CN109929271A - The method of modified Nano particle - Google Patents
The method of modified Nano particle Download PDFInfo
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Abstract
The invention discloses a kind of method of modified Nano particle, it is included in microwave field and the nanoparticle is modified using silane coupling agent, the dosage of the silane coupling agent is the 0.1~2% of the nanoparticle quality.It is greatly decreased by the modified nanoparticle surface hydroxyl value of method of the invention and the compatibility of resin and the intensity of resin greatly improves.
Description
Technical field
The present invention relates to a kind of method of modified Nano particle, in particular to one kind uses silane coupling agent in microwave field
The method of modified Nano particle belongs to nano particle surface modifying field.
Background technique
Nanoparticle is usually made of superfine crystal grain or non grain, is particle of the characteristic dimension size in nanometer scale,
It is one kind between macroscopic solid and intermolecular metastable intermediate state substance, therefore it has small-size effect, quantum size effect
With surface size effect.
Nanoparticle, such as nano silica, nano-titanium dioxide, nano zine oxide, nano zirconium dioxide, three oxygen of nanometer
Change two aluminium to be widely used in the fields such as coating, rubber, wire and cable, adhesive as filler.Nanoparticle is due to specific surface
Product is big, surface energy is high, easily reunites between particle, and once reunite, common mechanical means is difficult to again open it, disperse.
Not only the performance of nano material itself cannot be played normally in this way, also will affect the comprehensive performance of composite material.
It solves the problems, such as this, nanoparticle must be just surface-treated, to improve nanoparticle in polymer matrix
Dispersibility and durability in body.
The method being surface-treated to nanoparticle generally includes wet process and dry method.Wet process is first to be added to nanoparticle
The aqueous solution of water or ethyl alcohol is modulated into slurry, adds surface treatment agent (such as silane coupling agent), is sufficiently stirred, water
It washes, filter, reacting drying, crushing.Dry method is by the aqueous solution of deployed surface treatment agent aqueous solution or ethyl alcohol, by table
Surface treatment reagent aqueous solution is stirred when instilling or by spraying, and reacting drying crushes.In industrial applications, since wet method filtration produces
Raw filtrate, filtrate cost recovery are high.Dry method modification is generally used, but the dry of dry method modification uses common heat drying, this
Kind heating means heat transfer is uneven, causes modified nanoparticle uneven, is easy to be agglomerated into small group, is not easy to crush.
Although the nanoparticle in actual use, being so surface-treated can be used as filler, it is modified in this way
Nanoparticle can only improve the compatibility with resin since surface hydroxyl number is more to a certain extent, mechanical strength of resin
It improves limited.
Summary of the invention
For this purpose, the present invention provides a kind of method of modified Nano particle, by using silane coupling agent pair in microwave field
The nanoparticle is modified, so that the surface hydroxyl number of nanoparticle is greatly decreased, improves the phase of nanoparticle and resin
The intensity of capacitive and resin, to improve dispersibility of the nanoparticle in resin.
According to an aspect of the present invention, a kind of method of modified Nano particle is provided, is included in microwave field using silicon
Alkane coupling agent is modified the nanoparticle, the dosage of the silane coupling agent be the nanoparticle quality 0.1~
2%.
Preferably, the silane coupling agent is gamma-aminopropyl-triethoxy-silane, vinyltrimethoxysilane, ethylene
Ethyl triethoxy silicane alkane, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy
One of base silane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane are a variety of.
The nanoparticle is nano silica, nano-titanium dioxide, nano zine oxide, nano zirconium dioxide, nanometer
One of aluminum oxide is a variety of.
Further, it the described method comprises the following steps:
The silane coupling agent and nano-powder dry mixed is uniform；
The mixture of the silane coupling agent and nano-powder is put into microwave reaction device, microwave radiation is carried out, obtains
To silane coupler modified nanoparticle.
Preferably, the frequency of the microwave is 200MHz~1000MHz.
Wherein, microwave irradiation time is 1~30 minute, and temperature range is 100~200 DEG C.
Preferably, the dry mixed of the silane coupling agent and nano-powder is by being dissolved in water for the silane coupling agent
Or in ethanol water, then it is sprayed to the nanoparticle surface and carries out.
The ethanol water concentration is 70~95wt%.Preferably, the quality of the ethanol water is the silane
2~5 times of the quality of coupling agent.
