阅读说明：本技术 一种立方体羟基锡酸锌及其制备方法 (Cubic zinc hydroxystannate and preparation method thereof ) 是由 胡艳丽 谢德龙 谢于辉 吴华 梅毅 于 2021-09-17 设计创作，主要内容包括：本发明公开一种立方体羟基锡酸锌,其具有边长为70-120nm之间的正立方体结构。本发明还公开所述立方体羟基锡酸锌的制备方法,且是由锡酸钠与硫酸锌以锡酸根与锌离子按1:1的比例在4-6℃下反应3-8小时制成。本发明的有益效果是：采用的低温结晶法方法制备,结构均一可控,尺寸一致,纯度高,未引入其他杂质；尺寸更小,具有边长为70-120nm之间的正立方体结构,无卤无毒,协效阻燃抑烟效果更好；制备简单,成本低,便于操作。(The invention discloses cubic zinc hydroxystannate, which has a cubic structure with the side length of 70-120 nm. The invention also discloses a preparation method of the cubic zinc hydroxystannate, and the cubic zinc hydroxystannate is prepared by reacting sodium stannate and zinc sulfate according to a ratio of stannate radical to zinc ion of 1:1 at 4-6 ℃ for 3-8 hours. The invention has the beneficial effects that: the low-temperature crystallization method is adopted for preparation, the structure is uniform and controllable, the size is consistent, the purity is high, and other impurities are not introduced; the size is smaller, the flame-retardant smoke-suppressant material has a cubic structure with the side length of 70-120nm, is halogen-free and non-toxic, and has better synergistic flame-retardant and smoke-suppressant effects; simple preparation, low cost and convenient operation.)

1. A cubic zinc hydroxystannate is characterized in that the cubic zinc hydroxystannate has a cubic structure with side length of 70-120 nm.

2. A cubic zinc hydroxystannate as claimed in claim 1, which is prepared by reacting sodium stannate with zinc sulfate at a ratio of stannate to zinc ion of 1:1 at 4-6 deg.C for 3-8 hours.

3. A preparation method of zinc hydroxystannate with a cubic structure is characterized by comprising the following steps:

s1, preparing a zinc sulfate solution;

s2, preparing a sodium stannate solution;

s3, putting the zinc sulfate solution into a container;

s4, adjusting the temperature in the container to 4-6 ℃, and stirring;

s5, adding the sodium stannate solution into the container, and reacting for 3-8 h;

s6, after the reaction is finished, centrifugally separating, and washing and precipitating.

4. The method for preparing zinc hydroxystannate having a cubic structure as claimed in claim 3, wherein the concentration of zinc sulfate solution in the step of S1 is 0.01 mol/L.

5. The method for preparing zinc hydroxystannate having a cubic structure as claimed in claim 4, wherein the concentration of the sodium stannate solution in the step S2 is 0.05 mol/L.

6. The method for preparing zinc hydroxystannate having a cubic structure according to claim 3, wherein the temperature in the step S4 is constantly 5 ℃.

7. The method as claimed in claim 3, wherein the stirring speed in step S4 is 930-980 RPM.

8. The method of claim 5, wherein the volume of the sodium stannate solution is 1/2 of the zinc sulfate solution in the step S5.

9. The method for preparing zinc hydroxystannate with a cubic structure as claimed in claim 3, wherein the reaction time in step S5 is 5 h.

10. The method for preparing zinc hydroxystannate with a cubic structure as claimed in claim 3, wherein the ratio of stannate to zinc ion in step S5 is 1: 1.

Technical Field

The invention relates to the technical field of flame-retardant materials, in particular to cubic zinc hydroxystannate and a preparation method thereof.

Background

With the rapid development of synthetic polymer materials, the polymer materials are generally applied to the life of people; however, most of the high polymer materials are flammable, the limiting oxygen index is more than 21%, and some high polymer materials with low oxygen index are extremely easy to burn and cause fire due to poor self-extinguishing property. Meanwhile, a large amount of toxic gas and smoke are generated in the combustion process, and serious threat is caused to the life of people. Therefore, the problem of flame retardance is more and more emphasized by countries all over the world.

The high-efficiency flame retardant mainly used at present is a halogen flame retardant, but the halogen flame retardant cannot meet the requirements of the market on the performance of the halogen flame retardant, and can generate toxic gas. Therefore, the development of environment-friendly, safe and efficient flame retardants mainly comprises tin flame retardants, phosphorus flame retardants, nano flame retardants, and the like.

The zinc hydroxystannate is always applied to the flame-retardant smoke inhibitor, and has the advantages of no halogen, no toxicity, small dosage, smoke inhibition, green environmental protection compared with the traditional halogen-series and antimony-series flame retardants, but the flame-retardant property of the zinc hydroxystannate needs to be improved. In the prior literature, the preparation of cubic zinc hydroxystannate with uniform appearance and size by a low-temperature crystallization method is not seen before.

Disclosure of Invention

The invention aims to provide zinc hydroxystannate with a cubic structure, which has the advantages of uniform and controllable appearance and size, high purity, no introduction of other alkaline impurities and simple synthesis process, aiming at the defects of the prior art.

The invention also aims to provide a preparation method of zinc hydroxystannate with a cubic structure, which has low reaction temperature and simple synthesis process.

In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a cubic zinc hydroxystannate has a cubic structure with side lengths of 70-120 nm. The zinc hydroxystannate has high purity, does not introduce other impurities, is halogen-free and non-toxic, and has better flame retardant and smoke suppression effects compared with the common zinc hydroxystannate.

