CN1398908A - Organo-silicon and inorgano-silicon nano-composite and its prepn process - Google Patents
Organo-silicon and inorgano-silicon nano-composite and its prepn process Download PDFInfo
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- CN1398908A CN1398908A CN 01122768 CN01122768A CN1398908A CN 1398908 A CN1398908 A CN 1398908A CN 01122768 CN01122768 CN 01122768 CN 01122768 A CN01122768 A CN 01122768A CN 1398908 A CN1398908 A CN 1398908A
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Abstract
A nanometer organo-silicon and inorgano-silicon composite is prepared with fatty acid 5-45%, sodium silicate 5-45% and water the rest and through ten steps including charging and heating, decomposition, dispersion, hydrolysis, polymerization, etc. The present invention has the advantages of rich material source, low cost, simple production process, and good economic and social benefits.
Description
Technical Field
The invention relates to the technical field of organic silicon-inorganic silicon nano-composites.
Background
The organic silicon-inorganic silicon nano composite is a new material integrating a plurality of special properties of organic, inorganic and nano particles, and particularly has wide application prospect due to the interface characteristics of inorganic andorganic, so that the organic silicon-inorganic silicon nano composite draws attention of developed countries such as America, English, Germany, Japan and the like, puts the development of the organic silicon-inorganic silicon nano composite in an important position and makes a corresponding development plan.
The nano silicon dioxide has small particles which can not be seen by a common microscope, large specific surface area and high activity, and has technical problems in application. The biggest problems are three: how is one to disperse into the application system? Secondly, how to solve agglomeration and flocculation after adding the mixture into an application system? Three how do they continue to maintain their special functionality in the application hierarchy? It is reported that the problem is not solved at home and abroad at present. For successful application, the nanosilica must be modified, i.e. surface treated. The traditional modification method is to coat the modified material or seal the active points/active groups on the particle surface, which can not only lose the characteristics of the nano-silica, but also lose the application characteristics.
Disclosure of Invention
The invention is realized by the following technical scheme. The catalyst is prepared by the following materials in percentage by weight: 5-45% of fatty acid, 5-45% of sodium silicate and the balance of water. Wherein the fatty acid is non-substituted straight chain alkyl acid with different lengths, and the general formula is RCOOH; the sodium silicate is water glass, commonly called sodium silicate; the water is deionized water or natural water. The above-mentioned materials are passed through the processes of feeding, heating, decomposition and reaction, dispersion, decomposition reaction, hydrolysis and polymerization reaction, copolymerization and compounding, dealkalization, ageing treatment, compression and drying 10 steps so as to obtain the invented product. The preparation steps are as follows:
1) feeding and heating: adding water and fatty acid into the reaction kettle A respectively, and heating to 50-80 ℃.
2) Decomposition and reaction: adding sodium silicate into the reaction kettle in the step 1), and decomposing and reacting the sodium silicate. The reaction formula is as follows:
in the reaction kettle, the upper layer is RCOONa, the lower layer is silica sol, namely Si (OH)4。
3) Dispersing: continuously heating to 80-110 ℃. When boiling, the silica sol is gradually dispersed in RCOONa from bottom to top until uniform.
4) And (3) decomposition reaction: in the step 3), the decomposition reaction of RCOONa occurs while the heating is carried out:
5) hydrolysis and poly (condensation) reactions: adding water into the reaction kettle B; the water adding amount is 1-9 times of the feeding amount in the step 1) and 2), and the temperature is 6-normal temperature; the step 4) dispersion is added to produce hydrolysis and poly (condensation) reactions. At this point in the dispersion, the NaOH acts as a catalyst.
Under alkaline conditions, this is a more complex chemical reaction process, and the simplified reaction formula is described as follows:
in this step, the silica sol precipitates as SiO2The particle size is 5 to 40 nm. Under the above-mentioned process conditions, in the presence of silicone (RCOO)4Under microscopic control of Si, SiO2The primary particles do not restructure and retain the primary particle size.
