CN115974671A - A low-permeability short-wave ultraviolet absorber, preparation method and application - Google Patents

Abstract

The invention relates to a low-permeability short-wave ultraviolet absorbent, a preparation method and application, belonging to the field of high polymer materials.A substrate of the low-permeability short-wave ultraviolet absorbent is a transparent flexible film with activated carbon-carbon double bonds, the flexible film is provided with modified benzophenone-3 molecules through chemical crosslinking, the modified benzophenone-3 is a styrene group introduced on the basis of a benzophenone-3 molecular structure, and the obtained flexible sun-proof film has good ultraviolet absorption capacity and good aging resistance. The ultraviolet absorbent can absorb ultraviolet rays with the wavelength of 270-350 nm, has good ultraviolet absorption effect, and particularly has the best absorption effect under the short-wave ultraviolet rays with the wavelength of 270-290 nm.

Description

A low-permeability short-wave ultraviolet absorber, preparation method and application

technical field

The invention belongs to the field of polymer materials, and in particular relates to a modification method of benzophenone-3 ultraviolet absorber, and its subsequent use for chemical crosslinking with polymer substrates to prepare a benzophenone-3 ultraviolet absorber with ultraviolet absorbing ability, especially for short-wave Transparent polymer film with strong UV absorption capacity.

Background technique

Ultraviolet rays are part of sunlight, and ultraviolet rays can be divided into long-wave ultraviolet (UVA, 400nm-320nm), medium-wave ultraviolet (UVB, 320nm-280nm), and short-wave ultraviolet (UVC, 280nm-190nm). A small amount of sunlight can promote the transformation of vitamin D in the human body, promote the metabolism of the human body and enhance the body's physique. But if the skin is exposed to sunlight for a long time, ultraviolet rays can cause damage to the skin. For example, UVA has a strong penetrating ability. About 98% of UVA in ultraviolet rays can penetrate the atmosphere and clouds to reach low-altitude areas on the earth, and can penetrate the dermal tissue on the surface of the human body, destroying its collagen fibers and elastic fibers. suntan. Although the penetrating ability of UVB is slightly worse than that of UVA, some UVB will be absorbed by the atmosphere and clouds, but still about 2% of UVB will reach the low-altitude areas of the earth, and prolonged exposure will cause redness, swelling and peeling of the skin. The penetration of UVC is the weakest, but short-wave ultraviolet rays are very harmful to the human body. Short-term exposure can burn the skin, and long-term exposure can cause skin cancer. Although UVC has been absorbed by the ozone layer and cannot reach the surface of the earth, short-wave ultraviolet rays will have a huge impact on the human body, and sufficient attention should be paid to UVC.

In recent years, people's concept of beauty has been increasing. As the saying goes, "one beauty covers all ugliness", people use more and more sunscreen agents in cosmetics. 2-Hydroxy-4-methoxybenzophenone (trade name: UV -9. Benzophenone-3) belongs to benzophenone UV absorber, its chemical structure can effectively absorb high-energy ultraviolet light with a wavelength of 270-400nm, provide anti-ultraviolet protection, and has low toxicity and thermal stability Good performance, can be used in a small number of cosmetics and polymer products, and especially suitable for light-colored products, it is an ideal ultraviolet absorber. Benzophenone-3, as a UV absorber with high safety, good sun protection effect and low price, has been widely used in cosmetics and polymer fields. Although no benzophenone UV absorbers have been found to have side effects such as allergies, dermatitis, and carcinogenicity on human skin, some countries have imposed clear restrictions on their use: the European Union, the United States, Japan, and South Korea have stipulated that benzophenone The maximum allowable dosage of -3 in sunscreens is 10%, 6%, 5% and 5%, so the limitation of the dosage will limit the UV absorption effect to a certain extent. UV absorbers are usually added to products by blending, so benzophenone-3 in sunscreens will directly contact human skin. Existing studies have shown that 1% of benzophenone-3 after topical use ~2% will be absorbed through the skin within 10 hours, and then enter the body for metabolism. At the same time, benzophenone-3 has the disadvantages of low molecular weight, insolubility in water, and poor compatibility with polymer materials.

The above shortcomings limit the use of benzophenone-3. If benzophenone-3 is cross-linked with the polymer substrate through chemical bonds instead of blending, the polymer substrate will be better endowed with Ultraviolet absorption capacity, and benzophenone-3 will not come into direct contact with human skin, and there is no limit to the amount of benzophenone-3 used, so it can enhance the ultraviolet rays in the application of benzophenone-3 absorption effect.

Contents of the invention

In order to solve the problem of limited use of benzophenone-3 in sunscreen cosmetics in the prior art, the present invention modifies the benzophenone-3 ultraviolet absorber, and then chemically cross-links it with the polymer substrate, A polymer transparent film with ultraviolet absorbing ability, especially strong absorbing ability for short-wave ultraviolet rays, is prepared.

The concrete scheme that the present invention adopts is:

In the first aspect, the present invention provides a modified benzophenone-3, which introduces active styryl groups on the basis of the molecular structure of benzophenone-3, and the active groups interact with the polymer substrate. Linked, so as to reduce the permeability of UV absorbers to the skin, and at the same time have a certain absorption effect of full-band UV rays, especially for short-wave UV rays. The structure of the modified benzophenone-3 is:

In the second aspect, the present invention provides the preparation method of the above-mentioned modified benzophenone-3, the benzophenone-3 molecule reacts with p-chlorostyrene through Williams etherification reaction, and its reaction formula is:

Further, the preparation method of the modified benzophenone-3 comprises the following steps:

Take 2-hydroxy-4-methoxybenzophenone (subsequently referred to as benzophenone-3) and dissolve it in an organic solvent, under the protection of nitrogen, add potassium carbonate as a catalyst, and set the temperature of the oil bath to 70 ℃, after the temperature of the oil bath reaches 70 ℃, nitrogen gas is introduced, and chloromethyl styrene is gradually added dropwise. Minutes, followed by post-processing, adding ethanol to the reaction solution to dissolve the remaining unreacted benzophenone-3, filtering to obtain a powdery brown solid, cleaning and drying the filtered product, and then obtaining modified benzophenone-3 .

Preferably, the organic solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, dichlorotetrahydrofuran or dichloromethane; the benzophenone-3 and organic solvent The mass ratio is 1:(1.5～3).

Preferably, the molar ratio of the benzophenone-3 to the catalyst potassium carbonate is 2:(1-1.5).

In a third aspect, the present invention provides the use of the above-mentioned modified benzophenone-3 as a low-permeability short-wave ultraviolet absorber.

In a fourth aspect, the present invention provides a short-wave ultraviolet absorbing composition, including modified benzophenone-3 and a macromolecular active prepolymer as a polymer matrix, through modifying the styrene group of benzophenone-3 The free radical polymerization reaction, chemical bond cross-linking with the macromolecular active prepolymer to increase its molecular weight, and at the same time, the UV absorber cross-links with the macromolecular prepolymer to reduce its permeability, and finally obtains a flexible film with UV-absorbing properties. Transparent composition.

In a fifth aspect, the present invention provides a method for preparing the above-mentioned short-wave ultraviolet absorbing composition, comprising the following steps:

(1) Benzophenone-3 and chloromethyl styrene are synthesized through Williamson etherification to prepare modified benzophenone-3;

(2) Dissolving the modified benzophenone-3, the initiator and the polymer matrix in the organic solvent;

(3) In the step (2), the polymerization is initiated by heating or ultraviolet irradiation to form a film, and dried.

Preferably, in step (2), the initiator is at least one of azobisisobutyronitrile and benzoin dimethyl ether; the organic solvent is ethyl acetate. Furthermore, if the initiator is azobisisobutyronitrile, the heating temperature in step (3) is 80°C, and the heating time is 10 minutes; if the initiator is benzoin dimethyl ether, the ultraviolet light time in step (3) is 2 minutes ; If the initiator is a mixture of azobisisobutyronitrile and benzoin dimethyl ether, then step (3) adopts at least one of the heating temperature of 80° C., the heating time of 10 min and the ultraviolet irradiation time of 2 min.

Preferably, the polymer matrix described in step (2) is at least one of the reactants of a mixture of silicone oil/hydrogen-containing silicone oil and an allyl-modified polyether polyol; then the reaction formula is the formula ( 1) or/and formula (2):

Described ultraviolet absorption mechanism is characterized in that: benzene ring, carbonyl belong to the chromophoric group that itself produces ultraviolet absorption and visible light absorption, if introduce the auxochromic group that contains the element of lone pair electron such as chloromethyl styrene, will make The spectral absorption of the chromophore shifts to the longer wavelength direction, and the absorption intensity increases.

For the above transparent film, only 1% of the ultraviolet absorber is added, the ultraviolet absorption peak is increased from 0.1 to 1.7, and the ultraviolet absorption performance is increased by 17 times.

In a sixth aspect, the present invention provides the use of the above short-wave ultraviolet absorbing composition.

Compared with the prior art, the present invention has the following advantages and effects:

(1) After the chemical modification of benzophenone-3 in the present invention, the ultraviolet absorption wavelength range does not change, and the absorption effect on UVC can be increased.

(2) The conversion rate of this reaction is high, no by-products and impurities are generated, and the process is simple.

(3) The present invention can be chemically cross-linked with a polymer matrix with a double bond, wherein the invention is used as an ultraviolet absorber to endow the material with excellent ultraviolet light absorption performance, especially for short-wave ultraviolet UVC.

(4) The combination principle of the present invention and the polymer matrix is through the chemical bond after the polymerization reaction.

Description of drawings

Fig. 1 is the nuclear magnetic resonance ¹ HNMR figure of a kind of low permeability ultraviolet absorber;

Fig. 2 is a kind of low-permeability ultraviolet absorber and the ultraviolet absorption contrast figure of benzophenone-3;

Fig. 3 is the ultraviolet absorption quantitative analysis figure of a kind of low-permeability ultraviolet absorber;

Fig. 4 is the preparation principle of ultraviolet absorbing film;

Fig. 5 is the structural representation of ultraviolet absorbing film;

Figure 6 is a comparison chart of ultraviolet absorption whether the film is added with a low-permeability ultraviolet absorber.

Detailed ways

1. The present invention solves the disadvantage of poor compatibility between benzophenone-3 and polymers. First, chemically modify benzophenone-3, and then chemically cross-link with the polymer matrix to replace the method of physical blending , reducing the shedding of benzophenone-3 from the polymer matrix, resulting in a decrease in UV absorption performance.

2. The present invention can be applied in the field of cosmetics or artificial skin, and overcomes the permeability problem of benzophenone-3 in human skin.

3. The present invention endows the polymer substrate with the ability to absorb ultraviolet rays, so that it has the effect of absorbing ultraviolet rays, especially the short-wave ultraviolet rays that have great harm to the human body have a good absorption effect, and can also be applied to the shell of short-wave ultraviolet rays. Prepare materials or shielding materials to prevent personnel in contact with the instrument from being harmed by short-wave ultraviolet rays.

Therefore, the present invention chemically modifies the benzophenone-3, carries out chemical bond cross-linking with the polymer matrix, and endows the polymer matrix with an ultraviolet absorbing function. The method has the characteristics of simple process, friendly to human body, high conversion rate, good ultraviolet absorption ability and the like.

Technical scheme of the present invention is as follows:

A preparation and application method of a low-permeability short-wave ultraviolet absorber, the base of which is a flexible transparent film formed by chemical cross-linking, and the modified benzophenone-3 through chemical cross-linking is on the base transparent film.

The modified benzophenone-3 is synthesized by Williamson etherification reaction between benzophenone-3 and chloromethyl styrene. The reaction conversion rate is high, no by-product is generated, and the process is simple.

A kind of synthetic method of low-permeability short-wave ultraviolet absorber: get 2-hydroxy-4-methoxy benzophenone (subsequently referred to as benzophenone-3) and dissolve in organic solvent, put into there-necked flask, Under the protection of nitrogen, add potassium carbonate as a catalyst, set the temperature of the oil bath to 70°C, after the temperature of the oil bath reaches 70°C, feed nitrogen, and gradually add chloromethyl styrene dropwise through the dropping funnel, The dropping rate of chloromethyl styrene is controlled to be dripped at a constant speed within three hours. After the dropping, the three-neck flask is protected with constant temperature nitrogen for 30 minutes, followed by post-treatment. Ethanol is added to the reaction solution to dissolve the remaining unreacted diphenylmethane Ketone-3, filtered to obtain a pinkish-brown solid, followed by repeated washing with distilled water and ethanol three times, and drying in a vacuum oven to obtain a low-permeability short-wave ultraviolet absorber.

Generate described modified product chemical reaction formula with shown in (1):

Preferably, the mass ratio of the benzophenone-3 to the solvent N,N'-dimethylformamide or N,N'-dimethylacetamide is 1: (1.5-3).

Preferably, the molar ratio of the benzophenone-3 to the catalyst potassium carbonate is 2:(1-1.5). Preferably, the catalyst is potassium carbonate.

The preparation method for the short-wave ultraviolet composition is to dissolve the modified benzophenone-3 and the polymer substrate in an organic solvent, add an initiator or a photoinitiator, and make it polymerize by heating or illuminating, A flexible transparent composition with UV absorbing properties is obtained.

The above-mentioned preparation method for the short-wave ultraviolet ray composition specifically comprises the following steps:

(1) Benzophenone-3 and chloromethyl styrene are synthesized through Williamson etherification to prepare modified benzophenone-3;

(2) Dissolving the modified benzophenone-3, the initiator and the polymer matrix in the organic solvent;

(3) In the step (2), the polymerization is initiated by heating or ultraviolet irradiation to form a film, and dried.

Preferably, the initiator described in step (2) is at least one of azobisisobutyronitrile and benzoin dimethyl ether.

Preferably, the organic solvent described in step (2) is ethyl acetate.

Preferably, the polymer matrix described in step (2) is a mixture of silicone oil/hydrogen-containing silicone oil, and at least one of the reactants whose end groups are allyl-modified polyether polyols, wherein the following end groups are The reactant structural formula of allyl-modified polyether polyol:

The present invention does not limit the use of the polymer matrix, and the present invention selects the above two matrixes only to better demonstrate the application of the present invention.

Among them, Fig. 4 is the preparation principle of the two kinds of polymer substrates and the ultraviolet absorbing film of this patent; Fig. 5 is a schematic structural diagram of the ultraviolet absorbing film.

Preferably, if the initiator is azobisisobutyronitrile, the heating temperature in step (3) is 80° C., and the heating time is 10 minutes.

Preferably, if the initiator is benzoin dimethyl ether, the UV irradiation time in step (3) is 2 min.

Preferably, if the initiator is a mixture of azobisisobutyronitrile and benzoin dimethyl ether, the heating temperature in step (3) is 80° C., the heating time is 10 min and the ultraviolet irradiation time is at least one of 2 min.

Preferably, step (3) is dried by infrared light irradiation, oven drying or natural drying. The nuclear magnetic resonance ¹ HNMR spectrum of the short-wave ultraviolet light is shown in FIG. 1 .

The use of the ultraviolet absorbing composition is to be applied to skin substitutes artificially developed in vitro and human body surface sunscreens with ultraviolet absorbing properties, and can also be applied to places exposed to ultraviolet rays, especially short-wave ultraviolet rays, such as plateau areas, high-altitude Surface ultraviolet absorbing composite materials for operating devices and short-wave ultraviolet instruments.

The working principle of the present invention is:

The benzophenone-3 ultraviolet absorber has a strong absorption effect on almost the entire ultraviolet region, because the intramolecular hydrogen bond formed between the hydroxyl hydrogen on the benzene ring and the adjacent carbonyl oxygen forms a chelate ring, when absorbing ultraviolet light, the molecule undergoes thermal vibration, the hydrogen bond breaks and the chelating ring opens to form an ionic compound in an unstable high-energy state. The energy is released, and the chelate ring is closed again, so that the ultraviolet rays are absorbed continuously for protection. Secondly, the carbonyl group will be excited, and tautomerization to generate the enol structure will also consume part of the energy.

When benzophenone-3 is modified, the hydrogen bond is destroyed, and the opening and closing mechanism of its chelating ring is weakened, leaving only the carbonyl group excited to undergo tautomerization and absorb ultraviolet energy.

When some groups in the molecule absorb ultraviolet-visible radiation, they will generate electronic energy level transition by absorbing light energy. Since different substances have different molecular structures and spatial structures, the absorption of light energy will be different. The electronic energy level transition is accompanied by the transition of the vibrational energy level and the rotational energy level. Due to the intermolecular interaction, a wide band is usually seen. The electronic absorption spectrum in organic molecules is a broad spectrum. The influence of the bond strength is different, so the absorption band width and the symmetry of the band are also different. When two or more Π bonds are conjugated, the Π-Π* transition energy of the conjugated Π orbital decreases, and the corresponding absorption wavelength increases and red shifts to the near ultraviolet region. Introducing one more benzene ring group, the conjugated system makes the absorption band red shift, and the ultraviolet light absorption ability increases.

Secondly, since the benzene ring and the carbonyl group belong to the chromophoric group that itself produces ultraviolet absorption and visible light absorption, if an auxochromic group containing an element containing a lone pair of electrons such as chloromethyl styrene is introduced, the spectral absorption of the chromophore will shift to the long-wave The direction moves, and the absorption strength increases. Therefore, after the modified benzophenone-3 is modified, although the hydrogen bond is destroyed, the absorption capacity of UVA and UVB decreases slightly, but the absorption capacity of UVC increases.

In order to facilitate understanding of the present invention, the present invention will be described in detail below in conjunction with specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be pointed out that for those skilled in the art, without departing from the concept of the present invention, the present invention can also make some modifications and improvements, which all belong to the protection scope of the present invention.

Unless otherwise defined, all technical and scientific terms used herein belong to professional terms commonly used in the technical field of the present invention, and have the same meaning as commonly understood by those skilled in the technical field of the present invention. The terms used herein in the specification are for describing specific embodiments only, and are not intended to limit the present invention.

The preparation of modified benzophenone-3 in the example of this patent is as follows: take 3g of benzophenone-3 and dissolve it in 4.5g of dimethylacetamide, put it into a three-necked flask, and add 3.631g of potassium carbonate under the protection of nitrogen As a catalyst, set the temperature of the oil bath to 70°C. After the temperature of the oil bath reaches 70°C, nitrogen gas is introduced, and 3g of chloromethylstyrene is gradually added dropwise through the dropping funnel. The dropping speed of chloromethylstyrene The overall rate control was dripped at a constant speed within three hours. After the dripping, the three-necked flask was protected with constant temperature nitrogen for 30 minutes, and then post-treated. 20g of ethanol alcohol was added to the reaction solution to dissolve the remaining unreacted benzophenone-3, and filtered to obtain The powdery brown solid was washed three times repeatedly with distilled water and ethanol, and dried in a vacuum oven to obtain 2.54 g of modified benzophenone-3 with a yield of 56.69%.

In this application, the sample is named bp-X-A/B, where X represents the added mass of modified benzophenone-3 in the polymer matrix, where A represents the composition of the polymer matrix using silicone oil/hydrogen silicone oil, B represents the reactant whose end group is allyl-modified polyether polyol, and Fig. 4 of the accompanying drawing of the specification of this application illustrates the preparation principle of the ultraviolet absorbing composition.

In addition, the macromolecular matrix adopted in the present invention is the reactant and the silicone oil/hydrogen-containing silicone oil composition of the polyether polyol whose terminal group is allyl modification, just in order to better demonstrate the application of the present invention, the macromolecular matrix Use is not limited to these two.

Example 1

Preparation of BP-001-A Ultraviolet Absorbing Composite Film

Take 0.01g of modified benzophenone-3, 0.1mg of azobisisobutyronitrile, and 0.1mg of benzoin dimethyl ether obtained by the above preparation method in 1g of ethyl acetate, until the modified benzophenone-3 is completely dissolved After ethyl acetate, add 0.9g silicone oil and 0.1g hydrogen-containing silicone oil, then centrifuge at 10,000rpm for 5min, spread it on a glass petri dish, put it in a UV irradiation box for 5min, and take it out Finally, a transparent ultraviolet absorbing composition with a certain light transmittance can be obtained.

Example 2

Preparation of BP-002-A Ultraviolet Absorbing Composite Film

Take 0.02 g of modified benzophenone-3 obtained by the above preparation method, and the rest of the steps are the same as in Example 1.

Example 3

Preparation of BP-001-B ultraviolet absorbing composite film

Take 0.01g of modified benzophenone-3, 0.1mg of azobisisobutyronitrile, and 0.1mg of benzoin dimethyl ether obtained by the above preparation method in 1g of ethyl acetate, until the modified benzophenone-3 is completely dissolved After ethyl acetate, add 1g of polyether polyol with allyl-modified end group, then centrifuge at 10,000rpm for 5min, spread it on a glass petri dish, and put it in a UV irradiation box Irradiate in medium for 5 minutes, and after taking it out, a transparent ultraviolet absorbing composition with a certain light transmittance can be obtained.

Example 4

Preparation of BP-002-B ultraviolet absorbing composite film

Take 0.02 g of modified benzophenone-3 obtained by the above preparation method, and the rest of the steps are the same as in Example 3.

Comparative example A

Referring to Example 1 and Example 2, the difference from Example 1 and Example 2 is that no modified benzophenone-3 is added.

Comparative Example B

Referring to Example 3 and Example 4, the difference from Example 3 and Example 4 is that no modified benzophenone-3 is added.

Table 1

Standard detection environment conditions: temperature: (23±2)℃, relative humidity: (50±5)%.

1. Appearance: Lay the film flat on a clean glass plate, and after standing still, visually observe the color of the film, mechanical impurities, and gel under natural scattered light or fluorescent light. Record the test results.

2. Tensile strength: refer to the provisions of "GB/T528 Determination of Tensile Properties of Vulcanized Rubber and Thermoplastic Rubber", and the test data of the tensile machine shall prevail;

3. Aging test: Spread the film on a clean and impurity-free petri dish, place it in a UV curing lamp box, and raise the temperature inside the lamp box to (35±2)°C, and place it for 24 hours.

4. Human body surface penetration test: Apply the film evenly on the surface of the human arm, and the person can carry out normal work, but the surface should not sweat as much as possible and should not touch water. After 8 hours, use methanol to clean the body sticking surface, and conduct ultraviolet spectroscopic test on the methanol cleaning solution to detect whether there is ultraviolet absorber. (For the control experiment, soak the transparent film in the control examples A and B in 1% benzophenone-3 methanol solution, dry it, stick it on the surface of the human body for 8 hours, and test it after extraction.)

It can be seen from Table 1 that the invention can impart a certain ultraviolet absorption effect when the mass addition amount of the film is 1% and 2%, and does not affect the color and transparency of the transparent film. In the aging experiment, we can find that after 24h of ultraviolet lamp irradiation, the color of the transparent film that does not add the ultraviolet absorber of the present invention becomes light yellow, while the color of the transparent film that adds the ultraviolet absorber of the present invention does not change, and with the ultraviolet light The increase in the amount of absorbent added does not greatly affect its mechanical properties; from the tensile strength, we can find that the invented double bond crosslinking can enhance the mechanical properties of the transparent film and increase its tensile strength; from the penetration of the human body We can find from the experiment that the ultraviolet absorber cross-linked with the polymer base through the double bond will not fall off and penetrate into the human skin, and has good safety performance on the surface skin of the human body.

As can be seen from Figure 2, the present invention has strong ultraviolet absorption peaks in the UVA, UVB, and UVC bands, especially the ultraviolet absorption peak of UVC is stronger, indicating that a kind of short-wave ultraviolet absorption composition prepared by the present invention has the actual function of preventing ultraviolet rays .

It can be seen from Fig. 3 that, with the increase of the dosage of the short-wave ultraviolet absorber of the present invention, the ultraviolet absorption intensity is also gradually enhanced.

By comparing the ultraviolet absorption curves of Example 1 and Comparative Example 1 in Fig. 6, it can be seen that the absorbance value of Comparative Example 1 at 270-400nm without adding the ultraviolet absorber of the present invention is significantly lower than that of the compound with the ultraviolet absorber of the present invention Composition obtained in Example 1.

The preparation and application method of the low-permeability short-wave ultraviolet absorber of the present invention, its substrate is a transparent flexible film with activated carbon carbon double bonds, and the modified benzophenone-3 by chemical crosslinking is carried on the flexible film Molecules, its flexible sunscreen film has good UV absorption capacity and good anti-aging performance. Moreover, the ultraviolet absorber of the present invention can absorb ultraviolet rays at 270-350 nm, and has good ultraviolet absorption effect, especially the best absorption effect at short-wave ultraviolet rays with a wavelength of 270-290 nm.

The technical features of the above-mentioned embodiments can be combined arbitrarily. To make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, should be considered as within the scope of this specification.

The above-mentioned embodiments only express several implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the patent scope of the invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.

Claims (10)

1. a modified benzophenone-3 is characterized in that: on the basis of the benzophenone-3 molecular structure, an active styryl group is introduced; the modified benzophenone-3 The structure is:

2. the preparation method of modified benzophenone-3 according to claim 1 is characterized in that: benzophenone-3 molecule reacts with p-chlorostyrene by Williams etherification reaction, and its reaction formula is:

3. The preparation method according to claim 2, characterized in that: comprising the following steps: Take benzophenone-3 and dissolve it in an organic solvent, under the protection of nitrogen, add potassium carbonate as a catalyst, set the temperature of the oil bath to 70°C, and after the temperature of the oil bath reaches 70°C, introduce nitrogen, and gradually drop Add chloromethyl styrene, the rate of addition of chloromethyl styrene is controlled to drop at a constant speed within three hours. After the drop is completed, the constant temperature nitrogen protection is carried out for 30 minutes, and then post-treatment is carried out. Ethanol is added to the reaction solution to dissolve the remaining unreacted bis Benzophenone-3 is filtered to obtain a pinkish brown solid, and the filtered product is washed and dried to obtain modified benzophenone-3. 4. The preparation method according to claim 3, characterized in that: the organic solvent is N,N-dimethylformamide, N,N-dimethylacetamide, dichlorotetrahydrofuran or dichloromethane At least one; the mass ratio of the benzophenone-3 to the organic solvent is 1: (1.5-3); the molar ratio of the benzophenone-3 to the catalyst potassium carbonate is 2: (1-1.5) . 5. the application of modified benzophenone-3 according to claim 1 as low-permeability short-wave ultraviolet absorber. 6. A short-wave ultraviolet absorbing composition, characterized in that: it includes modified benzophenone-3 and a macromolecular active prepolymer as a macromolecular matrix, and the styrene group of modified benzophenone-3 Free radical polymerization, chemical bond cross-linking with macromolecular active prepolymers, to obtain flexible and transparent compositions with UV-absorbing properties. 7. The preparation method of short-wave ultraviolet absorbing composition according to claim 6, is characterized in that: comprise the following steps: (1) benzophenone-3 and chloromethyl styrene are synthetically prepared modified by Williamson etherification reaction Benzophenone-3; (2) Dissolving the modified benzophenone-3, the initiator and the polymer matrix in the organic solvent; (3) Initiate polymerization to form a film by heating or ultraviolet irradiation, and dry. 8. preparation method according to claim 7, is characterized in that: in step (2), described initiator is at least one in azobisisobutyronitrile, benzoin dimethyl ether; Azodiisobutyronitrile, the heating temperature of step (3) is 80°C, and the heating time is 10min; if the initiator is benzoin dimethyl ether, the ultraviolet light time of step (3) is 2min; if the initiator is azobisiso The mixture of butyronitrile and benzoin dimethyl ether, then step (3) adopts that heating temperature is 80 ℃, heating time is 10min and ultraviolet light time is at least one in 2min; Described organic solvent is ethyl acetate. 9. The preparation method according to claim 7, characterized in that: the polymer matrix described in step (2) is a mixture of silicone oil/hydrogen-containing silicone oil, and the end group is the reaction of allyl-modified polyether polyol At least one of the compounds, then the reaction formula is formula (1) or/and formula (2):

10. The use of the short-wave ultraviolet absorbing composition according to claim 6 or the short-wave ultraviolet absorbing composition prepared by any one of the preparation methods described in claims 7 to 9 in any of the following: A. Preparation of skin substitutes and human body surface sunscreens with ultraviolet absorption properties; B. Preparation of surface ultraviolet absorbing material.

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