阅读说明：本技术 用于氯硅烷除杂的吸附树脂及其制备方法 (Adsorption resin for impurity removal of chlorosilane and preparation method thereof ) 是由 曹玲玲 宗冰 鲍守珍 蔡延国 于 2021-06-10 设计创作，主要内容包括：本申请提供一种用于氯硅烷除杂的吸附树脂及其制备方法,涉及高分子材料技术领域。用于氯硅烷除杂的吸附树脂的制备方法包括：将氯球在有机溶剂中进行溶胀后与反应物进行反应,得到初始产物；反应物含有多胺,初始产物含有叔胺；将初始产物与优化试剂进行反应以使得叔胺转化为仲胺,得到吸附树脂。该制备方法制得的吸附树脂中,叔胺已转化为仲胺,从而能够抑制氯硅烷的歧化效应。(The application provides an adsorption resin for impurity removal of chlorosilane and a preparation method thereof, and relates to the technical field of high polymer materials. The preparation method of the adsorption resin for impurity removal of chlorosilane comprises the following steps: swelling chlorine spheres in an organic solvent, and reacting with reactants to obtain an initial product; the reactants comprise polyamine and the initial product comprises tertiary amine; the initial product is reacted with an optimizing reagent to convert the tertiary amine to a secondary amine, resulting in the adsorption resin. In the adsorption resin prepared by the preparation method, tertiary amine is converted into secondary amine, so that the disproportionation effect of chlorosilane can be inhibited.)

1. A preparation method of adsorption resin for impurity removal of chlorosilane is characterized by comprising the following steps:

swelling chlorine spheres in an organic solvent, and reacting with reactants to obtain an initial product; the reactants comprise a polyamine and the initial product comprises a tertiary amine;

reacting the initial product with an optimizing reagent to convert the tertiary amine to a secondary amine to yield the adsorbent resin.

2. The method for preparing the adsorption resin for impurity removal of chlorosilane as claimed in claim 1, wherein the optimizing reagent comprises a potassium permanganate solution or an iodine solution.

3. The preparation method of the adsorption resin for impurity removal of chlorosilane as claimed in claim 2, wherein the concentration of the potassium permanganate solution is 0.1-3 wt%.

4. The method for preparing the adsorption resin for removing impurities from chlorosilane as claimed in any one of claims 1 to 3, wherein the reactant comprises at least one of diethylenetriamine and triethylenetetramine.

5. The method for preparing the adsorption resin for removing impurities from chlorosilane as claimed in any one of claims 1 to 3, wherein the reactant is diethylenetriamine.

6. The preparation method of the adsorption resin for impurity removal of chlorosilane as claimed in any one of claims 1 to 3, wherein the mass ratio of the reactant to the chlorine balls is 100: 5-20.

7. The preparation method of the adsorption resin for impurity removal of chlorosilane as claimed in claim 6, wherein the mass ratio of the reactant to the chlorine balls is 100: 5-10.

8. The method for preparing the adsorption resin for removing impurities from chlorosilane as claimed in any one of claims 1 to 3, wherein the temperature of the reaction between the swelled chlorine balls and the reactant is 70-120 ℃.

9. The method for preparing the adsorption resin for removing the chlorosilane as claimed in any one of claims 1 to 3, wherein the organic solvent comprises any one of toluene, tetrahydrofuran and 1, 2-dichloroethylene.

10. An adsorption resin for impurity removal of chlorosilane, which is prepared by the preparation method of the adsorption resin for impurity removal of chlorosilane as claimed in any one of claims 1 to 9.

Technical Field

The application relates to the technical field of high polymer materials, in particular to an adsorption resin for impurity removal of chlorosilane and a preparation method thereof.

Background

With the rapid development of electronic information and solar photovoltaic industries, the market demand for polysilicon is increasing. The trichlorosilane hydrogen reduction process is a main method for producing polycrystalline silicon, wherein the purity of chlorosilane used determines the quality of the polycrystalline silicon, and impurities in the chlorosilane comprise metal chloride, boron-phosphorus-containing chloride, hydride, metal compounds and the like. The adsorption method for removing impurities is a research hotspot in recent years, and the effective adsorption component of adsorption impurity removal resin commonly adopted in chlorosilane is amino. However, in the research of the applicant, if the amine group in the adsorption resin is a tertiary amine group, the tertiary amine group can perform a disproportionation reaction with chlorosilane, so that the purity of chlorosilane is reduced, the production cost is increased, and particularly for industrial production of high-purity trichlorosilane, if the adsorption resin performs a disproportionation reaction with chlorosilane, a large amount of by-products are generated in the production process, and further purification is required in the production process.

Disclosure of Invention

The embodiment of the application aims to provide the adsorption resin for impurity removal of chlorosilane and the preparation method thereof.

