CN108530679B - Method for preparing nano-silica composite antioxidant through in-situ modification - Google Patents
Method for preparing nano-silica composite antioxidant through in-situ modification Download PDFInfo
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- CN108530679B CN108530679B CN201810381302.6A CN201810381302A CN108530679B CN 108530679 B CN108530679 B CN 108530679B CN 201810381302 A CN201810381302 A CN 201810381302A CN 108530679 B CN108530679 B CN 108530679B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2241—Titanium dioxide
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Abstract
The invention discloses a method for preparing a nano-silica composite antioxidant by in-situ modification, which improves the use temperature of the antioxidant 1330 and overcomes the defects of poor self-dispersibility, complex secondary dispersion modification process, high energy consumption and high pollution of nano-silica. On the basis of a sol-gel technology, the nano silicon dioxide composite antioxidant with uniform particle size and excellent appearance is prepared by in-situ modification of antioxidant self functional groups, dosage, addition temperature, addition time, reaction conditions and other technologies. The preparation and modification method has advanced process and precise data, the product is white powder particle with particle diameter of 80-120nm, and can be applied in various fields such as macromolecule antioxidation, strengthening and toughening, industrial coating and the like, thus being an ideal preparation method of the nano silicon dioxide composite antioxidant.
Description
Technical Field
The invention relates to a method for preparing a nano-silica composite antioxidant by in-situ modification, belonging to the technical field of preparation and application of inorganic nano-materials.
Background
The antioxidant 1330 belongs to a high molecular weight poly hindered phenol antioxidant, has the characteristics of no pollution, no coloring, low volatility and the like, is an excellent antioxidant for high-density polyethylene, polypropylene and rubber, and is mainly used for plastic products such as polyvinyl chloride, polyamide, ABS resin, polyester and the like. But the melting point is about 240 ℃, and the product is easy to decompose in the processing process, thereby influencing the processing process and the quality of the product.
The nano silicon dioxide has good thermal stability, thickening property, reinforcing property and the like. The method is widely applied to modification of composite materials such as rubber, engineering plastics, biomedicine, ceramics, building materials, resin matrix and the like, and is one of extremely important high-tech superfine inorganic new materials. However, because the particle size of the nano-silica is smaller and the surface activity is higher, soft and hard agglomeration is easily generated in the production and application processes, so that the application performance is reduced.
Disclosure of Invention
The invention provides a method for preparing a nano-silica composite antioxidant by in-situ modification, which aims to solve the technical problems of hard aggregate phenomena and complex process existing in the processes of high-temperature decomposition and nano-silica preparation in the use process of the antioxidant 1330 at present.
The invention is realized by adopting the following technical scheme: a method for preparing a nano-silica composite antioxidant by in-situ modification uses the following chemical substance materials: ethyl orthosilicate, ammonia water with the concentration of 25% calculated by mass fraction, absolute ethyl alcohol, acetone, an antioxidant 1330 and deionized water, wherein the dosage of the liquid chemical substance material is calculated by volume fraction; the basic chemical properties of the antioxidant 1330 are as follows:
chemical name: 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene
The molecular formula is as follows: c54H78O3
Molecular weight: 775.2
The molecular structural formula is as follows:
the preparation method comprises the following steps:
(1) selecting each chemical material
(2) In-situ modification preparation of nano silicon dioxide composite antioxidant
Firstly, preparing solution
