CN104119704A - Surface modification treatment method of halloysite nanotube - Google Patents
Surface modification treatment method of halloysite nanotube Download PDFInfo
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Abstract
The invention relates to a method for preparing a nanocomposite and particularly relates to a method for modifying a halloysite nanotube with a silane coupling agent and an epoxy resin nanocomposite prepared by mixing the modified halloysite nanotube obtained by the method and epoxy resin. The surface modification treatment method of the halloysite nanotube, which is disclosed by the invention comprises the following steps of adding the silane coupling agent into a suspension containing the acidified halloysite nanotube and carrying out condensation reaction on a hydrolyzable X group on the silane coupling agent and a hydroxy group on the lamella on the surface of the halloysite nanotube to obtain the halloysite nanotube which is modified by the silane coupling agent and of which an inner cavity and the outer surface are grafted by the silane coupling agent, and mixing the modified halloysite nanotube and epoxy resin to prepare the epoxy resin nanocomposite. The epoxy resin nanocomposite can obtain the desired mechanical properties and thermal properties.
Description
Technical field
The present invention relates to the preparation method of nano composite material, particularly relate to the method with silane coupler modified halloysite nanotubes, and the epoxy resin nano composites that is mixed with of the modification halloysite nanotubes being obtained by the method and epoxy resin, the epoxy resin nano composites making can obtain desirable mechanical property and thermal characteristics.
Background technology
Epoxy resin because of its excellent agglutinating value(of coal), shrinking percentage is low, chemical stability good, electrical insulation capability is good, easy machine-shaping and the advantage such as with low cost, is widely used in the fields such as sizing agent, electronic instrument, light industry, building, machinery, coating and electric insulation.Yet due to highly cross-linked network molecular structure, epoxy resin tends to show poor toughness, easily stress cracking and the shortcoming such as fatigue lifetime is short, has limited its application.For the problem of epoxy resin poor toughness, many scholars improve by introducing the method for weighting material, but also have the difficulty that is difficult to overcome.As the intensity that adds membership loss material, rigidity and the thermotolerance of rubber elastomer; Thermoplastic polymer need to form network structure in epoxy resin just can play obvious toughening effect; Rigidity micron particle generally adds highly malleablized effect that more amount just can have etc.
In recent years, natural mineral modified by nano particles polymkeric substance arouses widespread concern because of its remarkable over-all properties, nano particle source is wide, cheap, biological suitability etc.Epoxy resin can obtain high rigidity, high specific surface area, high shock resistance by nano combined; Can not cause the obvious decline of system intensity and thermal characteristics, there is stronger practicality simultaneously.Wherein the nano combined system of Epoxy Resin/Montmorillonite has more research, and publication number is that " CN1250790A ", " CN1978525A ", " CN1793195A " etc. are the patents of invention about this kind of material.But be mostly by organo montmorillonite on the basis of medium swelling, under the effect of high temperature, shearing force or particular molecule, help epoxy resin and solidifying agent molecule to enter between cheating engaging layer, thereby realize intercalation and even peel off.Simultaneously for the selection of solvent in system, organo montmorillonite in epoxy resin effectively peel off and dispersed relate to less.And general course of processing more complicated, has more harsh requirement to intercalator and solidifying agent, can not realize the state of peeling off in complete meaning.
Halloysite nanotubes (HNTs) is a kind of cheap natural nano pipe, is double-deck 1:1 type aluminosilicate, and its molecular formula is Al
2siO
5(OH)
4nH
2o (n=0 or 2), has typical crystalline texture, is often multi-walled pipes shape structure, and by unlined aluminium oxygen octahedra and curling the forming of outer field silicon-oxy tetrahedron lattice dislocation, its interlayer exists crystal water.By analysis, halloysite nanotubes contains two class hydroxyls: the silicon hydroxyl and the more aluminium hydroxyl that is positioned at interlayer that are positioned at outside surface.Because halloysite nanotubes has unique nanostructure and tubular character, therefore can be compound with polymkeric substance, prepare the Preparing Organic-inorganic Nano Hybrid Material of premium properties.Patent US8124678 and the US20110160345 of U.S. Natural Nano company have introduced respectively use halloysite nanotubes modification of nylon and polypropylene composite material, make to have obtained raising through the nylon of halloysite nanotubes modification and the mechanical property of polypropylene composite material, and had corresponding product.
In polymer composites, halloysite nanotubes can reach to a certain degree dispersed, but dispersion situation is still undesirable, halloysite nanotubes coacervate and single disperse halloysite nanotubes and deposit in polymer composites often, some Water-borne paint is very large (tens microns) also.Therefore need to carry out surface treatment modification to halloysite nanotubes, to improve its dispersing property.The present invention uses silane coupling agent to carry out surface treatment and modification to halloysite nanotubes, thereby and with mechanical property and the thermal property of modification halloysite nanotubes and the compound raising of epoxy resin epoxy resin.Between halloysite nanotubes and epoxy resin, do not have the problem of peeling off between lamella, processing is simple simultaneously.(the Composites Science and Technology such as Shiqiang Deng, 2009,69:2497 – 2505) by coupling agent γ-(β aminoethyl) aminopropyl trimethoxysilane (Z-6020), halloysite nanotubes is carried out to graft modification, and mix by ball mill with epoxy resin.But use infrared grade, SEM means to characterize, do not change, do not show than the excellent how many mechanical property of pure epoxy resin system, and halloysite nanotubes exists a certain amount of coacervate in system.The patent of invention that publication number is " CN1746216A " is used ethenylphenyl Edamine propyl trimethoxy silicane to be sprayed on halloysite nanotubes after being dissolved in ethanol hydrolysis, after drying, mix with epoxy resin, made epoxy resin/halloysite nanotubes matrix material.
