CN109749131A - Modified halloysite nanotubes and preparation method thereof and epoxy resin nano composites and its application - Google Patents

Abstract

The present invention relates to epoxy resin nano composites field, a kind of modified halloysite nanotubes and preparation method thereof and epoxy resin nano composites and its application are disclosed.The modification halloysite nanotubes include halloysite nanotubes, be in turn attached to halloysite nanotubes surface the first shell and the second shell, first shell is formed by the mixed liquor containing the first modifying agent by copolycondensation, first modifying agent is ethyl orthosilicate and amino silane, second shell is formed with active end group liquid nitrile rubber by graft reaction by the first shell, active end group liquid nitrile rubber is carboxyl-terminated liguid nitrile rubber and/or epoxy terminated liquid nitrile rubber, the pure and mild water of saturated fat for being also 1-3 containing carbon atom number in mixed liquor.Modified halloysite nanotubes can effectively improve the mechanical property of epoxy resin nano composites.

Description

Modified halloysite nanotubes and preparation method thereof and epoxy resin nano composites and It is applied

Technical field

The present invention relates to epoxy resin nano composites technical fields, and in particular, to a kind of modified galapectite nanometer Pipe, a kind of preparation method of modified halloysite nanotubes, a kind of modification halloysite nanotubes being prepared by this method are a kind of The application of epoxy resin nano composites and the epoxy resin nano composites.

Background technique

Epoxy resin because its excellent in mechanical performance, cohesive force is strong, shrinking percentage is low, good chemical stability be widely applied In fields such as aerospace, electronic apparatus, civil construction, automobile mechanicals.But with the development of science and technology, epoxy resin application The continuous extension in field, more stringent requirements are proposed for comprehensive mechanical property of the people to epoxy resin.

Halloysite nanotubes (HNTs) are a kind of natural tubulose nano materials of cheap rich reserves.General pipe outside diameter 40~100nm, length are about 0.2~2 μm.HNTs is that similar kaolinic aluminosilicate lamella crimps, and molecular formula is Al₂SiO₅(OH)₄·nH₂O (n=0 or 2).The outer surface of HNTs is mainly made of Si-O-Si key, and inner wall is then mainly aluminium hydroxyl Base, there are a small amount of silicon/aluminium hydroxyls in nanotube surface and end face.Since HNTs has longer draw ratio, high-strength and high-modulus is The novel nano filler of modified epoxy.Although the interface cohesion of HNTs and epoxy resin is preferable, but still unavoidably go out Existing 5~10 μm of aggregate, this is unfavorable to High performance nanometer composite material is obtained.It is generally necessary to HNTs is surface-treated, Improve HNTs dispersion and the interface cohesion with matrix.

Nano particle is used further to the method that polymer is simple general-purpose after silane coupling agent is handled.Silane-modified rear and ring The problem of oxygen resin compounded, the HNTs that do not have clear improvement reunites.Deng et al. (Composites Science and Technology, 2009,69,2497-2505) use amino silane N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane (Z-6020) with epoxy resin ball milling dispersion mixing after processing HNTs, not more for the mechanical property for the composite material being prepared It is few to improve, also, it is observed that there are still a certain amount of HNTs reunions by section.Vahedi and Pasbakhsh (Polymer Testing, 2014,39,101-114) activates gamma-aminopropyl-triethoxy-silane (APTES) modified aqueous slkali HNTs ultrasonic disperse in epoxy resin, although the impact strength of composite material can be improved in modification HNTs a small amount of addition, But the tensile strength of composite material can be reduced, while the impact value fluctuation of composite material is larger, illustrates the equal of composite material One property is relatively poor, still unavoidably occurs biggish aggregate, nano particle and basal body interface knot in nanocomposite Merging is not improved a lot, few this is mainly due to the hydroxy radical content on the surface HNTs and be unevenly distributed, so that being grafted on Ai Luo The silane of stone nanotube surface is relatively fewer and uneven.In addition, conventionally used hydrogen peroxide, acid solution or alkaline solution are living Change processing HNTs and is difficult fundamentally to improve silane on the surface HNTs although can be improved Silane Grafted amount to a certain extent The uniformity of grafting amount and graft surface active groups, and then influence the interface cohesion between nanotube and resin matrix.And And it is activated the structure for destroying nanotube to a certain extent, the intensity of nanotube itself is necessarily also reduced, thus one Determine the reinforcement ability that halloysite nanotubes are had lost in degree to matrix.

For modified by nano particles epoxy-resin systems, interface phase size and boundary strength play weight to activeness and quietness resin The effect wanted.By coupling agent surface-modified nano particles, although can improve to a certain extent particle dispersion and with matrix Interface cohesion, but interface phase size is limited, is unfavorable for more energies to failure that dissipate.Silane coupling agent is only relied on to halloysite nanotubes Surface treatment, is difficult to further increase the comprehensive mechanical property of epoxy resin.

Therefore it is urgent to provide a kind of nanocomposites that new modification halloysite nanotubes and epoxy resin are formed.

Summary of the invention

It is nano combined the purpose of the invention is to overcome halloysite nanotubes in the prior art and epoxy resin to be formed Material has that mechanical property is poor, provides a kind of modified halloysite nanotubes, a kind of system of modified halloysite nanotubes Preparation Method, a kind of modification halloysite nanotubes being prepared by this method and a kind of epoxy resin nano composites and its Using.Modified halloysite nanotubes provided by the invention can effectively improve the mechanical property of epoxy resin nano composites Can, specifically, it can be improved the toughness, mechanical strength and stretch modulus of epoxy resin nano composites.

To achieve the goals above, the first aspect of the present invention provides a kind of modified halloysite nanotubes, wherein described Modified halloysite nanotubes include halloysite nanotubes, be in turn attached to halloysite nanotubes surface the first shell and second Shell, first shell are formed by the mixed solution containing the first modifying agent by copolycondensation, first modifying agent For ethyl orthosilicate and amino silane, second shell is by first shell with active end group liquid nitrile rubber by connecing Branch reaction is formed, wherein the active end group liquid nitrile rubber is carboxyl-terminated liguid nitrile rubber and/or epoxy terminated liquid Nitrile rubber, the pure and mild water of saturated fat for being also 1-3 containing carbon atom number in the mixed solution.

The present inventor has found after study, by the copolycondensation of ethyl orthosilicate and amino silane and specific activity End group liquid nitrile rubber (carboxyl-terminated liguid nitrile rubber and/or epoxy terminated liquid nitrile rubber) modification successively introduces angstrom Lip river During the surface of stone nanotube is modified, the nanocomposite formed by modification halloysite nanotubes and the epoxy resin can be improved Mechanical property.This may be because are as follows: the introducing of ethyl orthosilicate has further activated the surface of halloysite nanotubes, improves Amino silane halloysite nanotubes surface grafting efficiency so that the active group on modified halloysite nanotubes surface increases It is more.The copolycondensation of ethyl orthosilicate and amino silane makes in halloysite nanotubes surface grafting containing a large amount of activity hydroxies and ammonia The hard grafting nitride layer of base, and amino therein has uniform topological structure；Then, active end group butyronitrile is made by covalent bonding Rubber successfully connects on the surface through ethyl orthosilicate and amino silane modified halloysite nanotubes (that is, being grafted nitride layer firmly) Branch active soft rubber layer (rubber shell, that is, soft grafting nitride layer), it is ensured that halloysite nanotubes and matrix resin (epoxy resin) Between biggish interface phase size, can more store elastic energy.Hard grafting nitride layer and soft grafting nitride layer can be actively engaged in Curing reaction between epoxy resin greatly improves the interface binding force between halloysite nanotubes and matrix, is conducive to sufficiently Halloysite nanotubes are played to the reinforcement of epoxy resin and toughening effect (stress effectively transmits).

In addition, the modification simple to operation, and obtaining of the preparation method of modified halloysite nanotubes provided by the invention Halloysite nanotubes are easily isolated purifying.Meanwhile the modification halloysite nanotubes can be dispersed in by simple method In epoxy resin-base, processing technology dependence is reduced.

According to the second aspect of the invention, the present invention provides a kind of preparation method of modified halloysite nanotubes, the party Method the following steps are included:

(1) in the presence of the mixed solution containing the pure and mild water of saturated fat that carbon atom number is 1-3, pass through ethyl orthosilicate Surface is carried out to halloysite nanotubes with the copolycondensation of amino silane to be modified, and obtains the modified halloysite nanotubes in surface；

(2) the modified halloysite nanotubes in the surface that step (1) obtains are contacted to form suspension with dispersing agent, it will be described Suspension and active end group liquid nitrile rubber carry out graft reaction, and the active end group liquid nitrile rubber is carboxyl end group liquid Nitrile rubber and/or epoxy terminated liquid nitrile rubber.