Another reactant for this step is organosilicon (RCOO)4And (3) Si. The organic silicon is not a conventional variety, is a new variety in monomers, and can be classified as an organic silicon monomer containing organic functional groups. According to the definition of the surfactant, the organic silicon is also called as an anionic surfactant, is a new variety and belongs to polymerizable emulsifiers. At present, the polymerizable emulsifier in China is still blank and can be used as a polymerizable emulsifier.
6) Copolymerization and compounding: in the course of hydrolysis and poly (condensation) reaction, nano SiO2And Organosilicon (RCOO)4Si is copolymerized and compounded to form (RCOO)4Si/nano SiO2I.e., silicone-inorganic silicon nanocomposites. The key of the copolymerization compounding of the two is the correct calculation of the prior formula. Because it has unique composite stability principle, namely, the organosilicon is used for microcosmically controlling the nanometerSiO2Stability of (2).
It is known that the bond type of the silicon atom is a single bond, the valence is 4, the valence is represented by ortho-silicic acid, and the molecular formula is H4SiO4Or Si (OH)4The structural formula is as follows:
hydroxyl group OH of ortho silicic acid-The activity is strong, and the compound can chemically react with RCOOH, and the reaction formula is as follows:the organosilicon is condensed into a film, the film forms a space barrier, and the surface energy of the interface is low, so that nano SiO is prevented between the film and the film2And (5) restructuring. See figure 1-a graph of a stabilization model of silicone-inorganic silicon nanocomposites.
From the model of FIG. 1, it can be seen that ① the hydroxyl orthosilicate chemically reacts with RCOOH to form a new compound, i.e., organosilicon, ② and condenses to form a silicone film, ③ a silicon atom will form 4 films2Stability of (2). Meanwhile, the organic silicon is nano SiO2The vector of (1).
7) Dealkalization: in the hydrolysis and poly (condensation) reaction process, as the organic silicon-inorganic silicon nano compound is not dissolved in water, and NaOH is dissolved in water, the organic silicon-inorganic silicon nano compound can not be chemically reacted under the process condition, and the dealkalization is called.
8) Aging treatment: the materials in the original reaction kettle are aged for 4-48 hours, so that the hydrolysis and poly (condensation) reaction are complete, and the subsequent processing is convenient.
9) Compression: compressing the aged product obtained in step 8), wherein the compression is performed by compressing the volume of the complex and dehydrating and dealkalizing the complex.
10) Drying: drying the compressed matter at normal temperature to 180 deg.c to obtain the powdered product.
The organic silicon-inorganic silicon nano composite prepared by the steps has the characteristics of organic silicon, inorganic silicon and nano particles, and also has the synergistic effect of the organic silicon, the inorganic silicon and the nano particles to generate new characteristics. Specifically, the method comprises the following steps: 1) amphiphobic property. Namely hydrophobic and oleophobic properties. It can be used as plastic and rubber additiveThe strengthening agent is directly applied. 2) Is amphiphilic. Namely hydrophilic and lipophilic. This property is produced by adding water to the compound and heating it until it is hydrolyzed to form the active microgel. Hydrophilicity is manifested in the carboxylic acid groups in the silicone. Nano SiO2Has hydrophilicity, and enhances the hydrophilicity of the compound. Lipophilicity is shown in R, which is an unsubstituted linear alkyl acid of varying length, is structurally similar to polymers and therefore has excellent compatibility with polymers.The amphipathy improves the compatibility of the compound with polymers and inorganic substances, and expands the application field. 3) High activity. This is manifested in two ways: one having two kinds of reactive groups, namely a carboxylic acid group and a hydroxyl group. And the second group has large active amount. The high activity is formed by the special structure of the organic silicon-inorganic silicon nano composite. 4) (RCOO)4Si is not only a new variety of organic silicon monomer containing organic functional groups, but also a novel anionic surfactant. The activator is different from the traditional activator, is called as a polymerizable emulsifier abroad, can overcome the defects of the traditional activator, and has excellent characteristics particularly for emulsification. 5) Lowering the interfacial surface energy. In (RCOO)4In Si, R belongs to a long chain and can effectively reduce the surface energy of an interface; at the same time, silicon also has the property of reducing the interfacial surface energy. This compound is particularly effective in reducing the interfacial surface energy. In the final product, the stain resistance was exhibited well. 6) And the waterproof performance is good. Because of being (RCOO)4In Si, R belongs to a long chain and has good waterproofness. According to the requirement, different R (long chain) can be adopted, and the contact angle (theta) of the final product can be controlled to be 60-120 degrees.
