CN114436270B - Double-spherical silicon dioxide and preparation method and application thereof - Google Patents

Double-spherical silicon dioxide and preparation method and application thereof Download PDF

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CN114436270B
CN114436270B CN202011214878.7A CN202011214878A CN114436270B CN 114436270 B CN114436270 B CN 114436270B CN 202011214878 A CN202011214878 A CN 202011214878A CN 114436270 B CN114436270 B CN 114436270B
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雷群
江波
王平美
肖沛文
贾新利
彭宝亮
罗健辉
叶银珠
王小聪
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Abstract

The invention provides double-spherical silicon dioxide and a preparation method and application thereof. The double-spherical silica is obtained by chemically combining an aminosilane coupling agent modified silica with a halosilane coupling agent modified silica under aqueous phase conditions. The invention also provides a preparation method of the double-spherical silicon dioxide, which comprises the steps of mixing and reacting the silicon dioxide modified by the amino silane coupling agent and the silicon dioxide modified by the halogenated silane coupling agent to obtain the double-spherical silicon dioxide. The preparation method can prepare the water-phase double-spherical silicon dioxide under the mild water-phase condition, the reaction condition is environment-friendly and pollution-free, the preparation process is simple, the large-scale preparation is realized, and the cost is low. The double-spherical silica has important application in the aspects of oil stain prevention, hydrophilic fabric preparation, oil field recovery ratio improvement and the like.

Description

Double-spherical silicon dioxide and preparation method and application thereof
Technical Field
The invention relates to the technical field of nano material preparation, in particular to double-spherical silicon dioxide which has important application in the aspects of oil stain resistance, hydrophilic fabric preparation, oil field recovery ratio improvement and the like, and a preparation method and application thereof.
Background
In nature, many attractive symmetrical shapes or modes exist, and people prefer visual sense brought by symmetry, but see through the nature of the phenomenon, go deep into each object, and we find that the structure and the organization of the object have certain degree of asymmetry in chemistry and shape, and the asymmetry, namely anisotropy, enriches the colorful world. This unique anisotropy can be described by "Janus" which originates from the ancient Roman god, i.e. "double sided god", which has two oppositely directed faces, one representing the past and the other representing the future, and the earliest recognition of the potential and importance of this particle was that Nobel's primary Pierre-Gilles de Gennes, which was referred to in 1991 by Nobel's lecture "soft mass", after which such particles developed vigorously, mostly to describe those particles with anisotropic, different chemical properties on the two hemispheric surfaces of the particle. The double-sided god particle (Janus parts) has special structure, excellent performance and wide application prospect. Nanoparticles of double sphere structure also belong to one of the "double sided god" particles because of the asymmetry that they contain different functional groups at both ends. The method for preparing the particles with the double-spherical structure mainly comprises the following steps: template directed self-assembly, phase separation, and controlled surface nucleation and template assisted methods.
The silicon dioxide raw material is easy to obtain and low in cost, and is an ideal raw material for preparing the double-spherical nano particles. However, there are also nanoparticles having a double spherical structure prepared by using styrene and divinylbenzene as monomer materials and adopting a phase separation and surface nucleation control method. For example, a crosslinked polystyrene core is first prepared by emulsion polymerization of styrene and divinylbenzene, then a chlorinated shell is applied to the outer layer of the crosslinked polymer core, the chlorinated shell is expanded with a mixture of monomeric styrene and divinylbenzene, and liquid protrusions are formed on the surface of the core particle by phase separation between the monomeric and expanded polymer networksSeparately, these liquid protrusions were solidified by polymerization to obtain double spherical colloidal particles (Bas g.p., journal of Colloid and Interface Science 2017,490,462-477) having chemical anisotropy. In addition, silica prepared by the Stober method is used as an inner core, silica particles are uniformly covered with cross-linked polymethyl methacrylate (PMMA), and are protruded from a PMMA shell layer by polymerization of polystyrene (PSt), and then the asymmetric double spherical particles are coated with silica, and finally the polymer is removed by heating, in summary, hollow asymmetric silica double spherical particles with a movable inner core are prepared by a template-assisted method (Daisuke nagao., langmuir 2010,26 (7), 5208-5212). Furthermore, magnetic Fe stabilized with 16-Heptadecenoic Acid (HAD) aqueous solution 3 O 4 Nanoparticle-based, then a mixture of styrene and divinylbenzene is added, by (NH 4 ) 2 S 2 O 8 Initiating polymerization reaction to generate polystyrene spheres at the interface of two phases, and Fe 3 O 4 Is fixed at one end of polystyrene near water phase, and is added with proper concentration of TEOS to prepare SiO through hydrolysis condensation of TEOS 2 Will selectively coat Fe 3 O 4 Sites, thereby preparing nano magnetic particles having a double sphere structure (e.passas-lagos., langmuir 2015,31, 7749-7757). The particle size of the double-spherical nano particles prepared in the first example is about 500nm, the process is complex, various experimental parameters are required to be regulated in the experimental process to obtain the ideal double-spherical nano particles, the preparation amount at one time is small, the cost is high, and the large-scale application is difficult; the particle size of the double spherical nano particles prepared in the second example is also about 500nm, and the problem of larger particle size is also solved; the second example requires strict conditions for preparation, such as magnetic nano Fe 3 O 4 The preparation of the particles must be carried out in an argon atmosphere, and the concentration of TEOS needs to be accurately controlled to obtain the ideal double-sphere nano particles.