According to the third aspect of the invention we, the present invention provides modified galapectite nanometers prepared by the above method Pipe.

According to the fourth aspect of the invention, the present invention provides a kind of epoxy resin nano composites, the asphalt mixtures modified by epoxy resin Resin nano composite material is formed by being modified halloysite nanotubes and the cured reaction of epoxy resin, wherein the modified galapectite Nanotube is above-mentioned modified halloysite nanotubes.

According to the fifth aspect of the invention, the present invention also provides the epoxy resin nano composites in adhesive And/or the application in carbon fibre composite.

Modified halloysite nanotubes provided by the invention can effectively improve the mechanics of epoxy resin nano composites Performance specifically can be improved the toughness, mechanical strength and stretch modulus of epoxy resin nano composites.

Detailed description of the invention

Fig. 1 is the transmission electron microscope figure of the unmodified halloysite nanotubes in embodiment 1；

Fig. 2 is the transmission electron microscope figure of the halloysite nanotubes of the modification in embodiment 1；

Fig. 3 is the halloysite nanotubes transmission electron microscope figure of the modification of embodiment 2；

Fig. 4 is the scanning electron microscope (SEM) photograph of the halloysite nanotubes of the modification of embodiment 3.

Specific embodiment

The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.

According to the first aspect of the invention, the present invention provides a kind of modified halloysite nanotubes, wherein the modification angstrom Lip river stone nanotube include halloysite nanotubes, be in turn attached to halloysite nanotubes surface the first shell and the second shell, First shell is formed by the mixed solution containing the first modifying agent by copolycondensation, and first modifying agent is positive silicon Acetoacetic ester and amino silane, second shell pass through graft reaction by first shell and active end group liquid nitrile rubber It is formed, wherein the active end group liquid nitrile rubber is carboxyl-terminated liguid nitrile rubber and/or epoxy terminated liquid butyronitrile rubber Glue, the pure and mild water of saturated fat for being also 1-3 containing carbon atom number in the mixed solution.

According to the present invention, ethyl orthosilicate and amino silane are modified the surface of halloysite nanotubes, form the One shell (that is, hard grafting nitride layer), ethyl orthosilicate and amino silane primarily serve the ammonia for increasing halloysite nanotubes surface The effect of the quantity of base and hydroxyl group.Galapectite can be effectively controlled by the dosage of allotment ethyl orthosilicate and amino silane to receive The amount of the active function groups of nanotube surface.Generally, the halloysite nanotubes and amino silane weight ratio can be 1:0.03- 0.5, preferably 1:0.03-0.15.

According to the present invention, generally, the weight ratio of the ethyl orthosilicate and amino silane can be 1:0.1-8, preferably For 1:0.2-6.

According to the present invention, in order to enable reaction is hydrolyzed in ethyl orthosilicate, to be conducive to increase halloysite nanotubes The active group amount on surface, the pure and mild water of saturated fat for being also 1-3 containing carbon atom number in the mixed liquor are generally, described The weight ratio of halloysite nanotubes and the mixed solution can be 1:15-300, preferably 1:20-120.

According to the present invention, the weight ratio for the pure and mild water of saturated fat that the carbon atom number is 1-3 can be (80:20)- (99:1)。

According to the present invention, the saturated fatty alcohol that the carbon atom number is 1-3 is in methanol, ethyl alcohol, normal propyl alcohol and isopropanol At least one.Under preferable case, the saturated fatty alcohol is ethyl alcohol.

According to the present invention, the first shell and active end group liquid nitrile rubber are subjected to graft reaction, form the second shell (that is, soft grafting nitride layer), active end group liquid nitrile rubber primarily serves the interface phase size that increase is contacted with epoxy resin, With more energy that dissipate.Generally, the halloysite nanotubes and the weight ratio of active end group liquid nitrile rubber can be 1:0.1-10 preferably 1:0.2-5.

According to the present invention, the reaction condition of the copolycondensation is can be realized the active group for increasing halloysite nanotubes surface Subject to group's quantity, generally, reaction temperature can be 50-90 DEG C, preferably 60-80 DEG C.Reaction time can be according to reaction temperature Degree is reasonably selected, and generally, the time of reaction can be 0.5-5h, preferably 1-4.5h.

According to the present invention, the condition of the graft reaction with can be formed on first shell soft grafting nitride layer from And play the role of subject to the interface phase size that increase is contacted with epoxy resin, generally, reaction temperature can be 50-150 DEG C, Preferably 80-140 DEG C.Reaction time can reasonably be selected according to reaction temperature, and generally, the time of reaction can be 2-48h, preferably 3-24h.

According to the present invention, amino silane is can play to the modified quantity for increasing active group in halloysite nanotubes surface Subject to, generally, the amino silane is selected from gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, N- (β-ammonia second Base)-γ-aminopropyltriethoxy dimethoxysilane, N- (β-aminoethyl)-γ-aminopropyltriethoxy diethoxy silane, γ-ammonia third One in ylmethyl diethoxy silane, γ-aminopropyltriethoxy dimethoxysilane and γ-aminopropyl ethyoxyl dimethylsilane Kind is a variety of, preferably gamma-aminopropyl-triethoxy-silane, N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane and N- At least one of (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane.

According to the present invention, the active end group liquid nitrile rubber on the first shell can form soft grafting nitride layer To play the role of subject to the interface phase size that increase is contacted with epoxy resin, generally, the active end group liquid butyronitrile The number-average molecular weight of rubber can be 1500-5000, preferably 3000-4500；Using the total amount of active end group nitrile rubber as base Standard, the content of derived from propylene nitrile structural unit can be 10-40 weight %, preferably 15-30 weight %；The active end group Viscosity at 27 DEG C of nitrile rubber is 20-500Pas, preferably 40-350Pas.

It is further preferred that the active end group liquid nitrile rubber is carboxyl-terminated liguid nitrile rubber, carboxyl equivalent is 0.04-0.08phr；The active end group liquid nitrile rubber is epoxy terminated liquid nitrile rubber, epoxide equivalent 2000- 3000g/eq。

According to the present invention, the halloysite nanotubes can for it is existing it is various can be used in improve epoxide resin nano material The halloysite nanotubes of the mechanical property of material, and it can be commercially available, for example, can be for purchased from Xingtai origin clay The halloysite nanotubes of Co., Ltd.The present invention is not particularly limited the size of the halloysite nanotubes, as long as can It forms halloysite nanotubes in mixed liquor to disperse well, under preferable case, the outer diameter of halloysite nanotubes is 40- 150nm, internal diameter 10-25nm, length 100-2000nm.

According to the second aspect of the invention, the present invention provides a kind of preparation method of modified halloysite nanotubes, this method The following steps are included:

(1) in the presence of the mixed solution containing the pure and mild water of saturated fat that carbon atom number is 1-3, pass through ethyl orthosilicate Surface is carried out to halloysite nanotubes with the copolycondensation of amino silane to be modified, and obtains the modified halloysite nanotubes in surface；

(2) halloysite nanotubes by the surface treatment that step (1) obtains contact to form suspension with dispersing agent, will be described Suspension and active end group liquid nitrile rubber carry out graft reaction, and the active end group liquid nitrile rubber is carboxyl end group liquid Nitrile rubber and/or epoxy terminated liquid nitrile rubber.

According to the method for the present invention, ethyl orthosilicate and amino silane are modified the surface of halloysite nanotubes, It is formed the first shell (that is, hard grafting nitride layer), ethyl orthosilicate and amino silane primarily serve and increase halloysite nanotubes table The active group amino in face and the effect of hydroxyl quantity.It can be effectively controlled by the dosage of allotment ethyl orthosilicate and amino silane The amount of the active function groups on halloysite nanotubes surface.The dosage of the ethyl orthosilicate and amino silane and above description one It causes, details are not described herein.

According to the present invention, in order to enable reaction is hydrolyzed in ethyl orthosilicate, to be conducive to increase halloysite nanotubes The active group amount on surface, the copolycondensation is in the mixed solution containing the pure and mild water of saturated fat that carbon atom number is 1-3 In the presence of carry out, the dosage of the pure and mild water of the mixed solution, saturated fat is consistent with above description, and details are not described herein.

According to the method for the present invention, the saturated fatty alcohol plays the role of balancing hydrolysis, and the carbon atom number is The saturated fatty alcohol of 1-3 is at least one of methanol, ethyl alcohol, normal propyl alcohol and isopropanol, preferably ethyl alcohol.

