CN102633635B - Clean production method of dipentaerythritol hexaacrylate - Google Patents
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Abstract
The invention belongs to the field of a photo-curing material and relates to a clean production method of dipentaerythritol hexaacrylate. The method comprises the following concrete steps: (1) carrying out esterification and reflux dehydration on dipentaerythritol, acrylic acid, a catalyst, a solvent, a polymerization inhibitor and an antioxidant; (2) adding caustic soda flakes and a little amount of water to neutralize; (3) adding a magnesium polysilicate adsorbent to absorb salt generated by neutralization; (4) dewatering and removing the solvent at reduced pressure; (5) carrying out filter pressing to filter out magnesium polysilicate and absorbed salt thereof; (6) adding alkaline Ca-bentonite and calcium oxide, destaining, and removing trace water and trace acid; (7) carrying out filter pressing; and (8) detecting a product index. The clean production method disclosed by the invention is the clean production method of dipentaerythritol hexaacrylate, with high yield, economic benefit and environmental benefit, so the pollution problem of organic waste water in the production process of dipentaerythritol hexaacrylate is fundamentally solved.
Description
Technical field
The invention belongs to photo-curing material field, relate to the clean preparation method of double pentaerythritol methacrylate.
Background technology
Along with developing rapidly and the strict restriction of legislations of environmental protection to solvent of science and technology, photocuring macromolecular material is more and more subject to people's attention.Photo-curing material have quick solidifying, energy consumption low, pollute less, the premium properties such as efficiency height, thereby be widely used in the fields such as coating, printing and electronic industry, development in recent years is rapid.Double pentaerythritol methacrylate (DPHA) is the novel photo-curing material of a class---six functionality photo-curing monomers, have that low stimulation, curing speed are fast, the premium properties such as high crosslink density, high rigidity, wear-resisting, scratch resistance, high transparent, being widely used in the field ， U.S., Japan, the countries in Europes such as light-curable ink, coating, tackiness agent is widely used.In recent years, along with the rise of UV-curing technology in China, novel photo-curing material is more and more wider as the raw material purposes of UV coating, ink, tackiness agent, and usage quantity is increasing year by year.
Yet existing acrylate production method normally adopts first esterification, then neutralizes, washes excessive vinylformic acid, then the traditional technology route of desolventizing.This production method exists three large defects:
1. used catalyst adopts the catalyzer such as sulfuric acid, tosic acid, methanesulfonic mostly, conventionally adopts the method for neutralization, washing, layering to remove, and can produce a large amount of industrial organic waste waters, and water body environment is polluted;
2. the vinylformic acid of excessive in reaction process (8%-15%) is water-washed away entirely, conventionally adopt the method for neutralization, washing, layering to remove, the problems such as meeting produces the industrial organic waste water of a large amount of high COD, and difficult and processing costs is high make cost of goods manifactured higher;
When 3. neutralizing, washing, can take away part propylene acid esters product, yield is declined, cost rises.
According to the requirement of cleaner Production in Chemical Industry, the conventional production methods of acrylate must be improved.
Summary of the invention
Technical problem to be solved by this invention is the above-mentioned deficiency for prior art, and the clean preparation method of a kind of double pentaerythritol methacrylate (DPHA) is provided.
