A chemical additive UVAO-358 and its synthesis method and use

Abstract

The present invention provides a chemical auxiliary agent UVAO-358 and its synthesis method and use. This method has readily available raw materials, simple operation, relatively mild reaction conditions, and high product yield and purity. The efficient catalytic synthesis method of the novel carbon free radical scavenger with ultraviolet absorption ability provided by the present invention opens a path for the multifunctional application of the novel carbon free radical scavenger. Its advantages are: the novel carbon free radical scavenger with ultraviolet absorption ability has both ultraviolet absorption and carbon free radical capture capabilities, and the raw materials are widely available. The selectivity and yield of the target product are both high, the reaction conditions are mild, the reaction operation is simple, and no harmful byproducts are generated, which is environmentally friendly.

Description

Technical Field

[0001] The invention belongs to the field of catalytic organic synthesis and relates to a novel chemical auxiliary agent UVAO-358 with ultraviolet absorption and carbon free radical capture capabilities and a synthesis method thereof. Background Art

[0002] UVAO-358 is a new type of carbon free radical scavenger with ultraviolet absorption ability. Its structural formula is as follows:

[0003]

[0004] Currently, polymers are widely used in materials, energy, chemicals, communications equipment, and other fields. However, during use, polymers are inevitably exposed to ultraviolet light, which often degrades their performance and service life. Adding UV absorbers is an effective way to prevent aging in polymers. 2,4-Dihydroxybenzophenone (UV-0) and its derivatives are widely used UV absorbers in resins and other polymers. They are applied to materials such as polyvinyl chloride, polyacrylates, and polyolefins, as well as in coatings based on polyacrylates and epoxy resins to improve their anti-aging properties. They are also used in cosmetics, aerospace, and pharmaceuticals, and serve as intermediates for the preparation of other UV absorbers. However, in current coatings applications, while UV-0 offers excellent UV absorption, the finished product is generally dark in color, hindering the development of diversified coatings. UV-351, an optimized derivative of UV-0, produces a lighter finished product, but its UV absorption capacity is reduced. Furthermore, both UV absorbers have poor stability and lack antioxidant properties.

[0005] Relevant research results show that benzofuranone-based free radical scavengers can capture alkoxy free radicals under both aerobic and anaerobic conditions. The most representative product is HP-136, a benzofuranone-based carbon free radical scavenger developed by Ciba Specialty Chemicals. It can terminate the chain reaction of polymer thermal oxidative aging in the bud state, so it has a good anti-thermal oxidative aging effect. However, HP-136 does not have ultraviolet absorption ability and is not very competitive in some fields.

[0006] At present, major companies at home and abroad are actively developing chemical materials with ultraviolet absorption and antioxidant properties.

[0007] Against this backdrop, we have developed a novel chemical additive, UVAO-358, that possesses both UV absorption and carbon radical capture capabilities. This material not only reacts with carbon radicals to generate stable products, but also exhibits UV absorption properties, as detected by UV spectroscopy, making it a novel multifunctional material.

[0008] In summary, our developed UVAO-358 is a novel chemical additive with UV absorption and carbon radical capture capabilities. Its UV absorption performance and thermal oxidative aging resistance surpass those of commonly available materials. Its synthesis method utilizes readily available raw materials, is simple to operate, employs mild reaction conditions, and produces high yields and high purity. Currently, there are no published literature or patent applications for this multifunctional material, both domestically and internationally. Summary of the Invention

[0009] The present invention aims to provide a method for synthesizing a novel chemical auxiliary agent UVAO-358 having ultraviolet absorption and carbon free radical capture capabilities using 2,4-dihydroxybenzophenone, glyoxylic acid solution, and o-xylene as raw materials. This method has readily available raw materials, simple operation, relatively mild reaction conditions, and high product yield and purity.

[0010] To achieve the above object, the technical solution of the present invention is as follows:

[0011] A chemical additive UVAO-358, the chemical formula of the chemical additive UVAO-358 is as follows:

[0012] .

[0013] A use of the chemical auxiliary agent UVAO-358, wherein the chemical auxiliary agent UVAO-358 is as described above, and the chemical auxiliary agent UVAO-358 is used as an ultraviolet absorber or a carbon free radical scavenger.

