CN120553719B - A method for preparing a nano-silica dispersion - Google Patents
A method for preparing a nano-silica dispersionInfo
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- CN120553719B CN120553719B CN202510951268.1A CN202510951268A CN120553719B CN 120553719 B CN120553719 B CN 120553719B CN 202510951268 A CN202510951268 A CN 202510951268A CN 120553719 B CN120553719 B CN 120553719B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- Medicinal Chemistry (AREA)
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Abstract
本发明涉及纳米二氧化硅领域，具体涉及一种纳米二氧化硅分散液的制备方法，所述制备步骤如下：将改性聚乙二醇甲基丙烯酸酯加入乙醇与去离子水混合溶剂中，升温至30‑50℃，搅拌15‑25min，加入正硅酸乙酯，搅拌8‑12min，本发明通过在二氧化硅溶胶形成过程中同步引入特定嵌段结构的分散液并精准控制反应梯度，实现粒子生长与表面修饰的一步协同，与现有技术相比，该方法所得分散液兼具超高固含下的低粘度特性、干燥后可自发再分散的永久稳定性，以及pH响应智能释放功能，同时工艺过程采用闭环溶剂系统，降低能耗，在隔膜涂层与光学增透薄膜等领域具有广阔应用前景。This invention relates to the field of nano-silica, specifically to a method for preparing a nano-silica dispersion. The preparation steps are as follows: modified polyethylene glycol methacrylate is added to a mixed solvent of ethanol and deionized water, heated to 30-50°C, stirred for 15-25 min, tetraethyl orthosilicate is added, and stirred for 8-12 min. This invention achieves one-step synergistic effect of particle growth and surface modification by simultaneously introducing a dispersion with a specific block structure during the formation of silica sol and precisely controlling the reaction gradient. Compared with the prior art, the dispersion obtained by this method has the characteristics of low viscosity under ultra-high solid content, permanent stability that can spontaneously redisperse after drying, and intelligent release function in response to pH. At the same time, the process adopts a closed-loop solvent system, reducing energy consumption, and has broad application prospects in the fields of membrane coating and optical antireflection films.
Description
Technical Field
The invention relates to the field of nano silicon dioxide, in particular to a preparation method of nano silicon dioxide dispersion liquid.
Background
The nano silicon dioxide dispersion liquid is a semitransparent liquid material taking nano silicon dioxide particles as a core component, is a functional auxiliary agent endowing the nano silicon dioxide particles with anti-agglomeration capability mainly through chemical modification or physical coating means, and is mainly applied to the fields of coating, refractory materials, textile industry and the like.
In the prior art, because the nano silicon dioxide dispersion liquid has small particle size and high surface hydroxyl density, hydrogen bonds are easy to form among particles, so that agglomeration is initiated, and the traditional process needs to be dried into powder, in the dehydration process, irreversible condensation reaction can be carried out on silicon hydroxyl groups of adjacent particles to form firm Si-O-Si covalent bonds, so that hard agglomeration is difficult to be redispersed by conventional mechanical force, meanwhile, along with the increase of solid content, the inter-particle distance is reduced, the van der Waals attraction and hydrogen bond effect are obviously enhanced, the viscosity of the dispersion system is greatly increased, the processability of the dispersion system is seriously influenced, the drying and irreversible hardening are caused, and meanwhile, the viscosity is greatly increased when the solid content is high, so that the application range of the dispersion system is influenced.
Therefore, according to the related art described above, there is a need to develop a method for preparing a nano silica dispersion.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a nano silica dispersion, which solves the problems of agglomeration, high solid content, high viscosity and single function in the prior art.
Based on the above objects, the present invention provides a method for preparing a nano silica dispersion.