Preferably, the surface hydroxyl number of the nanoparticle modified is 0.1~3.5/nm2。
The method of modified Nano particle of the invention compared with prior art, has the advantages that
(1) this microwave heating method will not generation environment pollution and low energy consumption.
(2) method of the invention is used, compared with direct-fired drying mode, nanoparticle surface hydroxyl value is reduced
30%~80%.
(3) additive amount of silane coupling agent is few, and the mass percent of silane coupling agent is about nanoparticle quality
0.1%~2%.
Specific embodiment
The method of the modified Nano particle provided according to the present invention is included in microwave field using silane coupling agent to described
Nanoparticle is modified, and the dosage of the silane coupling agent is the 0.1~2% of the nanoparticle quality.
Preferably, above-mentioned silane coupling agent is gamma-aminopropyl-triethoxy-silane, vinyltrimethoxysilane, ethylene
Ethyl triethoxy silicane alkane, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy
One of base silane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane are a variety of.
Above-mentioned nanoparticle is nano silica, nano-titanium dioxide, nano zine oxide, nano zirconium dioxide, nanometer
One of aluminum oxide is a variety of.
Further, it the described method comprises the following steps:
The silane coupling agent and nano-powder dry mixed is uniform；
The mixture of the silane coupling agent and nano-powder is put into microwave reaction device, microwave radiation is carried out, obtains
To silane coupler modified nanoparticle.
Preferably, the dry mixed of the silane coupling agent and nano-powder is by being dissolved in water for the silane coupling agent
Or in ethanol water, then it is sprayed to the nanoparticle surface and carries out, wherein the concentration of ethanol water is preferably 70~
95wt%, preferably 75wt% are used after preferably 2 times dilutions usually through 2~5 times.
Preferably, the frequency of the microwave is 200MHz~1000MHz.If microwave frequency is too low, can not achieve
The function of heating entirely；If microwave frequency is excessively high, energy consumption is excessively high, and the influence to reaction is no longer obvious.Wherein, microwave irradiation time
It is 1~30 minute, temperature range is 100~200 DEG C.
After microwave radiation ,-the OH of Si-OH and nano powder surface after silane coupling agent hydrolysis can be rapidly and equal
It chemically reacts evenly, so that powder particle is not easy to reunite, is easier to crush.Nanoparticle is by silane coupling agent as a result,
It is modified, and the hydroxyl value of particle surface is greatly decreased.Specifically, silane coupler modified nanoparticle according to the present invention
With 0.1~3.5/nm2Surface hydroxyl number, preferably 0.5~3.0/nm2, more preferable 1.0~2.5/nm2, such as 1.5
A/nm2.To which modified nanoparticle good dispersion in resin is obtained with the compatibility of resin and the intensity of resin
It greatly improves.
The surface hydroxyl number of nano-powder is usually measured by titration.Above-mentioned microwave reaction device can generate to be any
The device that microwave is heated.
The present invention is further illustrated by way of the following example, the scope of the invention is not limited to following implementations
Example.
Embodiment
Embodiment 1
1. the gamma-aminopropyl-triethoxy-silane ethanol water of 75wt% is stirred evenly by 2 times of dilutions, it is spraying to add
Enter into nano silica, is uniformly mixed.The quality of gamma-aminopropyl-triethoxy-silane accounts for nano silica quality
0.1%.
2. the mixture of gamma-aminopropyl-triethoxy-silane obtained in step 1 and nano silica is put into microwave
In reactor, the frequency of microwave is 200MHz, radiated time 1min, controls 100 DEG C of temperature.Microwave reaction terminates, and obtains γ-
The modified nano silica of aminopropyl triethoxysilane.
3. measuring the hydroxyl value of nano powder surface by the following method.
Surface hydroxyl measuring method is to weigh the modified Nano-meter SiO_2 of 2.0g or more2Sample is added in 200mL beaker, is added
25mL ethanol wet adds the NaCl solution of 75mL mass fraction 20%, stirring；PH to 4 is adjusted with the HCl of 0.1mol/L,
It is non-discolouring in 9,3min for being finally titrated to pH with the NaOH of 0.1mol/L.It is molten that silicone hydroxyl number pH value from 4 fades to 9 consumed NaOH
Liquid product is to indicate.