A clean preparation method for double pentaerythritol methacrylate (DPHA), this production method comprises following steps:
(1) esterification: by dipentaerythritol: vinylformic acid: catalyzer: solvent: stopper: the proportioning of oxidation inhibitor=1 (mol): 6-9 (mol): 5-150 (g): 60-1400 (g): 0.3-15 (g): 0.2-15 (g) drops into whole raw materials, to the mixed air that passes into continuously pressurized air or air and nitrogen in still, be warming up to 70-120 ℃ and start reflux dewatering, when reflux dewatering is to anhydrous while going out, reaction finishes, detect acid number, and be cooled to≤40 ℃;
(2) neutralization: add sheet alkali and water to neutralize;
(3) absorption: the salt that adds multi-silicate magnesium sorbent material absorption neutralization to generate;
(4) dehydration, precipitation: underpressure distillation dehydration, desolventizing, and recycle-water and solvent; The water reclaiming can be directly used while once neutralizing upper without any need for processing; Institute's recovered solvent can directly be used when upper once esterification;
(5) filter: press filtration, filters out the salt of multi-silicate magnesium and absorption thereof;
(6) decolouring: add alkaline calcium bentonite, calcium oxide, decolour, take off minor amount of water, de-Determining Micro Acid;
(7) filter: press filtration, filters out alkaline calcium bentonite, calcium oxide;
(8) product index detects: outward appearance: limpid hyalomucoid, ester content >=98%, acid number≤1mgKOH, colourity≤50APHA, water ratio≤0.2%.
In wherein said esterification according to dipentaerythritol: vinylformic acid: catalyzer: solvent: stopper: the proportioning of oxidation inhibitor=1 (mol): 6-8 (mol): 10-150 (g): 160-1100 (g): 3.0-15 (g): 0.5-15 (g) drops into whole raw materials; Preferably according to dipentaerythritol: vinylformic acid: catalyzer: solvent: stopper: the proportioning of oxidation inhibitor=1 (mol): 6.5-7.7 (mol): 11-130 (g): 165-1035 (g): 3.0-14 (g): 0.8-13 (g) drops into whole raw materials.
Described catalyzer is wherein a kind of of tosic acid, Phenylsulfonic acid, methanesulfonic, or the arbitrary proportion miscellany of two kinds, or the arbitrary proportion miscellany of three kinds.
Described esterification solvent used is one or both in normal hexane, normal heptane, benzene, toluene, hexanaphthene, methylcyclohexane, ethyl cyclopentane, or two or more miscellanys; Preferably one or both in toluene, hexanaphthene, methylcyclohexane, or two or more miscellanys.
Described esterification stopper used is MEHQ.
Described esterification oxidation inhibitor used is the miscellany of one or both arbitrary proportions in Hypophosporous Acid, 50, sodium hypophosphite.
In described neutralization procedure, add the sheet alkali of the 1%～3wt% that accounts for described each raw materials quality summation of esterification and the water of 2%～10wt% to neutralize.
The salt that adds the multi-silicate magnesium absorption neutralization procedure generation of the 0.1%～1.0wt% that accounts for each raw materials quality summation of esterification in described adsorption step.Described multi-silicate magnesium chemical name is synthetic magnesium silicate.Molecular formula: 2MgO6SiO2nH2O (n=0-6), for all there are production and selling in ，Ru Wuhan, commercially available prod East China Chemical Co., Ltd., Shangyu Jie Hua Chemical Co., Ltd. etc.
The amount that adds alkaline calcium bentonite and calcium oxide in described decolouring step be each raw materials quality summation of esterification 1%～6wt%,, wherein the mass ratio of alkaline calcium bentonite and calcium oxide is 1～3: 1.
Double pentaerythritol methacrylate (DPHA) product of preparing according to the clean preparation method of described double pentaerythritol methacrylate (DPHA).
DPHA reaction equation:
Beneficial effect of the present invention:
Inventive point of the present invention is mainly reflected in the improvement of the resulting double pentaerythritol methacrylate of esterification (DPHA) work in-process post-treating method.This production method does not adopt traditional washing, delaminating process, the water that neutralization adds is reusable after underpressure distillation is reclaimed, and without sewage discharge, does not need to invest sewage disposal device, there is no high cost of sewage disposal, is the clean preparation method of green, environmental protection, low-carbon (LC).
