CN103127955A - Catalyst for synthesizing dipentaerythritol hexaacrylate, preparation method and application thereof - Google Patents
Catalyst for synthesizing dipentaerythritol hexaacrylate, preparation method and application thereof Download PDFInfo
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- CN103127955A CN103127955A CN2013100767076A CN201310076707A CN103127955A CN 103127955 A CN103127955 A CN 103127955A CN 2013100767076 A CN2013100767076 A CN 2013100767076A CN 201310076707 A CN201310076707 A CN 201310076707A CN 103127955 A CN103127955 A CN 103127955A
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Abstract
The invention discloses a catalyst for synthesizing dipentaerythritol hexaacrylate and a preparation method and application thereof and belongs to the field of chemical industry. The catalyst is a composite catalyst which consists of phosphotungstic acid and para-toluenesulfonic acid, wherein the mass ratio of phosphotungstic acid to para-toluenesulfonic acid is 1:2-6:1. The molecular formula of phosphotungstic acid is H3PO4.12WO3.xH2O in which x is an integer from 1 to 12. The molecular formula of para-toluenesulfonic acid is CH3C6H4SO3H. The catalyst is a mixture of phosphotungstic acid and para-toluenesulfonic acid. The preparation method comprises the following steps of: first, sequentially adding dipentaerythritol, acrylic acid and a solvent into a reactor; then, adding a polymerization inhibitor and a catalyst to obtain a mixture 1, and reacting to obtain a mixture 2; extracting to obtain an oil layer; adjusting the PH value; washing and drying to obtain a mixture 3; and extracting to obtain dipentaerythritol hexaacrylate. The catalyst is high in activity, good in selectivity, short in reaction time, high in yield, fewer in byproduct, free from corrosion and environmental-friendly.
Description
Technical field
The present invention relates to a kind of catalyst, preparation method and application of synthetic double pentaerythritol methacrylate, belong to chemical field.
Background technology
Esterification is the important reaction of class in organic synthesis, normally by organic acid and alcohol reaction, generates ester and water.Traditional esterification is made catalyst with the concentrated sulfuric acid usually, its synthesis and production process is that reaction mass is joined in enamel reaction still, alcohol reacts under sulfuric acid catalysis with carboxylic acid at a certain temperature, and the ester that reaction generates evaporates from esterifying kettle, then obtains the finished product ester through rectifying.Because the heat transfer efficiency of enamel reaction still is low, need higher steam pressure just can reach reaction temperature, usually adopt during industrial production to connect snakelike heat(ing) coil in external stainless steel reboiler or still, satisfy manufacturing condition.Because metal material directly contacts with sulfuric acid catalyst, usually cause the hardware heavy corrosion.In addition, also occur with side reactions such as oxidation, charing, sulfonation and isomerization in traditional sulfuric acid catalysis reaction, environmental pollution is larger.The ester class of bipentaerythrite can be used for making the high-grade synthetic lubricant fluid with good weatherability properties, synthetic lubricating oil is compared with traditional mineral oil, have that volatility is low, cryogenic property good, thermal oxidation stability is good, long service life, the advantage such as energy-conservation, be widely used in the fields such as military affairs, aviation, machinery.The Japan Patent report is arranged, and take the concentrated sulfuric acid as catalyst, under the existence of polymerization inhibitor, acrylic acid and bipentaerythrite have synthesized double pentaerythritol methacrylate through esterification.The problems such as this method exists catalyst serious to metal equipment corrosion in building-up process, and side reaction is many, and is big for environment pollution, and the acrylic acid input amount is large, and aftertreatment technology is complicated.Therefore, find to have high activity, can substitute the concentrated sulfuric acid, etching apparatus not, the new catalyst for esterification reaction that environmental pollution is little has great importance.
Summary of the invention
Reaction for existing synthetic double pentaerythritol methacrylate exists catalyst serious to metal equipment corrosion, side reaction is many, defective big for environment pollution, the object of the present invention is to provide a kind of catalyst, preparation method and application of synthetic double pentaerythritol methacrylate, described catalyst activity is high, selectively good, reaction time is short, and yield is high, and side reaction is few.Simultaneously can effectively avoid catalyst itself to the corrosion of consersion unit, and the environmental pollution of catalyst own is slight, impels the preparation of multi-hydroxy ester to change to green is synthetic, significantly reduce the social cost of Chemical Manufacture.