The specific surface area of known sample measurement is S (m2/ g), titration measuring 2g sample consumes 0.1mol/LNaOH standard
Liquor capacity is V (mL), SiO2/nm2Hydroxyl number calculation formula on surface is as follows:
SiO2Hydroxyl number (a/the nm on surface2)=6.02 × 1023×V/2×104×S×10-18, bibliography is " drop
Determine the theory of method measurement fume colloidal silica specific surface area, Pan is diligent, chemistry world, the 8th phase in 1993: 380~383 ".
It is modified that gamma-aminopropyl-triethoxy-silane is added under microwave field, according to changing for the method for the present embodiment preparation
Property nano-silica surface hydroxyl value be 0.8/nm2。
Comparative example 1
1. the gamma-aminopropyl-triethoxy-silane ethanol water of 75wt% is stirred evenly by 2 times of dilutions, it is spraying to add
Enter into nano silica, is uniformly mixed.The quality of gamma-aminopropyl-triethoxy-silane accounts for nano silica quality
0.1%.
2. the mixture of gamma-aminopropyl-triethoxy-silane obtained in step 1 and nano silica is put into baking oven
In, 100 DEG C of temperature are controlled, heating time is 30 minutes.Reaction terminates, and obtains receiving for gamma-aminopropyl-triethoxy-silane modification
Rice silica.
3. being 4.0/nm by the surface hydroxyl number that the method for embodiment 1 measures the modified nano powder2。
It can thus be concluded that going out, the nano-silica surface hydroxyl value prepared with the method for the embodiment of the present invention 1 is than comparative example 1
Nano-silica surface hydroxyl value reduce 80%.
Embodiment 2
1. the aqueous solution 75wt% of γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane ethyl alcohol is stirred by 5 times of dilutions
It mixes uniformly, is sprayed to and is added in nano silica, be uniformly mixed.γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane
Quality account for the 2% of nano silica quality.
2. by the mixed of (the third oxygen of the 2,3- epoxy) propyl trimethoxy silicane of γ-obtained in step 1 and nano silica
It closes object to be put into microwave reactor, radiated time 20min controls 150 DEG C of temperature, and microwave reaction terminates, and obtains γ-(2,3-
The third oxygen of epoxy) the modified nano silica of propyl trimethoxy silicane.
3. being 0.3/nm by the surface hydroxyl number that the titration of embodiment 1 measures the modified nano powder2。
Comparative example 2
1. γ-(the third oxygen of 2,3- epoxy) the propyl trimethoxy silicane ethanol water of 75wt% is stirred by 5 times of dilutions
It mixes uniformly, is added in nano silica by spraying, be uniformly mixed.γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane
Quality accounts for the 2% of nano silica quality.
2. by the mixed of (the third oxygen of the 2,3- epoxy) propyl trimethoxy silicane of γ-obtained in step 1 and nano silica
It closes object to be put into baking oven, controls 150 DEG C of temperature, heating time is 30 minutes.Reaction terminates, and obtains γ-(2,3- the third oxygen of epoxy)
The modified nano silica of propyl trimethoxy silicane.
3. being 1.8/nm by the surface hydroxyl number that the method for embodiment 1 measures the modified nano powder2。
It can thus be concluded that going out, the nano-silica surface hydroxyl value prepared with the method for the embodiment of the present invention 2 is than comparative example 2
Nano-silica surface hydroxyl value reduce 83%.
Embodiment 3
1. the vinyltrimethoxysilane ethanol water of 80wt% is stirred evenly by 3 times of dilutions, it is sprayed to and adds
Enter into nano-titanium dioxide, is uniformly mixed.The quality of vinyltrimethoxysilane accounts for the 2% of nano-titanium dioxide quality.
2. the mixture of vinyltrimethoxysilane obtained in step 1 and nano-titanium dioxide is put into microwave reaction
In device, radiated time 5min controls 120 DEG C of temperature, and microwave reaction terminates, and obtains receiving for vinyltrimethoxysilane modification
Rice titanium dioxide.
3. being 0.5/nm by the surface hydroxyl number that the titration of embodiment 1 measures the modified nano powder2。
Comparative example 3
1. the vinyltrimethoxysilane ethanol water of 80wt% is stirred evenly by 3 times of dilutions, it is spraying to be added
Into nano-titanium dioxide, it is uniformly mixed.The quality of vinyltrimethoxysilane accounts for the 2% of the siliceous amount of nano-titanium dioxide.