Key of the present invention has also been to select three kinds of effective sorbent materials---multi-silicate magnesium, alkaline calcium bentonite, calcium oxide.Multi-silicate magnesium sorbent material, outward appearance is a kind of spherical surface body particle or powder of white cellular structure, it belongs to amphoteric substance, as sorbent material, shows good absorption and decoloration performance; Adsorber acid or alkali and potassium, sodium ion from organic-matter chemical product, and play filtrating aid function, adsorption moisture from air.
Alkaline calcium bentonite, is a kind of brand-new layer mineral material, due to its special anionresin performance, has wide application and development prospect, and in edible oil field, existing people studies and uses that alkaline calcium bentonite decolours, depickling, comes unstuck.Calcium oxide can act synergistically with alkaline calcium bentonite, reaches the effect of better decolouring, de-minor amount of water, de-Determining Micro Acid.
The catalyzer that the present invention uses when esterification is wherein a kind of of tosic acid, Phenylsulfonic acid, methanesulfonic, or the arbitrary proportion of two is mixed, or the arbitrary proportion of three is mixed.These several catalyzer can not cause system color and luster to be deepened, and under the existence of appropriate oxidation inhibitor, double pentaerythritol methacrylate (DPHA) product does not need washing, after three kinds of sorbent material decolourings, just can reach good colourity (≤50APHA).
Double pentaerythritol methacrylate (DPHA) is six functional group's acrylate monomers, in its building-up process, the kind of catalyzer and consumption, the kind of stopper and consumption, these technological parameters of feed proportioning are very big on the quality of product and productive rate impact, the present invention is optimized the processing parameter of esterification, from source, sets about, and has improved the yield of double pentaerythritol methacrylate (DPHA).
In sum, it is high that double pentaerythritol methacrylate of the present invention (DPHA) clean preparation method has yield, the advantage of economic benefit, environmental benefit excellence, when guaranteeing product yield and quality, the organic waste water pollution problem that fundamentally solves double pentaerythritol methacrylate (DPHA) production process.The present invention can overcome the industrial organic waste water that can produce a large amount of high COD in traditional post-treating method, difficult and processing costs is high, the deficiency easily water body environment being polluted, the work in-process of esterification make double pentaerythritol methacrylate (DPHA) finished product through neutralization, absorption, dehydration, filtration, decolouring, filtration step, the water that neutralization adds is reusable after underpressure distillation is reclaimed, without sewage discharge, do not need to invest sewage disposal device, there is no high cost of sewage disposal, is the clean preparation method of green, environmental protection, low-carbon (LC).
Embodiment
Embodiment 1:
In 3000L reactor, drop into 500 kilograms of toluene, 290 kilograms of hexanaphthenes, 348.3 kilograms of dipentaerythritol, 651.7 kilograms, vinylformic acid, 8 kilograms of MEHQ, 4 kilograms of Hypophosporous Acid, 50,55 kilograms of tosic acid; Open stirring, by sparger at the bottom of still, in still, pass into continuously pressurized air, be warming up to 85-95 ℃ and start reflux dewatering, esterification 9-10 hour, still temperature 95-105 ℃, when reflux dewatering is to anhydrous while going out, detect acid number 30～60mgKOH/g, reaction finishes, and is cooled to 40 ℃; Add 25 kilograms of sheet alkali and 60 kg of water, stir 30 minutes; Add 6 kilograms of multi-silicate magnesium, whip attachment 30 minutes; Then more than vacuum tightness-0.098MPa, 50-95 ℃ of underpressure distillation water outlet and solvent, the water reclaiming and solvent are after layering, and water can be directly used while once neutralizing upper without any need for processing, and solvent can directly be used when upper once esterification; Distillation finishes, press filtration; Add again 50 kilograms of alkaline calcium bentonites and 20 jin of calcium oxide, stir 30 minutes, then the press filtration that circulates, until product clear obtains double pentaerythritol methacrylate (DPHA) product.Product index detected result: outward appearance is limpid transparent, ester content 98.8%, acid number 0.15mgKOH, colourity 40APHA, water ratio 0.06%, 25 ℃ of viscosity 7500cps@.780.3 kilograms of dischargings, 792.59 kilograms of theoretical dischargings, yield is 98.45%.
