CN109957147A - A kind of tiny balloon and its preparation method and application that surface is modified - Google Patents
A kind of tiny balloon and its preparation method and application that surface is modified Download PDFInfo
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- CN109957147A CN109957147A CN201711432338.4A CN201711432338A CN109957147A CN 109957147 A CN109957147 A CN 109957147A CN 201711432338 A CN201711432338 A CN 201711432338A CN 109957147 A CN109957147 A CN 109957147A
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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
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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
- C08K7/28—Glass
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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
- C08K9/04—Ingredients treated with organic substances
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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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention provides a kind of modified tiny balloons and its preparation method and application in surface, processing is cooperateed with to introduce aldehyde radical on tiny balloon surface with the silane coupling agent with Amino End Group using dialdehyde (such as glutaraldehyde), the surface for not only reducing tiny balloon in this way can, alleviate the reunion between particle, be conducive to the dispersing uniformity of particle, and improve the interface performance between microballoon and matrix in the curing reaction that the aldehyde functions of microsphere surface participate in phenolic aldehyde in filled phenolic resin, mechanical property is also ensured while lighting.It present invention can be extensively applied in the phenolic resin-base composite field of such as solar heat protection heat-barrier material.
Description
Technical field
The present invention relates to field of compound material, specifically, modified tiny balloon in a kind of surface and preparation method thereof and
Using.
Background technique
Although the surface of inorganic non-metallic filler can be higher, since hydrophilic and oleophobic feature is presented in its surface,
When inorganic non-metallic filler to be filled into polymer, the combination not only resulted between the two is poor, and due to inorganic
Non-metallic fillers are not easy to be soaked by polymer, so will lead to the group of being easy to happen between the inorganic non-metallic filler in polymer
It is poly-, if be directly appended in polymer, it be easy to cause dispersion uneven, so, wherein the part reunited or dispersion
The part more concentrated can become the stress concentration point in composite material, become the weak link in composite material, and then cause
The mechanical property of composite material is poor.
Summary of the invention
For the problems in the relevant technologies, the present invention has studied a kind of preparation method of tiny balloon that surface is modified, with
A kind of tiny balloon that the preferable surface of mechanical property is modified is provided.
The preparation method of the modified tiny balloon in surface provided by the invention, comprising: tiny balloon is added in solvent,
PH value is adjusted, the first coupling agent is then added, is stirred, it is dry, obtain pretreated tiny balloon；And it will be described pretreated
Tiny balloon is added in buffer solution, adds the second coupling agent, is stirred, dry, obtains the modified tiny balloon in surface.
In the above preparation method, the mass ratio of the tiny balloon, first coupling agent and second coupling agent
Are as follows: 90~110:1~5:1~5.
In the above preparation method, the tiny balloon is selected from hollow glass micro-ball, hollow ceramic microspheres, hollow carbosphere
One of or multiple combinations.
In the above preparation method, the solvent is water and C1~C4The mixed solvent of alcohol, wherein the C1~C4Alcohol exists
Volume fraction in the solvent is 80%~85%.
In the above preparation method, the pH value is adjusted between 5~6 using acetic acid or hydrochloric acid.
In the above preparation method, the pH value is adjusted to 5~6.
In the above preparation method, first coupling agent is the silicone coupling agents with Amino End Group, second coupling
Agent agent is dialdehyde.
In the above preparation method, the temperature of the stirring is 40~80 DEG C, and the time of the stirring is 4~8h.
In the above preparation method, the pH value of the buffer solution is 7.2~7.4.
The tiny balloon being modified by surface prepared by above-mentioned preparation method.
By application of the modified tiny balloon in the surface of above method preparation in phenolic resin-base composite.
The preparation method of the modified tiny balloon in surface provided by the invention, by using the silane coupling agent with Amino End Group
The surface of tiny balloon is pre-processed, recycles aldehyde radical to react with the Schiff of amino so that tiny balloon has terminal aldehyde group
Function matrix not only reduces the surface energy of tiny balloon in this way, alleviates the reunion between particle, be conducive to the dispersion of particle
Uniformity, and can also be participated in the curing reaction of phenolic resin-base composite using aldehyde radical, enhance composite material
Interface performance also ensures mechanical property while lighting.It present invention can be extensively applied to the heat-insulated material of such as solar heat protection
In the phenolic resin-base composite field of material.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution in the embodiment of the present invention is clearly and completely retouched
It states, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the present invention
In embodiment, those of ordinary skill in the art's every other embodiment obtained shall fall within the protection scope of the present invention.
