阅读说明：本技术 一种含溴化合物及其制备方法与应用 (Bromine-containing compound and preparation method and application thereof ) 是由 李净植 梅泽群 王明乾 安瑞斌 于 2019-04-08 设计创作，主要内容包括：本发明公开了一种含溴化合物及其制备方法与应用,属于有机合成技术领域。本发明采用特殊的制备工艺,壬二酸为原料,先使用溴素溴代生成二溴代壬二酸,然后再进行酰氯封端,将其变为二溴代壬二酰氯,而后加入单N-叔丁氧羰基乙二胺(Boc-乙二胺)生成带有Boc保护基的目标产物,最后脱Boc保护基得到N1,N9-双(2-氨基乙基)-2,8二溴壬二酰胺最终产物,产物纯度高达90％及以上；添加了N1,N9-双(2-氨基乙基)-2,8二溴壬二酰胺的聚脲涂料在提升其阻燃性的同时,并没有对聚脲涂料的力学机械性能产生不利的影响,反而有效的改善了其各项力学性能。(The invention discloses a bromine-containing compound and a preparation method and application thereof, belonging to the technical field of organic synthesis. The invention adopts a special preparation process, wherein azelaic acid is used as a raw material, bromine is firstly used for bromination to generate dibromo azelaic acid, then acyl chloride is used for end capping to change the dibromo azelaic acid into dibromo azelaic acid chloride, then single N-tert-butyloxycarbonyl ethylenediamine (Boc-ethylenediamine) is added to generate a target product with a Boc protecting group, finally the Boc protecting group is removed to obtain a final product of N1, N9-bis (2-aminoethyl) -2,8 dibromo azelaic acid diamide, and the purity of the product is up to 90 percent or more; the polyurea coating added with N1, N9-bis (2-aminoethyl) -2, 8-dibromo-nonane diamide improves the flame retardance thereof, does not generate adverse effect on the mechanical property of the polyurea coating, and effectively improves the mechanical properties of the polyurea coating.)

1. A bromine-containing compound characterized by: the bromine-containing compound is N1, N9-bis (2-aminoethyl) -2, 8-dibromo-nonane diamide, and the structural formula is

2. A method of synthesizing the bromine-containing compound of claim 1, wherein: the method comprises the following steps:

the method comprises the following steps: reacting azelaic acid serving as a starting material and phosphorus tribromide serving as a catalyst with liquid bromine to obtain bromoazelaic acid;

step two: carrying out acyl chloride end capping treatment on the bromoazelaic acid by using an end capping agent to obtain dibromoazelaic acid chloride;

step three: dibromo-nonanedioyl chloride reacts with mono-N-tert-butoxycarbonyl ethylenediamine to obtain bromo-nonanedioyl di (tert-butylcarbonyl) ethylamine with a Boc protecting group;

step four: the bromo-nonane-diacyl-di (tert-butylcarbonyl) ethylamine product with Boc protecting group is dissolved in solvent, and the final N1, N9-bis (2-aminoethyl) -2,8 dibromo-nonane-diamide is obtained after Boc protecting group removal.

3. The method for synthesizing a bromine-containing compound according to claim 2, characterized in that: in the first step, the adding molar ratio of azelaic acid to phosphorus tribromide is (10-1): 1.

4. The method for synthesizing a bromine-containing compound according to claim 2, characterized in that: and in the second step, thionyl chloride or thionyl chloride is used as a blocking agent to carry out acyl chloride blocking treatment on the bromoazelaic acid.

5. The method for synthesizing a bromine-containing compound according to claim 2, characterized in that: in the third step, the addition amount of the mono-N-tert-butoxycarbonylethylenediamine is 2-2.5 equivalents.

6. The method for synthesizing a bromine-containing compound according to claim 2, characterized in that: in the fourth step, the solvent is one of dichloromethane, dimethylformamide or hydrochloric acid.