CN 106984825a prepares asymmetric double-sphere polymer-silver composite nano-particles based on silver reduction and caffeic acid oxidation polymerization. The preparation of the double-spherical particles by adopting the above methods is generally carried out on the basis of one particle, namely, a liquid protruding part grows on the surface of the selected particle through phase separation, and then the protruding part is solidified to obtain the required double-spherical particles, but the process needs to regulate and control various experimental parameters (swelling ratio, crosslinking density, shell thickness and shell composition), the preparation process is complex, the cost is expensive, and the particle size of the obtained double-spherical particles is larger, about 500nm and is not a nano material in a strict sense. In addition, the product obtained by the preparation method for preparing the double-spherical nano particles by compounding certain metals and polymers is not advantageous compared with nano silicon dioxide, the method comprises more complicated steps, the control difficulty is higher, and the corresponding purification is carried out after the asymmetric double-spherical nano particles are prepared.
In addition, in the existing research on the surface modification of the silica nanoparticles, the modification process needs to be performed in an alcohol/water or oil/water mixed system, so that organic wastewater is generated and the production cost is increased. There is a need to propose a silica modification method which can be completed in pure water phase, and which can obtain a stable system of modified silica aqueous solution to meet the demands of industrial production and practical use.
Disclosure of Invention
In order to solve the problems, the invention provides double-spherical silicon dioxide and a preparation method and application thereof. The method can realize the surface modification of the silicon dioxide under the pure water phase condition, and can obtain the monodisperse double-spherical silicon dioxide particles which exist stably under the pure water phase condition, and has the characteristics of simple preparation process, large-scale preparation, low cost, environmental protection and the like.
In order to achieve the above object, the present invention provides a double spherical silica obtained by chemically combining an aminosilane coupling agent-modified silica with a halosilane coupling agent-modified silica under aqueous phase conditions, wherein the mass ratio of the aminosilane coupling agent-modified silica to the halosilane coupling agent-modified silica is 0.85 to 1.15.
In the specific embodiment of the invention, the double-spherical silica nanoparticle is obtained by modifying an amino hydrocarbon group on the surface of silica by an amino silane coupling agent, modifying a halogenated hydrocarbon group on the surface of silica by a halogenated silane coupling agent, and combining two silica particles by a chemical bond generated by the reaction of the amino group and halogen.
In a specific embodiment of the present invention, the above-mentioned aminosilane coupling agent-modified silica and halosilane coupling agent-modified silica can form a stable monodisperse system in an aqueous phase, because the surfaces of silica particles reacted with an aminosilane coupling agent or halosilane coupling agent are modified with organic segments having a higher steric hindrance effect than the active hydroxyl groups distributed on the surface of the unmodified silica, and the modified silica can be effectively prevented from agglomerating, and at the same time, a part of hydroxyl groups remain on the surface of the modified silica ion, so that the modified silica ion is uniformly dispersed and stably present in the aqueous phase, and further, the bispherical silica formed by the chemical combination of the silica particles modified with the two silane coupling agents can stably exist in a higher concentration (mass concentration 5 to 35%) in the aqueous phase.
In the above-mentioned double spherical silica, there are various combinations of the aminosilane coupling agent-modified silica and the halosilane coupling agent-modified silica. For example, it may be:
Figure BDA0002760029360000031
in a specific embodiment of the invention, the particle size of the dual spherical silica is generally less than 100nm, preferably 30nm to 80nm.
In the specific embodiment of the invention, the double-spherical silica with uniform particle size can be obtained by controlling the dosage of the silica modified by the aminosilane coupling agent and the silica modified by the halogenated silane coupling agent. The mass ratio of the aminosilane coupling agent modified silica to the halosilane coupling agent modified silica may be 0.95 to 1.15, preferably 1.
In particular embodiments of the invention, the dual spherical silica may be present in an aqueous solution, and the dual spherical silica solution may have a mass concentration of 5-35%, such as 5-30%, that is higher than the mass concentration of a generally uniformly dispersed aqueous silica solution.
In particular embodiments of the present invention, the probability of gelation or agglomeration of silica particles can be reduced by controlling the pH of the dual spherical silica solution, and generally, the stability of the dual spherical silica solution increases with increasing pH. In some embodiments, the pH of the solution of the dual spherical silica is generally controlled to be 8-11, which may be 8, for example.
In a specific embodiment of the present invention, the carbon number of the hydrocarbon chain of the aminosilane coupling agent is generally controlled to be 1 to 3. Preferably, the aminosilane coupling agent comprises one or more than two of N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyl dimethoxysilane and 3-aminopropyl methyl diethoxysilane.
In a specific embodiment of the present invention, the carbon number of the hydrocarbon chain of the halosilane coupling agent is generally controlled to 1 to 3. Preferably, the halogenated silane coupling agent comprises one or more of 3-chloropropyl trimethoxysilane, 3-chloropropyl triethoxysilane, 3-chloropropyl methyl dimethoxy silane and 3-chloropropyl methyl diethoxy silane.
The invention also provides a preparation method of the double-spherical silicon dioxide, which comprises the following steps: mixing and reacting the silicon dioxide modified by the aminosilane coupling agent and the silicon dioxide modified by the halogenated silane coupling agent in a water phase to obtain the double-spherical silicon dioxide.