A method for preparing nano silicon dioxide dispersion liquid, which comprises the following steps:
Step S1, adding modified polyethylene glycol methacrylate into a mixed solvent of ethanol and deionized water, heating to 30-50 ℃, stirring for 15-25min, adding tetraethoxysilane, stirring for 8-12min, adding 0.1mol/L HCl solution, adjusting pH to 1.8-2.2, reacting for 1-3h, and obtaining a mixed solution after the reaction is completed;
S2, adding the mixed solution into a flask, adding 0.1mol/L ammonia water, adjusting the pH to 8.8-9.2, heating to 55-65 ℃, adding the mixed solution of tetraethoxysilane, modified polyethylene glycol methacrylate and ethanol, stirring and reacting for 5-7h at the rotating speed of 350-450rpm, and obtaining sol after the reaction is completed;
step S3, adding the sol into a flask, heating to 50-70 ℃, reacting for 10-14 hours, replacing the solvent with deionized water by an ultrafiltration device after the reaction is completed, and concentrating under reduced pressure to obtain nano silicon dioxide dispersion liquid;
Through HCl solution, tetraethoxysilane is fully hydrolyzed into active silicon hydroxyl, then under the alkaline environment created by matching with ammonia water, tetraethoxysilane and modified polyethylene glycol methacrylate are synchronously added, through precisely controlling the reaction condition, the active group in the dispersion liquid molecule and Si-OH on the surface of newly generated silicon dioxide particles are subjected to condensation reaction to form covalent bond Si-O-Si, so that in-situ synchronization of particle growth and surface modification is realized, and at the same time, the alkaline environment and proper temperature are favorable for forming sol with uniform granularity;
The dispersion liquid is permanently anchored on the surface of the silicon dioxide particles through covalent bonds Si-O-Si, and in the drying process, a steric hindrance layer formed by long chain polyethylene glycol in molecules can effectively and physically isolate adjacent particles, so that polycondensation reaction between silicon hydroxyl groups on the surfaces of the particles is prevented, hard agglomeration is avoided, and therefore, when the dried powder encounters water, polyethylene glycol chains can be rapidly hydrated and spread to enable the particles to be redispersed, and permanent stability is realized;
meanwhile, the ethylene glycol long chain anchored on the particle surface is fully stretched in water to form a thick hydration layer and steric hindrance, so that the van der Waals attractive force between particles can be greatly weakened, and the low viscosity of the system can be maintained when the particles are in high concentration, and the processability is obviously improved.
Preferably, the volume ratio of the ethanol to the deionized water in the step S1 is 4:1.
Preferably, the mass ratio of the modified polyethylene glycol methacrylate to the tetraethoxysilane in the step S1 is 1:4.6-4.7.
Preferably, the mass ratio of the mixed solution, the tetraethoxysilane and the modified polyethylene glycol methacrylate in the step S2 is 1:0.32-0.33:0.008-0.01.
Preferably, the mass ratio of the modified polyethylene glycol methacrylate to the ethanol in the step S2 is 1:17-19.
Preferably, the preparation steps of the modified polyethylene glycol methacrylate are as follows:
Under the nitrogen atmosphere, adding dimethylaminoethyl methacrylate, sodium styrene sulfonate and polyethylene glycol methacrylate into an absolute ethanol solvent, stirring and mixing, adding an initiator azodiisobutyronitrile, heating to 65-75 ℃, reacting for 22-26h, cooling to 5-10 ℃, adding hydroquinone, standing for precipitation, filtering, washing and drying to obtain modified polyethylene glycol methacrylate;
The modified polyethylene glycol methacrylate contains a zwitterionic segmented copolymer of dimethylaminoethyl methacrylate and sodium styrene sulfonate, in a neutral environment, a tertiary amine part is protonated and forms an inner salt structure with a sulfonate group, so that charge stability can be provided, meanwhile, the structure can effectively load a medicament with true electricity through electrostatic action, in a slightly acidic environment, the degree of protonation of the tertiary amine matrix is increased, so that the net positive charge density on the surface of particles is increased, electrostatic repulsion is generated, the particles are combined with the medicament with positive charge to induce molecular isomerism, and in addition, the charge balance with the sulfonate group is broken, and the rapid desorption and release of the medicament are realized through the synergistic effect of the two, so that intelligent response is realized.
