Chemical additive UVAO-358 as well as synthesis method and application thereof

Abstract

The invention provides a chemical additive UVAO-358 as well as a synthesis method and application thereof. The method has the advantages that the raw materials are easy to obtain, the operation is simple, the reaction conditions are relatively mild, and the product yield and purity are high. The efficient catalytic synthesis method of the novel carbon free radical trapping agent with the ultraviolet absorption capacity opens up a multifunctional application way for the novel carbon free radical trapping agent, and has the advantages that the novel carbon free radical trapping agent with the ultraviolet absorption capacity has the ultraviolet absorption capacity and also has the function of efficient catalytic synthesis of the carbon free radical trapping agent with the ultraviolet absorption capacity; the method has the advantages of high selectivity and yield of the target product, wide raw material source, high selectivity and yield of the target product, mild reaction conditions, simple reaction operation, no generation of harmful by-products, and environmental protection.

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 technology]

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

[0003]

[0004] At present, polymer materials are widely used in materials, energy, chemical industry, communication equipment and other fields. However, polymer materials will inevitably be exposed to ultraviolet light during use, which often reduces the various properties and service life of polymer materials. Adding ultraviolet absorbers is an effective way to prevent the aging of polymer materials. 2,4-Dihydroxybenzophenone (UV-0) and its derived benzophenone compounds are widely used ultraviolet absorbers in polymers such as resins. They are used in materials such as polyvinyl chloride, polyacrylate, polyolefin, and added to coatings based on polyacrylate, epoxy resin, etc. to improve their anti-aging properties. They are also used in cosmetics, aerospace, medicine and other fields. At the same time, they are also intermediates for preparing other ultraviolet absorbers. However, in today's coating application field, although UV-0 has excellent ultraviolet absorption ability, the overall color of the finished material is darker, which is not conducive to the development of diversified coatings; UV-351 is an optimized product derived from UV-0. Although the overall color of the finished material is lighter, the ultraviolet absorption ability is reduced; and the stability of both is poor and does not have antioxidant properties.

[0005] Relevant research results show that benzofuranone free radical scavengers can capture alkoxy free radicals under both aerobic and anaerobic conditions. The most representative product is HP-136, a benzofuranone 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] In this context, we developed a new chemical additive UVAO-358 with UV absorption and carbon free radical capture capabilities. This material can not only react with carbon free radicals to generate stable products, but also has UV absorption properties when tested by UV spectroscopy technology, making it a new multifunctional material.

[0008] In summary, the UVAO-358 we developed is a new type of chemical additive with UV absorption and carbon free radical capture capabilities, and its UV absorption performance and thermal oxidation aging resistance are better than common materials on the market. Its synthesis method has easy-to-obtain raw materials, simple operation, mild reaction conditions, and high product yield and purity. At present, there are no public documents and patent applications for this type of multifunctional material at home and abroad. [Summary of the invention]

[0009] The purpose of the present invention is to provide a method for synthesizing a novel chemical auxiliary agent UVAO-358 with ultraviolet absorption and carbon free radical capture ability by using 2,4-dihydroxybenzophenone, glyoxylic acid solution and o-xylene as raw materials. The method has easy-to-obtain raw materials, simple operation, 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 a chemical additive UVAO-358, wherein the chemical additive UVAO-358 is as described in claim 1, and the chemical additive 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] The chemical auxiliary agent UVAO-358 is obtained by using 3,4-dimethylmandelic acid and 2,4-dihydroxybenzophenone as raw materials and Lewis acid as catalyst and stirring at 160° C. for 4-5 hours.

[0017] As a 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, stirring at 120° C. 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] In a 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] The invention discloses a method for synthesizing a novel chemical auxiliary agent UVAO-358 with ultraviolet absorption and carbon free radical capture capabilities. The method has a wide source of raw materials, high selectivity and yield of target products, mild reaction conditions, simple reaction operation, no generation of harmful by-products, and is a green and environmentally friendly reaction.

Brief Description of the Drawings

[0026] Figure 1 The invention provides a route map for preparing a novel chemical auxiliary agent UVAO-358 having ultraviolet absorption and carbon free radical capture capabilities.

[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 graph of UVAO-358 with ethyl acetate as the reference solution;

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

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

[0032] Figure 5a Methanol is used as the reference solution, UVAO-358 UV 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 UV 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 of HP-136 [Specific implementation method]

[0038] In order to make the above features, advantages and purposes of the present invention more clearly understood, the specific implementation of the present invention is described in detail below in conjunction with the accompanying drawings. Many specific details are described in the following description to facilitate a full understanding of the present invention.

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

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

[0041]

[0042] The present invention will be further described below in conjunction with specific preparation examples:

[0043] Embodiment 1:

[0044] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen dripping, and the lower layer liquid is approximately 56 mL measured with a measuring cylinder, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidified to pH 1-2, extracted twice with ethyl acetate, combined the organic phases, and dried; then added 2,4-dihydroxybenzophenone 96.40g (0.45mol), nickel trifluoromethanesulfonate 8.03g (5mol%, 0.0225mol), installed a water separator, turned on stirring, slowly raised the temperature to 160°C, reacted for 5h, allowed to stand and cool, added ethyl acetate to dissolve, washed with water twice, added sodium bicarbonate aqueous solution, separated, took the organic phase, added anhydrous sodium sulfate, dried, dissolved the crude product by heating with methanol, cooled naturally, and precipitated 146.65g of white solid with a yield of 91%. 1 H NMR(400MHz,Chloroform-d)δ12.48(d,J=1.8Hz,1H),7.71(dd,J=8.7,1.8Hz,1H),7.66(d,J=7.8Hz,2H),7.61(dd,J=8.3,6.4Hz,1H),7.5 5–7.49(m,2H),7.14(d,J=7.7Hz,1H),7.06(s,1H),7.00(d,J=7.9Hz,1H),6.76(dd,J=8.7,1.8Hz,1H),4.95(s,1H),2.25(d,J=3.9Hz,6H). 13 C NMR(101MHz,Chloroform-d)δ201.03,174.69,160.27,159.64,137.68,137.55,137.00,136.42,132.14,13 0.82,130.33,129.20,129.06,128.52,125.29,116.62,114.20,102.45,47.67,19.92,19.57.GC-MS:358.12

[0045] Embodiment 2:

[0046] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen dripping, and the lower layer liquid is approximately 56 mL measured with a measuring cylinder, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidified to pH 1-2, extracted twice with ethyl acetate, combined the organic phases, and dried; then added 2,4-dihydroxybenzophenone 96.40g (0.45mol), zinc trifluoromethanesulfonate 8.18g (5mol%, 0.0225mol), installed a water separator, turned on stirring, slowly raised the temperature to 160°C, reacted for 5h, allowed to stand and cool, added ethyl acetate to dissolve, washed with water twice, added sodium bicarbonate aqueous solution, separated, took the organic phase, added anhydrous sodium sulfate, dried, dissolved the crude product by heating with methanol, cooled naturally, and precipitated 143.43g of white solid, with a yield of 89%.

[0047] Embodiment 3:

[0048] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen dripping, and the lower layer liquid is approximately 56 mL measured with a measuring cylinder, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidified to pH 1-2, extracted twice with ethyl acetate, combined the organic phases, and dried; then added 2,4-dihydroxybenzophenone 96.40g (0.45mol), copper trifluoromethanesulfonate 5.42g (5mol%, 0.0225mol), installed a water separator, turned on stirring, slowly raised the temperature to 160°C, reacted for 5h, allowed to stand and cool, added ethyl acetate to dissolve, washed with water twice, added sodium bicarbonate aqueous solution, separated, took the organic phase, added anhydrous sodium sulfate, dried, dissolved the crude product by heating with methanol, cooled naturally, and precipitated 33.84g of white solid, with a yield of 21%.

[0049] Embodiment 4:

[0050] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen dripping, and the lower layer liquid is approximately 56 mL measured with a measuring cylinder, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidify to pH 1-2, extract twice with ethyl acetate, combine the organic phases, and spin dry; then add 96.40g (0.45mol) of 2,4-dihydroxybenzophenone and 3.00g (5mol%, 0.0225mol) of aluminum chloride, install a water separator, start stirring, slowly raise the temperature to 160°C, react for 5h, 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, dissolve the crude product by heating with methanol, cool naturally, and precipitate 31.10g of white solid with a yield of 19.3%.

[0051] Embodiment 5:

[0052] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen dripping, and the lower layer of liquid measured with a measuring cylinder is approximately 56 mL, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly drip while stirring Add concentrated hydrochloric acid, acidify to pH 1-2, extract twice with ethyl acetate, combine the organic phases, and spin dry; then add 2,4-dihydroxybenzophenone 96.40g (0.45mol), ferric chloride 3.65g (5mol%, 0.0225mol), install a water separator, turn on stirring, slowly raise the temperature to 160°C, react for 5h, 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 crude product by heating with methanol, cool naturally, and precipitate 20.95g of white solid with a yield of 13%.

[0053] Embodiment 6:

[0054] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen dripping, and the lower layer liquid is approximately 56 mL measured with a measuring cylinder, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidified to pH 1-2, extracted twice with ethyl acetate, combined the organic phases, and dried; then added 2,4-dihydroxybenzophenone 96.40g (0.45mol), nickel trifluoromethanesulfonate 8.03g (5mol%, 0.0225mol), installed a water separator, turned on stirring, slowly raised the temperature to 120°C, reacted for 5h, allowed to stand and cool, added ethyl acetate to dissolve, washed with water twice, added sodium bicarbonate aqueous solution, separated, took the organic phase, added anhydrous sodium sulfate, dried, heated and dissolved the crude product with methanol, cooled naturally, and precipitated 104.75g of white solid with a yield of 65%.

[0055] Embodiment 7:

[0056] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen dripping, and the lower layer liquid is approximately 56 mL measured with a measuring cylinder, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidified to pH 1-2, extracted twice with ethyl acetate, combined the organic phases, and dried; then added 2,4-dihydroxybenzophenone 96.40g (0.45mol), nickel trifluoromethanesulfonate 8.03g (5mol%, 0.0225mol), installed a water separator, turned on stirring, slowly raised the temperature to 130°C, reacted for 5h, allowed to stand and cool, added ethyl acetate to dissolve, washed with water twice, added sodium bicarbonate aqueous solution, separated, took the organic phase, added anhydrous sodium sulfate, dried, heated and dissolved the crude product with methanol, cooled naturally, and precipitated 109.58g of white solid with a yield of 68%.

[0057] Embodiment 8:

[0058] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen dripping, and the lower layer liquid is approximately 56 mL measured with a measuring cylinder, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidified to pH 1-2, extracted twice with ethyl acetate, combined the organic phases, and dried; then added 2,4-dihydroxybenzophenone 96.40g (0.45mol), nickel trifluoromethanesulfonate 8.03g (5mol%, 0.0225mol), installed a water separator, turned on stirring, slowly raised the temperature to 140°C, reacted for 5h, allowed to stand and cool, added ethyl acetate to dissolve, washed with water twice, added sodium bicarbonate aqueous solution, separated, took the organic phase, added anhydrous sodium sulfate, dried, heated and dissolved the crude product with methanol, cooled naturally, and precipitated 122.48g of white solid with a yield of 76%.

[0059] Embodiment 9:

[0060] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen dripping, and the lower layer liquid is approximately 56 mL measured with a measuring cylinder, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidified to pH 1-2, extracted twice with ethyl acetate, combined the organic phases, and dried; then added 2,4-dihydroxybenzophenone 96.40g (0.45mol), nickel trifluoromethanesulfonate 8.03g (5mol%, 0.0225mol), installed a water separator, turned on stirring, slowly raised the temperature to 150°C, reacted for 5h, allowed to stand and cool, added ethyl acetate to dissolve, washed with water twice, added sodium bicarbonate aqueous solution, separated, took the organic phase, added anhydrous sodium sulfate, dried, heated and dissolved the crude product with methanol, cooled naturally, and precipitated 136.98g of white solid with a yield of 85%.

[0061] Embodiment 10:

[0062] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen dripping, and the lower layer liquid is approximately 56 mL measured with a measuring cylinder, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidified to pH 1-2, extracted twice with ethyl acetate, combined the organic phases, and dried; then added 2,4-dihydroxybenzophenone 96.40g (0.45mol), nickel trifluoromethanesulfonate 8.03g (5mol%, 0.0225mol), installed a water separator, turned on stirring, slowly raised the temperature to 170°C, reacted for 5h, allowed to stand and cool, added ethyl acetate to dissolve, washed with water twice, added sodium bicarbonate aqueous solution, separated, took the organic phase, added anhydrous sodium sulfate, dried, dissolved the crude product by heating with methanol, cooled naturally, and precipitated 117.64g of white solid with a yield of 73%.

[0063] Embodiment 11:

[0064] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen dripping, and the lower layer liquid is approximately 56 mL measured with a measuring cylinder, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidified to pH 1-2, extracted twice with ethyl acetate, combined the organic phases, and dried; then added 2,4-dihydroxybenzophenone 96.40g (0.45mol), nickel trifluoromethanesulfonate 8.03g (5mol%, 0.0225mol), installed a water separator, turned on stirring, slowly raised the temperature to 160°C, reacted for 2h, allowed to stand and cool, added ethyl acetate to dissolve, washed with water twice, added sodium bicarbonate aqueous solution, separated, took the organic phase, added anhydrous sodium sulfate, dried, the obtained crude product was dissolved by heating with methanol, cooled naturally, and 83.80g of white solid was precipitated, with a yield of 52%.

[0065] Embodiment 12:

[0066] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen dripping, and the lower layer liquid is approximately 56 mL measured with a measuring cylinder, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidified to pH 1-2, extracted twice with ethyl acetate, combined the organic phases, and dried; then added 2,4-dihydroxybenzophenone 96.40g (0.45mol), nickel trifluoromethanesulfonate 8.03g (5mol%, 0.0225mol), installed a water separator, turned on stirring, slowly raised the temperature to 160°C, reacted for 4h, allowed to stand and cool, added ethyl acetate to dissolve, washed with water twice, added sodium bicarbonate aqueous solution, separated, took the organic phase, added anhydrous sodium sulfate, dried, heated and dissolved the crude product with methanol, cooled naturally, and precipitated 135.37g of white solid with a yield of 84%.

[0067] Embodiment 13:

[0068] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen dripping, and the lower layer liquid is approximately 56 mL measured with a measuring cylinder, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidified to pH 1-2, extracted twice with ethyl acetate, combined the organic phases, and dried; then added 2,4-dihydroxybenzophenone 96.40g (0.45mol), nickel trifluoromethanesulfonate 8.03g (5mol%, 0.0225mol), installed a water separator, turned on stirring, slowly raised the temperature to 160°C, reacted for 8h, allowed to stand and cool, added ethyl acetate to dissolve, washed with water twice, added sodium bicarbonate aqueous solution, separated, took the organic phase, added anhydrous sodium sulfate, dried, dissolved the crude product by heating with methanol, cooled naturally, and precipitated 117.64g of white solid with a yield of 73%.

[0069] Embodiment 14:

[0070] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat under reflux until the upper layer of the water separator is clear and no water droplets can be seen. Measure the lower layer of liquid with a measuring cylinder to be approximately 56 mL, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add concentrated Hydrochloric acid, acidify to pH 1-2, extract twice with ethyl acetate, combine the organic phases and spin dry; then add 96.40g (0.45mol) of 2,4-dihydroxybenzophenone and 8.03g (5mol%, 0.0225mol) of nickel trifluoromethanesulfonate, install a water separator, start stirring, slowly raise the temperature to 160°C, react for 12h, 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, dissolve the obtained crude product by heating with methanol, cool naturally, and precipitate 109.58g of white solid with a yield of 68%.

[0071] Embodiment 15:

[0072] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 123 mL (1.0 mol, 1.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen. Measure the lower layer of liquid with a measuring cylinder to be approximately 56 mL, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidified to pH 1-2, extracted twice with ethyl acetate, combined the organic phases, and dried; then added 2,4-dihydroxybenzophenone 96.40g (0.45mol), nickel trifluoromethanesulfonate 8.03g (5mol%, 0.0225mol), installed a water separator, turned on stirring, slowly raised the temperature to 160°C, reacted for 5h, allowed to stand and cool, added ethyl acetate to dissolve, washed with water twice, added sodium bicarbonate aqueous solution, separated, took the organic phase, added anhydrous sodium sulfate, dried, heated and dissolved the crude product with methanol, cooled naturally, and precipitated 85.41g of white solid with a yield of 53%.

[0073] Embodiment 16:

[0074] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 369 mL (3.0 mol, 3.0 equivalent) of o-xylene, and 400 mL of methylcyclohexane to a 2000 mL three-necked flask, install a water separator, start stirring, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen. Measure the lower layer of liquid with a measuring cylinder to be approximately 56 mL, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidified to pH 1-2, extracted twice with ethyl acetate, combined the organic phases, and dried; then added 2,4-dihydroxybenzophenone 96.40g (0.45mol), nickel trifluoromethanesulfonate 8.03g (5mol%, 0.0225mol), installed a water separator, turned on stirring, slowly raised the temperature to 160°C, reacted for 5h, allowed to stand and cool, added ethyl acetate to dissolve, washed with water twice, added sodium bicarbonate aqueous solution, separated, took the organic phase, added anhydrous sodium sulfate, dried, heated and dissolved the crude product with methanol, cooled naturally, and precipitated 120.87g of white solid with a yield of 75%.

[0075] Embodiment 17:

[0076] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat under reflux until the upper layer of the water separator is clear and no water droplets can be seen. Measure the lower layer of liquid with a measuring cylinder to be approximately 56 mL, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add concentrated Hydrochloric acid, acidify to pH 1-2, extract twice with ethyl acetate, combine the organic phases and spin dry; then add 2,4-dihydroxybenzophenone 192.80g (0.9mol), nickel trifluoromethanesulfonate 16.06g (5mol%, 0.045mol), install a water separator, start stirring, slowly raise the temperature to 160°C, react for 12h, 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, dissolve the crude product by heating with methanol, cool naturally, and precipitate 203.05g of white solid with a yield of 63%.

[0077] Embodiment 18:

[0078] Add 112 mL (1.0 mol, 1.0 equivalent) of 50% aqueous solution of glyoxylic acid, 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, slowly raise the temperature to 120°C, heat to reflux until the upper layer of the water separator is clear and no water droplets can be seen dripping, and the lower layer liquid is approximately 56 mL measured with a measuring cylinder, add 8.79 g (5 mol%) of p-toluenesulfonic acid, continue the reaction for 4 h, let it stand and cool, add 50% aqueous sodium hydroxide solution until the solid is completely dissolved, separate the liquids, take the aqueous phase, and slowly add dropwise while stirring Concentrated hydrochloric acid, acidified to pH 1-2, extracted twice with ethyl acetate, combined the organic phases, and dried; then added 2,4-dihydroxybenzophenone 385.60g (1.8mol), nickel trifluoromethanesulfonate 32.11g (5mol%, 0.09mol), installed a water separator, turned on stirring, slowly raised the temperature to 160°C, reacted for 12h, allowed to stand and cool, added ethyl acetate to dissolve, washed twice with water, added sodium bicarbonate aqueous solution, separated, took the organic phase, added anhydrous sodium sulfate, dried, heated and dissolved the crude product with methanol, cooled naturally, and precipitated 309.42g of white solid with a yield of 48%.

[0079] Through horizontal comparison, we found that:

[0080] In terms of ultraviolet absorption capacity, by using ethyl acetate ( Figure 4a-4c ) and methanol ( Figure 5a-5c ) is the UV absorption test of the reference solution. 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 ultraviolet regions is not much different. In addition, the color of UVAO-358 material is the best, which is off-white ( Figure 6 ).

[0081] In terms of thermal stability, the thermogravimetric analysis test ( Figure 7a and Figure 7b ), we found that HP-136 began to decompose at 185.6℃ and lost half of its weight at 293.3℃, ​​while UVAO-358 began to decompose at 258.1℃ and lost half of its weight at 368.5℃. Obviously, the thermal stability of UVAO-358 is better than that of HP-136.

[0082] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached 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 of 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: The chemical auxiliary agent UVAO-358 is obtained by using 3,4-dimethylmandelic acid and 2,4-dihydroxybenzophenone (molar ratio 2:1) as raw materials and Lewis acid as catalyst and stirring at 120-160° C. for 4-5 hours.

5. The method for synthesizing the chemical auxiliary agent UVAO-358 as claimed in claim 4, characterized in that: 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, stirring at 120° C. for 4-5 hours to obtain 3,4-dimethylmandelic acid.

6. The method for synthesizing 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 in the reaction system, and then p-toluenesulfonic acid is added to start the reaction.

7. The method for synthesizing the chemical auxiliary agent UVAO-358 as claimed in claim 5, characterized in that: 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, characterized in that: 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, characterized in that: 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%.

10. The method for synthesizing the chemical auxiliary agent UVAO-358 according to any one of claims 4 to 9, characterized in that: The chemical formula of the 3,4-dimethylmandelic acid is as follows:

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