Embodiment 2:
In 3000L reactor, drop into 162 kilograms of methylcyclopentanes, 198 kilograms of toluene, 550 kilograms of dipentaerythritol, 1185 kilograms, vinylformic acid, 7.2 kilograms of MEHQ, 1.8 kilograms of Hypophosporous Acid, 50,25.6 kilograms of methanesulfonics; Open stirring, by sparger at the bottom of still, in still, pass into continuously pressurized air, be warming up to 85-95 ℃ and start reflux dewatering, esterification 9-10 hour, still temperature 95-105 ℃, when reflux dewatering is to anhydrous while going out, detect acid number 30～60mgKOH/g, reaction finishes, and is cooled to 40 ℃; Add 43 kilograms of sheet alkali and 108 kg of water, stir 30 minutes; Add 17.3 kilograms of multi-silicate magnesium, whip attachment 30 minutes; Then more than vacuum tightness-0.098MPa, 50-95 ℃ of underpressure distillation water outlet and solvent, the water reclaiming and solvent are after layering, and water can be directly used while once neutralizing upper without any need for processing, and solvent can directly be used when upper once esterification; Distillation finishes, press filtration; Add again 65 kilograms of alkaline calcium bentonites and 65 jin of calcium oxide, stir 30 minutes, then the press filtration of entering to circulate, until product clear obtains double pentaerythritol methacrylate (DPHA) product.Product index detected result: outward appearance is limpid transparent, ester content 98.2%, acid number 0.17mgKOH, colourity 30APHA, water ratio 0.06%, 25 ℃ of viscosity 7500cps@.1230.7 kilograms of dischargings, 1251.57 kilograms of theoretical dischargings, yield is 98.33%.
Embodiment 3:
In 3000L reactor, drop into 630 kilograms of hexanaphthenes, 570 kilograms of methylcyclohexanes, 295.5 kilograms of dipentaerythritol, 603 kilograms, vinylformic acid, 15 kilograms of MEHQ, 15 kilograms of Hypophosporous Acid, 50,150 kilograms of Phenylsulfonic acids; Open stirring, by sparger at the bottom of still, in still, pass into continuously pressurized air, be warming up to 80-85 ℃ and start reflux dewatering, esterification 10-12 hour, still temperature 85-92 ℃, when reflux dewatering is to anhydrous while going out, detect acid number 30～60mgKOH/g, reaction finishes, and is cooled to 40 ℃; Add 68 kilograms of sheet alkali and 205 kg of water, stir 30 minutes; Add 6.8 kilograms of multi-silicate magnesium, whip attachment 30 minutes; Then more than vacuum tightness-0.098MPa, 50-95 ℃ of underpressure distillation water outlet and solvent; The water reclaiming and solvent are after layering, and water can be directly used while once neutralizing upper without any need for processing, and solvent can directly be used when upper once esterification; Distillation finishes, press filtration; Add again 85.5 kilograms of alkaline calcium bentonites and 28.5 kilograms of calcium oxide, stir 30 minutes, then the press filtration that circulates, until product clear obtains double pentaerythritol methacrylate (DPHA) product.Product index detected result: outward appearance is limpid transparent, ester content 98.8%, acid number 0.16mgKOH, colourity 30APHA, water ratio 0.06%, 25 ℃ of viscosity 7500cps@.660.8 kilograms of dischargings, 672.44 kilograms of theoretical dischargings, yield is 98.27%.
