Field of the Invention

The invention relates to the field of synthesis of organic compounds, specifically to the synthesis of a compound of diamines with fluorescent properties, the method of its preparation, a polyimide film and a polyepoxide containing this diamine.

Background of the Invention

Diamines are organic compounds containing two amino groups that show high reactivity which is of substitutional origin. They are mainly used as monomers in the manufacture of polyamides or polyimides. Building up a pyridine nucleus through a reaction between substituted acetophenones, aldehyde and ammonium acetate in acetic acid has been known reaction for many years. The potential for this reaction to be used for the preparation of diaminopyridine is already mentioned in the literature.

The effort to prepare new diamines that would improve certain property of the polymers prepared therefrom is a topic for many research groups all over the world. Diamines are prepared on the basis of a wide range of structures and the influence is studied of their structure on the thermal stability, optical properties, mechanical properties and many other properties of the polymers prepared therefrom. Very few diamines that would cause the fluorescent properties of polymers are described in the literature.

The demand for fluorescent materials is increasing with the development of technology and optoelectronics. Commonly used compounds based on push-pull chromophores are thoroughly investigated and a large number of them are described in the literature. Compounds were prepared for specific applications with specific properties. However, low-molecular- weight organic compounds have limitations. They have significantly lower thermal stability and are generally better soluble compared to polymeric materials. In contrast, polymeric materials are stable even at higher temperatures and are resistant to washout, which significantly extends the lifespan of the material. Polymeric materials are easier to handle mechanically and machine. Therefore, there is also a growing interest in the creation of such a polymer that would have fluorescent properties and would replace fluorescent push-pull chromophores. However, the disadvantage of the monomers used so far for the preparation of these polymers is that their fluorescent activity is lost after incorporation into the polymer matrix.

The object of the invention is to prepare such compounds of diamines with a pyridine centre that would have good fluorescent properties, whereas their polymers, in particular polyimides and polyepoxides, would have these properties too. Another object of this invention is to prepare such compounds of diamines with a pyridine centre that would provide high thermally stable and flexible fluorescent polyimide films.

Summary of the Invention

This object is achieved by development of a diamine compound with fluorescent properties according to the present invention. It is the subject matter of the invention that the diamine compound consists of a pyridine centre of the general formula: where R is 3,4,5-trimethoxyphen-4-yl or 6-methoxynaphth-2-yl or ferrocenyl. These are fluorescent molecules with two amino groups. The presence of two primary amino groups allows incorporation into a polymer chain such as polyamides, polyimides, polyepoxy resins and others.

In a preferred embodiment, the given molecules were prepared by a two-step synthesis method. First, a 4-substituted (ferrocene, 1 ,2,3-trimethoxyphen-4-yl or 6-methoxynaphthalen- 2-yl) 2,6-bis(4-nitrophenyl)pyridine was prepared and synthesized from 4-nitroacetophenone and substituted aldehyde in the medium of ammonium acetate and acetic acid. The resulting dinitro compound was subsequently reduced to a diamino compound with hydrazine catalysed by palladium on activated carbon. This procedure was used for the preparation of 4-(3,4,5- trimethoxyphenyl)-2,6-bis(4-aminophenyl)pyridine referred to as PyDA-1 :

4-(6-methoxynaphth-2-yl)-2,6-bis(4-aminophenyl)pyridine referred to as PyDA-2: and 4-ferrocenyl-2,6-bis(4-aminophenyl)pyridine referred to as PyDA-3:

In a preferred embodiment, high thermally stable and flexible fluorescent polyimide films, which generally consist of at least one diamine and at least one dianhydride, may be preferably prepared from the mentioned diamines. Polyimide film may be prepared by substituting a portion of commercial diamine ranging from 0.001 to 100 wt% with newly prepared pyridine diamine. 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), cyclohexanetetracarboxylic dianhydride (CH DA) and pyromellitic acid dianhydride (PM DA) can be used as dianhydride for the preparation of fluorescent polyimide films. 4,4'-(4,4'- isopropylidenediphenyl-1 ,1'-diyldioxy)dianiline (BAPP), 2,2'-bis(trifluoromethyl)benzidine (TFMB) and 4,4'-oxydianiline (ODA) may be preferably used as diamine.