In a specific embodiment of the present invention, in the above-mentioned production method, the temperature at which the aminosilane coupling agent-modified silica and the halosilane coupling agent-modified silica are mixed and reacted is generally controlled to 20 to 45 ℃ (preferably 35 to 45 ℃, for example 40 ℃). The reaction time may be adjusted according to the reaction temperature, and may be, for example, 3 to 6 hours.
In a specific embodiment of the present invention, the above preparation method may include: step one, in a water phase, modifying silicon dioxide by utilizing an aminosilane coupling agent to obtain a first reaction solution; step two, modifying silicon dioxide in a water phase by utilizing a halogenated silane coupling agent to obtain a second reaction solution; step three, mixing the first reaction liquid and the second reaction liquid for reaction to obtain the double-spherical silicon dioxide; in the first step, the mass of the aminosilane coupling agent is 2.5-10% of the mass of silicon dioxide, and the reaction temperature is 20-45 ℃; in the second step, the mass of the halogenated silane coupling agent is 2.5-10% of the mass of the silicon dioxide, and the reaction temperature is 20-45 ℃.
In the specific embodiment of the invention, the silicon dioxide is modified by the aminosilane coupling agent and the silicon dioxide is modified by the halogenated silane coupling agent independently, the first step and the second step are not mutually interfered and can be synchronously performed, the reaction processes of the first step and the second step are respectively controlled, and the amino hydrocarbon group and the halogenated hydrocarbon group are respectively distributed on the surface of the silicon dioxide in an oriented way, so that the surface modification of the optimal degree is realized.
In the specific embodiment of the invention, the sizes of the modified silica particles can be regulated and controlled on one hand by controlling the dosage of the aminosilane coupling agent and the halogenated silane coupling agent so as to obtain double-spherical silica nanoparticles with different particle diameters; on the other hand, the water consumption during the hydrolysis of the silane coupling agent can be controlled, and the problems of gelation and agglomeration and the like caused by too small silica particle spacing are avoided. In some embodiments, in step one, the mass of the aminosilane coupling agent is preferably 7.5% of the mass of silica; in the second step, the mass of the halogenated silane coupling agent is preferably 7.5% of the mass of the silica.
In the specific embodiment of the invention, when the aminosilane coupling agent or the halogenated silane coupling agent is adopted to carry out surface modification on the silicon dioxide, the stability of the modified silicon dioxide in an aqueous solution can be improved by controlling the reaction temperature. As the reaction temperature increases, the gel time of the silica in water shortens and the stability decreases. The modification temperature of the silicon dioxide is controlled below 45 ℃ in the invention, so as to ensure that the modified silicon dioxide has higher stability in aqueous solution. In a specific embodiment, in step one, the reaction time is generally controlled to be 3-6 hours, and the reaction temperature is preferably 35-45 ℃, for example 40 ℃. In step two, the reaction time is generally controlled to 3 to 6 hours, and the reaction temperature is preferably 35 to 45 ℃, for example 40 ℃. In step three, the reaction time may be controlled to be 3 to 6 hours, and the reaction time is generally controlled to be 20 to 45 ℃, preferably 35 to 45 ℃, for example 40 ℃.
In particular embodiments of the present invention, the silica used in step one and/or step two is typically a nanosilica hydrosol prepared with water as a solvent. The particle size of the silica is generally from 10nm to 50nm. In a specific embodiment, a commercial nano silica hydrosol (generally prepared at 20-45 ℃) with a silica particle size of 10-50 nm can be adopted, so that the large-scale preparation is facilitated.
In the specific embodiment of the invention, the aminosilane coupling agent and the halogenated silane coupling agent are oily liquids, an oil-water mixing system is automatically formed when the aminosilane coupling agent and the halogenated silane coupling agent are mixed with the silica hydrosol, the oil-water mixing system is subjected to strong stirring, so that the occurrence of modification reaction can be promoted, the gelation or agglomeration tendency of silica particles can be reduced, and the stability of the modified silica in water can be improved. The first and/or second step may be carried out with stirring, and the stirring speed is generally controlled to 150-400 rpm.
In a specific embodiment of the present invention, in addition to the water in the nanosilica hydrosol as a raw material, the first and/or second steps may further include an operation of adding water to the reaction system formed by the silica and the aminosilane coupling agent or the halosilane coupling agent, and these additional added water may provide water required for hydrolysis of the aminosilane coupling agent and the halosilane coupling agent on the one hand, avoid the stability of the reaction system from being impaired, and on the other hand, may suitably reduce the concentration of silica in the reaction system, and slow down the gelation tendency of the modified silica.
In a specific embodiment of the present invention, the first step may further include an operation of aging the obtained first reaction liquid for 3d to 7 d.
In a specific embodiment of the present invention, the second step may further comprise an operation of aging the obtained second reaction liquid for 3d to 7 d.
In a specific embodiment of the present invention, the preparation method of the above-mentioned dual spherical silica may include:
adding an aminosilane coupling agent into the silica hydrosol, reacting and aging to obtain a first reaction solution, wherein the mass of the aminosilane coupling agent is 2.5-10% (preferably 7.5%) of the mass of the silica in the silica hydrosol, the reaction temperature is 20-45 ℃ (preferably 35-45 ℃), and the reaction time is 3-6 hours;
step two, adding a halogenated silane coupling agent into the silica hydrosol, reacting and aging to obtain a second reaction solution, wherein the mass of the halogenated silane coupling agent is 2.5-10% (preferably 7.5%) of the mass of the silica in the silica hydrosol, the reaction temperature is 20-45 ℃ (preferably 35-45 ℃), and the reaction time is 3-6 hours;
and thirdly, mixing the first reaction solution and the second reaction solution according to the mass ratio of the silicon dioxide modified by the aminosilane coupling agent in the first reaction solution to the silicon dioxide modified by the halogenosilane coupling agent in the second reaction solution of 0.85-1.15 (preferably 0.95-1.15, more preferably 1), and reacting for 3-6 hours at 20-45 ℃ (preferably 35-45 ℃) to obtain the double-spherical silicon dioxide.