2. the mixture of vinyltrimethoxysilane obtained in step 1 and nano-titanium dioxide is put into baking oven,
120 DEG C of temperature of control, heating time are 30 minutes.Reaction terminates, and obtains the modified nano-silica of vinyltrimethoxysilane
Change titanium.
3. being 3.2/nm by the surface hydroxyl number that the method for embodiment 1 measures the modified nano powder2。
It can thus be concluded that going out, the nano-silica surface hydroxyl value prepared with the method for the embodiment of the present invention 3 is than comparative example 3
Nano-silica surface hydroxyl value reduce 84%.
Embodiment 4
1. the vinyltriethoxysilane ethanol water of 95wt% is stirred evenly by 5 times of dilutions, it is sprayed to and adds
Enter into nano-titanium dioxide, is uniformly mixed.The quality of vinyltriethoxysilane accounts for the 2% of nano-titanium dioxide quality.
2. the mixture of vinyltriethoxysilane obtained in step 1 and nano-titanium dioxide is put into microwave reaction
In device, radiated time 10min controls 150 DEG C of temperature, and microwave reaction terminates, and obtains what vinyltriethoxysilane was modified
Nano-titanium dioxide.
3. being 0.7/nm by the surface hydroxyl number that the titration of embodiment 1 measures the modified nano powder2。
Comparative example 4
1. the vinyltriethoxysilane ethanol water of 95wt% is stirred evenly by 5 times of dilutions, it is spraying to be added
Into nano-titanium dioxide, it is uniformly mixed.The quality of vinyltriethoxysilane accounts for the 2% of the siliceous amount of nano-titanium dioxide；
2. the mixture of vinyltriethoxysilane obtained in step 1 and nano-titanium dioxide is put into baking oven,
150 DEG C of temperature of control, heating time are 10 minutes.Reaction terminates, and obtains the modified nano-silica of vinyltriethoxysilane
Change titanium.
3. being 2.0/nm by the surface hydroxyl number that the method for embodiment 1 measures the modified nano powder2。
It can thus be concluded that going out, the nano-silica surface hydroxyl value prepared with the method for the embodiment of the present invention 4 is than comparative example 4
Nano-silica surface hydroxyl value reduce 65%.
Embodiment 5
1. γ-(the third oxygen of 2,3- epoxy) the propyl trimethoxy silicane ethanol water of 80wt% is stirred by 4 times of dilutions
It mixes uniformly, is sprayed to and is added in nano zine oxide, be uniformly mixed.γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane
Quality accounts for the 2% of nano zine oxide quality.
2. by the mixing of γ-obtained in step 1 (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane and nano zine oxide
Object is put into microwave reactor, radiated time 30min, controls 180 DEG C of temperature, microwave reaction terminates, and obtains γ-(2,3- rings
The third oxygen of oxygen) the modified nano zine oxide of propyl trimethoxy silicane.
3. being 0.4/nm by the surface hydroxyl number that the titration of embodiment 1 measures the modified nano powder2。
Comparative example 5
1. γ-(the third oxygen of 2,3- epoxy) the propyl trimethoxy silicane ethanol water of 80wt% is stirred by 4 times of dilutions
It mixes uniformly, is added in nano zine oxide by spraying, be uniformly mixed.The matter of γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane
Amount accounts for the 2% of nano zine oxide quality；
2. by the mixing of γ-obtained in step 1 (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane and nano zine oxide
Object is put into baking oven, controls 180 DEG C of temperature, heating time is 30 minutes.Reaction terminates, and obtains γ-(2,3- the third oxygen of epoxy) third
The modified nano zine oxide of base trimethoxy silane.
3. being 1.8/nm by the surface hydroxyl number that the method for embodiment 1 measures the modified nano powder2。
It can thus be concluded that going out, the nano-silica surface hydroxyl value prepared with the method for the embodiment of the present invention 5 is than comparative example 5
Nano-silica surface hydroxyl value reduce 78%.
Embodiment 6
1. the gamma-mercaptopropyltriethoxysilane ethanol water of 90wt% is stirred evenly by 3 times of dilutions, it is sprayed to
It is added in nano zine oxide, is uniformly mixed.The quality of gamma-mercaptopropyltriethoxysilane accounts for the 2% of nano zine oxide quality.
