CN109957147B - Surface-modified hollow microsphere and preparation method and application thereof - Google Patents
Surface-modified hollow microsphere and preparation method and application thereof Download PDFInfo
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- CN109957147B CN109957147B CN201711432338.4A CN201711432338A CN109957147B CN 109957147 B CN109957147 B CN 109957147B CN 201711432338 A CN201711432338 A CN 201711432338A CN 109957147 B CN109957147 B CN 109957147B
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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
Abstract
The invention provides a surface modified hollow microsphere and a preparation method and application thereof, aldehyde groups are introduced on the surface of the hollow microsphere by adopting the cooperative treatment of binary aldehyde (such as glutaraldehyde) and a silane coupling agent with terminal amino groups, so that the surface energy of the hollow microsphere is reduced, the agglomeration among particles is relieved, the dispersion uniformity of the particles is facilitated, the aldehyde functional groups on the surface of the microsphere participate in the curing reaction of phenolic aldehyde during the filling of phenolic resin to improve the interface performance between the microsphere and a matrix, and the mechanical property is ensured while the weight is reduced. The invention can be widely applied to the field of phenolic resin-based composite materials such as heat-proof heat-insulating materials.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a surface-modified hollow microsphere and a preparation method and application thereof.
Background
Although the surface energy of the inorganic non-metallic filler is higher, the surface of the inorganic non-metallic filler has the characteristics of hydrophilicity and lipophobicity, so that when the inorganic non-metallic filler is filled into a polymer, the combination between the inorganic non-metallic filler and the polymer is poorer, and the inorganic non-metallic filler is not easy to be wetted by the polymer, so that the inorganic non-metallic filler in the polymer is easy to agglomerate, if the inorganic non-metallic filler is directly added into the polymer, the dispersion is easy to be uneven, and thus, the agglomerated part or the part with concentrated dispersion can become a stress concentration point in the composite material and become a weak link in the composite material, and further, the mechanical property of the composite material is poorer.
Disclosure of Invention
Aiming at the problems in the related art, the invention researches a preparation method of a surface modified hollow microsphere so as to provide the surface modified hollow microsphere with better mechanical property.
The preparation method of the surface modified hollow microsphere provided by the invention comprises the following steps: adding the hollow microspheres into a solvent, adjusting the pH value, adding a first coupling agent, stirring and drying to obtain pretreated hollow microspheres; and adding the pretreated hollow microspheres into a buffer solution, adding a second coupling agent, stirring, and drying to obtain the surface-modified hollow microspheres.
In the above preparation method, the mass ratio of the hollow microsphere, the first coupling agent and the second coupling agent is: 90-110: 1-5: 1 to 5.
In the preparation method, the hollow microspheres are selected from one or more of hollow glass microspheres, hollow ceramic microspheres and hollow carbon microspheres.
In the preparation method, the solvents are water and C1～C4A mixed solvent of alcohols, wherein, C1～C4The volume fraction of the alcohol in the solvent is 80-85%.
In the preparation method, acetic acid or hydrochloric acid is adopted to adjust the pH value to be 5-6.
In the preparation method, the pH value is adjusted to 5-6.
In the preparation method, the first coupling agent is a siloxane coupling agent with terminal amino groups, and the second coupling agent is dialdehyde.
In the preparation method, the stirring temperature is 40-80 ℃, and the stirring time is 4-8 hours.
In the preparation method, the pH value of the buffer solution is 7.2-7.4.
The surface-modified hollow microspheres prepared by the above preparation method.
The surface-modified hollow microsphere prepared by the method is applied to phenolic resin matrix composite materials.
According to the preparation method of the surface-modified hollow microsphere provided by the invention, the surface of the hollow microsphere is pretreated by using the silane coupling agent with the terminal amino group, and the Schiff reaction of aldehyde group and amino group is utilized to enable the hollow microsphere to have the functional matrix with the terminal aldehyde group, so that the surface energy of the hollow microsphere is reduced, the agglomeration among particles is relieved, the dispersion uniformity of the particles is facilitated, the aldehyde group can be used for participating in the curing reaction of the phenolic resin-based composite material, the interface performance of the composite material is enhanced, and the mechanical property is ensured while the weight is reduced. The invention can be widely applied to the field of phenolic resin-based composite materials such as heat-proof heat-insulating materials.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The preparation method of the surface modified hollow microsphere provided by the invention comprises the following steps:
firstly, adding the hollow microspheres into a solvent, adjusting the pH value, then adding a first coupling agent, stirring and drying to obtain the pretreated hollow microspheres. In the step, 90-110 parts of hollow microspheres are added into water and C according to the parts by weight1～C4A mixed solvent of alcohol, wherein the mass ratio of the hollow microspheres to the mixed solvent is 1: 18-22, and C1～C4The volume fraction of the alcohol in the mixed solvent is 80-85 percent, C1～C4The alcohol is one or a combination of more of methanol, ethanol, ethylene glycol, propanol, isopropanol and n-butanol, the pH value of the solution is adjusted to 5-6 by using acetic acid or hydrochloric acid, then 1-5 parts of silane coupling agent with terminal amino groups is added to pretreat the hollow microspheres, the mixture is stirred for 4-8 hours at the temperature of 40-80 ℃, the pretreated hollow microspheres are filtered out from the solution, and then the mixture is dried to obtain the pretreated hollow microspheres, the hollow microspheres are selected from one or a combination of hollow glass microspheres, hollow ceramic microspheres and hollow carbon microspheres, the silane coupling agent with terminal amino groups can be selected from gamma-Aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane and N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane.