The embodiment of the application is realized as follows:

the embodiment of the application provides a preparation method of adsorption resin for impurity removal of chlorosilane, which comprises the following steps:

swelling chlorine spheres in an organic solvent, and reacting with reactants to obtain an initial product; the reactants comprise polyamine and the initial product comprises tertiary amine;

the initial product is reacted with an optimizing reagent to convert the tertiary amine to a secondary amine, resulting in the adsorption resin.

The embodiment of the application also provides an adsorption resin for impurity removal of chlorosilane, which is prepared by the preparation method of the adsorption resin for impurity removal of chlorosilane.

The adsorption resin for impurity removal of chlorosilane and the preparation method thereof provided by the embodiment of the application at least have the following beneficial effects:

the chlorine ball and the reactant containing polyamine are subjected to crosslinking reaction to obtain an initial product, and the compound modification of the polyamine is introduced on the chlorine ball. The initial product obtained by the reaction contains tertiary amine, the tertiary amine reacts with the optimizing reagent to be converted into secondary amine, and finally the obtained adsorption resin can inhibit the disproportionation effect of chlorosilane. Experimental results show that the adsorption resin prepared by the method is high in adsorption capacity, and the disproportionation effect of chlorosilane can be remarkably reduced.

Detailed Description

Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The effective adsorption component of the adsorption impurity removal resin commonly adopted in chlorosilane is amino. However, in the research of the applicant, if the amine group in the adsorption resin is a tertiary amine group, the tertiary amine group can perform a disproportionation reaction with chlorosilane, so that the purity of chlorosilane is reduced, the production cost is increased, and particularly for industrial production of high-purity trichlorosilane, if the adsorption resin performs a disproportionation reaction with chlorosilane, a large amount of by-products are generated in the production process, and further purification is required in the production process.

The embodiment of the application provides an adsorption resin for impurity removal of chlorosilane and a preparation method thereof.

The following description is made specifically for the adsorption resin for impurity removal of chlorosilane and the preparation method thereof in the embodiments of the present application:

the embodiment of the application provides a preparation method of adsorption resin for impurity removal of chlorosilane, which comprises the following steps:

swelling chlorine spheres in an organic solvent, and reacting with reactants to obtain an initial product; the reactants contain a polyamine and the initial product contains a tertiary amine.

Illustratively, the chlorine spheres are chloromethylated polystyrene microspheres. Alternatively, the organic solvent includes any one of toluene, tetrahydrofuran, and 1, 2-dichloroethylene. The chloromethylated polystyrene microsphere can well swell in solution of toluene tetrahydrofuran or 1, 2-dichloroethylene.

After the chlorine spheres swell in the organic solvent, the chlorine spheres can generate a crosslinking reaction with a reactant containing polyamine, and polyamine compound modification is introduced to the chlorine spheres. In addition, the initial resin may be present in the initial product, and a certain side reaction may occur, and the product of the side reaction may contain a tertiary amine.

In some embodiments, the chlorine spheres are placed in toluene to swell, and then reactants are added to react with the swollen chlorine spheres. Optionally, the temperature condition of the reaction is 70-120 ℃, for example, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃. In other embodiments, the swollen chlorine spheres may be filtered from toluene and then mixed with the reactants to perform the crosslinking reaction.

Optionally, the reactant includes at least one of diethylenetriamine and triethylenetetramine. That is, the reactant may be diethylenetriamine, triethylenetetramine, or a combination of diethylenetriamine and triethylenetetramine.

Taking diethylenetriamine as an example of the reactant, chloromethylated polystyrene undergoes a crosslinking reaction with diethylenetriamine after swelling, and the obtained product comprises initial resin and side reaction resin, and the reaction mechanism is as follows:

whereinThe structural formula of the initial resin isThe structural formula of the side reaction resin isThe side reaction resin contains tertiary amine.

Furthermore, the mass ratio of the reactants to the chlorine balls is 100: 5-20.

Through research by the inventors of the present application, it is found that the reaction of the reactants and the chlorine spheres in the weight ratio can achieve a high degree of crosslinking reaction between the chlorine spheres and the reactants. Illustratively, the mass ratio of reactants to chlorine spheres is 20:1, 25:2, 10:1, 20:3, 50:9, or 5: 1. Further optionally, the mass ratio of the reactants to the chlorine balls is 100: 5-10.

(2) The initial product is reacted with an optimizing reagent to convert the tertiary amine to a secondary amine, resulting in the adsorption resin.

The initial product contains tertiary amine which reacts with the optimizing reagent to be converted into secondary amine, so that the finally obtained adsorption resin can inhibit the disproportionation effect of chlorosilane.

Optionally, the optimizing agent comprises a potassium permanganate solution or an iodine solution, the reaction of which with the initial product is capable of converting the tertiary amine in the initial product to a secondary amine.

