CN106279772A - The method that a kind of halloysite nanotubes surface in situ growth silicon dioxide prepares hydridization filler - Google Patents
The method that a kind of halloysite nanotubes surface in situ growth silicon dioxide prepares hydridization filler Download PDFInfo
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- CN106279772A CN106279772A CN201610740697.5A CN201610740697A CN106279772A CN 106279772 A CN106279772 A CN 106279772A CN 201610740697 A CN201610740697 A CN 201610740697A CN 106279772 A CN106279772 A CN 106279772A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses the method that a kind of halloysite nanotubes surface in situ growth silicon dioxide prepares hydridization filler.First halloysite nanotubes is distributed in solvent by the method, is subsequently adding ammonia and catalyst, after ultrasonic disperse, then adds silicon source monomer, stirring reaction 1 10 hours, centrifugal filtration, washing under the conditions of 30 80 DEG C, outwell the supernatant, dry, obtain hydridization filler.Compared with halloysite nanotubes, the specific surface area of hydridization filler prepared by the present invention dramatically increases, after adding in polymer as filler, the silicon dioxide on surface does not haves in the course of processing of polymer composites and comes off, more polymer molecular chain can be adsorbed, it is obviously enhanced organic/inorganic interface cohesion effect, and the irregular surface of hydridization filler is that the process of further functional surface provides more active group, and the preparation field at functionalization filler and high-performance composite materials has potential using value.
Description
Technical field
The present invention relates to the preparing technical field of novel hybride filler, be specifically related to a kind of halloysite nanotubes surface in situ
The method that growth silicon dioxide prepares hydridization filler.
Background technology
Along with the development of material science, there is high-performance and multi-functional hybrid material causes researcher and engineering
The extensive concern of personnel.Common inorganic filler can be divided into one-dimensional rod-like filler (such as CNT, Ai Luo according to its geometry
Stone nanotube etc.), two-dimensional sheet filler (such as Graphene, montmorillonite etc.) and three-dimensional manometer particle (such as silicon dioxide granule etc.),
And the final performance of composite is had a very big impact by the geometry of inorganic filler and structure.Therefore, current researcher
Begin attempt to utilize two or more fillers with different geometry to prepare novel hydridization filler, this kind of novel hydridization
Filler is capable of good reinforcement and toughening effect in polymeric matrix.
Halloysite nanotubes is a kind of one-dimensional to have the natural tubular filler compared with high length-diameter ratio, is commonly added to polymer
Matrix improves the mechanical property of composite, heat stability and fire resistance, and it is cheap, extensively deposit at nature
, it is easy to industrialization, halloysite nanotubes also has important application in medicament slow release thin film, super hydrophobic material field in addition.
Silicon dioxide is a kind of important light reinforced filling, and mechanical property and dynamic property to composite have the biggest side
Help.The hydridization filler utilizing one-dimensional halloysite nanotubes and three-dimensional silicon dioxide granule to prepare not only has certain major diameter
Ratio, and its specific surface area significantly improves, and is strengthened with the interface cohesion of polymeric matrix, is that a kind of preferably nanometer is filled out
Material.But the novel hybride filler prepared at halloysite nanotubes nonloaded silica currently with the method for growth in situ yet there are no
Report.
Growth in situ is to utilize silicon source monomer to carry out sol gel reaction on the surface of halloysite nanotubes, by chemistry
Key is at the irregular silica dioxide granule of area load last layer of halloysite nanotubes.This method is simple to operate, the most multiple
Between miscellaneous preparation and post-processing step, it is easy to accomplish industrialization, and the halloysite nanotubes-SiO 2 hybrid filler of preparation
Being to be connected by chemical bond, silica dioxide granule will not come off in follow-up Polymer Processing from halloysite nanotubes, tool
There is the biggest potential using value.
Summary of the invention
The method that it is an object of the invention to utilize easy growth in situ, in the Surface Creation nanometer of halloysite nanotubes
Silicon dioxide, prepares a kind of hydridization filler.In this hydridization filler, silicon dioxide is grown in galapectite by chemical bond and receives
The surface of mitron, it is to avoid produce the separation that comes off in follow-up Polymer Processing, and this hydridization filler has irregularly
Surface, compared with halloysite nanotubes, specific surface area is greatly improved, and is also remarkably reinforced with the interface cohesion of polymeric matrix,
In high-performance composite materials modification field, there is the highest practical value, additionally, the irregular silicon dioxide grain on galapectite surface
The existence of son, the preparation for multi-functional filler provides more reactive group, also has in functional new packing application
There is the highest application prospect.
