CN1903722A - Method of preparing nano-zinc borate - Google Patents
Method of preparing nano-zinc borate Download PDFInfo
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- CN1903722A CN1903722A CN 200610028724 CN200610028724A CN1903722A CN 1903722 A CN1903722 A CN 1903722A CN 200610028724 CN200610028724 CN 200610028724 CN 200610028724 A CN200610028724 A CN 200610028724A CN 1903722 A CN1903722 A CN 1903722A
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Abstract
The present invention relates to a method for preparing nano zinc borate. Said method includes the following steps: A, uniformly mixing borax, zinc sulfate and zinc oxide according to the weight ratio of 1-7:1-5:0.1-0.08; B, adding water whose added quantity is 0.01%-70% of total weight of borax, zinc sulfate and zinc oxide, stirring them to form rheological state; C, adding surfactant in the product obtained by step B, then retaining constant temperature for 3-5hr at 60-100deg.C; and D, cooling the product obtained by step C to 20-30deg.C, filtering, water-washing and drying at 120-140deg.C so as to obtain the invented product.
Description
Technical Field
The invention relates to a method for preparing nano zinc borate.
Background
The inorganic flame retardant does not contain halogen and has good heat resistance. The most important advantage is that no toxic and corrosive gas is generated, and the product belongs to a physiological harmless substance and is environment-friendly. The flame retardant does not cause secondary pollution during combustion, and becomes a popular research subject in the field of the flame retardant at present. However, since the inorganic flame retardant has poor flame retardant effect, it is necessary to modify the inorganic flame retardant by new techniques such as refinement and surface modification to improve the flame retardant effect.
The zinc borate is one kind of inorganic fire retardant, and is excellent fire retardant for plastic, rubber, chemical building material and other organic polymer composite material. Has the advantages of good thermal stability, fine granularity, small specific gravity, easy dispersion, no toxicity and the like. The flame-retardant coating is widely applied to products such as various cable plastic sheaths, electric appliance plastics, flame-retardant coatings and the like.The molecular structure of boron atoms is complicated due to their multiple bonds, and is usually expressed as 2ZnO 3B2O3·3.5H2O, fire retardant ZB-2335, is a popular problem in the field of fire retardation for the preparation of zinc borate and the surface modification, refinement and microencapsulation thereof.
The research result of the nanometer polymer shows the advantages of the application of the nanometer additive in the polymer material. The granularity of the synthesized zinc borate reported at home and abroad is smaller and is 1-10 um, but is much worse than that of nano particles (1-100 nm), and if the nano zinc borate can be synthesized, the zinc borate has wider application and better performance.
1. Main synthesis process and product quality of zinc borate
Since the last 80 s, some scientific research units, large-scale colleges and universities and enterprises in China have studied the synthesis technology of zinc borate. According to the different raw materials, the developed synthesis processes mainly include zinc oxide method, zinc hydroxide method and borax-zinc sulfate double decomposition method.
(1) Zinc oxide process
The reaction formula for synthesizing zinc borate by a zinc oxide method is as follows:
putting zinc oxide and boric acid into a reactor according to a certain proportion; reacting for 5-7 h at 90-100 ℃ under a certain liquid-solid ratio, and then filtering, washing and drying to obtain the zinc borate product.
(2) Zinc hydroxide process
The reaction formula for synthesizing zinc borate by using a zinc hydroxide method is as follows:
the synthesis conditions for producing zinc borate by the zinc hydroxide method are basically the same as those of the zinc oxide method.
(3) Borax-zinc sulfate double decomposition method
The reaction formula for synthesizing zinc borate by a borax-zinc sulfate double decomposition method is as follows:
the reaction temperature for synthesizing the zinc borate by the method is about 90 ℃, and the synthesis time is about 8 hours.
The three synthesis methods have good product quality by the zinc oxide method, and the zinc hydroxide method needs to prepare the zinc hydroxide raw material on site, and the product quality is equivalent to that of the zinc oxide method. The borax-zinc sulfate double decomposition method has lower product cost (about 12 percent lower than that of a zinc oxide method). However, this method requires that Na in the mother liquor be removed2SO4The mother liquor can be recycled after separation and recovery, and the byproduct Na is relatively complicated in the subsequent treatment process2SO4Economic benefits may also be created.