Purpose of the present invention is realized by following technical scheme:
A kind of catalyst of synthetic double pentaerythritol methacrylate, described catalyst are composite catalyst, are comprised of phosphotungstic acid and p-methyl benzenesulfonic acid, and wherein, the mass ratio of phosphotungstic acid and p-methyl benzenesulfonic acid is 1:2～6:1; Described phosphotungstic acid molecular formula is H
3PO
4﹒ 12WO
3﹒ xH
2O, x are 1～12 integer; The p-methyl benzenesulfonic acid molecular formula is CH
3C
6H
4SO
3H。
The preparation method of the catalyst of described synthetic double pentaerythritol methacrylate, described method step is as follows:
Phosphotungstic acid and p-methyl benzenesulfonic acid are mixed in proportion, namely obtain the catalyst of described synthetic double pentaerythritol methacrylate.
The application of the catalyst of described synthetic double pentaerythritol methacrylate, described application is as follows:
Add successively bipentaerythrite, acrylic acid and solvent in reactor, add again polymerization inhibitor and catalyst after stirring, obtain mixture 1, under agitation add 1 to 110 ℃～130 ℃ of hot mixts, reaction 2h～5h, reaction finishes, stop stirring, stopped heating is cooled to room temperature, obtains mixture 2; Add toluene and sodium chloride solution in mixture 2, extraction obtains oil reservoir, regulates the pH value of described oil reservoir to neutral, then washs oil reservoir with distilled water, after then using anhydrous sodium sulfate drying 6～8h, obtains mixture 3, the outstanding toluene of removing in mixture 3 that steams of decompression; And the mixture 3 silicagel column purification excessively after outstanding steaming of reducing pressure, namely obtain described double pentaerythritol methacrylate;
Bipentaerythrite and acrylic acid molar ratio are 1:6.0～1:9.0;
Described catalyst is the catalyst of synthetic double pentaerythritol methacrylate of the present invention;
Described bipentaerythrite, acrylic acid, solvent, polymerization inhibitor and catalyst anabolic reaction liquid, take the oeverall quality of reactant liquor as 100%, wherein, the quality percentage composition of solvent is 40%～60%, the quality percentage composition of polymerization inhibitor is 2.0%～3.0%, and the quality percentage composition of catalyst is 1.0%～3.0%;
Described solvent is toluene, and polymerization inhibitor is hydroquinones;
The toluene quality that adds during extraction is 2.5 times of reactant liquor gross mass, and the quality of sodium chloride solution is 20% of reactant liquor gross mass, and its specification is that mass fraction is 20% sodium chloride solution;
When described silicagel column is purified, solvent used is that carrene and absolute ethyl alcohol volume ratio are the mixed liquor of 50:3.
Beneficial effect
Catalyst activity of the present invention is high, selectively good, and the reaction time is short, and yield is high, and side reaction is few, uses described catalyst to synthesize double pentaerythritol methacrylate, and yield selectively can reach more than 90% between 60%～80%.Simultaneously can effectively avoid catalyst itself to the corrosion of consersion unit, and the environmental pollution of catalyst own is slight, impels the preparation of multi-hydroxy ester to change to green is synthetic, significantly reduce the social cost of Chemical Manufacture.
Description of drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of double pentaerythritol methacrylate in embodiment 1;
Fig. 2 is the mass spectrogram of double pentaerythritol methacrylate in embodiment 1;
Fig. 3 is the second order ms figure of double pentaerythritol methacrylate in embodiment 1;
Fig. 4 is the infrared spectrum of double pentaerythritol methacrylate in embodiment 1.
The specific embodiment
Below in conjunction with the drawings and specific embodiments in detail the present invention is described in detail, but is not limited to this.
When silicagel column described in following examples is purified, solvent used is that carrene and absolute ethyl alcohol volume ratio are the mixed liquor of 50:3.