The effect of the final product made using the composite is also amphiphobic. Hydrophobic except that R in organic silicon is long chain, nano SiO2The condensed film has insolubility and good water resistance. Is the oleophobicity due to organic and inorganic silicon? Forming a highly dense film. The amphiphobicity greatly improves the application performance and the application value.
The compound is particularly suitable for water-based products, and a new material is added to the water-based products. When the method is applied, a cold splicing method and a chemical grafting method can be adopted. But can not be directly cold spliced and needs to be processed into active microgel. The preparation method comprises the following steps: taking 0.1-3 wt% of organic silicon-inorganic silicon nano composite and the balance of water, heating to dissolve and hydrolyze, then cooling, aging for 24 hours, and slowly stirring for 3-5 minutes to obtain the active microgel.
In the hydrolysis process, under the action of a catalyst NaOH, the following reactions are generated:
The catalyst does not need to be added additionally, and NaOH which is not removedcompletely is contained in the organic silicon-inorganic silicon nano composite (in the compression step).
According to the literature, a SiO2The base particle can yield 1000 silanol groups. Within this active microgel is a large group of silanol groups.
The active microgel is chemically stable and generally does not undergo self-polycondensation. It has a stabilization mechanism, which is shown in figure 2-a model diagram of the stabilization mechanism of silanol groups.
As can be seen from the model of FIG. 2, ① SiO2Converted to silanol groups, having the formula:
② Silicone also converted to RCOOH and Si (OH)4Structural formula of silanol group and SiO2The silanol groups converted are the same, ③ RCOOH is between the hydroxyl and hydroxyl groups of the silanol groups, ④ RCOOH forms a steric barrier to prevent the condensation reaction between the hydroxyl and hydroxyl groups, thereby forming a stable active microgel dispersion stabilizer.
Drawings
FIG. 1 is a graph showing a stable model of an organosilicon-inorganic silicon nanocomposite, wherein small dots indicate nano SiO2，；
FIG. 2 is a model diagram of the mechanism of silanol group stabilization, in which the small circles indicate RCOOH.
In fig. 1 and 2 → a sign for reminding a person of attention is shown.
Detailed Description
Depending on the characteristics of the silicone-inorganicsilicon nanocomposite, there will be the following uses: 1. a new generation of emulsions; 2. a new generation of latex paint; 3. a new generation of aqueous varnishes; 4. modifying a water-soluble resin; 5. a new generation of waterproof engineering and waterproof material treating agent; 6. a new generation of leather soft, waterproof and anti-staining treatment agent; 7. a new-generation papermaking sizing agent, a special paper auxiliary agent (release paper, waterproof paper and oilproof paper) and a coating dispersant; 8. a new generation of textile waterproof, anti-stain and anti-ultraviolet treating agent; 9. cosmetic emulsifier, thickener, water retention agent, sunscreen agent, and emollient; 10. dispersing (modifying) agents such as nano calcium carbonate; 11. inorganic pigment and filler modifier (for rubber and plastic); 12. viscosity reducing agents for petroleum, and the like.
In a word, the organic silicon-inorganic silicon nano composite is a new material for modifying the waterborne product, promotes the updating of the waterborne product and expands the development field of the waterborne product. In addition, the modifier is also a novel modifier for non-aqueous inorganic pigments and fillers; can also be used as plastic and rubber reinforcing agent.
