CN112939884A - Bis-benzoxazinone compounds and preparation method thereof - Google Patents
Bis-benzoxazinone compounds and preparation method thereof Download PDFInfo
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- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
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Abstract
The invention discloses a bis-benzoxazinone compound and a preparation method thereof, belonging to the technical field of fine chemical engineering. The invention adopts a one-step method to prepare the bis-benzoxazinone compound by taking isatoic anhydride and aromatic diformyl chloride as raw materials, reacting under the action of ultrasonic waves, and washing with water and cleaning with acetone to remove impurities, and the preparation method has the advantages that: (1) the used isatoic anhydride is not required to be purified and decolorized, and is directly put into reaction; (2) under the action of ultrasonic waves, the reaction rate is accelerated, the reaction time is shortened, and the yield is improved; (3) the one-step method is simple to operate, easy to produce, low in solvent consumption and low in cost.
Description
Technical Field
The invention relates to a bis-benzoxazinone compound and a preparation method thereof, belonging to the technical field of fine chemical engineering.
Background
The bis-benzoxazinone compounds have strong absorption to ultraviolet rays below 380nm, and have higher decomposition temperature and better heat resistance, thereby being suitable for high-temperature processing of ultraviolet-blocking transparent plastics. The modified polycarbonate resin has the advantages of small influence on transparency, plasticity and the like of materials and good long-term use durability when added into polymers, thereby being applied to high polymer materials such as thermoplastic polyester, polycarbonate, nylon and the like. In particular to a new generation of environment-friendly high-efficiency ultraviolet absorbent UV3638, 2,2' - (1, 4-phenylene) bis-4H-3, 1-benzoxazine-4-ketone, which can efficiently absorb ultraviolet rays in UVB and UVC wave bands, has high molecular weight, low volatility, no color pollution and thermal decomposition temperature TGA (10%) of more than 371 ℃, and is suitable for thermoplastic polyester, nylon and national defense industries with high processing temperature and strong ultraviolet absorption capacity.
The reported synthetic routes of the bis-benzoxazinone compounds UV3638 have three types: firstly, generating an imido ester intermediate by using anthranilic acid and terephthaloyl chloride, then performing cyclodehydration on the intermediate, and then washing with acetone and alkali to prepare a UV3638 product; secondly, in patent CN103304508A, anthranilic acid and terephthaloyl chloride are reacted in aprotic solvents such as benzene, toluene and xylene at high temperature for 5-10 hours under the action of a dehydrating agent to obtain a product; and thirdly, performing one-step reaction on the isatoic anhydride and the terephthaloyl chloride purified by DMF at the reflux temperature for 4 hours, washing with water, washing with acetone and methanol, and synthesizing the UV 3638. However, these preparation methods have some disadvantages, among them, the method one has many steps, the operation cost is increased, and the solvent consumption is large; the method II has high reaction temperature, long reaction time and high cost of unit product; in the third method, the isatoic anhydride needs to be purified, so that the production procedures are increased.
Disclosure of Invention
The present invention is implemented by the following technical solutions in view of the technical problems mentioned in the background art:
the bis-benzoxazinone compound is characterized in that the molecular structural general formula is as follows:
wherein, R is one of phenyl, naphthyl and biphenyl.
A method for preparing a bis-benzoxazinone compound has the following reaction equation:
the method comprises the following specific steps:
s1, directly putting isatoic anhydride into a reaction kettle, adding a proper amount of solvent, and ultrasonically mixing uniformly;
s2, adding an acid-binding agent, heating in water bath under the action of ultrasonic waves, slowly adding aromatic diformyl chloride in three batches to react and release gas, and continuing to react for a period of time after the addition is finished and no bubbles are generated;
s3, after the reaction is finished, naturally cooling to 25 ℃, directly filtering, and drying; adding a proper amount of deionized water into the obtained powder, uniformly dispersing, and performing suction filtration; adding the dried powder into an appropriate amount of acetone, uniformly mixing, and carrying out suction filtration to remove impurities;
s4, directly drying the product after being dried by suction in an oven.
