CN101723831B - Preparation method of hydroxypivalic acid neopentylglycol diacrylate - Google Patents
Preparation method of hydroxypivalic acid neopentylglycol diacrylate Download PDFInfo
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- CN101723831B CN101723831B CN200910231676.0A CN200910231676A CN101723831B CN 101723831 B CN101723831 B CN 101723831B CN 200910231676 A CN200910231676 A CN 200910231676A CN 101723831 B CN101723831 B CN 101723831B
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Abstract
The invention relates to an improvement of a preparation method of 3-hydroxypivalic acid neopentylglycol diacrylate, which is characterized by comprising the following steps of: absorbing reaction products of esterification reaction by macroporous resin and/or ion exchange resin till an acid value accords with requirements; and depriving a solvent. Compared with the prior art, the invention deprives (reduces) unreacted reactants (the acid value) of the reaction products through resin exchange absorption without washing, neutralizing by alkali and generating waste washing water basically in the production process, reduces the waste water discharge in the production process, recovers the exchange resin and reuse by activating the exchange resin after the exchange resin is absorbed to be saturated, is an energy-saving consumption-reducing environmental-friendly new process, has good environmental protection without washing and waste products generated due to the washing, also increases the yield of products and enhances the yield coefficient by 5 percent.
Description
Technical field
The present invention is the improvement to 3-hydroxypivalic acid neopentylglycol diacrylate (HPHPDA) preparation method, relates in particular to waste water in a kind of preparation process and produces less, the preparation method that yield is high.
Background technology
3-hydroxypivalic acid neopentylglycol diacrylate, is a kind of novel trifunctional acrylate monomer, and its cured film has stronger solvent resistance, low-shrinkage, be a kind of high performance reactive thinner, at numerous areas, be employed, as photo-cured coating, printing-ink, tackiness agent and matrix material etc.Produce after this monomer method is generally all esterification, through washing, alkali neutralization, and desolvation, obtain product.Specifically by hydroxypivalic acid neopentyl glycol and vinylformic acid, for example, for example, under catalyzer (organic sulfonic acid, inorganic heteropolyacid) and stopper (one or more in MEHQ, phenol, Resorcinol, ferrous sulfate, copper sulfate, gac) effect, after esterification, wash with water and add in alkali and excess acid, add alkali and extract stopper, finally remove institute's solubilizing agent in reaction process (one or more in benzene, toluene, normal hexane, hexanaphthene, sherwood oil).Actual production process, for esterification is fully carried out, improves esterification efficiency, and vinylformic acid is excessive conventionally, and excessive unreacted acrylic acid and stopper must be removed from reaction product.The unique employing washing of prior art, alkali neutralization and extraction process, therefore produce and have a large amount of waste water, and for example produce one ton of product and approximately produce 0.8 ton of waste water of waste water, not only not environmental protection of production process, and process these waste water, also increased processing cost.In addition, massive laundering disacidify process, also easily causes the loss of portioned product, causes product yield to reduce.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned prior art, and provide a kind of and can significantly reduce discharge of wastewater, and the preparation method of 3-hydroxypivalic acid neopentylglycol diacrylate that improves recovery rate.
The object of the invention realizes, after main improvement is esterification, by resins exchange, adsorb in washing in the original technique of replacement, alkali and extraction, by resins exchange, adsorb, excessive propene acid, stopper etc. in reaction product are adsorbed onto in resin, make not need washing and alkali neutralization, just can remove unreacted acrylic acid and stopper etc. in product, reach and significantly reduce waste water generation, overcome the deficiencies in the prior art, realize the object of the invention, realize clean, environmental protection production.Specifically, preparation method of 3-hydroxypivalic acid neopentylglycol diacrylate of the present invention, comprise hydroxypivalic acid neopentyl glycol and vinylformic acid catalytic esterification in solvent, disacidify, desolvation, it is characterized in that reaction product after esterification is adsorbed to acid number through macroporous resin and/or ion exchange resin and meets the requirements, carry out desolvation.
Resins exchange absorption in the present invention, mainly to remove unreacted reactant (such as vinylformic acid, stopper etc.) in reaction product, test shows, polymeric adsorbent of the present invention can be macroporous resin and/or ion exchange resin, chemistry and physisorption by resin, be adsorbed in the unreacted reactant in reaction product in resin.Resins exchange absorption, can for example,, by detecting product acid number (≤5mgKOH/g), judge whether to stop absorption.Resin absorption wherein more adopts two kinds of resin collocation to mix and uses, and has better removal effect.Adsorb saturated resin, through common resin activation method (for example, according to different resins, adopt Different Activation Methods, this is prior art), carry out desorption, make resin obtain regeneration and return to recycling.Resin absorption, a kind of is better to carry out at 20-60 ℃ of temperature.
Preparation method of 3-hydroxypivalic acid neopentylglycol diacrylate of the present invention, with respect to prior art, by resins exchange, adsorb and remove unreacted reactant (acid number) in (reduction) reaction product, do not wash with water with alkali and neutralize, production process produces without washes substantially, has reduced discharge of wastewater in production process, and exchange resin absorption is saturated can reclaim activated rear recycling, be a kind of energy-saving consumption-reducing environmental-protecting process, the feature of environmental protection is good.Secondly, do not wash with water, without product, by water washing, wasted, also improved product recovery rate, can increase yield 5% left and right.
Below in conjunction with a specific embodiment; the present invention is further understood in exemplary illustration and help; but embodiment detail is only for the present invention is described; do not represent that the present invention conceives lower whole technical scheme; therefore should not be construed as the total technical scheme of the present invention is limited, some are In the view of technician, and the unsubstantiality that does not depart from the present invention's design increases and/or changes; for example, to there is simple the change or replacement of technical characterictic of same or similar technique effect, all belong to protection domain of the present invention.
