Deuterated azaadenine as well as preparation method and application thereof

Abstract

The invention provides deuterated aza-adenine and a preparation method and application thereof.The deuterated aza-adenine has the structure shown in the formula (I), the deuterated aza-adenine compound can improve the molecular stability, the copper surface binding force of a product is improved when the deuterated aza-adenine compound is applied to a photosensitive composition, and the yield of the product is improved. And other application performances of the molecules are not influenced.

Description

Technical Field

[0001] The present invention belongs to the field of organic chemistry, and particularly relates to a deuterated azaadenine, a preparation method thereof, and an application thereof. Background Art

[0002] Polyimide is a kind of polymer material with high heat resistance, good chemical stability, excellent mechanical properties and electrical properties, which contains imide rings in the main chain. Since it was developed and industrialized by DuPont Company in the United States in the 1960s, polyimide has been widely used in high-tech fields such as aviation, aerospace, electrical, microelectronics, and automotive. It is one of the engineering plastics with the best heat resistance in the current market. The excellent properties of imide enable it to have a wide range of applications in the field of electronic technology. For example, on the printed circuit board of large-scale integrated circuits, it can be used as an interlayer insulating film connecting the thin film and the multi-chip module or a protective film for electronic components, and as a liquid crystal alignment film or packaging material in liquid crystal displays, etc.

[0003] Bio-based monomers represented by purine compounds such as 8-azaadenine have been widely used in the manufacture of polyimide compounds. However, in practical applications, the copper surface adhesion of the products after application still needs to be further improved. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a deuterated azaadenine, a preparation method thereof, and an application thereof.

[0005] To achieve this purpose, the present invention adopts the following technical solutions:

[0006] On the one hand, the present invention provides a deuterated azaadenine, and the deuterated azaadenine has a structure shown in formula (I):

[0007]

[0008] Wherein, R1 and R2 independently represent hydrogen or a straight-chain or branched-chain alkyl group of C1-C 10 30.

[0009] The inventors surprisingly found that for the purine compounds containing deuterium substitution as described above, the copper surface adhesion of the products after application is improved, and other application properties of the molecules are not affected.

[0010] In the present invention, the C1-C 10 38 can be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C 10 10.

[0011] Preferably, the deuterated azaadenine is any one of the following compounds:

[0012]

[0013] On the other hand, the present invention provides a method for preparing deuterated azaadenine as described above, and the preparation method includes the following steps:

[0014] Compound a reacts with heavy water in the presence of a catalyst to obtain the deuterated azaadenine shown in the formula (I), and the reaction formula is as follows:

[0015]

[0016] Preferably, the catalyst is selected from trifluoromethanesulfonic anhydride and / or pentafluoroethylsulfonic anhydride.

[0017] In the above reaction, the solvent is not particularly limited as long as it can dissolve the product and has no adverse effect on the reaction. Preferably, the solvent for the reaction is selected from dioxane and / or tetrahydropyran.

[0018] Preferably, compound a and heavy water are dissolved in a solvent, cooled to 10 - 15 °C (such as 10 °C, 11 °C, 12 °C, 13 °C, 14 °C or 15 °C) in an ice - water bath, and the catalyst is added.

[0019] Preferably, the reaction is carried out under heating and reflux, and the reaction time is 8 - 20 h, such as 8 h, 10 h, 12 h, 15 h, 18 h or 20 h.

[0020] In the present invention, after the reaction is completed, the solvent is removed by distillation under reduced pressure, cooled and filtered, washed with water and recrystallized to obtain the deuterated azaadenine shown in the formula (I).

[0021] On the other hand, the present invention provides the application of the deuterated azaadenine as described above in polyimide materials.

[0022] On the other hand, the present invention provides a photosensitive composition, and the photosensitive composition contains a polyimide resin, the deuterated purine compound as described above and an initiator.

[0023] Preferably, based on 100 parts by mass of the polyimide resin, the contents of the components in the photosensitive composition are as follows:

[0024] 0.1 - 10 parts (such as 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts) of the deuterated purine compound and 1 - 20 parts (such as 1 part, 3 parts, 5 parts, 7 parts, 9 parts, 10 parts, 12 parts, 15 parts, 18 parts or 20 parts) of the initiator.

[0025] Preferably, the polyimide resin is at least one resin selected from polyamic acid, polyamic acid ester of polyimide precursor, polyhydroxyamide which can be used as polyoxazole precursor, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole or polybenzothiazole.

[0026] Preferably, the initiator is selected from at least one of benzophenone initiators, α - aminoketone initiators, α - hydroxyketone initiators, thioxanthone initiators, organophosphorus initiators, oxime ester initiators or imidazole initiators.

[0027] On the other hand, the present invention provides a cured film, which is obtained by curing the photosensitive composition as described above.

[0028] On the other hand, the present invention provides a semiconductor chip buffer layer or a semiconductor package layer, which comprises the photosensitive composition or the cured film as described above.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] The deuterated azaadenine of the present invention can improve the copper surface binding force after the application of the composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 1H NMR spectrum of raw material 8 - azaadenine in Preparation Example 1;

[0032] Figure 2 1H NMR spectrum of the product in Preparation Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0033] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0034] Preparation Example 1

[0035]

[0036] 13.6 g of 8 - azaadenine, 5.0 g of heavy water and 50 mL of dioxane were added into a 500 mL four - necked flask, cooled in an ice - water bath, and the temperature was controlled at about 15°C. 56.4 g of trifluoromethanesulfonic anhydride was added in batches over about 1 h. After heating and stirring under reflux for 6 h, the reaction solvent and excess heavy water were removed by vacuum distillation. The product was poured into water, stirred continuously, filtered, washed with water, and recrystallized from tetrahydrofuran to obtain 12.5 g of white solid, which was the target product.