In particular embodiments of the present invention, the silica may also be surface-modified with other suitable silane coupling agents to yield a dual spherical silica by reaction between functional groups modified to the silica surface. The kind of the reaction system may be changed correspondingly depending on the kind of the silane coupling agent used.
The invention further provides application of the double-spherical silica in oil field enhanced oil recovery. Meanwhile, the double-spherical silica can also be applied to the fields of oil stain prevention, hydrophilic fabric preparation and the like.
The invention has the beneficial effects that:
the preparation method provided by the invention can realize surface modification of the silicon dioxide under the pure water phase condition, and can obtain the double-spherical silicon dioxide particles which are stably existing and uniformly dispersed under the pure water phase condition, and has the characteristics of simple preparation process, large-scale preparation, low cost, environmental protection and the like. The obtained double-spherical silica has smaller particle size and has important application in the aspects of oil stain prevention, hydrophilic fabric preparation, oil field recovery ratio improvement and the like.
Drawings
FIG. 1 is a TEM photograph of the dual spherical silica prepared in examples 1 to 3.
FIG. 2 is a TEM photograph of unmodified silica and silica prepared in comparative examples 1-2.
FIG. 3 is an infrared spectrum of an aminosilane coupling agent, a halosilane coupling agent, unmodified silica, silica modified with an aminosilane coupling agent, and silica modified with a halosilane coupling agent.
FIG. 4 shows XPS spectra of unmodified silica, silica modified with an aminosilane coupling agent at step 1 of example 2, silica modified with a halosilane coupling agent at step 2 of example 2, and double spherical silica prepared at step 3 of example 2.
FIG. 5 is a particle size distribution test result of the silica water-based nano-liquid prepared in comparative example 5.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
In the following examples and comparative examples, the mass fraction of silica in the silica hydrosol used was 20%.
Example 1
The embodiment provides a double-spherical silica water-based nano-liquid, and the preparation method comprises the following steps:
1. under the condition of water phase, adding 100g of nano silicon dioxide hydrosol into a glass reaction container, heating to 40 ℃, then adding 1.5g of gamma-aminopropyl triethoxysilane according to the proportion that the mass of gamma-aminopropyl triethoxysilane is 7.5% of that of pure silicon dioxide, fully stirring and reacting for 4 hours at 40 ℃, and ageing for 3 days at room temperature to obtain the silicon dioxide water-based nano liquid with the amino-modified surface, namely the first reaction liquid, wherein the average particle size of the modified silicon dioxide is about 22nm.
2. Under the condition of water phase, adding 100g of nano silicon dioxide hydrosol into a glass reaction container, heating to 40 ℃, then adding 1g of 3-chloropropyl triethoxysilane according to the proportion that the mass of 3-chloropropyl triethoxysilane is 5% of that of pure silicon dioxide, fully stirring at 40 ℃ for reaction for 4 hours, and aging at room temperature for 3 days to obtain the silicon dioxide water-based nano liquid with the surface modified chloropropyl, namely a second reaction liquid, wherein the average particle size of the modified silicon dioxide is about 16nm.
3. Under the condition of water phase, 30g of a first reaction solution and 30g of a second reaction solution (the mass ratio of modified silicon dioxide in the first reaction solution to modified silicon dioxide in the second reaction solution is close to 1:1) are mixed at 40 ℃ and stirred for reaction for 4 hours, so that the double-spherical silicon dioxide water-based nano-liquid is obtained. The mass concentration of the double-spherical silica in the solution was about 20%, and the average particle diameter of the double-spherical silica was 41nm.
Example 2
The embodiment provides a double-spherical silica water-based nano-liquid, and the preparation method comprises the following steps:
1. under the condition of water phase, adding 100g of nano silicon dioxide hydrosol into a glass reaction container, heating to 30 ℃, then adding 1.5g of gamma-aminopropyl triethoxysilane according to the proportion that the mass of gamma-aminopropyl triethoxysilane is 7.5% of that of pure silicon dioxide, fully stirring and reacting for 4 hours at 30 ℃, and ageing for 3 days at room temperature to obtain the silicon dioxide water-based nano liquid with the amino-modified surface, namely the first reaction liquid, wherein the particle size of the modified silicon dioxide is about 22nm.
2. Under the condition of water phase, adding 100g of nano silicon dioxide hydrosol into a glass reaction container, heating to 30 ℃, then adding 1.5g of 3-chloropropyl triethoxysilane according to the proportion that the mass of 3-chloropropyl triethoxysilane is 7.5% of that of pure silicon dioxide, fully stirring at 30 ℃ for reaction for 4 hours, and ageing at room temperature for 3 days to obtain a silicon dioxide water-based nano liquid with the surface modified with chloropropyl, namely a second reaction liquid, wherein the particle size of the modified silicon dioxide is about 21nm.
