CN110981752B - Preparation method of cyanoacrylate ultraviolet light absorber - Google Patents
Preparation method of cyanoacrylate ultraviolet light absorber Download PDFInfo
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- CN110981752B CN110981752B CN201911310798.9A CN201911310798A CN110981752B CN 110981752 B CN110981752 B CN 110981752B CN 201911310798 A CN201911310798 A CN 201911310798A CN 110981752 B CN110981752 B CN 110981752B
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- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
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- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
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Abstract
The invention provides a preparation method of cyanoacrylate ultraviolet absorbent, wherein benzophenone compounds shown in a general formula I and cyanoacetate react with acidic ionic liquid grafted by activated carbon as a catalyst under a weak alkaline condition to generate compounds shown in a general formula II. According to the preparation method of the cyanoacrylate ultraviolet absorbent, acetic acid is replaced by the acidic ionic liquid catalyst grafted by the activated carbon, so that the preparation method is easy to recycle, high in product yield, less in three wastes and convenient in post-treatment, and is an economical and practical green and environment-friendly technology.
Description
Technical Field
The invention belongs to the field of high polymer material functional additives, and particularly relates to a preparation method of a cyanoacrylate ultraviolet absorbent.
Background
We refer to invisible light with a wavelength in the range of 400-100 nm, called ultraviolet light, which reaches the ground mainly by solar irradiation. The wavelength range of the light can be divided into three bands, namely UVA (400-320 nm), UVB (320-290 nm) and UVC (290-100 nm). UVC can be completely absorbed by the atmosphere; UVA can react with melanin in human body, and long-time irradiation causes skin aging; UVB is substantially absorbed by the skin, and due to its high energy level, it can burn the skin, produce dark spots, even cause skin cancer, damage the immune system, and is an ultraviolet band of great importance to prevent. In order to eliminate the harm of excessive ultraviolet irradiation to people in production and life, the ultraviolet absorbent is widely applied to various sun-screening products. In recent years, research on ultraviolet absorbers has been under way, especially for ultraviolet absorber products that prevent mid-band ultraviolet radiation. Along with the aggravation of natural environmental pollution and the improvement of living standard, people pay attention to their health, and people are urgently required to find an ultraviolet absorbent with good safety and excellent absorption performance to prevent the adverse effect caused by ultraviolet.
Cyanoacrylate-based UV absorbers are an important class of UV absorbers, which are widely used in a variety of sunscreens, especially high-end sunscreens, and there are a number of commercially available products such as isooctyl 2-cyano-3, 3-diphenylacrylate (UV-3039, trade name: octocrylene, US FDA approved class I sunscreens), pentaerythritol 2-cyano-3, 3-diphenylacrylate (UV-3030), and ethyl 2-cyano-3, 3-diphenylacrylate (UV-3035, trade name: etoricine). Such UV absorbers are shown in formula III:
in formula III: r is 1 ，R 2 Is one of H or halogen; r is 4 Is C 1-20 Alkyl of (2)And (4) a base.
The current synthetic methods for cyanoacrylate ultraviolet-grade absorbents at home and abroad can be mainly summarized as the following three methods:
1. in the presence of a weak base catalyst, benzophenone and cyanoacetate are condensed by Knoevengal, and moisture generated by condensation needs to be timely separated out in the reaction process, so that the yield of the product is improved.
2. 2-cyano-3, 3-diphenylacrylate and another alcohol are obtained by transesterification. The synthesis method has the advantages of easy reaction, simple operation steps and short reaction time, and the finally generated by-product alcohol can be distilled out in time, so that the yield of the compound is high. And the post-treatment method is simple and easy to implement, and the purity and the crystal form of the obtained compound are also very good.
3. Benzophenone imine and isooctyl cyanoacetate are subjected to condensation reaction. Although the synthesis method of the compound is relatively easy to carry out the reaction, more industrial three wastes are generated in the reaction process.
The synthesis of the products is researched and reported by DE 4440055, WO 9615102 A2, CN1162955 and the like, but the documents adopt the third route for synthesis, the synthesis route is long, the operation requirement is high, the yield is low, and the amount of three wastes is large; the synthesis of octocrilin and derivatives thereof is systematically studied by cinnarizine et al (university of Tianjin science 2015, 3), which synthesizes intermediate cyanoacetate, reacts with benzophenone and derivatives thereof to generate corresponding substituted benzophenone cyanoacetate, and then performs ester exchange reaction with alcohol to obtain the final product.
