CN103553920A - Preparation method of phenoxy benzyl acrylic ester - Google Patents
Preparation method of phenoxy benzyl acrylic ester Download PDFInfo
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Abstract
The invention discloses a preparation method of phenoxy benzyl acrylic ester. The preparation method comprises the steps of: under the protection of nitrogen, taking cyclohexane as a solvent and adopting an organic acid as a catalyst, subjecting 3-phenoxy benzyl alcohol and acrylic acid to an esterification reaction in the presence of a polymerization inhibitor and a reducing agent; and at the end of the esterification reaction, removing the cyclohexane by means of alkali washing, water scrubbing, drying, and pressure reduction, thus obtaining the phenoxy benzyl acrylic ester. The dosage of the reducing agent accounts for 0.1-2wt% of the total weight of 3-phenoxy benzyl alcohol and acrylic acid. The method provided by the invention has the advantages of low reaction temperature and simple process, and can produce aromatic ring containing acrylic ester that has low chroma and is even colorless and transparent.
Description
Technical field
The present invention relates to a kind of preparation method of aromatic series acrylate, be specifically related to a kind of preparation method of phenoxy benzyl acrylate.
Background technology
The acrylic ester polymer or the multipolymer that in molecular structure, contain aromatic nucleus, because having the excellent transparency and high refractive index, be widely used in optical material as industries such as optical resin, optical coating, optical adhesive, optical lens and glasses manufactures.
Because these fields all need water white goods, so need monomer used, be that low colourity is even colourless product.General rudimentary acrylate is all to adopt vacuum distillation method to obtain water white transparency product, but the acrylate containing aromatic nucleus is very high because of boiling point, even interpolation stopper, polymerization also very easily occurs in vacuum distillation process, so vacuum distillation method is not suitable for the preparation of the acrylate monomer that low colourity contains aromatic nucleus.
The preparation method of industrial acrylate generally adopts esterification process, corresponding alcohol and vinylformic acid under an acidic catalyst and stopper exist, the method for utilizing aromatic solvent to remove as toluene, dimethylbenzene equal solvent the water generating in esterification reaction process.But because such aromatic solvent boiling point is higher, all higher with water azeotropic temperature, therefore need higher temperature of reaction, and some colored by products of the too high easy generation of temperature, if do not adopt underpressure distillation, are almost difficult to obtain low colourity product; And because temperature of reaction is high, very easily there is polymerization in raw material propylene acid and the acrylate generating, finally can cause yield to decline.For the catalyzer of esterification, generally adopted in the past the vitriol oil, the mineral acids such as strong phosphoric acid, but due to the vitriol oil, strong phosphoric acid is large to equipment corrosion, and because oxidisability is strong, the finished product often color are very dark, are even brownish black.Adopt hardly at present mineral acid to make catalyzer, and adopt as organic acids such as p-methyl benzenesulfonic acid, methylsulphonic acids the catalyzer such as solid acid or strong-acid ion exchange resin.But obtaining the product that colourity is very low is still difficult to.As stopper, Resorcinol, because inhibition efficiency is high, be often used as stopper, but its shortcoming is also to cause that the finished product are painted.In order to obtain light-coloured prods, MEHQ is commonly used for stopper, but will obtain approaching water white product, still hardly may.In order to obtain light-colored product, also have and adopt the method that the finished product are decoloured with discoloring agents such as gac or activated alumina, atlapulgites, but the method effect is also very limited, expect that being close to colourless product hardly may.In addition, the method, because product also needs the further aftertreatment technology such as decolouring and filtration, has therefore increased production cost.Based on this situation, be necessary very much to find a kind of preparation method that can access the low colourity acrylate that even water white transparency contains aromatic nucleus.
Summary of the invention
The object of the invention is to overcome the deficiency that above-mentioned prior art exists, a kind of preparation method of phenoxy benzyl acrylate is provided.The low colourity of phenoxy benzyl acrylate preparing is water white transparency even.
