CN112441593B - Preparation method of surface hydrophobic modified anhydrous nano zinc borate - Google Patents
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Abstract
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a preparation method of surface hydrophobic modified anhydrous nano zinc borate. The method comprises the steps of taking zinc acetate and boric acid as raw materials, zinc stearate as a surface hydrophobic modifier and ethanol as a solvent, and reacting to prepare the surface hydrophobic modified anhydrous nano zinc borate. The method has the advantages of few steps, short reaction time, low temperature and no three-waste discharge; the prepared zinc borate has small granularity and good dispersibility, and can be fully dispersed in high polymer materials such as PVC and the like; the surface of the modified zinc stearate not only enables the anhydrous zinc borate to have hydrophobicity, but also has lubricity, so that the consumption of a lubricant can be reduced, and the production cost of PVC and other plastics is reduced on the whole; the preparation method is simple, convenient and environment-friendly; the production equipment is simple and is suitable for large-scale industrial production; because of no water, the decomposition temperature is high, and the requirements of some special high-temperature resistant engineering plastics on the flame retardant are met.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a preparation method of surface hydrophobic modified anhydrous nano zinc borate.
Background
The zinc borate is an inorganic flame retardant commonly used in the market, and has the advantages that: non-volatile, no precipitation, good thermal stability, no generation of toxic smoke and the like; in addition, the zinc borate also has the characteristics of carbon deposit, smoke suppression and synergistic effect enhancement by being used together with other flame retardants. Zinc borate as an efficient inorganic flame retardant is widely applied to the fields of rubber, plastics, coatings and the like. At present, two main approaches for improving the flame retardant effect of zinc borate are as follows: the nano zinc borate can improve the contact area between the zinc borate and a polymer, and can better play a role in flame retardance; in addition, the nano zinc borate is easier to disperse, and the dosage can be reduced. Secondly, the surface of the zinc borate is subjected to hydrophobic modification, the compatibility between hydrophilic zinc borate and a hydrophobic polymer is poor, and the compatibility and the dispersibility of the zinc borate and the polymer are improved by performing hydrophobic modification on the surface of the zinc borate; meanwhile, the high dispersibility can also avoid the damage to the physical properties (such as tensile rate, breaking rate and the like) of the polymer caused by excessive aggregation of the zinc borate.
At present, the zinc borate preparation reported in the literature is almost all in aqueous solution. In the conventional preparation method, the boron source mainly comprises boric acid and sodium borate, and the zinc source generally adopts zinc oxide, zinc sulfate, zinc hydroxide and the like. Among zinc sources, other than zinc sulfate, are insoluble, resulting in a long reaction time. For example, Chinese patent CN 106904628A discloses a preparation method of hollow rod-shaped zinc borate, which adopts boric acid and zinc oxide to react for about 4 hours at the temperature of 100-160 ℃, and the energy consumption is higher. Chinese patent CN 1789135A discloses a hydrothermal preparation method of shape-controllable low-water zinc borate powder, which adopts a high-pressure reaction kettle with the temperature of 110-160 ℃ to react for 6-24h to prepare zinc borate with different shapes. The high-pressure reaction kettle adopted by the method is dangerous and is not beneficial to popularization and application; in addition, the reaction time is too long, which also results in high energy consumption.
Generally, the smaller the particle size of the zinc borate, the better its dispersibility and the better its performance. Most of the zinc borate prepared at present is micron-sized, for example, Chinese patent CN 103964455A discloses a preparation method of 3.5-water zinc borate, and the product is about 4 mu m zinc borate. For example, chinese patent CN 1903722a discloses a method for preparing nano zinc borate, which has many steps, complex operation, and difficult quality control. Chinese patent CN 1778868A discloses a method for preparing a nano zinc borate flame retardant by solid phase reaction of zinc oxide and boric acid, which comprises the steps of respectively grinding zinc oxide and boric acid into micron-sized particles, and carrying out ball milling or vacuum ball milling to obtain nano zinc borate.