The currently considered preferable process synthetic route in production is as follows: methyl cyanoacetate or ethyl cyanoacetate reacts with benzophenone and derivatives thereof to generate benzophenone cyanoacetate intermediates, and then the benzophenone cyanoacetate intermediates and target alcohol perform ester exchange reaction to generate target products, wherein the reaction mechanism is as follows:
a compound in a general formula II is generated from a general formula I through Knoevenagel condensation reaction, a large amount of acetic acid and ammonium acetate are used as catalysts in the reaction, and water needs to be continuously separated in the reaction process to facilitate the reaction to move towards the positive direction, so that a large amount of acetic acid and ammonium acetate are evaporated in the reaction process, side reaction occurs in a high-temperature process, a large amount of catalyst is wasted, a large amount of waste water containing acetic acid, ammonium acetate and byproducts is generated, the waste water is difficult to recycle, the environmental pollution is large, the reaction process of the reaction is complex, a large amount of side reactions are generated, a large amount of water is needed for removing the catalysts and the byproducts after the reaction is finished, the post-treatment process is complex, the waste water amount is large, and the yield is low.
The ionic liquid is an ionic system which is composed of organic cations and inorganic or organic anions and is in a liquid state at room temperature and adjacent temperature. Ionic liquids have many incomparable advantages with other substances, such as wide liquid temperature range, no significant vapor pressure, good thermal stability, good solubility for many inorganic compounds and organic compounds, etc., and based on these characteristics, ionic liquids are expected to become one of the most promising green solvents and catalysts.
The supported catalyst is easy to separate, has less active component consumption and is easy to control the catalyst cost, so that the supported catalyst is widely used in various chemical reactions, such as catalytic hydrogenation, petroleum cracking and the like, and the adopted carriers are porous materials, such as activated carbon, diatomite, molecular sieves and the like.
The ionic liquid loaded or modified loaded catalyst becomes a research hotspot, is widely researched and applied, and has a wide application prospect in industrial production as a novel environment-friendly catalyst technology, however, the application of the ionic liquid directly loaded catalyst is limited because the active components of the ionic liquid directly loaded catalyst are easy to lose.
As a novel environment-friendly catalyst and a solvent, the ionic liquid can overcome the defects of difficult separation and recovery of a homogeneous catalyst, great environmental pollution and the like, has the advantages of high reaction activity and easy separation and recovery, and has wide application prospect in industrial production.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method of cyanoacrylate ultraviolet light absorbers, which overcomes the defects of the prior art, and is characterized in that activated carbon is used for grafting acidic ionic liquid as an acidic catalyst to replace acetic acid which is commonly used in the original reaction, then organic ammonium salt solutions such as ammonium acetate and the like are added dropwise, reaction conditions are controlled, a compound of a general formula I reacts with cyanoacetic ester to generate a compound of a general formula II, and finally a target product of a general formula III is generated through a classical ester exchange reaction, so that the problems that a large amount of acetic acid is used as a catalyst in the original process route, the catalyst is difficult to recover, the environmental pollution is large, and the product yield is low are solved.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for preparing cyanoacrylate ultraviolet absorbent, benzophenone compound shown in general formula I and cyanoacetate react under alkalescent condition with acidic ionic liquid grafted by activated carbon as catalyst to generate compound shown in general formula II;
wherein R is 1 ，R 2 Each independently selected from H or halogen, R 3 Is methyl or ethyl.
The cyanoacetate is methyl cyanoacetate or ethyl cyanoacetate;
the weakly alkaline conditions are achieved by adding ammonium acetate.
The activated carbon grafted acidic ionic liquid is a compound D, and the structural formula of the compound D is as follows:
wherein n is an arbitrary integer of 2 to 6, X - Is HSO 4 - Or CH 3 COO - (ii) a R is C 1-20 Alkyl or haloalkyl of (a);
represents activated carbon.