And adding the pretreated hollow microspheres into a buffer solution, adding a second coupling agent, stirring, and drying to obtain the surface-modified hollow microspheres. In the step, adding the pretreated hollow microspheres into a buffer solution with a pH value of 7.2-7.4, then adding a dialdehyde coupling agent, stirring for 4-8 h at the temperature of 40-80 ℃, filtering, and drying to obtain the surface-modified hollow microspheres, wherein the mass ratio of the pretreated hollow microspheres to the buffer solution is 1: 18-22, and the mass ratio of the hollow microspheres to the second coupling agent is 90-110: 1-5, wherein the dialdehyde comprises glyoxal, malondialdehyde, glutaraldehyde and the like, and the buffer solution comprises a phosphate buffer solution prepared from sodium dihydrogen phosphate and disodium hydrogen phosphate. In the step, the Schiff reaction of aldehyde group and amino group is utilized to enable the hollow microsphere to have an aldehyde group-terminated functional matrix, so that the surface energy of the hollow microsphere is reduced, the agglomeration among particles is relieved, and the dispersion uniformity of the particles is facilitated.
And (3) performance testing:
the bending strength and the fracture toughness of a test sample are tested by adopting three-point bending, the size of the bending test sample is 80mm multiplied by 15mm multiplied by 4mm, the span is 60mm, and the loading rate of a crosshead is 2 mm/min. The size of a fracture toughness sample is 80mm multiplied by 8mm multiplied by 4mm, the plane strain condition is required to be met, the length of a prefabricated crack is 0.45-0.55 time of the width of the sample, the width of the prefabricated crack is 0.015 time or less of the width of the sample, the span is 4 times of the width of the sample, and the loading rate of a crosshead is 1 mm/min. The Charpy impact specimen size is 80mm by 10mm by 4mm, span is 60mm, and pendulum energy is 2J.
Fracture toughness KICAnd impact strength sigmakThe following were used:
where F is the maximum load, B is the specimen thickness, W is the specimen height (width), and a is the pre-crack length. A is the sample fracture energy, b is the open sample width, and d is the open sample thickness.
Example 1
According to the mass portion, 90 portions of hollow glass microspheres are taken and added into a mixed solvent of 1620 portions of ethanol and water (the volume fraction of the ethanol is 80%), acetic acid is dripped to adjust the pH value to 6, after uniform mixing, 1 portion of gamma-aminopropyltriethoxysilane is dripped to pretreat the microspheres, the microspheres are stirred for 8 hours at the temperature of 40 ℃, filtration and drying are carried out, the pretreated hollow glass microspheres are added into a phosphate buffer solution prepared from sodium dihydrogen phosphate and disodium hydrogen phosphate, wherein the mass ratio of the pretreated hollow microspheres to the buffer solution is 1:18, then 1 portion of glutaraldehyde is dripped, the mixture is stirred for 8 hours at the temperature of 40 ℃, and filtration and drying are carried out, so that the modified microspheres are obtained.
Example 2
According to the mass portion, 110 portions of hollow glass microspheres are taken and added into 2420 portions of mixed solvent of methanol and water (the volume fraction of the methanol is 85%), acetic acid is dripped to adjust the pH value to 5, after uniform mixing, 5 portions of gamma-aminopropyltriethoxysilane are dripped to pretreat the microspheres, the microspheres are stirred for 4 hours at the temperature of 80 ℃, filtration and drying are carried out, the pretreated hollow glass microspheres are added into phosphate buffer solution prepared from sodium dihydrogen phosphate and disodium hydrogen phosphate, wherein the mass ratio of the pretreated hollow microspheres to the buffer solution is 1:22, then 5 portions of glutaraldehyde is dripped, the mixture is stirred for 4 hours at the temperature of 80 ℃, and filtration and drying are carried out, so that the modified microspheres are obtained.