Measuring 49-51 parts of absolute ethyl alcohol, and placing the absolute ethyl alcohol in a beaker for later use; measuring 24-36 parts of ammonia water, and placing the ammonia water in a conical flask with a rubber plug for later use; measuring 5.0-5.2 parts of ethyl orthosilicate and 49-51 parts of absolute ethyl alcohol, placing the ethyl orthosilicate and the absolute ethyl alcohol in a beaker for mixing, and stirring the mixture by using a glass rod to uniformly mix the ethyl orthosilicate and the absolute ethyl alcohol for later use; weighing and dissolving the antioxidant 1330 in 150 parts of acetone, and uniformly stirring to prepare an acetone solution, wherein the mass-volume ratio of the antioxidant 1330 to the acetone is 8-10: 29-30 mg/ml; after completely dissolving, placing the mixture into a conical flask with a glass plug for standby;
② process for preparing nano silicon dioxide composite antioxidant by in-situ modification
Placing absolute ethyl alcohol and an ammonia water solution into a three-neck flask, then placing the three-neck flask into a magnetic stirring heating sleeve, starting a stirrer, starting heating, setting the rotating speed of the stirrer to be 200r/min, setting the heating temperature to be 65 ℃, and configuring a condensation reflux device; adding the tetraethoxysilane solution into a three-neck flask at the speed of 0.75 part/min when the temperature reaches 45 ℃ during the temperature rise; after the condensation reflux reaction is carried out for 1h, the acetone solution is dripped into the three-neck flask at the speed of 0.25 part/min; condensing and refluxing for 6 h;
③ ultrasonic water bath dispersion reaction
After the reaction is finished, placing the three-neck flask in an ultrasonic water bath pool for continuous reaction, wherein the water bath temperature is 60 ℃, the ultrasonic frequency is 80KHz, the power is 90W, and the reaction time is 2 h;
fourthly, washing and suction filtration
Putting the product solution obtained in the step (III) into a beaker, adding 150 parts of anhydrous ethanol, and stirring for 3min to obtain a washing solution; filtering the washing liquid to obtain a filter cake, placing the filter cake in 200 and 250 parts of absolute ethyl alcohol, stirring to obtain washing liquid, and filtering; performing the above steps for 5 times to obtain a filter cake;
adding the filter cake into 200 parts of deionized water, stirring and washing for 5min to obtain a washing solution; filtering and washing until the filtrate is neutral to obtain a product filter cake;
drying, grinding and sieving
Putting the product filter cake obtained in the step (IV) into a vacuum drying oven for drying, wherein the drying temperature is 60 ℃, the vacuum degree is 0.1MPa, and the drying time is 2 h;
and grinding the dried powder by using an agate mortar and a pestle, and then sieving by using a 400-mesh sieve to obtain the nano silicon dioxide composite antioxidant product.
Detecting, analyzing and characterizing the shape, color, components and chemical and physical properties of the prepared nano silicon dioxide composite antioxidant:
carrying out morphology analysis on the nano silicon dioxide composite antioxidant by using a JSM-6700F type field emission scanning electron microscope;
performing thermal stability analysis on the product by using a TGA4000 thermogravimetric analyzer;
and (4) conclusion: the nano silicon dioxide composite antioxidant prepared by the method is white powder particles, the particle diameter is 80-120nm, the appearance is regular, the particle size is uniform, the dispersion is good, and the chemical and physical properties are stable.
The nano silicon dioxide is stored in a brown transparent glass container, and is stored in a closed and dark way, and is waterproof, sun-proof and acid, alkali and salt corrosion resistant, the storage temperature is 25 ℃, and the relative humidity is less than or equal to 10%.
The invention has the beneficial effects that:
compared with the prior art, the method has obvious advancement, aims at the defects that the antioxidant 1330 is easy to decompose at high temperature in the using process, the nano silicon dioxide has poor dispersibility, more aggregates, complex secondary dispersion modification process and energy consumption, and prepares the nano silicon dioxide composite antioxidant with excellent appearance and uniform particle size by in-situ modification by utilizing the technologies such as the dosage of a modifier, the adding time, the adding temperature, the reaction condition and the like on the basis of the original sol-gel technology. The preparation and modification method has advanced process and precise data, the product is white powder particle with particle diameter of 80-120nm, and can be applied in various fields such as macromolecule anti-oxidation enhancement, industrial coating and the like, thus being an ideal preparation method of the nano silicon dioxide composite antioxidant.