Summary of the invention
One of object of the present invention is in order to overcome the deficiencies in the prior art, the method of the silane coupler modified halloysite nanotubes of a kind of use is provided, silane coupling agent is grafted on inner chamber and the outside surface of halloysite nanotubes by covalent linkage, when having improved the amphipathic property on halloysite nanotubes surface, make halloysite nanotubes there is higher thermostability, can also realize the further functionalization of halloysite nanotubes.
Two of object of the present invention is to provide the modification halloysite nanotubes of a kind of inner chamber and outside surface grafted silane coupling agent and the epoxy resin nano composites that epoxy resin is mixed with, the modification halloysite nanotubes that makes to add in epoxy resin has good dispersiveness and consistency, forms the be significantly improved epoxy resin nano composites of mechanical property of tool.
The surface modifying treatment of halloysite nanotubes of the present invention is that silane coupling agent is joined in the suspension of the halloysite nanotubes that contains acidifying, by silane coupling agent R
n-Si-X
(4-n)on hydrolyzable X group and the hydroxyl on the lamella of halloysite nanotubes surface between carry out condensation reaction, obtain through the inner chamber of silane coupler modified processing and the modification halloysite nanotubes of outside surface grafted silane coupling agent.Modification halloysite nanotubes and epoxy resin are mixed with and obtain epoxy resin nano composites, and this epoxy resin nano composites can obtain desirable mechanical property and thermal characteristics.
The surface modifying treatment of halloysite nanotubes of the present invention comprises the following steps:
(1) purification of halloysite nanotubes particle:
The halloysite nanotubes particle pulverizing and sieving is mixed according to the mass ratio of 1:8～1:25 with deionized water, add 0.1～2% the dispersion agent (it is a kind of in 2000～5000g/mol sodium polyacrylate etc. that described dispersion agent is selected from Sodium hexametaphosphate 99, tripoly phosphate sodium STPP, trisodium phosphate and molecular weight) that is equivalent to halloysite nanotubes particle mass, stir (the general time of stirring is 1～24 hour), until form the suspension that contains uniformly halloysite nanotubes particle; By described suspension standing (the general standing time is 8～48 hours), layering, getting upper strata slurry after standing puts into whizzer and carries out centrifugation (time of general centrifugation is 3～30 minutes), by centrifugation gained throw out solid, in baking oven, the temperature of baking oven (be preferably 50～100 ℃) dries to quality unchangedly, then with 150～250 mesh sieves, sieves the halloysite nanotubes particle that obtains purifying;
(2) the silane coupler modified processing of halloysite nanotubes particle:
The halloysite nanotubes particle of the purifying that step (1) is obtained mixes according to the mass ratio of 1:10～1:80 with acid reagent, ultrasonic dispersion stirring at room 6～24 hours after 5～60 minutes; Filter, by grind into powder after gained solids wash, obtain the halloysite nanotubes of acidifying; By the halloysite nanotubes of acidifying and organic solvent, according to mass ratio, be the suspension that 1:10～1:50 is made into the halloysite nanotubes that contains uniformly acidifying, then silane coupling agent is joined in this suspension, the add-on of silane coupling agent be equivalent to acidifying halloysite nanotubes quality 20～120%; In temperature, it is stirring reaction 4～48 hours at 25～200 ℃, filter, by gained solids wash dry rear grind into powder, and sieve with 150～250 mesh sieves, obtain through the inner chamber of silane coupler modified processing and the modification halloysite nanotubes of outside surface grafted silane coupling agent.
The described upper strata slurry of getting after stratification is put into whizzer and is carried out centrifugation, and preferably the rotating speed of whizzer is 4000～10000r/min.
Acid reagent used in the present invention is selected from one or more in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and hydrogen peroxide.
In the present invention, organic solvent used is selected from one or more in ethanol, methyl alcohol, Virahol, propyl carbinol, acetone, chloroform, methylene dichloride, tetrahydrofuran (THF), benzene,toluene,xylene, normal hexane, dioxane and DMF.
In the present invention, silane coupling agent used is following coupling agent R
n-Si-X
(4-n)in a kind of, wherein: n is 1～3; End hydrolysable group X is a kind of in triethoxy, trimethoxy, methyl dimethoxy oxygen base, methyl diethoxy, dimethyl oxyethyl group;
(1), containing amino silane coupling agent, function organic group R is γ-aminopropyl, γ-(β aminoethyl) aminopropyl, N-(β-aminoethyl)-γ-aminopropyl, 3-[2-(2-aminoethylamino) ethylamino] a kind of group in propyl group, anilinomethyl, N-(2-amino-ethyl)-3-aminopropyl, 3-aminopropyl;
(2), containing the silane coupling agent of epoxy group(ing), R is a kind of in γ-(2,3-epoxy the third oxygen) propyl group, β-(3,4-epoxycyclohexyl) ethyl;
(3) other silane coupling agent, R is a kind of in γ-isocyanate group propyl group, gamma-methyl allyl acyloxypropyl, γ-mercapto propyl group, γ-chloropropyl and vinyl, propyl group succinyl oxide base etc.