Weighing 0.648g phosphotungstic acid and 0.216g p-methyl benzenesulfonic acid will both mix, and namely obtain the catalyst of described synthetic double pentaerythritol methacrylate.Described phosphotungstic acid molecular formula is H3PO
4﹒ 12WO
3﹒ 8H
2O, the p-methyl benzenesulfonic acid molecular formula is CH
3C
6H
4SO
3H。
The application of described catalyst is as follows:
Add successively 6.121g bipentaerythrite, 13mL acrylic acid and 25mL toluene in reactor, add again 1.037g hydroquinones and the described catalyst of 0.864g after stirring, obtain mixture 1, under agitation add 1 to 120 ℃ of hot mixt, reaction 3h, reaction finishes, stop stirring, stopped heating is cooled to room temperature, obtains mixture 2; The sodium chloride solution 43mL that adds 125mL toluene and 20% in the mixture 2, extraction obtains oil reservoir, regulate the pH value of described oil reservoir with sodium hydroxide solution to neutral, wash oil reservoir with distilled water again, then after using anhydrous sodium sulfate drying 6h, obtain mixture 3, the outstanding toluene of removing in mixture 3 that steams of decompression; And the mixture 3 after outstanding steaming of reducing pressure crosses silicagel column and purifies, and obtains product, product carried out nucleus magnetic hydrogen spectrum detection, Mass Spectrometer Method, Fourier transform infrared spectrum (FT-IR) detect, and Analysis of test results is as follows:
Nucleus magnetic hydrogen spectrum
1H-NMR (CD
2Cl
2): as shown in Figure 1,6.35 (6H, 6C=CH) as can be known, 6.10 (6H, 6C=CH), 5.83 (6H, 6C=CH), 4.20 (12H, 6CH
2), 3.40 (4H, 2CH
2); Illustrate that described product is double pentaerythritol methacrylate.
Mass spectrum: as shown in Figure 2, can judge that primary product is double pentaerythritol methacrylate, the molecular weight M=578 of double pentaerythritol methacrylate, molecular weight in Fig. 2 [M+Na]=601.1891, [M+Na+H
2O]=619.2002, [M+Na+4H
2O]=673.2102, [M+Na+5H
2O]=691.2203, double pentaerythritol methacrylate accounts for 80% of product total mole number.Also contain a small amount of double pentaerythritol C5 methacrylate in product, the molecular weight M=524 of double pentaerythritol C5 methacrylate, [M+Na]=547.1790, double pentaerythritol C5 methacrylate accounts for 20% of product total mole number.Can judge further that by Fig. 3 described product is double pentaerythritol methacrylate.
Fourier transform infrared spectrum (FT-IR): data as shown in Figure 4
: 3500cm
-1The place is the stretching vibration peak of-OH; 1725.98cm
-1Stretching vibration peak for C=O; 1633.10cm
-1Stretching vibration peak for C=C; 1114.23cm
-1, 1184.70cm
-1Stretching vibration peak for C-O-C; 809.96cm
-1, 986.12cm
-1Out-of-plane bending deformation vibration peak for C-H; 1271.17cm
-1, 1405.69cm
-1Be in-plane bending deformation vibration peak; 2962.28cm
-1, 2901.42cm
-1For-CH
2Stretching vibration peak.Hence one can see that, and synthetic product has end alkene C-H flexural deformation vibration peak (809.96cm
-1), ester carbonyl group characteristic absorption peak (1725.98cm
-1) and the symmetrical antisymmetric stretching vibration absworption peak of ester type compound C-O-C (1184.70cm
-1); Illustrate that described product is double pentaerythritol methacrylate.
The yield of described double pentaerythritol methacrylate is 80.3%.
Embodiment 2
Weighing 0.335g phosphotungstic acid and 0.671g p-methyl benzenesulfonic acid will both mix, and namely obtain the catalyst of described synthetic double pentaerythritol methacrylate.Described phosphotungstic acid molecular formula is H
3PO
4﹒ 12WO
3﹒ H
2O, the p-methyl benzenesulfonic acid molecular formula is CH
3C
6H
4SO
3H。
The application of described catalyst is as follows:
Add successively 7.236g bipentaerythrite, 10.5mL acrylic acid and 15.7mL toluene in reactor, add again 0.671g hydroquinones and the described catalyst of 1.006g after stirring, obtain mixture 1, under agitation add 1 to 110 ℃ of hot mixt, reaction 2h, reaction finishes, stop stirring, stopped heating is cooled to room temperature, obtains mixture 2; The sodium chloride solution 34mL that adds 97mL toluene and 20% in the mixture 2, extraction obtains oil reservoir, regulate the pH value of described oil reservoir with sodium hydroxide solution to neutral, wash oil reservoir with distilled water again, then after using anhydrous sodium sulfate drying 6h, obtain mixture 3, the outstanding toluene of removing in mixture 3 that steams of decompression; And the mixture 3 after outstanding steaming of reducing pressure crosses silicagel column and purifies, and obtains product, product carried out nucleus magnetic hydrogen spectrum detection, Mass Spectrometer Method, Fourier transform infrared spectrum (FT-IR) detected, and Analysis of test results is as follows:
Nucleus magnetic hydrogen spectrum
1H-NMR (CD
2Cl
2): 6.33 (6H, 6C=CH), 6.11 (6H, 6C=CH), 5.80 (6H, 6C=CH), 4.22 (12H, 6CH
2), 3.39 (4H, 2CH
2); Illustrate that described product is double pentaerythritol methacrylate.
