CN115974671A - A low-permeability short-wave ultraviolet absorber, preparation method and application - Google Patents
A low-permeability short-wave ultraviolet absorber, preparation method and application Download PDFInfo
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Abstract
Description
技术领域technical field
本发明属于高分子材料领域,具体涉及一种二苯甲酮-3紫外线吸收剂的改性方法,及其后续用于与高分子基材进行化学交联,制备出具有紫外线吸收能力尤其对短波紫外线有极强吸收能力的高分子透明薄膜。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.
背景技术Background technique
紫外线是太阳光中的一部分,而紫外线可以分为长波紫外线(UVA,400nm-320nm)、中波紫外线(UVB,320nm-280nm)、短波紫外线(UVC,280nm-190nm)。少量的太阳光照射可以促进人体内维生素D的转化,促进人体的新城代谢及增强人的体质。但是如果皮肤长时间暴露于太阳光的照射下,紫外线会对皮肤造成伤害。比如UVA具有很强的穿透能力,紫外线中大约98%的UVA可以穿透大气层和云层到达地球低海拔地区,并且可以穿透人体表面的真皮组织,破坏其胶原蛋白纤维和弹性纤维,将皮肤晒黑。UVB的穿透能力虽然比UVA差一点,部分UVB会被大气层和云层吸收,但是仍然大约有2%的UVB会到达地球低海拔地区,长时间照射会使皮肤造成红肿脱皮等伤害。UVC的穿透最弱,但是短波紫外线对人体危害很大,短时间照射即可灼伤皮肤,长时间照射会造成皮肤癌。虽然UVC已经被臭氧层所吸收,不可以抵达地球表面,但是短波紫外线对人体会造成巨大影响,对UVC应该引起足够的重视。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.
近些年人们爱美的观念日益增强,俗话说“一美遮百丑”,人们在化妆品中对防晒剂的使用量日益增多,2-羟基-4-甲氧基二苯甲酮(商品名:UV-9、二苯甲酮-3)属于二苯甲酮类紫外线吸收剂,它的化学结构能有效地吸收高能量波长为270~400nm的紫外线光,提供抗紫外线保护,并且毒性低,热稳定性好,可用于少部分化妆品和高分子制品,且特别适用于浅色制品,是理想的紫外线吸收剂。而二苯甲酮-3作为一种安全性高、防晒效果好、价格低廉的紫外线吸收剂,在化妆品和高分子领域中得到了广泛的应用。尽管目前没有发现二苯酮类紫外线吸收剂会对人类皮肤产生过敏、皮炎、致癌等副作用,但有一些国家对其使用量作了明确的限制:欧盟、美国、日本及韩国规定二苯甲酮-3在防晒霜中的最大允许使用量为10%、6%、5%和5%,因此使用量的限制对紫外线吸收效果会造成一定的限制。紫外线吸收剂通常采用共混的方式加入产品当中,因此防晒霜中的二苯甲酮-3将会直接与人体皮肤直接接触,现有研究表明,二苯甲酮-3局部使用后其中1%~2%会在10h内通过皮肤吸收,随后进入体内代谢。同时二苯甲酮-3存在分子量低、不溶于水、与高分子材料相容性差等缺点。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.
上述的缺点限制了二苯甲酮-3的使用,如果二苯甲酮-3是通过化学键而非共混的方式与高分子基材进行交联,那么高分子基材就更好的被赋予紫外线吸收能力,而二苯甲酮-3也不会与人体皮肤进行直接接触,同时对二苯甲酮-3的使用量也没有了限制,因此可以增强二苯甲酮-3应用中的紫外线吸收效果。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.
发明内容Contents of the invention
为了解决现有技术中二苯甲酮-3在防晒化妆品中使用受限的问题,本发明通过对二苯甲酮-3紫外线吸收剂进行改性,然后与高分子基材进行化学交联,制备出具有紫外线吸收能力尤其对短波紫外线有极强吸收能力的高分子透明薄膜。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.