As a preferred example, the aromatic dicarboxylic acid dichloride is one of terephthaloyl dichloride, isophthaloyl dichloride, phthaloyl dichloride, 1, 4-naphthalenedicarboxylic acid dichloride, 2, 6-naphthalenedicarboxylic acid dichloride and 4, 4' -biphenylylacetyl chloride.
As a preferred example, the solvent is one of toluene, xylene, pyridine, N' -dimethylformamide, and N-methylimidazole.
As a preferable example, the acid scavenger is one of triethylamine, pyridine, 4-methylpyridine and N-methylimidazole.
As a preferred example, the mass ratio of the isatoic anhydride and the aromatic dicarboxylic acid dichloride is 1: (0.48 to 0.55); the mass of the solvent is 5-8 times of that of the isatoic anhydride; the mass ratio of the aromatic diformyl chloride to the acid binding agent is 1: (2-6).
As a preferred example, the ultrasonic power is 100W; the temperature of the water bath is 50-80 ℃; the reaction time after the addition of the raw materials is 0.5-2 h.
As a preferred example, the mass of the deionized water is 2-6 times of the mass of the obtained powder; the dosage of the acetone is 3-5 times of the mass of the powder.
As a preferable example, the drying temperature is 80-100 ℃, and the drying time is 6-10 h.
As a preferred example, the isatoic anhydride is off-white in appearance, with a purity of 98.4% or more; the purity of the aromatic diformyl chloride is more than 99.5 percent; the purity of the solvent used is technical grade.
It should be noted that: the isatoic anhydride is commercially available.
The invention has the beneficial effects that: the invention adopts a one-step method to prepare the bis-benzoxazinone compound by taking isatoic anhydride and aromatic diformyl chloride as raw materials, reacting under the action of ultrasonic waves, and washing with water and cleaning with acetone to remove impurities, and the preparation method has the advantages that: (1) the used isatoic anhydride is not required to be purified and decolorized, and is directly put into reaction; (2) under the action of ultrasonic waves, the reaction rate is accelerated, the reaction time is shortened, and the yield is improved; (3) the one-step method is simple to operate, easy to produce, low in solvent consumption and low in cost.
Drawings
Fig. 1 is an ultraviolet-visible light absorption spectrum of the UV3638 blocking PET film synthesized in example 1 of the present invention and a comparative example.
Detailed Description
In order to make the technical means, the original characteristics, the achieved purpose and the efficacy of the invention easily understood, the invention is further described with reference to the following embodiments.
Example 1.
Ultrasonic wave auxiliary synthesis method
The reaction equation of the bis-benzoxazinone compound is as follows:
the preparation process of the bis-benzoxazinone compound comprises the following steps:
s1, adding isatoic anhydride (0.82g,5.00mmol) into a 25ml reaction kettle, adding 4.92g of pyridine, and ultrasonically mixing uniformly;
s2, adding 0.42g of pyridine, uniformly mixing under 100W of ultrasonic waves, heating in a water bath to 70 ℃, slowly adding terephthaloyl chloride (0.53g,2.63mmol) for three times, reacting to release gas, and continuing to react for 2 hours after the addition is finished;
s3, after the reaction is finished, naturally cooling to room temperature, directly performing suction filtration, and performing suction drying; adding 4.60g of deionized water into the obtained powder, uniformly stirring, and performing suction filtration; adding the drained powder into 3.60g of acetone, uniformly mixing, and carrying out suction filtration to remove impurities;
s4, drying the drained product in an oven at 80 ℃ for 6h to obtain 0.82g of product, yield: 89.1 percent.
