CN112646569A

CN112646569A - Chemiluminescent composition and preparation method thereof

Info

Publication number: CN112646569A
Application number: CN202011502891.2A
Authority: CN
Inventors: 刘洋
Original assignee: Quanzhou Boyin Information Technology Co ltd
Current assignee: Quanzhou Boyin Information Technology Co ltd
Priority date: 2020-12-17
Filing date: 2020-12-17
Publication date: 2021-04-13

Abstract

A chemiluminescent composition comprises a luminescent agent and an oxidant, wherein the oxidant is glycerol triacetate as a solvent, the luminescent agent is n-tributyl citrate and butyl benzoate as solvents, and an organic blue fluorescent material is adopted as a fluorescent agent. The organic blue fluorescent material as the fluorescent agent can lead the fluorescence intensity to be higher, the luminescence duration to be longer, the material has good thermal stability and high luminescence quantum efficiency, and has little toxicity to the environment and human body, thereby having the characteristic of environmental protection.

Description

Chemiluminescent composition and preparation method thereof

Technical Field

The invention relates to the field of chemiluminescent compositions, in particular to a chemiluminescent composition and a preparation method thereof.

Background

Chemiluminescence refers to visible light emitted in the reaction process of certain chemical substances, and the chemiluminescence technology is mature and widely applied to multiple fields after development and research for forty years since the chemiluminescence principle was discovered in the 70 th 20 th century. In toy artworks, the manufacture of objects that emit light by means of chemical reactions has long been known, chemiluminescent compositions generally utilize a two-component system to produce light by chemical means, based on the chemiluminescence produced by mixing two components, requiring the two components to remain separate prior to emitting light, and mixing the two components in contact when emission is required to produce chemiluminescence, the intensity, duration and color of the light will depend on the composition of the two components. The two components are generally an oxidizing agent and a luminescent agent, and the selected solvent must be sufficiently compatible. The two components, which are typically in the form of chemical solutions, are referred to as the "activator" component and the "oxalate" component. When chemiluminescent light is desired, the activator and oxalate are mixed together. The activator component comprises a peroxide compound and a catalyst, and the oxalate component comprises an oxalate. The chemiluminescent substance also comprises a fluorescent agent (fluorophore), which may be present in either or both of the two components. The chemiluminescent composition also includes a solvent or solvent mixture for the activator component and a solvent for the oxalate component. The solvents used for the two components may be different, but miscible with each other.

The solvent selected for the oxalate component must dissolve the selected oxalate component and the solvent or solvent mixture used for the activator component must dissolve the selected peroxide and the selected catalyst. If fluorescer is present in the oxalate component, the solvent selected for the oxalate component must dissolve both the selected oxalate compound and the selected fluorescer. If a fluorescing agent is present in the activator component, the solvent must dissolve the selected fluorescing agent, the selected peroxide, and the selected catalyst. The solvents of choice in the prior art as the oxalate component are dimethyl phthalate and butyl benzoate. The solvent selected as the active agent component is dimethyl phthalate or a mixture of dibutyl phthalate and t-butanol. The prior solvent of the oxalate component has the defects of limited solvating capacity, short luminescence time and high cost in many aspects.

Dimethyl phthalate has a special aromatic hydrocarbon structure, cannot be dissolved with oxidants such as hydrogen peroxide and the like, and needs to be added with alcohol organic solvents such as tert-butyl alcohol and the like as a medium, while the addition of tert-butyl alcohol has strong irritation, slight toxicity, strong volatility and low flash point, and the safety of the oxidant is reduced, so that the oxidant does not meet the requirements of Europe and America on environmental protection. Phthalate has been used under strict control abroad due to its potential carcinogenicity. Related laws and regulations are also made in China, and the use of phthalate esters in food packaging materials, medical appliances, toys for children and the like is gradually eliminated.

The prior green environment-friendly chemiluminescent composition used for food packaging materials, medical appliances and children toys has the problems of insufficient luminous intensity and short luminous time.

