CN110981752A - Preparation method of cyanoacrylate ultraviolet absorbent - Google Patents
Preparation method of cyanoacrylate ultraviolet absorbent Download PDFInfo
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- CN110981752A CN110981752A CN201911310798.9A CN201911310798A CN110981752A CN 110981752 A CN110981752 A CN 110981752A CN 201911310798 A CN201911310798 A CN 201911310798A CN 110981752 A CN110981752 A CN 110981752A
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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
- B01J31/0281—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 the nitrogen being a ring member
- B01J31/0284—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 the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J31/0277—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
- 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 to post-treat, 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
The invisible light with the wavelength within the range of 400-100 nm is called ultraviolet light, and mainly reaches the ground through solar irradiation. The wavelength range of the light source can be divided into three bands, namely UVA (400-320 nm), UVB (320-290 nm) and UVC (290-100 nm) according to the difference of the wavelength range. UVC can be absorbed by the atmosphere completely; UVA can react with melanin in human body, and long-time irradiation causes skin aging; UVB is basically absorbed by skin, and due to the higher level energy of the UVB, the UVB can burn the skin, generate black spots, even cause canceration of the skin, damage the immune system and be an ultraviolet band which is mainly prevented. 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 sunscreen products, especially high-end sunscreen products, 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 sunscreen), pentaerythritol 2-cyano-3, 3-diphenylacrylate (UV-3030), and ethyl 2-cyano-3, 3-diphenylacrylate (UV-3035, trade name: etoricine). Such UV absorbers are represented by formula III:
in formula III: r1，R2Is one of H or halogen; r4Is C1-20Alkyl group of (1).
The current synthetic methods for cyanoacrylate ultraviolet-grade absorbents at home and abroad can be mainly summarized as the following three methods:
under the condition of a weak base catalyst, benzophenone and cyanoacetate are condensed by Knoevengal, and water generated by condensation is timely separated out in the reaction process, so that the yield of the product is improved.
Di, 2-cyano-3, 3-diphenyl acrylate 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.
And thirdly, performing condensation reaction on benzophenone imine and isooctyl cyanoacetate to obtain the benzophenone imine. 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 patents DE 4440055, WO 9615102A 2, 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 researched by Zhumeixia et al (university of Tianjin institute of technology, 2015,3), wherein intermediate cyanoacetate is synthesized, then corresponding substituted benzophenone cyanoacetate is generated after the intermediate cyanoacetate is reacted with benzophenone and derivatives thereof, and finally the final product is obtained after the product is subjected to ester exchange reaction with alcohol.
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 a benzophenone cyanoacetate intermediate, and then the benzophenone cyanoacetate intermediate and target alcohol are subjected to ester exchange reaction to generate a target product, 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. The ionic liquid has many incomparable advantages of other substances, such as wide liquid temperature range, no obvious vapor pressure, good thermal stability, good solubility to many inorganic compounds, organic compounds and the like, and based on the characteristics, the ionic liquid is expected to become one of the most promising green solvents and catalysts.
The supported catalyst is widely used in various chemical reactions, such as catalytic hydrogenation, petroleum cracking and the like, because the supported catalyst is easy to separate, the using amount of active components is small, and the cost of the catalyst is easy to control.
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 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 is1，R2Each independently selected from H or halogen, R3Is 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 HSO4 -Or CH3COO-(ii) a R is C1-20Alkyl 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 HSO4 -Or CH3COO-(ii) a R is C1-20Alkyl 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 is1，R2Each independently selected from H or halogen, R3Is methyl or ethyl, R4Is C1-20An 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 is1，R2Each independently selected from H or halogen, R3Is methyl or ethyl.
The reaction belongs to Knoevenagel condensation reaction, namely the condensation reaction of benzophenone and cyanoacetate with active α -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 HSO4 -Or CH3COO-；
Is active carbon;
r is C1-20Or a halogenated alkyl group corresponding thereto, preferably C1-4And 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 HSO4 -Or CH3COO-(ii) a R is C1-20Alkyl or halogen-substituted alkyl of (a);
is active carbon.