According to the method for the present invention, the type of the amino silane, the selection of halloysite nanotubes are consistent with above description, Details are not described herein.

According to the method for the present invention, the reaction condition of the copolycondensation increases halloysite nanotubes surface can be realized Subject to active group quantity.The reaction condition of the copolycondensation is consistent with above description, and details are not described herein.

According to the method for the present invention, in order to be more advantageous to copolycondensation, under preferable case, the method includes by angstrom Lip river Stone nanotube is added to dispersion mixing in the mixed solution containing the pure and mild water of saturated fat that carbon atom number is 1-3, mixed to gained It closes species and ethyl orthosilicate and amino silane progress copolycondensation is added with modified to halloysite nanotubes progress surface.It is described Mixed condition, which is subject to, can be dispersed in halloysite nanotubes mixed liquor, and generally, the incorporation time can be 0.5-5h, mixed temperature can be 50-90 DEG C.

According to the method for the present invention, the influence in order to avoid unreacted reagent to subsequent reactions under preferable case, is also wrapped Include the step of being filtered and washed the halloysite nanotubes that the surface that step (1) obtains is modified.The washing examination that washing uses Agent is the mixed solvent for the pure and mild water composition of saturated fat that carbon atom number is 1-3, and the saturated fatty alcohol is preferably ethyl alcohol.Saturation The proportion of fatty alcohol and water is consistent with above description.

According to the method for the present invention, surface step (1) obtained modified halloysite nanotubes and dispersing agent contact shape At uniform suspension.The dispersing agent is evenly dispersed simultaneously with the modified halloysite nanotubes in the surface that step (1) can be made to obtain With active end group liquid nitrile rubber carry out graft reaction subject to, generally, the dispersing agent be benzene,toluene,xylene and N, Dinethylformamide one of or it is a variety of.

According to the method for the present invention, the dosage of the dispersing agent, which is subject to, plays the role of dispersion, generally, described angstrom of Lip river The weight ratio of stone nanotube and dispersing agent can be 1:15-300, preferably 1:20-120.

According to the method for the present invention, obtained suspension and active end group liquid nitrile rubber are subjected to graft reaction, shape At the second shell (that is, soft grafting nitride layer), the interface phase size that increase is contacted with epoxy resin is primarily served, it is more to dissipate Energy.The dosage of the active end group liquid nitrile rubber is consistent with above description, and details are not described herein.

According to the method for the present invention, the selection of the performance parameter of the active end group liquid butyl rubber and above description one It causes, is not repeating herein.

According to the method for the present invention, the condition of the graft reaction is to be capable of forming soft grafting nitride layer to play increase Subject to the effect of the interface phase size contacted with epoxy resin.The condition of the graft reaction is consistent with above description, herein not It repeats again.

In the case of with the method for the invention it is preferred to, in order to improve grafting efficiency, the graft reaction is deposited auxiliary agent A In lower progress, the auxiliary agent A is catalyst and/or co-catalyst, and the catalyst is triethylamine, trimethylamine, quinoline, dimethyl One of Bian amine, pyridine, picoline, 2,6- dimethylamino naphthyridine and N- methylmorpholine are a variety of；The co-catalyst For N, N'- diisopropylcarbodiimide and/or N, N'- dicyclohexylcarbodiimide.

According to the method for the present invention, the dosage of the auxiliary agent, which is subject to play, improves grafting efficiency, generally, described The weight ratio of halloysite nanotubes and auxiliary agent A can be 1:0.005-0.1, preferably 1:0.01-0.1.The auxiliary agent A is catalysis The dosage of agent and co-catalyst, the catalyst and co-catalyst can be 1:3-20.

In the case of with the method for the invention it is preferred to, the method also includes the mixture for obtaining graft reaction progress Washing and dry step.Wash the reagent that uses for benzene,toluene,xylene and N,N-dimethylformamide one of or It is a variety of.Dry temperature is 75-150 DEG C, and the dry time can reasonably be selected according to dry temperature.

According to the third aspect of the invention we, the present invention also provides a kind of modification galapectites that the above method is prepared to receive Mitron.

According to the fourth aspect of the invention, the present invention also provides a kind of epoxy resin nano composites, the epoxies Nanocomposite is formed by being modified halloysite nanotubes and the cured reaction of epoxy resin, wherein the modification angstrom Lip river Stone nanotube is above-mentioned modification halloysite nanotubes.

According to the present invention, the dosage of the modified halloysite nanotubes is can be realized the mechanical property for improving epoxy resin Subject to, generally, the weight ratio of the modified halloysite nanotubes and epoxy resin can be 0.2-25:100, preferably 0.5- 15:100.

According to the present invention, the epoxy resin can be epoxy resin commonly used in the art, such as bisphenol-A system asphalt mixtures modified by epoxy resin Rouge, hydrogenated bisphenol A epoxy resin, novolac epoxy resin, bisphenol S system epoxy resin, Bisphenol F system epoxy resin, aliphatic are shunk Glycerol ether resin, brominated epoxy resin, glycidyl ester type epoxy resin, aminoepoxy resin, cycloaliphatic epoxy resin, epoxy Change at least one of polyolefin, organosilicon epoxy resin and acrylic compounds epoxy resin, preferably bisphenol-A system epoxy resin And/or novolac epoxy resin.

In the case of, according to the invention it is preferred to, epoxy resin and modified halloysite nanotubes are consolidated again after mixing Change reaction.The mixed condition includes: that the temperature of mixing is 25-100 DEG C, and the mixed time can be 2-12 hours.

According to the present invention, the curing reaction carries out in the presence of curing agent and/or curing accelerator, the curing agent For alicyclic ring amine curing agent, acid anhydride type curing agent, aromatic amine curing agent, tertiary amines curing agent, fatty amines curing agent, imidazoles At least one of class curing agent, polyamide-based curing agent, polyether amine curing agent and dicyandiamide class curing agent；The solidification promotees It is tertiary amines curing accelerator, imidazoles curing accelerator, quaternary ammonium salt curing accelerator, organic phosphates solidification promotion into agent At least one of agent, substituted urea class curing accelerator and boron trifluoride amine complex.

According to the present invention, the dosage of the curing agent and curing accelerator generates epoxide resin nano to be cured reaction Subject to composite material, generally, the weight ratio of the curing agent and epoxy resin can be 3-80:100, preferably 5-72: 100.The dosage of the curing accelerator can be adjusted according to the dosage of curing agent, generally, the curing accelerator with The weight ratio of curing agent can be 1-20:100, preferably 3-15:100.Curing accelerator and curing agent can be distinguished by dosage.

According to the present invention, the condition of the curing reaction can be reasonably adjusted according to the curing agent used, generally, The condition of the curing reaction includes: that the temperature of reaction is 50-200 DEG C.Curing time temperature is according to different epoxy resin and admittedly Depending on agent type, generally, the cured time can be 1-20h.For example, the curing reaction may include successively carrying out Two stages, the condition of the curing reaction of first stage include: that the temperature of reaction is 50-130 DEG C, and the time of reaction is 1-5h； The condition of the solid reaction of second stage includes: that the temperature of reaction is 110-200 DEG C, and the time of reaction is 2-12h.

According to the present invention, on the basis of the total amount of the epoxy resin nano composites, the modified galapectite nanometer The content of pipe can be 0.2-20wt%.

According to the fifth aspect of the invention, the present invention also provides epoxy resin nano composites adhesive and/ Or the application in carbon fibre composite.Epoxy resin nano composites provided by the invention can be in automobile, electronics, function It is used in the fields such as material, aerospace as adhesive and/or carbon fibre composite.

The present invention will be described in detail by way of examples below.

In following embodiment and comparative example:

(1) scanning electron microscope (SEM) characterizes:

Sample is cut into 0.5cm × 0.5cm size, is sticked on sample stage with carbonaceous conductive glue, and with carbonaceous conductive glue The surface of sample is connect with sample stage.Sample is observed using the S4800 type field emission scanning electron microscope of Hitachi company Pattern, operating voltage 10kV.

(2) transmission electron microscope characterization (TEM) characterization:

Sample size: weighing appropriate amount of sample ultrasonic disperse in ethanol solution, is then coated uniformly on copper mesh surface and true Sky is dry.Using the JEM-2200FS transmission electron microscope observation sample topography of JEOL company, acceleration voltage 200kV.