Further, the step (1) is to select the chemical material for preparation, and control the quality purity and concentration: the purity of the ethyl orthosilicate is 99.9 percent, and the purity of the absolute ethyl alcohol is 99.9 percent; the purity of the acetone is 99.9 percent; the purity of the antioxidant 1330 is 99.9 percent; the purity of the deionized water is 99.9%.
Further, in the second step, firstly, carrying out condensation reflux reaction for 1h, and then dropwise adding an acetone solution for condensation reflux reaction for 6 h; the dropping speed of the ethyl orthosilicate solution is 0.75 part/min, and the dropping speed of the acetone solution is 0.25 part/min.
And further, washing with absolute ethyl alcohol and performing suction filtration in the step IV, and then washing with deionized water and performing suction filtration until the filtrate is neutral.
The raw materials with the purity, the dropping time and speed of the materials and the times of washing and suction filtration can effectively ensure better quality of the nano silicon dioxide composite antioxidant.
Drawings
FIG. 1 is a state diagram of in-situ modification for preparing nano-silica composite antioxidant.
FIG. 2 is an ultrasonic state diagram of in-situ modification for preparing nano-silica composite antioxidant.
FIG. 3 is a microscopic morphology of the nano-silica composite antioxidant.
FIG. 4 is a thermogravimetric diagram of the nano-silica composite antioxidant.
1-magnetic stirring heating sleeve seat, 2-three-neck flask, 3-liquid adding funnel, 4-liquid adding control valve, 5-condensing reflux device, 6-temperature sensor, 7-temperature sensor fixing frame, 8-in-situ modification preparation of nano silicon dioxide composite antioxidant mixed liquid, 9-liquid adding funnel fixing frame, 10-condensing reflux device fixing frame, 11-magnetic stirring rotor, 12-first temperature control button, 13-rotating speed control button, 14-ultrasonic emission module, 15-numerical control ultrasonic cleaner water bath seat, 16-pure liquid water, 17-power control button and 18-second temperature control button.
Detailed Description
Embodiment 1 a method for preparing a nano-silica composite antioxidant by in-situ modification, which uses the following chemical materials: ethyl orthosilicate, ammonia water with the concentration of 25 percent calculated by mass fraction, absolute ethyl alcohol, acetone, an antioxidant 1330 and deionized water.
The preparation method comprises the following steps:
(1) selecting each chemical material
(2) In-situ modification preparation of nano silicon dioxide composite antioxidant
Firstly, preparing solution
Measuring 51ml of absolute ethyl alcohol, and placing the absolute ethyl alcohol in a beaker for later use; measuring 29ml of ammonia water, and placing the ammonia water in a conical flask with a rubber plug for later use; measuring 5ml of ethyl orthosilicate and 50ml of absolute ethyl alcohol, placing the ethyl orthosilicate and the absolute ethyl alcohol in a beaker for mixing, and stirring the mixture by using a glass rod to uniformly mix the mixture for later use; 45mg of antioxidant 1330 is measured and dissolved in 150ml of acetone, the mixture is stirred evenly to prepare acetone solution, and the acetone solution is placed in a conical flask with a glass stopper for standby after being completely dissolved.
② process for preparing nano silicon dioxide composite antioxidant by in-situ modification
Placing absolute ethyl alcohol and an ammonia water solution into a three-neck flask, then placing the three-neck flask into a magnetic stirring heating sleeve, starting a stirrer, starting heating, setting the rotating speed of the stirrer at 200r/min, setting the heating temperature at 65 ℃, and configuring a condensation reflux device. Adding the tetraethoxysilane solution into a three-neck flask at the speed of 0.75ml/min when the temperature reaches 45 ℃ during the temperature rise; after the condensation reflux reaction is carried out for 1h, the acetone solution is dripped into the three-neck flask at the speed of 0.25 ml/min; the reaction was refluxed for 6 h.
③ ultrasonic water bath dispersion reaction
And step II, after the reaction is finished, placing the three-neck flask in an ultrasonic water bath pool for continuous reaction, wherein the water bath temperature is 60 ℃, the ultrasonic frequency is 80KHz, the power is 90W, and the reaction time is 2 h.
