CN101723831A - Preparation method of 3-hydroxypivalic acid neopentylglycol diacrylate - Google Patents
Preparation method of 3-hydroxypivalic acid neopentylglycol diacrylate Download PDFInfo
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- CN101723831A CN101723831A CN200910231676A CN200910231676A CN101723831A CN 101723831 A CN101723831 A CN 101723831A CN 200910231676 A CN200910231676 A CN 200910231676A CN 200910231676 A CN200910231676 A CN 200910231676A CN 101723831 A CN101723831 A CN 101723831A
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- neopentylglycol diacrylate
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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, relate in particular in a kind of preparation process waste water produce few, 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, be employed, as photo-cured coating, printing-ink, tackiness agent and matrix material etc. at numerous areas.Produce after this monomer method generally all is esterification,, and remove solvent, obtain product through washing, alkali neutralization.Specifically by hydroxypivalic acid neopentyl glycol and vinylformic acid, under catalyzer (for example organic sulfonic acid, inorganic heteropolyacid) and stopper (for example in MEHQ, phenol, Resorcinol, ferrous sulfate, copper sulfate, the gac one or more) effect, after esterification, wash with water and add in the alkali and excess acid, add alkali and extract stopper, remove institute's solubilizing agent in the reaction process (in benzene, toluene, normal hexane, hexanaphthene, the sherwood oil one or more) at last.Actual production process is fully carried out for making esterification, improves esterification efficient, and vinylformic acid is excessive usually, 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 producing has a large amount of waste water, and for example produce one ton of product and produce 0.8 ton of waste water of waste water approximately, not only not environmental protection of production process, and handle 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 reduce discharge of wastewater significantly, 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, adsorb in washing in the original technology of replacement, the alkali and extraction with resins exchange,, excessive propene acid, stopper etc. in the reaction product are adsorbed onto in the resin by resins exchange absorption, make and need not wash and the alkali neutralization, just can remove unreacted acrylic acid and stopper etc. in the product, reach and reduce the waste water generation significantly, overcome the deficiencies in the prior art, realize the object of the invention, realize cleaning, 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, remove solvent, it is characterized in that reaction product after the esterification is adsorbed to acid number through macroporous resin and/or ion exchange resin and meets the requirements, remove solvent.
Resins exchange absorption among the present invention, mainly be to remove unreacted reactant (for example vinylformic acid, stopper etc.) in the reaction product, test shows, polymeric adsorbent of the present invention can be macroporous resin and/or ion exchange resin, chemistry and physisorption by resin are adsorbed in the unreacted reactant in the reaction product in the resin.Resins exchange absorption can (for example≤5mgKOH/g), judge whether to stop absorption by detecting the product acid number.Resin absorption wherein more adopts two kinds of resin collocation to mix and uses, and has better removal effect.Adsorb saturated resin, carry out desorption, make resin obtain regeneration and return utilization again through common resin activation method (for example according to different resins, adopt Different Activation Methods, this is a prior art).Resin absorption, a kind of better is to carry out under 20-60 ℃ of temperature.
Preparation method of 3-hydroxypivalic acid neopentylglycol diacrylate of the present invention, with respect to prior art, remove unreacted reactant (acid number) in (reduction) reaction product by resins exchange absorption, do not wash with water with alkali and neutralize, production process does not have washes substantially and produces, and has reduced discharge of wastewater in the production process, and exchange resin absorption is saturated can reclaim and utilize after activated again, be a kind of energy-saving consumption-reducing environmental-protecting process, the feature of environmental protection is good.Secondly, do not wash with water, no product is wasted by water washing, has also improved the product recovery rate, can increase yield about 5%.
Below in conjunction with a specific embodiment; the present invention is further understood in exemplary illustration and help; but the embodiment detail only is for the present invention is described; do not represent the present invention to conceive whole technical schemes down; therefore should not be construed as the technical scheme qualification total to the present invention, some are In the view of the technician, and the unsubstantiality that does not depart from the present invention's design increases and/or change; for example simple the change or replacement of technical characterictic to have same or similar technique effect all belongs to protection domain of the present invention.
Embodiment
Comparative example:
(1) gets 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 and mix stirring, open steam valve and slowly heat, the control vapour pressure is about 0.5Mpa, be warmed up to 70-80 ℃ in 1 hour, and kept 30 minutes, control vapor pressure about 0.5Mpa, temperature of reaction 70-90 ℃, react that temperature rises to 105 ℃ after 4 hours, backflow 4-5 hour, reaction finished, the sampling censorship, when detection esterification acid number is the 20-50mgKOH/g left and right sides, show that reaction finishes.
(2) add 10wt% soda ash, the washing of 20wt% sodium-chlor three times in reactor, standing demix is got upper organic phase.
(3) open the vacuum unit, keep more than vacuum tightness-0.09Mpa, the control temperature of charge is sloughed solvent at 60-100 ℃, gets product through the cooling binder.Yield 85%.
Embodiment:
The same comparative example of step (1).
(2) material is in pump is squeezed into by 60wt% macroporous adsorbent resin and 40wt% Zeo-karb blended adsorption tower after the esterification, and the control flow velocity makes material slowly carry out depickling by ion exchange resin and handles.Temperature is controlled at 20-60 ℃, detects acid number≤5mgKOH/g, stops absorption.
(3) open the vacuum unit, keep more than vacuum tightness-0.09Mpa, the control temperature of charge is sloughed solvent at 60-100 ℃, gets product through the cooling binder.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 known technology commonly used in the prior art; and the mutual various combination between feature; the for example change of polymeric adsorbent kind; or the like unsubstantiality change; can be employed equally; can both realize and basic identical function of the foregoing description and effect, launch for example no longer one by one to describe in detail, all belong to this patent protection domain.
Claims (3)
1. preparation method of 3-hydroxypivalic acid neopentylglycol diacrylate, comprise hydroxypivalic acid neopentyl glycol and vinylformic acid catalytic esterification in solvent, disacidify, remove solvent, it is characterized in that reaction product after the esterification is adsorbed to acid number through macroporous resin and/or ion exchange resin and meets the requirements, remove solvent.
2. according to the described preparation method of 3-hydroxypivalic acid neopentylglycol diacrylate of claim 1, it is characterized in that resin absorption is to adopt macroporous resin and ion exchange resin collocation to mix to use.
3. according to claim 1 or 2 described preparation method of 3-hydroxypivalic acid neopentylglycol diacrylate, it is characterized in that resin absorption carries out under 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 true CN101723831A (en) | 2010-06-09 |
| CN101723831B CN101723831B (en) | 2014-02-19 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232497A (en) * | 2013-04-09 | 2013-08-07 | 浙江赞宇科技股份有限公司 | Alkyl glucoside preparation method |
| 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 |
| 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 |
Family Cites Families (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 |
| JPS51125479A (en) * | 1974-11-22 | 1976-11-01 | Ppg Industries Inc | Radiation curable composition containing organic silicon compound |
| 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
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232497A (en) * | 2013-04-09 | 2013-08-07 | 浙江赞宇科技股份有限公司 | Alkyl glucoside preparation method |
| 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 |
| 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 |
| 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 |
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| CN101723831B (en) | 2014-02-19 |
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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 |
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