(3) notch impact strength that epoxy resin nano composites are measured according to standard ISO179, according to ISO527-1 Measuring the tensile properties of epoxy resin nano composites, (including notch impact strength, tensile strength, stretch modulus, fracture are stretched Long rate)

(4) halloysite nanotubes: being purchased from Xingtai origin clay company, outer diameter 50nm, internal diameter 15-20nm, and length is 100-1000nm。

Carboxyl-terminated liguid nitrile rubber is purchased from Shenzhen Jia Dida new material Science and Technology Ltd., and number-average molecular weight is 3400；On the basis of the total amount of pendant carboxylic group nitrile rubber, the content of derived from propylene nitrile structural unit is 21.5%, and hydroxyl is worked as Measure 0.07phr；27 DEG C of viscosity of the nbr carboxyl terminal is 350Pas.

Epoxy terminated liquid nitrile rubber is purchased from Shenzhen Jia Dida new material Science and Technology Ltd., and number-average molecular weight is 3300；On the basis of the total amount of pendant carboxylic group nitrile rubber, the content of derived from propylene nitrile structural unit is 26%, epoxide equivalent For 2000g/eq；27 DEG C of viscosity of the epoxy terminated nitrile rubber is 40Pas.

Epoxy resin used in following embodiment and comparative example, ethyl orthosilicate, amino silane and curing agent are all from It is commercially available.

Embodiment 1-5 is multiple for illustrating modified halloysite nanotubes provided by the invention and preparation method thereof and epoxy nano Condensation material.

Embodiment 1

(1) at 60 DEG C, mixed liquor (ethyl alcohol and water that the second alcohol and water of 1g halloysite nanotubes particle and 20g are formed Weight ratio be 99:1) be stirred 2h to evenly dispersed, ethyl orthosilicate and gamma-aminopropyl-triethoxy-silane are added to (halloysite nanotubes: the weight ratio of ethyl orthosilicate and gamma-aminopropyl-triethoxy-silane in the mixture of gained alcohol water dispersion For 1:0.025:0.125).It filters after gained mixed system is stirred to react 3h at 60 DEG C, and is formed with above-mentioned second alcohol and water Mixed liquor wash for 5 times or more, remove unreacting reagent, obtain the modified halloysite nanotubes in surface；

(2) the modified halloysite nanotubes in the surface that step (1) obtains are dispersed in the N of 25g, N- dimethyl formyl Form suspension in amine (DMF), the epoxy terminated liquid nitrile rubber (ETBN) of 4g be added in gained suspension, then plus The triethylamine for entering 0.1g is stirred to react 3h at 130 DEG C；Mixture 5 times or more washed with DMF；It is incited somebody to action at 145 DEG C To mixture be dried, obtain modified halloysite nanotubes ETBN-co-HNTs；

(3) mechanical mixing, at 65 DEG C, the halloysite nanotubes for the modification that 4.11g step (2) is obtained are used (ETBN-co-HNTs) it is added in the epoxy resin ON828 of 100g, is stirred 6h under conditions of revolving speed is 2000rpm To uniformly it is bright.The alicyclic ring amine curing agent 3,3- dimethyl -4,4- diamino of 33g-dicyclohexyl methyl hydride (DMDC) is added Into resulting mixed system, by above-mentioned mixed system, the vacuum defoamation degasification after mixing evenly at 60 DEG C, then mixes gained Object is closed to pour into the curing mold of preheating.It successively carries out the solidification process in two stages: solidifying 2 hours at 80 DEG C, then at 150 DEG C Lower solidification 2 hours, demoulding obtain epoxy resin nano composites E1 (EPON828/ETBN-co-HNTs), wherein according to object Expect that inventory calculates, on the basis of the total amount of resulting epoxy resin nano composites, the content of modified halloysite nanotubes For 3wt%.

Obtained epoxy resin nano composites E1 is carried out to the measurement of mechanical property, measurement result is referring to table 1.It will not Modified halloysite nanotubes and modified halloysite nanotubes carry out TEM measurement, as shown in Fig. 2, the surface shape of modified HNTs At nano projection, and irregular boundary layer is formed, can inhibit crack propagation in this way, it is multiple preferably to improve epoxide resin nano The toughness of condensation material.

Comparative example 1

Epoxide resin material is prepared using the method for embodiment 1, unlike, without step (1) and step (2), only Epoxy resin ON828 is carried out to the curing schedule of step (3), the specific method is as follows:

Alicyclic ring amine curing agent 3,3- dimethyl -4,4- diamino-dicyclohexyl methyl hydride (DMDC) of 33g is added to In the epoxy resin ON828 of 100g, after mixing evenly, then the vacuum defoamation degasification at 60 DEG C is poured into gained mixture In the curing mold of preheating.It successively carries out the solidification process in two stages: solidifying 2 hours at 80 DEG C, solidify 2 at 150 DEG C Hour, it demoulds to get cured epoxide resin material D1 is arrived.Mechanics performance determining is carried out, measurement result is shown in Table 1.

Comparative example 2

Epoxy resin nano composites are prepared using the method for embodiment 1, unlike, not to halloysite nanotubes into The modification of row step (1) and step (2), but the unmodified halloysite nanotubes particle of 4.11g is replaced into ETBN-co- HNTs is directly mixed and is solidified with epoxy resin, i.e. progress step (3).

Available epoxy resin/unmodified halloysite nanotubes nanocomposite D2 (EPON828/HNTs), with On the basis of the total amount of resulting epoxy resin nano composites, the content of modified halloysite nanotubes is 3wt%.Carry out mechanics The measurement of performance, measurement result are shown in Table 1.

Comparative example 3

Epoxy resin nano composites are prepared using the method for embodiment 1, unlike, not to halloysite nanotubes into The modification of row step (2), but directly will mix and solidify with epoxy resin by step (1) modified halloysite nanotubes, Specific method:

(1) at 60 DEG C, mixed liquor (ethyl alcohol and water that the second alcohol and water of 1g halloysite nanotubes particle and 20g are formed Mass ratio 99:1) be stirred 2h to evenly dispersed, ethyl orthosilicate and gamma-aminopropyl-triethoxy-silane are added to institute (halloysite nanotubes: the weight ratio of ethyl orthosilicate and gamma-aminopropyl-triethoxy-silane is in the mixture of alcohol water dispersion 1:0.025:0.125).It is filtered after gained mixed system is stirred to react 3h at 60 DEG C, and formed with above-mentioned second alcohol and water Mixed liquor washing 5 times or more, to remove unreacting reagent, obtain the modified halloysite nanotubes in surface；

(2) mechanical mixing is used, the modified halloysite nanotubes in the surface for 4.11g step (1) being obtained at 65 DEG C Be added in the epoxy resin ON828 of 100g, revolving speed be 2000rpm under conditions of be stirred 6h to uniformly it is bright.It will Resulting mixed system is added in 33g alicyclic ring amine curing agent 3,3- dimethyl -4,4- diamino-dicyclohexyl methyl hydride (DMDC), The vacuum outgas after mixing evenly at 60 DEG C after mixing evenly, then pours into gained mixture in the curing mold of preheating.According to The secondary solidification process for carrying out two stages: 80 DEG C solidify 2 hours, solidify 2 hours at 150 DEG C, demould to get asphalt mixtures modified by epoxy resin is arrived Resin nano composite material D3 (EPON828/co-HNTs), wherein calculated according to material amount, received with resulting epoxy resin On the basis of the total amount of nano composite material, the content of modified halloysite nanotubes is 3wt%.Carry out the measurement of mechanical property, measurement As a result referring to table 1.

Table 1

Embodiment 2

(1) at 80 DEG C, mixed liquor (ethyl alcohol and water that the second alcohol and water of 1g halloysite nanotubes particle and 100g are formed Weight ratio be 8:2) be stirred 0.5h to evenly dispersed, by three second of ethyl orthosilicate and N- (β-aminoethyl)-γ-aminopropyl Oxysilane is added in the mixture of alcohol water dispersion (halloysite nanotubes: ethyl orthosilicate and gamma-aminopropyl-triethoxy silicon The weight ratio of alkane is 15:5:1).It is filtered after gained mixed system is stirred to react 1h at 80 DEG C, and with above-mentioned second alcohol and water shape At mixed liquor wash for 5 times or more, to remove unreacting reagent, obtain the modified halloysite nanotubes in surface；

(2) the modified halloysite nanotubes in the surface that step (1) obtains are dispersed in the N of 30g, N- dimethyl formyl Suspension is formed in amine (DMF), and 5g carboxyl-terminated liguid nitrile rubber (CTBN) is added in gained suspension, is then added The dicyclohexylcarbodiimide of 0.08g and the 4-N of 0.01g, N- lutidines (DCC/DMAP) catalysis, are stirred at 120 DEG C React 8h；Mixture 5 times or more washed with DMF；Obtained mixture is dried at 140 DEG C, is modified Halloysite nanotubes CTBN-co-HNTs；

(3) mechanical mixing, at 85 DEG C, the halloysite nanotubes for the modification that (2) the step of 5g are obtained are used (CTBN-co-HNTs) it is added to four glycidyl group -4 65.5g, in 4 '-diaminodiphenylmethane epoxy resin (TGDDM), Revolving speed be 3500rpm under conditions of be stirred 4h to uniformly it is bright.The 4,4- diamino of 29.5g-diphenyl sulphone (DPS) (DDS) is added It in resulting mixed system, heats while stirring at 130 DEG C, is melted completely to DDS.Then by gained mixture in 100 DEG C Lower vacuum defoamation degasification, is subsequently poured into the curing mold of preheating.Successively carry out the solidification process in two stages: solid at 130 DEG C Change 2 hours, solidify 4 hours at 200 DEG C, demoulds to get epoxy resin nano composites E2 (TGDDM/CTBN-co- is arrived HNTs), wherein it is calculated according to material amount, on the basis of the total amount of resulting epoxy resin nano composites, modified angstrom The content of Lip river stone nanotube is 5wt%.

