击机上选用0.5J的摆锤，冲击速度为2.9m/s。从图6冲击强度随改性和未改性HNTs变化曲线可以看出：含改性HNTs的体系的冲击强度要大于含未改性HNTs的体系。当在环氧树脂中加入2.3wt％的HNTs、KH560-HNTs和PEI-KH560-HNTs后，复合材料的冲击强度分别比纯环氧树脂增加了27.3％、36.4％和80％。加入5wt％改性和未改性HNTs的环氧树脂，其冲击强度比加入2.3wt％改性和未改性HNTs的要低。含2.3wt％的改性和未改性HNTs的环氧树脂复合材料的冲击断面，扫描电镜观察结果如图7所示。图7中显示出未改性埃洛石纳米管在环氧树脂EPON828中分散不均匀，会产生很大的团聚体，成为引发断裂的应力集中点。经过环氧基硅烷KH560改性处理后的埃洛石纳米管在环氧树脂EPON828中分散均匀，虽然也有一定小尺寸的团聚体出现，但与环氧树脂EPON828的界面结合较好，在断面处可以看到断裂而伸出的改性埃洛石纳米管。而经过超支化聚乙烯亚胺的进一步接枝改性，可以看到团聚体基本上消失，PEI-KH560-HNTs在环氧树脂中分散较好，且与环氧树脂有更强的界面结合作用。The epoxy resin nanocomposite material strips containing different contents of modified halloysite nanotubes were polished, and the gaps were milled. The Charpy impact performance test is based on the ASTM5942 standard. A 0.5J pendulum is used on the impact machine, and the impact speed is 2.9m/s. From the change curve of impact strength with modified and unmodified HNTs in Figure 6, it can be seen that the impact strength of the system containing modified HNTs is greater than that of the system containing unmodified HNTs. When 2.3wt% of HNTs, KH560-HNTs, and PEI-KH560-HNTs were added to the epoxy resin, the impact strength of the composites increased by 27.3%, 36.4%, and 80%, respectively, compared with pure epoxy resin. The impact strength of epoxy resin with 5wt% modified and unmodified HNTs was lower than that with 2.3wt% modified and unmodified HNTs. The impact sections of the epoxy resin composites containing 2.3wt% modified and unmodified HNTs are shown in Fig. 7 by SEM. Figure 7 shows that the unmodified halloysite nanotubes are not uniformly dispersed in the epoxy resin EPON828, and large agglomerates will be produced, which will become the stress concentration points that cause fracture. The halloysite nanotubes modified by epoxy silane KH560 are uniformly dispersed in the epoxy resin EPON828. Although there are certain small-sized agglomerates, the interface with the epoxy resin EPON828 is well bonded. Modified halloysite nanotubes protruding from fracture can be seen. After further grafting modification of hyperbranched polyethyleneimine, it can be seen that the agglomerates basically disappear, PEI-KH560-HNTs are well dispersed in epoxy resin, and have stronger interfacial bonding with epoxy resin .
对比例2：Comparative example 2:
配方和制备方法同实施例1，区别在于，省略步骤1中的酸活化处理HNTs，以下使用未酸化的埃洛石纳米管环氧化，以及使用聚乙烯亚胺接枝改性埃洛石纳米管。得到的材料的参数对比如图8所示。The formula and preparation method are the same as in Example 1, the difference is that the acid activation treatment of HNTs in step 1 is omitted, and the unacidified halloysite nanotubes are used for epoxidation, and polyethyleneimine is used to graft and modify halloysite nanotubes. Tube. The parameter comparison of the obtained materials is shown in Fig. 8.
对比例3：Comparative example 3:
配方和制备方法同实施例1，区别在于，省略使用支化聚乙烯亚胺改性的步骤。对HNTs使用盐酸处理后，再通过带环氧基团的硅烷偶联剂进行表面修饰，环氧树脂纳米复合材料的制备同实施例1。得到的材料的参数对比如图9所示。The formula and preparation method are the same as those in Example 1, except that the step of modifying with branched polyethyleneimine is omitted. After the HNTs were treated with hydrochloric acid, the surface was modified by a silane coupling agent with epoxy groups. The preparation of the epoxy resin nanocomposite was the same as in Example 1. The parameter comparison of the obtained materials is shown in Fig. 9 .
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