Comparative example
Heating reflux method
The reaction equation of the bis-benzoxazinone compound is as follows:
the preparation process of the bis-benzoxazinone compound comprises the following steps:
s1, recrystallizing isatoic anhydride (1.03g,6.31mmol) in N, N' -Dimethylformamide (DMF), and purifying to obtain isatoic anhydride (0.82g,5.00mmol) which is added into a 25ml reaction kettle;
s2, adding 4.92g of pyridine, uniformly mixing, heating to 60 ℃, slowly adding terephthaloyl chloride for three times to react and release gas, and after the addition is finished, heating and refluxing for continuously reacting for 4 hours;
s3, after the reaction is finished, naturally cooling to room temperature, directly performing suction filtration, and performing suction drying; adding 10.00g of deionized water into the obtained powder, uniformly stirring, and performing suction filtration; adding the drained powder into 4.00g of acetone, uniformly mixing, and carrying out suction filtration to remove impurities; adding the drained powder into 4.00g of methanol, uniformly mixing, and carrying out suction filtration to remove impurities;
s4, drying the drained product in an oven at 120 ℃ for 15h to obtain 0.69g of product, yield: 75 percent.
In summary, combining example 1 and comparative example, the basic performance comparison of UV3638 synthesized by different methods is summarized (see table one):
as shown in the table I, the synthesized bis-benzoxazinone compound UV3638 has shorter reaction time and higher yield by using an ultrasonic-assisted synthesis method than a heating reflux method, and the prepared UV3638 powder has similar appearance and the same melting point.
The ultraviolet blocking ability of the ultraviolet absorber UV3638 synthesized in combination with example 1 and comparative example was compared (see fig. 1).
a. UV-blocking PET film for UV 3638:
crushing PET film grade particles in a crusher, wherein the particle size of the particles is 60 meshes.
Uniformly mixing the ultraviolet absorbent UV3638 synthesized by different methods with PET film-grade particles, blending and extruding the mixture in a casting machine at 280 ℃ to form a film with the thickness of 300 mu m, wherein the addition amount of the ultraviolet absorbent UV3638 is 1.5 percent; the addition amount of the PET film grade particles is 98.5 percent.
And thirdly, preparing the prepared PET film for blocking ultraviolet into a PET ultraviolet blocking film with the thickness of 23um in a biaxial stretching film drawing machine. Since the thickness of the commonly used PET ultraviolet-blocking film in practical application is 23um, the performance of the ultraviolet absorbent UV3638 synthesized by different methods is compared with that of the ultraviolet-blocking film of 23 um.
b. The UV-visible absorption spectrum of the UV-blocking PET film manufactured using the properties of UV3638 synthesized in example 1 and comparative example is shown in fig. 1, wherein the abscissa λ is the wavelength of light and the ordinate a is the absorption intensity of light of a certain wavelength.
As can be seen from fig. 1, the ultraviolet-blocking PET films made of the ultraviolet absorbent UV3638 synthesized in example 1 and the comparative example can completely absorb ultraviolet rays below 380nm, can effectively block the ultraviolet rays, and can avoid the damage of the ultraviolet rays to human skin and the damage to the polymer material.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The bis-benzoxazinone compound is characterized in that the molecular structural general formula is as follows:
wherein, R is one of phenyl, naphthyl and biphenyl.
2. The method for preparing bis-benzoxazinones according to claim 1, wherein the reaction equation is as follows:
the method comprises the following specific steps:
s1, directly putting isatoic anhydride into a reaction kettle, adding a proper amount of solvent, and ultrasonically mixing uniformly;
s2, adding an acid-binding agent, heating in water bath under the action of ultrasonic waves, slowly adding aromatic diformyl chloride in three batches to react and release gas, and continuing to react for a period of time after the addition is finished and no bubbles are generated;
s3, after the reaction is finished, naturally cooling to 25 ℃, directly filtering, and drying; adding a proper amount of deionized water into the obtained powder, uniformly dispersing, and performing suction filtration; adding the dried powder into an appropriate amount of acetone, uniformly mixing, and carrying out suction filtration to remove impurities;
s4, directly drying the product after being dried by suction in an oven.
3. The method for preparing a bis-benzoxazinone compound according to claim 2, wherein the aromatic diformyl chloride is one of terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, 1, 4-naphthalenedicarboxylic acid chloride, 2, 6-naphthalenedicarboxylic acid chloride, and 4, 4' -biphenylacetyl chloride.