Taking the reactant selected from diethylenetriamine and chloromethylated polystyrene as an example, the structural formula of the side reaction resin is shown in the specificationThe side reaction resin contains tertiary amine, and the reaction mechanism of the potassium permanganate and the side reaction resin is as follows:

the potassium permanganate can effectively convert the tertiary amine into secondary amine, and the probability of the disproportionation reaction between the finally obtained adsorption resin and chlorosilane is greatly reduced.

Optionally, the concentration of the potassium permanganate solution is 0.1 to 3 wt%, such as 0.1 wt%, 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, or 3 wt%.

The embodiment of the application also provides an adsorption resin for impurity removal of chlorosilane, which is prepared by the preparation method of the adsorption resin for impurity removal of chlorosilane.

In the adsorption resin, tertiary amine is converted into secondary amine, so that the probability of disproportionation reaction with chlorosilane can be greatly reduced.

The characteristics and properties of the adsorption resin for impurity removal of chlorosilane and the preparation method thereof according to the present application are further described in detail with reference to the following examples.

Example 1

The embodiment provides a preparation method of adsorption resin for impurity removal of chlorosilane, which comprises the following steps:

swelling chloromethylated polystyrene microspheres in toluene, adding diethylenetriamine, reacting for 4h at the temperature of 90 ℃ to obtain a solution containing an initial product, filtering to obtain a filtrate, alternately washing the filtrate with water and ethanol to neutrality, and drying in vacuum to constant weight to obtain the initial product. Wherein the mass ratio of the chloromethylated polystyrene microspheres to the diethylenetriamine is 1: 12.

Mixing the initial product with 0.5 wt% potassium permanganate solution, stirring and refluxing at 30 deg.C for 2 hr to obtain adsorbent resin, cooling, washing to neutrality, and vacuum drying at 80 deg.C. Wherein the ratio of the potassium permanganate solution to the initial product is 10mL:1 g.

Example 2

The embodiment provides a preparation method of adsorption resin for impurity removal of chlorosilane, which comprises the following steps:

swelling chloromethylated polystyrene microspheres in toluene, adding triethylene tetramine, reacting for 5 hours at the temperature of 120 ℃ to obtain a solution containing an initial product, filtering to obtain a filtrate, alternately washing the filtrate with water and ethanol to neutrality, and drying in vacuum to constant weight to obtain the initial product. Wherein the mass ratio of the chloromethylated polystyrene microspheres to the triethylene tetramine is 1: 14.4.

Mixing the initial product with a potassium permanganate solution with the concentration of 1.0 wt%, stirring and refluxing at the temperature of 60 ℃ for 4 hours to react to obtain adsorption resin, cooling, washing to be neutral, and drying in vacuum at 80 ℃. Wherein the ratio of the potassium permanganate solution to the initial product is 10mL:1 g.

Example 3

The embodiment provides a preparation method of adsorption resin for impurity removal of chlorosilane, which comprises the following steps:

swelling chloromethylated polystyrene microspheres in toluene, adding diethylenetriamine, reacting for 3h at the temperature of 100 ℃ to obtain a solution containing an initial product, filtering to obtain a filtrate, alternately washing the filtrate with water and ethanol to neutrality, and drying in vacuum to constant weight to obtain the initial product. Wherein the mass ratio of the chloromethylated polystyrene microspheres to the diethylenetriamine is 1: 16.

Mixing the initial product with 0.5 wt% iodine solution, stirring and refluxing at 40 deg.C for 2 hr to obtain adsorbent resin, cooling, washing to neutrality, and vacuum drying at 70 deg.C. Wherein the ratio of the iodine solution to the initial product is 10mL to 1 g.

Examples of the experiments

The initial product after vacuum drying and the adsorption resin after vacuum drying of examples 1 to 3 were respectively used to adsorb and remove impurities from trichlorosilane containing impurities, and the boron adsorption rates of the initial product and the adsorption resin and the disproportionation rate of trichlorosilane were tested, and the specific results are recorded in table 1. It should be noted that the initial product and the trichlorosilane acted on the adsorption resin are the same in each example.

B, detecting the boron adsorption rate and the disproportionation rate: weighing 2g of the adsorption resin of the embodiment 1, the embodiment 2 and the embodiment 3, respectively adding the adsorption resin into a PFA bottle filled with 20mL of the same trichlorosilane, soaking and standing for 1h, filtering, respectively detecting the boron impurity content of the original sample and the filtered sample by adopting ICP-OES, calculating the adsorption rate, detecting the component content of the original sample and the filtered sample by adopting a gas chromatograph, and calculating the disproportionation rate, wherein the results are shown in Table 1.

TABLE 1 boron adsorption and disproportionation Effect

As can be seen from the results of Table 1, the adsorption resin of each example had a higher boron adsorption rate than the initial product of the corresponding example, and the disproportionation rate of trichlorosilane was decreased. The adsorption resin prepared in the embodiment of the application has strong adsorption capacity, and can obviously reduce the disproportionation rate of trichlorosilane.

The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.