Chemiluminescent compositions are typically contained in a device in which the two components are kept physically separated prior to reactivation by a variety of methods. Typically, the device contains the components in separate chambers, and when chemiluminescent light is required from the western han, the chambers are destroyed in a manner that allows the two components to mix with each other. One widely used example of such a device is a "glow stick". Here, a sealed frangible glass vial containing one component is broken, releasing the component, allowing the two components to mix and generate light. Although this method has been widely adopted, it is still limited to specific applications.

For example, chinese patent publication No. CN109265310A discloses an organic blue fluorescent material having good thermal stability and high luminescence quantum efficiency. Compared with 9,10- (diacetylene) anthracene, the material has higher luminous intensity and longer luminous time, has lower toxicity to the environment and human bodies, and has the characteristic of environmental protection. The material is connected with two diphenyl anthracene luminescent units through a delta bridge chain, so that the regulation and control of molecular conjugate form are realized; and 3, a corresponding steric hindrance group is introduced to the delta bridge chain, so that the fluorescence quenching effect brought by pi-pi stacking among molecules is inhibited.

Disclosure of Invention

The invention aims to provide a chemiluminescent composition which is green and environment-friendly and has sufficient luminous intensity and luminous duration.

In a first aspect, the technical scheme adopted by the invention is as follows: a chemiluminescent composition comprises a luminescent agent and an oxidizing agent, wherein the oxidizing agent comprises an oxide and a solvent A, the luminescent agent comprises a fluorescent agent and a solvent B, the solvent B is tributyl citrate and dipropylene glycol dimethyl ether, the fluorescent agent is an organic blue fluorescent material, and the solvent A is glyceryl triacetate.

Further, the luminescent agent comprises 100 parts by weight of oxalate, 0.01-0.05 part by weight of catalyst A and 1-1.5 parts by weight of fluorescent agent, and the oxidant comprises 1-60 parts by weight of tributyl citrate, 1-100 parts by weight of dipropylene glycol dimethyl ether, 2-5 parts by weight of 90% hydrogen peroxide and 0.01-0.05 part by weight of catalyst B.

Further, the mass ratio of the luminescent agent to the oxidizing agent is 1: (2-3).

Further, the oxalate is bis (n-amyl 2, 4, 5-trichlorosalicylate) oxalate or bis (isoamyl 2, 4, 5-trichlorosalicylate) oxalate.

Further, the tributyl citrate includes tributyl citrate and acetyl tributyl citrate.

Further, the catalyst A is sodium salicylate.

Further, the catalyst B is sodium salicylate or tetrabutyl ammonium salicylate.

Compared with the prior art, the chemiluminescent composition has the beneficial effects that:

according to the green environment-friendly luminescent composition, the benzoic acid ester solvent harmful to human bodies is replaced by the green environment-friendly solvents of tributyl citrate and dipropylene glycol dimethyl ether, so that the green environment-friendly luminescent composition is non-toxic and harmless, does not have adverse effects on human health, and achieves the same luminescent effect. In addition, the fluorescent agent in the luminescent composition adopts an organic blue fluorescent material, and the material has good thermal stability, high luminescent quantum efficiency, higher luminescent intensity, longer luminescent time, less toxicity to the environment and human body and environmental protection characteristic.

In a second aspect, a method of preparing a chemiluminescent composition comprises the steps of:

the preparation method of the luminescent agent comprises the following steps: dissolving bis (2, 4, 5-trichloro salicylic acid n-amyl) oxalate (CPPO) and an organic blue fluorescent material in a mixed solution of tributyl citrate and butyl benzoate, and stirring until the materials are completely dissolved to obtain a luminescent agent;

the preparation method of the oxidant comprises the following steps: dissolving hydrogen peroxide and tetrabutyl amine salicylate in glycerol triacetate, and stirring to obtain an oxidant;

mixing the prepared luminous agent and the prepared oxidant to obtain a green environment-friendly chemiluminescent composition, and measuring the composition to be 300LUS by using a TES-1330A illumination instrument to be close to the wall of a luminous test tube until the complete extinguishment duration is about 12 hours.