Preferably, the mass ratio of the dimethylaminoethyl methacrylate, the sodium styrenesulfonate, the polyethylene glycol methacrylate and the initiator azodiisobutyronitrile to the hydroquinone is 1:1.25-1.35:4.9-5.1:0.008-0.012:0.0008-0.0012.
Preferably, the hydroquinone is a polymerization inhibitor, and the molecular weight of the polyethylene glycol methacrylate is 500.
The invention has the beneficial effects that:
The invention provides a preparation method of nano silicon dioxide dispersion liquid, which realizes one-step synergy of particle growth and surface modification by synchronously introducing dispersion liquid with specific block structure and precisely controlling reaction gradient in the process of forming silicon dioxide sol, the dispersion liquid obtained by the method has the characteristics of low viscosity under ultrahigh solid content, permanent stability of spontaneous redispersion after drying and an intelligent pH response release function, and meanwhile, the technical process adopts a closed-loop solvent system, so that the energy consumption is reduced, and the dispersion liquid has wide application prospect in the fields of diaphragm coating, optical anti-reflection film and the like.
Detailed Description
The present invention will be further described in detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
Example 1A modified polyethylene glycol methacrylate was prepared as follows:
Under the nitrogen atmosphere, adding 100g of dimethylaminoethyl methacrylate, 125g of sodium styrene sulfonate and 490g of polyethylene glycol methacrylate into 1000mL of absolute ethanol solvent, stirring and mixing, adding 0.8g of initiator azodiisobutyronitrile, heating to 65 ℃, reacting for 26 hours, cooling to 5 ℃, adding 0.08g of hydroquinone, standing and precipitating, filtering, washing and drying to obtain the modified polyethylene glycol methacrylate.
Example 2A modified polyethylene glycol methacrylate was prepared as follows:
Under the nitrogen atmosphere, adding 100g of dimethylaminoethyl methacrylate, 130g of sodium styrenesulfonate and 500g of polyethylene glycol methacrylate into 1000mL of absolute ethanol solvent, stirring and mixing, adding 1g of initiator azodiisobutyronitrile, heating to 70 ℃, reacting for 24 hours, cooling to 8 ℃, adding 0.1g of hydroquinone, standing for precipitation, filtering, washing and drying to obtain the modified polyethylene glycol methacrylate.
Example 3A modified polyethylene glycol methacrylate was prepared as follows:
Under the nitrogen atmosphere, adding 100g of dimethylaminoethyl methacrylate, 135g of sodium styrene sulfonate and 510g of polyethylene glycol methacrylate into 1000mL of absolute ethanol solvent, stirring and mixing, adding 1.2g of initiator azodiisobutyronitrile, heating to 75 ℃, reacting for 22 hours, cooling to 10 ℃, adding 0.12g of hydroquinone, standing for precipitation, filtering, washing and drying to obtain the modified polyethylene glycol methacrylate.
Example 4 preparation of nanosilica dispersion:
S1, adding 100g of modified polyethylene glycol methacrylate into a mixed solvent of 400mL of ethanol and 100mL of deionized water, heating to 30 ℃, stirring for 25min, adding 460g of tetraethoxysilane, stirring for 8min, adding 0.1mol/L of HCl solution, adjusting the pH to 1.8-2.2, reacting for 3h, and obtaining a mixed solution after the reaction is completed;
S2, adding 100g of mixed solution into a flask, adding 0.1mol/L ammonia water, adjusting the pH to 8.8-9.2, heating to 55 ℃, adding 32g of tetraethoxysilane and 0.8g of mixed solution of modified polyethylene glycol methacrylate and 13.6g of ethanol, stirring and reacting for 7 hours at the rotating speed of 350rpm, and obtaining sol after the reaction is completed;
And S3, adding 100g of sol into a flask, heating to 50 ℃, reacting for 14 hours, replacing the solvent with deionized water by using an ultrafiltration device, and concentrating under reduced pressure to obtain the nano silicon dioxide dispersion liquid.