The modification halloysite nanotubes of inner chamber of the present invention and outside surface grafted silane coupling agent mixes and can prepare epoxy resin nano composites with epoxy resin, the modification halloysite nanotubes that makes to add in epoxy resin has good dispersiveness and consistency, forms the be significantly improved epoxy resin nano composites of mechanical property of tool.
The preparation method of described epoxy resin nano composites comprises the following steps:
(1) in epoxy resin, adding is the acetone of epoxy resin quality 30～300%, stirs (the general time of stirring is 3～20 minutes) and is made into diluent;
(2) by the ultrasonic dispersion of modification halloysite nanotubes (time of general ultrasonic dispersion is 10～60 minutes) in the acetone with respect to 10～100 times of modification halloysite nanotubes quality, stir and to be made into the suspension that contains uniformly modification halloysite nanotubes;
(3) diluent step (1) being obtained mixes with the suspension that contains modification halloysite nanotubes that step (2) obtains, and be at 25～100 ℃, to stir (the general time of stirring is 2～5 hours) in temperature, obtain the mixed system of epoxy resin and modification halloysite nanotubes, wherein the quality of the modification halloysite nanotubes in mixed system is 0.1～20% of epoxy resin quality; In the mixed system obtaining, add epoxy curing agent (can further add epoxy resin cure promotor as required), the amount of the epoxy curing agent adding be for can make epoxy resin contained in mixed system can solidify required amount completely, and mixes; Then the mixed solution mixing is transferred in vacuum drying oven, in temperature, be at 40～80 ℃, to carry out vacuum defoamation degasification, reactant after deaeration degasification is poured in curing mold, self-vulcanizing (time of general self-vulcanizing is 0.5～5 hour), in temperature, be to solidify 2～24 hours at 50～200 ℃ again, obtain the epoxy resin nano composites that modification halloysite nanotubes mixes with epoxy resin.
Selecting of described epoxy resin do not have special requirement, can be that to belong to dihydroxyphenyl propane be that epoxy resin, Bisphenol F are that epoxy resin, bisphenol S are a kind of in epoxy resin, hydrogenated bisphenol A epoxy resin, novolac epoxy, aliphatic glycidyl ether resin, brominated epoxy resin, Racemic glycidol esters resin, aminoepoxy resin, cycloaliphatic epoxy resin, epoxidation polyolefine, organosilicon epoxy resin and acrylic acid or the like epoxy resin etc.
Described epoxy curing agent can be a kind of in aliphatics amine, alicyclic amine, aromatic amine, tertiary amines, anhydrides, imidazoles, polyamide-based, polyether monoamine, polythiol class, the class of hiding solidifying agent (comprise in amine complex compound, trimeric cyanamide and derivative thereof, Diaminomaleonitrile, the micro capsule curing agent that is selected from Dyhard RU 100 class, imidazoles metal salt complex, organic hydrazides, boron trifluoride a kind of) etc.
For epoxy curing agent, be aromatic amine, anhydrides, polythiol class or the solidifying agent such as class of hiding, operable epoxy resin cure promotor is a kind of in tertiary amines, imidazoles, quaternary ammonium salt, organic phosphates, substituted urea class and boron trifluoride amine complex etc.
The present invention carries out modification with silane coupling agent to the halloysite nanotubes of acidifying in organic solvent, and silane coupling agent is grafted on halloysite nanotubes by covalent linkage, and the efficiency of its grafting is high, and the integrated artistic of silanization modification is simple, reliable.Meanwhile, Fourier transform infrared spectroscopy (FTIR) and thermogravimetic analysis (TGA) (TGA) have confirmed the generation of Surface grafting reaction.
The present invention adds the halloysite nanotubes after silane coupler modified in epoxy resin, to have made the epoxy resin nano composites that modification halloysite nanotubes mixes with epoxy resin to, in modification, given halloysite nanotubes surface-functionalized, make itself and epoxy resin effect stronger, the dispersion in epoxy resin is more even; By sign proofs such as scanning electronic microscope (SEM), the dispersion effect of the halloysite nanotubes after silane coupler modified in matrix material obtained obvious improvement.The impelling strength of the matrix material that the epoxy resin nano composites that the halloysite nanotubes after silane coupler modified obtains after mixing with epoxy resin always mixes with epoxy resin than halloysite nanotubes is high 3～5 times.
More than illustrate that the halloysite nanotubes after silane coupler modified can play the enhancing of epoxy resin and toughening effect simultaneously, the thermal characteristics of described epoxy resin nano composites has also obtained obvious improvement simultaneously.The described epoxy resin nano composites preparing has obdurability and better thermostability, and epoxy resin nano composites of the present invention has broad application prospects in fields such as automobile, tackiness agent, coating, aerospace.
Accompanying drawing explanation
Fig. 1 is the unmodified halloysite nanotubes of the embodiment of the present invention 1 and the FTIR spectrogram of the halloysite nanotubes after γ-aminopropyl triethoxysilane modification.