Fourthly, washing and suction filtration
Putting the product solution obtained in the step (III) into a beaker, adding 150ml of absolute ethyl alcohol, and stirring for 3min to obtain a washing solution; filtering the washing liquid to obtain a filter cake, placing the filter cake in 200ml of absolute ethyl alcohol, stirring to obtain washing liquid, and filtering; performing the above steps for 5 times to obtain a filter cake;
adding the filter cake into 200ml of deionized water, stirring and washing for 5min to obtain a washing liquid; and (4) performing suction filtration and washing until the filtrate is neutral to obtain a product filter cake.
Drying, grinding and sieving
Putting the product filter cake into a vacuum drying oven for drying, wherein the drying temperature is 60 ℃, the vacuum degree is 0.1MPa, and the drying time is 2 h;
and grinding the dried powder by using an agate mortar and a pestle, and then sieving by using a 400-mesh sieve to obtain the nano silicon dioxide composite antioxidant product.
The invention is further described below with reference to the accompanying drawings:
FIG. 1 shows a state diagram of in-situ modification for preparing nano-silica composite antioxidant, wherein the positions of all parts are correct, and the operations are carried out according to the proportion and the sequence.
The amount of chemical substance used for preparation is determined in a predetermined range, and is measured in grams and milliliters.
The three-neck flask 2 is arranged on the magnetic stirring heating sleeve 1, and the heating temperature of the magnetic stirring heating sleeve 1 is controlled by a first temperature control button 12; a liquid adding funnel 3, a condensing reflux device 5 and a temperature sensor 6 are sequentially arranged on the upper part of the three-neck flask 2 from left to right; the lower part of the liquid feeding funnel 3 is provided with a liquid feeding control valve 4 which is fixed by a liquid feeding funnel fixing frame 9; the condensing reflux device 5 is fixed by a condensing reflux device control frame 10; the temperature sensor 6 is fixed by a sensor fixing frame 7; preparing a nano silicon dioxide composite antioxidant mixed solution 8 by in-situ modification in the three-neck flask 2; the bottom of the three-mouth flask 2 is provided with a magnetic stirring rotor 11; the rotation speed of the magnetic stirring rotor 11 is controlled by a rotation speed control knob 13.
FIG. 2 is an ultrasonic water bath diagram of the preparation of nano-silica composite antioxidant by in-situ modification, wherein the positions of all parts are correct, and the parts are proportioned according to the amount and operated sequentially.
The three-neck flask 2 is arranged on a water bath seat 15 of the numerical control ultrasonic cleaner, pure liquid water 16 is added into a water bath pool, the water bath temperature of the water bath seat 15 of the numerical control ultrasonic cleaner is controlled by a second temperature control button 18, and the power of an ultrasonic emission module 14 is controlled and adjusted by a power control button 17; a liquid adding funnel 3, a condensing reflux device 5 and a temperature sensor 6 are sequentially arranged on the upper part of the three-neck flask 2 from left to right; the lower part of the liquid feeding funnel 3 is provided with a liquid feeding control valve 4 which is fixed by a liquid feeding funnel fixing frame 9; the condensing reflux device 5 is fixed by a condensing reflux device control frame 10; the temperature sensor 6 is fixed by a sensor fixing frame 7; the three-neck flask 2 is internally provided with a nano-silica composite antioxidant mixed solution 8 prepared by in-situ modification.
FIG. 3 is a microscopic morphology of the in-situ modified nano-silica composite antioxidant, in which: the surface appearance of the nano silicon dioxide is smooth and mellow, the particle size is uniform and full, the particle size is between 80 and 120nm, and the nano silicon dioxide is in a monodisperse state.
FIG. 4 is a thermogravimetric plot of the in-situ modified preparation of the nano-silica composite antioxidant and the pure antioxidant 1330, the weight loss temperature in the comparison plot is visible, after the initial decomposition temperature of the nano-silica composite antioxidant is delayed, the weight loss temperature is obviously higher than the pure antioxidant 1330, and the thermal stability is improved.