The preparation of the organic silicon-inorganic silicon nano composite has the advantages of rich raw materials, low price and paper price, not very complicated process, lower production cost and good economic and social benefits.
The present invention will be further described with reference to the following examples.
Example 1:
1) feeding and heating. 10kg of water and 45kg of fatty acid are respectively added into the reaction kettle A, and the temperature is raised to 80 ℃.
2) Decomposition and reaction thereof. And (2) adding 45kg of sodium silicate with the modulus of 1.5 into the reaction kettle A in the step (1), and decomposing and reacting the sodium silicate in the presence of acid to respectively generate sodium aliphatate and silica sol.
3) And (4) dispersing. Heating is continued to 105 ℃, so that the silica sol is dispersed into the sodium aliphatate from bottom to top, and finally, a uniform dispersion is formed.
4) And (4) carrying out decomposition reaction. During the dispersion process, the sodium aliphatate is decomposed due to the heating.
5) Hydrolysis and poly (condensation) reactions. Adding 100kg of water into a reaction kettle B, wherein the water temperature is 6 ℃, adding the dispersion obtained in the step (4) into the reaction kettle B, immediately hydrolyzing and polymerizing to respectively generate nano SiO2And organosilicon [ (RCOO)4Si]。
6) And (4) copolymerization and compounding. In the course of hydrolysis and poly (condensation) reaction, nano SiO2And organosilicon [ (RCOO)4Si]Form an organosilicon microcosmic control nano SiO2The complex of (1).
7) And (4) dealkalizing. During the hydrolysis and poly (condensation) process, due to the nano SiO2And organosilicon [ (RCOO)4Si]It is insoluble in water, and NaOH is soluble in water, and can not react, i.e. dealkalize.
8) And (5) aging treatment. The hydrolysis and poly (condensation) reactants were aged for 4 hours.
9) And (4) compressing. And (4) performing pressure filtration on the aged substance, reducing the volume of the compound, and dehydrating and dealkalizing.
10) And (5) drying. And further dehydrating the compressed matter at normal temperature to obtain the product.
Example 2:
1) feeding and heating. 90kg of water and 5kg of fatty acid are added into a reaction kettle and heated to 50 ℃.
2) Decomposition and reaction thereof. The same procedure as in example 1 was repeated except that 5kg of sodium silicate having a modulus of 2 was used.
3) And (4) dispersing. Heating to 100 deg.C, the same as example 1.
4) And (4) carrying out decomposition reaction. The same as in example 1.
5) Hydrolysis and poly (condensation) reactions. 1000kg of water was taken, and the water temperature was 14 ℃ as in example 1.
6) And (4) copolymerization and compounding. The same as in example 1.
7) And (4) dealkalizing. The same as in example 1.
8) And (5) aging treatment. And aging for 48 hours.
9) And (4) compressing. The same as in example 1.
10) And (5) drying. The drying temperature is 90-100 ℃, and the rest is the same as example 1.
Example 3:
1) feeding and heating. 40kg of water and 30kg of fatty acid are respectively added into a reaction kettle, and the temperature is raised to 60 ℃ by heating, and the rest is the same as the example 1.
2) Decomposition and reaction thereof. 30kg of sodium silicate having a modulus of 2.5 was used in the same manner as in example 1.
3) And (4) dispersing. Heating to 110 ℃ was carried out as in example 1.
4) And (4) carrying out decomposition reaction. The rest is the same as example 1.
5) Hydrolysis and poly (condensation) reactions. The same procedureas in example 1 was repeated except that water was taken 500kg and the temperature was 22 ℃.
6) And (4) copolymerization and compounding. The same as in example 1.
7) And (4) dealkalizing. The same as in example 1.
8) And (5) aging treatment. And aging for 28 hours.
9) And (4) compressing. The same as in example 1.
10) And (5) drying. The drying temperature is 70-80 ℃, and the rest is the same as example 1.