In order to further improve the dispersibility of zinc borate in organic materials, hydrophilic zinc borate surfaces are treated by a surface modification method to prepare hydrophobic zinc borate. Commonly used surface modifiers are silane coupling agents, oleic acid, and the like. For example, chinese patent CN 1167730a discloses a technique for preparing ultra-fine low water zinc borate by introducing a nonionic surfactant such as fatty alcohol-polyoxyethylene ether to control the particle size, the particle size of the prepared product is in the range of 0.1-10 μm, but the ultra-fine product obtained by the method needs to be added with a surfactant, and the surfactant is too expensive.
The water loss temperature of the common zinc borate hydrate is lower than 290 ℃, with the rapid development of high polymer materials, a series of special engineering plastics are continuously emerged, and the processing or using temperature is high at about 400 ℃, so that the anhydrous zinc borate with higher water loss temperature is urgently needed. The patent related to the preparation of anhydrous zinc borate is rare, and Chinese patent CN 101514002A discloses a method for preparing superfine anhydrous zinc borate, which adopts nano-scale zinc borate as a raw material and uses an organic solvent to extract crystal water in the nano-scale zinc borate at high temperature, and the method has multiple steps and high cost.
Aiming at the problems of high energy consumption, complex steps, large particle size of the prepared zinc borate and the like of the existing zinc borate preparation method, the preparation method of the surface hydrophobic modified anhydrous nano zinc borate with less steps, low energy consumption and small particle size of the prepared zinc borate is urgently needed.
Disclosure of Invention
The invention aims to provide a preparation method of surface hydrophobic modified anhydrous nano zinc borate, which has the advantages of few steps, short reaction time, low energy consumption, no three-waste discharge and small particle size of the prepared nano zinc borate.
The preparation method of the surface hydrophobic modified anhydrous nano zinc borate provided by the invention is characterized in that zinc acetate and boric acid are used as raw materials, zinc stearate is used as a surface hydrophobic modifier, and ethanol is used as a solvent, and the surface hydrophobic modified anhydrous nano zinc borate is prepared by reaction.
The zinc acetate is anhydrous zinc acetate.
The concentration of the ethanol is 98-99.5%.
The mass ratio of the zinc acetate to the boric acid to the zinc stearate is 36.7-40: 37.1-41.2: 1.5-1.7.
The reaction temperature is 85-90 ℃, and the reaction time is 1.5-2.0 h.
The particle size of the surface hydrophobic modified anhydrous nano zinc borate is 200-300 nm.
The preparation method of the surface hydrophobic modified anhydrous nano zinc borate comprises the following steps:
(1) adding zinc acetate and zinc stearate into preheated ethanol, stirring and dissolving to obtain a solution A;
(2) adding boric acid into preheated ethanol, stirring and dissolving to obtain a solution B;
(3) adding the solution A into the solution B under the stirring condition, and preserving heat to obtain a suspension;
(4) centrifuging the suspension to obtain a precipitate, washing, drying and grinding the precipitate to obtain the surface hydrophobic modified anhydrous nano zinc borate.
The ratio of the zinc acetate to the ethanol in the step (1) is 36.7-40: 1.5-1.8, wherein the zinc acetate is calculated by g, and the ethanol is calculated by L.
The preheating temperature in the step (1) is 85-90 ℃.
The ratio of the boric acid to the ethanol in the step (2) is 37.1-41.2: 1.0-1.2, wherein the boric acid is calculated by g and the ethanol is calculated by L.
The preheating temperature in the step (2) is 85-90 ℃.
The rate of adding the solution A in the step (3) is 1.0-1.5 mL/s.
The heat preservation temperature in the step (3) is 85-90 ℃, and the heat preservation time is 1.5-2.0 h.
The centrifugation speed in the step (4) is 3800-4500r/min, and the centrifugation time is 3-5 min.
The washing in the step (4) is washing with ethanol.
The drying temperature in the step (4) is 50-60 ℃, and the drying time is 0.5-1.0 h.
