CN111793004B - Bromine-containing compound and preparation method and application thereof - Google Patents
Bromine-containing compound and preparation method and application thereof Download PDFInfo
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- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
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Abstract
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 nonane 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 dibromononane diamide improves the flame retardance thereof, does not have adverse effect on the mechanical properties of the polyurea coating, and effectively improves the mechanical properties of the polyurea coating.
Description
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 most important two types of flame retardants, and are favored by people due to their high cost performance, and have wide application, for example, wu Wenwen et al (preparation and performance characterization [ 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 poly-linear material 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 can be widely applied to reaction flame retardants in the industries of coating, plastics and the like. However, so far, no report on N1, N9-bis (2-aminoethyl) -2,8 dibromononanediamide has been found.
The N1, N9-bis (2-aminoethyl) -2,8 dibromo-nonane diamide applied to the polyurea coating can increase the flame retardant property of the polyurea coating and cannot generate great influence on the mechanical property of the polyurea coating.
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 with 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 dibromononane diamide, and the structural formula is
The synthesis method of the N1, N9-bis (2-aminoethyl) -2,8 dibromononane 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 molar ratio of the azelaic acid to the phosphorus tribromide is (10-1): 1.
Preferably, in the second step, the end capping treatment is carried out on the bromoazelaic acid by using thionyl chloride or thionyl chloride as an end capping agent, and the ratio of the addition mass A (g) of the bromoazelaic acid to the addition volume B (mL) of the end capping agent is 1 (5-10).
Preferably, in the third step, the volume ratio of the acyl chloride terminated bromo-azelaic acid to the dichloromethane solvent is 1, and the addition amount of Boc ethylenediamine is 2-2.5 equivalents.
Preferably, in the fourth step, the ratio of the added mass C (g) of bromononanedioyl di (tert-butylcarbonyl) ethylamine to the added volume D (mL) of the solvent is 1; 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 h 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 h 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 dibromononanedioyl chloride 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 bromononanedioyl bis (tert-butylcarbonyl) ethylamine product, wherein the yield is more than or equal to 90%;
the addition volume ratio of the dibromo-nonanedioyl chloride to the solvent is 1;
the stirring speed is 700-800 r/min;
step four: taking bromo-nonanedioyl di (tert-butylcarbonyl) ethylamine, reacting in a dichloromethane solution of 10% trifluoroacetic acid for 2 hours, performing rotary evaporation treatment, and removing a Boc protecting group to obtain the final N1, N9-bis (2-aminoethyl) -2,8 dibromo-nonanedioyl amide, wherein the yield can reach 98%;
the ratio of the addition mass C of the bromo-azelaic acid di (tert-butylcarbonyl) ethylamine to the addition volume D of the solvent is 1; 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 an 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.
The N1, N9-bis (2-aminoethyl) -2,8 dibromononane diamide, which is used as a flame retardant, is applied to the field of flame retardants.
N1, N9-bis (2-aminoethyl) -2,8 dibromononanoylamine, 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 dibromononane 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 dibromononane 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 the 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 mechanical properties of the polyurea coatings are not influenced while the flame retardant effect of the polyurea coatings is improved, through tests, the oxygen index of the polyurea coatings added with the N1, N9-bis (2-aminoethyl) -2,8 dibromo-nonane diamide is up to 27.6%, and 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, the mechanical properties of the polyurea coatings are not adversely influenced, 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 dibromononanediamide, which has the following structure:
the preparation method of the N1, N9-bis (2-aminoethyl) -2,8 dibromononane 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 the formula:
the invention is further described with reference to specific examples.