[0037] The structure of Product 1 was confirmed by mass spectrometry and proton nuclear magnetic resonance spectroscopy: MS (m / z): 138 (M+H) + .

[0038] 1 H-NMR (DMSO3, 400 MHz, pyrazine internal standard): δ 7.88 (s, 3H).

[0039] The proton nuclear magnetic resonance spectrum of its raw material 8-azapurine is as shown in Figure 1 , and the proton nuclear magnetic resonance spectrum of the product is as shown in Figure 2 . By comparing the two, it can be seen that the peak at 8.17 - 8.30 ppm in the product disappears.

[0040] Furthermore, by referring to the method of Preparation Example 1, the following Compounds 2 - 11 were prepared from different starting material Compound a:

[0041]

[0042] Compounds 2 - 11 were also confirmed by mass spectrometry.

[0043] Application Example

[0044] By formulating an exemplary photosensitive resin composition, the application performance of the compound represented by Formula (I) of the present invention was tested.

[0045] The formulation of the photosensitive resin composition is as follows:

[0046]

[0047]

[0048] The polyimide resin is TR-PSPI-RS101 produced by Changzhou Lidel Material Co., Ltd.; the purine compound is the deuterated compound represented by General Formula (I) of the present invention or a conventional purine compound for comparison, the photoinitiator is 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-3-cyclopentyl-propane-1-one-acetoxime ester, the monomer is tetraethylene glycol dimethacrylate, and the solvent is N-methylpyrrolidone;

[0049] The above-mentioned photocurable composition was stirred under a yellow light until it was transparent and uniform, and then coated on a Cu substrate with a coater. After soft baking, a coating film with a thickness of 10 μm was formed. Then it was exposed in a step exposure machine at 500 mj / cm 2 , and then developed in cyclopentanone for 60 seconds to obtain a cured film.

[0050] The obtained cured film was heat-treated at 350 °C for 1 hour under nitrogen protection. The prepared film was placed in a high-temperature, high-humidity, and high-pressure chamber (temperature 130 °C, relative humidity 85%), and after 200 hours, the change in the copper surface adhesion of the film before and after was observed. The copper surface adhesion was tested by the cross-cut method, and the evaluation results are shown in Table 2 below.

[0051] Table 2

[0052]

[0053] Comparative compound 1 is: Comparative compound 2 is: Comparative compound 3 is: Comparative compound 4 is

[0054] As can be seen from the above table, for the deuterium-substituted purine compound of the present invention when applied in a curing composition, the copper surface binding force before and after the reliability test under high temperature, high humidity, and high pressure does not change, indicating broad application prospects.

[0055] The applicant declares that the present invention uses the above embodiments to illustrate the deuterated nitrogen heteroadenine of the present invention and its preparation method and application, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A deuterated azaadenine, characterized in that, The deuterated azaadenine has a structure shown in formula (I): Among them, R1 and R2 independently represent hydrogen or a linear or branched alkyl group containing C1-C 10 alkyl.

2. The deuterated nitrogenous adenine according to claim 1, wherein The deuterated azaadenine is any one of the following compounds:

3. The preparation method of deuterated azaadenine according to claim 1 or 2, characterized in that, The preparation method includes the following steps: Compound a reacts with heavy water in the presence of a catalyst to obtain the deuterated azaadenine shown in formula (I), and the reaction formula is as follows:

4. The preparation method according to claim 3, characterized in that, The catalyst is selected from trifluoromethanesulfonic anhydride and / or pentafluoroethylsulfonic anhydride; Preferably, the solvent for the reaction is selected from dioxane and / or tetrahydropyran.

5. The preparation method according to claim 3 or 4, characterized in that, Compound a and heavy water are dissolved in a solvent, cooled to 10-15 °C in an ice-water bath, and a catalyst is added; Preferably, the reaction is carried out under heating reflux, and the reaction time is 8-20 h.

6. Use of the deuterated azaadenine according to claim 1 or 2 in a polyimide material.

7. A photosensitive composition, characterized in that, The photosensitive composition contains a polyimide resin, the deuterated purine compound according to claim 1 or 2, and an initiator.

8. The photosensitive composition according to claim 7, characterized in that, In the photosensitive composition, based on 100 parts by mass of the polyimide resin, the contents of each component are as follows: 0.1-10 parts of the deuterated purine compound according to claim 1 or 2 and 1-20 parts of an initiator; Preferably, the polyimide resin is at least one resin selected from polyamic acid of a polyimide precursor, polyamic acid ester, polyhydroxyamide that can be used as a polyoxazole precursor, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, or polybenzothiazole; Preferably, the initiator is selected from at least one of benzophenone initiators, α-amino ketone initiators, α-hydroxy ketone initiators, thioxanthone initiators, organophosphorus initiators, oxime ester initiators, or imidazole initiators.

9. A cured film, characterized in that, The cured film is obtained by curing the photosensitive composition according to claim 8.

10. A semiconductor chip buffer layer or semiconductor package layer, characterized in that, The semiconductor chip buffer layer or semiconductor encapsulation layer includes the photosensitive composition according to claim 8 or the cured film according to claim 9.

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