And (4) drying in a vacuum drying oven with the pressure of 0.07-0.09 MPa.
The drying temperature in the step (4) is 110-120 ℃, and the drying time is 0.5-1.0 h.
The surface hydrophobic modified anhydrous nano zinc borate prepared by the invention is used as a PVC flame retardant.
The invention adopts 98-99.5% ethanol as solvent, boric acid and zinc acetate as raw materials, zinc stearate as surface modifier, and the hydrophobic anhydrous nano zinc borate is prepared by one-pot method after heat preservation for 1.5-2.0h at 85-90 ℃. The zinc oxide or zinc hydroxide adopted by the conventional preparation of zinc borate is insoluble in water, and must react at high temperature and high pressure for a long time, so that the energy consumption is relatively high.
According to the invention, zinc stearate is used as a surface modifier, and based on a similar compatibility principle, zinc ions in the zinc stearate are easily adsorbed to the surface of zinc borate, so that the zinc borate is hydrophobic, and the compatibility of the zinc borate with PVC can be obviously improved. In addition, zinc borate contains zinc, and the zinc borate is easy to react with chloride ions generated by PVC degradation in PVC to generate ZnCl2，ZnCl2Can catalyze PVC to degrade rapidly, so the zinc borate can not be directly used as a PVC flame retardant and must be modified. The invention uses zinc stearate as zinc borate surface modifier, zinc stearate is heat stabilizer and lubricant for PVC, the product of the invention also proves the following: the zinc borate is used as the PVC flame retardant, so that the PVC product can obviously yellow; the zinc borate is modified by the zinc stearate, so that the zinc borate has good lubricity and hydrophobicity, and has good compatibility with PVC and improved thermal stability of PVC.
The invention has the following beneficial effects:
the invention provides a preparation method of flame retardant surface hydrophobic modified anhydrous nano zinc borate for PVC, which has the advantages of few steps (one-pot method), short reaction time, low temperature and no three-waste discharge; the prepared zinc borate has small granularity (200-300nm), good dispersibility and can be fully dispersed in high polymer materials such as PVC and the like; the surface of the modified zinc stearate not only enables the anhydrous zinc borate to have hydrophobicity, but also has lubricity, so that the consumption of a lubricant can be reduced, and the production cost of PVC and other plastics is reduced on the whole; the preparation method is simple, convenient and environment-friendly; the production equipment is simple and is suitable for large-scale industrial production; because of no water, the decomposition temperature is high, and the requirements of some special high-temperature resistant engineering plastics on the flame retardant are met.
Drawings
Fig. 1 is an XRD spectrum of the surface hydrophobic modified anhydrous nano zinc borate prepared in example 1.
FIG. 2 is an infrared spectrum of the surface hydrophobically modified anhydrous nano zinc borate prepared in example 1.
Fig. 3 is a photograph of the surface hydrophobically modified anhydrous nano zinc borate prepared in example 1 floating on the water surface.
FIG. 4 is a scanning electron microscope image of the surface hydrophobically modified anhydrous nano zinc borate prepared in example 1, wherein a is a scanning electron microscope image magnified by 2 ten thousand times, and b is a scanning electron microscope image magnified by 10 ten thousand times.
Fig. 5 is a thermogravimetric test result of the surface hydrophobically modified anhydrous nano zinc borate prepared in example 1.
FIG. 6 is a graph of the results of oven static aging tests.
Fig. 7 is a graph of torque rheometer test results.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
(1) Adding 36.7g zinc acetate and 1.5g zinc stearate into 1.5L 98% ethanol preheated to 90 deg.C, stirring thoroughly to dissolve to obtain solution A;
(2) adding 1.0L of 98% ethanol into a 5L flask, preheating to 90 ℃, adding 37.1g of boric acid, stirring, and obtaining a solution B after the boric acid is completely dissolved;
(3) adding the solution A into a flask filled with the solution B at the speed of 1.0mL/min under vigorous stirring, then installing a condenser tube, and preserving heat at 90 ℃ for 1.5h to obtain a suspension;
(4) centrifuging the suspension at a rotation speed of 3800r/min for 3min to obtain precipitate, washing the precipitate with 98% ethanol for three times, drying in a vacuum drying oven at 50 deg.C under 0.07MPa for 1.0h to remove ethanol adsorbed by zinc borate, drying in a forced air drying oven at 110 deg.C for 1.0h, taking out, and grinding to obtain the final product.