Example 1
The method comprises the following steps: adding 0.1mol of azelaic acid into 200mL of liquid bromine and 0.01mol of phosphorus tribromide, heating to 80 ℃, reacting for 8h, and performing rotary evaporation at 50 ℃ and 0.1MPa to remove a byproduct, namely liquid bromine, to obtain a light yellow oily liquid product, namely brominated azelaic acid, wherein the yield is 98%;
step two: dissolving 10g of bromoazelaic acid in the first step into 50mL of thionyl chloride (the ratio of the addition mass A (g) of the bromoazelaic acid to the addition volume B (mL) of the thionyl chloride is 1:5), stirring at 400r/min, refluxing for 24 hours at 120 ℃, performing rotary evaporation (the rotary evaporation temperature is 60 ℃, the pressure is 0.1MPa, the treatment time is 1 hour) after the reflux is finished, removing thionyl chloride and hydrogen chloride serving as a byproduct, and obtaining a light yellowish-brown oily liquid product, namely dibromoazelaic acid chloride, with the yield of 90%; the purity is 95 percent;
step three: dissolving dibromo-nonanedioyl chloride in a dichloromethane solvent, adding a dichloromethane solution of Boc ethylenediamine, stirring at 800r/min, reacting for 12 hours, adding water, and performing suction filtration for a certain time of 60 minutes to obtain a white product bromo-nonanedioyl di (tert-butylcarbonyl) ethylamine;
step four: dissolving bromo-nonanedioyl di (tert-butylcarbonyl) ethylamine in a solvent (the solvent can be any one of dichloromethane, dimethylformamide or hydrochloric acid), carrying out rotary evaporation treatment (the rotary evaporation temperature is 60 ℃, the pressure is 0.1MPa, the treatment time is 1 h), and removing Boc protecting groups to obtain a final product N1, N9-bis (2-aminoethyl) -2,8 dibromo-nonanedioyl amide, wherein the yield is 90% and the purity is 91%.
Example 2
The method comprises the following steps: adding 0.1mol of azelaic acid into 150mL of liquid bromine and 0.1mol of phosphorus tribromide, heating to 50 ℃, reacting for 4 hours, and performing rotary evaporation (the rotary evaporation temperature is 30 ℃, and the pressure is 0.05 MPa) to remove a byproduct, namely liquid bromine, to obtain a light yellow oily liquid product, namely bromoazelaic acid, wherein the yield is 95%;
step two: dissolving 14g of dibromo-azelaic acid in the step one in 70mL of thionyl chloride (the ratio of the addition mass A (g) of the bromo-azelaic acid to the addition volume B (mL) of the thionyl chloride is 1:5), stirring at 400r/min, refluxing for 3 hours at the temperature of 100 ℃, and removing the thionyl chloride and a byproduct hydrogen chloride by rotary evaporation (the rotary evaporation temperature is 30 ℃, the pressure is 0.08MPa, the treatment time is 0.6 hour) after the reflux reaction is finished to obtain a light yellowish-brown oily liquid product, namely bromo-azelaic acid chloride, wherein the yield is 95% and the purity is 92%;
step three: and (2) dissolving 10g of dibromononanedioyl chloride in the second step into 100mL of dichloromethane solvent (the quantitative ratio of the addition mass of bromononanedioic acid blocked by bromononanedioic chloride to the addition volume of the dichloromethane solvent is 1).
Step four: dissolving bromo-nonanedioyl di (tert-butylcarbonyl) ethylamine in dimethylformamide, carrying out rotary evaporation treatment (the rotary evaporation temperature is 30 ℃, the pressure is 0.1MPa, the treatment time is 0.5 h), and removing Boc protective groups to obtain a final product N1, N9-bis (2-aminoethyl) -2,8 dibromo-nonanedioyl amide, wherein the yield is 92% and the purity is 93%.
Example 3
The method comprises the following steps: adding 0.1mol of azelaic acid into 150mL of liquid bromine and 0.1mol of phosphorus tribromide, heating to 50 ℃ for reaction for four hours, and performing rotary evaporation (the rotary evaporation temperature is 50 ℃, and the pressure is 0.1 MPa) to remove a byproduct, namely liquid bromine, so as to obtain a light yellow oily liquid product, namely bromoazelaic acid, with the yield of 95%;
step two: dissolving 14g of dibromo-azelaic acid in the step one in 70mL of thionyl chloride (the ratio of the addition mass A (g) of the bromo-azelaic acid to the addition volume B (mL) of the thionyl chloride is 1:5), stirring at the rotating speed of 500r/min, refluxing at 100 ℃ for 5 hours, and performing rotary evaporation (the rotary evaporation temperature is 50 ℃, the pressure is 0.09MPa, the treatment time is 0.75 hours) to remove the thionyl chloride and the byproduct hydrogen chloride after the reaction is finished, so as to obtain a light yellowish-brown oily liquid product, namely bromo-azelaic acid chloride, with the yield of 95%;
step three: dissolving 10g of dibromononanedioyl chloride in the step two in 100mL of dichloromethane solvent, slowly dropwise adding 2.5 equivalents of Boc ethylenediamine at 0 ℃, stirring at the speed of 800r/min, recovering to room temperature after dropwise adding, reacting for 5 hours, adding water, and performing suction filtration for 60min to obtain a white bromononanedioyl di (tert-butylcarbonyl) ethylamine product with the yield of 96%;
step four: 10g of bromononanedioic acid bis (tert-butylcarbonyl) ethylamine prepared in example 6 was dissolved in 10% trifluoroacetic acid in dichloromethane, and the reaction was carried out for 2 hours, followed by rotary evaporation (the rotary evaporation temperature was 50 ℃, the pressure was 0.08MPa, and the treatment time was 1 hour) to obtain the final target product with a yield of 98%.