Examples Main technical parameters of the finished product
| Item | Computing Unit of | Index (I) | ||
| Example 1 | Example 2 | Example 3 | ||
| Appearance of the product | White agglomerates | |||
| pH value | 1% suspension | 6.5～10.5 | 6.5～10.5 | 6.5～10.5 |
| Humidity | ％≤ | 5 | 5 | 5 |
| (RCOO)4Si content | ％≤ | 77 | 73 | 74 |
| Nano SiO2Content (wt.) | ％≥ | 18 | 22 | 21 |
| Na2O | ％≤ | 0.1 | 0.1 | 0.1 |
| Al2O3 | ％≤ | 0.001 | 0.001 | 0.001 |
| CaO | ％≤ | 0.001 | 0.001 | 0.001 |
| TiO2 | ％≤ | 0.001 | 0.001 | 0.001 |
| MgO | ％≤ | 0.001 | 0.001 | 0.001 |
| Specific gravity of | Grams per liter | 200～900 | ||
| X-ray structural analysis | Amorphous form | |||
Claims (2)
1. An organosilicon-inorganic silicon nanocomposite, characterized by:
1) the material is prepared by the following reaction of the following materials in percentage by weight:
5 to 45 percent of fatty acid,
5 to 45 percent of sodium silicate,
the balance of water;
2) the above-mentioned materials are passed through the processes of feeding, heating, decomposition and reaction, dispersion, decomposition reaction, hydrolysis and polymerization reaction, copolymerization and compounding, dealkalization, ageing treatment, compression and drying 10 steps so as to obtain the invented product.
2. The method for preparing a silicone-inorganic silicon nanocomposite as claimed in claim 1, wherein the steps are:
1) feeding and heating: respectively adding water and fatty acid into a reaction kettle A, and heating to 50-80 ℃;
2) decomposition and reaction thereof: adding sodium silicate, decomposing and reacting sodium silicate, layering in reaction kettle, wherein the upper layer is RCOONa, and the lower layer is silica sol, i.e. Si (OH)4；
3) Dispersing: continuously heating to 80-110 ℃, and gradually dispersing the silica sol in RCOONa from bottom to top in boiling until the silica sol is uniform;
4) and (3) decomposition reaction: and (3) when the compound is co-dispersed with the step 3), the RCOONa undergoes decomposition reaction:
5) hydrolysis and poly (condensation) reactions: adding water into the reaction kettle B, wherein the water amount is 1-9 times of the feeding amount in the step 1) and the step 2), and the temperature is 6-normal temperature; adding the dispersoid in the step 4), and generating hydrolysis and poly (condensation) reaction under the action of a catalyst of NaOH in the dispersoid to generate silica sol SiO2And Organosilicon (RCOO)4Si；
6) Copolymerization and compounding: in the course of hydrolysis and poly(condensation) reaction, nano SiO2And Organosilicon (RCOO)4Si is copolymerized and compounded to form (RCOO)4Si/nano SiO2I.e., silicone-inorganic silicon nanocomposites;
7) dealkalization: in the hydrolysis and poly (condensation) reaction process, as the organic silicon-inorganic silicon nano compound is insoluble in water and NaOH is soluble in water, the organic silicon-inorganic silicon nano compound can not chemically react with the organic silicon-inorganic silicon nano compound under the process condition;
8) aging treatment: aging the raw materials in the reaction kettle for 4-48 hours;
9) compression: compressing the aged material in the step 8), and further dehydrating and dealkalizing;
10) drying: drying the compressed matter at normal temperature to 180 deg.c to obtain the product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011227680A CN1168762C (en) | 2001-07-21 | 2001-07-21 | Organo-silicon and inorgano-silicon nano-composite and its prepn process |
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| CNB011227680A CN1168762C (en) | 2001-07-21 | 2001-07-21 | Organo-silicon and inorgano-silicon nano-composite and its prepn process |
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| Publication Number | Publication Date |
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| CN1398908A true CN1398908A (en) | 2003-02-26 |
| CN1168762C CN1168762C (en) | 2004-09-29 |
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