2. Synthesis research of nano zinc borate
Zinc borate belongs to inorganic additive type flame retardant, which is successfully developed in the 70 s by borax and chemicals in the United states. The flame retardant is nontoxic and has good thermal stability, can retard flame and smoke, can extinguish electric arc, and can be widely applied to the flame retardance of various fibers, resins, rubber products, electronic part equipment, electric wires, cables and the like. At present, the research on the product is wide at home and abroad, and industrialization is realized. The granularity of the existing zinc borate products in the market is small, but the size of the zinc borate products is different from the size of nano particles. The particle size of the zinc borate micropowder is reduced from micron level to nanometer level, so that the mechanical properties of the material, such as toughness, tear resistance, bending resistance and the like, can be improved due to the good compatibility of the nanometer ions and the matrix material.
The granularity of the synthesized zinc borate reported at home and abroad is smaller and is 1-10 um, but is much worse than that of nano particles (1-100 nm), and if the nano zinc borate can be synthesized, the application of the zinc borate is wider and the performance is more excellent. The nano zinc borate product prepared by the improved method is added into a high polymer material, so that the flame retardant property of the material can be obviously improved, and the transparency of the resin can be retained to the maximum extent.
Disclosure of Invention
The invention aims to provide a method for producing nano zinc borate mainly according to the defects in the prior art.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the method for preparing the nano zinc borate is characterized by comprising the following steps of:
A. uniformly mixing borax, zinc sulfate and zinc oxide in a weight ratio of 1-7: 1-5: 0.01-0.08;
B. adding water according to 5.0-70% of the total weight of borax, zinc sulfate and zinc oxide, and stirring to form a flow state;
C. adding a surfactant into the product obtained in the step B, and keeping the temperature at 60-100 ℃ for 3-5 hours;
D. and D, cooling the product obtained in the step C to 20-30 ℃, filtering, washing with water, and drying at 120-140 ℃.
The rheological state is a non-solid and non-liquid state consisting of borax, zinc sulfate, a small amount of zinc oxide and water.
Preferably, the weight ratio of the borax to the zinc sulfate to the zinc oxide is 2-5: 2-4: 0.02-0.06.
More preferably, the weight ratio of the borax to the zinc sulfate to the zinc oxide is 3-4: 2.5-3.5: 0.03-0.05.
Wherein the surfactant is selected from one or two of a zirconium-containing surfactant or a silane surfactant.
Preferably, the dosage of the surfactant is 0.01-3% of the weight of the borax, the zinc sulfate and the zinc oxide.
Wherein, during the reaction, the boric acid concentration in the reaction mixture is maintained at 0.2-0.8 mol/l.
Preferably, boric acid is added to the reaction mixture to maintain a boric acid concentration of 0.3 to 0.6mol/l in the solution.
The zirconium-containing surfactant is zirconium oxychloride.
The silane surfactant is selected from JH-N313, chemical name is N-propyl trimethoxy silane, and molecular formula is CH3CH2CH2Si(OCH3)3(ii) a JH-N303, chemical name is N-propyl triethoxy silane, molecular formula is CH3CH2CH2Si(OCH2CH3)3；JH-N308，N-octyl triethoxysilane of the molecular formula CH3(CH2)7Si(OCH2CH3)3All of them are commercially available.
During the reaction, the concentration of boric acid in the solution is maintained at 0.2-0.8 mol/l.
Preferably, boric acid is added to the solution to maintain a boric acid concentration of 0.3 to 0.6mol/l in the solution.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. easy dispersivity, the molecular diameter reaches nanometer level, and the primary particle size is only 22.56 nm. The ultrafine pulverization of the powdery flame retardant is not only beneficial to the dispersion of particles in a polymer matrix material, but also can improve the interface bonding force between the flame retardant and the polymer material.
2. The product has high temperature resistance, stable crystal water below 300 ℃, and flame retardant and smoke suppression effects above 320 ℃.
3. The product is especially suitable for PVC materials, and is widely used in industries of halogen-free plastics, rubber, paint, textile and the like, and the product is applicable to the following materials: polyvinyl chloride, unsaturated polyester, polyurethane, epoxy resin, ABS resin, polycarbonate, polyethylene, polypropylene, and the like.
4. The product has no toxicity, mildew resistance and sterilization, constantly generates trace zinc ions and borate ions, can naturally generate mildew resistance and sterilization performance on the surface of materials, is widely used for home decoration materials in Europe and America, and is particularly suitable for humid environments.