本发明采用的具体方案为:The concrete scheme that the present invention adopts is:
第一方面,本发明提供一种改性二苯甲酮-3,是在二苯甲酮-3分子结构的基础上,引入活性的苯乙烯基基团,活性基团与高分子基材交联,从而降低紫外线吸收剂对皮肤的渗透性,同时具备一定的全波段紫外线的吸收效果,对短波紫外线更甚。所述改性二苯甲酮-3的结构为: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:
第二方面,本发明提供上述改性二苯甲酮-3的制备方法,二苯甲酮-3分子通过Williams醚化反应与对氯苯乙烯反应,其反应式为: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:
进一步地,所述改性二苯甲酮-3的制备方法,包括以下步骤:Further, the preparation method of the modified benzophenone-3 comprises the following steps:
取2-羟基-4-甲氧基二苯甲酮(后续称为二苯甲酮-3)溶于有机溶剂中,在氮气的保护下,加入碳酸钾作为催化剂,设置油浴锅温度为70℃,待油浴锅温度到达70℃后,通入氮气,逐步滴加氯甲基苯乙烯,氯甲基苯乙烯的滴加速率控制在三小时内匀速滴完,滴完后恒温氮气保护30分钟,随后进行后处理,反应液中加入乙醇溶解剩余未反应的二苯甲酮-3,过滤得到粉棕色固体,对过滤产物进行清洗、烘干,即可得到改性二苯甲酮-3。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 .
优选地,有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二氯四氢呋喃或二氯甲烷中的至少一种;所述二苯甲酮-3与有机溶剂的质量比为1:(1.5~3)。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).
优选地,所述二苯甲酮-3与催化剂碳酸钾的摩尔比为2:(1~1.5)。Preferably, the molar ratio of the benzophenone-3 to the catalyst potassium carbonate is 2:(1-1.5).
第三方面,本发明提供上述改性二苯甲酮-3在作为低渗透性短波紫外线吸收剂中的应用。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.
第四方面,本发明提供一种短波紫外线吸收组合物,包括改性二苯甲酮-3和作为高分子基体的大分子活性预聚物,通过改性二苯甲酮-3的苯乙烯基的自由基聚合反应,与大分子活性预聚物进行化学键交联,使其分子量增大,同时紫外线吸收剂与大分子预聚物交联,降低其渗透性能,最终获得具有吸收紫外线性能的柔性透明组合物。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.
第五方面,本发明提供上述短波紫外线吸收组合物的制备方法,包括以下步骤: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)二苯甲酮-3和氯甲基苯乙烯通过Williamson醚化反应合成制备改性二苯甲酮-3;(1) Benzophenone-3 and chloromethyl styrene are synthesized through Williamson etherification to prepare modified benzophenone-3;
(2)将改性二苯甲酮-3、引发剂与高分子基体溶于有机溶剂中;(2) Dissolving the modified benzophenone-3, the initiator and the polymer matrix in the organic solvent;
(3)将步骤(2)中通过加热或者紫外线照射引发聚合成膜,烘干。(3) In the step (2), the polymerization is initiated by heating or ultraviolet irradiation to form a film, and dried.
优选地,步骤(2)中,所述的引发剂为偶氮二异丁腈、安息香二甲醚中的至少一种;所述的有机溶剂为乙酸乙酯。更进一步地,若引发剂为偶氮二异丁腈,则步骤(3)加热温度为80℃,加热时间为10min;若引发剂为安息香二甲醚,则步骤(3)紫外光照时间为2min;若引发剂为偶氮二异丁腈和安息香二甲醚的混合物,则步骤(3)采用加热温度为80℃、加热时间为10min和紫外光照时间为2min中的至少一种。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.
优选地,步骤(2)所述的高分子基体为硅油/含氢硅油的混合物、端基为烯丙基改性的聚醚多元醇的反应物中的至少一种;则反应式为式(1)或/和式(2):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):
所述的紫外线吸收机理其特征在于:苯环、羰基属于本身产生紫外吸收及可见光吸收的发色基团,若引入含有孤对电子的元素的助色基团如氯甲基苯乙烯,会使发色团的光谱吸收向长波方向移动,且吸收强度增大。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.
上述透明膜,仅添加1%紫外线吸收剂用量,紫外线吸收峰从0.1提升到1.7,紫外线吸收性能提升17倍。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.
第六方面,本发明提供上述短波紫外线吸收组合物的用途。In a sixth aspect, the present invention provides the use of the above short-wave ultraviolet absorbing composition.