The object of the invention is to be achieved through the following technical solutions:
The preparation method who the present invention relates to a kind of phenoxy benzyl acrylate, comprises the steps:
Steps A, 3-phenoxy benzenemethanol and vinylformic acid, under nitrogen protection, be take hexanaphthene as solvent, take organic acid as catalyzer, under the condition of stopper and reductive agent existence, carry out esterification;
Step B, through conventional alkali cleaning, washing, anhydrous magnesium sulfate drying, add a small amount of MEHQ, decompression, except after hexanaphthene, obtains described phenoxy benzyl acrylate.
In steps A, the mol ratio of vinylformic acid and 3-phenoxy benzenemethanol is 1.05～1.5:1.The consumption of solvent for use hexanaphthene is 3-phenoxy benzenemethanol and acrylic acid gross weight 0.8～4.2 times.The reflux temperature that 3-phenoxy benzenemethanol and acrylic acid esterification reaction temperature are hexanaphthene, i.e. 80～85 degree.Reaction times is 6～10 hours, particularly, with after generating the water yield and no longer changing, then reacts 2 hours as the end reaction time.
Preferably, described organic acid is tosic acid or methylsulphonic acid.Usage quantity with respect to 3-phenoxy benzenemethanol is 1～10mol%.
Preferably, described stopper is one or both the mixing in MEHQ, cupric chloride.Consumption is the 0.1～1wt% (mass percentage content) of 3-phenoxy benzenemethanol and acrylic acid gross weight.
Preferably, the consumption of described reductive agent is the 0.1～2wt% (mass percentage content) of 3-phenoxy benzenemethanol and acrylic acid gross weight.
Preferably, described reductive agent is Hypophosporous Acid, 50, Hypophosporous Acid, 50 compound, sulfurous acid or hydrosulfide.
Preferably, described reductive agent is Hypophosporous Acid, 50 or Hypophosporous Acid, 50 compound.
Preferably, described Hypophosporous Acid, 50 compound is sodium hypophosphite or Hypophosporous Acid, 50 diethyl ester.
Compared with prior art, the present invention has following beneficial effect:
1, adopt hexanaphthene to make solvent, to make solvent phase lower than temperature of reaction with conventional toluene, and product color can be relatively shallow.In addition, harmless to operator ' s health.
2, catalyzer adopts organic acid as tosic acid and methylsulphonic acid, compare with the vitriol oil, and operational safety, corrosion-free to equipment, particularly the colourity of esterification products is low.Compare with Zeo-karb and some solid acids, catalytic efficiency is high.
3, stopper adopts MEHQ or cupric chloride to make catalyzer, replaces the general Resorcinol using, and esterification products colourity is low.
4, use Hypophosporous Acid, 50 class reductive agent to add reaction system, in reaction process, can suppress the generation of coloured product, and obtain the low even water white product of colourity.Product colourity, lower than 100APHA, can be applied in and need the optical material of water white transparency raw material field.
5, do not need the product aftertreatment of further decolouring, technique is simple, cost-saved.
Accompanying drawing explanation
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is with the phenoxy benzyl acrylate of deuterochloroform solvent
1h-NMR spectrogram;
Fig. 2 is with the phenoxy benzyl acrylate of deuterochloroform solvent
13c-NMR spectrogram.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
Particularly, the mol ratio of the vinylformic acid in the embodiment of the present invention and 3-phenoxy benzenemethanol is 1.2:1, but can adopt mol ratio other mol ratios within the scope of 1.05～1.5:1 as the distortion of invention.
Solvent hexanaphthene consumption in the embodiment of the present invention is 3-phenoxy benzenemethanol) and 2.1 times of vinylformic acid gross weight, but can adopt other consumptions in 0.8～4.2 scope as the distortion of invention.
Catalyzer methylsulphonic acid in the embodiment of the present invention or the add-on of tosic acid (with respect to 3-phenoxy benzenemethanol) are 5mol%, but as the distortion of invention other add-ons within the scope of can 1～10mol%.