Example 3
According to the mass parts, 100 parts of hollow ceramic microspheres are added into 2000 parts of mixed solvent of ethylene glycol and water (the volume fraction of the ethylene glycol is 82%), acetic acid is dripped to adjust the pH value to 5.5, after uniform mixing, 3 parts of gamma-aminopropyltrimethoxysilane is dripped to pretreat the microspheres, the microspheres are stirred for 6 hours at the temperature of 50 ℃, filtered and dried, the pretreated hollow ceramic microspheres are added into phosphate buffer solution prepared from sodium dihydrogen phosphate and disodium hydrogen phosphate, wherein the mass ratio of the pretreated hollow microspheres to the buffer solution is 1:19, then 3.5 parts of malonaldehyde is dripped, the mixture is stirred for 5 hours at the temperature of 60 ℃, filtered and dried, and the modified microspheres are obtained.
Example 4
According to the mass portion, 95 portions of hollow ceramic microspheres are added into 2000 portions of mixed solvent of propanol and water (the volume fraction of the propanol is 84%), hydrochloric acid is dripped to adjust the pH value to 5.7, 2.5 portions of gamma-aminopropyl trimethoxy silane are dripped to pretreat the microspheres after uniform mixing, the microspheres are stirred for 7 hours at the temperature of 45 ℃, and then the filtration is carried out. And (2) drying, namely adding the pretreated hollow ceramic microspheres into a phosphate buffer solution prepared from sodium dihydrogen phosphate and disodium hydrogen phosphate, wherein the mass ratio of the pretreated hollow ceramic microspheres to the buffer solution is 1:20, then dropwise adding 3 parts of malondialdehyde, stirring at the temperature of 50 ℃ for 6 hours, filtering and drying to obtain the modified microspheres.
Example 5
Taking 105 parts of hollow carbon microspheres by mass, adding the hollow carbon microspheres into 1800 parts of a mixed solvent of isopropanol and water (the volume fraction of the isopropanol is 80%), dropwise adding hydrochloric acid to adjust the pH value to 5.2, uniformly mixing, dropwise adding 4 parts of N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane to pretreat the microspheres, stirring for 5 hours at the temperature of 55 ℃, filtering and drying, adding the pretreated hollow carbon microspheres into a phosphate buffer solution prepared from sodium dihydrogen phosphate and disodium hydrogen phosphate, wherein the mass ratio of the pretreated hollow carbon microspheres to the buffer solution is 1:20, dropwise adding 3.5 parts of glyoxal, stirring for 7 hours at the temperature of 45 ℃, filtering and drying to obtain the modified microspheres.
Example 6
According to the mass parts, 100 parts of hollow carbon microspheres are taken and added into 2200 parts of mixed solvent of N-butanol and water (the volume fraction of the N-butanol is 85%), hydrochloric acid is dripped to adjust the pH value to 5.1, after uniform mixing, 4 parts of N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane are dripped to pretreat the microspheres, the microspheres are stirred for 4.5 hours at the temperature of 60 ℃, filtered and dried, the pretreated hollow carbon microspheres are added into phosphate buffer solution prepared from sodium dihydrogen phosphate and disodium hydrogen phosphate, wherein the mass ratio of the pretreated hollow microspheres to the buffer solution is 1:21, then 4.5 parts of glyoxal is dripped, the mixture is stirred for 5 hours at the temperature of 50 ℃, filtered and dried, and the modified microspheres are obtained.
The mechanical property test results of the surface-modified glass microspheres prepared in the above examples are shown in table 1 below, wherein the comparative sample is hollow glass microspheres without surface treatment.
TABLE 1
| Name of sample | Flexural Strength/MPa | Fracture toughness/MPa.m0.5 | Impact Strength/KJ.m-2 |
| Control sample | 20.11 | 3.04 | 3.26 |
| Example 1 | 24.37 | 3.29 | 3.39 |
| Example 2 | 29.23 | 3.57 | 3.79 |
| Example 3 | 28.67 | 3.55 | 3.82 |
| Example 4 | 25.68 | 3.45 | 3.80 |
| Example 5 | 29.12 | 3.62 | 3.75 |
| Example 6 | 28.51 | 3.58 | 3.79 |
As can be seen from the comparative examples and examples, the hollow microspheres obtained by modifying the siloxane coupling agent with terminal amino groups and the glutaraldehyde coupling agent have the bending strength of more than 24MPa and the fracture toughness of 3.25 MPa-m0.5Above, the impact strength is 3.3KJ · m-2Above, and mostly in the range of 3.5KJ · m-2The above shows that the mechanical properties of the hollow microspheres are greatly improved by surface modification, so that the mechanical properties of the phenolic resin must be improved after the hollow microspheres are filled into the phenolic resin.
