Chemiluminescent composition


(57) Abstract:

Objective: development of a new chemiluminescent compositions on the basis of bis [1-(1H)-2-pyridinyl] glyoxal, which would have improved lighting performance (time or more illumination created by the recipe). This was based on the objective to reduce the composition through the use of cheaper domestic components. This goal is achieved by using as the acid activator is a mixture of acids. The application describes a method of preparation of chemiluminescent compositions of different colors, including the possibility of obtaining light sources of white light phosphors, overlapping peaks of fluorescence in the whole visible range of the spectrum. 10 table.

The invention relates to organic chemistry, in particular to compositions for obtaining light emission in the course of the chemiluminescent reaction.

Chemiluminescent compositions (Khibiny-Lovozero alkaline complex), as a source of visible light, are well known and are produced in the global industry. Light sources based on the Khibiny-Lovozero alkaline complex are widely used mainly as a safe, nadejnogo lighting or signalling.

The industry produces Khibiny-Lovozero alkaline complex on the basis of the most efficient currently on the light output peroxide-oxalate systems, in particular on the basis of the bis/2,4,5-trichloro-6-carbomethoxybiphenyl/oxalate or other similar chlorinated aromatic substances. Further the industrial production of such Khibiny-Lovozero alkaline complex insurmountable difficulties because of the increasing demands of environmentalists lead to the prohibition of the use of such chlorinated aromatic substances because of the danger of infection of nature powerful toxicants, such as 2,3,7,8-tetrachlorodibenzo-p-dioxin or its analogs.

Increasing environmental and other complex requirements for the competitiveness of the Khibiny-Lovozero alkaline complex has forced researchers to refer to the Khibiny-Lovozero alkaline complex based on the derivatives of glyoxal, for example bis/1-(1H)-2-pyridinyl/glyoxal. This substance is capable under the influence of oxidizing agents to cause sensitization of the chemiluminescent reaction with a lower quantum yield than chlorinated derivatives of oxalic acid, but in contrast to the latter is not able to generate in the Khibiny-Lovozero alkaline complex ecotoxicants and can be used to create environmentally safe chemical sources of conformitiy for over twenty-five years [1 6] the professionals they are available mainly in laboratories and test samples, as suitable for mass-production technology, competitive Khibiny-Lovozero alkaline complex must meet the complex hard diversified requirements.

Data on composition, light and energy characteristics known from literary sources chemiluminescent compositions based on bis/1-(1H)-2-pyridinyl/glyoxal are given in table. 1 with reference to the source.

It should be noted that in table. 1 includes data from the most effective of the Khibiny-Lovozero alkaline complex described in the literature. In addition, for comparison and evaluation of the Khibiny-Lovozero alkaline complex, are presented in table. 1, was calculated their specific light energy QIDas a General characteristic of the composition employed as a light source. The value of QIDcalculated in accordance with Einstein's law:


where is the quantum yield, Einstein/mol;

to the light radiation efficiency (683 LM/W);

c BPG concentration, mol/l;

v() is the relative spectral luminous efficiency;

wavelength, nm.

Best lighting characteristics of the table. 1 Khibiny-Lovozero alkaline complex is under 3, which emits light energy after adding hydrogen peroxide to the mixture of the other is a rule high lighting performance and not suitable for to this Khibiny-Lovozero alkaline complex to put in the technology of industrial production of chemical light sources (maximum brightness 89,8 CD/m2the value of specific light energy 3,05105Mel/l, the actual illuminance at a distance of 50 mm from the sensor luxora Yu-117 with a diameter of 60 mm for post glowing Khibiny-Lovozero alkaline complex with height of 85 mm and a diameter of 14 mm is 8,01 Suite).

The aim of the invention is to develop new environmentally friendly chemiluminescent composition based on bis/1-(1H)-2-pyridinyl/glyoxal with improved lighting performance, and the cheapening of the chemiluminescent composition.

This is achieved by using as the acid activator is a mixture of acids.

The invention consists in that the Khibiny-Lovozero alkaline complex contains bis/1-(1H)-2-pyridinyl/glyoxal, a source of hydrogen peroxide, a phosphor, an acid activator (which is used as the mixture of acids) and the solvent, and the components of the composition used in the following ratio,mol/l:

Bis/1-(1H)-2-pyridinyl/glyoxal 0,03 0,7

The source of hydrogen peroxide (in terms of 98% H2ABOUT2) 0,03 0,85

The phosphor 1-CL-9,10-BAFE 1,2510-31,2010-2< / BR>
Strong acid 1,010-31,5
An industrial version of the chemiluminescent composition is a composition in which the components to bring the composition to a working state with the purpose of reception of the light are two, preferably three isolated from other tanks, which at the right moment destroyed with the aim of combining and mixing components of the composition to bring the Khibiny-Lovozero alkaline complex in working condition with the aim of obtaining light. Implemented composition most often in the next version.

