CN103087553A - Maleic anhydride grafted modified halloysite nanotube and preparation method thereof - Google Patents
Maleic anhydride grafted modified halloysite nanotube and preparation method thereof Download PDFInfo
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- CN103087553A CN103087553A CN2013100372334A CN201310037233A CN103087553A CN 103087553 A CN103087553 A CN 103087553A CN 2013100372334 A CN2013100372334 A CN 2013100372334A CN 201310037233 A CN201310037233 A CN 201310037233A CN 103087553 A CN103087553 A CN 103087553A
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Abstract
The invention relates to a maleic anhydride grafted modified halloysite nanotube and a preparation method thereof, belonging to the field of inorganic nanoparticle surface modification. The preparation method comprises the following steps of: purifying a halloysite nanotube, reacting the halloysite nanotube and a silane coupling agent, and introducing an active amino group onto the surface of the halloysite nanotube, reacting the amino group and maleic anhydride, thereby grafting the maleic anhydride onto the surface of the halloysite nanotube through a chemical bond. The preparation method disclosed by the invention aims at grafting the maleic anhydride onto the surface of the halloysite nanotube through the chemical bond to obtain a novel maleic anhydride grafted modified halloysite nanotube which can mix with a plurality of resin substrates, so that not only are dispersion and compatibility of the nanotube in the resin substrate improved, but also mechanical performance and flame-resistance performance of the composite material are enhanced.
Description
Technical field
The present invention relates to inorganic nano-particle surface modification field, be specifically related to a kind of MALEIC ANHYDRIDE graft modification halloysite nanotubes and preparation method thereof.
Background technology
Halloysite is a kind of natural clay mineral, and also referred to as metakaolin, its even size distribution belongs to monodimension nanometer material.There are abundant reserves in the halloysite ore deposit countries such as nearly all there is distribution in each continent in the whole world, and is Chinese, French, Belgian, and China's halloysite ore deposit mainly is distributed in the provinces such as Guangdong, Hunan, Hubei, Sichuan.Halloysite nanotubes is by kaolinic lamella curling forming under natural condition, and general halloysite nanotubes is that several lamellas are curling forms by 20, and the pipe external diameter is about 50nm, and internal diameter is about 15-20nm, and length is about 100-1500nm, is natural many walls nanotube.Due to its special construction, demonstrate good mechanical property, flame retardant properties and thermostability based on the polymer based nanocomposites goods of halloysite nanotubes, its unique performance causes that people study interest widely.But there are a lot of hydroxyls in the halloysite nanotubes surface, makes halloysite nanotubes polarity larger, thereby when preparation halloysite nanotubes matrix material, due to the difference of polarity, it is dispersed and consistency is often not fully up to expectations.in recent years, researcher is attempted halloysite nanotubes is carried out surface modification successively both at home and abroad, use respectively 3-(2-aminoethyl) aminopropyl triethoxysilane (Applied Catalysis A:General as people such as S.Barrientos-Ram í rez and Yuan, 2011, 406, 22 – 33) and 3-aminopropyl triethoxysilane (J.Phys.Chem.C2008, 112, 15742 – 15751) halloysite nanotubes is carried out surface modification, thereby improve its consistency, Chinese invention patent (CN101284670A) has been introduced to process through certain physico-chemical process and has been obtained surperficial keyed jointing with the halloysite nanotubes of-NCO group, has good reactive behavior, for the preparation polymer based nanocomposites provides various selection.
The present invention adopts two step process, first by silane coupling agent being grafted to the halloysite nanotubes surface, and then by active amino and maleic acid anhydride reactant, thereby MALEIC ANHYDRIDE is grafted to the halloysite nanotubes surface.The introducing of MALEIC ANHYDRIDE and silane coupling agent can effectively improve the consistency of halloysite in resin matrix, simultaneously, for flame retardant resistance, certain synergistic effect is arranged also.
Summary of the invention
The objective of the invention is to be to prepare a kind of halloysite nanotubes of novel surface graft modification, MALEIC ANHYDRIDE by coupling agent, is grafted to the halloysite nanotubes surface in the mode of chemical bond, improve its dispersiveness and consistency in resin matrix.
For achieving the above object, the present invention adopts following technical scheme:
A kind of MALEIC ANHYDRIDE graft modification halloysite nanotubes and preparation method thereof is characterized in that comprising the steps:
(1) purification halloysite nanotubes: halloysite nanotubes is dispersed in deionized water, and stirred 5-30 minute; Again the turbid liquid in upper strata derived and add appropriate hydrogen peroxide, 50-90 ℃ of lower stirring reaction 8-24h; With millipore filtration or filter paper vacuum filtration, product is complete drying under 40 ℃ of-140 ℃ of vacuum states with products therefrom.
