CN1172967C - Process for preparing composite nano SiO2 particle/polymer material - Google Patents
Process for preparing composite nano SiO2 particle/polymer material Download PDFInfo
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- CN1172967C CN1172967C CNB011153105A CN01115310A CN1172967C CN 1172967 C CN1172967 C CN 1172967C CN B011153105 A CNB011153105 A CN B011153105A CN 01115310 A CN01115310 A CN 01115310A CN 1172967 C CN1172967 C CN 1172967C
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Abstract
The present invention belongs to the technical field of nanometer material, which is particularly relates to a method for preparing silicon dioxide nanometer particle/polymer composite material. Mixed solution of methacrylic ester monomers and siloxane compounds is taken according to the weight ratio of 5: 1 to 50: 1. Azo or peroxide initiating agents accounting for 0.1% to 1% of the total weight of the mixed solution are added, and then, the mixed solution is poured into a mold with a required shape and is heated for polymerization to obtain high molecular material forming bodies. The prepared high molecular material forming bodies are soaked into mixed solution of ammonia water and alcohol to be swelled and to react in high molecular material to generate SiO2 nanometer particles. High molecular material is extracted from the mixed solution, and alcohol and ammonia water are volatilized thoroughly. The high molecular/SiO2 nanometer composite material obtained finally has the advantages of favorable performance and high stability.
Description
The invention belongs to the technical field of nano materials, and particularly relates to a method for preparing a silicon dioxide nano particle/polymer composite material.
The nano material has special properties which are not possessed by a plurality of traditional materials, draws high attention at home and abroad, and is successfully applied to a plurality of high and new technical fields such as fine chemical engineering, bioengineering, instruments and meters, and the like, and the nano material is called as a new material in twenty-first century. In recent years, nanotechnology in the field of polymer materials has been rapidly developed, and organic/inorganic nanocomposite materials with dispersion sizes between 1 and 200nm can be prepared, and are still transparent materials macroscopically despite microscopic phase separation. And inorganic and high molecular components are doped together by a proper means, and a main valence bond or a secondary valence bond is formed among the components, so that the inorganic/high molecular nano composite material is endowed with new optical properties, electrical properties, mechanical properties, functional gradient properties and the like, has a very wide application prospect, and has attracted great attention of people.
The current methods for preparing polymer/inorganic nanocomposite materials mainly comprise: sol-gel method, nano-particle direct dispersion method and intercalation compounding method. However, these methods have the disadvantages of complicated preparation, easy shrinkage and brittle fracture of the prepared nano composite material, poor transparency, difficult control of particle size and the like.
The invention aims to provide a novel method for preparing a silicon dioxide nanoparticle/polymer composite material, which has the advantages of simple operation, mild reaction conditions and easily controlled component ratio.
The invention also aims to ensure that the prepared nano composite material has the characteristics of high transparency, high purity and high uniformity; easy to machine and form and small in volume shrinkage deformation.
The technical scheme of the invention is as follows:
(1) mixing siloxane compounds in methacrylate monomers, adding an initiator, and heating and polymerizing to prepare a high polymer material forming body;
(2) immersing the prepared polymer material forming body into a mixed solution of ammonia water and alcohol, wherein the alcohol gradually swells the polymer material, and simultaneously, the water reacts with siloxane compounds under the condition of ammonia water until the reaction is complete; formation of SiO2And (3) nanoparticles. The reaction formula is as follows:
wherein: r is methyl, ethyl, propyl or gamma-aminopropyl, etc. because the reaction is carried out between solid polymer chains, the nano particles are stabilized and protected and are not easy to be secondarily aggregated into large particles.
In this method, the reactant mixture may be introduced into a mold before the heating polymerization, so that the resulting polymer material is in the form of a desired film, fiber or block.
(3) The polymer material is taken out from the mixed solution to completely volatilize the alcohol and the ammonia water.
The specific method for preparing the silicon dioxide nano-particle/polymer composite material comprises the following steps:
(1) preparing a mixed solution from a methacrylate monomer and a siloxane compound, wherein the weight ratio of the methacrylate monomer to the siloxane compound is 5: 1-50: 1; adding azo or peroxide initiator in 0.1-1 wt% of the mixture liquid, pouring into mold of required shape, heating and polymerizing to obtain the polymer material forming body.