In the step (1), the active carbon rich in hydroxyl, alkali and a compound A dissolved in an organic solvent 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, the alkali and the compound A is 1:0.1-1: 0.5-1.
More preferably, the mass ratio of the active carbon rich in hydroxyl groups to the alkali to the compound A is 1:0.2-0.5: 0.6-1.0.
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 compound B, N-alkylimidazole is present in a molar ratio of 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: 1.05-2.0. More preferably, the molar ratio of the benzophenone compound shown in the general formula I to the cyanoacetate is 1: 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 in the general formula I to the solvent is 1: 1.5-3.0. More preferably, the mass volume ratio of the compound in the general formula I to the solvent is 1: 2-2.5. 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 is1，R2Each independently selected from H or halogen, R3Is methyl or ethyl. R4Is C1-20An 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: 1.5-5.0;
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 in the general formula II to the solvent is 1: 1.5-3.0. More preferably, the mass volume ratio of the compound in the general formula II to the solvent is 1: 2-2.5. 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 UV 3035; 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 on activated carbon
Adding 10g of commercial 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, putting the flask into magnetic stirring, starting 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, starting stirring with magnetic stirring, dropwise adding 8g of butylimidazole at room temperature, then heating and refluxing for 10h, then cooling to 30 ℃, filtering, then drying, then adding the dried mixture into a 250mL four-neck flask, adding 100mL of acetone, starting stirring with 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, except for changing dichloroethane to dichloropropane, and the procedure of example 1 was repeated, to obtain catalyst 2 comprising activated carbon-grafted acidic ionic liquid.
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 42 preparation of Ethyl-3, 3-cyanophenyl acrylate and Recycling of the catalyst
82g of benzophenone (0.45mol), 150mL of n-heptane, 102g of ethyl cyanoacetate (0.72mol) and 5g of the catalyst 1 obtained in example 1 and 20g of ammonium acetate (0.26mol) grafted with acidic ionic liquid by activated carbon are sequentially added into a three-neck flask provided with a thermometer, a stirring pipe and a return pipe, the temperature is raised under stirring until the reflux starts to react, the solvent flowing back returns to a reactor, water is continuously separated from the bottom of a water separator, then 5g of ammonium acetate is added every 1h, after the last addition, the reaction is carried out for 2h, sampling analysis is carried out every 30min until the conversion rate of the benzophenone is more than 99%, the catalyst is filtered and separated when the reaction is finished, the catalyst is used for indiscriminate application or recovery, the filtrate is kept stand for demixing, the lower-layer aqueous phase is treated, the upper-layer organic phase is washed twice by 50mL of distilled water, then dried by 3g of anhydrous sodium, then, n-heptane was distilled off under reduced pressure, unreacted ethyl cyanoacetate was distilled off under reduced pressure, and 114.8g of ethyl 2-cyano-3, 3-diphenylacrylate was obtained by distillation under reduced pressure, with a yield of 92% and a purity of 99.0% by HPLC.
The results of using the above catalyst 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 52 preparation of Ethyl-cyano-3, 3-diphenylacrylate
The procedure of example 4 was repeated, except for using 8g of the catalyst 2 prepared by grafting the acidic ionic liquid onto the activated carbon obtained in example 2, to obtain 113.3g of ethyl 2-cyano-3, 3-diphenylacrylate in a yield of 90.8% and a HPLC purity of 99.4%.
EXAMPLE 62 preparation of Ethyl-cyano-3, 3-diphenylacrylate
The procedure of example 4 was followed, wherein the ammonium acetate was charged in an amount of 10g for the first time, and after 1 hour of reaction, 1.5g was added every half an hour for a total reaction time of about 15 hours, and the remainder was unchanged, to obtain 117.1g of ethyl 2-cyano-3, 3-diphenylacrylate in a yield of 94.1% and a HPLC purity of 99.3%.
EXAMPLE 72 preparation of Ethyl-cyano-3, 3-diphenylacrylate
According to the scheme of the example 4, the catalyst is changed to the catalyst 3 of the activated carbon grafted acidic ionic liquid prepared in the example 3, the ethyl cyanoacetate is changed to 81.5g, and the rest is not changed, so that 113.5g of ethyl 2-cyano-3, 3-diphenyl acrylate is finally obtained, the yield is 91.5%, and the HPLC purity is 99.0%.