The mass spectrometry results shown in FIG. 1 show the [ M + H ] and [ M + Na ] peaks of the compound; nuclear magnetic hydrogen spectrum as shown in fig. 2: 1H NMR (400mhz, dmso-d 6) δ 8.52 (t, J =5.6hz, 2h), 7.87 (s, 4H), 4.32 (dd, J =1.2,8.0hz, 2h), 3.40-3.22 (m, 4H), 2.92-2.81 (m, 4H), 2.03-1.78 (m, 4H), 1.43-1.78 (m, 6H); the nuclear magnetic spectrum of 13C NMR (100MHz, DMSO-d 6) delta 169.57,49.97,38.52,37.21,34.71,28.09,27.06.MS (ESI, m/z): 431.05[ mu ] M + H ] +,453.05[ mu ] M + Na ] +, all of which indicate that the molecular weight of the compound is correct.
Example 4
The method comprises the following steps: adding 0.1mol of azelaic acid into 150mL of liquid bromine and 0.1mol of phosphorus tribromide, heating to 50 ℃ for reaction for four hours, and performing rotary evaporation (the rotary evaporation temperature is 50 ℃, and the pressure is 0.1 MPa) to remove a byproduct, namely liquid bromine, so as to obtain a light yellow oily liquid product, namely bromo-azelaic acid, wherein the yield is 95%.
Step two: and (3) dissolving 14g of dibromo-azelaic acid in the step one in 70mL of thionyl chloride (the ratio of the addition mass A (g) of the bromo-azelaic acid to the addition volume B (mL) of the thionyl chloride is 1:5), stirring at the speed of 600r/min, refluxing at 100 ℃ for 5 hours, and performing rotary evaporation (the rotary evaporation temperature is 50 ℃, the pressure is 0.1MPa, and the treatment time is 0.5 hours) after the reflux reaction is finished to remove the thionyl chloride and the byproduct hydrogen chloride to obtain a light yellowish-brown oily liquid product, namely dibromo-nonanedioyl chloride, with the yield of 95%.
Step three: and (2) dissolving 10g of dibromononanedioyl chloride in the second step in 100mL of dichloromethane solvent, slowly dropwise adding 2.5 equivalents of Boc ethylenediamine at 0 ℃, stirring at the speed of 800r/min, returning to room temperature after dropwise addition, reacting for 5 hours, adding water, and performing suction filtration to obtain a white bromononanedioyl bis (tert-butylcarbonyl) ethylamine product with the yield of 96%.
Step four: synthesis of N1, N9-bis (2-aminoethyl) -2,8 dibromononanedioamide. 10g of bromononanedioic acid bis (tert-butylcarbonyl) ethylamine from example 6 was dissolved in 1M hydrochloric acid solution and heated to 90 ℃ to react, the hydrochloric acid was neutralized with an alkali solution (such as sodium hydroxide), ethyl acetate extraction was carried out, and rotary evaporation treatment (rotary evaporation temperature 60 ℃, pressure 0.1MP, rotary evaporation time 1 h) was carried out with a yield of 90%.
Comparative example 1
This comparative example differs from example 3 only in that
The method comprises the following steps: adding 0.1mol of azelaic acid into 150mL of liquid bromine, heating to 50 ℃ for reacting for four hours, and performing rotary evaporation (the rotary evaporation temperature is 50 ℃, and the pressure is 0.1 MPa.) to remove the by-product liquid bromine, thereby obtaining a light yellow oily liquid product, namely bromoazelaic acid, with the yield of 87%.
The remaining steps were as in example 3, and:
step two: the yield of the dibromo-nonanedioyl chloride product is 84 percent;
step three: yield 76% of white bromononanedioyl bis (tert-butylcarbonyl) ethylamine with Boc protecting group;
step four: the final yield of N1, N9-bis (2-aminoethyl) -2,8 dibromononanedioamide was 76%;
it can be seen that the yield of the product from each step is lower than that of example 3 under the reaction conditions without adding phosphorus tribromide.