本发明与现有技术相比具有如下优点和效果:Compared with the prior art, the present invention has the following advantages and effects:
(1)本发明对二苯甲酮-3进行化学改性后,紫外线吸收波长范围没有变化,并能增加了对UVC的吸收效果。(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)本反应转化率高,无副产物、杂质生成,工艺简单。(2) The conversion rate of this reaction is high, no by-products and impurities are generated, and the process is simple.
(3)本发明可以与带双键的高分子基体进行化学交联,其中发明物作为紫外线吸收剂,赋予材料优异的紫外光吸收性能,尤其是针对短波紫外线UVC。(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)本发明与高分子基体的结合原理是通过聚合反应后的化学键结合。(4) The combination principle of the present invention and the polymer matrix is through the chemical bond after the polymerization reaction.
附图说明Description of drawings
图1为一种低渗透性紫外线吸收剂的核磁共振1HNMR图;Fig. 1 is the nuclear magnetic resonance 1 HNMR figure of a kind of low permeability ultraviolet absorber;
图2为一种低渗透性紫外线吸收剂与二苯甲酮-3的紫外线吸收对比图;Fig. 2 is a kind of low-permeability ultraviolet absorber and the ultraviolet absorption contrast figure of benzophenone-3;
图3为一种低渗透性紫外线吸收剂的紫外线吸收定量分析图;Fig. 3 is the ultraviolet absorption quantitative analysis figure of a kind of low-permeability ultraviolet absorber;
图4为紫外线吸收薄膜的制备原理;Fig. 4 is the preparation principle of ultraviolet absorbing film;
图5为紫外线吸收薄膜的结构示意图;Fig. 5 is the structural representation of ultraviolet absorbing film;
图6为薄膜是否加入低渗透性紫外线吸收剂的紫外线吸收对比图。Figure 6 is a comparison chart of ultraviolet absorption whether the film is added with a low-permeability ultraviolet absorber.
具体实施方式Detailed ways
1、本发明解决了二苯甲酮-3与高分子相容性差的缺点,首先将二苯甲酮-3进行化学改性,再通过与高分子基体化学交联以代替物理共混的方法,减少了二苯甲酮-3从高分子基体中的脱落,导致紫外线吸收性能下降的问题。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、本发明可应用于化妆品领域或人工皮肤领域,克服了二苯甲酮-3在人体皮肤的渗透性问题。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、本发明对高分子基材赋予了吸收紫外线的性能,从而使其具备紫外线吸收效果,尤其是对人体产生巨大危害的短波紫外线有很好的吸收效果,也可应用于短波紫外线仪器外壳的制备材料或屏蔽材料,防止仪器接触人员受到短波紫外线的伤害。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.
因此本发明通过对二苯甲酮-3进行化学改性,与高分子基体进行化学键交联,对高分子基体赋予紫外线吸收功能。所述方法具有工艺简单、对人体友好、转化率高,紫外线吸收能力好等特点。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.
本发明的技术方案如下:Technical scheme of the present invention is as follows:
一种低渗透性短波紫外线吸收剂的制备及应用方法,其基底为具有化学交联而成的柔性透明膜,所述基底透明膜上有通过化学交联的改性二苯甲酮-3。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.
所述改性二苯甲酮-3通过二苯甲酮-3与氯甲基苯乙烯通过Williamson醚化反应合成制备,该反应转化率高、无副产物生成,工艺简单。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.
一种低渗透性短波紫外线吸收剂的合成方法:取2-羟基-4-甲氧基二苯甲酮(后续称为二苯甲酮-3)溶于有机溶剂中,放入三口烧瓶中,在氮气的保护下,加入碳酸钾作为催化剂,设置油浴锅温度为70℃,待油浴锅温度到达70℃后,通入氮气,并且通过滴液漏斗,逐步滴加氯甲基苯乙烯,氯甲基苯乙烯的滴加速率控制整体在三小时内匀速滴完,滴完后对三口烧瓶进行恒温氮气保护30分钟,随后进行后处理,反应液中加入乙醇溶解剩余未反应的二苯甲酮-3,过滤得到粉棕色固体,随后用蒸馏水、乙醇反复清洗三次,放入真空烘箱烘干,即可得到低渗透性短波紫外线吸收剂。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.