2. it is anti-that the mixture of gamma-mercaptopropyltriethoxysilane obtained in step 1 and nano zine oxide is put into microwave
It answers in device, radiated time 20min, controls 150 DEG C of temperature, microwave reaction terminates, and obtains gamma-mercaptopropyltriethoxysilane and changes
The nano zine oxide of property.
3. being 0.6/nm by the surface hydroxyl number that the titration of embodiment 1 measures the modified nano powder2。
Comparative example 6
1. the gamma-mercaptopropyltriethoxysilane ethanol water of 80wt% is stirred evenly by 4 times of dilutions, it is spraying to add
Enter into nano zine oxide, is uniformly mixed.The quality of gamma-mercaptopropyltriethoxysilane accounts for the 2% of nano zine oxide quality；
2. the mixture of gamma-mercaptopropyltriethoxysilane obtained in step 1 and nano zine oxide is put into baking oven,
150 DEG C of temperature of control, heating time are 20 minutes.Reaction terminates, and obtains the modified nano oxygen of gamma-mercaptopropyltriethoxysilane
Change zinc.
3. being 2.5/nm by the surface hydroxyl number that the method for embodiment 1 measures the modified nano powder2。
It can thus be concluded that going out, the nano-silica surface hydroxyl value prepared with the method for the embodiment of the present invention 6 is than comparative example 6
Nano-silica surface hydroxyl value reduce 76%.
Embodiment 7
1. the γ-mercaptopropyl trimethoxysilane ethanol water of 90wt% is stirred evenly by 3 times of dilutions, it is sprayed to
It is added in nano zine oxide, is uniformly mixed.The quality of γ-mercaptopropyl trimethoxysilane accounts for the 2% of nano zine oxide quality.
2. it is anti-that the mixture of γ-mercaptopropyl trimethoxysilane obtained in step 1 and nano zine oxide is put into microwave
It answers in device, radiated time 30min, controls 180 DEG C of temperature, microwave reaction terminates, and obtains γ-mercaptopropyl trimethoxysilane and changes
The nano zine oxide of property.
3. being 0.4/nm by the surface hydroxyl number that the titration of embodiment 1 measures nano-powder2。
Comparative example 7
1. the γ-mercaptopropyl trimethoxysilane ethanol water of 90wt% is stirred evenly by 3 times of dilutions, it is spraying to add
Enter into nano zine oxide, is uniformly mixed.The quality of γ-mercaptopropyl trimethoxysilane accounts for the 2% of nano zine oxide quality；
2. the mixture of γ-mercaptopropyl trimethoxysilane obtained in step 1 and nano zine oxide is put into baking oven,
180 DEG C of temperature of control, heating time are 30 minutes.Reaction terminates, and obtains the modified nano oxygen of γ-mercaptopropyl trimethoxysilane
Change zinc.
3. being 2.3/nm by the surface hydroxyl number that the method for embodiment 1 measures the modified nano powder2。
It can thus be concluded that going out, the nano-silica surface hydroxyl value prepared with the method for the embodiment of the present invention 7 is than comparative example 7
Nano-silica surface hydroxyl value reduce 83%.
Embodiment 8
1. γ-(methacryloxypropyl) the propyl trimethoxy silicane ethanol water of 85wt% is stirred by 5 times of dilutions
It mixes uniformly, is sprayed to and is added in nano zirconium dioxide, be uniformly mixed.γ-(methacryloxypropyl) propyl trimethoxy silicane
Quality account for the 2% of nano zirconium dioxide quality.
2. by the mixed of (methacryloxypropyl) propyl trimethoxy silicane of γ-obtained in step 1 and nano zirconium dioxide
It closes object to be put into microwave reactor, radiated time 5min controls 180 DEG C of temperature, and microwave reaction terminates, and obtains γ-(methyl-prop
Alkene acyl-oxygen) the modified nano zirconium dioxide of propyl trimethoxy silicane.
3. being 0.7/nm by the surface hydroxyl number that the titration of embodiment 1 measures the modified nano powder2。
Comparative example 8
1. γ-(methacryloxypropyl) the propyl trimethoxy silicane ethanol water of 85wt% is stirred by 5 times of dilutions
It mixes uniformly, is added in nano zirconium dioxide by spraying, be uniformly mixed.γ-(methacryloxypropyl) propyl trimethoxy silicane
Quality accounts for the 2% of nano zirconium dioxide quality.