Example 5 preparation of nanosilica dispersion:
S1, adding 100g of modified polyethylene glycol methacrylate into a mixed solvent of 400mL of ethanol and 100mL of deionized water, heating to 40 ℃, stirring for 20min, adding 465g of tetraethoxysilane, stirring for 10min, adding 0.1mol/L of HCl solution, adjusting the pH to 1.8-2.2, reacting for 2h, and obtaining a mixed solution after the reaction is completed;
S2, adding 100g of mixed solution into a flask, adding 0.1mol/L ammonia water, adjusting the pH to 8.8-9.2, heating to 60 ℃, adding 32.5g of mixed solution of tetraethoxysilane, 0.9g of modified polyethylene glycol methacrylate and 16.2g of ethanol, stirring and reacting for 6 hours at the rotating speed of 400rpm, and obtaining sol after the reaction is completed;
And S3, adding 100g of sol into a flask, heating to 60 ℃, reacting for 12 hours, replacing the solvent with deionized water by using an ultrafiltration device, and concentrating under reduced pressure to obtain the nano silicon dioxide dispersion liquid.
Example 6 preparation of nanosilica dispersion:
S1, adding 100g of modified polyethylene glycol methacrylate into a mixed solvent of 400mL of ethanol and 100mL of deionized water, heating to 50 ℃, stirring for 15min, adding 33g of tetraethoxysilane, stirring for 8min, adding 0.1mol/L of HCl solution, adjusting the pH to 1.8-2.2, reacting for 3h, and obtaining a mixed solution after the reaction is completed;
S2, adding 100g of mixed solution into a flask, adding 0.1mol/L ammonia water, adjusting the pH to 8.8-9.2, heating to 65 ℃, adding 33g of mixed solution of tetraethoxysilane, 1g of modified polyethylene glycol methacrylate and 19g of ethanol, stirring and reacting for 5 hours, and rotating at 450rpm, so that the sol is obtained;
and S3, adding 100g of sol into a flask, heating to 70 ℃, reacting for 10 hours, replacing the solvent with deionized water by using an ultrafiltration device, and concentrating under reduced pressure to obtain the nano silicon dioxide dispersion liquid.
Comparative example 1:
compared with the embodiment 4, the comparative example eliminates the step S2 of preparing in the step of preparing the nano silicon dioxide dispersion liquid, directly and physically mixes, and other steps and parameters are the same, and the comparative example does not repeat the detailed description, and finally the nano silicon dioxide dispersion liquid is obtained.
Comparative example 2:
Compared with the comparative example 4, the comparative example only replaces modified polyethylene glycol methacrylate with dimethylaminoethyl methacrylate, sodium styrene sulfonate and polyethylene glycol methacrylate mixture, and the rest steps and parameters are the same, so that the comparative example does not repeat any more description, and finally the nano silicon dioxide dispersion liquid is obtained.
Comparative example 3:
compared with the comparative example 4, the modified polyethylene glycol methacrylate is replaced by polyethylene glycol methacrylate, the other steps and parameters are the same, and the comparative example is not repeated, so that the nano silicon dioxide dispersion liquid is finally obtained.
Comparative example 4:
Compared with the comparative example 4, the reaction temperature of 55 ℃ in S2 is replaced by 70 ℃ only, the rest steps and parameters are the same, and the comparative example is not repeated, so that the nano silicon dioxide dispersion liquid is finally obtained.
Comparative example 5:
in this comparative example, only polyethylene glycol methacrylate "mn=500" was replaced with "mn=350" compared with example 4, and the other steps and parameters were the same, so that the comparative example will not be repeated, and finally a nano silica dispersion was obtained.
Performance test:
Particle size and distribution
Referring to ISO 22412-2017 test standard, adopting a Markov nanometer particle size analyzer;
1. respectively taking nano silicon dioxide dispersion solutions of examples 4-6 and comparative examples 1-5, respectively diluting to 0.1wt%, heating to 25 ℃, and balancing for 10min;
2. The particle size and the PDI value of the polydispersion index are recorded by using a Markov nanometer particle size analyzer, wherein the detection angle is 173 degrees, and the average value is obtained by running 3 times.