Obtained epoxy resin nano composites E2 is carried out to the measurement of mechanical property, measurement result is referring to table 2.It will change Property halloysite nanotubes carry out TEM measurement, as shown in figure 3, the surface of modified HNTs forms nanometer protrusion, and formed irregular Boundary layer, can inhibit crack propagation in this way, can preferably improve the toughness of epoxy resin nano composites.

Comparative example 4

Epoxide resin material is prepared using the method for embodiment 2, unlike, without step (1) and step (2), only Epoxy resin TGDDM is carried out to the curing schedule of step (3), the specific method is as follows:

At 85 DEG C, 4, the 4- diamino of 29.5g-diphenyl sulphone (DPS) (DDS) is added to four glycidols of the preheating of 65.5g In 4,4 '-diaminodiphenylmethane epoxy resin (TGDDM) of base-, heats while stirring at 130 DEG C, is melted completely to DDS, Then the vacuum defoamation degasification at 100 DEG C by gained mixture, is subsequently poured into the curing mold of preheating.Successively carry out two ranks The solidification process of section: solidifying 2 hours at 130 DEG C, solidify 4 hours at 200 DEG C, demoulds to get cured epoxy resin is arrived Material D4.Mechanics performance determining is carried out, measurement result is shown in Table 1.

Comparative example 5

Epoxy resin nano composites are prepared using the method for embodiment 2, unlike, not to halloysite nanotubes into The modification of row step (1) and step (2), but the unmodified halloysite nanotubes particle of 5g is replaced into CTBN-co-HNTs and ring Oxygen resin directly mixes and solidifies, i.e. progress step (3).

Epoxy resin/unmodified halloysite nanotubes nanocomposite D5 (TGDDM/HNTs) is obtained, with resulting On the basis of the total amount of epoxy resin nano composites, the content of modified halloysite nanotubes is 5wt%.Carry out mechanical property Measurement, measurement result are shown in Table 2.

Comparative example 6

Epoxy resin nano composites are prepared using the method for embodiment 2, unlike, not to halloysite nanotubes into The modification of row step (2), but directly will mix and solidify with epoxy resin by step (1) modified halloysite nanotubes, Specific method:

(1) at 80 DEG C, mixed liquor (ethyl alcohol and water that the second alcohol and water of 1g halloysite nanotubes particle and 100g are formed Mass ratio be 8:2) be stirred 0.5h to evenly dispersed, by three second of ethyl orthosilicate and N- (β-aminoethyl)-γ-aminopropyl Oxysilane is added in the mixture of alcohol water dispersion (halloysite nanotubes: ethyl orthosilicate and gamma-aminopropyl-triethoxy silicon The weight ratio of alkane is 15:5:1).It is filtered after gained mixed system is stirred to react 1h at 80 DEG C, and with above-mentioned second alcohol and water shape At mixed liquor wash for 5 times or more, to remove unreacting reagent, obtain the modified halloysite nanotubes in surface；

(2) halloysite nanotubes for the modification that 5g step (1) obtains are added at 85 DEG C using mechanical mixing 65.5g epoxy resin four glycidyl group -4, in 4 '-diaminodiphenylmethane (TGDDM), in the condition that revolving speed is 3500rpm Under be stirred 4h to uniformly it is bright.4, the 4- diamino of 29.5g-diphenyl sulphone (DPS) (DDS) is added in resulting mixed system, in It heats while stirring at 130 DEG C, is melted completely to DDS.Then the vacuum defoamation degasification at 100 DEG C by gained mixture, then It pours into the curing mold of preheating.It successively carries out the solidification process in two stages: solidifying 2 hours at 130 DEG C, at 200 DEG C Solidification 4 hours demoulds to get epoxy resin nano composites D6 (TGDDM/co-HNTs) is arrived, wherein according to material Amount calculates, and on the basis of the total amount of resulting epoxy resin nano composites, the content of modified halloysite nanotubes is 5wt%.The measurement of mechanical property is carried out, measurement result is referring to table 2.

Table 2

Embodiment 3

(1) at 50 DEG C, mixed liquor (ethyl alcohol and water that the second alcohol and water of 1g halloysite nanotubes particle and 300g are formed Weight ratio be 18:1) be stirred 4h to evenly dispersed, by ethyl orthosilicate and N- (β-aminoethyl)-γ-aminopropyltriethoxy Dimethoxysilane is added in the mixture of alcohol water dispersion (halloysite nanotubes: three ethoxy of ethyl orthosilicate and γ-aminopropyl The weight ratio of base silane is 50:2:1).Filtered after gained mixed system is stirred to react 5h at 50 DEG C, and with above-mentioned ethyl alcohol and The mixed liquor washing that water is formed 5 times or more, to remove unreacting reagent, obtain the modified halloysite nanotubes in surface；

(2) the modified halloysite nanotubes in the surface that step (1) obtains are dispersed in be formed in the toluene of 120g and are hanged The epoxy terminated liquid nitrile rubber of 3g (ETBN) is added in gained suspension, the dimethyl Bian of 0.04g is then added by supernatant liquid Amine catalysis reaction, is stirred to react for 24 hours at 90 DEG C；Mixture 5 times or more washed with toluene；It will be obtained at 110 DEG C Mixture be dried, obtain modified halloysite nanotubes ETBN-co-HNTs；

(3) mechanical mixing, at 80 DEG C, the halloysite nanotubes for the modification that (2) the step of 2g are obtained are used (ETBN-co-HNTs) it is added in the novolac epoxy resin F44 of 57g preheating, stirring is mixed under conditions of revolving speed is 3000rpm Close 3h to uniformly it is bright.Obtained mixed system is down to 25 DEG C, the acid anhydride type curing agent of 41g is added (that is, methyl hexahydrophthalic anhydride With N, the weight ratio of N- dimethyl benzylamine is the mixture of 100:1), mixing is stirred at 80 DEG C.By above-mentioned mixed system The vacuum defoamation degasification at 80 DEG C, then pours into gained mixture in the curing mold of preheating.Successively carry out two stages Solidification process: solidifying 1 hour at 120 DEG C, solidifies 2 hours at 160 DEG C.It demoulds to get epoxide resin nano composite wood is arrived Expect E3 (F44/ETBN-co-HNTs), wherein calculated according to material amount, with resulting epoxy resin nano composites On the basis of total amount, the content of modified halloysite nanotubes is 2wt%.

Obtained epoxy resin nano composites E3 is carried out to the measurement of mechanical property, measurement result is referring to table 3.It will change Property halloysite nanotubes carry out SEM measurement, as shown in Figure 4.The surface of modified HNTs forms nano projection, and is formed irregular Boundary layer, in this way can be conducive to Anticrack, can preferably improve the toughness of epoxy resin nano composites.

Comparative example 7

Epoxide resin material is prepared using the method for embodiment 3, unlike, without step (1) and step (2), only Novolac epoxy resin F44 is carried out to the curing schedule of step (3), the specific method is as follows:

At 25 DEG C, by the acid anhydride type curing agent of 41g (that is, methyl hexahydrophthalic anhydride and N, the weight ratio of N- dimethyl benzylamine For the mixture of 100:1) it is added in the novolac epoxy resin F44 of 57g preheating.Above-mentioned mixed system is stirred at 80 DEG C mixed Vacuum defoamation degasification, then pours into gained mixture in the curing mold of preheating after closing uniformly.Successively carry out two stages Solidification process: solidifying 1 hour at 120 DEG C, solidifies 2 hours at 160 DEG C.It demoulds to get cured epoxide resin material is arrived D7。

Comparative example 8

Epoxy resin nano composites are prepared using the method for embodiment 3, unlike, not to halloysite nanotubes into The modification of row step (1) and step (2), but by the unmodified halloysite nanotubes particle of 2g replace ETBN-co-HNTs with Epoxy resin directly mixes and solidifies, i.e. progress step (3).