生成所述的改性产物化学反应式用(1)所示:Generate described modified product chemical reaction formula with shown in (1):
优选地,所述二苯甲酮-3与溶剂N,N'-二甲基甲酰胺或N,N'-二甲基乙酰胺质量比为1:(1.5~3)。Preferably, the mass ratio of the benzophenone-3 to the solvent N,N'-dimethylformamide or N,N'-dimethylacetamide is 1: (1.5-3).
优选地,所述二苯甲酮-3与催化剂碳酸钾的摩尔比为2:(1~1.5)。优选地,所述催化剂为碳酸钾。Preferably, the molar ratio of the benzophenone-3 to the catalyst potassium carbonate is 2:(1-1.5). Preferably, the catalyst is potassium carbonate.
所述针对短波紫外线组合物的制备方法,是将改性二苯甲酮-3与高分子基底溶于有机溶剂中,通过添加引发剂或者光引发剂,通过加热或者光照使其发生聚合反应,获得具有吸收紫外线性能的柔性透明组合物。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.
上述针对短波紫外线组合物的制备方法,具体包括下述步骤:The above-mentioned preparation method for the short-wave ultraviolet ray composition specifically comprises the following steps:
(1)二苯甲酮-3和氯甲基苯乙烯通过Williamson醚化反应合成制备改性二苯甲酮-3;(1) Benzophenone-3 and chloromethyl styrene are synthesized through Williamson etherification to prepare modified benzophenone-3;
(2)将改性二苯甲酮-3、引发剂与高分子基体溶于有机溶剂中;(2) Dissolving the modified benzophenone-3, the initiator and the polymer matrix in the organic solvent;
(3)将步骤(2)中通过加热或者紫外线照射引发聚合成膜,烘干。(3) In the step (2), the polymerization is initiated by heating or ultraviolet irradiation to form a film, and dried.
优选地,步骤(2)所述的引发剂为偶氮二异丁腈、安息香二甲醚中的至少一种。Preferably, the initiator described in step (2) is at least one of azobisisobutyronitrile and benzoin dimethyl ether.
优选地,步骤(2)所述的有机溶剂为乙酸乙酯。Preferably, the organic solvent described in step (2) is ethyl acetate.
优选地,步骤(2)所述的高分子基体为硅油/含氢硅油的混合物、端基为烯丙基改性的聚醚多元醇的反应物中的至少一种,其中以下为端基为烯丙基改性的聚醚多元醇的反应物结构式: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:
本发明并不限制高分子基体的使用,本发明选用以上两种基体只为更好展示其中本发明的应用。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.
其中,图4为本专利的两种高分子基体、紫外线吸收薄膜的制备原理;图5为紫外线吸收薄膜的结构示意图。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.
优选地,若引发剂为偶氮二异丁腈,步骤(3)加热温度为80℃,加热时间为10min。Preferably, if the initiator is azobisisobutyronitrile, the heating temperature in step (3) is 80° C., and the heating time is 10 minutes.
优选地,若引发剂为安息香二甲醚,步骤(3)紫外光照时间为2min。Preferably, if the initiator is benzoin dimethyl ether, the UV irradiation time in step (3) is 2 min.
优选地,若引发剂为偶氮二异丁腈和安息香二甲醚的混合物,步骤(3)加热温度为80℃,加热时间为10min和紫外光照时间为2min中至少一种。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.
优选地,步骤(3)干燥是采用红外灯光照、烘箱干燥或自然干燥。所述的短波紫外线的核磁共振1HNMR谱图在图1展示。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 .
所述紫外线吸收组合物的用途,是应用于具有紫外线吸收性能的体外人工研制的皮肤代用品、人体表面防晒剂,也可以应用于暴露在紫外线尤其是短波紫外线集中的地方,例如高原地区、高空作业装置、短波紫外线仪器的表面紫外线吸收复合材料。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.
本发明的工作原理是:The working principle of the present invention is:
二苯甲酮-3紫外线吸收剂几乎对整个紫外光区域都有较强的吸收作用,是因为其苯环上羟基氢和相邻的羰基氧之间形成的分子内氢键构成了一个螯合环,当吸收紫外光后,分子发生热振动,氢键破裂螯合环打开,形成不稳定的高能状态下的离子型化合物,这个化合物要恢复到原来的低能稳定状态,把多余的能量以其他能量释放出来,螯合环又闭环,这样不断循环地吸收紫外线起保护作用。其次,羰基会被激发,发生互变异构现象生成烯醇式结构也会消耗一部分能量。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.