3. Under the condition of water phase, 30g of a first reaction solution and 30g of a second reaction solution (the mass ratio of the silicon dioxide in the first reaction solution to the modified silicon dioxide in the second reaction solution is close to 1:1) are mixed at 40 ℃ and stirred for reaction for 4 hours, so that the double-spherical silicon dioxide water-based nano-liquid is obtained. The mass concentration of the double-spherical silica in the solution was about 20%, and the average particle diameter of the obtained double-spherical silica was 45nm.
Example 3
The embodiment provides a double-spherical silica water-based nano-liquid, and the preparation method comprises the following steps:
1. under the condition of water phase, adding 100g of nano silicon dioxide hydrosol into a glass reaction container, heating to 40 ℃, then adding 2g of gamma-aminopropyl triethoxysilane according to the proportion that the mass of gamma-aminopropyl triethoxysilane is 10% of that of pure silicon dioxide, fully stirring at 40 ℃ for reaction for 4 hours, and aging at room temperature for 3 days to obtain silicon dioxide water-based nano liquid with amino groups modified on the surface, namely a first reaction liquid, wherein the particle size of the modified silicon dioxide is about 37nm.
2. Under the condition of water phase, adding 100g of nano silicon dioxide hydrosol into a glass reaction container, heating to 40 ℃, then adding 2g of 3-chloropropyl triethoxysilane according to the proportion that the mass of 3-chloropropyl triethoxysilane is 10% of that of pure silicon dioxide, fully stirring at 40 ℃ for reaction for 4 hours, and ageing at room temperature for 3 days to obtain a silicon dioxide water-based nano liquid with the surface modified with chloropropyl, namely a second reaction liquid, wherein the particle size of the modified silicon dioxide is about 22nm.
3. Under the condition of water phase, 30g of a first reaction solution and 30g of a second reaction solution (the mass ratio of the silicon dioxide in the first reaction solution to the modified silicon dioxide in the second reaction solution is close to 1:1) are mixed at 40 ℃ and stirred for reaction for 4 hours, so that the double-spherical silicon dioxide water-based nano-liquid is obtained. The mass concentration of the double-spherical silica in the solution was about 20%, and the average particle diameter of the obtained double-spherical silica was 65nm.
In examples 1-3, when the modified silica obtained in step 1 was mixed with the modified silica obtained in step 2, two modified silica particles had a plurality of possible binding modes, and a double spherical silica having a different molecular structure was obtained. Wherein, the main molecular structure of the silica with double spherical structures is as follows:
Figure BDA0002760029360000091
the other molecular structure of the bis-spherical silica is less abundant in the final product and is not described here.
FIG. 1 is a SEM photograph of dual spherical silica prepared according to examples 1-3. Wherein, a is a double-spherical silica SEM photograph prepared in example 1, b is a double-spherical silica SEM photograph prepared in example 2, and c is a double-spherical silica SEM photograph prepared in example 3.
From the results of the particle diameter measurements of examples 1 to 3, it was found that the particle diameter of the synthesized double spherical silica was 100nm or less, and the particle diameter was approximately equal to the sum of the particle diameters of the silica modified with the aminosilane coupling agent and the silica modified with the halosilane coupling agent; it can also be seen from the TEM photograph of the products of the examples in FIG. 1 that the products have a pronounced double-sphere structure. The prepared silica of examples 1-3 was demonstrated to have a double spherical structure and the structure was formed by chemical bond coupling between two modified silicas.
Comparative example 1
The comparative example provides a silica water-based nano-liquid, the preparation method of which comprises the following steps:
1. under the condition of water phase, adding 100g of nano silicon dioxide hydrosol into a glass reaction container, heating to 40 ℃, then adding 1.5g of gamma-aminopropyl triethoxysilane according to the proportion that the mass of gamma-aminopropyl triethoxysilane is 7.5% of that of pure silicon dioxide, fully stirring and reacting for 4 hours at 40 ℃, and ageing for 3 days at room temperature to obtain the silicon dioxide water-based nano liquid with the amino groups modified on the surface, namely the first reaction liquid, wherein the particle size of the modified silicon dioxide is about 22nm.
2. Under the condition of water phase, 30g of the first reaction solution and 30g of nano silicon dioxide hydrosol (namely unmodified silicon dioxide hydrosol) are mixed at 40 ℃ and stirred for reaction for 4 hours, so as to obtain the silicon dioxide nano liquid. The average particle size of the obtained silica was 27nm.
Comparative example 2
The comparative example provides a silica water-based nano-liquid, the preparation method of which comprises the following steps:
1. under the condition of water phase, adding 100g of nano silicon dioxide hydrosol into a glass reaction container, heating to 40 ℃, then adding 1.5g of gamma-aminopropyl triethoxysilane according to the proportion that the mass of 3-chloropropyl triethoxysilane is 7.5% of that of pure silicon dioxide, fully stirring at 40 ℃ for reaction for 4 hours, and ageing at room temperature for 3 days to obtain a silicon dioxide water-based nano solution with the surface modified chloropropyl, namely a second reaction solution, wherein the particle size of the modified silicon dioxide is about 21nm.
2. Under the condition of water phase, 30g of the second reaction solution and 30g of nano silicon dioxide hydrosol (namely unmodified silicon dioxide hydrosol) are mixed at 40 ℃ and stirred for reaction for 4 hours, so as to obtain the silicon dioxide nano liquid. The average particle size of the obtained silica was 24nm.