The preparation method of the modified tiny balloon in surface provided by the invention, comprising the following steps:
Firstly, tiny balloon is added in solvent, pH value is adjusted, the first coupling agent is then added, stirred, it is dry, it obtains
To pretreated tiny balloon.In this step, by mass fraction, 90~110 parts of tiny balloons are added to water and C1~C4Alcohol
Mixed solvent, wherein the mass ratio of tiny balloon and mixed solvent be 1:18~22, C1~C4Body of the alcohol in the mixed solvent
Fraction is 80%~85%, C1~C4Alcohol is one of methanol, ethyl alcohol, ethylene glycol, propyl alcohol, isopropanol, n-butanol or a variety of
Combination, the pH value of above-mentioned solution is then adjusted to 5~6 using acetic acid or hydrochloric acid, then, be added 1~5 part with Amino End Group
Silane coupling agent pre-processes tiny balloon, 40~80 DEG C at a temperature of stir 4~8h, from filtered out in solution it is pre- from
Tiny balloon after reason, is then dried, and obtains pretreated tiny balloon, and tiny balloon is selected from hollow glass micro-ball, hollow pottery
One of porcelain microballoon, hollow carbosphere or multiple combinations, the silane coupling agent with Amino End Group can be selected from three second of γ-aminopropyl
One of oxysilane, γ-aminopropyltrimethoxysilane, N- β (aminoethyl)-γ-aminopropyltrimethoxysilane are more
The combination of kind.
Pretreated tiny balloon is added in buffer solution, the second coupling agent is added, is stirred, it is dry, obtain table
The modified tiny balloon in face.In this step, pretreated tiny balloon is added to the buffer solution that pH value is 7.2~7.4
In, dialdehyde coupling agent is then added, in 40~80 DEG C of at a temperature of 4~8h of stirring, is filtered, it is dry, it is modified to obtain surface
Tiny balloon, wherein the mass ratio of pretreated tiny balloon and buffer solution be 1:18~22, tiny balloon with second idol
The mass ratio for joining agent is 90~110:1~5, wherein dialdehyde includes glyoxal, malonaldehyde, glutaraldehyde etc., and buffer solution includes
The phosphate buffer solution that sodium dihydrogen phosphate and disodium hydrogen phosphate are prepared.In this step, the Schiff of aldehyde radical and amino is utilized
Reaction is so that tiny balloon not only reduces the surface energy of tiny balloon in this way, alleviate particle with terminal aldehyde group function matrix
Between reunion, be conducive to the dispersing uniformity of particle.
Performance test:
Using the bending strength and fracture toughness of three-point bend test sample, bend specimen having a size of 80mm × 15mm ×
4mm, span 60mm, crosshead loading speed 2mm/min.Fracture toughness specimen need to meet flat having a size of 80mm × 8mm × 4mm
Face strained condition, the length of precrack are 0.45~0.55 times of specimen width, and precrack width is specimen width
0.015 times or smaller, span is 4 times of specimen width, crosshead loading speed 1mm/min.Charpy impact specimen having a size of
80mm × 10mm × 4mm, span 60mm, pendulum energy are 2J.
Fracture toughness KICWith impact strength σkIt is as follows:
Wherein, F is maximum load, and B is sample thickness, and W is specimen height (width), and a is precrack length.A is examination
Sample energy to fracture, b are opening specimen width, and d is opening sample thickness.
Embodiment 1
By mass fraction, take 90 parts of hollow glass micro-balls, be added to 1620 parts of second alcohol and waters in the mixed solvent (ethyl alcohol
Volume fraction is 80%), vinegar acid for adjusting pH value to be added dropwise to 6,1 part of gamma-aminopropyl-triethoxy-silane is added dropwise after mixing to microballoon
Pre-processed, 40 DEG C at a temperature of stir 8h, pretreated hollow glass micro-ball is added to di(2-ethylhexyl)phosphate by filtration drying
In the phosphate buffer solution that hydrogen sodium and disodium hydrogen phosphate are prepared, wherein the quality of pretreated tiny balloon and buffer solution
Than 1 part of glutaraldehyde being added dropwise then for 1:18,40 DEG C at a temperature of stirring 8h after, filtration drying obtains modified microballoon.