(2) Immersing the prepared polymer material forming body into a mixed solution of 25% ammonia water and alcohol for swelling, and reacting in the polymer material to generate SiO2Nano particles, wherein the weight ratio of ammonia water to alcohol is 1: 10-1: 100.
(3) Taking the high polymer material prepared in the step (2), and completely volatilizing alcohol and a small amount of ammonia water in the high polymer material under the normal pressure or reduced pressure condition.
The methacrylate monomer is methyl methacrylate, ethyl methacrylate, phenyl methacrylate or the like; the siloxane compound is tetramethyl orthosilicate, tetraethyl orthosilicate or gamma-aminopropyltriethoxysilane, etc.; the alcohol is methanol, ethanol, propanol or isopropanol; the initiator is azobisisobutyronitrile or benzoyl peroxide, etc.
The silicon dioxide nano-particle/polymer composite material prepared by the invention has the characteristics of high transparency, strong hardness, good aging resistance, high temperature resistance and the like; the preparation method is simple and easy to implement, the reaction conditions are mild, the material shrinkage deformability is small, and the material can be prepared into various shapes. The nano-particles can be controlled between 10-300nm according to requirements.
The silicon dioxide nano-particle/polymer composite material prepared by the invention improves the photoelectric property, the thermal property and the mechanical property of common high polymer materials, and can be widely applied to the aspects of chemical building materials, daily necessities or photoelectric instruments and equipment and the like.
The technical solution of the present invention is further described below with reference to the following embodiments and accompanying drawings:
FIG. 1 SiO prepared in example 1 of the invention2SEM image of nanoparticles in PMMA.
Example 1
Taking methyl methacrylate and tetraethyl orthosilicate with the weight ratio of 20: 1 to prepare a mixed solution, and adding azodicarbon with the percentage concentration of 0.1 percent of the total weight of the mixed solutionIsobutyronitrile, pouring the solution into a mould, and heating until the polymerization reaction is complete; soaking the prepared polymer material forming body into a mixed solution of 25% ammonia water and methanol for swelling and reacting to complete, and reacting in the polymer material to generate SiO2Nano particles, wherein the weight ratio of ammonia water to methanol is 1: 20; taking out the high molecular material, and completely volatilizing the methanol and the ammonia water from the material under normal pressure.
Example 2
Taking methyl methacrylate and tetraethyl orthosilicate, and weighing the methyl methacrylate and the tetraethyl orthosilicatePreparing a mixed solution according to the weight ratio of 20: 1, adding azodiisobutyronitrile with the concentration of 0.5 percent of the total weight of the mixed solution, pouring the solution into a mold, and heating until the polymerization reaction is completed; soaking the prepared polymer material forming body into a mixed solution of 25% ammonia water and ethanol, and reacting in the polymer material to generate SiO with the progress of swelling2Nano particles, wherein the weight ratio of ammonia water to ethanol is 1: 40; the polymer material was taken out, and ethanol and aqueous ammonia were completely volatilized from the material under reduced pressure.
Example 3
Taking methyl methacrylate and tetraethyl orthosilicate in a weight ratio of 5: 1 to prepare a mixed solution, adding azodiisobutyronitrile with the concentration of 1 percent of the total weight of the mixed solution, pouring the solution into a mold, and heating until the polymerization reaction is completed. Immersing the prepared polymer material forming body into a mixed solution of 25% ammonia water and isopropanol, and reacting to generate SiO in the polymer material along with the swelling2Nano particles, wherein the weight ratio of ammonia water to isopropanol is 1: 20; the polymer material was taken out, and isopropanol and aqueous ammonia were thoroughly evaporated from the material under reduced pressure.
Example 4
Taking methyl methacrylate and tetramethyl orthosilicate according to the weight ratio of 20: 1, preparing a mixed solution, adding azodiisobutyronitrile with the concentration of 0.1 percent of the total weight of the mixed solution, pouring the solution into a mold, and heating until the polymerization reaction is completed. Soaking the prepared polymer material forming body into a mixed solution of25% ammonia water and methanol for swelling and reacting to complete, and reacting in the polymer material to generate SiO2Nano particles, wherein the weight ratio of ammonia water to methanol is 1: 100; methanol and ammonia were completely volatilized from the material at normal pressure.