Hydridization filler of the present invention is to utilize silicon source monomer in the suspension of halloysite nanotubes, is coagulated by colloidal sol
Glue method hydrolytic condensation goes out silicon dioxide granule in halloysite nanotubes superficial growth, and then obtains this hydridization filler.
The purpose of the present invention is achieved through the following technical solutions.
The method that a kind of halloysite nanotubes surface in situ growth silicon dioxide prepares hydridization filler, comprises the following steps:
The first step: first halloysite nanotubes (HNTs) is distributed in solvent, adds ammonia and catalyst, after ultrasonic disperse,
Add silicon source monomer, stirring reaction 1-10 hour under the conditions of 30-80 DEG C；
Second step: by first step products therefrom centrifugal filtration, washing, remove the supernatant, dry, obtain hydridization filler.
Further, described solvent is water, ethanol, toluene, acetone, petroleum ether, ethyl acetate, dimethylbenzene and Pentamethylene.
In one or both mixed solvent.
Further, described catalyst is dibutyl tin laurate, Bis(lauroyloxy)dioctyltin and tetrabutyl phosphonium bromide
More than one in ammonium.
Further, described silicon source monomer is the one in methyl silicate, tetraethyl orthosilicate (TEOS) and sodium silicate.
Further, the solid content that described halloysite nanotubes is distributed in solvent is 3%-10%.
Further, the addition of described ammonia accounts for the 5%-15% of solvent volume.
Further, the addition of described catalyst is 0.1-1.5ml.
Further, described silicon source monomer accounts for the 50wt%-75 wt% of halloysite nanotubes.
Further, the number of times of described washing is 3-8 time.
Further, the condition of described drying is baking 8-24h in the vacuum drying oven of 50-100 DEG C.
Compared with prior art, the hydridization filler that prepared by the present invention has the advantage that and characteristic:
(1) the hydridization filling surface of the present invention is irregular, and specific surface area significantly improves, it is possible to formed higher with polymeric matrix
Interface cohesion effect；And the silicon dioxide of surface attachment provides more active group, for further surface modification and function
The preparation changing filler provides the foundation.
(2) halloysite nanotubes-SiO 2 hybrid filler utilizing growth in situ to prepare achieves halloysite nanotubes
Chemical bonds with silicon dioxide granule, it is to avoid the de-of silicon dioxide granule occurs in follow-up polymer processing
Fall, expand the range of application of this hydridization filler.
(3) growth in situ is a kind of preparation method simple to operate, it is not necessary to complicated preparation process and post-processing step,
And the raw material of preparing of hydridization filler naturally occurs, with low cost, be conducive to realizing in high-performance and multi-functional hybrid material field
Industrialization.
Accompanying drawing explanation
Fig. 1 is the SEM figure of halloysite nanotubes-SiO 2 hybrid filler.
Fig. 2 is the TEM figure of halloysite nanotubes-SiO 2 hybrid filler.
Fig. 3 is the thermogravimetric curve figure of halloysite nanotubes, silicon dioxide and hydridization filler.
Fig. 4 is galapectite and the infrared spectrum of galapectite-SiO 2 hybrid filler.
Fig. 5 is the impact property figure of unsaturated polyester composite.
Fig. 6 is the principle schematic preparing hydridization filler with halloysite nanotubes and silicon source monomer tetraethyl orthosilicate.
Detailed description of the invention
In order to be better understood from the present invention, below in conjunction with embodiment and accompanying drawing, the present invention done further careful saying
Bright, but the scope of protection of present invention is not limited only to the scope of embodiment statement.