FIG. 2 is a TEM photograph of unmodified silica (raw silica) and silica prepared in comparative examples 1-2. Among them, fig. 2 a shows the unmodified silica (silica in silica hydrosol), fig. b shows the silica prepared in comparative example 1, and fig. c shows the silica prepared in comparative example 2. It can be seen that the silica in fig. 2 is all single spherical particles, and the presence of double spherical silica is not observed.
Meanwhile, as is clear from the measurement results of the particle diameter of the silica of comparative examples 1 to 2, the particle diameter of the product formed by using the aminosilane coupling agent or the halosilane coupling agent with unmodified silica is close to the particle diameter of the silica modified by the silane coupling agent. In combination with TEM observation, it was revealed that the silica modified with the silane coupling agent and the unmodified silica cannot be joined, and it was further confirmed that the silica products having a double-sphere structure obtained in examples 1 to 3 were formed by forming chemical bond bonds between the surface-modified silica.
Test example 1
The test example adopts infrared spectrum and XPS test to characterize the molecular structure of the silicon dioxide before and after modification.
FIG. 3 is an infrared spectrum of an aminosilane coupling agent (a), a halosilane coupling agent (b), an unmodified silica (c), an aminosilane coupling agent modified silica (d) from step 1 of example 2 and a halosilane coupling agent modified silica (e) from step 2 of example 2. As can be seen from FIG. 3, the silica (d and e) modified with the silane coupling agent was at 2975cm compared with the unmodified silica (c) -1 And 2882cm -1 Obvious absorption peak, asymmetric stretching vibration and symmetric stretching vibration which are attributed to C-H in methylene appear, and the absorption peak is in 3440cm -1 The characteristic absorption peak of Si-OH is obviously weakened. Silica (d) modified with aminosilane coupling agent at 1578cm -1 The N-H bending vibration absorption peak was observed, and the silica (e) modified with the halosilane coupling agent was found to be 644cm in length -1 There appears a C-Cl telescopic vibration absorption peak. The above results demonstrate that the aminosilane coupling agent and the halosilane coupling agent can react with the silicon hydroxyl groups on the silica surface, respectively, and the amino groups and the halogenated hydrocarbon groups can be modified on the silica particle surfaces, respectively, under pure water phase conditions.
FIG. 4 shows XPS spectra of unmodified silica (a), aminosilane coupling agent modified silica (b) from step 1 of example 2, halosilane coupling agent modified silica (c) from step 2 of example 2, and bis-spherical silica (d) prepared from step 3 of example 2.
As can be seen from a, b and d in fig. 4, the aminosilane coupling agent modified silica contains N and C elements of the aminoalkyl group in addition to Si and O elements, which indicates that the aminosilane coupling agent can modify the aminoalkyl group to the silica surface and that such aminoalkyl group structure is retained in the double spherical silica formed by coupling.
Also, as can be seen from comparison of a, C and d in fig. 4, the halosilane coupling agent-modified silica contains Cl element and C element of chlorohydrocarbon group, which indicates that the halosilane coupling agent is capable of modifying the halohydrocarbon group to the silica surface, and such halohydrocarbon group structure is maintained in the double spherical silica formed by coupling. The XPS results further demonstrate that the dual spherical silica is formed by chemical coupling of an aminosilane coupling agent modified silica and a halosilane coupling agent modified silica.
Comparative example 3
The comparative example provides a silica water-based nano-liquid, the preparation method of which comprises the following steps:
1. under the condition of water phase, adding 100g of nano silicon dioxide hydrosol into a glass reaction container, heating to 30 ℃, then adding 1.5g of gamma-aminopropyl triethoxysilane according to the proportion that the mass of gamma-aminopropyl triethoxysilane is 7.5% of that of pure silicon dioxide, fully stirring and reacting for 4 hours at 30 ℃, and ageing for 3 days at room temperature to obtain the silicon dioxide water-based nano liquid with the amino-modified surface, namely the first reaction liquid, wherein the particle size of the modified silicon dioxide is about 22nm.
2. Under the condition of water phase, adding 100g of nano silicon dioxide hydrosol into a glass reaction container, heating to 30 ℃, then adding 1.5g of 3-chloropropyl triethoxysilane according to the proportion that the mass of 3-chloropropyl triethoxysilane is 7.5% of that of pure silicon dioxide, fully stirring at 30 ℃ for reaction for 4 hours, and ageing at room temperature for 3 days to obtain a silicon dioxide water-based nano liquid with the surface modified with chloropropyl, namely a second reaction liquid, wherein the particle size of the modified silicon dioxide is about 21nm.
3. Under the condition of water phase, mixing 30g of the first reaction liquid and 60g of the second reaction liquid at 40 ℃ (the mass ratio of the silicon dioxide in the first reaction liquid to the silicon dioxide in the second reaction liquid is 1:2), and stirring and reacting for 4 hours to obtain the silicon dioxide water-based nano liquid. The average particle size of the resulting silica was about 32nm.
Comparative example 4
The comparative example provides a silica water-based nano-liquid, the preparation method of which comprises the following steps:
1. under the condition of water phase, adding 100g of nano silicon dioxide hydrosol into a glass reaction container, heating to 30 ℃, then adding 1.5g of gamma-aminopropyl triethoxysilane according to the proportion that the mass of gamma-aminopropyl triethoxysilane is 7.5% of that of pure silicon dioxide, fully stirring and reacting for 4 hours at 30 ℃, and ageing for 3 days at room temperature to obtain the silicon dioxide water-based nano liquid with the amino-modified surface, namely the first reaction liquid, wherein the particle size of the modified silicon dioxide is about 22nm.