In another preferred embodiment, fluorescent polyepoxide networks may be prepared from diamines with a pyridine centre. Fluorescent polyepoxide networks may be prepared by incorporating pyridine diamine into polyepoxide prepared from commercially available epoxy resins and amines.

The main advantage of diamine compounds with a pyridine centre is that they have good fluorescent properties, whereas their polymers, in particular polyimides and polyepoxides, have these properties too. Another advantage of diamine compounds with a pyridine centre is that they provide high thermally stable and flexible fluorescent polyimide films.

Examples of the invention embodiments

Example 1

1 g of 6-methoxynaphthalene-2-carbaldehyde, 1.772 g of 1-(4-nitrophenyl)ethanone, and 15.89 g of ammonium acetate were mixed in 30 ml of glacial acetic acid in a reflux flask. The mixture was refluxed for 24 hours. After the reaction time, the precipitate formed was filtered and washed with water, ethanol and pentane. The resulting dinitro compound was dried for 24 hours in a vacuum oven. 1 .33 g was obtained with a yield of 52 wt% in the form of a red powder. 500 mg and 10 mg of Pd/C were suspended in 3 ml of ethanol and 1 ml of DMF in a threenecked flask. The resulting suspension was heated to 80°C and a solution of 1.4 ml of N2H2 H2O in 2 ml of ethanol was added dropwise. The resulting solution was then heated for 4 hours. After the reaction time, the solution was hot filtered through celite, dissolved in water, extracted with dichloromethane and concentrated on a vacuum evaporator. The product was purified by column chromatography with a mobile phase of DCM. 202 mg was obtained, corresponding to a yield of 46 wt% in the form of an orange powder, with Rf = 0.65 (DCM).

Example 2

1 g of 3,4,5-trimethoxybenzaldehyde, 1.683 g of 1-(4-nitrophenyl)ethanone, and 15.71 g of ammonium acetate were mixed in 30 ml of glacial acetic acid in a reflux flask. The mixture was refluxed for 24 hours. The precipitate formed was filtered and washed with water, ethanol and pentane after the reaction time. The resulting dinitro compound was dried for 24 hours in a vacuum oven. 0.95 g was obtained, corresponding to a yield of 38 wt% in the form of an orange powder. 500 mg and 10 mg of Pd/C were suspended in 3 ml of ethanol and 1 ml of DMF in a three-necked flask. The resulting suspension was heated to 80°C and a solution of 1.4 ml of N2H2 H2O in 2 ml of ethanol was added dropwise. The resulting solution was then heated for 4 hours. After the reaction time, the solution was hot filtered through celite, dissolved in water, extracted with dichloromethane and concentrated on a vacuum evaporator. The product was purified by column chromatography with a mobile phase of dichloromethane (DCM). 327 mg was obtained, corresponding to a yield of 76 wt% in the form of an orange powder, with Rf = 0.7 (DCM). Example 3

1 g of ferrocenecarbaldehyde, 1.542 g of 1-(4-nitrophenyl)ethanone, and 13.83 g of ammonium acetate were mixed in 30 ml of glacial acetic acid in a reflux flask. The mixture was refluxed for 24 hours. After the reaction time, the precipitate formed was filtered and washed with water, ethanol and pentane. The resulting dinitro compound was dried for 24 hours in a vacuum oven. 1.06 g was obtained, corresponding to a yield of 45 wt% in the form of a black powder. 500 mg and 10 mg of Pd/C were suspended in 3 ml of ethanol and 1 ml of DM F in a three-necked flask. The resulting suspension was heated to 80°C and a solution of 1.4 ml of N2H2 H2O in 2 ml of ethanol was added dropwise. The resulting solution was then heated for 4 hours. After the reaction time, the solution was hot filtered through celite, dissolved in water, extracted with dichloromethane and concentrated on a vacuum evaporator. The product was purified by column chromatography with a mobile phase of DCM. 101 mg was obtained, corresponding to a yield of 23 wt% in the form of a black powder, with Rf = 0.4 (DCM).