Comparative example:
In 3000L reactor, drop into 1000 kilograms of toluene, 329 kilograms of dipentaerythritol, 671 kilograms, vinylformic acid, 1 kilogram of MEHQ, 2 kilograms of cupric chlorides, 4 kilograms of sodium hypophosphites, 50 kilograms of tosic acid; Open stirring, by sparger at the bottom of still, in still, pass into continuously pressurized air, be warming up to 98-110 ℃ and start reflux dewatering, esterification 6-8 hour, still temperature 110-120 ℃, when reflux dewatering while going out, detects acid number 30～60mgKOH/g to anhydrous, reaction finishes, and is cooled to 60 ℃ and neutralizes washing: 1. add salt solution stirring, the static layering of 200 kilogram 5%, divide to fall lower layer of water; 2. add 200 kilograms of saturated aqueous sodium carbonate stirrings, neutralization, static layering, divide to fall lower layer of water, 3. add salt solution stirring, the static layering of 200 kilogram 5%, divide to fall lower layer of water, 4. add salt solution stirring, the static layering of 200 kilogram 5%, divide to fall lower layer of water; Wash completely, more than vacuum tightness-0.098MPa, 50-98 ℃ of underpressure distillation goes out solvent, and distillation finishes; Press filtration to product clear obtains double pentaerythritol methacrylate (DPHA) product.Product index detected result: outward appearance is limpid transparent, ester content 98.5%, acid number 0.15mgKOH, colourity 50APHA, water ratio 0.1%, 25 ℃ of viscosity 8200cps@.692.8 kilograms of dischargings, 748.67 kilograms of theoretical dischargings, yield is 92.54%.
Ester content in above-described embodiment, acid number, colourity, moisture, the detection method of viscosity is shown in that Chinese sensitometry can radiation curing Professional Committee industry standard HB/FG02-2009.
Claims (1)
1. a clean preparation method for double pentaerythritol methacrylate, is characterized in that this production method comprises following steps:
(1) esterification: by dipentaerythritol: vinylformic acid: catalyzer: solvent: stopper: the proportioning of oxidation inhibitor=1 (mol): 6-9 (mol): 5-150 (g): 60-1400 (g): 0.3-15 (g): 0.2-15 (g) drops into whole raw materials, to the mixed air that passes into continuously pressurized air or air and nitrogen in still, be warming up to 70-120 ℃ and start esterification reflux dewatering, when reflux dewatering is to anhydrous while going out, reaction finishes, detect acid number, and be cooled to≤40 ℃;
(2) neutralization: add sheet alkali and water to neutralize;
(3) absorption: the salt that adds multi-silicate magnesium sorbent material absorption neutralization to generate;
Dehydration, precipitation: underpressure distillation dehydration, desolventizing, and recycle-water and solvent;
(5) filter: press filtration, filters out the salt of multi-silicate magnesium and absorption thereof;
(6) decolouring: add alkaline calcium bentonite, calcium oxide, decolour, take off minor amount of water, de-Determining Micro Acid;
(7) filter: press filtration, filters out alkaline calcium bentonite, calcium oxide;
(8) product index detects: outward appearance: limpid hyalomucoid, ester content >=98%, acid number≤1mgKOH, colourity≤50APHA, water ratio≤0.2%;
In described neutralization procedure, add the sheet alkali of the 1% ~ 3wt% that accounts for described each raw materials quality summation of esterification and the water of 2% ~ 10wt% to neutralize;
The salt that adds the multi-silicate magnesium absorption neutralization procedure generation of the 0.1% ~ 1.0wt% that accounts for each raw materials quality summation of esterification in described adsorption step;
The amount that adds alkaline calcium bentonite and calcium oxide in described decolouring step be each raw materials quality summation of esterification 1% ~ 6wt%,, wherein the mass ratio of alkaline calcium bentonite and calcium oxide is 1 ~ 3:1.
2, the clean preparation method of double pentaerythritol methacrylate according to claim 1, is characterized in that in described esterification according to dipentaerythritol: vinylformic acid: catalyzer: solvent: stopper: the proportioning of oxidation inhibitor=1 (mol): 6-8 (mol): 10-150 (g): 160-1100 (g): 3.0-15 (g): 0.5-15 (g) drops into whole raw materials.