Fig. 2 is the shock strength comparison diagram after the unmodified halloysite nanotubes of the embodiment of the present invention 2 and epoxy-resin systems and the halloysite nanotubes after N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane modification and epoxy-resin systems solidify.
Fig. 3 is after the unmodified halloysite nanotubes of the embodiment of the present invention 2 and epoxy-resin systems and the halloysite nanotubes after N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane modification and epoxy-resin systems solidify, the SEM of section figure after Impact Test.
Fig. 4 is the unmodified halloysite nanotubes of the embodiment of the present invention 4 and through the SEM of the halloysite nanotubes of γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane modification figure.
Fig. 5 is the unmodified halloysite nanotubes of the embodiment of the present invention 5 and through the thermogravimetric curve of the halloysite nanotubes of β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane modification.
Embodiment
For the present invention will be described better, by the following examples, come further to be described, but the present invention is not limited to these embodiment.
Comparative example: unmodified halloysite nanotubes and epoxy resin are compound
The halloysite nanotubes particle 50g pulverizing and sieving and deionized water 500g are made into mixed solution, add the Sodium hexametaphosphate 99 of 0.1g, stir 8 hours until form uniform suspension.By standing 8 hours of suspension, get upper strata slurry, at rotating speed, be under 10000r/min centrifugal 3 minutes; Centrifugal sediment is dried to quality unchanged in baking oven at 80 ℃, then with 250 mesh sieve screenings, obtains the halloysite nanotubes of purifying.
Get 10g purifying halloysite nanotubes and join in 200g acetone, after ultrasonic 10 minutes, stir and within 30 minutes, be made into unit for uniform suspension; In 144g bisphenol A epoxide resin EPON828, add 50g acetone, stir and within 5 minutes, be made into diluent.Above-mentioned diluent and suspension are mixed, and at 75 ℃, 500r/min rotating speed stirs 2 hours, obtains epoxy resin/halloysite nanotubes mixed system.By measuring than the alicyclic ring type solidifying agent 3 adding in mixed system, 3-dimethyl-4,4-diamino-dicyclohexyl methyl hydride (DMDC) 46g, mixes with above-mentioned epoxy resin/halloysite nanotubes mixed system; Then be transferred to deaeration degasification in vacuum drying oven, reactant is poured in curing mold, self-vulcanizing 5 hours, then solidify 5 hours at 150 ℃, make the epoxy resin nano composites containing unmodified halloysite nanotubes 5wt%.
With reference to above step, can prepare the epoxy resin nano composites containing unmodified halloysite nanotubes 0.1～20wt%.
Embodiment 1
(1) purification of halloysite nanotubes particle:
The halloysite nanotubes particle that 50g is pulverized and sieved mixes and is made into mixed solution with 1250g deionized water, adds the trisodium phosphate of 0.25g, stirs 24 hours until form the suspension that contains uniformly halloysite nanotubes particle; By standing 18 hours of described suspension, layering, the upper strata slurry of getting after standing is put into whizzer, with 7000r/min, carry out centrifugation 30 minutes, centrifugation gained throw out solid is 60 ℃ in temperature in baking oven and dries to quality unchangedly, then with 150 mesh sieves, sieve the halloysite nanotubes particle that obtains purifying;
(2) the silane coupler modified processing of halloysite nanotubes particle:
The halloysite nanotubes particle of the purifying that 12g step (1) is obtained joins in the hydrochloric acid soln (2.5mol/L) of 200mL, ultrasonic dispersion stirring at room 24 hours after 15 minutes; Filter, by grind into powder after gained solids wash, obtain the halloysite nanotubes of acidifying; The halloysite nanotubes of getting 10g acidifying mixes with 100g toluene the suspension that is made into the halloysite nanotubes that contains uniformly acidifying, then the γ-aminopropyl triethoxysilane of 12g (KH550) is joined in this suspension; In temperature, it is stirring reaction 12 hours at 200 ℃, filter, by gained solids wash dry rear grind into powder, and sieve with 150 mesh sieves, obtain through the inner chamber of γ-aminopropyl triethoxysilane modification and the modification halloysite nanotubes of outside surface grafting γ-aminopropyl triethoxysilane.
Gained modification halloysite nanotubes is carried out to infrared analysis, result FTIR spectrogram as shown in Figure 1.In the infrared spectrum of modification halloysite nanotubes, there is 3363cm
-1and 3282cm
-1nH
2asymmetric and symmetrical stretching vibration peak, 2931cm
-1and 2866cm
-1cH
2symmetry and asymmetric stretching vibration peak, and 1565cm
-1, 1480cm
-1and 1386cm
-1nH
2scissors movement, CH
2scissors movement and CH
2rocking vibration absorption peak, above explanation γ-aminopropyl triethoxysilane is coupled to halloysite nanotubes well.
The modification halloysite nanotubes and the epoxy resin that by above-mentioned preparation method, obtain are mixed with epoxy resin nano composites.