4. The method for preparing bis-benzoxazinones according to claim 2, wherein the solvent is one of toluene, xylene, pyridine, N' -dimethylformamide and N-methylimidazole.
5. The method for preparing a bis-benzoxazinone compound according to claim 2, wherein the acid-binding agent is one of triethylamine, pyridine, 4-methylpyridine, and N-methylimidazole.
6. The method for preparing a bis-benzoxazinone compound according to claim 2, wherein the mass ratio of the isatoic anhydride to the aromatic dicarboxylic acid dichloride is 1: (0.48 to 0.55); the mass of the solvent is 5-8 times of that of the isatoic anhydride; the mass ratio of the aromatic diformyl chloride to the acid binding agent is 1: (2-6).
7. The method for preparing a bis-benzoxazinone compound according to claim 2, wherein the ultrasonic power is 100W; the temperature of the water bath is 50-80 ℃; the reaction time after the addition of the raw materials is 0.5-2 h.
8. The method for preparing a bis-benzoxazinone compound according to claim 2, characterized in that: the mass of the deionized water is 2-6 times of that of the obtained powder; the dosage of the acetone is 3-5 times of the mass of the powder.
9. The method for preparing a bis-benzoxazinone compound according to claim 2, characterized in that: the drying temperature is 80-100 ℃, and the drying time is 6-10 h.
10. The method for preparing a bis-benzoxazinone compound according to any one of claims 2-9, wherein the isatoic anhydride is off-white in appearance and has a purity of 98.4% or more; the purity of the aromatic diformyl chloride is more than 99.5 percent; the purity of the solvent used is technical grade.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1420138A (en) * | 2001-11-20 | 2003-05-28 | 竹本油脂株式会社 | Ultraviolet absorber for thermoplastic polymer and preparation method thereof |
| CN101395144A (en) * | 2006-01-05 | 2009-03-25 | 特姆萨国际公司 | Process for preparing a benzoxazinone |
| JP2012122000A (en) * | 2010-12-08 | 2012-06-28 | Fujifilm Corp | Polyester film and method for producing the same, back sheet for solar cell and solar cell module |
| CN102725275A (en) * | 2009-11-26 | 2012-10-10 | 帝人化成株式会社 | Bisbenzoxazinone compound |
| CN103304508A (en) * | 2012-03-14 | 2013-09-18 | 山东科技大学 | Novel synthetic method of bis-benzoxazine ketone ultraviolet absorbent |
-
2021
- 2021-02-26 CN CN202110222803.1A patent/CN112939884A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1420138A (en) * | 2001-11-20 | 2003-05-28 | 竹本油脂株式会社 | Ultraviolet absorber for thermoplastic polymer and preparation method thereof |
| CN101395144A (en) * | 2006-01-05 | 2009-03-25 | 特姆萨国际公司 | Process for preparing a benzoxazinone |
| CN102725275A (en) * | 2009-11-26 | 2012-10-10 | 帝人化成株式会社 | Bisbenzoxazinone compound |
| JP2012122000A (en) * | 2010-12-08 | 2012-06-28 | Fujifilm Corp | Polyester film and method for producing the same, back sheet for solar cell and solar cell module |
| CN103304508A (en) * | 2012-03-14 | 2013-09-18 | 山东科技大学 | Novel synthetic method of bis-benzoxazine ketone ultraviolet absorbent |
Non-Patent Citations (2)
| Title |
|---|
| MEHDI SHARIAT等: ""Microwave Assisted Synthesis of 2,2"-Arylene-substituted Bis(4H-3,1-Benzoxazin-4-one) Derivatives Using the Complex Cyanuric Chloride/N,N-Dimethylformamide"", 《MEHDI SHARIAT等》 * |
| 姚其正: "《药物合成反应》", 31 December 2019, 中国医药科技出版社 * |
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Application publication date: 20210611 |