The activated carbon grafted acidic ionic liquid compound D is prepared by the following method:
(1) Reacting the active carbon rich in hydroxyl, alkali and the compound A to obtain a compound B;
(2) Reacting the compound B with N-alkyl imidazole to obtain a compound C;
(3) Reacting the compound C with acid salt NaX, filtering and drying to obtain a compound D;
wherein n is any integer from 2 to 6; x - Is HSO 4 - Or CH 3 COO - (ii) a R is C 1-20 Alkyl or haloalkyl of (a);
represents activated carbon.
The preparation method also comprises the step of carrying out ester exchange reaction on the compound of the general formula II and target alcohol to generate a target product of a general formula III;
wherein R is 1 ，R 2 Each independently selected from H or halogen, R 3 Is methyl or ethyl, R 4 Is C 1-20 An alkyl group.
On the basis of the common knowledge in the field, the above preferred conditions can be combined with each other to obtain the preferred embodiments of the invention.
Compared with the prior art, the preparation method of the cyanoacrylate ultraviolet absorbent has the following advantages:
according to the preparation method of the cyanoacrylate ultraviolet absorbent, the acidic ionic liquid catalyst grafted by the activated carbon is adopted to replace the traditional acetic acid as the catalyst, the solid catalyst is easy to separate, can be recycled and reused, is convenient to post-treat, greatly reduces the generation amount of three wastes, is environment-friendly, has high product yield, reduces the production cost and reduces the environmental pollution.
Drawings
FIG. 1 is an infrared spectrum of the structure detection of ethyl 2-cyano-3, 3-diphenylacrylate of example 4.
FIG. 2 is an infrared spectrum of pentaerythritol tetrakis (2-cyano-3, 3-diphenylacrylate) of example 8.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
A preparation method of cyanoacrylate ultraviolet absorbent comprises reacting benzophenone compound shown in general formula I with cyanoacetate under alkalescent condition with acidic ionic liquid grafted by activated carbon as catalyst to generate compound shown in general formula II;
wherein R is 1 ，R 2 Each independently selected from H or halogen, R 3 Is methyl or ethyl.
The reaction belongs to Knoevenagel condensation reaction, namely the condensation reaction of benzophenone and cyanoacetate with active alpha-hydrogen atoms under the catalysis of weak base (amine, pyridine and the like).
In the invention, the activated carbon grafted acidic ionic liquid is a compound D, and the structural formula of the compound D is as follows:
wherein n is an arbitrary integer of 2 to 6, X - Is HSO 4 - Or CH 3 COO - ；
Is active carbon;
r is C 1-20 Or a halogenated alkyl group corresponding thereto, preferably C 1-4 And their corresponding halogen-substituted alkyl groups.
For example, there may be mentioned alkyl groups: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, undecyl, dodecyl.
The preparation method of the activated carbon grafted acidic ionic liquid compound D comprises the following steps:
(1) Reacting the active carbon rich in hydroxyl, alkali and the compound A to obtain a compound B;
(2) Reacting the compound B with N-alkyl imidazole to obtain a compound C;
(3) Reacting the compound C with acid salt NaX, filtering and drying to obtain a final catalyst D;
wherein n is any integer from 2 to 6; x - Is HSO 4 - Or CH 3 COO - (ii) a R is C 1-20 Alkyl or halogen-substituted alkyl of (a);
is active carbon.
In the step (1), active carbon rich in hydroxyl dissolved in an organic solvent, alkali and a compound A react to obtain a compound B; preferably at room temperature.
Preferably, the organic solvent is tetrahydrofuran, and the base is sodium hydroxide, potassium hydroxide, or the like.
Preferably, the mass ratio of the active carbon rich in hydroxyl, alkali and the compound A is 1.
More preferably, the weight ratio of the active carbon rich in hydroxyl groups, the alkali and the compound A is 1.
In the step (2), the compound B reacts with N-alkyl imidazole, and is heated for reflux reaction, and then is cooled and filtered to obtain a compound C.
Preferably, the molar ratio of compound B to N-alkyl imidazole is 1:1.1-2, more preferably, the molar ratio of compound B, N-alkyl imidazole is 1:1.5,
in the step (3), heating, refluxing and reacting the compound C dissolved in acetone and NaX acid salt, filtering and drying to obtain a final catalyst D;
preferably, the molar ratio of compound C to acid salt NaX is 1:1.1-2.
