CN102030717B - Synthesis method and application of trialkynyl monomer 1,3, 5-tripropargyl-1, 3, 5-triazine-2, 4, 6-trione - Google Patents

Abstract

The invention discloses a synthetic method and application of a trialkynyl monomer 1,3, 5-tripropargyl-1, 3, 5-triazine-2, 4, 6-trione, wherein the synthetic method takes isocyanuric acid and bromopropyne as raw materials to synthesize the trialkynyl monomer under the action of a phase transfer catalyst; curing the 1,3, 5-tripropargyl-1, 3, 5-triazine-2, 4, 6-trione at high temperature to obtain the poly-1, 3, 5-tripropargyl-1, 3, 5-triazine-2, 4, 6-trione. The method has the advantages of simple operation, high safety, low raw material cost, mild reaction conditions and easy large-scale production.

Description

Synthesis method and application of triynyl monomer 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione

1. Technical field

The invention relates to a method for synthesizing an alkynyl organic monomer, in particular a trialkynyl monomer 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-tri Synthesis methods and applications of ketones.

2. Background technology

Alkyne-based resins are a new type of thermosetting resins. This type of resin has high reactivity. Under the conditions of heat, radiation or catalysts, alkyne groups can react to form aromatic rings or conjugated polyene structures. This type of resin has different advantages from other resins, such as: no volatile by-products are produced during the curing process, and a dense cured product is obtained; the cured product has good heat resistance and mechanical properties, and can be used in harsh conditions. The basic performance of the material can be maintained under the condition of the alkyne-based resin has been a hot research topic. In recent years, the focus of research is to introduce polycyclic structures or heteroatoms into resins, such as N, Si, O, S, etc., to improve the performance of alkyne-based resins or to endow resins with some special properties. In addition to being used alone, alkyne-based resins can also be used as a matrix to prepare many high-performance or composite materials with special properties. The main prerequisite for the preparation of such high-performance resins is the synthesis of alkyne-based monomers. 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione is an important alkynyl monomer, the main feature of which is that the compound has Heteroatom N, and contains three alkynyl groups, which is a feature that general alkynyl monomers do not have, which allows more crosslinking of the monomer during the crosslinking process, resulting in better mechanical properties and durability thermal performance. Therefore, 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione has great advantages in the preparation of high-performance resins and related modifications. Regarding the preparation of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione, it has been documented that potassium cyanate, propyne bromide can be prepared in dimethylformamide or the alkaline salt solution of dimethyl sulfoxide, but this method has a low yield in the solvent dimethyl sulfoxide, and the organic solvent used in the reaction is difficult to recycle, has a large impact on the environment, and relatively high cost, The post-treatment process of the product is complex, and more toxic solvents such as benzene have been introduced.

3. Contents of the invention

The purpose of the present invention is to avoid the shortcomings of the above-mentioned prior art, and to provide a triacetylene-based monomer 1,3,5- Synthesis method and application of tripropargyl-1,3,5-triazine-2,4,6-trione.

The present invention adopts following technical scheme for solving technical problems:

The characteristics of the synthetic method of triacetylene monomer 1,3,5-triargyl-1,3,5-triazine-2,4,6-trione of the present invention are that its reaction formula is as follows:

The reaction temperature is 75-80° C., and the reaction time is 15-20 hours.

The characteristics of the synthetic method of triacetylenyl monomer 1,3,5-triargyl-1,3,5-triazine-2,4,6-triketone of the present invention also are to carry out as follows:

Add isocyanuric acid, alkali metal hydroxide, phase transfer catalyst and water into the flask, heat it to the reaction temperature in a water bath with stirring, then add propyne bromide dropwise to the reaction vessel, cool to room temperature after the reaction, and let stand to separate The solid was separated after the layers, and the solid was washed with absolute ethanol to white and then dried in vacuum at 55°C for 6 hours to obtain 1,3,5-tripropargyl-1,3,5-triazine-2 , 4,6-triketone;

The phase transfer catalyst is tetrabutyl ammonium chloride, tetrabutyl phosphorus chloride, 18-crown-6-ether or polyvinyl alcohol;

Wherein, the molar ratio of isocyanuric acid and propyne bromide is 1:6, 1:8 or 1:10, the molar ratio of isocyanuric acid and alkali metal hydroxide is 1:4, the ratio of isocyanuric acid and phase transfer catalyst The molar ratio is 1:0.2, and the amount of water used is 100 mL.