Claims (2)
1. A method for preparing a nano silicon dioxide composite antioxidant by in-situ modification is characterized in that the used chemical substance materials are as follows: ethyl orthosilicate, ammonia water with the concentration of 25 percent calculated by mass fraction, absolute ethyl alcohol, acetone, an antioxidant 1330 and deionized water; the basic chemical properties of the antioxidant 1330 are as follows:
chemical name: 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene
The molecular formula is as follows: c54H78O3
Molecular weight: 775.2
The molecular structural formula is as follows:
the preparation method comprises the following steps:
(1) selecting each chemical material
(2) In-situ modification preparation of nano silicon dioxide composite antioxidant
Firstly, preparing solution
Measuring 51ml of absolute ethyl alcohol, and placing the absolute ethyl alcohol in a beaker for later use; measuring 29ml of ammonia water, and placing the ammonia water in a conical flask with a rubber plug for later use; measuring 5.0ml of tetraethoxysilane and 50ml of absolute ethyl alcohol, placing the tetraethoxysilane and the absolute ethyl alcohol in a beaker for mixing, and stirring the mixture by using a glass rod to uniformly mix the mixture for later use; weighing an antioxidant 1330, dissolving in 150ml of acetone, and uniformly stirring to prepare an acetone solution, wherein the mass-volume ratio of the antioxidant 1330 to the acetone is 3: 10 mg/ml; after completely dissolving, placing the mixture into a conical flask with a glass plug for standby;
② process for preparing nano silicon dioxide composite antioxidant by in-situ modification
Placing absolute ethyl alcohol and an ammonia water solution into a three-neck flask, then placing the three-neck flask into a magnetic stirring heating sleeve, starting a stirrer, starting heating, setting the rotating speed of the stirrer to be 200r/min, setting the heating temperature to be 65 ℃, and configuring a condensation reflux device; adding the tetraethoxysilane solution into a three-neck flask at the speed of 0.75ml/min when the temperature reaches 45 ℃ during the temperature rise; after the condensation reflux reaction is carried out for 1h, the acetone solution is dripped into the three-neck flask at the speed of 0.25 ml/min; condensing and refluxing for 6 h;
③ ultrasonic water bath dispersion reaction
After the reaction is finished, placing the three-neck flask in an ultrasonic water bath pool for continuous reaction, wherein the water bath temperature is 60 ℃, the ultrasonic frequency is 80KHz, the power is 90W, and the reaction time is 2 h;
fourthly, washing and suction filtration
Putting the product solution obtained in the step (III) into a beaker, adding 150ml of absolute ethyl alcohol, and stirring for 3min to obtain a washing solution; filtering the washing liquid to obtain a filter cake, placing the filter cake in 200ml of absolute ethyl alcohol, stirring to obtain washing liquid, and filtering; performing the above steps for 5 times to obtain a filter cake;
adding the filter cake into 200ml of deionized water, stirring and washing for 5min to obtain a washing liquid; filtering and washing until the filtrate is neutral to obtain a product filter cake;
drying, grinding and sieving
Putting the product filter cake obtained in the step (IV) into a vacuum drying oven for drying, wherein the drying temperature is 60 ℃, the vacuum degree is 0.1MPa, and the drying time is 2 h;
and grinding the dried powder by using an agate mortar and a pestle, and then sieving by using a 400-mesh sieve to obtain the nano silicon dioxide composite antioxidant product.
2. The method for preparing the nano-silica composite antioxidant through in-situ modification as claimed in claim 1, wherein the chemical material used in the preparation in the step (1) is selected, and the quality purity and the concentration are controlled as follows: the purity of the ethyl orthosilicate is 99.9 percent, and the purity of the absolute ethyl alcohol is 99.9 percent; the purity of the acetone is 99.9 percent; the purity of the antioxidant 1330 is 99.9 percent; the purity of the deionized water is 99.9%.
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