Further preferably, the molar ratio of compound C to acid salt NaX is 1:1.5.
preferably, the dosage of the acidic ionic liquid catalyst grafted by the active carbon is 5-10% (dry weight) of the mass of the benzophenone compound shown in the general formula I.
The preparation method of the cyano propionate ultraviolet absorbent comprises the following steps:
preferably, the cyanoacetate is methyl cyanoacetate or ethyl cyanoacetate.
In the preparation method of the general formula II, the weak alkaline condition is realized by adding ammonium acetate into the reaction solution. Meanwhile, in order to avoid the decomposition of ammonium acetate, ammonium acetate is continuously added or dripped at intervals. Preferably, the molar ratio of the benzophenone compound shown in the general formula I to the ammonium acetate is 1:0.5 to 2.0; more preferably, the molar ratio of the benzophenone compound shown in the general formula I to the ammonium acetate is 1:0.8 to 1.5.
In the preparation method of the general formula II, the molar ratio of the benzophenone compound shown in the general formula I to the cyanoacetate is 1.05-2.0. More preferably, the molar ratio of the benzophenone compound shown in the general formula I to the cyanoacetate is 1.2-1.6.
In the invention, the preparation of the general formula II is carried out in a solvent, wherein the solvent is one or more selected from toluene, xylene, cyclohexane or n-heptane; preferably, the mass volume ratio of the compound of the general formula I to the solvent is 1.5-3.0. More preferably, the mass-to-volume ratio of the compound of the general formula I to the solvent is 1. The reaction temperature for the preparation of the compound of formula II is the reflux temperature.
The preparation method of the cyanoacrylate ultraviolet absorbent further comprises the following post-treatment steps: filtering and recovering the catalyst of the acidic ionic liquid grafted by the activated carbon, standing and layering reaction liquid, washing an upper organic phase by using distilled water, drying a drying agent, then evaporating the solvent by reduced pressure, and evaporating unreacted cyanoacetate to obtain the compound of the general formula II.
Preferably, the drying agent is anhydrous sodium sulfate.
The preparation method of the cyanoacrylate ultraviolet absorbent further comprises the step of carrying out ester exchange reaction on the compound in the general formula II and target alcohol to generate a target product in the general formula III;
wherein R is 1 ，R 2 Each independently selected from H or halogen, R 3 Is methyl or ethyl. R 4 Is C 1-20 An alkyl group; examples thereof include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl.
Preferably, the molar ratio of the compound of the general formula II to the target alcohol is 1.5 to 5.0;
further preferably, the catalyst for the transesterification reaction is a solid base catalyst, and the molar ratio of the compound of formula II to the catalyst in the transesterification reaction is 1:0.05-0.2.
The solid base catalyst can be selected according to requirements, such as sodium methoxide and sodium ethoxide.
The target alcohol is selected according to the target product, such as pentaerythritol when pentaerythritol tetrakis (2-cyano-3, 3-diphenylacrylate) is prepared and isooctyl alcohol when isooctyl 2-cyano-3, 3-diphenylacrylate is prepared.
In the invention, the preparation of the general formula III is carried out in a solvent, wherein the solvent is one or more selected from toluene, xylene, cyclohexane or n-heptane; preferably, the mass volume ratio of the compound of formula II to the solvent is 1.5 to 3.0. More preferably, the mass volume ratio of the compound of the general formula II to the solvent is 1. The reaction temperature for the preparation of formula III is the reflux temperature.
The compounds prepared by the process of the present invention include compounds of formula II, such as UV3035; compounds of formula III, such as UV3039 and UV3030, have the following structural formulae:
the present invention will be described in detail with reference to the following examples and accompanying drawings.
THF: tetrahydrofuran.
