CN102718732B - Method for purifying bisphenol A diglycidyl ether - Google Patents
Method for purifying bisphenol A diglycidyl ether Download PDFInfo
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Abstract
The invention discloses a method for purifying bisphenol A diglycidyl ether, and the method is characterized by comprising the following steps of: adding 100 parts by weight of liquid bisphenol A type epoxy resin and 6-16 parts by weight of selective auxiliary agent into a reactor (1), heating up to 80-90 DEG C while stirring, carrying out heat preservation for 30-60 minutes, adding 500-950 parts by weight of solvent I, heating the material up to 45-75 DEG C within 30-80 minutes, carrying out heat preservation for 60-80 minutes and standing still; separating upper-layer liquid A and lower-layer liquid B in the reactor (1) and respectively putting the upper-layer liquid A and the lower-layer liquid B into a reactor (2) and a reactor (3); distilling the upper-layer liquid A in the reactor (2) at 65-95 DEG C to obtain 70-90% of solvent I, and then carrying out reduced pressure distillation, wherein the residue in the reactor (2) is the prepared bisphenol A diglycidyl ether; and finally, further recovering the selective auxiliary agent. The method is easy to operate, the solvent, the selective auxiliary agent and the like in the system can be recycled, and the yield and purity of the product are high.
Description
Technical field
The invention belongs to the separation of organic epoxy compounds, relate to a kind of method of utilizing similar close principle separating-purifying bisphenol A diglycidyl ether.Be specially adapted to separating-purifying bisphenol A diglycidyl ether from bisphenol A type epoxy resin.
Background technology
Bisphenol A type epoxy resin is generally the aggregate consisting of different polymerization degree " n " value, and the polymerization degree " n " value is different causes epoxy resin to have different forms and characteristic.High purity low-viscosity bisphenol A type epoxy resin has the characteristic that common bisphenol A type epoxy resin does not have, its main ingredient is the bisphenol A diglycidyl ether of " n=0 ", (mass percentage content >=90% when this component concentration is very high in resin, be that purity is high) present low viscosity characteristics, viscosity in the time of 25 ℃ is 4000～7000mPa.s only, be only 1/3～1/2 of ordinary epoxy resin (E-51) viscosity, at aspects such as the high performance filament wound composite of preparation and high voltage withstanding solvent-free insulated impregnating resins, need not add and easily cause the thinner of degradation just can meet the demands, because purity is high, the foreign matter contents such as the interior hydroxyl of molecule and hydrolyzable chlorine are low simultaneously, and epoxy group content is high, it is coordinated because hydroxy radical content in molecule is low with acid anhydrides after, have the longer safe-use period, the large-size machine insulated impregnating resin longer to the requirement in enormous quantities usage period brings great convenience.Along with low " carbon " economic arrival, the environmental consciousness that economizes on resources, reduces discharge is rooted in the hearts of the people gradually.Therefore, pure epoxy acid anhydrides type vacuum pressure impregnation (VPI) resin that adopts high purity low viscosity epoxy resin to prepare is favored gradually, has the characteristic of the non-volatile component of low-carbon environment-friendly, at motor and field of electrical equipment, is well worth doing.On the other hand, because low viscosity epoxy resin purity is high, narrow molecular weight distribution, thereby can meet the high special requirement of many performance requriementss, as the direct material of electric casting, medium-to-high grade sealing resin for photodiode (LED), dipping, the purposes such as bonding and can become the ideal basic resin that synthesizes high molecular expoxy resin by scorification.
In prior art, all there is many deficiencies in the method for preparation high purity low viscosity epoxy resin (bisphenol A type epoxy resin that refers to mass percentage content>=90% of bisphenol A diglycidyl ether in bisphenol A type epoxy resin): the research method of bibliographical information comprises: (1) solvent extration: generally adopt mixed solvent to be difficult for recycle and temperature influence is large, efficiency of selection is low; (2) recrystallization method: exist crystallisation process length to need the deficiency of low temperature; (3) short-path distillation technology: though realized the industrial production of purifying bisphenol-A diglycidylether, because 200 ℃ of left and right of needs high temperature, high vacuum (approach pressure 0～10
-5pa), facility investment is very high.Therefore, develop a kind of preparation method of economic and practical purifying bisphenol-A diglycidylether especially aobvious important.
Summary of the invention
Object of the present invention is intended to overcome above-mentioned deficiency of the prior art, provides that a kind of technique is simple, the method for purification of the bisphenol A diglycidyl ether of good separation.