Stopper MEHQ in the embodiment of the present invention or the add-on of cupric chloride are 3-phenoxy benzenemethanol) and the 0.5wt% of vinylformic acid gross weight, but can adopt other add-ons within the scope of 0.1～1wt% as the distortion of invention.
embodiment 1
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of MEHQ, 0.286 gram of the 50wt% Hypophosporous Acid, 50 aqueous solution, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is washed 2 times by 5% aqueous sodium hydroxide washes, and then with distilled water wash 3 times, finally uses anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, removes desolventizing hexanaphthene, obtain (11.56 grams of water white transparency product-phenoxy benzyl acrylate, yield is 91%), gas chromatographic analysis device purity is 96.7%, colourity is 18APHA.Specific refractory power is 1.565, and viscosity is 15cps.Its 1H-NMR and 13C-NMR spectrogram are shown in Fig. 1 and Fig. 2, by nuclear magnetic data and refractive index data, can be proved, product is phenoxy benzyl acrylate.
embodiment 2
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of MEHQ, 0.029 gram of the 50wt% Hypophosporous Acid, 50 aqueous solution, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is washed 2 times by 5% aqueous sodium hydroxide washes, and then with distilled water wash 3 times, finally uses anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, removes desolventizing hexanaphthene, obtain (11.94 grams of water white transparency product-phenoxy benzyl acrylate, yield is 94%), gas chromatographic analysis device purity is 97.3%, colourity is 73APHA.
embodiment 3
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of MEHQ, 0.572 gram of the 50wt% Hypophosporous Acid, 50 aqueous solution, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is washed 2 times by 5% aqueous sodium hydroxide washes, and then with distilled water wash 3 times, finally uses anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, removes desolventizing hexanaphthene, obtain (12.32 grams of water white transparency product-phenoxy benzyl acrylate, yield is 97%), gas chromatographic analysis device purity is 98.1%, colourity is 48APHA.
embodiment 4
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of MEHQ, 0.072 gram of sodium hypophosphite, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is washed 2 times by 5% aqueous sodium hydroxide washes, and then with distilled water wash 3 times, finally uses anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, removes desolventizing hexanaphthene, obtain (12.44 grams of water white transparency product-phenoxy benzyl acrylate, yield is 98%), gas chromatographic analysis device purity is 97.2%, colourity is 45APHA.
embodiment 5
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of MEHQ, 0.015 gram of sodium hypophosphite, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is washed 2 times by 5% aqueous sodium hydroxide washes, and then with distilled water wash 3 times, finally uses anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, removes desolventizing hexanaphthene, obtain (12.19 grams of water white transparency product-phenoxy benzyl acrylate, yield is 96%), gas chromatographic analysis device purity is 95.8%, colourity is 69APHA.
embodiment 6
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of MEHQ, 0.286 gram of sodium hypophosphite, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is washed 2 times by 5% aqueous sodium hydroxide washes, and then with distilled water wash 3 times, finally uses anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, removes desolventizing hexanaphthene, obtain (11.81 grams of water white transparency product-phenoxy benzyl acrylate, yield is 93%), gas chromatographic analysis device purity is 96.5%, colourity is 67APHA.
embodiment 7
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of MEHQ, 0.144 gram of Hypophosporous Acid, 50 diethyl ester, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is washed 2 times by 5% aqueous sodium hydroxide washes, and then with distilled water wash 3 times, finally uses anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, removes desolventizing hexanaphthene, obtain (12.1 grams of water white transparency product-phenoxy benzyl acrylate, yield is 95%), gas chromatographic analysis device purity is 97.2%, colourity is 56APHA.
embodiment 8
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of MEHQ, 0.014 gram of Hypophosporous Acid, 50 diethyl ester, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is washed 2 times by 5% aqueous sodium hydroxide washes, and then with distilled water wash 3 times, finally uses anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, removes desolventizing hexanaphthene, obtain (11.8 grams of water white transparency product-phenoxy benzyl acrylate, yield is 93%), gas chromatographic analysis device purity is 95.6%, colourity is 76APHA.