Example 5
Taking ethyl methacrylate and tetraethyl orthosilicate, wherein the weight ratio of the ethyl methacrylate to the tetraethyl orthosilicatePreparing a mixed solution at a ratio of 30: 1, adding benzoyl peroxide with a concentration of 1 percent based on the total weight of the mixed solution, pouring the solution into a mold, and heating until the polymerization reaction is completed. Soaking the prepared polymer material forming body into a mixed solution of 25% ammonia water and methanol for swelling and reacting to complete, and reacting in the polymer material to generate SiO2Nano particles, wherein the weight ratio of ammonia water to methanol is 1: 10; methanol and ammonia were completely volatilized from the material at normal pressure.
Example 6
Taking methyl methacrylate and gamma-aminopropyltriethoxysilane, wherein the weight ratio of the methyl methacrylate to the gamma-aminopropyltriethoxysilane is 40: 1, preparing a mixed solution, adding azobisisobutyronitrile with the percentage concentration of 0.1 percent of the total weight of the mixed solution, pouring the solution into a mold, and heating until the polymerization reaction is completed. Soaking the prepared polymer material forming body into a mixed solution of 25% ammonia water and isopropanol for swelling and reacting to be complete, and reacting in the polymer material to generate SiO2Nano particles, wherein the weight ratio of ammonia water to isopropanol is 1: 60; the isopropanol and ammonia were allowed to evaporate completely from the materialat atmospheric pressure.
Claims (7)
1. A method of preparing a silica nanoparticle/polymer composite, characterized in that the method comprises the steps of:
(1) mixing siloxane compounds in methacrylate monomers to prepare a mixed solution, wherein the weight ratio of the methacrylate monomers to the siloxane compounds is 5: 1-50: 1, adding an initiator, and heating and polymerizing to prepare a high polymer material forming body;
(2) mixing ammonia water and alcohol to prepare a mixed solution of the ammonia water and the alcohol, wherein the weight ratio of the ammonia water to the alcohol is 1: 10-1: 100, and the concentration of the ammonia water is 25%; then, the polymer material formed body prepared in the step (1) is immersed into a mixed solution of ammonia and alcohol, wherein the alcohol gradually swells the polymer material, and meanwhile, the water and the alcohol are added under the condition of ammonia waterReacting the siloxane compound until the reaction is complete; formation of SiO2A nanoparticle;
(3) the polymer material is taken out from the mixed solution to completely volatilize the alcohol and the ammonia water.
2. The method of claim 1, wherein the initiator added in step (1) is azo or peroxide initiator added in an amount of 0.1-1% by weight based on the total weight of the mixture.
3. The method of claim 1, wherein: the methacrylate monomer is methyl methacrylate, ethyl methacrylate or phenyl methacrylate.
4. The method of claim 1, wherein: the siloxane compound is tetramethyl orthosilicate, tetraethyl orthosilicate or gamma-aminopropyltriethoxysilane.
5. The method of claim 1 or 2, wherein: the initiator is azobisisobutyronitrile or benzoyl peroxide.
6. The method of claim 1, wherein: the alcohol is methanol, ethanol, propanol or isopropanol.
7. The method of claim 1, wherein: in the method, before the heating polymerization, the reactant mixed solution can be added into a mold, so that the generated high polymer material is in a required film, fiber or block shape.
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| CNB011153105A CN1172967C (en) | 2001-04-18 | 2001-04-18 | Process for preparing composite nano SiO2 particle/polymer material |
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| CNB011153105A CN1172967C (en) | 2001-04-18 | 2001-04-18 | Process for preparing composite nano SiO2 particle/polymer material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101293115B (en) * | 2008-06-25 | 2011-05-04 | 山东大学 | Method for preparing stephanoporate bracket with biological activity by introducing SiO2 into polymer |
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| CN110128597B (en) * | 2019-05-21 | 2020-08-04 | 清华大学 | Low-temperature forming self-lubricating material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293115B (en) * | 2008-06-25 | 2011-05-04 | 山东大学 | Method for preparing stephanoporate bracket with biological activity by introducing SiO2 into polymer |
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