Bis/1-(1H)-2-pyridinyl/glyoxal in the form of a solution, suspension, paste or powder, and a source of hydrogen peroxide are sealed in two separate glass vials, which are placed in series (train), in parallel (side by side) or coaxial (one ampoule inside the other) in a plastic, for example polyethylene, the container in the form of a cylinder, flat boxes, hemisphere, etc., in which is located an acid activator, the phosphor and part or all of the solvent. Option two isolated from other containers (vials). In this case, part of the components, preferably solid state, placed in a glass ampoule with the aim of increasing the timeframe for the possible storage of the composition, solid-phase components may be separated layers is lohanulsya options ampoules are placed in a larger container, plastic container, wherein the ampoule razduplyayutsya without violating the integrity of the plastic container (housing). The ideal model of industrial chemical light source is a product containing a transparent casing only sealed glass ampoules. The shelf life of such products is the highest possible.

As a source of hydrogen peroxide (oxidant) may be used hydrogen peroxide solution in water, dimethylphthalate or mixture dimethylphthalate with tert-butanol in the so-called Salvaterra proportions, and also complexes of hydrogen peroxide with urea, ndimethylacetamide, urethane, etc.

As the phosphor can be used preferably 1-chloro-9,10-bis(phenylethynyl)anthracene or 1,4-dimethyl-9,10-bis(phenylethynyl)anthracene, and 9,10-bis(chloromethyl)anthracene; 9,10-bis(parameterfor)anthracene; 9,10-bis(phenylethynyl)anthracene, and other aromatic compounds, are able to participate and influence the process of sensitized chemiluminescence.

As the acid activator is a mixture of acids, for which the logarithm of the ionization constants in water first acid differs from lagarith is lifocolor, aromatic, carboxylic and mineral acids.

The solvent in the chemiluminescent composition is s-dimethylphthalate.

In particular, used in the Khibiny-Lovozero alkaline complex mixture of phosphors having a fluorescence maxima in different areas of the spectrum of visible radiation, enables the production of chemical sources of light of a desired color, for example white. To achieve this goal is necessary to use additives as phosphors or dyes of compounds such as rhodamine, butyl ether rhodamine, tetrachloro-9,10-bis(phenylethynyl)anthracene, daylight fluorescent pigments orange-red region of the spectrum of visible radiation.

Offer chemiluminescent composition prepared according to the following procedure.

1. In a separate container prepare a solution of two acids and phosphor in dimethylphthalate. When the complete dissolution of the components receive the acidic activator.

2. In a separate container prepare a solution of 10% hydrogen peroxide; 76.5% of dimethylphthalate and 13.5% of tertiary-butyl alcohol.

3. In a separate flask (capacity) prepare a solution or suspension, or paste, or solid powder material, smesi and make the necessary measurements.

The proposed composition of the chemiluminescent compositions are given in table. 3.

The lighting characteristics of the proposed chemiluminescent composition compared to the Khibiny-Lovozero alkaline complex of the prototype are given in table. 4.

Thus, the proposed Khibiny-Lovozero alkaline complex ensures the creation of the industrial version of Khibiny-Lovozero alkaline complex for equipment chemical light sources with higher values of the specific light energy, the maximum luminance and the maximum luminance in the comparable measurement conditions.

Example 1. Lighting measurements were carried out at the facility, which included: light bench (GOST 17616-82), in which the integrated sensor photometer radiometer "Quartz-01" with a measuring range of 10-2w102w or 10-2Luke 102Luke with a digital voltmeter and a potentiometer for recording functions of time, the intensity of light emission. On the development stage of the formulation in an industrial variant of the measurements were carried out using the original rotating light tripod, equipped with a sensor luxora Yu-117 or s-116, as well as using a photometer DRF-PI.4.2.