The cubic zinc hydroxystannate is prepared by reacting sodium stannate and zinc sulfate at a ratio of stannate radical to zinc ion of 1:1 at 4-6 ℃ for 3-8 hours.

A preparation method of zinc hydroxystannate with a cubic structure comprises the following steps:

s1, preparing a zinc sulfate solution;

s2, preparing a sodium stannate solution;

s3, putting the zinc sulfate solution into a container;

s4, adjusting the temperature in the container to 4-6 ℃, and stirring;

s5, adding the sodium stannate solution into the container, and reacting for 3-8 h;

s6, after the reaction is finished, centrifugally separating, washing and precipitating to obtain a product which is a zinc hydroxystannate cube and has a cubic structure with the side length of 70-120 nm.

Preferably, in the step S1, the concentration of the zinc sulfate solution is 0.01 mol/L.

Preferably, in the step S2, the concentration of the sodium stannate solution is 0.05mol/L

Preferably, in the step S4, the temperature is constantly 5 ℃.

Preferably, in the step S4, the stirring speed is 930-980 RPM.

Preferably, in the step S5, the volume of the sodium stannate solution is 1/2 of the zinc sulfate solution, so that impurities can be reduced and higher yield can be obtained.

Preferably, in the step S5, the reaction time is 5 hours.

Preferably, in the step S5, the ratio of stannate to zinc ions is 1: 1.

Compared with the prior art, the invention has the beneficial effects that: the low-temperature crystallization method is adopted for preparation, the structure is uniform and controllable, the size is consistent, the purity is high, and other impurities are not introduced; the size is smaller, the flame-retardant smoke-suppressant material has a cubic structure with the side length of 70-120nm, is halogen-free and non-toxic, and has better synergistic flame-retardant and smoke-suppressant effects; simple preparation, low cost and convenient operation.

Drawings

FIG. 1 is a scanning electron microscope image of a cubic zinc hydroxystannate sample prepared in example 2 of the present invention;

FIG. 2 is an X-ray diffraction analysis chart of a cubic zinc hydroxystannate sample prepared in example 2 of the present invention.

Detailed Description

The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.

A cubic zinc hydroxystannate is prepared from sodium stannate and zinc sulfate through reaction at 4-6 deg.C for 3-8 hr in the ratio of stannate radical to zinc ion of 1:1, and features cubic structure with side length of 70-120nm, no impurities, no halogen and poison, and better flame-retarding and smoke-suppressing effect.

Example 1

A preparation method of cubic zinc hydroxystannate comprises the following steps:

s1, preparing a zinc sulfate solution with the concentration of 0.01 mol/L;

s2, preparing a sodium stannate solution with the concentration of 0.05 mol/L;

s3, placing 100ml of the zinc sulfate solution into a three-neck flask;

s4, placing the three-neck flask into a low-temperature constant-temperature tank, adjusting the temperature to 4 ℃, and stirring by adopting magnetic force at the rotating speed of 930 RPM;

s5, 50ml of sodium stannate solution is added into the three-neck flask, and the reaction is carried out for 3h at the rotation speed of 930RPM by keeping the temperature at 5 ℃.

S6, after the reaction is finished, centrifugally separating, washing and precipitating to obtain a product, namely a zinc hydroxystannate cube.

Example 2

A preparation method of cubic zinc hydroxystannate comprises the following steps:

s1, preparing a zinc sulfate solution with the concentration of 0.01 mol/L;

s2, preparing a sodium stannate solution with the concentration of 0.05 mol/L;

s3, placing the zinc sulfate solution into a container;

s4, adjusting the temperature in the container to 5 ℃, and stirring at the rotation speed of 950 RPM;

s5, adding the sodium stannate solution into the container while stirring, wherein the addition amount of the sodium stannate solution is one half of that of the zinc sulfate solution, and reacting for 5 hours at the temperature of 5 ℃.

S6, after the reaction is finished, centrifugally separating, washing and precipitating to obtain a product, namely a zinc hydroxystannate cube.

Example 3

A preparation method of cubic zinc hydroxystannate comprises the following steps:

s1, preparing a zinc sulfate solution with the concentration of 0.01 mol/L;

s2, preparing a sodium stannate solution with the concentration of 0.05 mol/L;

s3, placing 100L of the zinc sulfate solution into a container;

s4, adjusting the temperature in the container to 6 ℃, and stirring at the rotating speed of 970 RPM;

s5, 50L of sodium stannate solution is added into the container, and the temperature of 6 ℃ is kept for reaction for 8 h.

S6, after the reaction is finished, centrifugally separating, washing and precipitating to obtain a product, namely a zinc hydroxystannate cube.

The sample prepared in the embodiment 2 is detected by a scanning electron microscope, and the detected result is shown in fig. 1, and it can be seen from the figure that the sample prepared in the embodiment has a cubic structure with the size of 70-120nm, and the size and the appearance are uniform. The sample prepared in example 2 was analyzed by X-ray diffraction, and the measured spectrum is shown in fig. 2, which shows that the X-ray diffraction peak coincides with the standard peak of zinc hydroxystannate, and the crystallinity is high. Other embodiments pass the above test, and the results are also described above.

The above embodiments are only some of the embodiments of the present invention, and the embodiments are not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present invention are covered by the scope of the present invention claimed in the claims.