5. The transparency is similar to that of plastic in refractive index, so that the flame retardant can be used for flame retardance of transparent plastic.
The nano zinc borate prepared by the invention is a novel inorganic material and has very wide application. Especially, the alkaline earth metal borate has excellent tribological performance, has good application prospect as a lubricating oil additive, is limited due to poor solubility and dispersibility of the borate in oil, and the nano-powder has good dispersibility in the oil, so that the application limit of the borate in the lubricating oil additive can be broken through by using the nano-zinc borate particles in a lubricating system.
The superfine nano zinc borate particle has great activity, is compounded with other natural flux material to form eutectic mixture easily, and this can lower the burning temperature of raw glaze material and react with silicate to form microcrystal glass with amorphous phase favorable to raising the strength of ceramic.
Drawings
FIG. 1 is a flow chart of a preparation method of nano zinc borate;
FIG. 2 is a particle size distribution curve diagram for the nano zinc borate prepared by the method;
Detailed Description
The invention is further described below with reference to examples:
example 1: respectively weighing 3.24Kg of borax, 3.24Kg of zinc sulfate and 0.0324Kg of zinc oxide, mixing, adding 4.56Kg of water and 0.15Kg of N-propyltrimethoxysilane, preparing into a liquid state, transferring into a closed container, reacting at 80 ℃ for 3 hours, keeping the concentration of boric acid at 0.6mol/l during the reaction, cooling to room temperature, taking out the reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product. As shown in the flow chart of the attached figure 1, the mother liquor of sodium sulfate in the last production process is returned to the synthesis reactor to react with newly added zinc sulfate, borax and zinc oxide. And after the reaction is completed, standing for half an hour, filtering while the solution is hot, and feeding the obtained nano zinc borate into a drying oven to obtain a finished product. And (4) feeding the mother liquor into an evaporator, evaporating to saturation points of sodium sulfate and boric acid, and separating out sodium sulfate crystals to be sold as a byproduct. The sodium sulfate mother liquor is returned to the synthesis reactor for synthesis again.
Both washings are returned to the synthesis reactor with the sodium sulfate mother liquor for reuse as a source of make-up water.
Example 2:
respectively weighing 7.00Kg of borax, 5.00Kg of zinc sulfate and 0.08Kg of zinc oxide, mixing, adding 7.5Kg of water and 0.12 KgN-propyl trimethoxy silane, preparing into a liquid state, transferring into a closed container, reacting for 3 hours at 100 ℃, keeping the concentration of boric acid at 0.3mol/l during the reaction process, cooling to room temperature, taking out the reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product.
Example 3:
respectively weighing 1.0Kg of borax, 5.0Kg of zinc sulfate and 0.08Kg of zinc oxide, mixing, adding 1.82Kg of water and 0.12 KgN-propyltriethoxysilane, preparing into a liquid state, transferring into a closed container, reacting for 5 hours at 100 ℃, keeping the concentration of boric acid at 0.4mol/l during the reaction process, cooling to room temperature, taking out a reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product.
Example 4:
respectively weighing 1.00Kg of borax, 5.00Kg of zinc sulfate and 0.01Kg of zinc oxide, mixing, adding 3.00Kg of water and 0.06 KgN-propyltriethoxysilane, preparing into a liquid state, transferring into a closed container, reacting for 5 hours at 90 ℃, keeping the concentration of boric acid at 0.35mol/l during the reaction process, cooling to room temperature, taking out the reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product.
Example 5:
respectively weighing 70.00Kg of borax, 10.00Kg of zinc sulfate and 0.10Kg of zinc oxide, mixing, adding 8.00Kg of water and 0.008Kg of N-octyltriethoxysilane, preparing into a liquid state, transferring into a closed container, reacting at 90 ℃ for 3 hours, keeping the concentration of boric acid at 0.45mol/l during the reaction process, cooling to room temperature, taking out the reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product.
Example 6:
respectively weighing 70.00Kg of borax, 10.00Kg of zinc sulfate and 0.80Kg of zinc oxide, mixing, adding 16.00Kg of water and 0.04 KgN-propyl trimethoxy silane, preparing into a flow state, transferring into a closed container, reacting for 3 hours at 100 ℃, keeping the concentration of boric acid at 0.42mol/l during the reaction, keeping the concentration of boric acid at 0.50mol/l during the reaction, cooling to room temperature, taking out the reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product.