Embodiment 2
By mass fraction, 110 parts of hollow glass micro-balls are taken, are added to the in the mixed solvent (methanol of 2420 parts of first alcohol and waters
Volume fraction be 85%), vinegar acid for adjusting pH value to be added dropwise to 5,5 parts of gamma-aminopropyl-triethoxy-silanes are added dropwise after mixing to micro-
Ball is pre-processed, 80 DEG C at a temperature of stir 4h, pretreated hollow glass micro-ball is added to phosphoric acid by filtration drying
In the phosphate buffer solution that sodium dihydrogen and disodium hydrogen phosphate are prepared, wherein the matter of pretreated tiny balloon and buffer solution
Then 5 parts of glutaraldehydes are added dropwise than being 1:22 in amount, 80 DEG C at a temperature of stirring 4h after, filtration drying obtains modified microballoon.
Embodiment 3
By mass fraction, 100 parts of hollow ceramic microspheres are taken, are added to the in the mixed solvent (second of 2000 parts of ethylene glycol and water
The volume fraction of glycol is 82%), vinegar acid for adjusting pH value to be added dropwise to 5.5,3 parts of γ-aminopropyl trimethoxy silicon is added dropwise after mixing
Alkane pre-processes microballoon, 50 DEG C at a temperature of stir 6h, pretreated hollow ceramic microspheres are added filtration drying
In the phosphate buffer solution prepared to sodium dihydrogen phosphate and disodium hydrogen phosphate, wherein pretreated tiny balloon and buffering are molten
The mass ratio of liquid be 1:19, then be added dropwise 3.5 parts of malonaldehyde, 60 DEG C at a temperature of stirring 5h after, filtration drying is modified
Microballoon.
Embodiment 4
By mass fraction, take 95 parts of hollow ceramic microspheres, be added to 2000 part of third alcohol and water in the mixed solvent (propyl alcohol
Volume fraction is 84%), salt acid for adjusting pH value to be added dropwise to 5.7,2.5 parts of γ-aminopropyltrimethoxysilanes pair are added dropwise after mixing
Microballoon is pre-processed, 45 DEG C at a temperature of stir 7h, filter.It is dry, pretreated hollow ceramic microspheres are added to
In the phosphate buffer solution that sodium dihydrogen phosphate and disodium hydrogen phosphate are prepared, wherein pretreated tiny balloon and buffer solution
Mass ratio be 1:20, then be added dropwise 3 parts of malonaldehyde, 50 DEG C at a temperature of stirring 6h after, filtration drying obtains being modified micro-
Ball.
Embodiment 5
By mass fraction, 105 parts of hollow carbospheres are taken, are added to the in the mixed solvent (isopropyl of 1800 parts of isopropyl alcohol and waters
The volume fraction of alcohol is 80%), salt acid for adjusting pH value to be added dropwise to 5.2,4 parts of N- β (aminoethyl)-γ-aminopropyls are added dropwise after mixing
Trimethoxy silane pre-processes microballoon, 55 DEG C at a temperature of stir 5h, filtration drying, by pretreated hollow carbon
Microballoon is added in the phosphate buffer solution that sodium dihydrogen phosphate and disodium hydrogen phosphate are prepared, wherein pretreated tiny balloon
Be 1:20 with the mass ratio of buffer solution, 3.5 parts of glyoxals be then added dropwise, 45 DEG C at a temperature of stirring 7h after, filtration drying,
Obtain modified microballoon.
Embodiment 6
By mass fraction, 100 parts of hollow carbospheres are taken, are added in the mixed solvent (the positive fourth of 2200 parts of n-butanols and water
The volume fraction of alcohol is 85%), salt acid for adjusting pH value to be added dropwise to 5.1,4 parts of N- β (aminoethyl)-γ-aminopropyls are added dropwise after mixing
Trimethoxy silane pre-processes microballoon, 60 DEG C at a temperature of stir 4.5h, filtration drying will be pretreated hollow
Carbosphere is added in the phosphate buffer solution that sodium dihydrogen phosphate and disodium hydrogen phosphate are prepared, wherein pretreated hollow micro-
The mass ratio of ball and buffer solution be 1:21, then be added dropwise 4.5 parts of glyoxals, 50 DEG C at a temperature of stirring 5h after, cross be filtered dry
It is dry, obtain modified microballoon.