7. The method for synthesizing a bromine-containing compound according to any one of claims 2 to 6, characterized in that: the specific implementation mode is as follows:

the method comprises the following steps: dissolving azelaic acid in liquid bromine, adding phosphorus tribromide, reacting for 1-8 hours at the temperature of 50-80 ℃, and then removing the liquid bromine and byproduct hydrobromic acid by rotary evaporation to obtain a light yellow oily liquid product, namely bromoazelaic acid, wherein the yield is more than or equal to 95%;

the specific conditions of the rotary steaming are as follows: the temperature is 30-50 ℃, and the pressure is 0.05-0.1 MPa;

step two: dissolving the bromoazelaic acid prepared in the step one in a blocking agent, stirring, reacting for 3-24 hours under a reflux state at 100-120 ℃, and after the reaction is finished, removing the blocking agent and byproducts thereof by rotary evaporation to obtain a light yellow brown oily liquid product, namely, the dibromononanedioyl chloride, wherein the yield is more than or equal to 90 percent, and the purity is more than or equal to 90 percent;

the ratio of the addition mass A of the bromoazelaic acid to the addition volume B of the end-capping agent is 1 (5-10) g/mL;

the stirring speed is 400-600 r/min;

the specific conditions of the rotary steaming are as follows: the temperature is 30-60 ℃, the pressure is 0.08-0.1 MPa, and the treatment time is 0.5-1 h;

step three: dissolving the dibromononanedioic acid dichloride in the step two in a solvent, adding 2-2.5 equivalents of Boc ethylenediamine at 0 ℃, stirring, reacting for 2-12 h, adding water, and performing suction filtration to obtain a white bromononanedioic acid bis (tert-butylcarbonyl) ethylamine product, wherein the yield is not less than 90%;

the addition volume ratio of the dibromo-nonanedioyl chloride to the solvent is 1: 10;

the stirring speed is 700-800 r/min;

step four: dissolving bromo-nonanedioic acid bis (tert-butylcarbonyl) ethylamine in a solvent, carrying out rotary evaporation treatment, and removing Boc protecting groups to obtain the final N1, N9-bis (2-aminoethyl) -2, 8-dibromo-nonanedioic acid amide, wherein the yield is more than or equal to 90%, and the purity is more than or equal to 90%;

the ratio of the addition mass C of the bromononanedioyl di (tert-butylcarbonyl) ethylamine to the addition volume D of the solvent is 1:10 g/mL; the solvent is dichloromethane or dimethylformamide;

the specific conditions of the rotary steaming are as follows: the temperature is 30-60 ℃, the pressure is 0.08-0.1 MPa, and the treatment time is 0.5-1 h.

8. Use of the bromine-containing compound of claim 1 in the field of flame retardants.

9. Use of a bromine-containing compound according to claim 1 in polyurea coatings.

Technical Field

The invention belongs to the technical field of organic matters and synthesis thereof, and particularly relates to a bromine-containing compound and a preparation method and application thereof.

Background

The polyurea coating is widely applied due to the advantages of good flexibility, high strength, high curing speed, insensitivity to environmental temperature and humidity, capability of achieving a thick coating by one-time construction and the like. However, the coating is composed of a semi-prepolymer generated by the reaction of isocyanate and hydroxyl-terminated polyether, amino curing agent and the like, and is easy to ignite and burn as a high polymer material, and emits a large amount of toxic gas to cause a large amount of casualties, so that the research on smoke suppression and flame retardance of the polyurea coating is equally important. Therefore, how to improve the flame retardance of the polyurea coating and inhibit the generation of the smoke is a problem which needs to be solved urgently, and the polyurea coating has important social and economic significance. There are two ways to improve the flame retardancy of spray polyurea coatings: firstly, the chemical structure of the coating is changed, and flame retardant elements such as halogen, phosphorus, antimony and the like are usually introduced into polyether; and secondly, adding a flame retardant containing the flame retardant element into the coating.