2. Under the condition of water phase, adding 100g of nano silicon dioxide hydrosol into a glass reaction container, heating to 30 ℃, then adding 1.5g of 3-chloropropyl triethoxysilane according to the proportion that the mass of 3-chloropropyl triethoxysilane is 7.5% of that of pure silicon dioxide, fully stirring at 30 ℃ for reaction for 4 hours, and ageing at room temperature for 3 days to obtain a silicon dioxide water-based nano liquid with the surface modified with chloropropyl, namely a second reaction liquid, wherein the particle size of the modified silicon dioxide is about 21nm.
3. Under the condition of water phase, 60g of the first reaction liquid and 30g of the second reaction liquid are mixed at 40 ℃ (the mass ratio of the silicon dioxide in the first reaction liquid to the silicon dioxide in the second reaction liquid is 2:1), and the mixture is stirred and reacted for 4 hours to obtain the silicon dioxide water-based nano liquid. The average particle size of the resulting silica was about 33nm.
Comparative examples 3 to 4 are experiments conducted with respect to example 2, in which the mass ratio of the aminosilane coupling agent-modified silica to the halosilane coupling agent-modified silica in example 2 is 1:1, comparative example 3 is a case where the halosilane coupling agent-modified silica is excessive with respect to the aminosilane coupling agent-modified silica, and comparative example 4 is a case where the aminosilane coupling agent-modified silica is excessive with respect to the halosilane coupling agent-modified silica, and it is understood from the results of the particle size test that the particle size of the final product obtained in comparative examples 3 to 4 is between the particle size of a single modified silica and the sum of the particle sizes of two modified silicas. This is because the excess of one modified silica relative to the other modified silica in step 3 of comparative examples 3 to 4 results in that the resulting silica-based nano-liquid has, in addition to the double spherical particles having a large particle diameter formed by the ionic coupling of two modified silicas, also some monodisperse particles which do not participate in the reaction, and therefore the measurement result of the particle diameter of the solution is the average particle diameter of a mixed system of double spherical particles and monodisperse particles. From this, it was found that the mass ratio of the two modified silica particles was controlled within a proper range, and that the double spherical silica particles having a uniform particle diameter and a complete structure were obtained.
Comparative example 5
The comparative example provides a silica water-based nano-liquid, the preparation method of which comprises the following steps:
1. under the condition of water phase, adding 100g of nano silicon dioxide hydrosol into a glass reaction vessel, heating to 30 ℃, then adding 1.5g of gamma-glycidoxypropyl trimethoxysilane (manufactured by Nanjing dao Ninger chemical Co., ltd.) according to the proportion that the mass of the gamma-glycidoxypropyl trimethoxysilane is 7.5% of that of pure silicon dioxide, fully stirring at 30 ℃ for reaction for 4 hours, and aging at room temperature for 3 days to obtain a first reaction liquid. The first reaction liquid was an emulsion, and after standing for a period of time, delamination was formed, and therefore, the particle size distribution thereof was not measured.
2. Under the condition of water phase, adding 100g of nano silicon dioxide hydrosol into a glass reaction container, heating to 30 ℃, then adding 1.5g of 3-chloropropyl triethoxysilane according to the proportion that the mass of 3-chloropropyl triethoxysilane is 7.5% of that of pure silicon dioxide, fully stirring at 30 ℃ for reaction for 4 hours, and ageing at room temperature for 3 days to obtain a silicon dioxide water-based nano liquid with the surface modified with chloropropyl, namely a second reaction liquid, wherein the particle size of the modified silicon dioxide is about 21nm.
3. Under the condition of water phase, 30g of a first reaction liquid and 30g of a second reaction liquid (the mass ratio of the silicon dioxide in the first reaction liquid to the modified silicon dioxide in the second reaction liquid is close to 1:1) are mixed at 40 ℃ and stirred for reaction for 4 hours, so as to obtain a water phase silicon dioxide solution. The average particle diameter of the obtained aqueous phase silica was 294nm, and FIG. 5 is a distribution chart of the particle diameters obtained by measurement.
Comparative example 5 is a silica water-based solution prepared according to the same procedure as in example 2. Except that the gamma-aminopropyl triethoxysilane used in the preparation of the first reaction solution in example 2 was replaced with hydrophilic gamma-glycidoxypropyl trimethoxysilane for modification. As can be seen from the results of the particle size test in FIG. 5, the product prepared in this comparative example had a particle size of greater than 100nm, and the vast majority of the product had a particle size much greater than that of the products prepared in examples 1-3. The reason is that the gamma-glycidol ether oxypropyl trimethoxy silane in the first reaction liquid cannot effectively modify silicon dioxide in the water phase, and meanwhile, the dispersion stability of the silicon dioxide in water is affected, so that the silicon dioxide is agglomerated; after the first reaction liquid and the second reaction liquid are mixed, the unmodified silicon dioxide in the first reaction liquid and the modified silicon dioxide in the second reaction liquid can not obtain the nano material with a double-spherical structure connected by chemical bonds, and the existence of the gamma-glycidoxypropyl trimethoxysilane damages the uniformity of a system and unmodified or modified silicon dioxide particles are easy to agglomerate to form large-size aggregates.