当二苯甲酮-3进行改性后,氢键被破坏,其螯合环打开关闭机理减弱,仅剩下羰基激发发生互变异构现象吸收紫外线能量。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.
分子中某些基团在吸收紫外可见辐射时,会通过吸收光能量,产生电子能级迁越。由于不同物质具备不同的分子结构、空间结构,吸收光能量的情况就会不同。电子能级迁越的同时伴有振动能级和转动能级的迁越,由于分子间相互作用,通常会看到宽带,有机分子中的电子吸收光谱为宽谱,不同的迁越方式,对键强度的影响不同,因而吸收带宽度及谱带的对称性也有不同。两个或两个以上Π键共轭,共轭Π轨道的Π-Π*迁越能量降低,对应吸收波长增加红移至近紫外区。引入多一个苯环基团,共轭体系使吸收带红移,紫外光吸收能力增大。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.
其次由于苯环、羰基属于本身产生紫外吸收及可见光吸收的发色基团,若引入含有孤对电子的元素的助色基团如氯甲基苯乙烯,会使发色团的光谱吸收向长波方向移动,且吸收强度增大。因此改性二苯甲酮-3经过改性后,虽然氢键被破坏,UVA、UVB的吸收能力略微下降,但是UVC的吸收能力上升。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.
为了便于理解本发明,下面将结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但是,不以任何形式限制本发明。应该指出的是,对本领域的技术人员来说,在不脱离本发明构思的前提下,本发明还可以做出若干变形和改进,这些都属于本发明的保护范围。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.
除非另有定义,本文中使用的所有技术和科学术语属于本发明的技术领域常用的专业术语,与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在说明书中所使用的术语只是为了描述具体的实施例,不是旨在限制本发明。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.
本专利实施例改性二苯甲酮-3制备如下:取3g二苯甲酮-3溶于4.5g二甲基乙酰胺,放入三口烧瓶中,在氮气的保护下,加入3.631g碳酸钾作为催化剂,设置油浴锅温度为70℃,待油浴锅温度到达70℃后,通入氮气,并且通过滴液漏斗,逐步滴加3g氯甲基苯乙烯,氯甲基苯乙烯的滴加速率控制整体在三小时内匀速滴完,滴完后对三口烧瓶进行恒温氮气保护30分钟,随后进行后处理,反应液中加入20g乙醇醇溶解剩余未反应的二苯甲酮-3,过滤得到粉棕色固体,随后用蒸馏水、乙醇反复清洗三次,放入真空烘箱烘干,即可得到2.54g改性二苯甲酮-3,产率为56.69%。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%.
在本申请中,样品命名为bp-X-A/B,其中X表示高分子基体中与改性二苯甲酮-3的加入质量,其中A代表高分子基体采用硅油/含氢硅油的组合物,B代表端基为烯丙基改性的聚醚多元醇的反应物,在本申请说明书附图图4说明了该紫外线吸收组合物的制备原理。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.
另外,本发明采用的高分子基体为端基为烯丙基改性的聚醚多元醇的反应物和硅油/含氢硅油组合物,只是为了更好的演示本发明的应用,高分子基体的使用并不局限于这两种。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.
实施例1Example 1
BP-001-A紫外线吸收组合膜的制备Preparation of BP-001-A Ultraviolet Absorbing Composite Film
取上述制备方法所得的0.01g改性二苯甲酮-3、0.1mg偶氮二异丁腈、0.1mg安息香二甲醚于1g乙酸乙酯中,待改性二苯甲酮-3完全溶解于乙酸乙酯后,再加入0.9g硅油与0.1g含氢硅油,随后进行离心,离心转速为10000rpm,离心时间为5min,铺到玻璃培养皿中,放入紫外光照射箱中照射5min,取出后可得一定透光度的透明紫外线吸收组合物。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.
实施例2Example 2
BP-002-A紫外线吸收组合膜的制备Preparation of BP-002-A Ultraviolet Absorbing Composite Film
取上述制备方法所得0.02g改性二苯甲酮-3,其余步骤与实施例1相同。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.