The flame retardant is a material which can inhibit or delay combustion and is not inflammable, and is widely applied to the fields of clothing, petroleum, chemical engineering, metallurgy, shipbuilding, fire fighting, national defense and the like. Existing flame retardants are divided into inorganic flame retardants and organic flame retardants. The inorganic flame retardant is mainly magnesium-based, aluminum-based, boron-based, and the like, and although it is environmentally friendly, it is added in a large amount and has poor compatibility with polyurea coating materials. Generally, organic flame retardant has good affinity, has high flame retardant efficiency when added into a coating, and is divided into halogen series, phosphorus series, nitrogen-phosphorus series and nitrogen series. Halogen flame retardants and phosphorus flame retardants are the two most important types of flame retardants, are favored by people due to their high cost performance, and have wide application, for example, wuwen et al (preparation and performance characterization of flame-retardant spray polyurea coating [ J ], surface technology, 2016, 6: 22-27) have adopted organic solvent type phosphorus flame retardants to improve the flame-retardant performance of polyurea coatings, and although the flame-retardant spray polyurea coatings are successfully prepared, the physical properties of the vein-gathering materials are easily greatly reduced. For another example, the patent of the invention in china, application number: 201310457509.4, filing date: 2013.09.30, discloses a method for preparing tribromophenyl methacrylate, and the obtained tribromophenyl methacrylate is widely applied to reaction flame retardants in the industries of paint, plastics and the like. However, no report on N1, N9-bis (2-aminoethyl) -2, 8-dibromononanedioamide has been made so far.

The N1, N9-bis (2-aminoethyl) -2, 8-dibromo-nonane diamide related by the invention is applied to the polyurea coating, so that the mechanical and mechanical properties of the polyurea coating are not greatly influenced while the flame retardant property of the polyurea coating is improved.

Disclosure of Invention

1. Problems to be solved

One of the objects of the present invention is to provide N1, N9-bis (2-aminoethyl) -2, 8-dibromononanedioamide having a novel structure; the invention also aims to provide a preparation method of N1, N9-bis (2-aminoethyl) -2, 8-dibromononane diamide, which has the advantages of easily obtained raw materials, easy monitoring and control, easy product separation and high purity; the invention also aims to provide a novel flame retardant, and the novel flame retardant is applied to the polyurea coating, so that the flame retardant property of the polyurea coating can be improved, and the mechanical properties of the coating cannot be influenced.

2. Technical scheme

In order to solve the problems, the technical scheme adopted by the invention is as follows:

a bromine-containing compound, wherein the bromine-containing compound is N1, N9-bis (2-aminoethyl) -2, 8-dibromo-nonane diamide, and the structural formula is

The synthesis method of the N1, N9-bis (2-aminoethyl) -2, 8-dibromo-nonane diamide comprises the following steps:

the method comprises the following steps: reacting azelaic acid serving as a starting material and phosphorus tribromide serving as a catalyst with liquid bromine to obtain bromoazelaic acid;

step two: carrying out acyl chloride end capping treatment on the bromoazelaic acid by using an end capping agent to obtain dibromoazelaic acid chloride;

step three: dibromo-nonanedioyl chloride reacts with mono-N-tert-butoxycarbonyl ethylenediamine to obtain bromo-nonanedioyl di (tert-butylcarbonyl) ethylamine with a Boc protecting group;

step four: the bromo-nonane-diacyl-di (tert-butylcarbonyl) ethylamine product with Boc protecting group is dissolved in solvent, and the final N1, N9-bis (2-aminoethyl) -2,8 dibromo-nonane-diamide is obtained after Boc protecting group removal.

Preferably, in the first step, the adding molar ratio of azelaic acid to phosphorus tribromide is (10-1): 1.