Mass spectrum: can judge that primary product is double pentaerythritol methacrylate, the molecular weight M=578 of double pentaerythritol methacrylate, molecular weight in spectrogram [M+Na]=601.1982, [M+Na+H
2O]=619.2016, [M+Na+4H
2O]=673.2372, [M+Na+5H
2O]=691.2106, double pentaerythritol methacrylate accounts for 61% of product total mole number.Also contain a small amount of double pentaerythritol C5 methacrylate in product, the molecular weight M=524 of double pentaerythritol C5 methacrylate, [M+Na]=547.1762, double pentaerythritol C5 methacrylate accounts for 39% of product total mole number.
The Fourier transform infrared spectroscopic data
: 3500cm
-1The place is the stretching vibration peak of-OH; 1725.82cm
-1Stretching vibration peak for C=O; 1633.27cm
-1Stretching vibration peak for C=C; 1115.03cm
-1, 1183.20cm
-1Stretching vibration peak for C-O-C; 810.36cm
-1, 985.19cm
-1Out-of-plane bending deformation vibration peak for C-H; 1272.37cm
-1, 1406.89cm
-1Be in-plane bending deformation vibration peak; 2962.22cm
-1, 2901.30cm
-1For-CH
2Stretching vibration peak.Hence one can see that, and synthetic product has end alkene C-H flexural deformation vibration peak (810.36cm
-1), ester carbonyl group characteristic absorption peak (1725.82cm
-1) and the symmetrical antisymmetric stretching vibration absworption peak of ester type compound C-O-C (1183.20cm
-1); Illustrate that described product is double pentaerythritol methacrylate.
The yield of described double pentaerythritol methacrylate is 61.4%.
Embodiment 3
Weighing 0.287g phosphotungstic acid and 0.048g p-methyl benzenesulfonic acid will both mix, and namely obtain the catalyst of described synthetic double pentaerythritol methacrylate.Described phosphotungstic acid molecular formula is H
3PO
4﹒ 12WO
3﹒ 12H
2O, the p-methyl benzenesulfonic acid molecular formula is CH
3C
6H
4SO
3H。
The application of described catalyst is as follows:
Add successively 3.657g bipentaerythrite, 8.0mL acrylic acid and 23mL toluene in reactor, add again 1.005g hydroquinones and the described catalyst of 0.335g after stirring, obtain mixture 1, under agitation add 1 to 130 ℃ of hot mixt, reaction 5h, reaction finishes, stop stirring, stopped heating is cooled to room temperature, obtains mixture 2; The sodium chloride solution 33mL that adds 96mL toluene and 20% in the mixture 2, extraction obtains oil reservoir, regulate the pH value of described oil reservoir with sodium hydroxide solution to neutral, wash oil reservoir with distilled water again, then after using anhydrous sodium sulfate drying 8h, obtain mixture 3, the outstanding toluene of removing in mixture 3 that steams of decompression; And the mixture 3 after outstanding steaming of reducing pressure crosses silicagel column and purifies, and obtains product, product carried out nucleus magnetic hydrogen spectrum detection, Mass Spectrometer Method, Fourier transform infrared spectrum (FT-IR) detected, and Analysis of test results is as follows:
Nucleus magnetic hydrogen spectrum
1H-NMR (CD
2Cl
2): 6.36 (6H, 6C=CH), 6.20 (6H, 6C=CH), 5.89 (6H, 6C=CH), 4.15 (12H, 6CH
2), 3.27 (4H, 2CH
2); Illustrate that described product is double pentaerythritol methacrylate.