[0014] As a further improvement, the chemical auxiliary agent UVAO-358 is used as an ultraviolet absorber for ultraviolet light in the wavelength range of 260nm-280nm.

[0015] A method for synthesizing a chemical auxiliary agent UVAO-358 comprises the following steps:

[0016] 3, 4-dimethylmandelic acid and 2, 4-dihydroxybenzophenone were used as raw materials and Lewis acid was used as catalyst at 160 o C and stirred for 4-5 hours to obtain the chemical auxiliary agent UVAO-358.

[0017] Further improvement, the preparation method of 3, 4-dimethylmandelic acid is as follows: using glyoxylic acid solution and o-xylene as raw materials, Bronsted acid as catalyst, methylcyclohexane as solvent, at 120 o C and stirred for 4-5 hours to obtain 3, 4-dimethylmandelic acid.

[0018] As a further improvement, when preparing 3, 4-dimethylmandelic acid, methylcyclohexane is first used to remove all water in the reaction system, and then p-toluenesulfonic acid is added to start the reaction.

[0019] In a further improvement, the molar ratio of the glyoxylic acid solution, o-xylene and 2, 4-dihydroxybenzophenone is 1:1-2:0.5-1.

[0020] In a further improvement, the molar ratio of the glyoxylic acid solution, o-xylene and 2, 4-dihydroxybenzophenone is 1:2:0.5.

[0021] In a further improvement, the Bronsted acid is hydrochloric acid, sulfuric acid or p-toluenesulfonic acid; the Lewis acid is aluminum chloride, ferric chloride, nickel trifluoromethanesulfonate, zinc trifluoromethanesulfonate or copper trifluoromethanesulfonate; the molar addition amount of the Bronsted acid is 5.0%, and the molar addition amount of the Lewis acid is 5.0%.

[0022] Further improvement, the chemical formula of the 3,4-dimethylmandelic acid is as follows:

[0023] .

[0024] The advantages of the present invention are as follows:

[0025] A new method for synthesizing UVAO-358, a novel chemical additive with ultraviolet absorption and carbon radical capture capabilities, is a green and environmentally friendly reaction with a wide range of raw material sources, high selectivity and yield of the target product, mild reaction conditions, simple reaction operation, and no generation of harmful byproducts. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a roadmap for preparing a new type of chemical auxiliary agent UVAO-358 with ultraviolet absorption and carbon free radical capture capabilities provided by the present invention.

[0027] Figure 2 This is the H NMR spectrum of UVAO-358 compound

[0028] Figure 3 This is the NMR carbon spectrum of UVAO-358 compound

[0029] Figure 4a This is the UV absorption test chart of UVAO-358 with ethyl acetate as the reference solution;

[0030] Figure 4b This is the UV absorption test chart of UV-0 with ethyl acetate as the reference solution;

[0031] Figure 4c This is the UV absorption test chart of UV-531 with ethyl acetate as the reference solution;

[0032] Figure 5a Methanol is used as the reference solution, UVAO-358 ultraviolet absorption test chart

[0033] Figure 5b Methanol is used as the reference solution, UV-0 ultraviolet absorption test chart

[0034] Figure 5c Methanol is used as the reference solution, UV-531 ultraviolet absorption test chart

[0035] Figure 6 This is the color chart of UVAO-358 material;

[0036] Figure 7a This is the thermogravimetric analysis diagram of UVAO-358

[0037] Figure 7b This is the thermogravimetric analysis diagram of HP-136 DETAILED DESCRIPTION

[0038] In order to make the above features, advantages and purposes of the present invention more clearly understood, the following detailed description of the specific embodiments of the present invention is given in conjunction with the accompanying drawings. The following description sets forth many specific details to facilitate a full understanding of the present invention.