(1) in 122.6g novolac epoxy F44, add 367.8g acetone, stir and within 20 minutes, be made into diluent;
(2) get 0.15g modification halloysite nanotubes and join in the acetone of 15g, ultrasonic dispersion is stirred after 10 minutes and within 15 minutes, is made into the suspension that contains uniformly modification halloysite nanotubes;
(3) diluent step (1) being obtained mixes with the suspension that contains modification halloysite nanotubes that step (2) obtains, and be that at 25 ℃, the rotating speed with 500r/min stirs 5 hours in temperature, obtain the mixed system of novolac epoxy and modification halloysite nanotubes; In the mixed system obtaining, add aromatic amine curing agent 4,4-diamino-ditan (DDM) is 29.4g altogether, and mixes; Then the mixed solution mixing is transferred in vacuum drying oven, in temperature, be at 80 ℃, to carry out vacuum defoamation degasification, reactant after deaeration degasification is poured in curing mold, self-vulcanizing 0.5 hour, in temperature, be to solidify 3 hours at 200 ℃ again, obtain the epoxy resin nano composites containing modification halloysite nanotubes 0.1wt%.
With reference to above step, can prepare the epoxy resin nano composites containing modification halloysite nanotubes 0.1～20wt%.
Embodiment 2
(1) purification of halloysite nanotubes particle:
The halloysite nanotubes particle that 30g is pulverized and sieved mixes and is made into mixed solution with 240g deionized water, adds the Sodium hexametaphosphate 99 of 0.03g, stirs 1 hour until form the suspension that contains uniformly halloysite nanotubes particle; By standing 48 hours of described suspension, layering, the upper strata slurry of getting after standing is put into whizzer, with 10000r/min, carry out centrifugation 3 minutes, centrifugation gained throw out solid is 80 ℃ in temperature in baking oven and dries to quality unchangedly, then with 250 mesh sieves, sieve the halloysite nanotubes particle that obtains purifying;
(2) the silane coupler modified processing of halloysite nanotubes particle:
The halloysite nanotubes particle of the purifying that 15g step (1) is obtained joins in the hydrogen peroxide of 1000mL, ultrasonic dispersion stirring at room 6 hours after 5 minutes; Filter, by grind into powder after gained solids wash, obtain the halloysite nanotubes of acidifying; The halloysite nanotubes of getting 12g acidifying mixes with 600g dehydrated alcohol the suspension that is made into the halloysite nanotubes that contains uniformly acidifying, then the N-of 3g (β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH791) is joined in this suspension; In temperature, it is stirring reaction 48 hours at 25 ℃, filter, by gained solids wash dry rear grind into powder, and sieve with 200 mesh sieves, obtain through the inner chamber of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane modification and the modification halloysite nanotubes of outside surface graft N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.
The modification halloysite nanotubes and the epoxy resin that by above-mentioned preparation method, obtain are mixed with epoxy resin nano composites.
(1) in 115g epoxy resin ON828, add 38.5g acetone, stir and within 20 minutes, be made into diluent;
(2) get 38g modification halloysite nanotubes and join in the acetone of 380g, ultrasonic dispersion is stirred after 60 minutes and within 30 minutes, is made into the suspension that contains uniformly modification halloysite nanotubes;
(3) diluent step (1) being obtained mixes with the suspension that contains modification halloysite nanotubes that step (2) obtains, and be that at 75 ℃, the rotating speed with 500r/min stirs 2 hours in temperature, obtain the mixed system of epoxy resin ON828 and modification halloysite nanotubes; In the mixed system obtaining, add alicyclic ring type solidifying agent 3,3-dimethyl-4,4-diamino-dicyclohexyl methyl hydride (DMDC) 36.8g, and mix; Then the mixed solution mixing is transferred in vacuum drying oven, in temperature, be at 40 ℃, to carry out vacuum defoamation degasification, reactant after deaeration degasification is poured in curing mold, self-vulcanizing 5 hours, in temperature, be to solidify 5 hours at 150 ℃ again, obtain the epoxy resin nano composites containing modification halloysite nanotubes 5wt%.
With reference to above step, can prepare the epoxy resin nano composites containing modification halloysite nanotubes 0.1～20wt%.
By the epoxy resin nano composites sample of the modification halloysite nanotubes that contains different content making, and the epoxy resin nano composites sample of the unmodified halloysite nanotubes that contains different content (can be prepared with reference to comparative example), under shock-testing machine, by ASTM5942 standard, do respectively shock test.The shock strength of surveying with the variation of the increase of modification and unmodified halloysite nanotubes content as shown in Figure 2.Can see, after adding respectively the modification and unmodified halloysite nanotubes of 0.5wt%, 1wt%, 3wt% and 5wt%, the epoxy resin nano composites that contains modification halloysite nanotubes increases respectively 51.6%, 49.1%, 37.3% and 300.3% than the shock strength of the epoxy resin nano composites that contains unmodified halloysite nanotubes.Get impact fracture surface and observe under SEM, gained electromicroscopic photograph as shown in Figure 3.The halloysite nanotubes demonstrating in Fig. 3 after N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane modification is uniformly dispersed in epoxy resin ON828, and be combined better with the interface of epoxy resin ON828, at section part, can see the modification halloysite nanotubes that ruptures and stretch out.And that unmodified halloysite nanotubes disperses in epoxy resin ON828 is inhomogeneous, can produce very large coacervate, become the starting point that causes fracture, toughness increases limited.