Obtain epoxy resin nano composites D8 (F44/HNTs), wherein with resulting epoxide resin nano composite wood On the basis of the total amount of material, the content of modified halloysite nanotubes is 2wt%.The measurement of mechanical property is carried out, measurement result is shown in Table 3。

Comparative example 9

Epoxy resin nano composites are prepared using the method for embodiment 3, unlike, not to halloysite nanotubes into The modification of row step (2), but directly will mix and solidify with epoxy resin by step (1) modified halloysite nanotubes, Specific method:

(1) at 50 DEG C, mixed liquor (ethyl alcohol and water that the second alcohol and water of 1g halloysite nanotubes particle and 120g are formed Weight ratio be 18:1) be stirred 4h to evenly dispersed, by ethyl orthosilicate and N- (β-aminoethyl)-γ-aminopropyltriethoxy Dimethoxysilane is added in the mixture of alcohol water dispersion (halloysite nanotubes: three ethoxy of ethyl orthosilicate and γ-aminopropyl The weight ratio of base silane is 50:2:1).It is filtered after gained mixed system is stirred to react 5h at 50 DEG C, and with second alcohol and water shape At mixed liquor wash for 5 times or more, to remove unreacting reagent, obtain the modified halloysite nanotubes in surface；

(2) mechanical mixing is used, at 80 DEG C, the halloysite nanotubes for the modification that (1) the step of 2g is obtained are added To 57g preheat novolac epoxy resin F44 in, revolving speed be 3000rpm under conditions of be stirred 3h to uniformly it is bright.Will To mixed system be down to 25 DEG C, be added 41g acid anhydride type curing agent (that is, methyl hexahydrophthalic anhydride and N, N- dimethyl benzylamine Weight ratio is the mixture of 100:1).The vacuum defoamation degasification after mixing evenly at 80 DEG C by above-mentioned mixed system, then by institute Mixture is obtained to pour into the curing mold of preheating.It successively carries out the solidification process in two stages: solidifying 1 hour at 120 DEG C, then at Solidify 2 hours at 160 DEG C.It demoulds to get epoxy resin nano composites D9 (F44/co-HNTs) is arrived, wherein according to material Inventory calculates, and on the basis of the total amount of resulting epoxy resin nano composites, the content of modified halloysite nanotubes is 2wt%.The measurement of mechanical property is carried out, measurement result is referring to table 3.

Table 3

Embodiment 4

(1) at 75 DEG C, by mixed liquor (the second alcohol and water of the second alcohol and water of 1g halloysite nanotubes particle and 40g formation Weight ratio be 49:1) be stirred 2.5h to evenly dispersed, by ethyl orthosilicate and γ-aminopropyltriethoxy diethoxy silane (halloysite nanotubes: ethyl orthosilicate and gamma-aminopropyl-triethoxy-silane are added in the mixture of gained alcohol water dispersion Weight ratio is 180:1:6).It is filtered after gained mixed system is stirred to react 4.5h at 75 DEG C, and with above-mentioned second alcohol and water shape At mixed liquor wash for 5 times or more, to remove unreacting reagent, obtain the modified halloysite nanotubes in surface；

(2) it is formed in the dimethylbenzene of the modified evenly dispersed 100g of halloysite nanotubes in the surface for obtaining step (1) outstanding The epoxy terminated liquid nitrile rubber of 3.5g (ETBN) is added in gained suspension, 2, the 6- bis- of 0.08g is then added by supernatant liquid Methylamino pyridine catalysis reaction, is stirred to react 10h at 145 DEG C；Mixture 5 times or more washed with xylene solvent； Obtained mixture is dried at 125 DEG C；Obtain modified halloysite nanotubes ETBN-co-HNTs；

(3) mechanical mixing, at 50 DEG C, the halloysite nanotubes (ETBN- for the modification that 1g step (2) is obtained are used Co-HNTs it) is added in 62.5g aliphatic epoxy resin polypropylene glycol diglycidyl ether (DER732), is in revolving speed Be stirred under conditions of 1000rpm 9h to uniformly it is bright.- 4 methylimidazole of 3.2g curing agent 2- ethyl is added to In mixed system, it is uniformly mixed at 25 DEG C.By above-mentioned mixed system, the vacuum defoamation degasification at 60 DEG C, then mixes gained Object is closed to pour into the curing mold of preheating.Solidify 9 hours at 75 DEG C, demoulds, obtain epoxy resin nano composites E4 (DER732/ETBN-co-HNTs), wherein calculated according to material amount, with resulting epoxy resin nano composites On the basis of total amount, the content of modified halloysite nanotubes is 1.5wt%.Obtained epoxy resin nano composites E4 is carried out The measurement of mechanical property, measurement result is referring to table 4.

Comparative example 10

Epoxide resin material is prepared using the method for embodiment 4, unlike, without step (1) and step (2), only Epoxy resin DER732 is carried out to the curing schedule of step (3), the specific method is as follows:

At 25 DEG C, -4 methylimidazole of 3.2g curing agent 2- ethyl is added to 62.5g aliphatic epoxy resin poly- the third two In alcohol diglycidyl ether (DER732), it is uniformly mixed.The vacuum defoamation degasification at 60 DEG C by above-mentioned mixed system, then Gained mixture is poured into the curing mold of preheating.Solidify 9 hours at 75 DEG C, demoulds, obtain cured epoxide resin material D10。

Comparative example 11

Epoxy resin nano composites are prepared using the method with embodiment 4, unlike, not to halloysite nanotubes The modification of step (1) and step (2) is carried out, but the unmodified halloysite nanotubes particle of 1g is replaced into ETBN-co-HNTs It directly mixes and solidifies with epoxy resin DER732, is i.e. progress step (3).

Obtain epoxy resin nano composites D11 (DER732/HNTs), wherein multiple with resulting epoxide resin nano On the basis of the total amount of condensation material, the content of modified halloysite nanotubes is 1.5wt%.Carry out the measurement of mechanical property, measurement knot Fruit is shown in Table 4.

Comparative example 12

Epoxy resin nano composites are prepared using the method for embodiment 4, unlike, not to halloysite nanotubes into The modification of row step (2), but directly will mix and solidify with epoxy resin by step (1) modified halloysite nanotubes, Specific method:

(1) at 75 DEG C, by mixed liquor (the second alcohol and water of the second alcohol and water of 1g halloysite nanotubes particle and 40g formation Weight ratio be 49:1) be stirred 2.5h to evenly dispersed, by ethyl orthosilicate and γ-aminopropyltriethoxy diethoxy silane (halloysite nanotubes: ethyl orthosilicate and gamma-aminopropyl-triethoxy-silane are added in the mixture of gained alcohol water dispersion Weight ratio is 180:1:6).It is filtered after gained mixed system is stirred to react 4.5h at 75 DEG C, and with above-mentioned second alcohol and water shape At mixed liquor wash for 5 times or more, to remove unreacting reagent, obtain the modified halloysite nanotubes in surface；

(2) halloysite nanotubes for the modification that 1g step (1) obtains are added at 50 DEG C using mechanical mixing In 62.5g aliphatic epoxy resin polypropylene glycol diglycidyl ether (DER732), stirred under conditions of revolving speed is 1000rpm Mix 9h to uniformly it is bright.In the mixed system that -4 methylimidazole of 3.2g curing agent 2- ethyl is added to, stirred at 25 DEG C It mixes uniformly mixed.By above-mentioned mixed system, gained mixture, is then poured into the solidification of preheating by the vacuum defoamation degasification at 60 DEG C In mold.Solidify 9 hours at 75 DEG C, demould, obtain epoxy resin nano composites D12 (DER732/co-HNTs), wherein It is calculated according to material amount, on the basis of the total amount of resulting epoxy resin nano composites, according to material meter It calculates, the content of modified halloysite nanotubes is 1.5wt%.Obtained epoxy resin nano composites D12 is subjected to mechanical property The measurement of energy, measurement result is referring to table 4.