Embodiment 1
The halloysite nanotubes of 5g purification is distributed in the dehydrated alcohol of 100ml 95%, and adds the ammonia of 5ml 25wt%,
Ultrasonic disperse 20min at 30 DEG C, then dropping 0.2ml dibutyl tin laurate, at 40 DEG C, stir 0.5 hour, then
The tetraethyl orthosilicate of dropping 2.5g, after dropping, 40 DEG C of stirring reactions 3 hours, product centrifugation also used washing with alcohol
Five times, put into 80 DEG C of vacuum drying ovens and dry 10 hours, obtain halloysite nanotubes-SiO 2 hybrid filler.Fig. 6 is with an angstrom Lip river
Stone nanotube and silicon source monomer tetraethyl orthosilicate prepare the principle schematic of hydridization filler.Fig. 1 is halloysite nanotubes-titanium dioxide
The SEM figure of silicon hybridization filler, Fig. 2 is the TEM figure of halloysite nanotubes-SiO 2 hybrid filler.It can be seen that
One layer of irregular silicon dioxide granule of the superficial growth of halloysite nanotubes, and there's almost no single galapectite nanometer
Pipe and silicon dioxide granule, so not being both simple and mechanical mixing, but silicon dioxide granule is successfully given birth to by chemical bond
Long on the surface of halloysite nanotubes.
Embodiment 2
In 250 ml beakers, add 15g halloysite nanotubes, be subsequently adding 150ml dehydrated alcohol, 5ml deionized water, 10.5
The ammonia of ml 25 wt%, ultrasonic disperse 0.5 hour at 30 DEG C, then dropping 0.5ml dibutyl tin laurate, and drip
10g methyl silicate, reacts 10 hours at 30 DEG C, after centrifugation, and with absolute ethanol washing 8 times, 60 DEG C of vacuum bakings
Case is dried 24 hours, obtains halloysite nanotubes-SiO 2 hybrid filler.Fig. 3 is halloysite nanotubes, silicon dioxide and miscellaneous
Changing the thermogravimetric curve figure of filler, the Thermogravimetric Data of this figure shows that the silicon dioxide granule of the surface attachment at halloysite nanotubes is
35wt%, compared with the silicon dioxide of the halloysite nanotubes of higher weightlessness and relatively low weightlessness, the hydridization filler of preparation has medium
Heat stability.
Embodiment 3
In 500ml there-necked flask, 20g halloysite nanotubes is distributed to 237.5ml dehydrated alcohol, is subsequently adding
The ammonia of 15ml25wt%, 12.5ml deionized water, 0.1ml tin dilaurate dioctyl tin, ultrasonic disperse 20min at 30 DEG C, will
12.5g tetraethyl orthosilicate is added drop-wise in suspension, stirring reaction 8 hours at 60 DEG C, and centrifuge washing 5 times is then true at 100 DEG C
Empty baking oven dries 8 hours, obtains halloysite nanotubes-SiO 2 hybrid filler；Fig. 4 is galapectite and galapectite-titanium dioxide
The infrared spectrum of silicon hybridization filler, as can be seen from the figure compared with pure halloysite nanotubes, Si-O key stretching vibration peak from
1093 cm-1Become 1082 cm-1, occur in that obvious chemical shift, and 754 cm-1With 794 cm-1The ratio at peak and
1030 cm-1With 1082-1093 cm-1The ratio going out peak substantially reduces, and this is primarily due to one layer of titanium dioxide of superficial growth
Silicon particle, for the aluminum hydroxyl within halloysite nanotubes, the ratio of silicone hydroxyl is greatly improved.
Embodiment 4
3g halloysite nanotubes is distributed in the dehydrated alcohol of 100ml 95%, and adds the ammonia of 15ml 25wt%, at 30 DEG C
Lower ultrasonic disperse 15 min, then dropping 1.5ml Bis(lauroyloxy)dioctyltin, at 80 DEG C, stir 1 hour, then to mixed
Compound drips the sodium silicate of 2.25g, after dropping, stirs 8 hours, after centrifugation, with absolute ethanol washing 3 times, put
Enter 80 DEG C of vacuum drying ovens to dry 12 hours, obtain halloysite nanotubes-SiO 2 hybrid filler.
Embodiment 5
As a example by unsaturated polyester resin matrix, by the 5g halloysite nanotubes-SiO 2 hybrid filler of preparation in embodiment 1
The halloysite nanotubes pure with 5g is respectively added in 100g unsaturated polyester resin, is prepared for unsaturated polyester composite,
And having probed into the impact on composite impact performance of the hydridization filler, Fig. 5 is about unsaturated polyester composite impact strength
Data, it can be seen that compared with the unsaturated polyester composite toughness reinforcing with pure halloysite nanotubes, surface attachment
The hydridization filler of silicon dioxide has a most excellent impact property.