Mechanics Performance Testing is carried out to the modified glass microsphere in surface prepared in the above embodiments, as a result as shown in table 1 below,
Wherein, comparative sample is the hollow glass micro-ball without surface treatment.
Table 1
| Sample name | Bending strength/MPa | Fracture toughness/MPam0.5 | Impact strength/KJm-2 |
| Comparative sample | 20.11 | 3.04 | 3.26 |
| Embodiment 1 | 24.37 | 3.29 | 3.39 |
| Embodiment 2 | 29.23 | 3.57 | 3.79 |
| Embodiment 3 | 28.67 | 3.55 | 3.82 |
| Embodiment 4 | 25.68 | 3.45 | 3.80 |
| Embodiment 5 | 29.12 | 3.62 | 3.75 |
| Embodiment 6 | 28.51 | 3.58 | 3.79 |
The changing by the silicone coupling agents with Amino End Group and glutaraldehyde coupling agent it can be seen from comparative example and embodiment
The bending strength for the tiny balloon that property obtains is in 24Mpa or more, and fracture toughness is in 3.25MPam0.5More than, impact strength exists
3.3KJ·m-2More than, and it is most of in 3.5KJm-2More than, this shows, the mechanical property of tiny balloon modified by surface
There is very big improvement, it is therefore, subsequent after tiny balloon is filled into phenolic resin, it will also be conducive to phenolic resin
The improvement of mechanical property.
The preparation method of the modified tiny balloon in surface provided by the invention, using dialdehyde (such as glutaraldehyde) and band edge
The collaboration of the silane coupling agent of amino, which is handled, introduces aldehyde radical on tiny balloon surface, not only reduces the table of tiny balloon in this way
Face energy, alleviates the reunion between particle, is conducive to the dispersing uniformity of particle, and the microsphere surface in filled phenolic resin
Aldehyde functions participate in the curing reaction of phenolic aldehyde the interface performance improved between microballoon and matrix, while lighting
It ensure that mechanical property.It present invention can be extensively applied to the phenolic resin-base composite field of such as solar heat protection heat-barrier material
In.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the modified tiny balloon in surface characterized by comprising
Tiny balloon is added in solvent, pH value is adjusted, the first coupling agent is then added, is stirred, it is dry, it obtains pretreated
Tiny balloon；And
The pretreated tiny balloon is added in buffer solution, the second coupling agent is added, is stirred, it is dry, obtain table
The modified tiny balloon in face.
2. preparation method according to claim 1, which is characterized in that the tiny balloon, first coupling agent and institute
State the mass ratio of the second coupling agent are as follows: 90~110:1~5:1~5.
3. preparation method according to claim 1, which is characterized in that the tiny balloon is selected from hollow glass micro-ball, sky
One of heart ceramic microsphere, hollow carbosphere or multiple combinations.
4. preparation method according to claim 1, which is characterized in that the solvent is water and C1~C4The mixed solvent of alcohol,
Wherein, the C1~C4Volume fraction of the alcohol in the solvent is 80%~85%.
5. preparation method according to claim 1, which is characterized in that adjust the pH value to 5~6 using acetic acid or hydrochloric acid
Between.
6. preparation method according to claim 1, which is characterized in that first coupling agent is the siloxanes with Amino End Group
Coupling agent, the second coupling agent agent are dialdehyde.
7. preparation method according to claim 1, which is characterized in that the temperature of the stirring is 40~80 DEG C, described
The time of stirring is 4~8h.
8. preparation method according to claim 1, which is characterized in that the pH value of the buffer solution is 7.2~7.4.
9. a kind of tiny balloon that the surface of preparation method preparations described in any item according to claim 1~8 is modified.
10. the modified tiny balloon in the surface of described in any item preparation method preparations is in phenolic resin according to claim 1~8
Application in based composites.
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| CN201711432338.4A CN109957147B (en) | 2017-12-26 | 2017-12-26 | Surface-modified hollow microsphere and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111808321A (en) * | 2020-07-13 | 2020-10-23 | 万华化学集团股份有限公司 | Preparation method and application of hollow glass beads |
| CN114456424A (en) * | 2022-03-14 | 2022-05-10 | 西安交通大学 | Medium-density phenolic resin matrix composite material and preparation method thereof |
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