Embodiment 3
(1) purification of halloysite nanotubes particle:
The halloysite nanotubes particle that 15g is pulverized and sieved mixes and is made into mixed solution with 180g deionized water, and the sodium polyacrylate that the molecular weight that adds 0.015g is 5000g/mol stirs 10 hours until form the suspension that contains uniformly halloysite nanotubes particle; By standing 8 hours of described suspension, layering, the upper strata slurry of getting after standing is put into whizzer, with 4000r/min, carry out centrifugation 30 minutes, centrifugation gained throw out solid is 100 ℃ in temperature in baking oven and dries to quality unchangedly, then with 150 mesh sieves, sieve the halloysite nanotubes particle that obtains purifying;
(2) the silane coupler modified processing of halloysite nanotubes particle:
The halloysite nanotubes particle of the purifying that 10g step (1) is obtained joins in the vitriol oil of 500mL, ultrasonic dispersion stirring at room 6 hours after 40 minutes; Filter, by grind into powder after gained solids wash, obtain the halloysite nanotubes of acidifying; The halloysite nanotubes of getting 9g acidifying mixes with 250g normal hexane the suspension that is made into the halloysite nanotubes that contains uniformly acidifying, then the gamma-methyl allyl acyloxypropyl trimethoxysilane of 1.8g (KH570) is joined in this suspension; In temperature, it is stirring reaction 36 hours at 70 ℃, filter, by gained solids wash dry rear grind into powder, and sieve with 250 mesh sieves, obtain through the inner chamber of gamma-methyl allyl acyloxypropyl trimethoxysilane modification and the modification halloysite nanotubes of outside surface grafting gamma-methyl allyl acyloxypropyl trimethoxysilane.
The modification halloysite nanotubes and the epoxy resin that by above-mentioned preparation method, obtain are mixed with epoxy resin nano composites.
(1) in 100g four glycidyl group-4, in 4 '-diaminodiphenylmethane (polyfunctional epoxy resin TGDDM), add 60g acetone, stir and within 20 minutes, be made into diluent;
(2) get 8g modification halloysite nanotubes and join in the acetone of 200g, ultrasonic dispersion is stirred after 18 minutes and within 45 minutes, is made into the suspension that contains uniformly modification halloysite nanotubes;
(3) diluent step (1) being obtained mixes with the suspension that contains modification halloysite nanotubes that step (2) obtains, and be that at 100 ℃, the rotating speed with 500r/min stirs 3 hours in temperature, obtain four glycidyl group-4, the mixed system of 4 '-diaminodiphenylmethane and modification halloysite nanotubes; In the mixed system obtaining, add acid anhydride type curing agent MNA (methyl carbic anhydride) 120g, and add the curing catalyst DMP-30 of 1g, and mix; Then the mixed solution mixing is transferred in vacuum drying oven, in temperature, be at 70 ℃, to carry out vacuum defoamation degasification, reactant after deaeration degasification is poured in curing mold, self-vulcanizing 2 hours, in temperature, be to solidify 15 hours at 120 ℃ again, obtain the epoxy resin nano composites containing modification halloysite nanotubes 3.2wt%.
With reference to above step, can prepare the epoxy resin nano composites containing modification halloysite nanotubes 0.1～20wt%.
Embodiment 4
(1) purification of halloysite nanotubes particle:
The halloysite nanotubes particle that 24g is pulverized and sieved mixes and is made into mixed solution with 250g deionized water, and the sodium polyacrylate that the molecular weight that adds 0.05g is 2000g/mol stirs 20 hours until form the suspension that contains uniformly halloysite nanotubes particle; By standing 30 hours of described suspension, layering, the upper strata slurry of getting after standing is put into whizzer, with 6000r/min, carry out centrifugation 25 minutes, centrifugation gained throw out solid is 80 ℃ in temperature in baking oven and dries to quality unchangedly, then with 200 mesh sieves, sieve the halloysite nanotubes particle that obtains purifying;
(2) the silane coupler modified processing of halloysite nanotubes particle:
The halloysite nanotubes particle of the purifying that 18g step (1) is obtained joins in the phosphoric acid of 240mL, ultrasonic dispersion stirring at room 15 hours after 28 minutes; Filter, by grind into powder after gained solids wash, obtain the halloysite nanotubes of acidifying; The halloysite nanotubes of getting 11g acidifying mixes with 450g dioxane the suspension that is made into the halloysite nanotubes that contains uniformly acidifying, then the γ of 4g-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH560) is joined in this suspension; In temperature, it is stirring reaction 23 hours at 105 ℃, filter, by gained solids wash dry rear grind into powder, and sieve with 200 mesh sieves, obtain through γ-(2,3-epoxy the third oxygen) the modification halloysite nanotubes of the inner chamber of propyl trimethoxy silicane modification and outside surface grafting γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane.
SEM figure by Fig. 4 can analyze the pattern of modification and unmodified halloysite nanotubes and dispersion, unmodified halloysite nanotubes can occur large-scale reunite and surface profile clear; γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane modification halloysite nanotubes later disperses better, large reunion can not occur, and surface has bedded substance to be deposited in the outside of nanotube.
The modification halloysite nanotubes and the epoxy resin that by above-mentioned preparation method, obtain are mixed with epoxy resin nano composites.