Example 7:
respectively weighing 70.00Kg of borax, 50.00Kg of zinc sulfate and 0.10Kg of zinc oxide, mixing, adding 50.00Kg of water and 0.28Kg of N-propyltriethoxysilane, preparing into a liquid state, transferring into a closed container, reacting for 5 hours at 100 ℃, keeping the concentration of boric acid at 0.38mol/l during the reaction process, cooling to room temperature, taking out the reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product.
Example 8:
respectively weighing 100.00Kg of borax, 100.00Kg of zinc sulfate and 0.80Kg of zinc oxide, mixing, adding 20.00Kg of water and 3.00Kg of N-propyltriethoxysilane, preparing into a liquid state, transferring into a closed container, reacting for 5 hours at 90 ℃, keeping the concentration of boric acid at 0.46mol/l during the reaction process, cooling to room temperature, taking out the reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product.
Example 9:
respectively weighing 70.00Kg of borax, 50.00Kg of zinc sulfate and 0.80Kg of zinc oxide, mixing, adding 40.00Kg of water and 0.6Kg of zirconium oxychloride, preparing into a flow modification, transferring into a closed container, reacting at 90 ℃ for 3 hours, keeping the concentration of boric acid at 0.55mol/l during the reaction process, cooling to room temperature, taking out the reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product.
Example 10:
respectively weighing 30.00Kg of borax, 30.00Kg of zinc sulfate and 0.60Kg of zinc oxide, mixing, adding 36.00Kg of water and 1.2Kg of zirconium oxychloride, preparing into a flow modification, transferring into a closed container, reacting at 90 ℃ for 3 hours, keeping the concentration of boric acid at 0.53mol/l during the reaction, cooling to room temperature, taking out the reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product.
Example 11:
respectively weighing 20.00Kg of borax, 40.00Kg of zinc sulfate and 0.30Kg of zinc oxide, mixing, adding 12.00Kg of water and 0.048Kg of zirconium oxychloride, preparing into a flow state, transferring into a closed container, reacting at 90 ℃ for 3 hours, keeping the concentration of boric acid at 0.43mol/l during the reaction process, cooling to room temperature, taking out the reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product.
Example 12:
respectively weighing 30.00Kg of borax, 40.00Kg of zinc sulfate and 0.20Kg of zinc oxide, mixing, adding 48.00Kg of water and 2.1Kg of zirconium oxychloride, preparing into a flow modification, transferring into a closed container, reacting at 90 ℃ for 3 hours, keeping the concentration of boric acid at 0.80mol/l during the reaction process, cooling to room temperature, taking out the reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product.
Example 13:
respectively weighing 40.00Kg of borax, 30.00Kg of zinc sulfate and 0.70Kg of zinc oxide, mixing, adding 20.00Kg of water and 2.1Kg of zirconium oxychloride, preparing into a flow modification, transferring into a closed container, reacting at 90 ℃ for 3 hours, keeping the concentration of boric acid at 0.32mol/l during the reaction process, cooling to room temperature, taking out the reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product.
Example 14:
respectively weighing 20.00Kg of borax, 20.00Kg of zinc sulfate and 0.80Kg of zinc oxide, mixing, adding 20.00Kg of water and 1.2Kg of zirconium oxychloride, preparing into a flow modification, transferring into a closed container, reacting at 90 ℃ for 3 hours, keeping the concentration of boric acid at 0.25mol/l during the reaction process, cooling to room temperature, taking out the reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product.
Example 15:
respectively weighing 10.00Kg of borax, 10.00Kg of zinc sulfate and 0.60Kg of zinc oxide, mixing, adding 14.00Kg of water and 0.6Kg of zirconium oxychloride, preparing into a flow modification, transferring into a closed container, reacting at 90 ℃ for 3 hours, keeping the concentration of boric acid at 0.2mol/l during the reaction process, cooling to room temperature, taking out the reaction product, filtering, and drying at 120-140 ℃ to obtain the required nano zinc borate product.
In the above embodiment, the purpose of the present invention can be achieved by using zirconium oxychloride and a silane surfactant as the surfactant.
The particle size of the material prepared by the method is tested by a physical and chemical analysis test center in Beijing, and the used instrument is a NOVAE particle size analyzer of Congta company in America, and the test range is more than or equal to 3.5-2000 Å (particle size).