Theoretical basis of the present invention is the different qualities having according to different functional groups in bisphenol A type epoxy resin; Using in molecule not only hydroxyl but also with the immiscible material of system solvent for use as selectivity auxiliary agent, employing is conducive to the single solvent of the bisphenol A diglycidyl ether dissolving of " n=0 ", according to similar close molecules principle, selectivity auxiliary agent be easy to the hydroxyl effect in the bisphenol A epoxide resin molecule with " n >=1 " and in the solvent system of low-pole, dissolve few, thereby realize the method for preparing target product.In recycling selection auxiliary agent process, adopt relative density to be less than 0.9 be easy to dissolved epoxy and can not dissolve the solvent of selecting auxiliary agent, two liquid phases that form have certain density difference to be beneficial to phase-splitting, thereby realize the independent recycling of selecting auxiliary agent and epoxy resin, its process is more easy to control, and the solvent using in system is single solvent, completely can recycling use, treating processes is gentle, is comparatively economic, safe Technology.
Content of the present invention is: a kind of method of purification of bisphenol A diglycidyl ether, is characterized in that comprising: the following step:
A, selection separation:
At reactor, add successively in 1. 100 mass parts liquid bisphenol A epoxy resins and 6～16 mass parts to select auxiliary agent, under agitation heating makes temperature of charge be raised to 80～90 ℃, be incubated after 30～60 minutes, add again 500～950 mass parts solvent I, make material in 30～80 minutes, be warmed up to gradually 45～75 ℃, and then be incubated standing 60～80 minutes, the material of reactor in is 1. divided into (significantly) upper strata feed liquid A and the feed liquid B of lower floor, by reactor, the upper strata feed liquid A in is 1. separated with the feed liquid B of lower floor and to put into respectively (clean) reactor 2. 3. standby with reactor again,
Described selection auxiliary agent is to contain the compound that hydroxyl and polarity are large, relative density is greater than 1;
Described solvent I is any in sherwood oil, hexanaphthene, normal hexane, isopropyl ether, it is characterized in that molecular polarity is very little, relative density is less than 0.8;
The major ingredient of described upper strata feed liquid A is: the bisphenol A diglycidyl ether of the polymerization degree " n=0 ", solvent I;
The major ingredient of the described feed liquid B of lower floor is: the bisphenol A type epoxy resin of selecting auxiliary agent, polymerization degree n >=1;
B, aftertreatment:
Reactor upper strata feed liquid A 2., first under 65～95 ℃ of temperature and normal pressure, distill out after 70%～90% solvent I, again the remainder of this upper strata feed liquid A is carried out to underpressure distillation, to distillation temperature, be finally that 70～110 ℃, vacuum tightness are while reaching 50～110 handkerchief, distillation completes, and the remaining thing of reactor in is 2. (high purity) bisphenol A diglycidyl ether making.
The method of purification of the bisphenol A diglycidyl ether described in content of the present invention, is characterized in that comprising the following steps:
Auxiliary agent is selected in c, recovery:
At room temperature, at the reactor that the feed liquid B of lower floor is housed, add in 3. and be easy to dissolve bisphenol A type epoxy resin and the single solvent II insoluble to the selection auxiliary agent described in step a adds the amount of solvent II to be: mass ratio=100:50～120 of the feed liquid B of lower floor and solvent II; Stir at normal temperatures and pressures 30～60 minutes, then standing 60～80 minutes, separation (obviously) is divided into containing the upper strata solvent II layer of bisphenol A type epoxy resin and containing the lower floor of bisphenol A type epoxy resin, does not select auxiliary agent layer, thereby realizes recovery and the recycle of selecting auxiliary agent.
Institute's recovered solvent II layer (mixing solutions of the bisphenol A type epoxy resin that the polymerization degree is n >=1 and solvent II) can be directly used in the glue that glass cloth laminated board and moulding compound are produced in preparation, also can pass through distillating recovering solvent II, the epoxy resin that the polymerization degree that obtains higher molecular weight is n >=1.
In content of the present invention: liquid bisphenol A epoxy resin described in step a is oxirane value eq/100g at 0.51～0.56 bisphenol A type epoxy resin, wherein: the viscosity when content of the bisphenol A diglycidyl ether of the polymerization degree " n=0 " is 70%～82%, 23 ℃ is 11000～15000mPa.s.