Embodiment
Comparative example:
(1) get hydroxypivalic acid neopentyl glycol 20wt%, vinylformic acid 40wt%, toluene sulfonic acide catalyzer 2wt%, MEHQ 400ppm, phenol 100ppm, Resorcinol 10ppm, ferrous sulfate 200ppm, copper sulfate 300ppm, gac 400ppm, hexanaphthene 30wt%.Drop into reactor mix and blend, open steam valve and slowly heat, control vapour pressure in 0.5Mpa left and right, in 1 hour, be warmed up to 70-80 ℃, and keep 30 minutes, control vapor pressure at 0.5Mpa left and right, temperature of reaction 70-90 ℃, react temperature after 4 hours and rise to 105 ℃, backflow 4-5 hour, reaction finished, sampling censorship, when detection esterification acid number is 20-50mgKOH/g left and right, show that reaction finishes.
(2) in reactor, add 10wt% soda ash, the washing of 20wt% sodium-chlor three times, stratification, gets upper organic phase.
(3) open vacuum unit, more than keeping vacuum tightness-0.09Mpa, control temperature of charge at 60-100 ℃, slough solvent, through cooling binder, get product.Yield 85%.
Embodiment:
The same comparative example of step (1).
(2) after esterification, material is in pump is squeezed into the adsorption tower being mixed by 60wt% macroporous adsorbent resin and 40wt% Zeo-karb, and coutroi velocity makes material slowly by ion exchange resin, carry out depickling processing.Temperature is controlled at 20-60 ℃, detects acid number≤5mgKOH/g, stops absorption.
(3) open vacuum unit, more than keeping vacuum tightness-0.09Mpa, control temperature of charge at 60-100 ℃, slough solvent, through cooling binder, get product.Yield 90%
To those skilled in the art, under this patent design and specific embodiment enlightenment, some distortion that can directly derive or associate from this patent disclosure and general knowledge, those of ordinary skills will recognize also can adopt additive method, or the substituting of conventional known technology in prior art, and the mutual various combination between feature, the for example change of polymeric adsorbent kind, etc. unsubstantiality change, can be employed equally, can realize and the basic identical function of above-described embodiment and effect, launch for example no longer one by one to describe in detail, all belong to this patent protection domain.
Claims (3)
1. hydroxypivalic acid DOPCP diacrylate preparation method, comprise hydroxypivalic acid DOPCP and vinylformic acid catalytic esterification in solvent, disacidify, desolvation, it is characterized in that reaction product after esterification is adsorbed to acid number through macroporous resin and/or ion exchange resin and meets the requirements, carry out desolvation.
2. hydroxypivalic acid DOPCP diacrylate preparation method according to claim 1, is characterized in that resin absorption is to adopt macroporous resin and ion exchange resin collocation to mix to use.
3. according to hydroxypivalic acid DOPCP diacrylate preparation method described in claim 1 or 2, it is characterized in that resin absorption carries out at 20-60 ℃ of temperature.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910231676.0A CN101723831B (en) | 2009-12-14 | 2009-12-14 | Preparation method of hydroxypivalic acid neopentylglycol diacrylate |
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| CN200910231676.0A CN101723831B (en) | 2009-12-14 | 2009-12-14 | Preparation method of hydroxypivalic acid neopentylglycol diacrylate |
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| CN101723831A CN101723831A (en) | 2010-06-09 |
| CN101723831B true CN101723831B (en) | 2014-02-19 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103232497B (en) * | 2013-04-09 | 2015-11-18 | 浙江赞宇科技股份有限公司 | A kind of preparation method of alkyl glycoside |
| CN106748762A (en) * | 2016-11-15 | 2017-05-31 | 惠州市长润发涂料有限公司 | A kind of preparation method of propylene glycol diacrylate |
| CN106748761A (en) * | 2016-11-15 | 2017-05-31 | 惠州市长润发涂料有限公司 | A kind of preparation method of trimethylolpropane trimethacrylate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3645984A (en) * | 1969-04-30 | 1972-02-29 | Ppg Industries Inc | Novel acrylic monomers their preparation and treatment |
| US4064286A (en) * | 1974-11-22 | 1977-12-20 | Ppg Industries, Inc. | Radiation curable compositions containing organosilicon compounds |
| US4187382A (en) * | 1976-12-28 | 1980-02-05 | Union Carbide Corporation | Process for producing low color residue acrylate ester monomers |
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2009
- 2009-12-14 CN CN200910231676.0A patent/CN101723831B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3645984A (en) * | 1969-04-30 | 1972-02-29 | Ppg Industries Inc | Novel acrylic monomers their preparation and treatment |
| US4064286A (en) * | 1974-11-22 | 1977-12-20 | Ppg Industries, Inc. | Radiation curable compositions containing organosilicon compounds |
| US4187382A (en) * | 1976-12-28 | 1980-02-05 | Union Carbide Corporation | Process for producing low color residue acrylate ester monomers |
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Denomination of invention: Preparation method of 3-hydroxypivalic acid neopentylglycol diacrylate Effective date of registration: 20160719 Granted publication date: 20140219 Pledgee: Fenghui Leasing Co. Ltd. Pledgor: Jiangsu Sanmu Chemical Industry Co., Ltd. Registration number: 2016990000610 |
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Date of cancellation: 20190923 Granted publication date: 20140219 Pledgee: Fenghui Leasing Co. Ltd. Pledgor: Jiangsu Sanmu Chemical Industry Co., Ltd. Registration number: 2016990000610 |