(2) produce coupling agent modified halloysite nanotubes: the halloysite nanotubes ultrasonication with purifying is well dispersed in toluene it; Add afterwards silane coupling agent, react 12-36h under 80-130 ℃; With products therefrom acetone repetitive scrubbing, after millipore filtration or filter paper vacuum filtration, complete drying under vacuum state obtains coupling agent modified halloysite nanotubes.
(3) produce MALEIC ANHYDRIDE graft modification halloysite nanotubes: described coupling agent modified halloysite nanotubes is fully mixed by a certain percentage with MALEIC ANHYDRIDE, toluene, and the supersound process certain hour makes it fully dissolve dispersion.Logical nitrogen deoxygenation is after 20-60 minute, under 80 ℃-120 ℃ and strong magnetic agitation, and reaction 4h-24h.After reaction finished, with millipore filtration or filter paper vacuum filtration, and after repeatedly washing with toluene and acetone, product is complete drying under 80 ℃ of-140 ℃ of vacuum states, obtains MALEIC ANHYDRIDE graft modification halloysite nanotubes with products therefrom.
Step of the present invention (1) halloysite nanotubes used is 600-100 order white powder.
Step of the present invention (1) purification step proportioning used is: the halloysite nanotubes of the every 10-50 mass parts hydrogen peroxide of 100-500 parts by volume.
Step of the present invention (2) coupling agent used is 3-aminopropyl triethoxysilane or 3-(2-aminoethyl) aminopropyl triethoxysilane.
Step of the present invention (1), (2) and step (3) millipore filtration used aperture are 0.3-0.6 μ m, and filter paper is conventional filter paper, and the vacuum-drying time is 10h-30h.
Step of the present invention (2) halloysite nanotubes consumption used is the 30-60 mass parts, and the silane coupling agent consumption is the 3-6 mass parts, and the toluene consumption is the 300-500 parts by volume.
Step of the present invention (3) halloysite nanotubes consumption used is the 30-60 mass parts, and the MALEIC ANHYDRIDE consumption is the 30-60 mass parts, and the toluene consumption is the 300-500 parts by volume
The present invention has prepared a kind of brand-new surface modification halloysite nanotubes, MALEIC ANHYDRIDE is grafted to the halloysite nanotubes surface, technique is simple, raw material is easy to get, preparation amount is large, and transformation efficiency is high, when improving consistency, also can play certain synergistic effect to flame retardant properties, can be used as a kind of novel polymeric additive.
In practical application, the MALEIC ANHYDRIDE graft modification halloysite nanotubes of the present invention preparation can with the blend of various kinds of resin matrix, thereby the nano composite material of obtaining.The modification halloysite nanotubes can well improve original halloysite nanotubes dispersed, the poor problem of consistency in resin matrix, improves simultaneously flame retardant properties and the mechanical property of matrix resin material.
Description of drawings
Fig. 1 is the schematic flow sheet of a kind of surface modification halloysite nanotubes of providing of the embodiment of the present invention;
Fig. 2 is a kind of surface modification halloysite nanotubes of providing of the embodiment of the present invention and the infrared comparison diagram of original halloysite nanotubes;
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is carried out comparatively detailed explanation.
Embodiment 1:
(1) the 2g halloysite nanotubes is dispersed in deionized water, and stirred 15 minutes; Again the turbid liquid in upper strata is imported Erlenmeyer flask and adds the 45ml hydrogen peroxide, 80 ℃ of lower stirring reaction 12h; With the products therefrom vacuum filtration, product is complete drying under 80 ℃ of vacuum states.
(2) halloysite nanotubes of getting the 2g purification fully mixes with the toluene of 50ml drying, and ultrasonic 30min makes it fully dissolve dispersion, adds afterwards the 0.5g3-aminopropyl triethoxysilane, 120 ℃ of lower stirring reaction 24h; With products therefrom acetone repetitive scrubbing, after vacuum filtration, complete drying under vacuum state obtains coupling agent modified halloysite nanotubes.