Preferably, in the second step, an end-capping treatment is performed on the bromoazelaic acid by using an end-capping agent thionyl chloride or thionyl chloride, and the ratio of the added mass A (g) of the bromoazelaic acid to the added volume B (mL) of the end-capping agent is 1 (5-10).

Preferably, in the third step, the addition volume ratio of the acyl chloride terminated bromoazelaic acid to the dichloromethane solvent is 1:10, and the addition amount of the Boc ethylenediamine is 2-2.5 equivalents.

Preferably, in the fourth step, the ratio of the added mass C (g) of the bromononanedioyl di (tert-butylcarbonyl) ethylamine to the added volume D (mL) of the solvent is 1: 10; the solvent is dichloromethane or dimethylformamide.

Preferably, the specific embodiments are as follows: the method comprises the following steps: dissolving azelaic acid in liquid bromine, adding phosphorus tribromide, reacting for 1-8 hours at the temperature of 50-80 ℃, and then removing the liquid bromine and byproduct hydrobromic acid by rotary evaporation to obtain a light yellow oily liquid product, namely bromoazelaic acid, wherein the yield is more than or equal to 95%;

the specific conditions of the rotary steaming are as follows: the temperature is 30-50 ℃, and the pressure is 0.05-0.1 MPa;

step two: dissolving the bromoazelaic acid prepared in the step one in an end-capping reagent, stirring, reacting for 3-24 hours under a reflux state, and after the reaction is finished, removing thionyl chloride and hydrogen chloride serving as a byproduct of the thionyl chloride by rotary evaporation to obtain a light yellowish-brown oily liquid product, namely, dibromononanedioyl chloride, wherein the yield is more than or equal to 90 percent, and the purity is more than or equal to 90 percent;

the ratio of the addition mass A of the bromoazelaic acid to the addition volume B of the end-capping agent is 1 (5-10) g/mL;

the stirring speed is 400-600 r/min;

the specific conditions of the rotary steaming are as follows: the temperature is 30-60 ℃, the pressure is 0.08-0.1 MPa, and the treatment time is 0.5-1 h;

step three: dissolving the dibromononanedioic acid dichloride in the step two in a solvent, adding a dichloromethane solution of Boc ethylenediamine at 0 ℃, stirring, reacting for 2-12 h, adding water, and performing suction filtration for 20-60 min to obtain a white bromononanedioic acid bis (tert-butylcarbonyl) ethylamine product, wherein the yield is not less than 90%;

the addition volume ratio of the dibromo-nonanedioyl chloride to the solvent is 1: 10;

the stirring speed is 700-800 r/min;

step four: bromo-nonane diacid bis (tert-butylcarbonyl) ethylamine is taken to react for 2 hours in dichloromethane solution of 10 percent trifluoroacetic acid, rotary evaporation treatment is carried out, Boc protecting group is removed to obtain the final N1, N9-bis (2-aminoethyl) -2,8 dibromo-nonane diacid amide, and the yield can reach 98 percent;

the ratio of the addition mass C of the bromononanedioyl di (tert-butylcarbonyl) ethylamine to the addition volume D of the solvent is 1:10 g/mL; the solvent is dichloromethane or dimethylformamide; the specific conditions of the rotary steaming are as follows: the temperature is 30-60 ℃, the pressure is 0.08-0.1 MPa, and the treatment time is 0.5-1 h.

Preferably, in the fourth step, bromo-nonanedioyl di (tert-butylcarbonyl) ethylamine may be taken, heated to 90 ℃ in 1M hydrochloric acid solution for reaction, neutralized hydrochloric acid with alkali solution (such as sodium hydroxide for adjustment), extracted with ethyl acetate, rotary evaporated, and Boc-protecting group removed to obtain the final N1, N9-bis (2-aminoethyl) -2,8 dibromo-nonanedioyl amide.

N1, N9-bis (2-aminoethyl) -2, 8-dibromononanedioamide as described in any of the above is used as a flame retardant in the field of flame retardants.