Mass spectrum: can judge that primary product is double pentaerythritol methacrylate, the molecular weight M=578 of double pentaerythritol methacrylate, molecular weight in spectrogram [M+Na]=601.1692, [M+Na+H
2O]=619.2105, [M+Na+4H
2O]=673.20041, [M+Na+5H
2O]=691.2153, double pentaerythritol methacrylate accounts for 70% of product total mole number.Also contain a small amount of double pentaerythritol C5 methacrylate in product, the molecular weight M=524 of double pentaerythritol C5 methacrylate, [M+Na]=547.1698, double pentaerythritol C5 methacrylate accounts for 30% of product total mole number.
The Fourier transform infrared spectroscopic data
: 3500cm
-1The place is the stretching vibration peak of-OH; 1725.12cm
-1Stretching vibration peak for C=O; 1634.09cm
-1Stretching vibration peak for C=C; 1114.03cm
-1, 1182.35cm
-1Stretching vibration peak for C-O-C; 808.76cm
-1, 984.37cm
-1Out-of-plane bending deformation vibration peak for C-H; 1271.19cm
-1, 1405.31cm
-1Be in-plane bending deformation vibration peak; 2961.27cm
-1, 2902.43cm
-1For-CH
2Stretching vibration peak.Hence one can see that, and synthetic product has end alkene C-H flexural deformation vibration peak (808.76cm
-1), ester carbonyl group characteristic absorption peak (1725.12cm
-1) and the symmetrical antisymmetric stretching vibration absworption peak of ester type compound C-O-C (1182.35cm
-1); Illustrate that described product is double pentaerythritol methacrylate.
The yield of described double pentaerythritol methacrylate is 68.8%.
Weighing 0.342g phosphotungstic acid and 0.171g p-methyl benzenesulfonic acid will both mix, and namely obtain the catalyst of described synthetic double pentaerythritol methacrylate.Described phosphotungstic acid molecular formula is H
3PO
4﹒ 12WO
3﹒ 12H
2O, the p-methyl benzenesulfonic acid molecular formula is CH
3C
6H
4SO
3H。
The application of described catalyst is as follows:
Add successively 5.443g bipentaerythrite, 10.3mL acrylic acid and 17mL toluene in reactor, add again 0.738g hydroquinones and the described catalyst of 0.513g after stirring, obtain mixture 1, under agitation add 1 to 125 ℃ of hot mixt, reaction 4h, reaction finishes, stop stirring, stopped heating is cooled to room temperature, obtains mixture 2; The sodium chloride solution 32mL that adds 93mL toluene and 20% in the mixture 2, extraction obtains oil reservoir, regulate the pH value of described oil reservoir with sodium hydroxide solution to neutral, wash oil reservoir with distilled water again, then after using anhydrous sodium sulfate drying 7h, obtain mixture 3, the outstanding toluene of removing in mixture 3 that steams of decompression; And the mixture 3 after outstanding steaming of reducing pressure crosses silicagel column and purifies, and obtains product, product carried out nucleus magnetic hydrogen spectrum detection, Mass Spectrometer Method, Fourier transform infrared spectrum (FT-IR) detected, and Analysis of test results is as follows:
Nucleus magnetic hydrogen spectrum 1H-NMR (CD
2Cl
2): 6.40 (6H, 6C=CH), 6.19 (6H, 6C=CH), 5.88 (6H, 6C=CH), 4.23 (12H, 6CH
2), 3.47 (4H, 2CH
2); Illustrate that described product is double pentaerythritol methacrylate.
Mass spectrum: can judge that primary product is double pentaerythritol methacrylate, the molecular weight M=578 of double pentaerythritol methacrylate, molecular weight in spectrogram [M+Na]=601.1813, [M+Na+H
2O]=619.2052, [M+Na+4H
2O]=673.2207, [M+Na+5H
2O]=691.2209, double pentaerythritol methacrylate accounts for 75% of product total mole number.Also contain a small amount of double pentaerythritol C5 methacrylate in product, the molecular weight M=524 of double pentaerythritol C5 methacrylate, [M+Na]=547.1725, double pentaerythritol C5 methacrylate accounts for 25% of product total mole number.