(3) get the described coupling agent modified halloysite nanotubes of 2g and fully mix with 2g MALEIC ANHYDRIDE, 50ml toluene, ultrasonic 30min makes it fully dissolve dispersion.Logical nitrogen deoxygenation is after 20 minutes, under 110 ℃ and strong magnetic agitation, and reaction 6h.After reaction finished, with the products therefrom vacuum filtration, and after repeatedly washing with toluene and acetone, product is complete drying under 80 ℃ of vacuum states, obtains MALEIC ANHYDRIDE graft modification halloysite nanotubes.
Modification halloysite nanotubes and original halloysite nanotubes are carried out infrared analysis, compare with unmodified halloysite nanotubes, the halloysite nanotubes after modification is at 2920cm
-1The characteristic peak of methylene radical, 1700cm have appearred in the place
-1The characteristic peak of the two keys of C=O, 1400cm have appearred in the place
-1The characteristic peak of the two keys of C=C has appearred in the place.The MALEIC ANHYDRIDE that can judge thus on halloysite nanotubes successful grafting.
Embodiment 2:
(1) the 2g halloysite nanotubes is dispersed in deionized water, and stirred 15 minutes; Again the turbid liquid in upper strata is imported Erlenmeyer flask and adds the 45ml hydrogen peroxide, 80 ℃ of lower stirring reaction 12h; With the products therefrom vacuum filtration, product is complete drying under 80 ℃ of vacuum states.
(2) halloysite nanotubes of getting the 2g purification fully mixes with the toluene of 50ml drying, and ultrasonic 30min makes it fully dissolve dispersion, adds afterwards the 0.4g3-aminopropyl triethoxysilane, 110 ℃ of lower stirring reaction 24h; With products therefrom acetone repetitive scrubbing, after vacuum filtration, complete drying under vacuum state obtains coupling agent modified halloysite nanotubes.
(3) get the described coupling agent modified halloysite nanotubes of 2g and fully mix with 2g MALEIC ANHYDRIDE, 50ml toluene, ultrasonic 30min makes it fully dissolve dispersion.Logical nitrogen deoxygenation is after 20 minutes, under 110 ℃ and strong magnetic agitation, and reaction 6h.After reaction finished, with the products therefrom vacuum filtration, and after repeatedly washing with toluene and acetone, product is complete drying under 80 ℃ of vacuum states, obtains MALEIC ANHYDRIDE graft modification halloysite nanotubes.
Embodiment 3:
(1) the 2g halloysite nanotubes is dispersed in deionized water, and stirred 15 minutes; Again the turbid liquid in upper strata is imported Erlenmeyer flask and adds the 45ml hydrogen peroxide, 90 ℃ of lower stirring reaction 12h; With the products therefrom vacuum filtration, product is complete drying under 80 ℃ of vacuum states.
(2) halloysite nanotubes of getting the 2g purification fully mixes with the toluene of 50ml drying, and ultrasonic 30min makes it fully dissolve dispersion, adds afterwards the 0.5g3-aminopropyl triethoxysilane, 110 ℃ of lower stirring reaction 24h; With products therefrom acetone repetitive scrubbing, after vacuum filtration, complete drying under vacuum state obtains coupling agent modified halloysite nanotubes.
(3) get the described coupling agent modified halloysite nanotubes of 2g and fully mix with 2g MALEIC ANHYDRIDE, 50ml toluene, ultrasonic 30min makes it fully dissolve dispersion.Logical nitrogen deoxygenation is after 20 minutes, under 100 ℃ and strong magnetic agitation, and reaction 6h.After reaction finished, with the products therefrom vacuum filtration, and after repeatedly washing with toluene and acetone, product is complete drying under 80 ℃ of vacuum states, obtains MALEIC ANHYDRIDE graft modification halloysite nanotubes.
Embodiment 4:
(1) the 2g halloysite nanotubes is dispersed in deionized water, and stirred 15 minutes; Again the turbid liquid in upper strata is imported Erlenmeyer flask and adds the 45ml hydrogen peroxide, 70 ℃ of lower stirring reaction 10h; With the products therefrom vacuum filtration, product is complete drying under 80 ℃ of vacuum states.
(2) halloysite nanotubes of getting the 2g purification fully mixes with the toluene of 50ml drying, and ultrasonic 30min makes it fully dissolve dispersion, adds afterwards the 0.4g3-aminopropyl triethoxysilane, 120 ℃ of lower stirring reaction 24h; With products therefrom acetone repetitive scrubbing, after vacuum filtration, complete drying under vacuum state obtains coupling agent modified halloysite nanotubes.