(1) in 100g polypropylene glycol diglycidyl ether DER732, add 50g acetone, stir and within 16 minutes, be made into diluent;
(2) get 10g modification halloysite nanotubes and join in the acetone of 100g, ultrasonic dispersion is stirred after 25 minutes and within 10 minutes, is made into the suspension that contains uniformly modification halloysite nanotubes;
(3) diluent step (1) being obtained mixes with the suspension that contains modification halloysite nanotubes that step (2) obtains, and be that at 65 ℃, the rotating speed with 300r/min stirs 3 hours in temperature, obtain the mixed system of polypropylene glycol diglycidyl ether and modification halloysite nanotubes; In the mixed system obtaining, add polyetheramine solidifying agent D400 33g altogether, and mix; Then the mixed solution mixing is transferred in vacuum drying oven, in temperature, be at 55 ℃, to carry out vacuum defoamation degasification, reactant after deaeration degasification is poured in curing mold, self-vulcanizing 2 hours, in temperature, be to solidify 8 hours at 100 ℃ again, obtain the epoxy resin nano composites containing modification halloysite nanotubes 7wt%.
With reference to above step, can prepare the epoxy resin nano composites containing modification halloysite nanotubes 0.1～20wt%.
Embodiment 5
(1) purification of halloysite nanotubes particle:
The halloysite nanotubes particle that 24g is pulverized and sieved mixes and is made into mixed solution with 250g deionized water, adds the tripoly phosphate sodium STPP of 0.15g, stirs 20 hours until form the suspension that contains uniformly halloysite nanotubes particle; By standing 30 hours of described suspension, layering, the upper strata slurry of getting after standing is put into whizzer, with 6000r/min, carry out centrifugation 25 minutes, centrifugation gained throw out solid is 80 ℃ in temperature in baking oven and dries to quality unchangedly, then with 150 mesh sieves, sieve the halloysite nanotubes particle that obtains purifying;
(2) the silane coupler modified processing of halloysite nanotubes particle:
The halloysite nanotubes particle of the purifying that 20g step (1) is obtained joins in the vitriol oil/hydrogen peroxide (volume ratio 8:3) mixed solution of 450mL, ultrasonic dispersion stirring at room 26 hours after 14 minutes; Filter, by grind into powder after gained solids wash, obtain the halloysite nanotubes of acidifying; The halloysite nanotubes of getting 16g acidifying mixes with 600g dimethylbenzene the suspension that is made into the halloysite nanotubes that contains uniformly acidifying, then the β of 10g-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (KH530) is joined in this suspension; In temperature, it is stirring reaction 30 hours at 150 ℃, filter, by gained solids wash dry rear grind into powder, and sieve with 200 mesh sieves, obtain through β-(3,4-epoxycyclohexyl) the modification halloysite nanotubes of the inner chamber of ethyl trimethoxy silane modification and outside surface grafting β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane.
As can be seen from Figure 5, the halloysite nanotubes after modification, the percentage of grafting of β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane on pipe is about 5%.
The modification halloysite nanotubes and the epoxy resin that by above-mentioned preparation method, obtain are mixed with epoxy resin nano composites.
(1) in the TDE85 of 100g (alicyclic glycidyl ester three-functionality-degree epoxy) and E51 blending epoxy, (mass ratio 3:1) adds 75g acetone, stirs and within 32 minutes, is made into diluent;
(2) get 15g modification halloysite nanotubes and join in the acetone of 105g, ultrasonic dispersion is stirred after 35 minutes and within 24 minutes, is made into the suspension that contains uniformly modification halloysite nanotubes;
(3) diluent step (1) being obtained mixes with the suspension that contains modification halloysite nanotubes that step (2) obtains, and be that at 75 ℃, the rotating speed with 300r/min stirs 3 hours in temperature, obtain the mixed system of above-mentioned blending epoxy and modification halloysite nanotubes; In the mixed system obtaining, add pnenolic aldehyde amine hardener T31 45g altogether, and mix; Then the mixed solution mixing is transferred in vacuum drying oven, in temperature, be at 60 ℃, to carry out vacuum defoamation degasification, reactant after deaeration degasification is poured in curing mold, self-vulcanizing 1 hour, in temperature, be to solidify 7 hours at 140 ℃ again, obtain the epoxy resin nano composites containing modification halloysite nanotubes 9.4wt%.
With reference to above step, can prepare the epoxy resin nano composites containing modification halloysite nanotubes 0.1～20wt%.
Claims (11)
1. a surface modifying treatment for halloysite nanotubes, is characterized in that, described method comprises the following steps:
(1) the halloysite nanotubes particle pulverizing and sieving is mixed according to the mass ratio of 1:8～1:25 with deionized water, add 0.1～2% the dispersion agent that is equivalent to halloysite nanotubes particle mass, stir, until form the suspension that contains uniformly halloysite nanotubes particle; Described suspension is standing, layering, getting upper strata slurry puts into whizzer and carries out centrifugation, centrifugation gained throw out solid is dried to quality in baking oven unchanged, then with 150～250 mesh sieves, sieve the halloysite nanotubes particle that obtains purifying;
(2) the halloysite nanotubes particle of purifying step (1) being obtained mixes according to the mass ratio of 1:10～1:80 with acid reagent, ultrasonic dispersion stirring at room 6～24 hours after 5～60 minutes; Filter, by grind into powder after gained solids wash, obtain the halloysite nanotubes of acidifying; By the halloysite nanotubes of acidifying and organic solvent, according to mass ratio, be the suspension that 1:10～1:50 is made into the halloysite nanotubes that contains uniformly acidifying, then silane coupling agent is joined in this suspension, the add-on of silane coupling agent be equivalent to acidifying halloysite nanotubes quality 20～120%; In temperature, it is stirring reaction 4～48 hours at 25～200 ℃, filter, by gained solids wash dry rear grind into powder, and sieve with 150～250 mesh sieves, obtain through the inner chamber of silane coupler modified processing and the modification halloysite nanotubes of outside surface grafted silane coupling agent;
It is a kind of in 2000～5000g/mol sodium polyacrylate that described dispersion agent is selected from Sodium hexametaphosphate 99, tripoly phosphate sodium STPP, trisodium phosphate and molecular weight.