[0039] The present invention provides a method for synthesizing a novel chemical auxiliary agent UVAO-358 having ultraviolet absorption and carbon free radical capture capabilities using 2,4-dihydroxybenzophenone, glyoxylic acid solution, and o-xylene as raw materials. The method comprises the following steps: placing the glyoxylic acid solution, o-xylene, and methylcyclohexane in a reaction vessel, stirring at 120°C for 2 hours, removing water from the reaction system, and then adding p-toluenesulfonic acid as a catalyst to react for 4 hours to obtain the first product, 3,4-dimethylmandelic acid, with a yield of 90%. Subsequently, under solvent-free conditions, using 3,4-dimethylmandelic acid and 2,4-dihydroxybenzophenone as raw materials and nickel trifluoromethanesulfonate as a catalyst, stirring at 160°C for 5 hours to obtain the target product UVAO-358. The target product is then purified by recrystallization to obtain a pure target product.

[0040] The following experimental groups 1 to 18 are compared with the above standard reactions as a reference:

[0041] project Differences from standard reaction conditions Yield% 1 No difference 91% 2 Zinc trifluoromethanesulfonate (5 mol%) 89% 3 Copper trifluoromethanesulfonate (5 mol%) 21% 4 Aluminum trichloride (5 mol%) 18% 5 Ferric chloride (5 mol%) 13 6 120 ℃ reaction 65% 7 130 ℃ reaction 68% 8 140 ℃ reaction 76% 9 150 ℃ reaction 85% 10 170 ℃ reaction 73% 11 Reaction time: 2 h 52% 12 Reaction time: 4 h 84% 13 Reaction time 8 h 73% 14 Reaction time: 12 h 68% 15 Glyoxylic acid: o-xylene (molar ratio 1:1) 53 16 Glyoxylic acid: o-xylene (molar ratio 1:3) 75 17 3, 4-Dimethylmandelic acid: 2, 4-dihydroxybenzophenone (molar ratio 1:1) 63 18 3, 4-Dimethylmandelic acid: 2, 4-dihydroxybenzophenone (molar ratio 1:2) 48

[0042] The present invention will be further described below with reference to specific preparation examples: Example 1:

[0043] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 oC, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen. The lower layer liquid is measured with a graduated cylinder to be approximately 56 mL. 8.79 g (5 mol%) of p-toluenesulfonic acid is added. The reaction is continued for 4 h. The mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved. The solution is separated. The aqueous phase is taken and concentrated hydrochloric acid is slowly added dropwise while stirring. The pH is acidified to 1-2. The mixture is extracted twice with ethyl acetate. The organic phases are combined and spin-dried. 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 8.03 g (5 mol%, 0.0225 mol) of nickel trifluoromethanesulfonate are then added thereto. The water separator is installed. Stirring is turned on and the temperature is slowly raised to 160°C. o C, react for 5 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 146.65 g of white solid, with a yield of 91%. 1 H NMR (400 MHz, Chloroform- d ) δ 12.48 (d, J = 1.8 Hz, 1H), 7.71 (dd, J = 8.7, 1.8 Hz, 1H), 7.66 (d, J = 7.8 Hz, 2H), 7.61 (dd, J = 8.3, 6.4 Hz,1H), 7.55 – 7.49 (m, 2H), 7.14 (d, J = 7.7 Hz, 1H), 7.06 (s, 1H), 7.00 (d, J = 7.9 Hz, 1H), 6.76 (dd, J = 8.7, 1.8 Hz, 1H), 4.95 (s, 1H), 2.25 (d, J = 3.9Hz, 6H). 13 C NMR (101 MHz, Chloroform- d) δ 201.03, 174.69, 160.27, 159.64,137.68, 137.55, 137.00, 136.42, 132.14, 130.82, 130.33, 129.20, 129.06,128.52, 125.29, 116.62, 114.20, 102.45, 47.67, 19.92, 19.57. GC-MS: 358.12 Example 2:

[0044] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 o C, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen, the lower layer liquid is measured with a graduated cylinder to be approximately 56 mL, 8.79 g (5 mol%) of p-toluenesulfonic acid is added, the reaction is continued for 4 h, allowed to stand and cool, 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved, the liquid is separated, the aqueous phase is taken, concentrated hydrochloric acid is slowly added dropwise while stirring, acidified to a pH of 1-2, extracted twice with ethyl acetate, the organic phases are combined, and spin-dried; 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 8.18 g (5 mol%, 0.0225 mol) of zinc trifluoromethanesulfonate are added thereto, a water separator is installed, stirring is turned on, and the temperature is slowly raised to 160 o C, react for 5 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 143.43 g of white solid, with a yield of 89%. Example 3:

[0045] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 oC, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen. The lower layer liquid is measured with a graduated cylinder to be approximately 56 mL. 8.79 g (5 mol%) of p-toluenesulfonic acid is added. The reaction is continued for 4 h. The mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved. The solution is separated. The aqueous phase is taken and concentrated hydrochloric acid is slowly added dropwise while stirring. The pH is acidified to 1-2. The mixture is extracted twice with ethyl acetate. The organic phases are combined and spin-dried. 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 5.42 g (5 mol%, 0.0225 mol) of copper trifluoromethanesulfonate are added thereto. A water separator is installed. Stirring is started and the temperature is slowly raised to 160°C. o C, react for 5 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 33.84 g of white solid, with a yield of 21%. Example 4:

[0046] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 o C, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen dripping. The lower layer liquid is approximately 56 mL measured with a graduated cylinder, 8.79 g (5 mol%) of p-toluenesulfonic acid is added, the reaction is continued for 4 h, and the mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved, the liquid is separated, the aqueous phase is taken, concentrated hydrochloric acid is slowly added dropwise while stirring, acidified to a pH of 1-2, extracted twice with ethyl acetate, the organic phases are combined, and dried; 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 3.00 g (5 mol%, 0.0225 mol) of aluminum chloride are added thereto, the water separator is installed, stirring is turned on, and the temperature is slowly raised to 160 o C, react for 5 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 31.10 g of white solid with a yield of 19.3%. Example 5:

[0047] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 o C, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen dripping. The lower layer liquid is measured with a graduated cylinder to be approximately 56 mL, 8.79 g (5 mol%) of p-toluenesulfonic acid is added, the reaction is continued for 4 h, and the mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved, the liquid is separated, the aqueous phase is taken, concentrated hydrochloric acid is slowly added dropwise while stirring, acidified to a pH of 1-2, extracted twice with ethyl acetate, the organic phases are combined, and dried; 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 3.65 g (5 mol%, 0.0225 mol) of ferric chloride are added thereto, the water separator is installed, stirring is turned on, and the temperature is slowly raised to 160 o C, react for 5 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 20.95 g of white solid, with a yield of 13%. Example 6:

[0048] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 o C, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen dripping. The lower layer liquid is measured with a graduated cylinder to be approximately 56 mL. 8.79 g (5 mol%) of p-toluenesulfonic acid is added. The reaction is continued for 4 h. The mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved. The liquid is separated. The aqueous phase is taken and concentrated hydrochloric acid is slowly added dropwise while stirring. The pH is acidified to 1-2. The mixture is extracted twice with ethyl acetate. The organic phases are combined and spin-dried. 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 8.03 g (5 mol%, 0.0225 mol) of nickel trifluoromethanesulfonate are added thereto. The water separator is installed. Stirring is turned on and the temperature is slowly raised to 120 o C, react for 5 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 104.75 g of white solid with a yield of 65%. Example 7:

[0049] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 o C, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen dripping. The lower layer liquid is measured with a graduated cylinder to be approximately 56 mL. 8.79 g (5 mol%) of p-toluenesulfonic acid is added. The reaction is continued for 4 h. The mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved. The liquid is separated. The aqueous phase is taken and concentrated hydrochloric acid is slowly added dropwise while stirring. The pH is acidified to 1-2. The mixture is extracted twice with ethyl acetate. The organic phases are combined and spin-dried. 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 8.03 g (5 mol%, 0.0225 mol) of nickel trifluoromethanesulfonate are added thereto. The water separator is installed. Stirring is turned on and the temperature is slowly raised to 130 o C, react for 5 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 109.58 g of white solid with a yield of 68%. Example 8:

[0050] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 o C, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen, the lower layer liquid is measured with a graduated cylinder to be approximately 56 mL, 8.79 g (5 mol%) of p-toluenesulfonic acid is added, the reaction is continued for 4 h, allowed to stand and cool, 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved, the liquid is separated, the aqueous phase is taken, concentrated hydrochloric acid is slowly added dropwise while stirring, acidified to a pH of 1-2, extracted twice with ethyl acetate, the organic phases are combined, and dried; 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 8.03 g (5 mol%, 0.0225 mol) of nickel trifluoromethanesulfonate are added thereto, a water separator is installed, stirring is turned on, and the temperature is slowly raised to 140 oC, react for 5 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 122.48 g of white solid, with a yield of 76%. Example 9:

[0051] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 o C, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen. The lower layer liquid is measured with a graduated cylinder to be approximately 56 mL. 8.79 g (5 mol%) of p-toluenesulfonic acid is added. The reaction is continued for 4 h. The mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved. The solution is separated. The aqueous phase is taken and concentrated hydrochloric acid is slowly added dropwise while stirring. The pH is acidified to 1-2. The mixture is extracted twice with ethyl acetate. The organic phases are combined and spin-dried. 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 8.03 g (5 mol%, 0.0225 mol) of nickel trifluoromethanesulfonate are added thereto. A water separator is installed. Stirring is started and the temperature is slowly raised to 150°C. o C, react for 5 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 136.98 g of white solid, with a yield of 85%. Example 10:

[0052] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 oC, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen. The lower layer liquid is measured with a graduated cylinder to be approximately 56 mL. 8.79 g (5 mol%) of p-toluenesulfonic acid is added. The reaction is continued for 4 h. The mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved. The solution is separated. The aqueous phase is taken and concentrated hydrochloric acid is slowly added dropwise while stirring. The pH is acidified to 1-2. The mixture is extracted twice with ethyl acetate. The organic phases are combined and spin-dried. 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 8.03 g (5 mol%, 0.0225 mol) of nickel trifluoromethanesulfonate are added thereto. The water separator is installed. Stirring is turned on and the temperature is slowly raised to 170°C. o C, react for 5 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 117.64 g of white solid with a yield of 73%. Example 11:

[0053] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 o C, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen. The lower layer liquid is measured with a graduated cylinder to be approximately 56 mL. 8.79 g (5 mol%) of p-toluenesulfonic acid is added. The reaction is continued for 4 h. The mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved. The solution is separated. The aqueous phase is taken and concentrated hydrochloric acid is slowly added dropwise while stirring. The pH is acidified to 1-2. The mixture is extracted twice with ethyl acetate. The organic phases are combined and spin-dried. 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 8.03 g (5 mol%, 0.0225 mol) of nickel trifluoromethanesulfonate are then added thereto. The water separator is installed. Stirring is turned on and the temperature is slowly raised to 160°C. o C, react for 2 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 83.80 g of white solid with a yield of 52%. Example 12:

[0054] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 o C, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen. The lower layer liquid is measured with a graduated cylinder to be approximately 56 mL. 8.79 g (5 mol%) of p-toluenesulfonic acid is added. The reaction is continued for 4 h. The mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved. The solution is separated. The aqueous phase is taken and concentrated hydrochloric acid is slowly added dropwise while stirring. The pH is acidified to 1-2. The mixture is extracted twice with ethyl acetate. The organic phases are combined and spin-dried. 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 8.03 g (5 mol%, 0.0225 mol) of nickel trifluoromethanesulfonate are then added thereto. The water separator is installed. Stirring is turned on and the temperature is slowly raised to 160°C. o C, react for 4 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 135.37 g of white solid with a yield of 84%. Example 13:

[0055] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 o C, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen. The lower layer liquid is measured with a graduated cylinder to be approximately 56 mL. 8.79 g (5 mol%) of p-toluenesulfonic acid is added. The reaction is continued for 4 h. The mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved. The solution is separated. The aqueous phase is taken and concentrated hydrochloric acid is slowly added dropwise while stirring. The pH is acidified to 1-2. The mixture is extracted twice with ethyl acetate. The organic phases are combined and spin-dried. 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 8.03 g (5 mol%, 0.0225 mol) of nickel trifluoromethanesulfonate are then added thereto. The water separator is installed. Stirring is turned on and the temperature is slowly raised to 160°C. oC, react for 8 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 117.64 g of white solid with a yield of 73%. Example 14:

[0056] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 o C, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen. The lower layer liquid is measured with a graduated cylinder to be approximately 56 mL. 8.79 g (5 mol%) of p-toluenesulfonic acid is added. The reaction is continued for 4 h. The mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved. The solution is separated. The aqueous phase is taken and concentrated hydrochloric acid is slowly added dropwise while stirring. The pH is acidified to 1-2. The mixture is extracted twice with ethyl acetate. The organic phases are combined and spin-dried. 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 8.03 g (5 mol%, 0.0225 mol) of nickel trifluoromethanesulfonate are then added thereto. The water separator is installed. Stirring is turned on and the temperature is slowly raised to 160°C. o C, react for 12 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 109.58 g of white solid with a yield of 68%. Example 15:

[0057] To a 2000 mL three-necked flask, add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 123 mL (1.0 mol, 1.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane. Install a water separator, start stirring, and slowly raise the temperature to 120 oC, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen. The lower layer liquid is measured with a graduated cylinder to be approximately 56 mL. 8.79 g (5 mol%) of p-toluenesulfonic acid is added. The reaction is continued for 4 h. The mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved. The solution is separated. The aqueous phase is taken and concentrated hydrochloric acid is slowly added dropwise while stirring. The pH is acidified to 1-2. The mixture is extracted twice with ethyl acetate. The organic phases are combined and spin-dried. 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 8.03 g (5 mol%, 0.0225 mol) of nickel trifluoromethanesulfonate are then added thereto. The water separator is installed. Stirring is turned on and the temperature is slowly raised to 160°C. o C, react for 5 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 85.41 g of white solid with a yield of 53%. Example 16:

[0058] To a 2000 mL three-necked flask, add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 369 mL (3.0 mol, 3.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane. Install a water separator, start stirring, and slowly raise the temperature to 120 o C, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen. The lower layer liquid is measured with a graduated cylinder to be approximately 56 mL. 8.79 g (5 mol%) of p-toluenesulfonic acid is added. The reaction is continued for 4 h. The mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved. The solution is separated. The aqueous phase is taken and concentrated hydrochloric acid is slowly added dropwise while stirring. The pH is acidified to 1-2. The mixture is extracted twice with ethyl acetate. The organic phases are combined and spin-dried. 96.40 g (0.45 mol) of 2,4-dihydroxybenzophenone and 8.03 g (5 mol%, 0.0225 mol) of nickel trifluoromethanesulfonate are then added thereto. The water separator is installed. Stirring is turned on and the temperature is slowly raised to 160°C. o C, react for 5 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 120.87 g of white solid with a yield of 75%. Example 17:

[0059] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 o C, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen, the lower layer liquid is measured with a graduated cylinder to be approximately 56 mL, 8.79 g (5 mol%) of p-toluenesulfonic acid is added, the reaction is continued for 4 h, allowed to stand and cool, 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved, the liquid is separated, the aqueous phase is taken, concentrated hydrochloric acid is slowly added dropwise while stirring, acidified to a pH of 1-2, extracted twice with ethyl acetate, the organic phases are combined, and dried; 192.80 g (0.9 mol) of 2,4-dihydroxybenzophenone and 16.06 g (5 mol%, 0.045 mol) of nickel trifluoromethanesulfonate are added thereto, a water separator is installed, stirring is turned on, and the temperature is slowly raised to 160 o C, react for 12 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 203.05 g of white solid with a yield of 63%. Example 18:

[0060] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% glyoxylic acid aqueous solution, 246 mL (2.0 mol, 2.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, and slowly raise the temperature to 120 o C, heated to reflux until the upper layer of the water separator is clear and no water droplets are seen dripping. The lower layer liquid is measured with a graduated cylinder to be approximately 56 mL. 8.79 g (5 mol%) of p-toluenesulfonic acid is added. The reaction is continued for 4 h. The mixture is allowed to stand and cool. A 50% aqueous sodium hydroxide solution is added until the solid is completely dissolved. The liquid is separated. The aqueous phase is taken and concentrated hydrochloric acid is slowly added dropwise while stirring. The pH is acidified to 1-2. The mixture is extracted twice with ethyl acetate. The organic phases are combined and spin-dried. 385.60 g (1.8 mol) of 2,4-dihydroxybenzophenone and 32.11 g (5 mol%, 0.09 mol) of nickel trifluoromethanesulfonate are added thereto. The water separator is installed. Stirring is turned on and the temperature is slowly raised to 160°C. o C, react for 12 h, let stand and cool, add ethyl acetate to dissolve, wash twice with water, add sodium bicarbonate aqueous solution, separate the liquids, take the organic phase, add anhydrous sodium sulfate, spin dry, and dissolve the obtained crude product by heating with methanol and cooling naturally to precipitate 309.42 g of white solid with a yield of 48%.

[0061] Through horizontal comparison, we found that:

[0062] In terms of ultraviolet absorption capacity, by using ethyl acetate ( Figure 4a-4c ) and methanol ( Figure 5a-5c ) is the reference solution for the UV absorption test. We found that the absorption capacity of UVAO-358 in the 260nm-280nm wavelength range is significantly better than that of UV-351 and UV-0. The absorption capacity in other UV regions is not much different. In addition, the color of UVAO-358 material is the best, which is off-white ( Figure 6 ).

[0063] In terms of thermal stability, the thermogravimetric analysis test ( Figure 7a and Figure 7b ), we found that HP-136 was at 185.6 o C and began to decompose at 293.3 o C, and UVAO-358 lost half its weight at 258.1 o C and began to decompose at 368.5 o C, the weight loss is half, and it is obvious that the thermal stability of UVAO-358 is better than that of HP-136.

[0064] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A chemical additive UVAO-358, characterized in that, The chemical formula of the chemical auxiliary agent UVAO-358 is as follows: 。 2. A use of a chemical additive UVAO-358, characterized in that, The chemical auxiliary agent UVAO-358 is as described in claim 1, and the chemical auxiliary agent UVAO-358 is used as an ultraviolet absorber or a carbon free radical scavenger.

3. The use of the chemical auxiliary agent UVAO-358 as claimed in claim 2, characterized in that, The chemical auxiliary agent UVAO-358 is used as an ultraviolet absorber for ultraviolet light in the wavelength range of 260nm-280nm.

4. A method for synthesizing a chemical auxiliary agent UVAO-358, characterized in that: The steps include: 3, 4-dimethylmandelic acid and 2, 4-dihydroxybenzophenone were used as raw materials and Lewis acid was used as catalyst at 120~160 o C and stirred for 4-5 hours to obtain the chemical auxiliary agent UVAO-358 as claimed in claim 1.

5. The synthetic method of chemical auxiliary agent UVAO-358 as claimed in claim 4, characterized in that, The preparation method of 3, 4-dimethylmandelic acid is as follows: glyoxylic acid solution and o-xylene are used as raw materials, Bronsted acid is used as catalyst, methylcyclohexane is used as solvent, and the mixture is heated at 120 o C and stirred for 4-5 hours to obtain 3, 4-dimethylmandelic acid.

6. The synthetic method of the chemical auxiliary agent UVAO-358 as claimed in claim 5, characterized in that, When preparing 3, 4-dimethylmandelic acid, methylcyclohexane is first used to remove all water from the reaction system, and then p-toluenesulfonic acid is added to initiate the reaction.

7. The method for synthesizing the chemical auxiliary agent UVAO-358 as claimed in claim 5, wherein: The molar ratio of the glyoxylic acid solution, o-xylene and 2, 4-dihydroxybenzophenone is 1:1-2:0.5-1.

8. The method for synthesizing the chemical auxiliary agent UVAO-358 as claimed in claim 7, wherein: The molar ratio of the glyoxylic acid solution, o-xylene and 2, 4-dihydroxybenzophenone is 1:2:0.

5.

9. The method for synthesizing the chemical auxiliary agent UVAO-358 as claimed in claim 5, wherein: The Bronsted acid is hydrochloric acid, sulfuric acid or p-toluenesulfonic acid; the Lewis acid is aluminum trichloride, ferric trichloride, nickel trifluoromethanesulfonate, zinc trifluoromethanesulfonate or copper trifluoromethanesulfonate; the molar addition amount of the Bronsted acid is 5.0%, and the molar addition amount of the Lewis acid is 5.0%.

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