Storage stability:
Referring to GB/T6753.3-1986 test standard, a Markov nanometer particle size analyzer is adopted;
1. Taking the nano silicon dioxide dispersion liquid of the examples 4-6 and the nano silicon dioxide dispersion liquid of the comparative examples 1-5 respectively, heating to 25 ℃ for 10min, sealing in a transparent glass bottle, and standing for 6 months in a dark place;
2. taking 1.0mL of sample, centrifuging for 10min, rotating at 10000rpm, and calculating the sedimentation rate ;
3. The particle size 6 and the polydispersity index PDI 6 were measured after 6 months in the same manner as in the above-mentioned particle size and distribution measurement procedure.
TABLE 1
Dry redispersibility
1. Taking nano silicon dioxide dispersion solutions of examples 4-6 and comparative examples 1-5, freeze-drying, taking 10.0g of each dispersion, adding into 10mL of deionized water, heating to 25 ℃, and recording the time T Self-supporting (s) required for the solution to be uniform and semitransparent at the rotating speed of 500 rpm;
2. If spontaneous dispersion is not complete within 300s, performing ultrasonic treatment, sampling and detecting particle size every 30s with power of 200w, recovering the particle size to be +/-5% of an initial value, stopping ultrasonic treatment, and recording ultrasonic time T Super-energy storage device (min);
3. energy consumption calculation, accumulated energy consumption value=ultrasonic power (w) ×ultrasonic time (min).
TABLE 2
PH responsive release:
referring to the test standard of the dissolution and release degree measurement method of four general rules of Chinese pharmacopoeia, adopting an RC806D intelligent dissolution instrument;
1. Taking the nano silicon dioxide dispersion solutions of examples 4-6 and comparative examples 1-5, freeze-drying, taking 100.0mg of each dispersion, adding 10mL of phosphate buffer (pH=7.4), vortex-mixing uniformly, adding 10mg of doxorubicin, heating to 37 ℃, oscillating for 24 hours, filtering, centrifuging, washing, and determining the drug loading rate (DL%): ;
2. Placing the medicine carrying dispersion in a dialysis bag at the bottom of a dissolution cup, and sampling 1mL at regular time at the rotation speed of 50rpm and the temperature of 37 ℃ plus or minus 0.5 ℃ for 0.5,1,2,3,4 and 6 hours;
3. cumulative release rate;
TABLE 3 Table 3
Data analysis:
from tables 1-3, it can be seen that the nano silicon dioxide dispersion liquid prepared by the invention has better stability, redispersibility and intelligent responsiveness;
In comparative example 1, the precipitation rate is up to 52.3%, the redispersion requires strong ultrasound, the drug loading rate is only 9.5%, the dispersion is not effectively anchored by covalent bond formation due to lack of key synchronous in-situ modification, the physically adsorbed dispersion is separated from the surface of SiO 2 in the drying and concentrating process, so that the bare silicon hydroxyl groups undergo condensation reaction during dehydration to generate covalent bond connected hard aggregates, meanwhile, a covalent bond network forms mechanical locking, and the covalent bond network can be destroyed by ultrasonic shearing force, in addition, in example 4, copolymer grafting is synchronously completed during particle growth, the dispersion permanently anchors the surface by covalent bonds, thereby the sterically hindered layer (polyethylene glycol chain) physical isolation particles prevent condensation reaction, and simultaneously, the self-redispersion is realized by adding water without external force;
Comparative example 2 because the modified polyethylene glycol methacrylate is replaced by the mixture of dimethylaminoethyl methacrylate, sodium styrene sulfonate and polyethylene glycol methacrylate, the particle size is increased after 6 months of storage, redispersion energy consumption is 1600 W.min, and pH response release rate is only 45.2%, the mixture cannot be aligned on the particle surface, dimethylaminoethyl methacrylate and sodium styrene sulfonate are randomly adsorbed to form a local charge counteracting region, long chains of polyethylene glycol methacrylate are in a spiral conformation on the particle surface due to lack of anchoring support of a block structure, the steric layer thickness is reduced, the particle spacing is smaller than the debye length of the steric layer, van der Waals force dominates aggregation, so that redispersion needs high energy consumption, in addition, the cationic density increase and anion retention cannot be synchronously realized when the pH is reduced;
comparative example 3 the stability was lowered and the pH response function was lost due to the substitution of the modified polyethylene glycol methacrylate for the polyethylene glycol methacrylate, because the polyethylene glycol methacrylate relies only on sterically hindered ethylene oxide, but lacks the electrostatic repulsive force provided by the anionic group. When the ionic strength of the system is increased, the counter ions compress and diffuse the double electric layers, and the inter-particle van der Waals attraction is dominant. At this time, the single steric hindrance layer is extruded and thinned, and cannot resist particle collision aggregation, so as to cause irreversible sedimentation and drug loading package rupture, and tertiary amine groups (-N (CH 3)2) in a zwitterionic structure are key switches for pH response, so that the tertiary amine groups are protonated into cations (-N +(CH3)2 H) in an acidic environment, and the surface charge inversion and drug loading bonding destruction are triggered, wherein the cationization repels positively charged drug molecules, and pure polyethylene glycol methacrylate is free of the groups, and the drug cannot realize tumor micro-acid environment targeted release only through physical adsorption loading.