embodiment 9
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of MEHQ, 0.288 gram of Hypophosporous Acid, 50 diethyl ester, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is washed 2 times by 5% aqueous sodium hydroxide washes, and then with distilled water wash 3 times, finally uses anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, removes desolventizing hexanaphthene, obtain (12.3 grams of water white transparency product-phenoxy benzyl acrylate, yield is 97%), gas chromatographic analysis device purity is 97.3%, colourity is 67APHA.
embodiment 10
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of cupric chloride, 0.143 gram of the 50wt% Hypophosporous Acid, 50 aqueous solution, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (12.4 grams, yield is 98%), gas chromatographic analysis device purity is 96.2%, and colourity is 52APHA.
embodiment 11
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of cupric chloride, 0.0286 gram of the 50wt% Hypophosporous Acid, 50 aqueous solution, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (11.7 grams, yield is 92%), gas chromatographic analysis device purity is 94.5%, and colourity is 79APHA.
embodiment 12
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of cupric chloride, 0.572 gram of the 50wt% Hypophosporous Acid, 50 aqueous solution, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (12.3 grams, yield is 97%), gas chromatographic analysis device purity is 97.6%, and colourity is 32APHA.
embodiment 13
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of cupric chloride, 0.0143 gram of sodium hypophosphite, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (12.3 grams, yield is 97%), gas chromatographic analysis device purity is 97.5%, and colourity is 51APHA.
embodiment 14
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of cupric chloride, 0.143 gram of sodium hypophosphite, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (12.1 grams, yield is 95%), gas chromatographic analysis device purity is 98.2%, and colourity is 49APHA.
embodiment 15
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of cupric chloride, 0.286 gram of sodium hypophosphite, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (11.7 grams, yield is 92%), gas chromatographic analysis device purity is 96.8%, and colourity is 67APHA.
embodiment 16
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of cupric chloride, 0.143 gram of Hypophosporous Acid, 50 diethyl ester, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (12.3 grams, yield is 97%), gas chromatographic analysis device purity is 97.5%, and colourity is 55APHA.
embodiment 17
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of cupric chloride, 0.0143 gram of Hypophosporous Acid, 50 diethyl ester, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (12.2 grams, yield is 96%), gas chromatographic analysis device purity is 98.7%, and colourity is 94APHA.
embodiment 18
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of cupric chloride, 0.286 gram of Hypophosporous Acid, 50 diethyl ester, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (12.2 grams, yield is 96%), gas chromatographic analysis device purity is 98.7%, and colourity is 55APHA.
embodiment 19
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.48 gram of p-methyl benzenesulfonic acid; 0.072 gram of MEHQ, 50% 0.286 gram of the Hypophosporous Acid, 50 aqueous solution, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.90 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is first washed 2 times by 5% aqueous sodium hydroxide washes, and distilled water wash 3 times, then uses anhydrous magnesium sulfate drying, in the most backward dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, removes desolventizing hexanaphthene, obtain (12.0 grams of water white transparency product-phenoxy benzyl acrylate, yield is 94%), gas chromatographic analysis device purity is 98.6%, colourity is 91APHA.
embodiment 20
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.48 gram of p-methyl benzenesulfonic acid; 0.072 gram of MEHQ, 0.143 gram of sodium hypophosphite, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.9 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is first washed 2 times by 5% aqueous sodium hydroxide washes, and distilled water wash 3 times, then uses anhydrous magnesium sulfate drying, in the most backward dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, removes desolventizing hexanaphthene, obtain (11.8 grams of water white transparency product-phenoxy benzyl acrylate, yield is 93%), gas chromatographic analysis device purity is 97.5%, colourity is 49APHA.
embodiment 21
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.48 gram of p-methyl benzenesulfonic acid; 0.072 gram of MEHQ, 0.143 gram of Hypophosporous Acid, 50 diethyl ester, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.90 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is first washed 2 times by 5% aqueous sodium hydroxide washes, and distilled water wash 3 times, then uses anhydrous magnesium sulfate drying, in dried solution, add 0.02 gram of stopper MEHQ again, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, removes desolventizing hexanaphthene, obtain (11.6 grams of water white transparency product-phenoxy benzyl acrylate, yield is 91%), gas chromatographic analysis device purity is 97.2%, colourity is 57APHA.