Example 2
(1) Adding 40.0g of zinc acetate and 1.7g of zinc stearate into 1.8L of 99.5% ethanol preheated to 85 ℃, and fully stirring to dissolve the zinc acetate and the zinc stearate to obtain a solution A;
(2) adding 1.2L of 99.5% ethanol into a 5L flask, preheating to 85 ℃, adding 41.2g of boric acid, stirring, and obtaining a solution B after the boric acid is completely dissolved;
(3) adding the solution A into a flask filled with the solution B at the speed of 1.5mL/min under vigorous stirring, then installing a condenser tube, and preserving heat at 85 ℃ for 2.0h to obtain a suspension;
(4) centrifuging the suspension at the rotating speed of 4500r/min for 4min to obtain precipitate, washing the precipitate with 99.5% ethanol for three times, drying in a vacuum drying oven at 60 ℃ and 0.09MPa for 0.5h to remove ethanol adsorbed by zinc borate, further drying in a forced air drying oven at 120 ℃ for 0.5h, taking out, and grinding to obtain the surface hydrophobic modified anhydrous nano zinc borate.
Example 3
(1) Adding 38.0g of zinc acetate and 1.6g of zinc stearate into 1.6L of 99% ethanol preheated to 88 ℃, and fully stirring to dissolve the zinc acetate and the zinc stearate to obtain a solution A;
(2) adding 1.1L of 99% ethanol into a 5L flask, preheating to 90 ℃, adding 40.0g of boric acid, stirring, and obtaining a solution B after the boric acid is completely dissolved;
(3) adding the solution A into a flask filled with the solution B at the speed of 1.3mL/min under vigorous stirring, then installing a condenser tube, and preserving heat at 90 ℃ for 1.8h to obtain a suspension;
(4) centrifuging the suspension at the rotating speed of 4000r/min for 5min to obtain a precipitate, washing the precipitate with 99% ethanol for three times, drying the precipitate in a vacuum drying oven at 55 ℃ and 0.08MPa for 0.6h to remove ethanol adsorbed by the zinc borate, continuously drying the precipitate in a blast drying oven at 115 ℃ for 0.6h, taking out the dried precipitate, and grinding the dried precipitate to obtain the surface hydrophobic modified anhydrous nano zinc borate.
The surface hydrophobic modified anhydrous nano zinc borate prepared in the example 1 is tested, and the test results are as follows:
1. x-ray diffractometer (XRD) testing crystal form
The surface hydrophobically modified anhydrous nano zinc borate prepared in example 1 was tested by an X-ray diffractometer, and the test results are shown in fig. 1. The analysis shows that the zinc borate prepared in the example 1 is consistent with the addition of ICSD00-009-0153 and 01-071-2063, and the prepared zinc borate is anhydrous mixed crystal of the two zinc borates.
2. Fourier transform Infrared Spectroscopy (FTIR) testing
Fourier transform infrared spectroscopy was performed on the surface hydrophobically modified anhydrous zinc borate prepared in example 1, and the results are shown in FIG. 2. As can be seen from FIG. 2, 496.7cm-1The peak is a characteristic peak of Zn-O, 1255.4cm-1And 724cm-1The peak at (A) belongs to the characteristic peak of the B-O bond. 2919cm-1And 2845cm-1Belongs to methyl and methylene stretching vibration peaks, and shows that zinc stearate is successfully attached to the surface of zinc borate. 1621.3cm-1And 1460.9cm-1The two absorption peaks correspond to the antisymmetric and symmetric stretching vibrations of the ionized stearate structure. At 3200cm-1The absence of characteristic absorption peaks of O-H in the vicinity indicates that the zinc borate of the invention contains no water.