Comparative example 4 because the reaction temperature in S2 exceeded the normal temperature, resulting in abnormal growth of particle size, loss of redispersibility and failure of pH response function, the reason was that the pure polyethylene glycol methacrylate segment contained a large amount of ether linkages, triggering β -elimination reaction at 70 ℃ high temperature, initiating chain scission of polyethylene glycol chains, while the number of ethylene oxide units after chain scission was reduced from 11 to 4-5, solvated layer thickness collapsed, and van der waals forces and distances, steric layer thinning enhanced interparticle attractive force by 8 times, resulting in uncontrollable polycondensation in the curing stage.
Comparative example 5 because polyethylene glycol methacrylate provides a lower thickness of the sterically hindered layer due to the substitution of polyethylene glycol methacrylate chain molecular weight 500 for 350g, but it is insufficient to overcome inter-particle van der waals forces. In the storage process, particles gradually approach each other, irreversible agglomeration occurs after crossing an energy barrier, energy is still required for redispersion, and the release performance is also affected to a certain extent;
In conclusion, the invention designs the specific zwitterionic segmented copolymer dispersion liquid, creatively synchronously introduces the dispersion liquid into the key stage of the growth of the silica sol particles and carries out in-situ covalent anchoring, and is assisted with accurate process control, so that the 'one-step synergy of particle growth and surface modification' is successfully realized, meanwhile, the scheme effectively solves the problems of long-term existence of dry hard agglomeration, high solid content, high viscosity, lack of intelligent function and the like of the nano silica dispersion liquid, and endows the product with excellent performances of ultrahigh solid content, low viscosity, permanent and stable drying, spontaneous redispersion, intelligent pH response release and the like, and the process is green and environment-friendly. Furthermore, the validity of the technical scheme and the necessity of individual elements such as covalent anchoring, zwitterionic structure, suitable PEG chain length, etc. are fully verified by example data and comparison with comparative examples.
It will be appreciated by persons skilled in the art that the above discussion of any embodiment is merely exemplary and is not intended to imply that the scope of the invention is limited to these examples, that combinations of technical features in the above embodiments or in different embodiments may also be implemented in any order, and that many other variations of the different aspects of the invention as described above exist, which are not provided in detail for the sake of brevity.
The present invention is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Therefore, any omission, modification, equivalent replacement, improvement, etc. of the present invention should be included in the scope of the present invention.