embodiment 22
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.48 gram of p-methyl benzenesulfonic acid; 0.072 gram of cupric chloride, 50% 0.286 gram of the Hypophosporous Acid, 50 aqueous solution, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.90 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (11.9 grams, yield is 94%), gas chromatographic analysis device purity is 97.1%, and colourity is 53APHA.
embodiment 23
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.48 gram of p-methyl benzenesulfonic acid; 0.072 gram of cupric chloride, 50% 0.0286 gram of the Hypophosporous Acid, 50 aqueous solution, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.90 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (11.4 grams, yield is 90%), gas chromatographic analysis device purity is 97.5%, and colourity is 56APHA.
embodiment 24
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.48 gram of p-methyl benzenesulfonic acid; 0.072 gram of cupric chloride, 50% 0.286 gram of the Hypophosporous Acid, 50 aqueous solution, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.90 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (11.2 grams, yield is 92%), gas chromatographic analysis device purity is 96.8%, and colourity is 32APHA.
embodiment 25
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.48 gram of p-methyl benzenesulfonic acid; 0.072 gram of cupric chloride, 0.143 gram of sodium hypophosphite, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.90 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (11.6 grams, yield is 91%), gas chromatographic analysis device purity is 98.2%, and colourity is 30APHA.
embodiment 26
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.48 gram of p-methyl benzenesulfonic acid; 0.072 gram of cupric chloride, 0.0143 gram of sodium hypophosphite, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.90 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (11.8 grams, yield is 93%), gas chromatographic analysis device purity is 97.1%, and colourity is 61APHA.
embodiment 27
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.48 gram of p-methyl benzenesulfonic acid; 0.072 gram of cupric chloride, 0.286 gram of sodium hypophosphite, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.90 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (12.2 grams, yield is 96%), gas chromatographic analysis device purity is 98.5%, and colourity is 29APHA.
embodiment 28
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.48 gram of p-methyl benzenesulfonic acid; 0.072 gram of cupric chloride, 0.143 gram of Hypophosporous Acid, 50 diethyl ester, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.90 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (11.8 grams, yield is 93%), gas chromatographic analysis device purity is 97.2%, and colourity is 32APHA.
embodiment 29
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.48 gram of p-methyl benzenesulfonic acid; 0.072 gram of cupric chloride, 0.0143 gram of Hypophosporous Acid, 50 diethyl ester, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.90 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (12.1 grams, yield is 95%), gas chromatographic analysis device purity is 98.3%, and colourity is 57APHA.
embodiment 30
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.48 gram of p-methyl benzenesulfonic acid; 0.072 gram of cupric chloride, 0.286 gram of Hypophosporous Acid, 50 diethyl ester, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.90 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture first washes with water 1 time, then by 5% aqueous sodium hydroxide washes, wash 2 times, distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dried solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain water white transparency product-phenoxy benzyl acrylate (12.3 grams, yield is 97%), gas chromatographic analysis device purity is 97.6%, and colourity is 42APHA.
comparative example 1
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols; 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes, 0.48 gram of methylsulphonic acid; 0.072 gram of MEHQ; in reaction process, a straight-through nitrogen protection, after 5 hours, generates approximately 0.90 ml water 80～85 ℃ of back flow reaction; continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is first washed 2 times by 5% aqueous sodium hydroxide washes, and distilled water wash 3 times, then uses anhydrous magnesium sulfate drying, in dried solution, add 0.02 gram of stopper MEHQ again, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, removes desolventizing hexanaphthene, obtain (11.7 grams of light yellow opaque products-phenoxy benzyl acrylate, yield is 92%), gas chromatographic analysis device purity is 97.5%, colourity is 401APHA.