3. Hydrophobicity test
The surface hydrophobic modified anhydrous nano zinc borate prepared in example 1 was added into water for hydrophobic property test, and the test result is shown in fig. 3. As can be seen from fig. 3, the hydrophobic zinc borate prepared by the present invention floated on the water surface, indicating that the zinc borate prepared by the present invention was indeed hydrophobic.
4. Scanning Electron Microscope (SEM) testing
Scanning electron microscope tests were performed on the surface hydrophobically modified anhydrous nano zinc borate prepared in example 1, and the test results are shown in fig. 4. Fig. 4 a is a scanning electron microscope image magnified by 2 ten thousand times, and it can be seen from the image that zinc borate is a sheet structure, and there is no large agglomeration, which may be caused by zinc stearate coating modification, so that agglomeration of zinc borate is avoided in the centrifugal precipitation and drying processes. In FIG. 4, b is a scanning electron microscope image magnified by 10 ten thousand times, zinc borate is a flaky irregular structure with a diameter of 200-300nm, and the boundary between sheets is clear without agglomeration.
5. Thermogravimetric testing
Thermogravimetric testing was performed on the surface hydrophobically modified anhydrous nano zinc borate prepared in example 1, and the test results are shown in fig. 5. As can be seen from FIG. 5, the anhydrous zinc borate prepared according to the invention is reduced by only 2.26% before 400 ℃, which indicates that the zinc borate does not contain crystal water, and also indicates the thermal stability of the zinc borate. There was a significant mass loss at 440 ℃, indicating that anhydrous zinc borate can be used as a flame retardant for high melting engineering plastics.
6. Testing of PVC thermal stability, flame retardance and dynamic processability
And (3) testing the flame retardant property of the zinc borate by taking polyvinyl chloride (PVC) as a probe. Adding 20 parts by mass of the surface hydrophobic modified anhydrous nano zinc borate prepared in example 1 into 100 parts by mass of PVC, and then adding 4 parts by mass of TiO28 parts by mass of diisooctyl phthalate (DOP) and 5 parts by mass of CaCO3After being mixed uniformly, the mixture is plasticated on a double-roll plasticator with the roll temperature of 180 ℃ and the roll spacing of 1mm for 5min and plasticated into sheets. Commercially available zinc borate was used as a comparative example.
(1) Test for thermal stability
The PVC sample is cut into a sheet sample of 1cm multiplied by 1cm according to the standard ASTM2115-2004, the sheet sample is placed on aluminum foil paper and placed into a high-temperature oven at 180 ℃, the sample is taken out every 10min, the color change condition of the taken sample is observed, and the static aging test result of the oven is shown in figure 6.
As can be seen from FIG. 6, pure PVC turned dark at the initial stage, turned yellow-brown at 20min heating, and turned dark reddish-brown at 50min heating; using commercially available zinc borate as an additive, wherein the initial color of PVC is light brown, which indicates that the initial whiteness is not good, and heating to zinc baking for 40 min; when the inventive example 1 was added, the initial whiteness was very good, turning light brown at 40min, and zinc baking at 60 min. The results show that the PVC heat stabilizer zinc stearate is added as a modifier, so that the PVC heat stabilizer does not deteriorate the PVC heat stability.
(2) Test for flame retardancy
The flame retardant properties of pure PVC (without flame retardant), PVC with 20 parts by mass of commercially available zinc borate added and PVC with 20 parts by mass of zinc borate prepared in example 1 were tested, and the test results are shown in Table 1.
TABLE 1 PVC flame retardancy test results
Note: v: indicating that combustion is possible; x: indicating failure to burn
As can be seen from Table 1, pure PVC can be burned at an oxygen concentration of 39%; PVC added with a commercially available zinc borate flame retardant can be combusted at an oxygen concentration of about 42%; while the PVC sample to which the zinc borate prepared in example 1 was added was combustible at oxygen concentrations above 45%. Compared with the traditional flame retardant, the flame retardant has obviously improved performance and better smoke suppression effect.