2. method according to claim 1, is characterized in that: described centrifugation gained throw out solid is dried to quality in baking oven is unchanged, and the temperature of its baking oven is 50～100 ℃.
3. method according to claim 1, is characterized in that: described acid reagent is selected from one or more in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and hydrogen peroxide.
4. method according to claim 1, it is characterized in that: described organic solvent is selected from one or more in ethanol, methyl alcohol, Virahol, propyl carbinol, acetone, chloroform, methylene dichloride, tetrahydrofuran (THF), benzene,toluene,xylene, normal hexane, dioxane and DMF.
5. method according to claim 1, is characterized in that, described silane coupling agent is following coupling agent R
n-Si-X
(4-n)in a kind of, wherein: n is 1～3; End hydrolysable group X is a kind of in triethoxy, trimethoxy, methyl dimethoxy oxygen base, methyl diethoxy, dimethyl oxyethyl group;
(1), containing amino silane coupling agent, function organic group R is γ-aminopropyl, γ-(β aminoethyl) aminopropyl, N-(β-aminoethyl)-γ-aminopropyl, 3-[2-(2-aminoethylamino) ethylamino] a kind of group in propyl group, anilinomethyl, N-(2-amino-ethyl)-3-aminopropyl, 3-aminopropyl;
(2), containing the silane coupling agent of epoxy group(ing), R is a kind of in γ-(2,3-epoxy the third oxygen) propyl group, β-(3,4-epoxycyclohexyl) ethyl;
(3) other silane coupling agent, R is a kind of in γ-isocyanate group propyl group, gamma-methyl allyl acyloxypropyl, γ-mercapto propyl group, γ-chloropropyl and vinyl, propyl group succinyl oxide base.
6. an epoxy resin nano composites, is characterized in that: the modification halloysite nanotubes that described epoxy resin nano composites is prepared by the method described in claim 1～5 any one and epoxy resin are mixed with and obtain.
7. epoxy resin nano composites according to claim 6, is characterized in that, described epoxy resin nano composites is to be prepared by following methods:
(1) in epoxy resin, adding is the acetone of epoxy resin quality 30～300%, stirs and is made into diluent;
(2), by the ultrasonic acetone being scattered in respect to 10～100 times of modification halloysite nanotubes quality of modification halloysite nanotubes, stir and be made into the suspension that contains uniformly modification halloysite nanotubes;
(3) diluent step (1) being obtained mixes with the suspension that contains modification halloysite nanotubes that step (2) obtains, and be to stir at 25～100 ℃ in temperature, obtain the mixed system of epoxy resin and modification halloysite nanotubes, wherein the quality of the modification halloysite nanotubes in mixed system is 0.1～20% of epoxy resin quality; In the mixed system obtaining, add epoxy curing agent, the amount of the epoxy curing agent adding is for can make epoxy resin contained in mixed system can solidify required amount completely, and mixing mixes; Then the mixed solution mixing is transferred in vacuum drying oven, in temperature, be at 40～80 ℃, to carry out vacuum defoamation degasification, reactant after deaeration degasification is poured in curing mold, self-vulcanizing, in temperature, be to solidify 2～24 hours at 50～200 ℃ again, obtain the epoxy resin nano composites that modification halloysite nanotubes mixes with epoxy resin.
8. epoxy resin nano composites according to claim 7, is characterized in that: in described mixed system, add and have epoxy resin cure promotor.
9. epoxy resin nano composites according to claim 7, is characterized in that: it is that epoxy resin, Bisphenol F are that epoxy resin, bisphenol S are a kind of in epoxy resin, hydrogenated bisphenol A epoxy resin, novolac epoxy, aliphatic glycidyl ether resin, brominated epoxy resin, Racemic glycidol esters resin, aminoepoxy resin, cycloaliphatic epoxy resin, epoxidation polyolefine, organosilicon epoxy resin and acrylic acid or the like epoxy resin that described epoxy resin is selected from dihydroxyphenyl propane.
10. epoxy resin nano composites according to claim 7, is characterized in that: described epoxy curing agent is selected from fatty amine, cycloaliphatic amines, aromatic amine, tertiary amine, acid anhydrides, imidazoles, polymeric amide, polyetheramine, polythiol, a kind of in solidifying agent hides.
11. epoxy resin nano composites according to claim 10, is characterized in that: the described solidifying agent of hiding is selected from a kind of in amine complex compound, trimeric cyanamide and derivative thereof, Diaminomaleonitrile, the micro capsule curing agent of Dyhard RU 100, imidazoles metal salt complex, organic hydrazides, boron trifluoride.
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