Claims (10)
1. the method that a halloysite nanotubes surface in situ growth silicon dioxide prepares hydridization filler, it is characterised in that include
Following steps:
The first step: be first distributed in solvent by halloysite nanotubes, adds ammonia and catalyst, after ultrasonic disperse, adds silicon
Source monomer, stirring reaction 1-10 hour under the conditions of 30-80 DEG C；
Second step: by first step products therefrom centrifugal filtration, washing, remove the supernatant, dry, obtain hydridization filler.
A kind of halloysite nanotubes surface in situ the most according to claim 1 growth silicon dioxide prepares the side of hydridization filler
Method, it is characterised in that described solvent is in water, ethanol, toluene, acetone, petroleum ether, ethyl acetate, dimethylbenzene and Pentamethylene.
One or both mixed solvent.
A kind of halloysite nanotubes surface in situ the most according to claim 1 growth silicon dioxide prepares the side of hydridization filler
Method, it is characterised in that described catalyst is in dibutyl tin laurate, Bis(lauroyloxy)dioctyltin and tetrabutyl ammonium bromide
More than one.
A kind of halloysite nanotubes surface in situ the most according to claim 1 growth silicon dioxide prepares the side of hydridization filler
Method, it is characterised in that described silicon source monomer is the one in methyl silicate, tetraethyl orthosilicate and sodium silicate.
A kind of halloysite nanotubes surface in situ the most according to claim 1 growth silicon dioxide prepares the side of hydridization filler
Method, it is characterised in that the solid content that described halloysite nanotubes is distributed in solvent is 3%-10%.
A kind of halloysite nanotubes surface in situ the most according to claim 1 growth silicon dioxide prepares the side of hydridization filler
Method, it is characterised in that the addition of described ammonia accounts for the 5%-15% of solvent volume.
A kind of halloysite nanotubes surface in situ the most according to claim 1 growth silicon dioxide prepares the side of hydridization filler
Method, it is characterised in that the addition of described catalyst is 0.1-1.5ml.
A kind of halloysite nanotubes surface in situ the most according to claim 1 growth silicon dioxide prepares the side of hydridization filler
Method, it is characterised in that described silicon source monomer accounts for the 50wt%-75 wt% of halloysite nanotubes.
A kind of halloysite nanotubes surface in situ the most according to claim 1 growth silicon dioxide prepares the side of hydridization filler
Method, it is characterised in that the number of times of described washing is 3-8 time.
A kind of halloysite nanotubes surface in situ the most according to claim 1 growth silicon dioxide prepares hydridization filler
Method, it is characterised in that the condition of described drying is baking 8-24h in the vacuum drying oven of 50-100 DEG C.
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Cited By (5)
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| CN106894107A (en) * | 2017-03-06 | 2017-06-27 | 东华大学 | Polyphenylene sulfide/modified halloysite nanotubes hybridization compounding fiber and preparation method thereof |
| CN107189102A (en) * | 2017-06-27 | 2017-09-22 | 华南理工大学 | A kind of hydridization filler support type age resistor and preparation method and application |
| CN114149662A (en) * | 2021-12-03 | 2022-03-08 | 李存森 | Building energy-saving sound-insulation material and preparation method and application thereof |
| CN115872687A (en) * | 2022-11-29 | 2023-03-31 | 嘉华特种水泥股份有限公司 | High-strength toughened well cementation cement slurry system and preparation method thereof |
| CN115960530A (en) * | 2023-01-16 | 2023-04-14 | 陕西龙麟纳纤材料科技有限公司 | Calcium sulfate whisker composite silicon dioxide super-hydrophobic coating material and preparation method and application thereof |
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| CN115872687A (en) * | 2022-11-29 | 2023-03-31 | 嘉华特种水泥股份有限公司 | High-strength toughened well cementation cement slurry system and preparation method thereof |
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| CN115960530A (en) * | 2023-01-16 | 2023-04-14 | 陕西龙麟纳纤材料科技有限公司 | Calcium sulfate whisker composite silicon dioxide super-hydrophobic coating material and preparation method and application thereof |
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