2. by the mixed of (methacryloxypropyl) propyl trimethoxy silicane of γ-obtained in step 1 and nano zirconium dioxide
It closes object to be put into baking oven, controls 180 DEG C of temperature, heating time is 5 minutes.Reaction terminates, and obtains γ-(methacryloxypropyl) third
The modified nano zirconium dioxide of base trimethoxy silane.
3. being 2.8/nm by the surface hydroxyl number that the method for embodiment 1 measures the modified nano powder2。
It can thus be concluded that going out, the nano zirconium dioxide surface hydroxyl number prepared with the method for the embodiment of the present invention 8 is than comparative example 8
Nano zirconium dioxide surface hydroxyl number reduce 75%.
Embodiment 9
1. γ-(the third oxygen of 2,3- epoxy) the propyl trimethoxy silicane ethanol water of 80wt% is stirred by 3 times of dilutions
It mixes uniformly, is sprayed to and is added in nano zirconium dioxide, be uniformly mixed.γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane
Quality account for the 2% of nano zirconium dioxide quality.
2. by the mixed of (the third oxygen of the 2,3- epoxy) propyl trimethoxy silicane of γ-obtained in step 1 and nano zirconium dioxide
It closes object to be put into microwave reactor, radiated time 30min controls 180 DEG C of temperature.Microwave reaction terminates, and obtains γ-(2,3-
The third oxygen of epoxy) the modified nano zirconium dioxide of propyl trimethoxy silicane.
3. being 0.5/nm by the surface hydroxyl number that the titration of embodiment 1 measures the modified nano powder2。
Comparative example 9
1. γ-(the third oxygen of 2,3- epoxy) the propyl trimethoxy silicane ethanol water of 80wt% is stirred by 3 times of dilutions
It mixes uniformly, is added in nano zirconium dioxide by spraying, be uniformly mixed.γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane
Quality accounts for the 2% of nano zirconium dioxide quality.
2. by the mixed of (the third oxygen of the 2,3- epoxy) propyl trimethoxy silicane of γ-obtained in step 1 and nano zirconium dioxide
It closes object to be put into baking oven, controls 180 DEG C of temperature, heating time is 30 minutes.Reaction terminates, and obtains γ-(2,3- the third oxygen of epoxy)
The modified nano zirconium dioxide of propyl trimethoxy silicane.
3. being 2.4/nm by the surface hydroxyl number that the method for embodiment 1 measures the modified nano powder2。
It can thus be concluded that going out, the nano zirconium dioxide surface hydroxyl number prepared with the method for the embodiment of the present invention 9 is than comparative example 9
Nano zirconium dioxide surface hydroxyl number reduce 79%.
Embodiment 10
1. the vinyltrimethoxysilane ethanol water of 80wt% is stirred evenly by 3 times of dilutions, it is sprayed to and adds
Enter into nano-aluminium oxide, is uniformly mixed.The quality of vinyltrimethoxysilane accounts for nano-aluminium oxide quality
2%.
2. it is anti-that the mixture of vinyltrimethoxysilane obtained in step 1 and nano-aluminium oxide is put into microwave
It answers in device, radiated time 30min, controls 200 DEG C of temperature, microwave reaction terminates, and it is modified to obtain vinyltrimethoxysilane
Nano-aluminium oxide.
3. being 0.2/nm by the surface hydroxyl number that the titration of embodiment 1 measures the modified nano powder2。
Comparative example 10
1. the vinyltrimethoxysilane ethanol water of 80wt% is stirred evenly by 3 times of dilutions, it is spraying to be added
Into nano-aluminium oxide, it is uniformly mixed.The quality of vinyltrimethoxysilane accounts for nano-aluminium oxide quality
2%.
2. the mixture of vinyltrimethoxysilane obtained in step 1 and nano-aluminium oxide is put into baking oven
In, 200 DEG C of temperature are controlled, heating time is 30 minutes.Reaction terminates, and obtains the modified nanometer three of vinyltrimethoxysilane
Al 2 O.
3. being 1.9/nm by the surface hydroxyl number that the method for embodiment 1 measures the modified nano powder2。
It can thus be concluded that going out, the nano-aluminium oxide surface hydroxyl number prepared with the method for the embodiment of the present invention 10 is than comparison
The nano-aluminium oxide surface hydroxyl number of example 10 reduces 89%.