The characteristics of the synthetic method of the present invention's triynyl monomer 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione also lie in: the alkali metal hydroxide Sodium Hydroxide or Potassium Hydroxide.

A kind of preparation method of poly-1,3,5-triargyl-1,3,5-triazine-2,4,6-trione of the present invention is characterized in that: take 1,3,5-triargyl The base-1,3,5-triazine-2,4,6-trione is placed in a ceramic crucible, the ceramic crucible is placed in a high-temperature furnace, nitrogen gas is introduced, and the temperature rises to solidify to obtain a finished product.

A kind of preparation method of poly-1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione of the present invention is also characterized in that: the curing at elevated temperature is:

First raise the temperature to 200°C at a heating rate of 5°C/min, keep at 200°C for 2 hours, then raise the temperature to 220°C at a heating rate of 1°C/min, and keep at 220°C for 1 hour; then control the heating rate at 1°C /min to 240°C, 260°C, 280°C, and 300°C respectively, and during this process, keep warm at 240°C, 260°C, 280°C, and 300°C for 1 hour, and finally raise the temperature at a heating rate of 1°C/min to 310° C., and the curing process is completed after 0.5 hours of heat preservation.

Compared with the prior art, the beneficial effects of the present invention are reflected in:

1. The used isocyanuric acid, propyne bromide, sodium hydroxide and tetrabutylammonium chloride etc. of the present invention are all cheap and easy-to-get raw materials, and the production cost is low.

2. The preparation process of the present invention has the advantages of simple process, convenient operation, mild reaction conditions, and easy realization of industrial production.

3. The present invention uses water as the reaction solvent, has low cost and little pollution, and meets the requirements of green chemistry.

4. The post-treatment process of the product of the present invention is simple and can save resources.

4. Description of drawings

Fig. 1 is a ¹ H-NMR spectrum chart of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione.

Figure 2 is a TGA curve of poly 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione.

5. Specific implementation

The synthetic method of triacetylene monomer 1,3,5-triargyl-1,3,5-triazine-2,4,6-trione of the present invention is to use isocyanuric acid and bromopropyne as raw materials, Under the action of a phase transfer catalyst, 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione is generated through a synthesis reaction, and its synthesis reaction route is:

Example 1:

In the present embodiment, the synthetic method of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione is carried out according to the following process:

Add 6.45g (0.05mol) of isocyanuric acid, 8g (0.2mol) of sodium hydroxide, 2.78g (0.01mol) of tetrabutylammonium chloride and 100mL of water into a 250mL round-bottomed three-neck flask, heat up and stir until the isocyanuric acid Dissolve, then add 47.6g (0.4mol) propyne bromide dropwise with a constant pressure dropping funnel, react at 75°C for 20 hours, cool to room temperature after the reaction is complete, separate the product and the water phase, wash the product with distilled water, and wash away NaBr, NaOH, etc., and then washed with absolute ethanol, and dried under vacuum at 55° C. for 6 hours to obtain 7.2 g of a white solid product with a yield of 59.26%.

In this embodiment, the preparation method of poly 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione is to take 1,3,5-tripropargyl-1 , 3,5-triazine-2,4,6-trione in a ceramic crucible, then placed in a high-temperature furnace, blown with nitrogen, and heated up to cure the resin alkyne-based monomer. In order to fully cure, take the following heating rate:

First raise the temperature to 200°C at a heating rate of 5°C/min, hold at 200°C for 2 hours, then raise the temperature to 220°C at a heating rate of 1°C/min, keep at 220°C for 1 hour, and then control the heating rate at 1°C/ Min was raised to 240°C, 260°C, 280°C, and 300°C respectively. During this process, the temperature was kept at 240°C, 260°C, 280°C, and 300°C for 1 hour, and finally the temperature was raised to 310°C at a heating rate of 1°C/min. , After 0.5h of heat preservation, the curing process is completed, and the finished product is obtained after cooling to room temperature.