(3) get the described coupling agent modified halloysite nanotubes of 2g and fully mix with 2g MALEIC ANHYDRIDE, 50ml toluene, ultrasonic 30min makes it fully dissolve dispersion.Logical nitrogen deoxygenation is after 20 minutes, under 120 ℃ and strong magnetic agitation, and reaction 6h.After reaction finished, with the products therefrom vacuum filtration, and after repeatedly washing with toluene and acetone, product is complete drying under 80 ℃ of vacuum states, obtains MALEIC ANHYDRIDE graft modification halloysite nanotubes.
Embodiment 5:
(1) the 2g halloysite nanotubes is dispersed in deionized water, and stirred 15 minutes; Again the turbid liquid in upper strata is imported Erlenmeyer flask and adds the 45ml hydrogen peroxide, 80 ℃ of lower stirring reaction 12h; With the products therefrom vacuum filtration, product is complete drying under 80 ℃ of vacuum states.
(2) halloysite nanotubes of getting the 2g purification fully mixes with the toluene of 50ml drying, and ultrasonic 30min makes it fully dissolve dispersion, adds afterwards the 0.5g3-aminopropyl triethoxysilane, 120 ℃ of lower stirring reaction 24h; With products therefrom acetone repetitive scrubbing, after vacuum filtration, complete drying under vacuum state obtains coupling agent modified halloysite nanotubes.
(3) get the described coupling agent modified halloysite nanotubes of 2.5g and fully mix with 2.5g MALEIC ANHYDRIDE, 60ml toluene, ultrasonic 30min makes it fully dissolve dispersion.Logical nitrogen deoxygenation is after 20 minutes, under 120 ℃ and strong magnetic agitation, and reaction 12h.After reaction finished, with the products therefrom vacuum filtration, and after repeatedly washing with toluene and acetone, product is complete drying under 80 ℃ of vacuum states, obtains MALEIC ANHYDRIDE graft modification halloysite nanotubes.
Embodiment 6:
(1) the 2g halloysite nanotubes is dispersed in deionized water, and stirred 15 minutes; Again the turbid liquid in upper strata is imported Erlenmeyer flask and adds the 45ml hydrogen peroxide, 80 ℃ of lower stirring reaction 18h; With the products therefrom vacuum filtration, product is complete drying under 80 ℃ of vacuum states.
(2) halloysite nanotubes of getting the 2g purification fully mixes with the toluene of 50ml drying, and ultrasonic 30min makes it fully dissolve dispersion, adds afterwards the 0.5g3-aminopropyl triethoxysilane, 110 ℃ of lower stirring reaction 30h; With products therefrom acetone repetitive scrubbing, after vacuum filtration, complete drying under vacuum state obtains coupling agent modified halloysite nanotubes.
(3) get the described coupling agent modified halloysite nanotubes of 2g and fully mix with 2g MALEIC ANHYDRIDE, 50ml toluene, ultrasonic 30min makes it fully dissolve dispersion.Logical nitrogen deoxygenation is after 20 minutes, under 100 ℃ and strong magnetic agitation, and reaction 12h.After reaction finished, with the products therefrom vacuum filtration, and after repeatedly washing with toluene and acetone, product is complete drying under 80 ℃ of vacuum states, obtains MALEIC ANHYDRIDE graft modification halloysite nanotubes.
Claims (9)
1. a MALEIC ANHYDRIDE graft modification halloysite nanotubes, is characterized in that: MALEIC ANHYDRIDE is surperficial to halloysite nanotubes by the chemical bond grafting.
2. the preparation method of a MALEIC ANHYDRIDE graft modification halloysite nanotubes, is characterized in that comprising the steps:
(1) purification halloysite nanotubes: halloysite nanotubes is dispersed in deionized water, and stirred 5-30 minute; Again the turbid liquid in upper strata derived and add appropriate hydrogen peroxide, 50-90 ℃ of lower stirring reaction 8-24h; With millipore filtration or filter paper vacuum filtration, product is complete drying under 40 ℃ of-140 ℃ of vacuum states with products therefrom.
(2) produce coupling agent modified halloysite nanotubes: the halloysite nanotubes ultrasonication with purifying is well dispersed in toluene it; Add afterwards silane coupling agent, react 12-36h under 80-130 ℃; With products therefrom acetone repetitive scrubbing, after millipore filtration or filter paper vacuum filtration, complete drying under vacuum state obtains coupling agent modified halloysite nanotubes.