Quantitative lighting tests, designed to identify the effect of individual acids as l, were carried out as follows: 0.3 ml of a solution containing 10% anhydrous hydrogen peroxide; 13,5% tert-butyl alcohol and 76.5% of dimethylphthalate was sealed in a glass ampoule and placed inside a second, larger diameter, glass ampoules, which were placed a solution of 230 mg PLU in dimethylphthalate or suspension 230 ml PLU in 0,84 ml dimethylphthalate, or pasta 230 mg PLU in 0.1 ml of dimethylphthalate, or dry powder 230 mg PLU. The second vial was also sealed. In plastic case chemical light source is a tube length of 14 cm and a diameter of 1.4 cm was loaded 8,5 ml dimethylphthalate with dissolved 25 mg of phosphor 1-chloro-9,10-bis(phenylethynyl)anthracene or 23 mg of phosphor 1,4-dimethyl-9,10-bis(phenylethynyl)anthracene, or 34 mg of phosphor 9,10-bis(chloromethyl)anthracene, or 21 mg of phosphor 9,10-bis(parameterfor)anthracene, or 20 mg of phosphor 9,10-bis(phenylethynyl)anthracene. In addition, 8.5 ml dimethylphthalate add test acid or a mixture of individual acids as acidic activator chemiluminescent reaction in the quantities listed in the summary tables. After that the plastic housing was sealed, bent to fracture the glass vials and vigorously shook along the axis within 3 to 5, after which the output is shown the influence of individual aliphatic and aromatic acids on the maximum luminous intensity Khibiny-Lovozero alkaline complex Imax., (Rel. units), the brightness of the Khibiny-Lovozero alkaline complex kg/m2and duration of glow to the light intensity Ithe end.7,510-3kg.

Depending on the component ratio of the Khibiny-Lovozero alkaline complex, in accordance with the stoichiometry of the chemiluminescent process, the result of the reaction, i.e. the amount of light and the lighting time can be different. High concentrations of acid activator while maintaining constant concentrations of other reagents lead to a sharp increase in the values of optical characteristics and an equally dramatic decrease in the time interval of operation of the source of light. Therefore, the authors did not present the characteristics of one recipe, and give a complete overview of the properties of real recipes. The data presented in table. 5 9.

Examples 2 to 9. The experiments were conducted under the conditions described in example 1, but using as the acid activator is a mixture of two acids in the concentrations listed in table. 7. The use of a mixture of acids, unexpected and unpredictable theoretical effect of their influence on the Khibiny-Lovozero alkaline complex, allows to improve the lighting performance light source to increase the duration of the glow to the specified limit.

In addition, the use of mixtures of acids as acid activating environmental plan components.

Example 10. In the conditions of example 1, but at a concentration of BPG 50% below that there is a decrease in the brightness of the Khibiny-Lovozero alkaline complex 30 35%

Example 11. In the conditions of example 1, but with an increase in the concentration of BPG on 50% brightness Khibiny-Lovozero alkaline complex increases by 20 23% When using the Khibiny-Lovozero alkaline complex in the industrial light sources is not economically feasible to increase the brightness of the source by increasing the concentration of BPG.

Example 12. In the conditions of example 1, but by increasing the concentration of the phosphor 100% change of optical characteristics is negligible. Found the concentration of the phosphor of this system is the best.

Example 13. In the conditions of example 1, but at lower concentrations up to 50% of the phosphor increases the brightness of the Khibiny-Lovozero alkaline complex, not more than 10% but at the same time, the glow of the composition is reduced by 22%

Example 14. In the conditions of example 1, but by increasing the concentration of hydrogen peroxide at 100% dimming Khibiny-Lovozero alkaline complex, and reducing the time glow.

Example 15. In the conditions of example 1, but at a lower concentration of hydrogen peroxide at 50% dimming Khibiny-Lovozero alkaline complex and time glow.

Example 16. In the conditions of example 1, but using as the activator is a mixture of two

Thus, the authors have developed a new chemiluminescent composition for industrial chemical light sources based on bis/1-(1H)-2-pyridinyl/glyoxal using unexpectedly discovered effect of the mixture of acids as activators of light emission. The composition, as indicated in the text exceeds the prototype on lighting options and on-time glow. In addition, the acid used for the activator, are widely used in practice reagents.

Offer Khibiny-Lovozero alkaline complex does not contain in its composition of substances hazard class 1 according to GOST 12.1.007-88 and approved by the Ministry of health of the Russian Federation for use in the chemical light sources.

Chemiluminescent composition comprising bis-[1-(1H)-2-pyridinyl]glyoxal, hydrogen peroxide 98%, phosphor acid activator and an organic solvent, characterized in that the luminescent material it contains a derivative of anthracene, as the acid activator is a mixture of strong and weak acids, for which the difference of the logarithm of the ionization constants in water more than the value of 0.5, and as the organic solvent of tert-butanol and dimethylphthalate in the following ratio of components, mol/l:

Bis[2-(1H)-2-SUP>< / BR>
Strong acid 1,0 10-31,5

Weak acid 0,3 5,0

Tert-butanol 0,045 1,275

Dimethylphthalate Else


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