The Fourier transform infrared spectroscopic data
: 3500cm
-1The place is the stretching vibration peak of-OH; 1725.68cm
-1Stretching vibration peak for C=O; 1635.72cm
-1Stretching vibration peak for C=C; 1114.43cm
-1, 1183.52cm
-1Stretching vibration peak for C-O-C; 808.73cm
-1, 987.13cm
-1Out-of-plane bending deformation vibration peak for C-H; 1272.67cm
-1, 1405.78cm
-1Be in-plane bending deformation vibration peak; 2962.40cm
-1, 2902.48cm
-1For-CH
2Stretching vibration peak.Hence one can see that, and synthetic product has end alkene C-H flexural deformation vibration peak (808.73cm
-1), ester carbonyl group characteristic absorption peak (1725.72cm
-1) and the symmetrical antisymmetric stretching vibration absworption peak of ester type compound C-O-C (1183.52cm
-1); Illustrate that described product is double pentaerythritol methacrylate.
The yield of described double pentaerythritol methacrylate is 74.8%.
Embodiment 5
Weighing 0.668g phosphotungstic acid and 0.167g p-methyl benzenesulfonic acid will both mix, and namely obtain the catalyst of described synthetic double pentaerythritol methacrylate.Described phosphotungstic acid molecular formula is H
3PO
4﹒ 12WO
3﹒ 3H
2O, the p-methyl benzenesulfonic acid molecular formula is CH
3C
6H
4SO
3H。
The application of described catalyst is as follows:
Add successively 5.088g bipentaerythrite, 9.1mL acrylic acid and 23mL toluene in reactor, add again 0.944g hydroquinones and the described catalyst of 0.835g after stirring, obtain mixture 1, under agitation add 1 to 115 ℃ of hot mixt, reaction 4h, reaction finishes, stop stirring, stopped heating is cooled to room temperature, obtains mixture 2; The sodium chloride solution 36mL that adds 105mL toluene and 20% in the mixture 2, extraction obtains oil reservoir, regulate the pH value of described oil reservoir with sodium hydroxide solution to neutral, wash oil reservoir with distilled water again, then after using anhydrous sodium sulfate drying 7h, obtain mixture 3, the outstanding toluene of removing in mixture 3 that steams of decompression; And the mixture 3 after outstanding steaming of reducing pressure crosses silicagel column and purifies, and obtains product, product carried out nucleus magnetic hydrogen spectrum detection, Mass Spectrometer Method, Fourier transform infrared spectrum (FT-IR) detected, and Analysis of test results is as follows:
Nucleus magnetic hydrogen spectrum
1H-NMR (CD
2Cl
2): 6.41 (6H, 6C=CH), 6.17 (6H, 6C=CH), 5.74 (6H, 6C=CH), 4.26 (12H, 6CH
2), 3.48 (4H, 2CH
2); Illustrate that described product is double pentaerythritol methacrylate.
Mass spectrum: can judge that primary product is double pentaerythritol methacrylate, the molecular weight M=578 of double pentaerythritol methacrylate, molecular weight in spectrogram [M+Na]=601.1885, [M+Na+H
2O]=619.2102, [M+Na+4H
2O]=673.2027, [M+Na+5H
2O]=691.2204, double pentaerythritol methacrylate accounts for 78% of product total mole number.Also contain a small amount of double pentaerythritol C5 methacrylate in product, the molecular weight M=524 of double pentaerythritol C5 methacrylate, [M+Na]=547.1739, double pentaerythritol C5 methacrylate accounts for 22% of product total mole number.
The Fourier transform infrared spectroscopic data
: 3500cm
-1The place is the stretching vibration peak of-OH; 1725.65cm
-1Stretching vibration peak for C=O; 1633.79cm
-1Stretching vibration peak for C=C; 1114.03cm
-1, 1184.72cm
-1Stretching vibration peak for C-O-C; 809.08cm
-1, 986.22cm
-1Out-of-plane bending deformation vibration peak for C-H; 1271.35cm
-1, 1407.62cm
-1Be in-plane bending deformation vibration peak; 2963.26cm
-1, 2903.52cm
-1For-CH
2Stretching vibration peak.Hence one can see that, and synthetic product has end alkene C-H flexural deformation vibration peak (809.08cm
-1), ester carbonyl group characteristic absorption peak (1725.65cm
-1) and the symmetrical antisymmetric stretching vibration absworption peak of ester type compound C-O-C (1184.72cm
-1); Illustrate that described product is double pentaerythritol methacrylate.
The yield of described double pentaerythritol methacrylate is 77.2%.