实施例3Example 3
BP-001-B紫外线吸收组合膜的制备Preparation of BP-001-B ultraviolet absorbing composite film
取上述制备方法所得的0.01g改性二苯甲酮-3、0.1mg偶氮二异丁腈、0.1mg安息香二甲醚于1g乙酸乙酯中,待改性二苯甲酮-3完全溶解于乙酸乙酯后,再加入1g端基为烯丙基改性的聚醚多元醇,随后进行离心,离心转速为10000rpm,离心时间为5min,铺到玻璃培养皿中,放入紫外光照射箱中照射5min,取出后可得一定透光度的透明紫外线吸收组合物。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.
实施例4Example 4
BP-002-B紫外线吸收组合膜的制备Preparation of BP-002-B ultraviolet absorbing composite film
取上述制备方法所得0.02g改性二苯甲酮-3,其余步骤与实施例3相同。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.
对比例AComparative example A
参照实施例1与实施例2,与实施例1、实施例2区别在于,没有加入改性二苯甲酮-3。Referring to Example 1 and Example 2, the difference from Example 1 and Example 2 is that no modified benzophenone-3 is added.
对比例BComparative Example B
参照实施例3与实施例4,与实施例3、实施例4区别在于,没有加入改性二苯甲酮-3。Referring to Example 3 and Example 4, the difference from Example 3 and Example 4 is that no modified benzophenone-3 is added.
表1Table 1
标准检测环境条件:温度:(23±2)℃,相对湿度:(50±5)%。Standard detection environment conditions: temperature: (23±2)℃, relative humidity: (50±5)%.
1、外观:将薄膜平铺在清洁的玻璃板上,静置后,在自然散射光或日灯光下目视观察薄膜色泽、有无机械杂质、凝胶物。记录检测结果。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、拉伸强度:参照《GB/T528硫化橡胶和热塑性橡胶拉伸性能的测定》的规定进行,以拉力机的检测数据为准;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、老化实验:将薄膜平铺到干净无杂质的培养皿上,放置进紫外线固化灯盒内,灯盒内温度升至(35±2)℃,放置24h。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、人体表面渗透实验:将薄膜平整地贴敷粘在人体手臂表面,人可进行正常的工作,但贴敷表面尽量少出汗、不可碰水。8h后采用甲醇清洗人体贴敷面,对甲醇清洗液进行紫外分光测试,检测是否有紫外线吸收剂。(对照实验,将对照例A、B中的透明薄膜浸泡在1%二苯甲酮-3甲醇溶液中,烘干后贴敷在人体表面8h,提取后进行检测。)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.)
从表1可知,发明物在薄膜质量添加量1%与2%时可以赋予一定的紫外线吸收效果,并且不影响透明薄膜的颜色与透明度。老化实验中我们可以发现,经过紫外灯照射24h后,没有添加本发明紫外线吸收剂的透明薄膜颜色变成浅黄色,而添加了本发明紫外线吸收剂的透明薄膜颜色没有发生变化,并且随着紫外线吸收剂添加量的增加,其力学性能没有受到太大的影响;从拉伸强度我们可以发现,发明的双键交联可以增强透明薄膜的力学性能,使其拉伸强度增加;从人体渗透中实验我们可以发现,通过与高分子基地进行双键交联的紫外线吸收剂不会脱落渗透进人体皮肤,对人体表面皮肤具有很好的安全性能。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.
由图2可知,本发明在在UVA、UVB、UVC波段有强烈的紫外线吸收峰,尤其UVC的紫外线吸收峰更强烈,说明本发明制备的一种针对短波紫外线吸收组合物具有防紫外线的实际功能。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 .
由图3可知,本发明的一种针对短波紫外线吸收剂,随着用量的提升,紫外线吸收强度也逐渐增强。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.
通过对比图6中实施例1与对比例1的紫外吸收曲线可以看出,未加入本发明紫外线吸收剂的对比例1在270-400nm处的吸光度值明显低于加入了本发明紫外线吸收剂的实例1获得的组合物。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.
本发明所述低渗透性短波紫外线吸收剂的制备及应用方法,其基底为具有活性炭碳双键的透明柔性薄膜,所述柔性薄膜上带有通过化学交联的改性二苯甲酮-3分子,其柔性防晒薄膜紫外线吸收能力好、抗老化性能好。并且本发明的紫外线吸收剂均能吸收在270~350nm的紫外线,有很好的紫外线吸收效果,尤其是在270-290nm波长的短波紫外线下的吸收效果最佳。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.
以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。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.
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。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.
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