Table 4

Embodiment 5

(1) at 65 DEG C, mixed liquor (ethyl alcohol and water that the second alcohol and water of 1g halloysite nanotubes particle and 120g are formed Weight ratio be 40:1) be stirred 3h to evenly dispersed, ethyl orthosilicate and γ-aminopropyl ethyoxyl dimethylsilane are added Enter into the mixture of gained alcohol water dispersion (halloysite nanotubes: the weight of ethyl orthosilicate and gamma-aminopropyl-triethoxy-silane Amount is than being 36:1:3).It filters after gained mixed system is stirred to react 4h at 65 DEG C, and is mixed with what above-mentioned second alcohol and water was formed It closes liquid washing 5 times or more, to remove unreacting reagent, obtains the modified halloysite nanotubes in surface；

(2) halloysite nanotubes for the surface treatment that step (1) obtains are dispersed in the N of 45g, N- dimethyl formyl Form suspension in amine (DMF), the epoxy terminated liquid nitrile rubber of 0.5g (ETBN) be added in gained suspension, then plus The pyridine for entering 0.02g is stirred to react 6h at 100 DEG C；It is washed gained mixture 5 times or more with DMF solvent；It will at 140 DEG C Obtained mixture is dried, and obtains modified halloysite nanotubes ETBN-co-HNTs；

(3) mechanical mixing, at 60 DEG C, the halloysite nanotubes (ETBN- for the modification that 15g step (2) is obtained are used Co-HNTs it) is added in the resin that the cycloaliphatc glycidyl ester three-functionality-degree epoxy resin TDE85 of 100g is mixed with E51 In (weight ratio of TDE85 and E51 be 3:1), 7h is stirred under conditions of revolving speed is 1500rpm to uniformly bright.By 45g Pnenolic aldehyde amine hardener T31 be added to gained mixed system in, by above-mentioned mixed system, vacuum takes off after mixing evenly at 60 DEG C Degasification is steeped, then pours into gained mixture in the curing mold of preheating.Successively carry out the solidification process in two stages: at 55 DEG C Solidification 1 hour, then solidify 8 hours at 140 DEG C, it demoulds, obtains epoxy resin nano composites E5 (TDE85/E51/ ETBN-co-HNTs), wherein calculated according to material amount, using the total amount of resulting epoxy resin nano composites as base Standard, the content of modified halloysite nanotubes are 9.4wt%.Obtained epoxy resin nano composites E5 is subjected to mechanical property Measurement, measurement result is referring to table 5.

Comparative example 13

Epoxide resin material is prepared using the method for embodiment 5, unlike, without step (1) and step (2), only The epoxy resin that TDE85 is mixed with E51 carries out the curing schedule of step (3), and the specific method is as follows:

Using mechanical mixing, at 60 DEG C, the pnenolic aldehyde amine hardener T31 of 45g is added to the alicyclic shrink of 100g In the resin that glyceride three-functionality-degree epoxy resin TDE85 is mixed with E51 in (weight ratio of TDE85 and E51 are 3:1), and stir It mixes uniformly mixed.By above-mentioned mixed system, gained mixture, is then poured into the solidification of preheating by the vacuum defoamation degasification at 60 DEG C In mold.It successively carries out the solidification process in two stages: solidifying 1 hour at 55 DEG C, then solidify 8 hours at 140 DEG C, demould, Obtain cured epoxide resin material D13.The measurement of mechanical property is carried out, measurement result is referring to table 5.

Comparative example 14

Epoxy resin nano composites are prepared using the method for embodiment 5, unlike, not to halloysite nanotubes into The modification of row step (1) and step (2), but the unmodified halloysite nanotubes particle of 15g is replaced into ETBN-co-HNTs It directly mixes and solidifies with mixed epoxy resin, is i.e. progress step (3).

Epoxy resin/unmodified halloysite nanotubes nanocomposite D14 (TDE85/E51/HNTs) is obtained, with institute On the basis of the total amount of the epoxy resin nano composites obtained, the content of modified halloysite nanotubes is 9.4wt%.Carry out mechanics The measurement of performance, measurement result are shown in Table 5.

Comparative example 15

Epoxy resin nano composites are prepared using the method for embodiment 5, unlike, not to halloysite nanotubes into The modification of row step (2), but directly will mix and solidify with epoxy resin by step (1) modified halloysite nanotubes, Specific method:

(1) at 65 DEG C, mixed liquor (ethyl alcohol and water that the second alcohol and water of 1g halloysite nanotubes particle and 120g are formed Weight ratio be 40:1) be stirred 3h to evenly dispersed, ethyl orthosilicate and γ-aminopropyl ethyoxyl dimethylsilane are added Enter into the mixture of gained alcohol water dispersion (halloysite nanotubes: the weight of ethyl orthosilicate and gamma-aminopropyl-triethoxy-silane Amount is than being 36:1:3).It filters after gained mixed system is stirred to react 4h at 65 DEG C, and is mixed with what above-mentioned second alcohol and water was formed It closes solution washing 5 times or more, to remove unreacting reagent, obtains the modified halloysite nanotubes in surface；

(2) mechanical mixing, at 60 DEG C, the halloysite nanotubes (ETBN- for the modification that 15g step (1) is obtained are used Co-HNTs it) is added in the resin that the cycloaliphatc glycidyl ester three-functionality-degree epoxy resin TDE85 of 100g is mixed with E51 In (weight ratio of TDE85 and E51 be 3:1), 7h is stirred under conditions of revolving speed is 1500rpm to uniformly bright.By 45g Pnenolic aldehyde amine hardener T31 be added in gained mixed system, and be uniformly mixed.Above-mentioned mixed system is true at 60 DEG C Empty deaeration degasification, then pours into gained mixture in the curing mold of preheating.Successively carry out two stages solidification process: 55 Solidify 1 hour at DEG C, then solidify 8 hours at 140 DEG C, demoulds, obtain epoxy resin nano composites D15 (TDE85/ E51/ETBN-co-HNTs), wherein calculated according to material amount, with the total amount of resulting epoxy resin nano composites On the basis of, the content of modified halloysite nanotubes is 9.4wt%.Obtained epoxy resin nano composites D15 is subjected to power The measurement of performance is learned, measurement result is referring to table 5.

Table 5

From in the result of table 1- table 5 as can be seen that it can be found that epoxy resin is received after epoxy resin is added in unmodified HNTs Impact strength, tensile strength and the stretch modulus of nano composite material are to increase by a small margin, and elongation at break reduces.And it will be through Ethyl orthosilicate and amino silane modified HNTs are added to epoxy resin, and the impact of epoxy resin nano composites is strong Degree, tensile strength and stretch modulus increasing degree increase；By it is provided by the invention by ethyl orthosilicate and amino silane and After the acrylonitrile butadiene rubber modified HNTs of specific terminal reactive group, the intensity, toughness and modulus of epoxy resin nano composites There is raising by a relatively large margin, i.e., increased amplitude is maximum.

It can be seen that in step (1) from the result of table 1- table 5, it can be effective using specific alcohol water mixed solvent Improve the mechanical property of epoxy resin nano composites；Using the ethyl orthosilicate and amino silane of specific dosage and specific Active end group liquid nitrile rubber, the mechanical property of epoxy resin nano composites can be effectively improved.

The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (22)

1. a kind of modified halloysite nanotubes, which is characterized in that the modified halloysite nanotubes include halloysite nanotubes, according to First shell and the second shell on the secondary surface for being attached to halloysite nanotubes, first shell is by containing the first modifying agent Mixed solution is formed by copolycondensation, and first modifying agent is ethyl orthosilicate and amino silane, second shell It is formed with active end group liquid nitrile rubber by graft reaction by first shell, wherein the active end group liquid fourth Nitrile rubber is carboxyl-terminated liguid nitrile rubber and/or epoxy terminated liquid nitrile rubber, and it is former also to contain carbon in the mixed solution Subnumber is the pure and mild water of saturated fat of 1-3.

2. modified halloysite nanotubes according to claim 1, wherein the weight of the halloysite nanotubes and amino silane Amount is than being 1:0.03-0.5, preferably 1:0.03-0.15；The weight ratio of ethyl orthosilicate and amino silane is 1:0.1-8, preferably For 1:0.2-6；The weight ratio of halloysite nanotubes and mixed solution is 1:15-300, preferably 1:20-120；

Preferably, the weight ratio for the pure and mild water of saturated fat that carbon atom number is 1-3 is (80:20)-(99:1)；

Preferably, the weight ratio of the halloysite nanotubes and active end group liquid nitrile rubber is 1:0.1-10, further excellent It is selected as 1:0.2-5.

3. modified halloysite nanotubes according to claim 1, wherein the saturated fatty alcohol is methanol, ethyl alcohol, positive third At least one of pure and mild isopropanol, preferably ethyl alcohol.

4. modified halloysite nanotubes according to claim 1, wherein the condition of the copolycondensation includes: reaction Temperature is 50-90 DEG C, preferably 60-80 DEG C；The time of reaction is 0.5-5h, preferably 1-4.5h；

Preferably, it is 50-150 DEG C, more preferably 80-140 DEG C that the condition of the graft reaction, which includes: reaction temperature,；Reaction Time is 2-48h, more preferably 3-24h.