The invention has the beneficial effects that:

the invention provides a preparation method of a green environment-friendly luminescent composition, which uses green environment-friendly solvents of tributyl citrate and dipropylene glycol dimethyl ether to replace a benzoate solvent harmful to human bodies, is non-toxic and harmless, does not have adverse effect on human health, and obtains the same luminescent effect. In addition, the fluorescent agent in the luminescent composition adopts an organic blue fluorescent material, and the material has good thermal stability, high luminescent quantum efficiency, higher luminescent intensity, longer luminescent time, less toxicity to the environment and human body and environmental protection characteristic.

Drawings

The invention is described in further detail below with reference to the following figures and embodiments:

FIG. 1 is a nuclear magnetic spectrum of an organic blue fluorescent material;

FIG. 2 is a mass spectrum of the organic blue fluorescent material.

Detailed Description

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

Example 1:

the synthesis of the organic blue fluorescent material comprises the following specific steps:

preparing 9-phenylanthracene: adding 2.60-5.14 g of 9-bromoanthracene, 1.83-3.66 g of phenylboronic acid, 30-60 mL of potassium carbonate solution, 100-200 mL of Toluene (Toluene) and 30-60 mL of ethanol (EtOH) into a reaction bottle, wherein the potassium carbonate solution is prepared by adding 13.82-27.64 g of potassium carbonate into 30-60 mL of water; finally, 0.58 to 1.16g of tetrakis (triphenylphosphine) palladium is added. And then, vacuumizing the system, and refluxing for 12-24 hours at 100-110 ℃ under the protection of inert gas or nitrogen to perform Suzuki coupling reaction. After the reaction is finished, extracting, rotary steaming, column chromatography and recrystallization are carried out to obtain the product 9-phenylanthracene.

(ii) bromination of 9-phenylanthracene: adding 2.15-4.29 g of 9-phenylanthracene, 100-200 mL of N, N-Dimethylformamide (DMF) and 1.8-3.6 g of N-bromosuccinimide (NBS) into a reaction bottle, and then vacuumizing the system to react for 1-2 hours at 85-90 ℃ under the protection of nitrogen or inert gas. Washing with methanol, and vacuum filtering to obtain 9-bromo-10-phenylanthracene.

③ boration of 9-bromo-10-phenylanthracene: adding 1.40-2.80 g of 9-bromo-10-phenylanthracene, 1.34-2.67 g of isopropoxyborate, 0.42-0.81 g of n-butyllithium (added at 78 ℃) and 30-56 mL of THF into a reaction bottle, vacuumizing the system, and stirring at room temperature for 8-12 hours under the protection of nitrogen or inert gas. After the reaction is finished, extracting, rotary steaming, column chromatography and recrystallization are carried out to obtain the product 9-phenylanthracene-10 boric acid ester.

Bromination of 4, 4' -diaminodiphenyl disubstituted methane: adding 4,4 '-diaminodiphenyl disubstituted methane, 2.5-10 mmol and 5-20 mL of hydrogen bromide into a reaction bottle placed in an ice bath, then adding 6.25-25 mmol of sodium nitrite into the reaction bottle, stirring for 20 minutes, mixing 12.5-50 mmol of cuprous bromide and 5-20 mL of hydrogen bromide, adding into the reaction bottle, reacting for 1-2 hours at room temperature under the atmosphere, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography, and recrystallizing to obtain the product 4, 4' -dibromodiphenyl disubstituted methane.

Fifthly, synthesizing a final product: adding 1.5-6 mmol of 9-phenylanthracene-10 borate, 0.5-2 mmol of 4, 4' -dibromodiphenyl disubstituted methane, 0.1-0.4 mmol of palladium tetrakis (triphenyl) phosphine as a catalyst, 20-80 mL of toluene, 5-20 mL of ethanol and 311-44 mmol of K2CO (a solution prepared by using 5-20 mL of distilled water) into a reaction bottle, and refluxing for 12-24 h at 100-110 ℃ under the protection of nitrogen to perform Suzuki coupling reaction; after the reaction is finished, extracting, rotary steaming, carrying out column chromatography, and recrystallizing to obtain the product.