comparative example 2
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols; 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes, 0.12 gram of the vitriol oil; 0.072 gram of MEHQ; in reaction process, a straight-through nitrogen protection, after 5 hours, generates approximately 0.90 ml water 80～85 ℃ of back flow reaction; continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is washed 2 times by 5% aqueous sodium hydroxide washes, and then with distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dry rear solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain brown transparent phenoxy benzyl acrylate (11.4 grams, yield is 90%).This product is dissolved in methanol solvate, adds 5wt%pH7-9 gac, reflux 30 minutes, then filter, lower the concentrating of decompression removed methyl alcohol, obtains red-brown transparent liquid.
comparative example 3
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; 0.24 gram of methylsulphonic acid; 0.072 gram of Resorcinol, 0.143 gram of sodium hypophosphite, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.90 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is washed 2 times by 5% aqueous sodium hydroxide washes, and then with distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dry rear solution, add 0.02 gram of stopper MEHQ, at 50 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain orange transparent phenoxy benzyl acrylate (11.8 grams, yield is 93%).
comparative example 4
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols; 4.32 grams, vinylformic acid, 30 grams of toluene, 0.24 gram of methylsulphonic acid; 0.072 gram of MEHQ; in reaction process, a straight-through nitrogen protection, after 5 hours, generates approximately 0.90 ml water 80～85 ℃ of back flow reaction; continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is washed 2 times by 5% aqueous sodium hydroxide washes, and then with distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dry rear solution, add 0.2 gram of stopper MEHQ, at 60 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, remove solvent toluene, obtain the transparent phenoxy benzyl acrylate of red-brown (12.3 grams, yield is 97%).
comparative example 5
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols, 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes; to 0.48 gram of methylsulphonic acid; 0.072 gram of Resorcinol, 0.286 gram of Hypophosporous Acid, 50, a straight-through nitrogen protection in reaction process; 80～85 ℃ of back flow reaction after 5 hours; generate approximately 0.90 ml water, continue to reflux 2 hours, the water yield is constant.
After reaction finishes, reaction mixture is washed 2 times by 5% aqueous sodium hydroxide washes, and then with distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dry rear solution, add 0.2 gram of stopper MEHQ, at 60 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, except desolventizing hexanaphthene, obtain yellow transparent phenoxy benzyl acrylate (12.1 grams, yield is 95%).
comparative example 6
To being furnished with mechanical stirrer; in 100 milliliters of four-hole bottles of condenser and water trap, add 10 grams of 3-phenoxy benzenemethanols; 4.32 grams, vinylformic acid, 30 grams of hexanaphthenes, solid Zeo-karb Amberlyst150.72 gram; 0.072 gram of MEHQ; in reaction process, a straight-through nitrogen protection, after 24 hours, produces 0.6 gram, water 80～85 ℃ of back flow reaction; continue to react 2 hours, the water yield does not change again.Through gas chromatographic analysis, 3-phenoxy benzenemethanol also has 15.6% not reaction.
After reaction finishes, remove by filter Amberlyst15, reaction mixture is washed 2 times by 5% aqueous sodium hydroxide washes, and then with distilled water wash 3 times, finally use anhydrous magnesium sulfate drying, then in dry rear solution, add 0.2 gram of stopper MEHQ, at 60 ℃, vacuum tightness is under 0.1MPa condition, with rotatory evaporator, remove desolventizing hexanaphthene, obtain light yellow transparent phenoxy benzyl acrylate (11.2 grams, yield is 88%), colourity is 165APHA.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned particular implementation, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (7)
1. a preparation method for phenoxy benzyl acrylate, is characterized in that, comprises the steps:
Steps A, 3-phenoxy benzenemethanol and vinylformic acid, under nitrogen protection, be take hexanaphthene as solvent, take organic acid as catalyzer, under the condition of stopper and reductive agent existence, carry out esterification;
Step B, through alkali cleaning, washing, anhydrous magnesium sulfate drying, add a small amount of MEHQ, decompression remove described hexanaphthene, obtain described phenoxy benzyl acrylate.
2. the preparation method of phenoxy benzyl acrylate according to claim 1, is characterized in that, described organic acid is tosic acid or methylsulphonic acid.
3. the preparation method of phenoxy benzyl acrylate according to claim 1, is characterized in that, described stopper is one or both the mixing in MEHQ, cupric chloride.