Example 1 preparation of catalyst 1 having acidic ionic liquid grafted by activated carbon
Adding 10g of commercially available powdered coconut shell activated carbon (the specific surface area is 1200, the ash content is 1%) into a 250mL four-neck flask, then adding 50mL of THF, stirring while placing magnetic stirring, then adding 2g of caustic soda flakes, then adding 10g of dichloroethane, soaking for 5h, filtering, drying at 105 ℃ for 4h, then adding the mixture into a 250mL four-neck flask, adding 100mL of acetonitrile, stirring while magnetic stirring, dropwise adding 8g of butylimidazole at room temperature, heating to reflux for 10h, cooling to 30 ℃, filtering, drying, then adding the dried mixture into a 250mL four-neck flask, adding 100mL of acetone, stirring while magnetic stirring, then adding 5g of sodium bisulfate, stirring at room temperature for 4h, filtering, and drying a filter cake to obtain the catalyst 1 of the activated carbon grafted acidic ionic liquid.
Example 2 preparation of catalyst 2 having acidic ionic liquid grafted on activated carbon
The procedure of example 2 was followed to change dichloroethane to dichloropropane and carry out the same preparation as in example 1 to obtain catalyst 2 in which the acidic ionic liquid was grafted with activated carbon.
Example 3 preparation of catalyst 3 having acidic ionic liquid grafted on activated carbon
The procedure of example 2 was followed, wherein sodium bisulfate was replaced by sodium acetate, and the remaining preparation method was the same as example 1, to obtain catalyst 3 in which activated carbon was grafted with acidic ionic liquid.
EXAMPLE 4 preparation of ethyl 2-cyano-3, 3-diphenylacrylate and Recycling of the catalyst
82g of benzophenone (0.45 mol), 150mL of n-heptane, 102g of ethyl cyanoacetate (0.72 mol) and 5g of the catalyst 1 prepared by grafting the activated carbon with the acidic ionic liquid and 20g of ammonium acetate (0.26 mol) are sequentially added into a three-neck flask provided with a thermometer, a stirrer and a reflux pipe, the temperature is raised under stirring until the reflux starts to react, the refluxed solvent returns to a reactor, water is continuously separated from the bottom of a water separator, 5g of ammonium acetate is supplemented every 1h, the reaction is carried out for 2h after the last addition is finished, sampling analysis is carried out every 30min until the conversion rate of the benzophenone is more than 99%, the reaction is finished, the catalyst is filtered and separated when the reaction is finished, the catalyst is used for applying or recycling, standing and layering, the lower-layer aqueous phase is treated, the upper-layer organic phase is washed twice with 50mL of distilled water, then 3g of anhydrous sodium sulfate is used for drying, a drying agent is removed by filtering, then n-heptane is evaporated under reduced pressure, the unreacted ethyl cyanoacetate is evaporated, and the product is evaporated under reduced pressure to obtain 2-cyano-3, ethyl 3, 3-diphenylacrylic acid ethyl acrylate with the yield of 99.8.92%, the purity of HPLC (HPLC) is 0.8%.
The above catalyst was used mechanically, and the results are shown in table 1:
TABLE 1 results of applying the activated carbon-grafted acidic ionic liquid catalyst described in example 4
As can be seen from table 1, the activity of the activated carbon-grafted acidic ion liquid catalyst described in this example is not significantly reduced after 10 times of continuous application.
EXAMPLE 5 preparation of ethyl 2-cyano-3, 3-diphenylacrylate
The procedure is as in example 4, except that 8g of the catalyst 2 prepared in example 2 and prepared by grafting the acidic ionic liquid onto activated carbon is used, and 113.3g of ethyl 2-cyano-3, 3-diphenylacrylate is obtained in 90.8% yield and 99.4% HPLC purity.
Example 6 preparation of ethyl 2-cyano-3, 3-diphenylacrylate
The procedure is as in example 4, wherein the ammonium acetate is charged in a first 10g, after 1h of reaction, 1.5g is added every half an hour for a total reaction time of about 15h, and the remainder is unchanged, to obtain 117.1g of ethyl 2-cyano-3, 3-diphenylacrylate with a yield of 94.1% and an HPLC purity of 99.3%.
EXAMPLE 7 preparation of ethyl 2-cyano-3, 3-diphenylacrylate
The procedure of example 4 was followed, except for changing the catalyst to catalyst 3 prepared in example 3 and having acidic ionic liquid grafted on activated carbon and changing the amount of ethyl cyanoacetate to 81.5g and changing the remaining amount to 113.5g of ethyl 2-cyano-3, 3-diphenylacrylate with a yield of 91.5% and a HPLC purity of 99.0%.