The preparation method of the green environment-friendly luminescent composition comprises the following steps:

(1) the preparation method of the luminescent agent comprises the following steps:

dissolving 3.75g of bis (2, 4, 5-trichloro salicylic acid n-amyl) oxalate (CPPO) and 0.075g of organic blue fluorescent material in a mixed solution of tributyl citrate and butyl benzoate, and stirring until the materials are completely dissolved to obtain a luminescent agent; wherein the mass ratio of tributyl citrate to butyl benzoate is 6: 4; the mass percentage concentration of the oxalate component is 15 percent, and the mass percentage concentration of the organic blue fluorescent material is 0.30 percent;

(2) the preparation method of the oxidant comprises the following steps:

dissolving 1.5g of hydrogen peroxide and 0.0025g of tetrabutyl amine salicylate in glycerol triacetate, and stirring to obtain an oxidant; wherein, the mass percent concentration of the hydrogen peroxide is 1.5 percent, and the mass percent concentration of the tetrabutyl amine salt is 0.0025 percent.

(3) And (3) mixing the luminous agent prepared in the step (1) with the oxidizing agent prepared in the step (2) (wherein the volume ratio of the luminous agent to the oxidizing agent is 1:4) to obtain a green environment-friendly chemiluminescent composition, and measuring the composition to be 330LUS by using a TES-1330A illumination instrument to be close to the wall of a luminescent test tube until the complete extinguishment duration is about 4 hours.

Example 2:

the synthesis method of the organic blue fluorescent material was the same as in example 1.

dissolving 2.5g of bis (2, 4, 5-trichloro salicylic acid n-amyl) oxalate (CPPO) and 0.06g of organic blue fluorescent material in a mixed solution of tributyl citrate and butyl benzoate, and stirring until the materials are completely dissolved to obtain a luminescent agent; wherein the mass ratio of tributyl citrate to butyl benzoate is 6: 4; the mass percentage concentration of the oxalate component is 10 percent, and the mass percentage concentration of the organic blue fluorescent material is 0.24 percent;

(2) the preparation method of the oxidant comprises the following steps:

dissolving 2.5g of hydrogen peroxide and 0.01g of tetrabutyl amine salicylate in glycerol triacetate, and stirring to obtain an oxidant; wherein, the mass percent concentration of the hydrogen peroxide is 2.5 percent, and the mass percent concentration of the tetrabutyl ammonium salt is 0.013 percent.

(3) And (3) mixing the luminous agent in the step (1) and the oxidizing agent in the step (2) (wherein the volume ratio of the luminous agent to the oxidizing agent is 1:1) to obtain a green environment-friendly chemiluminescent composition, and measuring the green environment-friendly chemiluminescent composition to be 310LUS by using a TES-1330A illumination instrument to be close to the wall of a luminescent test tube until the complete extinguishment duration is about 8 hours.

Example 3:

dissolving 6g (2, 4, 5-trichloro salicylic acid n-amyl) oxalate (CPPO) and 0.16g of organic blue fluorescent material in a mixed solution of tributyl citrate and butyl benzoate, and stirring until the materials are completely dissolved to obtain a luminescent agent; wherein the mass ratio of tributyl citrate to butyl benzoate is 7: 2; the mass percentage concentration of the oxalate component is 6 percent, and the mass percentage concentration of the organic blue fluorescent material is 0.16 percent;

(2) the preparation method of the oxidant comprises the following steps:

dissolving 0.75g of hydrogen peroxide and 0.04g of tetrabutyl amine salicylate in glycerol triacetate, and stirring to obtain an oxidant; wherein, the mass percent concentration of the hydrogen peroxide is 3.0 percent, and the mass percent concentration of the tetrabutyl amine salicylate is 0.04 percent.

(3) Mixing the luminescent agent of step (1) and the oxidizing agent of step (2) (wherein the volume ratio of luminescent agent to oxidizing agent is 4: 1 chemiluminescent composition, measured as 300LUS by TES-1330A illumination meter adjacent to the wall of the luminophore, to a complete extinction duration of about 12 hours.