Example 2:

In this example, the preparation process of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione is the same as Example 1, except that the reaction temperature is 80°C , the reaction time was 15 hours, and 7.6 g of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione was prepared with a yield of 62.55%.

The preparation method of poly-1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione in this example is the same as that in Example 1.

Example 3:

In this embodiment, the preparation process of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione is the same as in Example 1, except that the amount of propyne bromide is added It was 35.67g (0.3mol), and 5.8g of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione was prepared with a yield of 47.74%.

The preparation method of poly-1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione in this example is the same as that in Example 1.

Example 4:

In this embodiment, the preparation process of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione is the same as in Example 1, except that the amount of propyne bromide is added It was 59.50 g (0.5 mol), and 7.8 g of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione was prepared with a yield of 64.20%.

The preparation method of poly-1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione in this example is the same as that in Example 1.

Example 5:

In this example, the preparation process of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione is the same as in Example 1, except that the added alkali metal hydroxide The compound was potassium hydroxide, and 7.3 g of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione was prepared with a yield of 60.08%.

The preparation method of poly-1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione in this example is the same as that in Example 1.

Embodiment 6:

In this embodiment, the preparation process of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione is the same as in Example 1, except that the added phase transfer catalyst is Tetrabutylphosphine chloride was prepared to obtain 7.2 g of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione with a yield of 59.26%.

The preparation method of poly-1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione in this example is the same as that in Example 1.

Embodiment 7:

In this embodiment, the preparation process of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione is the same as in Example 1, except that the added phase transfer catalyst is 18-crown-6-ether was prepared to obtain 7.3 g of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione with a yield of 60.08%.

The preparation method of poly-1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione in this example is the same as that in Example 1.

Embodiment 8:

In this embodiment, the preparation process of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione is the same as in Example 1, except that the added phase transfer catalyst is Polyvinyl alcohol was prepared to obtain 7.0 g of 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione with a yield of 57.61%.

The preparation method of poly-1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione in this example is the same as that in Example 1.

The 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione prepared in the present invention is characterized by ¹ H-NMR, as shown in Figure 1, the data are as follows, ¹ H-NMR (CDCl ₃ , TMS): δ2.30 (-CH ₂ -, s); 4.70 (-C≡CH, s). It shows that the obtained product is the monomer 1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione.

As can be seen from Fig. 2, the thermal decomposition temperature of the poly-1,3,5-tripropargyl-1,3,5-triazine-2,4,6-trione prepared by the present invention can reach more than 380°C, and at 400°C The thermal decomposition rate is the fastest nearby.

Claims (1)

1. the synthetic method of trialkynyl monomer 1,3,5-triargyl-1,3,5-triazine-2,4,6-triketone is characterized in that its reaction formula is as follows:

The reaction temperature is 75-80°C, and the reaction time is 15-20 hours; Specifically, proceed as follows: Add isocyanuric acid, alkali metal hydroxide, phase transfer catalyst and water into the flask, heat it to the reaction temperature in a water bath with stirring, then add propyne bromide dropwise to the reaction vessel, cool to room temperature after the reaction, and let stand to separate The solid was separated after the layers, and the solid was washed with absolute ethanol to white and then dried in vacuum at 55°C for 6 hours to obtain 1,3,5-tripropargyl-1,3,5-triazine-2 , 4,6-triketone; The phase transfer catalyst is tetrabutyl ammonium chloride, tetrabutyl phosphorus chloride, 18-crown-6-ether or polyvinyl alcohol; Wherein, the molar ratio of isocyanuric acid and propyne bromide is 1:6, 1:8 or 1:10, the molar ratio of isocyanuric acid and alkali metal hydroxide is 1:4, the ratio of isocyanuric acid and phase transfer catalyst The molar ratio is 1:0.2, and the consumption of water is 100mL; The alkali metal hydroxide is sodium hydroxide or potassium hydroxide.

Images