阅读说明：本技术 一种醇锆盐螯合物及其制备方法 (Zirconium alkoxide chelate and preparation method thereof ) 是由 刘丽 姜警 黄玉东 苑雪玉 吴谦 关胜杰 于 2020-07-23 设计创作，主要内容包括：一种醇锆盐螯合物及其制备方法,属于有机金属化合物稳定性处理研究技术领域。本发明的目的是为了进一步稳定延长醇锆盐在含水体系内与有机物反应杂化时凝胶现象的产生,所述方法为：按照醇锆盐：螯合剂：乙醇＝1：0～6：1～100的物质的量比称取原料；先将醇锆盐与乙醇在20℃～75℃下搅拌混合均匀；在搅拌作用下,按照10～100滴/分的速率逐滴滴加螯合剂；滴加完螯合剂后,继续搅拌10min～10h,即得到醇锆盐螯合物。本发明可以有效地将醇锆盐的高活性降低下来,使其可以在含水体系下与有机物发生进一步反应而不会迅速凝胶。本发明采用的技术方案适用于工业大规模配制稳定的醇锆盐螯合物,可以长期贮存运输。(A zirconium alkoxide chelate and a preparation method thereof, belonging to the technical field of organic metal compound stability treatment research. The invention aims to further stabilize and prolong the generation of gel phenomenon when zirconium alkoxide reacts and hybridizes with organic matters in an aqueous system, and the method comprises the following steps: according to the zirconium alkoxide: chelating agent: ethanol ═ 1: 0-6: weighing raw materials according to the mass ratio of 1-100; firstly, zirconium alkoxide and ethanol are stirred and mixed evenly at the temperature of 20-75 ℃; dropwise adding a chelating agent at a rate of 10-100 drops/min under the stirring action; after the chelating agent is dripped, stirring is continued for 10 min-10 h to obtain the zirconium alkoxide chelate. The invention can effectively reduce the high activity of zirconium alkoxide, so that the zirconium alkoxide can further react with organic matters in a water-containing system without rapid gelation. The technical scheme adopted by the invention is suitable for preparing stable zirconium alkoxide chelate in an industrial large scale, and can be stored and transported for a long time.)

1. A zirconium alkoxide chelate characterized by: the structural formula of the chelate is as follows:

Zr(OR)_n(X)_4-n

wherein OR is an alcohol group part of zirconium alkoxide, X is a chelate, and n is more than 0 and less than 4.

2. A zirconium alkoxide chelate according to claim 1 wherein: the alcohol group is one or more of ethanol group, propanol group, isopropanol group or butanol group.

3. A zirconium alkoxide chelate according to claim 1 wherein: the zirconium alkoxide is one or more of zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconium t-butoxide or zirconium n-amylate.

4. A method for preparing a zirconium alkoxide chelate complex as set forth in any one of claims 1 to 3, characterized in that: the method comprises the following steps:

the method comprises the following steps: according to the zirconium alkoxide: chelating agent: ethanol ═ 1: 0-6: weighing raw materials according to the mass ratio of 1-100;

step two: firstly, zirconium alkoxide and ethanol are stirred and mixed evenly at the temperature of 20-75 ℃;

step three: dropwise adding a chelating agent at a rate of 10-100 drops/min under the stirring action;

step four: after the chelating agent is dripped, stirring is continued for 10 min-10 h to obtain the zirconium alkoxide chelate.

5. The method of preparing a zirconium alkoxide chelate complex as set forth in claim 4, wherein: in the first step, the chelating agent is one or more of beta-diketone, carboxylic acid, amide, polyamine, isocyanate or polyalcohol.

6. The method of preparing a zirconium alkoxide chelate complex as set forth in claim 5, wherein: the chelating agent is acetylacetone (acacH), dibenzoylmethane (dbzmH), acetic acid (HAc), acrylic acid (HAA), N-Dimethylformamide (DMF), Ethylenediamine (EDA), diphenylmethane diisocyanate (MDI), 1, 2-propylene glycol (PDO).

7. The method of preparing a zirconium alkoxide chelate complex as set forth in claim 4, wherein: in the first step, the zirconium alkoxide: chelating agent: the mass ratio of ethanol is 1: 0-4: 1 to 20.

8. The method of preparing a zirconium alkoxide chelate complex as set forth in claim 4, wherein: in the second step, the stirring temperature is 30-70 ℃.

9. The method of preparing a zirconium alkoxide chelate complex as set forth in claim 4, wherein: in the third step, the dropping speed of the chelating agent is 30-80 drops/minute.

10. The method of preparing a zirconium alkoxide chelate complex as set forth in claim 4, wherein: in the fourth step, the stirring time is 30 min-5 h.