Example 4:

dissolving 8g (2, 4, 5-trichloro salicylic acid n-amyl) oxalate (CPPO) and 0.20g of organic blue fluorescent material in a mixed solution of tributyl citrate and butyl benzoate, and stirring until the materials are completely dissolved to obtain a luminescent agent; wherein the mass ratio of tributyl citrate to butyl benzoate is 7: 2; the mass percentage concentration of the oxalate component is 4 percent, and the mass percentage concentration of the organic blue fluorescent material is 0.16 percent;

(2) the preparation method of the oxidant comprises the following steps:

dissolving 0.50g of hydrogen peroxide and 0.08g of tetrabutyl amine salicylate in glycerol triacetate, and stirring to obtain an oxidant; wherein, the mass percent concentration of the hydrogen peroxide is 4.0 percent, and the mass percent concentration of the tetrabutyl amine salicylate is 0.06 percent.

(3) Mixing the luminescent agent of step (1) and the oxidizing agent of step (2) (wherein the volume ratio of luminescent agent to oxidizing agent is 4: 1 chemiluminescent composition, measured as 300LUS by TES-1330A illumination meter adjacent to the wall of the luminophore, to a complete extinction duration of about 10 hours.

Example 5:

dissolving 3.75g of bis (2, 4, 5-trichloro salicylic acid n-amyl) oxalate (CPPO) and 0.075g of 9,10 (diacetylene) anthracene in a mixed solution of tributyl citrate and butyl benzoate, and stirring until the materials are completely dissolved to obtain a luminescent agent; wherein the mass ratio of tributyl citrate to butyl benzoate is 6: 4; the mass percentage concentration of the oxalate component is 15 percent, and the mass percentage concentration of 9,10 (diacetylene) anthracene is 0.30 percent;

(2) the preparation method of the oxidant comprises the following steps:

(3) And (3) mixing the luminous agent in the step (1) and the oxidizing agent in the step (2) (wherein the volume ratio of the luminous agent to the oxidizing agent is 1:4) to obtain a green environment-friendly chemiluminescent composition, and measuring the green environment-friendly chemiluminescent composition to be 300LUS by using a TES-1330A illumination instrument to be close to the wall of a luminescent test tube until the complete extinguishment duration is about 3 hours.

Example 6:

the synthesis method of the organic blue fluorescent material was the same as in example 5.

dissolving 2.5g of bis (2, 4, 5-trichloro salicylic acid n-amyl) oxalate (CPPO) and 0.06g of 9,10 (diacetylene) anthracene in a mixed solution of tributyl citrate and butyl benzoate, and stirring until the materials are completely dissolved to obtain a luminescent agent; wherein the mass ratio of tributyl citrate to butyl benzoate is 6: 4; the mass percentage concentration of the oxalate component is 10 percent, and the mass percentage concentration of 9,10 (diacetylene) anthracene is 0.24 percent;

(2) the preparation method of the oxidant comprises the following steps:

(3) And (3) mixing the luminous agent in the step (1) and the oxidizing agent in the step (2) (wherein the volume ratio of the luminous agent to the oxidizing agent is 1:1) to obtain a green environment-friendly chemiluminescent composition, and measuring the green environment-friendly chemiluminescent composition to be 280LUS by using a TES-1330A illumination instrument to be close to the wall of a luminescent test tube until the complete extinguishment duration is about 6 hours.

Example 7:

dissolving 6g (2, 4, 5-trichloro salicylic acid n-amyl) oxalate (CPPO) and 0.16g di (phenylethynyl) anthracene in a mixed solution of tributyl citrate and butyl benzoate, and stirring until the materials are completely dissolved to obtain a luminescent agent; wherein the mass ratio of tributyl citrate to butyl benzoate is 7: 2; the mass percent concentration of the oxalate component is 6 percent, and the mass percent concentration of 9,10 (diacetylene) anthracene is 0.16 percent;

(2) the preparation method of the oxidant comprises the following steps:

(3) Mixing the luminescent agent of step (1) and the oxidizing agent of step (2) (wherein the volume ratio of luminescent agent to oxidizing agent is 4: 1 chemiluminescent composition, measured as 250LUS by TES-1330A illumination meter adjacent to the wall of the luminophore, to a complete extinction duration of about 9 hours.