According to the preparation method of the surface-modified hollow microspheres, aldehyde groups are introduced to the surfaces of the hollow microspheres by adopting the synergistic treatment of the dialdehyde (such as glutaraldehyde) and the silane coupling agent with terminal amino groups, so that the surface energy of the hollow microspheres is reduced, the agglomeration among particles is relieved, the dispersion uniformity of the particles is facilitated, the aldehyde functional groups on the surfaces of the microspheres participate in the phenolic aldehyde curing reaction during the filling of phenolic resin to improve the interface performance between the microspheres and a matrix, and the mechanical properties are ensured while the microspheres are lightened. The invention can be widely applied to the field of phenolic resin-based composite materials such as heat-proof heat-insulating materials.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The application of the surface modified hollow microsphere in the phenolic resin-based composite material is characterized in that the preparation method of the surface modified hollow microsphere comprises the following steps:
adding the hollow microspheres into a solvent, adjusting the pH value, adding a first coupling agent, stirring and drying to obtain pretreated hollow microspheres; and
adding the pretreated hollow microspheres into a buffer solution, adding a second coupling agent, stirring, and drying to obtain surface-modified hollow microspheres;
the first coupling agent is a siloxane coupling agent with terminal amino groups, and the second coupling agent is dialdehyde;
when the surface-modified hollow microspheres are filled into phenolic resin, aldehyde functional groups on the surfaces of the surface-modified hollow microspheres participate in the curing reaction of the phenolic resin, so that the interface performance of the surface-modified hollow microspheres and the phenolic resin matrix composite is improved.
2. The use of the surface-modified hollow microspheres of claim 1 in a phenolic resin-based composite material, wherein the mass ratio of the hollow microspheres to the first and second coupling agents is: 90-110: 1-5: 1 to 5.
3. The use of the surface-modified hollow microspheres of claim 1 in phenolic resin-based composites, wherein the hollow microspheres are selected from the group consisting of hollow glass microspheres, hollow ceramic microspheres, hollow carbon microspheres, or a combination thereof.
4. Use of the surface-modified hollow microspheres of claim 1 in phenolic resin based composites, wherein the solvent is water and C1～C4A mixed solvent of alcohols, wherein, C1～C4The volume fraction of the alcohol in the solvent is 80-85%.
5. The use of the surface-modified hollow microspheres of claim 1 in phenolic resin-based composites, wherein the pH is adjusted to between 5 and 6 using acetic acid or hydrochloric acid.
6. The application of the surface-modified hollow microspheres in the phenolic resin-based composite material according to claim 1, wherein the stirring temperature is 40-80 ℃, and the stirring time is 4-8 h.
7. The use of the surface-modified hollow microspheres of claim 1 in phenolic resin-based composites, wherein the buffer solution has a pH of 7.2-7.4.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102214828A (en) * | 2010-04-09 | 2011-10-12 | 北京化工大学 | Nanometer particulate matter modified compound proton exchange membrane and preparation method thereof |
| CN103102421A (en) * | 2013-01-30 | 2013-05-15 | 哈尔滨工业大学 | Preparation method of core-shell structure magnetic nano-molecular imprinting polymer for separating starch polysaccharides |
| KR101287362B1 (en) * | 2011-12-09 | 2013-07-19 | 고려대학교 산학협력단 | Branched polymer microspheres with silica shell |
| CN103627101A (en) * | 2012-08-23 | 2014-03-12 | 天津市江天统一科技有限公司 | Preparation method and applications of thermosetting phenolic resin coated hollow glass microspheres |
| CN103865295A (en) * | 2014-02-13 | 2014-06-18 | 甘肃康博丝特新材料有限责任公司 | Method for polymer surface modification of hollow glass micro-bead |
| CN103903827A (en) * | 2014-03-20 | 2014-07-02 | 哈尔滨益材新材料有限公司 | Preparation method and application of magnetic silicon dioxide composite microsphere |
-
2017
- 2017-12-26 CN CN201711432338.4A patent/CN109957147B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102214828A (en) * | 2010-04-09 | 2011-10-12 | 北京化工大学 | Nanometer particulate matter modified compound proton exchange membrane and preparation method thereof |
| KR101287362B1 (en) * | 2011-12-09 | 2013-07-19 | 고려대학교 산학협력단 | Branched polymer microspheres with silica shell |
| CN103627101A (en) * | 2012-08-23 | 2014-03-12 | 天津市江天统一科技有限公司 | Preparation method and applications of thermosetting phenolic resin coated hollow glass microspheres |
| CN103102421A (en) * | 2013-01-30 | 2013-05-15 | 哈尔滨工业大学 | Preparation method of core-shell structure magnetic nano-molecular imprinting polymer for separating starch polysaccharides |
| CN103865295A (en) * | 2014-02-13 | 2014-06-18 | 甘肃康博丝特新材料有限责任公司 | Method for polymer surface modification of hollow glass micro-bead |
| CN103903827A (en) * | 2014-03-20 | 2014-07-02 | 哈尔滨益材新材料有限公司 | Preparation method and application of magnetic silicon dioxide composite microsphere |
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