(3) Dynamic processability test
20 parts by mass of the surface-hydrophobically modified anhydrous nano zinc borate prepared in example 1 was added to 100 parts by mass of PVC, and 4 parts by mass of TiO was added28 parts by mass of diisooctyl phthalate (DOP) and 5 parts by mass of CaCO3After mixing, the dynamic processability of zinc borate on PVC was tested with a torque rheometer at a roll temperature of 180 ℃ with commercially available zinc borate as a comparative example, the results are shown in FIG. 7.
As is clear from FIG. 7, the addition of the zinc borate of example 1 of the present invention resulted in a torque rheometer equilibrium torque of 16.1 N.m, which was 1.3 N.m lower than 17.4 N.m obtained by adding commercially available zinc borate, indicating that the zinc borate of the present invention has a certain lubricity. The lubricating property is good, the use of lubricant can be reduced, and the energy consumption can be reduced during processing.
Claims (10)
1. A preparation method of surface hydrophobic modified anhydrous nano zinc borate is characterized in that zinc acetate and boric acid are used as raw materials, zinc stearate is used as a surface hydrophobic modifier, ethanol is used as a solvent, and the surface hydrophobic modified anhydrous nano zinc borate is prepared through reaction;
the zinc acetate is anhydrous zinc acetate.
2. The method for preparing the surface hydrophobically modified anhydrous nano zinc borate according to claim 1, wherein the concentration of ethanol is 98-99.5%.
3. The preparation method of the surface hydrophobically modified anhydrous nano zinc borate according to claim 1, wherein the mass ratio of the zinc acetate, the boric acid and the zinc stearate is 36.7-40: 37.1-41.2: 1.5-1.7.
4. The preparation method of the surface hydrophobically modified anhydrous nano zinc borate according to claim 1, characterized in that the reaction temperature is 85-90 ℃ and the reaction time is 1.5-2.0 h.
5. The method for preparing the surface hydrophobically modified anhydrous nano zinc borate according to claim 1, wherein the particle size of the surface hydrophobically modified anhydrous nano zinc borate is 200-300 nm.
6. The preparation method of the surface hydrophobically modified anhydrous nano zinc borate according to any one of claims 1 to 5, which is characterized by comprising the following steps:
(1) adding zinc acetate and zinc stearate into preheated ethanol, stirring and dissolving to obtain a solution A;
(2) adding boric acid into preheated ethanol, stirring and dissolving to obtain a solution B;
(3) adding the solution A into the solution B under the stirring condition, and preserving heat to obtain a suspension;
(4) centrifuging the suspension to obtain a precipitate, washing, drying and grinding the precipitate to obtain the surface hydrophobic modified anhydrous nano zinc borate.
7. The preparation method of the surface hydrophobically modified anhydrous nano zinc borate according to claim 6, wherein the ratio of the zinc acetate to the ethanol in the step (1) is 36.7-40: 1.5-1.8, wherein the preheating temperature is 85-90 ℃ when the zinc acetate is counted by g and the ethanol is counted by L.
8. The method for preparing the surface-hydrophobically modified anhydrous nano zinc borate according to claim 6, wherein the ratio of the boric acid to the ethanol in the step (2) is 37.1-41.2: 1.0-1.2, wherein the preheating temperature is 85-90 ℃ when the boric acid is counted by g, the ethanol is counted by L.
9. The method for preparing the surface hydrophobically modified anhydrous nano zinc borate according to claim 6, wherein the speed of adding the solution A in the step (3) is 1.0-1.5mL/s, the temperature is 85-90 ℃, and the holding time is 1.5-2.0 h.
10. The method for preparing the surface hydrophobically modified anhydrous nano zinc borate as claimed in claim 6, wherein the centrifugation speed in step (4) is 3800-.
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