N1, N9-bis (2-aminoethyl) -2, 8-dibromononanedioamide, as described in any of the above, is used in polyurea coatings.

3. Advantageous effects

Compared with the prior art, the invention has the beneficial effects that:

(1) the N1, N9-bis (2-aminoethyl) -2, 8-dibromo-nonane diamide provided by the invention has a novel structure, can be used as a flame retardant, and provides a new material for the flame retardant;

(2) the preparation method of the N1, N9-bis (2-aminoethyl) -2, 8-dibromo-nonane diamide provided by the invention has the advantages of easily available raw materials, simple synthesis process, easy monitoring and control, and easy separation of products in each step; in the first step, the yield of the bromoazelaic acid is more than or equal to 95 percent; in the second step, the yield of the acyl chloride end-capped bromoazelaic acid is more than or equal to 90 percent, and the purity is more than or equal to 90 percent; in the third step, the yield of the bromo-nonanedioyl di (tert-butylcarbonyl) ethylamine product is more than or equal to 90 percent; in the fourth step, the yield of N1, N9-bis (2-aminoethyl) -2, 8-dibromo-nonane diamide is more than or equal to 90 percent, the purity is more than or equal to 90 percent, the highest recovery rate of the final product can reach 98 percent, the purity is high, and the method can be used for large-scale industrial production;

(3) the N1, N9-bis (2-aminoethyl) -2, 8-dibromo-nonane diamide provided by the invention can be used as a flame retardant to be applied to polyurea coatings, the flame retardant effect of the polyurea coatings is improved, and the mechanical properties of the polyurea coatings are not influenced, through tests, the oxygen index of the polyurea coatings added with N1, N9-bis (2-aminoethyl) -2, 8-dibromo-nonane diamide is up to 27.6%, compared with the traditional polyurea coatings (the oxygen index is about 18%), the oxygen index is greatly improved, the flame retardant property of the polyurea coatings is obviously improved, in addition, the adverse influence on the mechanical properties of the polyurea coatings is avoided, and the mechanical properties of the polyurea coatings are effectively improved.

Drawings

FIG. 1 is a mass spectrum of a target product in example 3 of the present invention;

FIG. 2 is a nuclear magnetic hydrogen spectrum of a target product in example 3 of the present invention;

FIG. 3 is a nuclear magnetic carbon spectrum of a target product in example 3 of the present invention.

Detailed Description

This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.

The invention provides N1, N9-bis (2-aminoethyl) -2, 8-dibromo-nonane diamide, which has the following structure:

the preparation method of the N1, N9-bis (2-aminoethyl) -2, 8-dibromo-nonane diamide comprises the following steps:

the method comprises the following steps: dissolving azelaic acid in liquid bromine, adding phosphorus tribromide, reacting for 1-8 hours, and removing by-products, namely hydrobromic acid and liquid bromine by rotary evaporation to obtain a light yellow oily liquid product, wherein the reaction equation is as follows:

step two: dissolving the bromoazelaic acid in the first step in a blocking agent, refluxing for a certain time, removing redundant substances and a byproduct hydrogen chloride after the reaction is finished, and obtaining a light yellow brown oily liquid product, namely the dibromo-nonanedioyl chloride, according to the reaction equation:

step three: dissolving dibromo-nonanedioyl chloride in a solvent, adding a methylene dichloride solution of Boc-ethylenediamine, reacting for 2-12 hours, adding water, and performing suction filtration to obtain a white bromo-nonanedioyl di (tert-butylcarbonyl) ethylamine product with a Boc protecting group, wherein the reaction equation is as follows:

step four: taking bromo-nonanedioyl di (tert-butylcarbonyl) ethylamine product with Boc protecting group, removing Boc protecting group to obtain the target product N1, N9-bis (2-aminoethyl) -2,8 dibromo-nonanedioyl amide, and reacting according to the formula:

the invention is further described with reference to specific examples.