EXAMPLE 8 preparation of pentaerythritol tetrakis (2-cyano-3, 3-diphenylacrylate)
The batch was reacted as in example 4, after the reaction was completed, the post-treatment was carried out as in example 4, and finally, after unreacted ethyl cyanoacetate was distilled off, 300ml of xylene as a solvent was added, then the mixture is added into a three-neck flask which is provided with a thermometer, a stirring pipe and a reflux pipe, then 12g of pentaerythritol and 2.5g of sodium methoxide are added, heating to reflux under stirring for about 12 hr, cooling to 95-100 deg.C, then adding water to wash and remove sodium methoxide and impurities, separating a water phase, adding powdered activated carbon into an organic phase, washing by distilled water, drying by anhydrous sodium sulfate, cooling, crystallizing, filtering at 10 deg.C, drying to obtain 385.6g of pentaerythritol tetra (2-cyano-3, 3-diphenyl acrylate) with yield of 80.6%, detecting that the solvent contains 31.5g of product, so the total yield can reach 87.2%, and HPLC purity is 98.7%.
EXAMPLE 9 preparation of pentaerythritol tetrakis (2-cyano-3, 3-diphenylacrylate)
A reaction was carried out as in example 4, wherein ethyl cyanoacetate was changed to 89.1g of methyl cyanoacetate, the rest is unchanged, after the reaction post-treatment, 300ml of dimethylbenzene is added, the dimethylbenzene is directly added into a three-neck flask provided with a thermometer, a stirring pipe and a reflux pipe, then 12g of pentaerythritol and 2.5g of sodium ethoxide are added, heating to reflux under stirring for about 12 hr, cooling to 95-100 deg.C, then adding water to wash and remove sodium ethoxide and impurities, separating water phase, adding powdered activated carbon into organic phase to decolorize, washing by distilled water, drying by anhydrous sodium sulfate, cooling, crystallizing, filtering at 10 deg.C, drying to obtain 376.4g of pentaerythritol tetra (2-cyano-3, 3-diphenyl acrylate) with yield of 78.8%, detecting that the solvent contains 30.3g of product, so the total yield can reach 85.2%, and HPLC purity is 98.9%.
EXAMPLE 102 preparation of isooctyl 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, the product isooctyl 2-cyano-3, 3-diphenylacrylate is obtained by high vacuum distillation, the total yield is 88.6.
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 absorbent is characterized in that: reacting benzophenone compounds shown in the general formula I with cyanoacetate under a weak alkaline condition by taking acidic ionic liquid grafted by activated carbon as a catalyst to generate compounds shown in the general formula II;
wherein R is1，R2Each independently selected from H or halogen, R3Is methyl or ethyl.
2. The method of claim 1, wherein: 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 HSO4 -Or CH3COO-(ii) a R is C1-20Alkyl or halogen-substituted alkyl of (a);
represents activated carbon.
3. The production method according to claim 1 or 2, characterized in that: 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 HSO4 -Or CH3COO-(ii) a R is C1-20Alkyl or haloalkyl of (a);
represents activated carbon.
4. The production method according to claim 3, characterized in that:
the alkali in the step (1) is selected from sodium hydroxide and potassium hydroxide; and/or the presence of a gas in the gas,
the mass ratio of the active carbon rich in hydroxyl, alkali and the compound A is 1 (0.1-1) to 0.5-1.
5. The production method according to claim 3, characterized in that: 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).
6. The production method according to any one of claims 1 to 5, characterized in that: 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 of the reactant.
7. The production method according to any one of claims 1 to 6, characterized in that: the molar ratio of the benzophenone compound shown in the general formula I to the cyanoacetate is 1 (1.05-2.0); and/or the presence of a gas in the gas,
the alkalescent condition is realized by adding ammonium acetate; 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); and/or the presence of a gas in the gas,
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 7, 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 is1，R2Each independently selected from H or halogen, R3Is methyl or ethyl; r4Is C1-20An alkyl group.
9. The method of claim 8, wherein: 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 production method according to any one of claims 1 to 9, 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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