Claims (7)
1. A preparation method of nano silicon dioxide dispersion liquid, which is characterized by comprising the following preparation steps:
Step S1, adding modified polyethylene glycol methacrylate into a mixed solvent of ethanol and deionized water, heating to 30-50 ℃, stirring for 15-25min, adding tetraethoxysilane, stirring for 8-12min, adding 0.1mol/L HCl solution, adjusting pH to 1.8-2.2, reacting for 1-3h, and obtaining a mixed solution after the reaction is completed;
S2, adding the mixed solution into a flask, adding 0.1mol/L ammonia water, adjusting the pH to 8.8-9.2, heating to 55-65 ℃, adding the mixed solution of tetraethoxysilane, modified polyethylene glycol methacrylate and ethanol, stirring and reacting for 5-7h at the rotating speed of 350-450rpm, and obtaining sol after the reaction is completed;
step S3, adding the sol into a flask, heating to 50-70 ℃, reacting for 10-14 hours, replacing the solvent with deionized water by an ultrafiltration device after the reaction is completed, and concentrating under reduced pressure to obtain nano silicon dioxide dispersion liquid;
the preparation method of the modified polyethylene glycol methacrylate comprises the following steps:
Under the nitrogen atmosphere, adding dimethylaminoethyl methacrylate, sodium styrene sulfonate and polyethylene glycol methacrylate into an absolute ethanol solvent, stirring and mixing, adding an initiator azodiisobutyronitrile, heating to 65-75 ℃, reacting for 22-26h, cooling to 5-10 ℃, adding hydroquinone, standing for precipitation, filtering, washing and drying to obtain modified polyethylene glycol methacrylate;
the molecular weight of the polyethylene glycol methacrylate is 500.
2. The method of claim 1, wherein the volume ratio of ethanol to deionized water in step S1 is 4:1.
3. The method for preparing a nano silica dispersion according to claim 1, wherein the mass ratio of the modified polyethylene glycol methacrylate to the tetraethyl orthosilicate in the step S1 is 1:4.6-4.7.
4. The method for preparing a nano silica dispersion according to claim 1, wherein the mass ratio of the mixed solution, the tetraethyl orthosilicate and the modified polyethylene glycol methacrylate in the step S2 is 1:0.32-0.33:0.008-0.01.
5. The method for preparing a nano silica dispersion according to claim 1, wherein the mass ratio of the modified polyethylene glycol methacrylate to ethanol in the step S2 is 1:17-19.
6. The method for preparing the nano silica dispersion liquid according to claim 1, wherein the mass ratio of the dimethylaminoethyl methacrylate, the sodium styrene sulfonate, the polyethylene glycol methacrylate, the initiator azodiisobutyronitrile and the hydroquinone is 1:1.25-1.35:4.9-5.1:0.008-0.012:0.0008-0.0012.
7. The method for preparing a nano silica dispersion according to claim 1, wherein the hydroquinone is a polymerization inhibitor.
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| CN111422877A (en) * | 2020-05-22 | 2020-07-17 | 十九冶成都建设有限公司 | Preparation method and surface modification method of nano silicon dioxide |
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| CN1308233C (en) * | 2005-06-23 | 2007-04-04 | 武汉理工大学 | Process for preparing amphiphilic nano silicon dioxide |
| CN102616794B (en) * | 2012-04-11 | 2013-12-25 | 宣城晶瑞新材料有限公司 | Preparation method for high-dispersibility nanometer silicon dioxide |
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| KR101494617B1 (en) * | 2013-12-16 | 2015-02-24 | 한국세라믹기술원 | Manufacturing method of low refractive anti-reflection film using poly ethylene glycol |
| CN107522868B (en) * | 2017-10-16 | 2021-01-08 | 湖北工业大学 | Preparation method of epoxy nano-silica/block polymer composite emulsion |
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| CN118930768A (en) * | 2023-05-10 | 2024-11-12 | 大庆油田有限责任公司 | Block copolymer and block copolymer modified silicon dioxide nanoparticles and preparation method and application thereof |
| CN117467064A (en) * | 2023-08-03 | 2024-01-30 | 浙江桐昆新材料研究院有限公司 | Preparation method of a new type of composite nucleating agent and its application in the synthesis of highly crystalline polyester |
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| WO2008071248A1 (en) * | 2006-12-11 | 2008-06-19 | Merck Patent Gmbh | Particles surface-modified with copolymers |
| CN111422877A (en) * | 2020-05-22 | 2020-07-17 | 十九冶成都建设有限公司 | Preparation method and surface modification method of nano silicon dioxide |
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