Example 8 preparation of pentaerythritol tetrakis (2-cyano-3, 3-diphenylacrylate)
The materials are fed for reaction according to the embodiment 4, after the reaction is finished, the post-treatment is carried out according to the embodiment 4, finally, after unreacted ethyl cyanoacetate is removed by distillation, 300ml of dimethylbenzene is added, then the dimethylbenzene is added into a three-neck flask provided with a thermometer, a stirring pipe and a return pipe, 12g of pentaerythritol and 2.5g of sodium methoxide are added, the temperature is raised to reflux under stirring to start the reaction, the reflux reaction lasts for about 12 hours, after the reaction is finished, the temperature is reduced to 95-100 ℃, then water is added to wash the sodium methoxide and remove impurities, a water phase is separated, a powdered activated carbon color is added to an organic phase, the organic phase is washed by distilled water, after drying by anhydrous sodium sulfate, the temperature is reduced and crystallization is carried out, the filtration is carried out at 10 ℃, and the drying is carried out to obtain 385.6g of pentaerythritol tetra (2-cyano-3, 3-diphenylacrylate), the yield is 80.6%, and after detection, the solvent contains 31.5g of products, the total yield can reach 87.2%, and the HPLC purity is 98.7%.
Example 9 preparation of pentaerythritol tetrakis (2-cyano-3, 3-diphenylacrylate)
Feeding and reacting according to example 4, wherein ethyl cyanoacetate is changed into 89.1g of methyl cyanoacetate, the rest is not changed, after the reaction post-treatment, adding 300ml of dimethylbenzene, directly adding the dimethylbenzene into a three-neck flask provided with a thermometer, a stirring pipe and a return pipe, then adding 12g of pentaerythritol and 2.5g of sodium ethoxide, heating to reflux under stirring to start the reaction, carrying out reflux reaction for about 12 hours, cooling to 95-100 ℃ after the reaction is finished, then adding water to wash and remove the sodium ethoxide and impurities, separating out a water phase, adding an organic phase into powdered activated carbon to decolor, washing with distilled water, drying with anhydrous sodium sulfate, cooling and crystallizing, filtering at 10 ℃, and drying to obtain 376.4g of pentaerythritol tetra (2-cyano-3, 3-diphenylacrylate) and yield of 78.8%, wherein the solvent contains 30.3g of a product through detection, so the total yield can reach 85.2% and the purity of HPLC 98.9%.
Example 10 preparation of isooctyl 2-cyano-3, 3-diphenylacrylate
The materials are charged according to the embodiment 4 for reaction, after the reaction is finished, the post-treatment is carried out according to the embodiment 4, finally, after unreacted ethyl cyanoacetate is removed by distillation, the solvent 300ml toluene is added, then the mixture is added into a three-neck flask provided with a thermometer, a stirring and a reflux pipe, 54g isooctanol and 2g sodium methoxide are added, the mixture is heated to reflux under stirring to start the reaction, the reflux reaction lasts for about 8 hours, after the reaction is finished, the water is added to wash the sodium methoxide and impurities are removed, the water phase is separated, the organic phase is added with powdered activated carbon to decolor, the mixture is washed by distilled water, after anhydrous sodium sulfate is dried, the solvent is removed by reduced pressure distillation, and then the product isooctyl 2-cyano-3, 3-diphenylacrylate is obtained by high vacuum distillation, the total yield is 88.6 percent, and the HPLC purity is 99.0 percent.
In conclusion, the preparation method of the cyanoacrylate ultraviolet absorbent has the advantages that the used acidic ionic liquid grafted by the activated carbon has convenient recovery and can be reused, the defect that a large amount of acetic acid is used in the reaction is overcome, and the defect that the immobilized acidic ionic liquid is easy to lose in the conventional method is also overcome.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of cyanoacrylate ultraviolet light absorbers is characterized by comprising the following steps: benzophenone compounds shown in the general formula I and cyanoacetic ester react under the alkalescent condition by taking acidic ionic liquid grafted by activated carbon as a catalyst to generate compounds shown in the general formula II, wherein the compounds shown in the general formula II are the cyanopropionic acid ester ultraviolet absorbers;
wherein R is 1 ，R 2 Each independently selected from H or halogen, R 3 Is methyl or ethyl;
the activated carbon grafted acidic ionic liquid is a compound D, and the structural formula of the compound D is as follows:
wherein n is an arbitrary integer of 2 to 6, X - Is HSO 4 - Or CH 3 COO - (ii) a R is C 1-20 Alkyl or halogen-substituted alkyl of (a);
represents activated carbon.