3, the clean preparation method of double pentaerythritol methacrylate according to claim 1 and 2, it is characterized in that described catalyzer is wherein a kind of of tosic acid, Phenylsulfonic acid, methanesulfonic, or the arbitrary proportion mixture of two kinds, or the arbitrary proportion mixture of three kinds.
4, the clean preparation method of double pentaerythritol methacrylate according to claim 1 and 2, it is characterized in that described esterification solvent used is one or both in normal hexane, normal heptane, benzene, toluene, hexanaphthene, methylcyclohexane, ethyl cyclopentane, or two or more mixtures.
5, the clean preparation method of double pentaerythritol methacrylate according to claim 1 and 2, is characterized in that described esterification stopper used is MEHQ.
6, the clean preparation method of double pentaerythritol methacrylate according to claim 1 and 2, is characterized in that described esterification oxidation inhibitor used is the mixture of one or both arbitrary proportions in Hypophosporous Acid, 50, sodium hypophosphite.
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| CN103127955B (en) * | 2013-03-11 | 2015-04-22 | 北京理工大学 | Catalyst for synthesizing dipentaerythritol hexaacrylate, preparation method and application thereof |
| US9505880B2 (en) | 2013-06-04 | 2016-11-29 | Corning Incorporated | Synthesis of polyfunctional polyol acrylates |
| CN103819337B (en) * | 2013-09-29 | 2016-01-20 | 安庆飞凯高分子材料有限公司 | A kind of trifunctional pentaerythritol acrylate preparation method |
| CN107428665B (en) * | 2015-04-10 | 2021-10-15 | 东亚合成株式会社 | Method for producing (meth) acrylic ester |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007169193A (en) * | 2005-12-21 | 2007-07-05 | Osaka Organic Chem Ind Ltd | Method for producing (meth)acrylate |
| CN101054773A (en) * | 2007-04-24 | 2007-10-17 | 天津工大纺织助剂有限公司 | Fortifying fiber auxiliary agent and manufacturing method thereof |
| CN101462953A (en) * | 2007-12-17 | 2009-06-24 | 天津市化学试剂研究所 | Method for preparing pentaerythritol triacrylate |
-
2012
- 2012-03-31 CN CN201210103830.8A patent/CN102633635B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007169193A (en) * | 2005-12-21 | 2007-07-05 | Osaka Organic Chem Ind Ltd | Method for producing (meth)acrylate |
| CN101054773A (en) * | 2007-04-24 | 2007-10-17 | 天津工大纺织助剂有限公司 | Fortifying fiber auxiliary agent and manufacturing method thereof |
| CN101462953A (en) * | 2007-12-17 | 2009-06-24 | 天津市化学试剂研究所 | Method for preparing pentaerythritol triacrylate |
Non-Patent Citations (6)
| Title |
|---|
| 低色度双季戊四醇六丙烯酸酯的合成;贺楚华等;《精细与专用化学品》;20101130;第18卷(第11期);"1.2实验步骤"和"2.2催化剂影响" * |
| 双季戊四醇六丙烯酸酯的合成;贺楚华等;《应用化工》;20030831;第32卷(第4期);第40页"1. 2 实验方法" * |
| 双季戊四醇六丙烯酸酯的合成;贺楚华等;《应用化工》;20030831;第32卷(第4期);第40页"1. 2 实验方法"及表1 * |
| 贺楚华等.低色度双季戊四醇六丙烯酸酯的合成.《精细与专用化学品》.2010,第18卷(第11期),"1.2实验步骤"和"2.2催化剂影响". |
| 贺楚华等.双季戊四醇六丙烯酸酯的合成.《应用化工》.2003,第32卷(第4期),第40页"1. 2 实验方法". |
| 贺楚华等.双季戊四醇六丙烯酸酯的合成.《应用化工》.2003,第32卷(第4期),第40页"1. 2 实验方法"及表1. |
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