The result of above embodiments 1~10 and comparative example 1~10 is summarized and is shown in following table 1.
Table 1
It can be seen that by the above table 1, embodiment 1 to 10 passes through according to the method for the present invention by carrying out silane in microwave field
Coupling agent modified reaction, the modified Nano particle being thus prepared compared to comparative example 1 to 10 under the conditions of common heating into
The modified obtained nanoparticle of row, surface hydroxyl number substantially reduce.
Influence experiment of the modified Nano particle to sealant performance
Modified Nano aluminum oxide powder made from using according to embodiments of the present invention 10 respectively is made according to comparative example 10
Untreated nano-aluminium oxide powder in the modified Nano aluminum oxide powder and embodiment 10 obtained, with 1%
Mass percent is added in polyurethane sealant, is uniformly mixed obtained sealant specimen S1, S2 and S3 respectively.Respectively to obtained
Three kinds of sealant specimens test room temperature peel strength (GB/T7122-1996) and 100 DEG C at shear strength (GB/T
7124-2008) fineness, and with Hegman fineness grind instrument is tested, is as a result shown in following table 2.
Table 2
| Sample | Room temperature peel strength (kN/m) | 100 DEG C of shear strength (kN/mm2) | Fineness (μm) |
| S1 | 6.2 | 2.1 | 20 |
| S2 | 8.1 | 3.3 | 32 |
| S3 | 9.6 | 4.5 | 40 |
It can be seen that by the above table 2, modified Nano aluminum oxide powder S1 according to the present invention changes relative to common heating
Property processing sample S2, room temperature peel strength improves 23.5%, and relative to the sample S3 of non-modified processing, room temperature removing is strong
Degree improves 35.4%, and 53.3% and 36.4% has been respectively increased in 100 DEG C of shear strength.
Polyurethane sealant (addition mass percent is prepared with above-mentioned three kinds of nano-aluminium oxide powders S1, S2 and S3
Respectively 1%), fineness is tested with Hegman fineness grind instrument.Silane coupler modified nano-aluminium oxide powder according to the present invention
The fineness of polyurethane sealant made from body is 20 μm, made from the modified nano-aluminium oxide powder of common heating mode
The fineness of polyurethane sealant is 32 μm (improving 37.5%), unused silane coupler modified nano-aluminium oxide powder
The fineness of polyurethane sealant obtained is 40 μm (improving 50%).
Claims (10)
1. a kind of method of modified Nano particle, which is characterized in that the method includes using silane coupling agent in microwave field
The nanoparticle is modified, the dosage of the silane coupling agent is the 0.1~2% of the nanoparticle quality.
2. according to the method described in claim 1, wherein, the silane coupling agent is gamma-aminopropyl-triethoxy-silane, ethylene
Base trimethoxy silane, vinyltriethoxysilane, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, γ-(methyl
Acryloyl-oxy) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, one of γ-mercaptopropyl trimethoxysilane
Or it is a variety of.
3. according to the method described in claim 1, wherein, the nanoparticle is nano silica, nano-titanium dioxide, receives
One of rice zinc oxide, nano zirconium dioxide, nano-aluminium oxide are a variety of.
4. according to the method in any one of claims 1 to 3, wherein the described method comprises the following steps:
The silane coupling agent and nano-powder dry mixed is uniform；
The mixture of the silane coupling agent and nano-powder is put into microwave reaction device, microwave radiation is carried out, obtains silicon
The coupling agent modified nanoparticle of alkane.
5. according to the method in any one of claims 1 to 3, wherein the frequency of the microwave be 200MHz~
1000MHz。
6. according to the method in any one of claims 1 to 3, wherein microwave irradiation time is 1~30 minute, temperature model
Enclose is 100~200 DEG C.
7. according to the method described in claim 4, the dry mixed of the silane coupling agent and nano-powder is by by the silicon
Alkane coupling agent is dissolved in water or ethanol water, then is sprayed to the nanoparticle surface and is carried out.
8. according to the method described in claim 7, the ethanol water concentration is 70~95wt%.
9. according to the method described in claim 8, the quality of the ethanol water be the silane coupling agent quality 2~
5 times.
10. according to the method in any one of claims 1 to 3, wherein the surface hydroxyl of the nanoparticle modified
Radix is 0.1~3.5/nm2。
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