Example 4

1 g of cyclohexanetetracarboxylic dianhydride (CHDA) and 0.051 g of the fluorescent diamine 4-(3,4,5-trimethoxyphenyl)-2,6-bis(4-aminophenyl)pyridine were gradually added to 1.78 g of 4,4'-(4,4'-isopropylidenediphenyl-1 ,1'-diyldioxy)dianiline (BAPP) dissolved in 12 g of the solvent, i.e. N-methyl-2-pyrrolidone; the mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the dimethyl acetamide or dimethylformamide solvent was used. Example 5

1 g of CHDA and 0.050 g of the fluorescent diamine 4-(6-methoxynaphth-2-yl)-2,6-bis(4- aminophenyl)pyridine were gradually added to 1.78 g of diamine BAPP dissolved in 12 g of dimethyl acetamide; the mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethylformamide solvent was used.

Example 6

1 g of dianhydride CHDA and 0.044 g of the fluorescent diamine 4-ferrocenyl-2,6-bis(4- aminophenyl)pyridine were gradually added to 1.78 g of diamine BAPP dissolved in 12 g of dimethylformamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the dimethyl acetamide or N-methyl-2-pyrrolidone solvent was used.

Example 7

1 g of dianhydride CHDA and 0.051 g of the fluorescent diamine 4-(3,4,5-trimethoxyphenyl)- 2,6-bis(4-aminophenyl)pyridine were gradually added to 0.87 g of 4,4'-oxydianiline or (ODA) dissolved in 12 g of N-methyl-2-pyrrolidone. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the dimethyl acetamide or dimethylformamide solvent was used.

Example 8

1 g of dianhydride CHDA and 0.050 g of the fluorescent diamine 4-(6-methoxynaphth-2-yl)- 2,6-bis(4-aminophenyl)pyridine were gradually added to 0.87 g of diamine ODA dissolved in 12 g of dimethyl acetamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethylformamide solvent was used.

Example 9

1 g of dianhydride CHDA and 0.044 g of the fluorescent diamine 4-ferrocenyl-2,6-bis(4- aminophenyl)pyridine were gradually added to 0.87 g of diamine ODA dissolved in 12 g of dimethylformamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethyl acetamide solvent was used.

Example 10

1 g of dianhydride CHDA and 0.051 g of the fluorescent diamine 4-(3,4,5-trimethoxyphenyl)- 2,6-bis(4-aminophenyl)pyridine were gradually added to 1.39 g of diamine 2,2'- bis(trifluoromethyl)benzidine (TFMB) dissolved in 12 g of dimethylformamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethyl acetamide solvent was used.

Example 11

1 g of dianhydride CHDA and 0.050 g of the fluorescent diamine 4-(6-methoxynaphth-2-yl)- 2,6-bis(4-aminophenyl)pyridine were gradually added to 1.39 g of diamine TFMB dissolved in 12 g of N-methyl-2-pyrrolidone. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the dimethyl acetamide or dimethylformamide solvent was used.

Example 12

1 g of dianhydride CHDA and 0.044 g of the fluorescent diamine 4-ferrocenyl-2,6-bis(4- aminophenyl)pyridine were gradually added to 1.39 g of diamine TFMB dissolved in 12 g of dimethyl acetamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethylformamide solvent was used.

Example 13

1.98 g of dianhydride 4,4'-(hexafluoroisopropylidene)diphthalanhydride (6FDA) and 0.051 g of the fluorescent diamine 4-(3,4,5-trimethoxyphenyl)-2,6-bis(4-aminophenyl)pyridine were gradually added to 1.78 g of diamine BAPP dissolved in 12 g of dimethyl acetamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another nonillustrated embodiment, the N-methyl-2-pyrrolidone or dimethylformamide solvent was used.

Example 14

1 .98 g of dianhydride 6FDA and 0.050 g of the fluorescent diamine 4-(6-methoxynaphth-2-yl)- 2,6-bis(4-aminophenyl)pyridine were gradually added to 1.78 g of diamine BAPP dissolved in 12 g of dimethylformamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethyl acetamide solvent was used. Example 15

1.98 g of dianhydride 6FDA and 0.044 g of the fluorescent diamine 4-ferrocenyl-2,6-bis(4- aminophenyl)pyridine were gradually added to 1.78 g of diamine BAPP dissolved in 12 g of N- methyl-2-pyrrolidone dimethyl acetamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the dimethyl acetamide or dimethylformamide solvent was used.