(3) produce MALEIC ANHYDRIDE graft modification halloysite nanotubes: described coupling agent modified halloysite nanotubes is fully mixed by a certain percentage with MALEIC ANHYDRIDE, toluene, and the supersound process certain hour makes it fully dissolve dispersion.Logical nitrogen deoxygenation is after 20-60 minute, under 80 ℃-120 ℃ and strong magnetic agitation, and reaction 4h-24h.After reaction finished, with millipore filtration or filter paper vacuum filtration, and after repeatedly washing with toluene and acetone, product is complete drying under 80 ℃ of-140 ℃ of vacuum states, obtains MALEIC ANHYDRIDE graft modification halloysite nanotubes with products therefrom.
3. the preparation method of MALEIC ANHYDRIDE graft modification halloysite nanotubes according to claim 2, is characterized in that step (1) halloysite nanotubes used is 600-100 order white powder.
4. the preparation method of MALEIC ANHYDRIDE graft modification halloysite nanotubes according to claim 2, is characterized in that step (1) purification step proportioning used is: the halloysite nanotubes of the every 10-50 mass parts hydrogen peroxide of 100-500 parts by volume.
5. the preparation method of MALEIC ANHYDRIDE graft modification halloysite nanotubes according to claim 2, is characterized in that step (2) coupling agent used is 3-aminopropyl triethoxysilane or 3-(2-aminoethyl) aminopropyl triethoxysilane.
6. the preparation method of MALEIC ANHYDRIDE graft modification halloysite nanotubes according to claim 2 is characterized in that step (1), (2) and step (3) millipore filtration used aperture are 0.3-0.6 μ m, and filter paper is conventional filter paper.
7. the preparation method of MALEIC ANHYDRIDE graft modification halloysite nanotubes according to claim 2, is characterized in that step (1), (2) and step (3) vacuum-drying time are 10h-30h.
8. the preparation method of MALEIC ANHYDRIDE graft modification halloysite nanotubes according to claim 2, it is characterized in that step (2) halloysite nanotubes consumption used is the 30-60 mass parts, the silane coupling agent consumption is the 3-6 mass parts, and the toluene consumption is the 300-500 parts by volume.
9. the preparation method of MALEIC ANHYDRIDE graft modification halloysite nanotubes according to claim 2, it is characterized in that step (3) halloysite nanotubes consumption used is the 30-60 mass parts, the MALEIC ANHYDRIDE consumption is the 30-60 mass parts, and the toluene consumption is the 300-500 parts by volume.
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| CN105086520A (en) * | 2014-12-09 | 2015-11-25 | 西南石油大学 | Nanometer SiO2 surface controllable modification method |
| CN105482274A (en) * | 2016-01-01 | 2016-04-13 | 崇夕山 | High-performance rubber for ship fender |
| CN105860138A (en) * | 2016-04-21 | 2016-08-17 | 河南工程学院 | Preparation method of N-(substituted phenyl) maleimide grafted halloysite nanotube |
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| CN105086520A (en) * | 2014-12-09 | 2015-11-25 | 西南石油大学 | Nanometer SiO2 surface controllable modification method |
| CN105482274A (en) * | 2016-01-01 | 2016-04-13 | 崇夕山 | High-performance rubber for ship fender |
| CN105860138A (en) * | 2016-04-21 | 2016-08-17 | 河南工程学院 | Preparation method of N-(substituted phenyl) maleimide grafted halloysite nanotube |
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| CN109135184A (en) * | 2017-06-27 | 2019-01-04 | 洛阳尖端技术研究院 | A kind of epoxide resin wave-absorbing composite material and preparation method |
| CN109135184B (en) * | 2017-06-27 | 2023-03-03 | 洛阳尖端技术研究院 | Epoxy resin wave-absorbing composite material and preparation method thereof |
| CN107459931A (en) * | 2017-06-30 | 2017-12-12 | 天长市巨龙车船涂料有限公司 | A kind of water paint of water resistant abrasive proof |
| CN111704748A (en) * | 2020-06-29 | 2020-09-25 | 上海中镭新材料科技有限公司 | Modified nano-oxide particle, preparation method thereof and spraying-free polyamide material containing modified nano-oxide particle |
| CN111704748B (en) * | 2020-06-29 | 2022-07-08 | 上海中镭新材料科技有限公司 | Modified nano-oxide particle, preparation method thereof and spraying-free polyamide material containing modified nano-oxide particle |
| CN113549342A (en) * | 2021-09-02 | 2021-10-26 | 和也健康科技有限公司 | Method for modifying surface of stone needle powder |
| CN113861433A (en) * | 2021-09-06 | 2021-12-31 | 浙大宁波理工学院 | Synergistic flame retardant and preparation method and application thereof |
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