Technical Field

The invention belongs to the technical field of organic metal compound stability treatment research, and particularly relates to a zirconium alkoxide chelate and a preparation method thereof.

Background

The rapid development of alkoxide sol-gel method in recent 20 years has increased the use of alkoxide in organic reaction, which has promoted the research and development of alkoxide chemistry to a great extent. In recent years, with the excellent performance of titanium alkoxide in organic resin hybridization, zirconium, which is an element of the same family, has been favored by researchers. However, since the reaction between the zirconium alkoxide and water is extremely rapid, it is difficult to carry out the reaction for a long time in an aqueous system without gelation. Therefore, it is urgent to develop a treatment method of zirconium alkoxide having low toxicity and long-term stable storage.

Zirconium alkoxide is a product of combining an organic material with an inorganic metal, and has both the covalent nature of the organic material and a degree of inorganic nature of the metal. They are soluble in alcoholic solvents and exhibit a considerable degree of solubility, which allows chemical reactions between the zirconium alkoxide and the organic substance. The titanium alkoxide shows the phenomenon of hybridization reaction with organic silicon resin as early as years ago, and the early-synthesized hybrid resin is easy to gel due to the activity of titanium; in recent years, because the technology of hybridization reaction between titanium alkoxide and organic silicon resin is mature, zirconium alkoxide gradually enters researchers, but the activity of zirconium is far greater than that of titanium, so that before the reaction, the zirconium alkoxide needs to be modified to increase the stability and inhibit the gelation reaction with water.

According to the theory of hard and hard acids and bases, the principle that hard and hard, soft and unstable combination of soft and hard, zirconium salt belongs to hard acid, the chelating treatment of the zirconium salt is carried out by using hard base, common hard base contains N, O, F and other elements, and as F-containing organic matters are difficult to coordinate or chelate with zirconium, simple coordination makes a weak contribution to inhibition of hydrolysis reaction.

Disclosure of Invention

The invention aims to further stably prolong the generation of gel phenomenon when zirconium alkoxide reacts and hybridizes with organic matters in a water-containing system, and provides a low-toxicity long-term stable-storage zirconium alkoxide chelate and a preparation method thereof.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a zirconium alkoxide chelate having the formula:

Zr(OR)_n(X)_4-n

wherein OR is an alcohol group part of zirconium alkoxide, X is a chelate, and n is more than 0 and less than 4.

A preparation method of the zirconium alkoxide chelate comprises the following steps:

the method comprises the following steps: according to the zirconium alkoxide: chelating agent: ethanol ═ 1: 0-6: weighing raw materials according to the mass ratio of 1-100;

step two: firstly, zirconium alkoxide and ethanol are stirred and mixed evenly at the temperature of 20-75 ℃;

step three: dropwise adding a chelating agent at a rate of 10-100 drops/min under the stirring action;

step four: after the chelating agent is dripped, stirring is continued for 10 min-10 h to obtain the zirconium alkoxide chelate.

The solvent used in the invention is ethanol, and has low toxicity. The invention considers that the hydrolysis rate and the self-polymerization rate of the organic zirconium alkoxide are too fast, and the organic zirconium alkoxide and other organic matters are easy to generate gelation reaction in a water-containing system, so that the reaction with other organic matters is hindered. Therefore, the method adopts nontoxic reagent ethanol as a solvent, adopts a chelating agent to carry out dropwise adding chelation treatment, and then carries out continuous stirring treatment, so that the organic zirconium alkoxide can be stored for a long time without precipitation and gelation, and is convenient for further chemical reaction with other organic matters.

After titanium-containing organic matter is hybridized and applied in organic silicon resin, phenolic resin and the like, zirconium element is superior to titanium element due to self property and is gradually explored by researchers, but the research is slow due to the characteristic that zirconium alkoxide can be quickly gelled when meeting water. The scheme of the invention is suitable for preparing stable zirconium alkoxide chelate in large industrial scale, and can be stored and transported for a long time.

Drawings

FIG. 1 is a schematic diagram of the product state of example 1;

FIG. 2 is a structural formula diagram of example 1;

FIG. 3 is a schematic diagram of the product state of example 2;

FIG. 4 is a structural formula diagram of example 2;

FIG. 5 is a schematic diagram of the product state of example 3;

FIG. 6 is a structural formula diagram of example 3;

FIG. 7 is a schematic diagram of the product state of example 4;

FIG. 8 is a structural formula diagram of example 4;

FIG. 9 is a schematic diagram of the product state of example 5;

FIG. 10 is a structural formula diagram of example 5.

Detailed Description

The technical solutions of the present invention are further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.