Example 5
The method for synthesizing N1, N9-bis (2-aminoethyl) -2,8 dibromononanedioamide described in this embodiment specifically includes the following steps:
the method comprises the following steps: dissolving azelaic acid in liquid bromine, adding phosphorus tribromide, wherein the adding ratio of azelaic acid to phosphorus tribromide is 10; then reacting for 6 hours at 50 ℃, and then carrying out rotary evaporation (the rotary evaporation temperature is 50 ℃, and the pressure is 0.1 MPa) to remove by-products hydrobromic acid and liquid bromine, so as to obtain a light yellow oily liquid product, namely bromo-azelaic acid;
step two: dissolving the bromoazelaic acid obtained in the first step in thionyl chloride (the ratio of the addition mass A (g) of the bromoazelaic acid to the addition volume B (mL) of the thionyl chloride is 1:5), stirring at the speed of 600r/min, performing reflux reaction for a certain period of 8 hours, and performing rotary evaporation (the rotary evaporation temperature is 60 ℃, the pressure is 0.1MPa, and the treatment time is 0.5 hour) to remove the thionyl chloride and a byproduct hydrogen chloride thereof to obtain a light yellowish-brown oily liquid product, namely the dibromoazelaic acid chloride;
step three: dissolving dibromo-nonanedioic acid dichloride in a dichloromethane solvent (the volume ratio of the two is 1;
the mass ratio of the reactants to the solvent is 1:10, the stirring speed is 800r/min, and the suction filtration time t 3 It is 20min.
Step four: taking bromo-nonanedioyl di (tert-butylcarbonyl) ethylamine, and removing Boc protecting group to obtain the target product.
The mass ratio of the bromo-azelaic acid di (tert-butylcarbonyl) ethylamine to the solvent is 1; the rotary evaporation temperature is 60 ℃, the pressure is 0.1MPa, and the treatment time is 1h.
Example 6
Taking the N1, N9-bis (2-aminoethyl) -2,8 dibromononandiamide prepared in example 3 as an example, the polyurea coating added with the N1, N9-bis (2-aminoethyl) -2,8 dibromononandiamide has an oxygen index as high as 27.6% through a test (based on a GB/T23446-2009 ii water-spray polyurea anti-coating), compared with a conventional polyurea coating (with an oxygen index of about 18%), the oxygen index is greatly improved, and the flame retardant performance of the polyurea coating is obviously improved. And through the test, the performance of the polyurea coating added with N1, N9-bis (2-aminoethyl) -2,8 dibromononanamide is not adversely affected, and the specific results are shown in Table 1.
TABLE 1
As can be seen from Table 1, N9-bis (2-aminoethyl) -2,8 dibromononane diamide in example 3 is applied to polyurea coating, and the mechanical properties of the polyurea coating are not adversely affected while the flame retardance of the polyurea coating is improved, but the mechanical properties of the polyurea coating are effectively improved, and N1, N9-bis (2-aminoethyl) -2,8 dibromononane diamide prepared in example 1, example 2, example 4 and example 5 have similar properties.
Claims (9)
1. A bromine-containing compound characterized by: the bromine-containing compound is N1, N9-bis (2-aminoethyl) -2,8 dibromononanediamide, and the structural formula is as follows:
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 as a starting material and phosphorus tribromide as a catalyst with liquid bromine to obtain bromoazelaic acid, wherein the reaction equation is as follows:
step two: carrying out acyl chloride end capping treatment on the bromoazelaic acid by using an end capping agent to obtain dibromoazelaic acid chloride, wherein the reaction equation is as follows:
step three: dibromo-nonanedioyl chloride is reacted with mono-N-t-butoxycarbonylethylenediamine to give bromo-nonanedioyl di (t-butylcarbonyl) ethylamine with a Boc protecting group, according to the equation:
step four: taking bromo-nonanedioyl di (tert-butylcarbonyl) ethylamine product with Boc protecting group, dissolving in solvent, removing Boc protecting group to obtain final N1, N9-bis (2-aminoethyl) -2,8 dibromo-nonanedioyl amide, and reacting formula:
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 at 50-80 ℃ for 1-8 h, 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 h 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 yellowish-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 more than or equal to 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-nonanedioyl di (tert-butylcarbonyl) ethylamine in a solvent, carrying out rotary evaporation treatment, and removing a Boc protecting group to obtain the final N1, N9-bis (2-aminoethyl) -2,8 dibromo-nonanedioyl 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 1:10g/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 processing 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.
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| 陈海燕 ; 陈年丰 ; .溴系阻燃剂BN451的合成及其在聚丙烯中的应用.(第03期),第26-29页. * |
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