As can be seen from comparing the results of comparative example 5 with those of examples 1-3, the silica can be prepared in an aqueous phase system by modifying the silica by selecting a proper silane coupling agent, and the obtained silica aqueous phase system has high uniformity and good dispersibility and can be applied to the aspects of improving oil field recovery ratio and the like.

Claims (30)

1. The double-spherical silica is obtained by chemically combining silica modified by an aminosilane coupling agent and silica modified by a halogenated silane coupling agent under water phase conditions;
wherein the mass ratio of the silicon dioxide modified by the aminosilane coupling agent to the silicon dioxide modified by the halogenated silane coupling agent is 0.85-1.15.
2. The dual spherical silica according to claim 1, wherein the dual spherical silica has a particle size of less than 100nm.
3. The dual spherical silica according to claim 2, wherein the particle diameter of the dual spherical silica is 30nm to 80nm.
4. The double spherical silica according to claim 1, wherein the double spherical silica is a solution having a mass concentration of 5 to 35%.
5. The dual spherical silica according to claim 4, wherein the pH of the solution of dual spherical silica is 8-11.
6. The dual spherical silica according to claim 1, wherein the mass ratio of the aminosilane coupling agent-modified silica to the halosilane coupling agent-modified silica is 0.95 to 1.15.
7. The dual spherical silica according to claim 6, wherein the mass ratio of the aminosilane coupling agent modified silica to the halosilane coupling agent modified silica is 1.
8. The dual spherical silica according to claim 1, wherein the aminosilane coupling agent has a carbon number of a hydrocarbon chain of 1 to 3.
9. The dual spherical silica according to claim 8, wherein the aminosilane coupling agent comprises one or a combination of two or more of N- (β -aminoethyl) - γ -aminopropyl trimethoxysilane, γ -aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, 3-aminopropyl methyldiethoxysilane.
10. The dual spherical silica according to claim 1, wherein the hydrocarbon-based chain of the halosilane coupling agent has a carbon number of 1 to 3.
11. The dual spherical silica according to claim 10, wherein the halogenated silane coupling agent comprises one or a combination of two or more of 3-chloropropyl trimethoxysilane, 3-chloropropyl triethoxysilane, 3-chloropropyl methyl dimethoxy silane, 3-chloropropyl methyl diethoxy silane.
12. A process for the preparation of the double spherical silica according to any one of claims 1 to 11, which comprises: mixing and reacting the silicon dioxide modified by the aminosilane coupling agent and the silicon dioxide modified by the halogenated silane coupling agent in a water phase to obtain the double-spherical silicon dioxide.
13. The method of claim 12, wherein the temperature of the reaction is 20-45 ℃.
14. The preparation method according to claim 13, wherein the temperature of the reaction is 35-45 ℃ and the time of the reaction is 3-6h.
15. The method of claim 13, wherein the temperature of the reaction is 40 ℃.
16. The production method according to any one of claims 12 to 15, wherein the production method comprises:
step one, in a water phase, modifying silicon dioxide by utilizing an aminosilane coupling agent to obtain a first reaction solution;
step two, modifying silicon dioxide in a water phase by utilizing a halogenated silane coupling agent to obtain a second reaction solution;
step three, mixing the first reaction liquid and the second reaction liquid for reaction to obtain the double-spherical silicon dioxide;
in the first step, the mass of the aminosilane coupling agent is 2.5-10% of the mass of silicon dioxide, and the reaction temperature is 20-45 ℃;
in the second step, the mass of the halogenated silane coupling agent is 2.5-10% of the mass of the silicon dioxide, and the temperature of the reaction is 20-45 ℃.
17. The production method according to claim 16, wherein in the first step, the mass of the aminosilane coupling agent is 7.5% of the mass of silica.
18. The preparation method according to claim 16, wherein in the first step, the reaction time is 3 to 6 hours; the temperature of the reaction is 35-45 ℃.
19. The preparation method according to claim 17, wherein in the first step, the reaction time is 3 to 6 hours; the temperature of the reaction is 35-45 ℃.
20. The production method according to claim 18 or 19, wherein in the first step, the temperature of the reaction is 40 ℃.
21. The production method according to claim 16, wherein in the second step, the mass of the halogenated silane coupling agent is 7.5% of the mass of silica.
22. The preparation method according to claim 16, wherein in the second step, the reaction time is 3 to 6 hours; the temperature of the reaction is 35-45 ℃.
23. The preparation method according to claim 21, wherein in the second step, the reaction time is 3 to 6 hours; the temperature of the reaction is 35-45 ℃.
24. The production method according to claim 22 or 23, wherein in the second step, the temperature of the reaction is 40 ℃.
25. The method of claim 16, wherein in step one and/or step two, the silica is a nanosilica hydrosol; the particle size of the silicon dioxide is 10nm-50nm.
26. The method according to claim 16, wherein the first and/or second step comprises an operation of reacting while stirring.
27. The method of claim 26, wherein the stirring is at a speed of 150-400 rpm.
28. The production method according to claim 16, wherein step one includes an operation of aging the obtained first reaction liquid for 3d to 7 d;
and/or the second step comprises the operation of aging the obtained second reaction liquid for 3d-7 d.
29. The production method according to claim 26, wherein step one includes an operation of aging the obtained first reaction liquid for 3d to 7 d;
and/or the second step comprises the operation of aging the obtained second reaction liquid for 3d-7 d.
30. Use of the dual spherical silica of any one of claims 1-11 for enhanced oil recovery.
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