Example 16

1 .98 g of dianhydride 6FDA and 0.051 g of the fluorescent diamine 4-(3,4,5-trimethoxyphenyl)-

2.6-bis( 4-aminophenyl)pyridine were gradually added to 0.87 g of diamine ODA dissolved in 12 g of N-methyl-2-pyrrolidone. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the dimethyl acetamide or dimethylformamide solvent was used.

Example 17

1 .98 g of dianhydride 6FDA and 0.050 g of the fluorescent diamine 4-(6-methoxynaphth-2-yl)-

2.6-bis(4-aminophenyl)pyridine were gradually added to 0.87 g of diamine ODA dissolved in 12 g of dimethyl acetamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethylformamide solvent was used.

Example 18

1.98 g of dianhydride 6FDA and 0.044 g of the fluorescent diamine 4-ferrocenyl-2,6-bis(4- aminophenyl)pyridine were gradually added to 0.87 g of diamine ODA dissolved in 12 g of dimethylformamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethyl acetamide solvent was used.

Example 19

1 .98 g of dianhydride 6FDA and 0.051 g of the fluorescent diamine 4-(3,4,5-trimethoxyphenyl)- 2,6-bis(4-aminophenyl)pyridine were gradually added to 1.39 g of diamine TFMB dissolved in 12 g of N-methyl-2-pyrrolidone. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the dimethyl acetamide or dimethylformamide solvent was used.

Example 20

1 .98 g of dianhydride 6FDA and 0.050 g of the fluorescent diamine 4-(6-methoxynaphth-2-yl)- 2,6-bis(4-aminophenyl)pyridine were gradually added to 1.39 g of diamine TFMB dissolved in 12 g of dimethyl acetamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethylformamide solvent was used.

Example 21

1.98 g of dianhydride 6FDA and 0.044 g of the fluorescent diamine 4-ferrocenyl-2,6-bis(4- aminophenyl)pyridine were gradually added to 1.39 g of diamine TFMB dissolved in 12 g of dimethylformamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethyl acetamide solvent was used.

Example 22

0.97 g of dianhydride PMDA and 0.051 g of the fluorescent diamine 4-(3,4,5- trimethoxyphenyl)-2,6 -bis(4-aminophenyl)pyridine were gradually added to 1.78 g of diamine BAPP dissolved in 12 g of N-methyl-2-pyrrolidone. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the dimethyl acetamide or dimethylformamide solvent was used.

Example 23

0.97 g of dianhydride PMDA and 0.050 g of the fluorescent diamine 4-(6-methoxynaphth-2-yl)- 2,6-bis(4-aminophenyl)pyridine were gradually added to 1.78 g of diamine BAPP dissolved in 12 g of dimethyl acetamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethylformamide solvent was used.

Example 24

0.97 g of dianhydride PMDA and 0.044 g of the fluorescent diamine 4-ferrocenyl-2,6-bis(4- aminophenyl)pyridine were gradually added to 1.78 g of diamine BAPP dissolved in 12 g of dimethylformamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethyl acetamide solvent was used. Example 25

0.97 g of dianhydride PMDA and 0.051 g of the fluorescent diamine 4-(3,4,5- trimethoxyphenyl)-2,6-bis(4-aminophenyl)pyridine were gradually added to 0.87 g of diamine ODA dissolved in 12 g of N-methyl-2-pyrrolidone. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the dimethyl acetamide or dimethylformamide solvent was used.

Example 26

0.97 g of dianhydride PMDA and 0.050 g of the fluorescent diamine 4-(6-methoxynaphth-2-yl)- 2,6-bis(4-aminophenyl)pyridine were gradually added to 0.87 g of diamine ODA dissolved in 12 g of dimethyl acetamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethylformamide solvent was used.

Example 27

0.97 g of dianhydride PMDA and 0.044 g of the fluorescent diamine 4-ferrocenyl-2,6-bis(4- aminophenyl)pyridine were gradually added to 0.87 g of diamine ODA dissolved in 12 g of dimethylformamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethyl acetamide solvent was used.