2. The method of claim 1, wherein: the activated carbon grafted acidic ionic liquid compound D is prepared by the following method:
(1) Reacting the active carbon rich in hydroxyl, alkali and the compound A to obtain a compound B;
(2) Reacting the compound B with N-alkyl imidazole to obtain a compound C;
(3) Reacting the compound C with acid salt NaX, filtering and drying to obtain a compound D;
wherein n is any integer from 2 to 6; x - Is HSO 4 - Or CH 3 COO - (ii) a R is C 1-20 Alkyl or haloalkyl of (a);
represents activated carbon.
3. The method of claim 2, wherein:
the alkali in the step (1) is selected from sodium hydroxide and potassium hydroxide; and/or the presence of a gas in the atmosphere,
the mass ratio of the active carbon rich in hydroxyl, alkali and the compound A is 1 (0.1-1) to 0.5-1.
4. The method of claim 2, wherein: the molar ratio of the compound B in the step (2) to the N-alkyl imidazole is 1: (1.1-2); and/or the presence of a gas in the gas,
the molar ratio of the compound C to the acid salt NaX in the step (3) is 1: (1.1-2).
5. The production method according to any one of claims 1 to 4, characterized in that: the dosage of the acidic ionic liquid catalyst grafted by the active carbon is 5-10% of the mass of the benzophenone compound shown in the general formula I of the reactant.
6. The production method according to any one of claims 1 to 4, characterized in that: the molar ratio of the benzophenone compound shown in the general formula I to the cyanoacetic ester is 1 (1.05-2.0); and/or the presence of a gas in the gas,
the weakly alkaline conditions are achieved by adding ammonium acetate.
7. The method of claim 6, wherein: the molar ratio of the benzophenone compound shown in the general formula I to the ammonium acetate is 1: (0.5-2.0); and/or the presence of a gas in the atmosphere,
the preparation of the compound of the general formula II is carried out in a solvent, and the solvent is one or more selected from toluene, xylene, cyclohexane or n-heptane; the reaction temperature for the preparation of the compound of formula II is the reflux temperature.
8. The production method according to any one of claims 1 to 4, characterized in that: the method also comprises the step of carrying out ester exchange reaction on the compound of the general formula II and target alcohol to generate a target product of a general formula III;
wherein R is 1 ，R 2 Each independently selected from H or halogen, R 3 Is methyl or ethyl; r 4 Is C 1-20 An alkyl group.
9. The method for producing according to claim 8, characterized in that: the molar ratio of the compound in the general formula II to the target alcohol is 1 (1.5-5.0); and/or the presence of a gas in the gas,
the catalyst of the ester exchange reaction is a solid base catalyst, and the molar ratio of the compound in the general formula II to the catalyst in the ester exchange reaction is 1: (0.05-0.2).
10. The method for producing according to claim 8, characterized in that: the preparation of the general formula III is carried out in a solvent, and the solvent is one or more selected from toluene, xylene, cyclohexane or n-heptane; the reaction temperature for the preparation of formula III is the reflux temperature.
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| CN115260059B (en) * | 2022-07-26 | 2024-06-25 | 万华化学集团股份有限公司 | Method for preparing 2-cyano-3, 3-diphenyl ethyl acrylate |
| CN115353462A (en) * | 2022-08-23 | 2022-11-18 | 上海朗亿功能材料有限公司 | Preparation method of cyanoalkenoic acid ester |
| CN115745835B (en) * | 2022-12-02 | 2024-06-18 | 上海朗亿功能材料有限公司 | Preparation method of pentaerythritol tetra (2-cyano-3, 3-diphenyl acrylate) |
| CN115785628A (en) * | 2022-12-13 | 2023-03-14 | 广东省科学院生物与医学工程研究所 | Ultraviolet aging resistant phyllosilicate functional masterbatch and preparation method and application thereof |
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