4. the preparation method of phenoxy benzyl acrylate according to claim 1, is characterized in that, the consumption of described reductive agent is 0.1～2wt% of 3-phenoxy benzenemethanol and acrylic acid gross weight.
5. according to the preparation method of the phenoxy benzyl acrylate described in claim 1 or 4, it is characterized in that, described reductive agent is Hypophosporous Acid, 50, Hypophosporous Acid, 50 compound, sulfurous acid or hydrosulfide.
6. the preparation method of phenoxy benzyl acrylate according to claim 5, is characterized in that, described reductive agent is Hypophosporous Acid, 50 or Hypophosporous Acid, 50 compound.
7. the preparation method of phenoxy benzyl acrylate according to claim 6, is characterized in that, described Hypophosporous Acid, 50 compound is sodium hypophosphite or Hypophosporous Acid, 50 diethyl ester.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876822A (en) * | 2014-02-28 | 2015-09-02 | 上海飞凯光电材料股份有限公司 | Pentaerythritol tetraacrylate preparation method |
| CN104945255A (en) * | 2015-02-03 | 2015-09-30 | 安庆飞凯高分子材料有限公司 | Preparation method of cyclohexyl methacrylate |
| CN105061270A (en) * | 2015-09-21 | 2015-11-18 | 东莞市贝特利新材料有限公司 | Photocuring resin containing polyethoxy bisthiophenyl fluorene structure and preparation method thereof |
| CN105566114A (en) * | 2015-04-16 | 2016-05-11 | 湖南省金海科技有限公司 | Clean production method for monofuction acrylic ester reactive diluent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6458991B1 (en) * | 1999-06-25 | 2002-10-01 | Basf Aktiengesellschaft | Preparation of (meth)acrylates |
| CN101553458A (en) * | 2006-12-08 | 2009-10-07 | 巴斯夫欧洲公司 | Method for producing polymerizable carboxylic acid esters having alkoxy groups |
| CN102229529A (en) * | 2011-05-11 | 2011-11-02 | 华诺森（武汉）生物医药技术有限公司 | Preparation method of (methyl) crylic acid phenylethanol ester compounds |
| WO2012158317A2 (en) * | 2011-05-13 | 2012-11-22 | 3M Innovative Properties Company | Benzyl (meth)acrylate monomers suitable for microstructured optical films |
-
2013
- 2013-09-26 CN CN201310450262.3A patent/CN103553920A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6458991B1 (en) * | 1999-06-25 | 2002-10-01 | Basf Aktiengesellschaft | Preparation of (meth)acrylates |
| CN101553458A (en) * | 2006-12-08 | 2009-10-07 | 巴斯夫欧洲公司 | Method for producing polymerizable carboxylic acid esters having alkoxy groups |
| CN102229529A (en) * | 2011-05-11 | 2011-11-02 | 华诺森（武汉）生物医药技术有限公司 | Preparation method of (methyl) crylic acid phenylethanol ester compounds |
| WO2012158317A2 (en) * | 2011-05-13 | 2012-11-22 | 3M Innovative Properties Company | Benzyl (meth)acrylate monomers suitable for microstructured optical films |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876822A (en) * | 2014-02-28 | 2015-09-02 | 上海飞凯光电材料股份有限公司 | Pentaerythritol tetraacrylate preparation method |
| CN104945255A (en) * | 2015-02-03 | 2015-09-30 | 安庆飞凯高分子材料有限公司 | Preparation method of cyclohexyl methacrylate |
| CN105566114A (en) * | 2015-04-16 | 2016-05-11 | 湖南省金海科技有限公司 | Clean production method for monofuction acrylic ester reactive diluent |
| CN105566114B (en) * | 2015-04-16 | 2018-04-03 | 湖南省金海科技有限公司 | A kind of clean preparation method of single functionality acrylate reactive diluent |
| CN105061270A (en) * | 2015-09-21 | 2015-11-18 | 东莞市贝特利新材料有限公司 | Photocuring resin containing polyethoxy bisthiophenyl fluorene structure and preparation method thereof |
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