As shown in the attached figure 2 of the specification, according to pore test data, the average pore diameter of the nano zinc borate is 11.7nm, the highest peak of the pore diameter is about 10 nm, the size of most pore diameters is less than 50nm, and all the pore diameters in the test range are within 80 nm.
The above-mentioned embodiments are only for illustrating the present invention and do not limit the scope of the claims, and other alternative means that may be conceived by those skilled in the art are within the scope of the claims.
Claims (7)
1. The method for preparing the nano zinc borate is characterized by comprising the following steps of:
A. uniformly mixing borax, zinc sulfate and zinc oxide in a weight ratio of 1-7: 1-5: 0.01-0.08;
B. adding water according to 5.0-70% of the total weight of borax, zinc sulfate and zinc oxide, and stirring to form a flow state;
C. adding a surfactant into the product obtained in the step B, and keeping the temperature at 60-100 ℃ for 3-5 hours;
D. and D, cooling the product obtained in the step C to 20-30 ℃, filtering, washing with water, and drying at 120-140 ℃.
2. The method for preparing nano barium borate according to claim 1, wherein the weight ratio of borax, zinc sulfate and zinc oxide is 2-5: 2-4: 0.02-0.06.
3. The method for preparing nano barium borate according to claim 2, wherein the weight ratio of borax, zinc sulfate and zinc oxide is 3-4: 2.5-3.5: 0.03-0.05.
4. The method for preparing nano barium borate according to claim 1, wherein the surfactant is selected from one or two of a zirconium-containing surfactant and a silane surfactant.
5. The method for preparing nano barium borate according to claim 1, wherein the surfactant is used in an amount of 0.01-3% by weight of borax, zinc sulfate and zinc oxide.
6. The method for preparing nano zinc borate according to any one of claims 1 to 5, wherein the boric acid concentration in the reaction mixture is maintained at 0.2 to 0.8mol/l during the reaction.
7. The method for preparing nano zinc borate according to claim 6, characterized in that boric acid is added to the reaction mixture to maintain the concentration of boric acid in the solution at 0.3 to 0.6 mol/l.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659132A (en) * | 2012-04-26 | 2012-09-12 | 北京石油化工学院 | Method for preparing nano flaky zinc borate powder |
| CN104609437A (en) * | 2015-02-03 | 2015-05-13 | 中国科学院过程工程研究所 | Preparation method of superfine 2335 zinc borate fire retardant |
| CN105482161A (en) * | 2015-12-07 | 2016-04-13 | 重庆太岳新材料科技有限公司 | Production process of nano zinc calcium cyanurate |
| CN107673364A (en) * | 2017-10-13 | 2018-02-09 | 济南泰星精细化工有限公司 | A kind of preparation method of 2335 zinc borate flame retardant |
| CN111004663A (en) * | 2019-11-26 | 2020-04-14 | 杨俭英 | Novel borate additive and grease composition containing the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321060C (en) * | 2004-09-30 | 2007-06-13 | 武汉大学 | Preparation method for zinc borate |
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2006
- 2006-07-07 CN CNB2006100287242A patent/CN100398441C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659132A (en) * | 2012-04-26 | 2012-09-12 | 北京石油化工学院 | Method for preparing nano flaky zinc borate powder |
| CN102659132B (en) * | 2012-04-26 | 2015-05-13 | 北京石油化工学院 | Method for preparing nano flaky zinc borate powder |
| CN104609437A (en) * | 2015-02-03 | 2015-05-13 | 中国科学院过程工程研究所 | Preparation method of superfine 2335 zinc borate fire retardant |
| CN105482161A (en) * | 2015-12-07 | 2016-04-13 | 重庆太岳新材料科技有限公司 | Production process of nano zinc calcium cyanurate |
| CN105482161B (en) * | 2015-12-07 | 2018-08-17 | 重庆太岳新材料科技有限公司 | A kind of production technology of nanoscale cyanuric acid zinc calcium |
| CN107673364A (en) * | 2017-10-13 | 2018-02-09 | 济南泰星精细化工有限公司 | A kind of preparation method of 2335 zinc borate flame retardant |
| CN111004663A (en) * | 2019-11-26 | 2020-04-14 | 杨俭英 | Novel borate additive and grease composition containing the same |
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