Example 8:

dissolving 8g of bis (2, 4, 5-trichloro salicylic acid n-amyl) oxalate (CPPO) and 0.20g of 9,10 (diacetylene) anthracene in a mixed solution of tributyl citrate and butyl benzoate, and stirring until the materials are completely dissolved to obtain a luminescent agent; wherein the mass ratio of tributyl citrate to butyl benzoate is 7: 2; the mass percentage concentration of the oxalate component is 4 percent, and the mass percentage concentration of 9,10 (diacetylene) anthracene is 0.18 percent;

(2) the preparation method of the oxidant comprises the following steps:

dissolving 1.5g of hydrogen peroxide and 0.05g of tetrabutyl amine salicylate in glycerol triacetate, and stirring to obtain an oxidant; wherein the mass percent concentration of the hydrogen peroxide is 5 percent, and the mass percent concentration of the tetrabutyl amine salt is 0.02 percent.

(3) And (3) mixing the luminous agent in the step (1) and the oxidizing agent in the step (2) (wherein the volume ratio of the luminous agent to the oxidizing agent is 1:1) to obtain a green environment-friendly chemiluminescent composition, and measuring the green environment-friendly chemiluminescent composition to be 280LUS by using a TES-1330A illumination instrument to be close to the wall of a luminescent test tube until the complete extinguishment duration is about 12 hours.

The above examples show that, after the fluorescent agent is replaced by the organic blue fluorescent material from 9,10- (diacetylene) anthracene, the luminous intensity is improved by about 10%, and the luminous time is prolonged by about 30%, and the organic blue fluorescent material has an excellent effect of combining with a green environment-friendly solvent, is a non-toxic green compound, and conforms to a green environment-friendly chemiluminescent composition.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.

Claims

1. A chemiluminescent composition comprising a luminescent agent and an oxidizing agent, said oxidizing agent comprising an oxide and a solvent a, said luminescent agent comprising a fluorescent agent and a solvent B, characterized in that: the solvent B is tributyl citrate and dipropylene glycol dimethyl ether, the fluorescent agent is an organic blue fluorescent material, and the solvent A is glycerol triacetate.

2. A chemiluminescent composition according to claim 1 wherein: the organic blue fluorescent material is prepared by performing Suzuki coupling reaction on 9-phenylanthracene-10 borate and 4, 4' -dibromodiphenyl disubstituted methane.

3. A chemiluminescent composition according to claim 1 wherein: the luminescent agent comprises, by weight, 100 parts of oxalate, 0.01-0.05 part of catalyst A and 1-1.5 parts of fluorescent agent.

4. A chemiluminescent composition according to claim 1 wherein: the oxidant comprises 1-60 parts by weight of tributyl citrate, 1-100 parts by weight of dipropylene glycol dimethyl ether, 2-5 parts by volume of 90% hydrogen peroxide and 0.01-0.05 part by weight of catalyst B.

5. A chemiluminescent composition according to claim 1 wherein: the mass ratio of the luminescent agent to the oxidant is 1: (2-3).

6. A chemiluminescent composition according to claim 3 wherein: the oxalate is bis (2, 4, 5-trichloro salicylic acid n-amyl ester) oxalate or bis (2, 4, 5-trichloro salicylic acid isoamyl ester) oxalate.

7. A chemiluminescent composition according to claim 3 wherein: the tributyl citrate includes n-tributyl citrate and acetyl tributyl citrate.

8. A chemiluminescent composition according to claim 3 wherein: the catalyst A is sodium salicylate.

9. A chemiluminescent composition according to claim 3 wherein: the catalyst B is sodium salicylate or tetrabutyl ammonium salicylate.

10. A method of preparing a chemiluminescent composition of any one of claims 1 to 9 comprising the steps of: