CN115974671A - Low-permeability short-wave ultraviolet absorbent, preparation method and application - Google Patents
Low-permeability short-wave ultraviolet absorbent, preparation method and application Download PDFInfo
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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
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a modification method of a benzophenone-3 ultraviolet absorbent, which is subsequently used for carrying out chemical crosslinking with a high polymer base material to prepare a high polymer transparent film with ultraviolet absorption capacity, particularly with extremely strong absorption capacity to short-wave ultraviolet.
Background
Ultraviolet rays are part of sunlight, and ultraviolet rays can be classified into long-wave ultraviolet rays (UVA, 400nm-320 nm), medium-wave ultraviolet rays (UVB, 320nm-280 nm), and short-wave ultraviolet rays (UVC, 280nm-190 nm). A small amount of sunlight can promote the conversion of vitamin D in human body, promote metabolism in the new castle of human body and enhance physique of human body. However, if the skin is exposed to sunlight for a long time, the ultraviolet rays may cause damage to the skin. For example, UVA has a strong penetration ability, and about 98% of UVA in ultraviolet rays can penetrate the atmosphere and cloud to low-altitude areas of the earth, and can penetrate dermal tissue on the surface of the human body to destroy collagen fibers and elastic fibers thereof, thereby tanning the skin. Although the penetration capacity of UVB is slightly worse than that of UVA, part of UVB can be absorbed by the atmosphere and cloud layers, about 2 percent of UVB still reaches the low-altitude areas of the earth, and the skin is red, swollen and peeled due to long-time irradiation. The penetration of UVC is the weakest, but the short wave ultraviolet ray has great harm to human body, and the skin can be burnt after short-time irradiation, and skin cancer can be caused after long-time irradiation. Although UVC is absorbed by the ozone layer and cannot reach the earth's surface, the short-wave ultraviolet rays have a great influence on the human body and should be paid sufficient attention to UVC.
In recent years, people increasingly increase the concept of love and beauty, namely 'beautiful and ugly', people increasingly use sunscreen agents in cosmetics, 2-hydroxy-4-methoxybenzophenone (trade name: UV-9 and benzophenone-3) belongs to benzophenone ultraviolet absorbers, the chemical structure of the ultraviolet absorbers can effectively absorb ultraviolet light with high-energy wavelength of 270-400nm to provide ultraviolet protection, and the ultraviolet absorbers are low in toxicity and good in thermal stability, can be used for small parts of cosmetics and high-molecular products, are particularly suitable for light-colored products, and are ideal ultraviolet absorbers. Benzophenone-3 is an ultraviolet absorbent with high safety, good sun-screening effect and low price, and is widely applied to the fields of cosmetics and polymers. Although no benzophenone ultraviolet absorbent is found to generate side effects such as allergy, dermatitis, carcinogenesis and the like on human skin at present, certain countries have clear limits on the use amount of the benzophenone ultraviolet absorbent: the european union, the united states, japan and korea stipulate that benzophenone-3 is used in sunscreen cream in maximum allowable amounts of 10%, 6%, 5% and 5%, and thus the limitation of the amount of use imposes a certain limitation on the ultraviolet absorption effect. The ultraviolet absorbent is usually added into the product in a blending mode, so that benzophenone-3 in the sunscreen cream can be directly contacted with human skin, and the existing research shows that 1-2% of benzophenone-3 in the sunscreen cream can be absorbed through the skin within 10h after being locally used, and then enters the body for metabolism. Meanwhile, benzophenone-3 has the defects of low molecular weight, water insolubility, poor compatibility with high polymer materials and the like.
The above disadvantages limit the use of benzophenone-3, if benzophenone-3 is cross-linked with the polymer substrate by chemical bonds rather than blending, the polymer substrate is better endowed with ultraviolet absorption capability, and benzophenone-3 is not in direct contact with human skin, and the use amount of benzophenone-3 is not limited, so that the ultraviolet absorption effect in the application of benzophenone-3 can be enhanced.
Disclosure of Invention
In order to solve the problem that the use of benzophenone-3 in sunscreen cosmetics is limited in the prior art, the invention modifies benzophenone-3 ultraviolet absorbent, and then chemically cross-links the modified benzophenone-3 ultraviolet absorbent with a polymer base material to prepare a polymer transparent film with ultraviolet absorption capacity, particularly with strong absorption capacity to short-wave ultraviolet.
The invention adopts the specific scheme that:
in a first aspect, the invention provides a modified benzophenone-3, which is prepared by introducing an active styryl group on the basis of a molecular structure of benzophenone-3, and crosslinking the active group with a polymer substrate, so that the permeability of an ultraviolet absorbent to skin is reduced, and the modified benzophenone-3 has a certain full-band ultraviolet absorption effect and is more effective to short-wave ultraviolet. The structure of the modified benzophenone-3 is as follows:
in a second aspect, the present invention provides a method for preparing the above modified benzophenone-3, wherein benzophenone-3 molecule is reacted with p-chlorostyrene through Williams etherification, and the reaction formula is:
further, the preparation method of the modified benzophenone-3 comprises the following steps:
dissolving 2-hydroxy-4-methoxybenzophenone (hereinafter referred to as benzophenone-3) in an organic solvent, adding potassium carbonate as a catalyst under the protection of nitrogen, setting the temperature of an oil bath pot to be 70 ℃, introducing nitrogen after the temperature of the oil bath pot reaches 70 ℃, gradually dropwise adding chloromethyl styrene, controlling the dropwise adding rate of the chloromethyl styrene to be uniformly dropwise added within three hours, keeping the temperature of the nitrogen for 30 minutes at constant temperature after the dropwise adding is finished, then carrying out aftertreatment, adding ethanol into a reaction solution to dissolve residual unreacted benzophenone-3, filtering to obtain a brown solid, cleaning and drying a filtered product, and thus obtaining the modified benzophenone-3.
Preferably, the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, dichlorotetrahydrofuran, or dichloromethane; the mass ratio of the benzophenone-3 to the organic solvent 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 invention provides an application of the modified benzophenone-3 in being used as a low-permeability short-wave ultraviolet absorbent.
In a fourth aspect, the invention provides a short-wave ultraviolet absorption composition, which comprises modified benzophenone-3 and a macromolecular active prepolymer serving as a macromolecular matrix, wherein the modified benzophenone-3 is subjected to chemical bond crosslinking with the macromolecular active prepolymer through free radical polymerization of styryl of the modified benzophenone-3, so that the molecular weight of the modified benzophenone-3 is increased, and meanwhile, an ultraviolet absorbent is crosslinked with the macromolecular prepolymer to reduce the permeability of the ultraviolet absorbent, so that the flexible transparent composition with the ultraviolet absorption performance is finally obtained.
In a fifth aspect, the present invention provides a method for preparing the short-wave ultraviolet absorbing composition, comprising the steps of:
(1) Synthesizing benzophenone-3 and chloromethyl styrene through Williamson etherification to prepare modified benzophenone-3;
(2) Dissolving modified benzophenone-3, an initiator and a polymer matrix in an organic solvent;
(3) And (3) initiating polymerization to form a film by heating or ultraviolet irradiation in the step (2), and drying.
Preferably, in the step (2), the initiator is at least one of azobisisobutyronitrile and benzoin dimethyl ether; the organic solvent is ethyl acetate. Further, if the initiator is azobisisobutyronitrile, the heating temperature in the step (3) is 80 ℃, and the heating time is 10min; if the initiator is benzoin dimethyl ether, the ultraviolet illumination time in the step (3) is 2min; if the initiator is a mixture of azodiisobutyronitrile and benzoin dimethyl ether, at least one of heating temperature of 80 ℃, heating time of 10min and ultraviolet irradiation time of 2min is adopted in the step (3).
Preferably, the polymer matrix in the step (2) is at least one of a mixture of silicone oil/hydrogen-containing silicone oil and a reactant of polyether polyol with allyl modified end group; the reaction formula is represented by formula (1) or/and formula (2):
the ultraviolet absorption mechanism is characterized in that: benzene ring and carbonyl belong to chromophoric groups which generate ultraviolet absorption and visible light absorption, and if a chromophoric group containing an element with a lone pair electron such as chloromethyl styrene is introduced, the spectral absorption of the chromophoric group moves towards a long wave direction, and the absorption intensity is increased.
The transparent film only adds 1% of the ultraviolet absorbent, the ultraviolet absorption peak is improved from 0.1 to 1.7, and the ultraviolet absorption performance is improved by 17 times.
In a sixth aspect, the present invention provides the use of the short wavelength ultraviolet absorbing composition described above.
Compared with the prior art, the invention has the following advantages and effects:
(1) After benzophenone-3 is chemically modified, the ultraviolet absorption wavelength range is not changed, and the absorption effect on UVC can be improved.
(2) The reaction has high conversion rate, no by-product and impurity and simple process.
(3) The ultraviolet light absorbing material can be chemically crosslinked with a high polymer matrix with double bonds, wherein the ultraviolet light absorbing material is used as an ultraviolet light absorber, so that the ultraviolet light absorbing material has excellent ultraviolet light absorbing performance, especially for short-wave ultraviolet UVC.
(4) The principle of the invention for bonding with the polymer matrix is bonding through chemical bonds after polymerization reaction.
Drawings
FIG. 1 is a nuclear magnetic resonance of a low permeability UV absorber 1 A HNMR map;
FIG. 2 is a graph comparing UV absorption of a low permeability UV absorber with benzophenone-3;
FIG. 3 is a graph of UV absorption quantification for a low permeability UV absorber;
FIG. 4 shows the principle of preparing an ultraviolet absorbing film;
FIG. 5 is a schematic view of the structure of the ultraviolet absorbing film;
FIG. 6 is a graph comparing UV absorption with or without a low permeability UV absorber.
Detailed Description
1. The invention solves the defect of poor compatibility of the benzophenone-3 and a macromolecule, firstly, the benzophenone-3 is chemically modified, and then, the benzophenone-3 and the macromolecule matrix are chemically crosslinked to replace a physical blending method, thereby reducing the problem that the dropping of the benzophenone-3 from the macromolecule matrix causes the reduction of the ultraviolet absorption performance.
2. The invention can be applied to the field of cosmetics or artificial skin, and overcomes the problem of the permeability of benzophenone-3 in human skin.
3. The invention endows the polymer base material with the performance of absorbing ultraviolet rays, thereby leading the polymer base material to have the ultraviolet absorption effect, particularly having good absorption effect on short-wave ultraviolet rays which are greatly harmful to human bodies, and also being applied to the preparation material or the shielding material of the shell of a short-wave ultraviolet ray instrument to prevent the contact personnel of the instrument from being injured by the short-wave ultraviolet rays.
Therefore, the invention carries out chemical modification on the benzophenone-3 and carries out chemical bond crosslinking with a macromolecular matrix to endow the macromolecular matrix with an ultraviolet absorption function. The method has the characteristics of simple process, human body friendliness, high conversion rate, good ultraviolet absorption capacity and the like.
The technical scheme of the invention is as follows:
a preparation and application method of a low-permeability short-wave ultraviolet absorbent comprises the steps that a substrate is a flexible transparent film formed by chemical crosslinking, and modified benzophenone-3 through chemical crosslinking is arranged on the substrate transparent film.
The modified benzophenone-3 is synthesized by benzophenone-3 and chloromethyl styrene through Williamson etherification reaction, the reaction conversion rate is high, no by-product is generated, and the process is simple.
A synthetic method of a low-permeability short-wave ultraviolet absorbent comprises the following steps: dissolving 2-hydroxy-4-methoxybenzophenone (which is subsequently called benzophenone-3) in an organic solvent, putting the mixture into a three-neck flask, adding potassium carbonate as a catalyst under the protection of nitrogen, setting the temperature of an oil bath pot to be 70 ℃, introducing nitrogen when the temperature of the oil bath pot reaches 70 ℃, gradually dropwise adding chloromethyl styrene through a dropping funnel, controlling the dropwise adding rate of the chloromethyl styrene to be completely dropped within three hours at a constant speed, carrying out constant-temperature nitrogen protection on the three-neck flask for 30 minutes after the dropwise adding is completed, then carrying out post-treatment, adding ethanol into reaction liquid to dissolve the residual unreacted benzophenone-3, filtering to obtain a pink brown solid, repeatedly washing the mixture with distilled water and ethanol for three times, and putting the mixture into a vacuum oven for drying to obtain the low-permeability short-wave ultraviolet absorbent.
The chemical reaction formula for generating the modified product is shown as (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 potassium carbonate serving as a catalyst is 2: (1-1.5). Preferably, the catalyst is potassium carbonate.
The preparation method of the composition aiming at the short-wave ultraviolet ray comprises the steps of dissolving modified benzophenone-3 and a polymer substrate in an organic solvent, adding an initiator or a photoinitiator, and heating or irradiating to enable the mixture to generate a polymerization reaction, so that the flexible transparent composition with the ultraviolet ray absorption performance is obtained.
The preparation method of the short-wave ultraviolet composition specifically comprises the following steps:
(1) Synthesizing benzophenone-3 and chloromethyl styrene through Williamson etherification to prepare modified benzophenone-3;
(2) Dissolving modified benzophenone-3, an initiator and a polymer matrix in an organic solvent;
(3) And (3) initiating polymerization to form a film by heating or ultraviolet irradiation in the step (2), and drying.
Preferably, the initiator in step (2) is at least one of azobisisobutyronitrile and benzoin dimethyl ether.
Preferably, the organic solvent in step (2) is ethyl acetate.
Preferably, the polymer matrix in step (2) is at least one of a mixture of silicone oil/hydrogen-containing silicone oil and a reactant of polyether polyol with allyl modified end group, wherein the following is a reactant structural formula of polyether polyol with allyl modified end group:
the invention does not limit the use of the polymer matrix, and the two matrixes are selected only to better show the application of the invention.
Wherein, fig. 4 shows the preparation principle of two polymer substrates and ultraviolet absorption films in this patent; fig. 5 is a schematic view of the structure of the ultraviolet absorbing film.
Preferably, if the initiator is azobisisobutyronitrile, the heating temperature in step (3) is 80 ℃ and the heating time is 10min.
Preferably, if the initiator is benzoin dimethyl ether, the ultraviolet illumination time of the step (3) is 2min.
Preferably, if the initiator is a mixture of azobisisobutyronitrile and benzoin dimethyl ether, the heating temperature in step (3) is 80 ℃, the heating time is 10min, and the ultraviolet irradiation time is 2min.
Preferably, the drying in step (3) is infrared lamp illumination, oven drying or natural drying. Nuclear magnetic resonance of the short-wave ultraviolet 1 The HNMR spectra are shown in figure 1.
The ultraviolet absorbing composition is applied to skin substitutes and human body surface sun-screening agents which are artificially developed in vitro and have ultraviolet absorbing performance, and can also be applied to places exposed to ultraviolet rays, particularly places where short-wave ultraviolet rays are concentrated, such as plateau areas, aerial work devices and surface ultraviolet absorbing composite materials of short-wave ultraviolet instruments.
The working principle of the invention is as follows:
the benzophenone-3 ultraviolet absorbent has stronger absorption effect on almost the whole ultraviolet region because intramolecular hydrogen bonds formed between hydroxyl hydrogen on a benzene ring and adjacent carbonyl oxygen form a chelate ring, when ultraviolet light is absorbed, molecules generate thermal vibration, the hydrogen bonds break the chelate ring and are opened to form an ionic compound in an unstable high-energy state, the compound needs to be restored to the original low-energy stable state, redundant energy is released by other energy, and the chelate ring is closed again, so that the ultraviolet light is absorbed continuously and circularly to play a role in protection. Secondly, the carbonyl group is excited, and a part of energy is consumed for the formation of enol structure by tautomerism.
When benzophenone-3 is modified, hydrogen bonds are destroyed, the opening and closing mechanism of chelate rings is weakened, and only carbonyl groups are left to excite the tautomerism phenomenon to absorb ultraviolet energy.
Some groups in the molecule absorb ultraviolet visible radiation and absorb light energy to generate electron energy level migration. Because different substances have different molecular structures and spatial structures, the situation of absorbing light energy is different. The electron energy level migration is accompanied with the migration of the vibrational energy level and the rotational energy level, a wide band is generally seen due to the intermolecular interaction, the electron absorption spectrum in the organic molecule is a wide spectrum, and different migration modes have different influences on the bond strength, so that the absorption band width and the symmetry of the band are also different. Two or more pi bonds are conjugated, pi-pi transition energy of a conjugated pi orbit is reduced, and corresponding absorption wavelength is increased, and red shift is carried out to a near ultraviolet region. One more benzene ring group is introduced, and a conjugated system enables an absorption band to be red-shifted and ultraviolet light absorption capacity to be increased.
Secondly, because the benzene ring and the carbonyl belong to chromophoric groups which generate ultraviolet absorption and visible light absorption, if the chromophoric group containing elements with lone pair electrons such as chloromethyl styrene is introduced, the spectral absorption of the chromophoric group moves towards the long wave direction, and the absorption intensity is increased. Therefore, when the modified benzophenone-3 is modified, the hydrogen bond is broken, the absorption capacity of UVA and UVB is slightly reduced, but the absorption capacity of UVC is increased.
In order that the invention may be readily understood, reference will now be made in detail to the present invention as illustrated in the accompanying examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that, for a person skilled in the art, many variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The modified benzophenone-3 in the patent example is prepared as follows: dissolving 3g of benzophenone-3 in 4.5g of dimethylacetamide, putting the mixture into a three-mouth flask, adding 3.631g of potassium carbonate as a catalyst under the protection of nitrogen, setting the temperature of an oil bath pot to be 70 ℃, introducing nitrogen when the temperature of the oil bath pot reaches 70 ℃, gradually dropwise adding 3g of chloromethyl styrene through a dropping funnel, controlling the dropwise adding rate of the chloromethyl styrene to be uniformly dropped within three hours, carrying out constant-temperature nitrogen protection on the three-mouth flask for 30 minutes after dropping is finished, carrying out post-treatment, dissolving the residual unreacted benzophenone-3 in 20g of ethanol, filtering to obtain a powdery brown solid, repeatedly cleaning the powdery brown solid for three times by using distilled water and ethanol, putting the powdery brown solid into a vacuum oven and drying the powdery brown solid to obtain 2.54g of modified benzophenone-3, wherein the yield is 56.69%.
In the present application, the sample is named as bp-X-A/B, wherein X represents the added mass of modified benzophenone-3 in the polymer matrix, A represents the composition of silicone oil/hydrogen-containing silicone oil in the polymer matrix, B represents the reactant of polyether polyol with allyl modified end group, and the preparation principle of the ultraviolet absorption composition is illustrated in figure 4 in the specification of the present application.
In addition, the polymer matrix adopted by the invention is a reactant of polyether polyol with allyl modified end group and a silicone oil/hydrogen-containing silicone oil composition, and the application of the invention is just better demonstrated, and the use of the polymer matrix is not limited to the two.
Example 1
Preparation of BP-001-A ultraviolet absorption combined film
Taking 0.01g of modified benzophenone-3, 0.1mg of azodiisobutyronitrile and 0.1mg of benzoin dimethyl ether obtained by the preparation method in 1g of ethyl acetate, adding 0.9g of silicone oil and 0.1g of hydrogen-containing silicone oil after the modified benzophenone-3 is completely dissolved in the ethyl acetate, then centrifuging at the rotating speed of 10000rpm for 5min, spreading the mixture in a glass culture dish, putting the glass culture dish into an ultraviolet irradiation box for irradiating for 5min, and taking out the glass culture dish to obtain the transparent ultraviolet absorption composition with certain transmittance.
Example 2
Preparation of BP-002-A ultraviolet absorption combined film
0.02g of modified benzophenone-3 obtained by the above preparation method was taken, and the remaining steps were the same as in example 1.
Example 3
Preparation of BP-001-B ultraviolet absorption combined film
Taking 0.01g of modified benzophenone-3, 0.1mg of azodiisobutyronitrile and 0.1mg of benzoin dimethyl ether obtained by the preparation method in 1g of ethyl acetate, adding 1g of polyether polyol with allyl modified end group after the modified benzophenone-3 is completely dissolved in the ethyl acetate, then centrifuging at the rotating speed of 10000rpm for 5min, spreading the mixture in a glass culture dish, putting the glass culture dish into an ultraviolet irradiation box for irradiating for 5min, and taking out the glass culture dish to obtain the transparent ultraviolet absorption composition with certain transmittance.
Example 4
Preparation of BP-002-B ultraviolet absorption combined film
0.02g of modified benzophenone-3 obtained by the above preparation method was taken, and the remaining steps were 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 modified benzophenone-3 is not added.
Comparative example B
Referring to example 3 and example 4, the difference from example 3 and example 4 is that modified benzophenone-3 is not added.
TABLE 1
Standard test environmental conditions: temperature: (23 ± 2) ° c, relative humidity: (50. + -. 5)%.
1. Appearance: the film is laid on a clean glass plate, and after standing, the color and luster of the film, the existence of mechanical impurities and gel substances are observed visually under natural scattered light or daylight. And recording the detection result.
2. Tensile strength: the method is carried out according to the regulation of GB/T528 vulcanized rubber and thermoplastic rubber tensile property, and the detection data of a tensile machine is taken as the standard;
3. aging test: the film is spread on a clean culture dish without impurities and placed in an ultraviolet curing lamp box, the temperature in the lamp box is raised to (35 +/-2) DEG C, and the culture dish is placed for 24 hours.
4. Human body surface penetration test: the film is flatly pasted and adhered on the surface of the arm of the human body, so that the human body can work normally, but the pasted surface has less sweat and can not touch water. After 8h, the human body application surface is cleaned by methanol, and the methanol cleaning solution is subjected to ultraviolet light splitting test to detect whether an ultraviolet absorbent exists. (control experiment, the transparent film in control example A, B was soaked in 1% benzophenone-3 methanol solution, dried and then applied to the surface of human body for 8h, extracted and then tested.)
As is clear from Table 1, the invention can provide a certain ultraviolet absorption effect when the film is added in an amount of 1% or 2% by mass, and does not affect the color or transparency of the transparent film. In an aging experiment, the color of a transparent film without the ultraviolet absorbent is changed into light yellow after being irradiated by an ultraviolet lamp for 24 hours, the color of the transparent film without the ultraviolet absorbent is not changed, and the mechanical property of the transparent film is not greatly influenced along with the increase of the addition amount of the ultraviolet absorbent; from the tensile strength, the double bond crosslinking can enhance the mechanical property of the transparent film, so that the tensile strength of the transparent film is increased; experiments in human body permeation show that the ultraviolet absorbent crosslinked with the polymer base by double bonds can not fall off and permeate into the skin of the human body, and has good safety performance on the skin of the surface of the human body.
As can be seen from FIG. 2, the ultraviolet absorption peaks of the invention in UVA, UVB and UVC bands are strong, especially the ultraviolet absorption peak of UVC is stronger, which illustrates that the ultraviolet absorption composition prepared by the invention has the practical function of ultraviolet protection for short-wave ultraviolet absorption.
As can be seen from fig. 3, the ultraviolet absorption intensity of the short-wave ultraviolet absorber of the present invention is gradually increased with the increase of the dosage.
As can be seen by comparing the UV absorption curves of example 1 and comparative example 1 in FIG. 6, the absorbance values at 270 to 400nm of comparative example 1 without the addition of the UV absorber of the present invention were significantly lower than those of the composition obtained in example 1 with the addition of the UV absorber of the present invention.
The 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, and the flexible sun-proof film has good ultraviolet absorption capacity and ageing 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.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A modified benzophenone-3 is characterized in that: introducing an active styryl group on the basis of a benzophenone-3 molecular structure; the structure of the modified benzophenone-3 is as follows:
2. the process for preparing modified benzophenone-3 according to claim 1, wherein: benzophenone-3 molecule reacts with p-chlorostyrene through Williams etherification, and the reaction formula is as follows:
3. the method of claim 2, wherein: the method comprises the following steps:
dissolving benzophenone-3 in an organic solvent, adding potassium carbonate as a catalyst under the protection of nitrogen, setting the temperature of an oil bath kettle to be 70 ℃, introducing nitrogen when the temperature of the oil bath kettle reaches 70 ℃, gradually dropwise adding chloromethyl styrene, controlling the dropwise adding rate of the chloromethyl styrene to be dropwise added at a constant speed within three hours, keeping the temperature constant for 30 minutes under the protection of nitrogen after the dropwise adding is finished, then carrying out aftertreatment, adding ethanol into a reaction liquid to dissolve residual unreacted benzophenone-3, filtering to obtain a powdery brown solid, and cleaning and drying a filtered product to obtain the modified benzophenone-3.
4. The production method according to claim 3, characterized in that: the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, dichlorotetrahydrofuran or dichloromethane; the mass ratio of the benzophenone-3 to the organic solvent is 1: (1.5 to 3); the molar ratio of the benzophenone-3 to the catalyst potassium carbonate is 2: (1-1.5).
5. Use of the modified benzophenone-3 of claim 1 as a low permeability short wave uv absorber.
6. A short wave ultraviolet absorbing composition characterized by: comprises modified benzophenone-3 and macromolecule active prepolymer used as macromolecule matrix, which is cross-linked with the macromolecule active prepolymer through the free radical polymerization reaction of the styryl of the modified benzophenone-3, so as to obtain the flexible transparent composition with ultraviolet absorption performance.
7. The method of preparing a short wave ultraviolet absorbing composition of claim 6, wherein: the method comprises the following steps: (1) Synthesizing the benzophenone-3 and chloromethyl styrene through Williamson etherification to prepare modified benzophenone-3;
(2) Dissolving modified benzophenone-3, an initiator and a polymer matrix in an organic solvent;
(3) Polymerizing to form film by heating or ultraviolet irradiation, and drying.
8. The method of claim 7, wherein: in the step (2), the initiator is at least one of azodiisobutyronitrile and benzoin dimethyl ether; if the initiator is azobisisobutyronitrile, the heating temperature in the step (3) is 80 ℃, and the heating time is 10min; if the initiator is benzoin dimethyl ether, the ultraviolet illumination time in the step (3) is 2min; if the initiator is a mixture of azodiisobutyronitrile and benzoin dimethyl ether, at least one of heating temperature of 80 ℃, heating time of 10min and ultraviolet irradiation time of 2min is adopted in the step (3);
the organic solvent is ethyl acetate.
9. The method of claim 7, wherein: the polymer matrix in the step (2) is at least one of a mixture of silicone oil/hydrogen-containing silicone oil and a reactant of polyether polyol with an allyl modified end group, and the reaction formula is shown as formula (1) or/and formula (2):
10. use of the short wave uv absorbing composition of claim 6 or the short wave uv absorbing composition prepared by the preparation process of any one of claims 7 to 9 in any one of the following:
A. preparing a skin substitute and a human body surface sunscreen agent with ultraviolet absorption performance;
B. preparing the surface ultraviolet absorbing material.
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