The present invention includes but be not limited to above embodiment, every any being equal to of carrying out under the principle of spirit of the present invention, replace or local improvement, all will be considered as within protection scope of the present invention.
Claims (3)
1. the catalyst of a synthetic double pentaerythritol methacrylate, it is characterized in that: described catalyst is composite catalyst, is comprised of phosphotungstic acid and p-methyl benzenesulfonic acid, wherein, the mass ratio of phosphotungstic acid and p-methyl benzenesulfonic acid is 1:2～6:1; Described phosphotungstic acid molecular formula is H
3PO
4﹒ 12WO
3﹒ xH
2O, x are 1～12 integer; The p-methyl benzenesulfonic acid molecular formula is CH
3C
6H
4SO
3H。
2. preparation method of the catalyst of synthetic double pentaerythritol methacrylate as claimed in claim 1, it is characterized in that: described method step is as follows:
Phosphotungstic acid and p-methyl benzenesulfonic acid are mixed in proportion, namely obtain the catalyst of described synthetic double pentaerythritol methacrylate.
3. application of the catalyst of synthetic double pentaerythritol methacrylate as claimed in claim 1, it is characterized in that: described application is as follows:
Add successively bipentaerythrite, acrylic acid and solvent in reactor, add again polymerization inhibitor and catalyst after stirring, obtain mixture 1, under agitation add 1 to 110 ℃～130 ℃ of hot mixts, reaction 2h～5h, reaction finishes, stop stirring, stopped heating is cooled to room temperature, obtains mixture 2; Add toluene and sodium chloride solution in mixture 2, extraction obtains oil reservoir, regulates the pH value of described oil reservoir to neutral, then washs oil reservoir with distilled water, after then using anhydrous sodium sulfate drying 6～8h, obtains mixture 3, the outstanding toluene of removing in mixture 3 that steams of decompression; And the mixture 3 silicagel column purification excessively after outstanding steaming of reducing pressure, namely obtain described double pentaerythritol methacrylate;
Described bipentaerythrite and acrylic acid molar ratio are 1:6.0～1:9.0;
Described catalyst is the catalyst of synthetic double pentaerythritol methacrylate of the present invention;
Described bipentaerythrite, acrylic acid, solvent, polymerization inhibitor and catalyst anabolic reaction liquid, take the oeverall quality of reactant liquor as 100%, wherein, the quality percentage composition of solvent is 40%～60%, the quality percentage composition of polymerization inhibitor is 2.0%～3.0%, and the quality percentage composition of catalyst is 1.0%～3.0%;
Described solvent is toluene, and polymerization inhibitor is hydroquinones;
The toluene quality that adds during extraction is 2.5 times of reactant liquor gross mass, and the quality of sodium chloride solution is 20% of reactant liquor gross mass, and its specification is that mass fraction is 20% sodium chloride solution;
When described silicagel column is purified, solvent used is that carrene and absolute ethyl alcohol volume ratio are the mixed liquor of 50:3.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105753694A (en) * | 2016-03-31 | 2016-07-13 | 江苏博砚电子科技有限公司 | Polycarboxyl functionalization acrylate for color resistor and preparation method thereof |
| WO2020021187A1 (en) | 2018-07-27 | 2020-01-30 | Bostik Sa | Method for preparing compounds with an alkoxysilyl group |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803852A (en) * | 2015-03-11 | 2015-07-29 | 张家港康得新光电材料有限公司 | Post-processing method of ultraviolet curing monomer for optical film |
| CN105753694A (en) * | 2016-03-31 | 2016-07-13 | 江苏博砚电子科技有限公司 | Polycarboxyl functionalization acrylate for color resistor and preparation method thereof |
| CN105753694B (en) * | 2016-03-31 | 2018-08-03 | 江苏博砚电子科技有限公司 | A kind of how carboxy-functionalized acrylate and preparation method thereof for chromatic photoresist |
| WO2020021187A1 (en) | 2018-07-27 | 2020-01-30 | Bostik Sa | Method for preparing compounds with an alkoxysilyl group |
| FR3084367A1 (en) | 2018-07-27 | 2020-01-31 | Bostik Sa | PROCESS FOR THE PREPARATION OF COMPOUNDS WITH AN ALKOXYSILYL GROUP |
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| CN103127955B (en) | 2015-04-22 |
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