Example 28

0.97 g of dianhydride PMDA and 0.051 g of the fluorescent diamine 4-(3,4,5- trimethoxyphenyl)-2,6-bis(4-aminophenyl)pyridine were gradually added to 1.39 g of diamine TFMB dissolved in 12 g of N-methyl-2-pyrrolidone. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the dimethyl acetamide or dimethylformamide solvent was used.

Example 29

0.97 g of dianhydride PMDA and 0.050 g of the fluorescent diamine 4-(6-methoxynaphth-2-yl)- 2,6-bis(4-aminophenyl)pyridine were gradually added to 1.39 g of diamine TFMB dissolved in 12 g of dimethyl acetamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethylformamide solvent was used.

Example 30

0.97 g of dianhydride PMDA and 0.044 g of the fluorescent diamine 4-ferrocenyl-2,6-bis(4- aminophenyl)pyridine were gradually added to 1.39 g of diamine TFMB dissolved in 12 g of dimethylformamide. The mixture was stirred for 24 hours under an inert atmosphere to prepare polyamic acid. A film was then prepared from the resulting polyamic acid, which was pre-dried at 50°C for 4 hours. The actual curing of the protective film then took place under vacuum at the following temperatures: 150°C for 2 hours, 200°C for 2 hours and 300°C for 1 hour. In another non-illustrated embodiment, the N-methyl-2-pyrrolidone or dimethyl acetamide solvent was used.

Example 31

1 g of Jeffamine D-230 and 5 mg of PyDA-1 were added to 2.75 g of epoxy resin CHS 619. The resulting solution was intensively stirred for 10 minutes. The resulting solution was applied to a glass plate and dried in an oven at 80°C for 20 hours and at 130°C for 6 hours. Example 32

1 g of Jeffamine D-230 and 5 mg of PyDA-2 were added to 2.75 g of epoxy resin CHS 619. The resulting solution was intensively stirred for 10 minutes. The resulting solution was applied to a glass plate and dried in an oven at 80°C for 20 hours and at 130°C for 6 hours.

Example 33

1 g of Jeffamine D-230 and 5 mg of PyDA-3 were added to 2.75 g of epoxy resin CHS 619. The resulting solution was intensively stirred for 10 minutes. The resulting solution was applied to a glass plate and dried in an oven at 80°C for 20 hours and at 130°C for 6 hours.

Example 34

1 g of Jeffamine T-403 and 5 mg of PyDA-1 were added to 2.16 g of epoxy resin CHS 619. The resulting solution was intensively stirred for 10 minutes. The resulting solution was applied to a glass plate and dried in an oven at 80°C for 20 hours and at 130°C for 6 hours.

Example 35

1 g of Jeffamine T-403 and 5 mg of PyDA-2 were added to 2.16 g of epoxy resin CHS 619. The resulting solution was intensively stirred for 10 minutes. The resulting solution was applied to a glass plate and dried in an oven at 80°C for 20 hours and at 130°C for 6 hours.

Example 36

1 g of Jeffamine T-403 and 5 mg of PyDA-3 were added to 2.16 g of epoxy resin CHS 619. The resulting solution was intensively stirred for 10 minutes. The resulting solution was applied to a glass plate and dried in an oven at 80°C for 20 hours and at 130°C for 6 hours.

Example 37

1 g of I PDA and 5 mg of PyDA-1 were added to 3.72 g of epoxy resin CHS 619. The resulting solution was intensively stirred for 10 minutes. The resulting solution was applied to a glass plate and dried in an oven at 80°C for 20 hours and at 130°C for 6 hours.

Example 38

1 g of I PDA and 5 mg of PyDA-2 were added to 3.72 g of epoxy resin CHS 619. The resulting solution was intensively stirred for 10 minutes. The resulting solution was applied to a glass plate and dried in an oven at 80°C for 20 hours and at 130°C for 6 hours. Example 39

1 g of I PDA and 5 mg of PyDA-3 were added to 3.72 g of epoxy resin CHS 619. The resulting solution was intensively stirred for 10 minutes. The resulting solution was applied to a glass plate and dried in an oven at 80°C for 20 hours and at 130°C for 6 hours.

Industrial applicability

Diamine compounds with fluorescent properties, the method of its preparation, polyimide film and polyepoxide containing this diamine according to the present invention can be used to prepare polymers with fluorescent properties that can be used, in particular, in optoelectronics or as scintillators.