5. modified halloysite nanotubes according to claim 1, wherein the amino silane is selected from γ-aminopropyl three Ethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N- (β-ammonia second Base)-γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N- (β-ammonia second Base)-γ-aminopropyltriethoxy diethoxy silane, γ-aminopropyltriethoxy diethoxy silane, γ-aminopropyltriethoxy dimethoxy One of silane and γ-aminopropyl ethyoxyl dimethylsilane are a variety of, preferably gamma-aminopropyl-triethoxy-silane, N- In (β-aminoethyl)-γ-aminopropyltrimethoxysilane and N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane It is at least one.

6. modification halloysite nanotubes described in any one of -5 according to claim 1, wherein the halloysite nanotubes Outer diameter is 40-150nm, internal diameter 10-25nm, length 100-2000nm,

Preferably, the number-average molecular weight of the active end group liquid nitrile rubber is 1500-5000, preferably 3000-4500；With On the basis of the total amount of active end group nitrile rubber, the content of derived from propylene nitrile structural unit is 10-40 weight %, preferably 15-30 weight %；Viscosity at 27 DEG C of the active end group nitrile rubber is 20-500Pas, preferably 40-350Pa s；

It is further preferred that the active end group liquid nitrile rubber is carboxyl-terminated liguid nitrile rubber, carboxyl equivalent 0.04- 0.08phr；The active end group liquid nitrile rubber is epoxy terminated liquid nitrile rubber, epoxide equivalent 2000-3000g/ eq。

7. a kind of preparation method of modified halloysite nanotubes, method includes the following steps:

(1) in the presence of the mixed solution containing the pure and mild water of saturated fat that carbon atom number is 1-3, pass through ethyl orthosilicate and ammonia The copolycondensation of base silane carries out surface to halloysite nanotubes and is modified, and obtains the modified halloysite nanotubes in surface；

(2) the modified halloysite nanotubes in the surface that step (1) obtains are contacted to form suspension with dispersing agent, by the suspension Liquid and active end group liquid nitrile rubber carry out graft reaction, and the active end group liquid nitrile rubber is carboxyl end group liquid butyronitrile Rubber and/or epoxy terminated liquid nitrile rubber.

8. according to the method described in claim 7, wherein, the weight ratio of the halloysite nanotubes and amino silane is 1: 0.03-0.5, preferably 1:0.03-0.15；The weight ratio of ethyl orthosilicate and amino silane is 1:0.1-8, preferably 1:0.2- 6；The weight ratio of halloysite nanotubes and mixed solution is 1:15-300, preferably 1:20-120；

Preferably, the weight ratio for the pure and mild water of saturated fat that carbon atom number is 1-3 is (80:20)-(99:1)；

Preferably, the weight ratio of the halloysite nanotubes and dispersing agent is 1:15-300, preferably 1:20-120；

Preferably, the weight ratio of the halloysite nanotubes and active end group liquid nitrile rubber is 1:0.1-10, further excellent It is selected as 1:0.2-5.

9. according to the method described in claim 7, wherein, the condition of the copolycondensation includes: that reaction temperature is 50-90 DEG C, preferably 60-80 DEG C；The time of reaction is 0.5-5h, preferably 1-4.5h；

Preferably, it is 50-150 DEG C, more preferably 80-140 DEG C that the condition of the graft reaction, which includes: reaction temperature,；Reaction Time is 2-48h, more preferably 3-24h.

10. according to method described in claim 7-9 any one, wherein the amino silane is selected from three ethoxy of γ-aminopropyl Base silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N- (β-aminoethyl)- γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N- (β-aminoethyl)-γ- Aminopropyltriethoxy diethoxy silane, γ-aminopropyltriethoxy diethoxy silane, γ-aminopropyltriethoxy dimethoxysilane and One of γ-aminopropyl ethyoxyl dimethylsilane is a variety of, preferably gamma-aminopropyl-triethoxy-silane, N- (β-ammonia second Base) in-γ-aminopropyltrimethoxysilane and N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane at least one Kind.

11. method according to any one of claims of claim 7-10, wherein the outer diameter of the halloysite nanotubes is 40- 150nm, internal diameter 10-25nm, length 100-2000nm,

Preferably, the number-average molecular weight of the active end group liquid nitrile rubber is 1500-5000, preferably 3000-4500；With On the basis of the total amount of active end group nitrile rubber, the content of derived from propylene nitrile structural unit is 10-40 weight %, preferably 15-30 weight %；Viscosity at 27 DEG C of the nbr carboxyl terminal is 20-500Pas, preferably 40-350Pas；

It is further preferred that the active end group liquid nitrile rubber is carboxyl-terminated liguid nitrile rubber, carboxyl equivalent 0.04- 0.08phr；The active end group liquid nitrile rubber is epoxy terminated liquid nitrile rubber, epoxide equivalent 2000-3000g/ eq。

12. method according to any one of claims of claim 7-10, wherein the dispersing agent is selected from benzene, toluene, diformazan Benzene and N,N-dimethylformamide one of or it is a variety of；

Preferably, the saturated fatty alcohol is at least one of methanol, ethyl alcohol, normal propyl alcohol and isopropanol, preferably ethyl alcohol.

13. according to the method described in claim 7, wherein, the graft reaction carries out in the presence of auxiliary agent A, the auxiliary agent A For catalyst and/or co-catalyst, the catalyst is triethylamine, trimethylamine, quinoline, dimethyl Bian amine, pyridine, methyl pyrrole One of pyridine, 2,6- dimethylamino naphthyridine and N- methylmorpholine are a variety of；The co-catalyst is N, N'- diisopropyl carbon Diimine and/or N, N'- dicyclohexylcarbodiimide,

Preferably, the weight ratio of the halloysite nanotubes and auxiliary agent A is 1:0.005-0.1, preferably 1:0.01-0.1.

14. according to the method described in claim 7, wherein, the method includes halloysite nanotubes are added to containing carbon original Subnumber be 1-3 the pure and mild water of saturated fat mixed solution in dispersion mixing, into gained mixture be added ethyl orthosilicate and It is modified to carry out surface to halloysite nanotubes that amino silane carries out copolycondensation；

Preferably, the mixed time is 0.5-5h.

15. the method according to claim 7 or 14, wherein it is modified that the method also includes the surfaces for obtaining step (1) Halloysite nanotubes the step of being filtered and washed.

16. a kind of modification halloysite nanotubes that the method as described in any one of claim 7-15 is prepared.

17. a kind of epoxy resin nano composites, the epoxy resin nano composites by be modified halloysite nanotubes and The cured reaction of epoxy resin is formed, which is characterized in that the modified halloysite nanotubes are any in claim 1-6 and 16 Modification halloysite nanotubes described in one.

18. epoxy resin nano composites according to claim 17, wherein the modified halloysite nanotubes and ring The weight ratio of oxygen resin is 0.2-25:100, preferably 0.5-15:100.

19. epoxy resin nano composites according to claim 17, wherein the condition of the curing reaction includes: The temperature of reaction is 50-200 DEG C, and the time of reaction is 1-20h.

20. epoxy resin nano composites described in any one of 7-19 according to claim 1, wherein the asphalt mixtures modified by epoxy resin Rouge is bisphenol-A system epoxy resin, hydrogenated bisphenol A epoxy resin, novolac epoxy resin, bisphenol S system epoxy resin, Bisphenol F system ring Oxygen resin, aliphatic glycidyl ether resin, brominated epoxy resin, glycidyl ester type epoxy resin, aminoepoxy resin, rouge At least one of ring race epoxy resin, epoxidized polyolefin, organosilicon epoxy resin and acrylic compounds epoxy resin, preferably Bisphenol-A system epoxy resin and/or novolac epoxy resin.

21. epoxy resin nano composites described in any one of 7-19 according to claim 1, wherein the solidification is anti- It should be carried out in the presence of curing agent and/or curing accelerator, the curing agent is alicyclic ring amine curing agent, anhydride solidification Agent, tertiary amines curing agent, fatty amines curing agent, imidazole curing agent, polyamide-based curing agent, gathers aromatic amine curing agent At least one of ether amine curing agent and dicyandiamide class curing agent；The curing accelerator is tertiary amines curing accelerator, miaow Azole curing accelerator, quaternary ammonium salt curing accelerator, organic phosphates curing accelerator, substituted urea class curing accelerator and trifluoro Change at least one of Boron Amine Complex.

22. epoxy resin nano composites described in any one of claim 17-21 are multiple in adhesive and/or carbon fiber Application in condensation material.