In content of the present invention: select described in step a that auxiliary agent can (all can in the polymerization degree≤1000 for ethylene glycol, poly(oxyethylene glycol) 400, preferably the polymerization degree is 400), any in glycol ether, the granularity chromatographic silica gel that is 200～500, all have and in molecule, contain hydroxyl so polarity is large, relative density is greater than 1 feature.
In content of the present invention: the II of solvent described in step c can be any in benzene,toluene,xylene.
Compared with prior art, the present invention has following feature and beneficial effect:
(1) adopt the present invention, in reaction process, in the molecule of the auxiliary agent of hydroxyl and the polymerization degree " n>=1 ", between the bisphenol A epoxide resin of hydroxyl, there is stronger interaction, and and in molecule between the bisphenol A diglycidyl ether of the polymerization degree of hydroxyl " n=0 " effect very little, thereby reach the combination of selecting auxiliary agent and hydroxyl-containing epoxy resin
,realize the selectivity of the polymerization degree " n>=1 " and " n=0 " epoxy resin and distribute, there is good selection effect; Selection result from the listed embodiment of the present invention: the bisphenol A epoxide resin that the content that adopts the bisphenol A diglycidyl ether of " n=0 " is 70%～82% is raw material, the quality percentage composition that refining effect has reached bisphenol A diglycidyl ether is 91.09%～95.07%, best level can reach 98.7%;
(2) adopt the present invention, for containing the material of strong polarity hydroxy functional group and not the low polar material of hydroxyl in the single solvent of low-pole, there is different solubleness, according to similar close principle, the bisphenol A diglycidyl ether of the polymerization degree " n=0 " not only has higher solubility but also have good selectivity in solvent I (as: sherwood oil or hexanaphthene or normal hexane or isopropyl ether); Meanwhile, adopt single solvent I to temperature-insensitive, be conducive to maintain the good selectivity of target product (bisphenol A diglycidyl ether), recovered solvent I is directly reused; On the other hand, the target product (bisphenol A diglycidyl ether) in the feed liquid A of upper strata selects with the feed liquid B(of lower floor the bisphenol A type epoxy resin that auxiliary agent, the polymerization degree are n >=1) easily separated, good product quality and more stable;
(3) adopt the present invention, in realize to reclaim selecting the process of auxiliary agent, the solvent II based on using is aromatic solvent, is easy to dissolved epoxy and does not dissolve selection auxiliary agent, and there is density difference, can realize well and select the recycle of auxiliary agent and the recovery of remaining epoxy;
(4) adopt the present invention, required equipment is few and general, technological process is short, and postprocessing working procedures is easy, easy and simple to handle, is comparatively economic, safe Technology;
(5) technique of the present invention is simple, and good separation is practical.
Embodiment
Embodiment given below intends so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
the bisphenol A diglycidyl ether that first part's preparation is purified
Embodiment 1:
The first step: add successively 3000g epoxy resin (oxirane value 0.54) and 450g ethylene glycol in 1. at 30L reactor, under agitation temperature of charge is raised to 80 ℃, be incubated after 60 minutes, add again 20000g hexanaphthene, make material in 50 minutes, be warmed up to gradually 60 ℃, then at 60 ℃, be incubated standing 60 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 80～90 ℃ of temperature and normal pressure, distill out after 14000g cyclohexane solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 70 ℃, maximum vacuum reaches 50 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 2:
The first step: add successively 3000g epoxy resin (oxirane value 0.51) and 300g chromatographic silica gel (granularity 400～500 orders) in 1. at 30L reactor, under agitation temperature of charge is raised to 85 ℃, be incubated after 30 minutes, add again 17000g sherwood oil, make temperature of charge in 60 minutes, be raised to gradually 75 ℃, then at 75 ℃, be incubated standing 80 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 85～95 ℃ of temperature and normal pressure, distill out after 15300g petroleum ether solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 90 ℃, maximum vacuum reaches 80 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 3:
The first step: add successively 3000g epoxy resin (oxirane value 0.53) and 360g poly(oxyethylene glycol) 400 in 1. at 30L reactor, under agitation temperature of charge is raised to 90 ℃, be incubated after 50 minutes, add again 17000g normal hexane, make temperature of charge in 40 minutes, be raised to gradually 65 ℃, then at 65 ℃, be incubated standing 70 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 85～95 ℃ of temperature and normal pressure, distill out after 14500g normal hexane solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 100 ℃, maximum vacuum reaches 90 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 4:
The first step: add successively 3000g epoxy resin (oxirane value 0.54) and 480g glycol ether in 1. at 30L reactor, under agitation temperature of charge is raised to 85 ℃, be incubated after 30 minutes, add again 18500g isopropyl ether, make temperature of charge in 50 minutes, be raised to gradually 55 ℃, then at 55 ℃, be incubated standing 70 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 65～75 ℃ of temperature and normal pressure, distill out after 16000g isopropyl ether solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 80 ℃, maximum vacuum reaches 60 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 5:
The first step: add successively 3000g epoxy resin (oxirane value 0.52) and 360g chromatographic silica gel (granularity 200～300 orders) in 1. at 30L reactor, under agitation temperature of charge is raised to 85 ℃, be incubated after 60 minutes, add again 20000g hexanaphthene, make temperature of charge in 50 minutes, be raised to gradually 60 ℃, then at 60 ℃, be incubated standing 60 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 70～80 ℃ of temperature and normal pressure, distill out after 15000g cyclohexane solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 70 ℃, maximum vacuum reaches 50 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 6:
The first step: add successively 3000g epoxy resin (oxirane value 0.55) and 300g glycol ether in 1. at 50L reactor, under agitation temperature of charge is raised to 85 ℃, be incubated after 30 minutes, add again 27300g normal hexane, make temperature of charge in 45 minutes, be raised to gradually 55 ℃, then at 55 ℃, be incubated standing 70 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 80～90 ℃ of temperature and normal pressure, distill out after 23000g normal hexane solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 100 ℃, maximum vacuum reaches 90 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 7:
The first step: add successively 3000g epoxy resin (oxirane value 0.52) and 300g ethylene glycol in 1. at 50L reactor, under agitation temperature of charge is raised to 85 ℃, be incubated after 30 minutes, add again 22000g sherwood oil, make temperature of charge in 40 minutes, be raised to gradually 55 ℃, then at 55 ℃, be incubated standing 80 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 75～85 ℃ of temperature and normal pressure, distill out after 16000g petroleum ether solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 90 ℃, maximum vacuum reaches 70 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 8:
The first step: add successively 3000g epoxy resin (oxirane value 0.53) and 180g chromatographic silica gel (granularity 400～500 orders) in 1. at 30L reactor, under agitation temperature of charge is raised to 85 ℃, be incubated after 30 minutes, add again 18500g isopropyl ether, make temperature of charge in 80 minutes, be raised to gradually 45 ℃, then at 45 ℃, be incubated standing 60 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 65～75 ℃ of temperature and normal pressure, distill out after 15000g isopropyl ether solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 80 ℃, maximum vacuum reaches 60 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 9:
The first step: add successively 3000g epoxy resin (oxirane value 0.56) and 330g chromatographic silica gel (granularity 200～300 orders) in 1. at 30L reactor, under agitation temperature of charge is raised to 80 ℃, be incubated after 60 minutes, add again 20000g hexanaphthene, make temperature of charge in 50 minutes, be raised to gradually 60 ℃, then at 60 ℃, be incubated standing 60 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 80～90 ℃ of temperature and normal pressure, distill out after 16000g cyclohexane solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 75 ℃, maximum vacuum reaches 100 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 10:
The first step: add successively 3000g epoxy resin (oxirane value 0.54) and 480g ethylene glycol in 1. at 50L reactor, under agitation temperature of charge is raised to 85 ℃, be incubated after 40 minutes, add again 27000g sherwood oil, make temperature of charge in 45 minutes, be raised to gradually 55 ℃, then at 55 ℃, be incubated standing 70 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 75～85 ℃ of temperature and normal pressure, distill out after 24000g petroleum ether solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 90 ℃, maximum vacuum reaches 60 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 11:
The first step: add successively 3000g epoxy resin (oxirane value 0.53) and 480g poly(oxyethylene glycol) 400 in 1. at 30L reactor, under agitation temperature of charge is raised to 80 ℃, be incubated after 50 minutes, add again 17000g sherwood oil, make temperature of charge in 40 minutes, be raised to gradually 50 ℃, then at 50 ℃, be incubated standing 70 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 75～85 ℃ of temperature and normal pressure, distill out after 15000g petroleum ether solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 110 ℃, maximum vacuum reaches 70 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 12:
The first step: add successively 3000g epoxy resin (oxirane value 0.51) and 180g ethylene glycol in 1. at 30L reactor, under agitation temperature of charge is raised to 90 ℃, be incubated after 40 minutes, add again 15000g hexanaphthene, make temperature of charge in 30 minutes, be raised to gradually 70 ℃, then at 70 ℃, be incubated standing 65 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 65～75 ℃ of temperature and normal pressure, distill out after 12000g cyclohexane solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 70 ℃, maximum vacuum reaches 110 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 13:
The first step: add successively 3000g epoxy resin (oxirane value 0.54) and 300g poly(oxyethylene glycol) 400 in 1. at 30L reactor, under agitation temperature of charge is raised to 90 ℃, be incubated after 45 minutes, add again 21000g isopropyl ether, make temperature of charge in 45 minutes, be raised to gradually 60 ℃, then at 60 ℃, be incubated standing 65 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 80～90 ℃ of temperature and normal pressure, distill out after 14700g cyclohexane solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 110 ℃, maximum vacuum reaches 80 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 14:
The first step: add successively 3000g epoxy resin (oxirane value 0.53) and 180g chromatographic silica gel (granularity is 300～400 orders) in 1. at 30L reactor, under agitation temperature of charge is raised to 80 ℃, be incubated after 45 minutes, add again 16000g hexanaphthene, make temperature of charge in 60 minutes, be raised to gradually 55 ℃, then at 55 ℃, be incubated standing 60 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 75～85 ℃ of temperature and normal pressure, distill out after 13000g cyclohexane solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 90 ℃, maximum vacuum reaches 100 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 15:
The first step: add successively 3000g epoxy resin (oxirane value 0.55) and 250g Polyethylene Glycol-600 in 1. at 30L reactor, under agitation temperature of charge is raised to 85 ℃, be incubated after 40 minutes, add again 15000g isopropyl ether, make temperature of charge in 40 minutes, be raised to gradually 50 ℃, then at 50 ℃, be incubated standing 70 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 85～95 ℃ of temperature and normal pressure, distill out after 13500g cyclohexane solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 80 ℃, maximum vacuum reaches 70 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 16:
The first step: add successively 3000g epoxy resin (oxirane value 0.52) and 400g ethylene glycol in 1. at 30L reactor, under agitation temperature of charge is raised to 80 ℃, be incubated after 40 minutes, add again 22000g normal hexane, make temperature of charge in 70 minutes, be raised to gradually 60 ℃, then at 60 ℃, be incubated standing 80 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 80～90 ℃ of temperature and normal pressure, distill out after 18000g cyclohexane solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 105 ℃, maximum vacuum reaches 110 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 17:
The first step: add successively 3000g epoxy resin (oxirane value 0.54) and 480g glycol ether in 1. at 30L reactor, under agitation temperature of charge is raised to 90 ℃, be incubated after 30 minutes, add again 28500g sherwood oil, make temperature of charge in 80 minutes, be raised to gradually 75 ℃, then at 75 ℃, be incubated standing 75 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 65～75 ℃ of temperature and normal pressure, distill out after 22000g cyclohexane solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 80 ℃, maximum vacuum reaches 60 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 18:
The first step: add successively 3000g epoxy resin (oxirane value 0.56) and 450g chromatographic silica gel (granularity is 300～400 orders) in 1. at 30L reactor, under agitation temperature of charge is raised to 80 ℃, be incubated after 50 minutes, add again 28500g isopropyl ether, make temperature of charge in 70 minutes, be raised to gradually 50 ℃, then at 50 ℃, be incubated standing 80 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 70～80 ℃ of temperature and normal pressure, distill out after 21000g cyclohexane solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 75 ℃, maximum vacuum reaches 100 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 19:
The first step: add successively 3000g epoxy resin (oxirane value 0.53) and 200g Liquid Macrogol in 1. at 30L reactor, under agitation temperature of charge is raised to 90 ℃, be incubated after 50 minutes, add again 18000g normal hexane, make temperature of charge in 50 minutes, be raised to gradually 45 ℃, then at 45 ℃, be incubated standing 65 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 80～90 ℃ of temperature and normal pressure, distill out after 16200g cyclohexane solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 110 ℃, maximum vacuum reaches 70 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
Embodiment 20:
The first step: add successively 3000g epoxy resin (oxirane value 0.52) and 480g ethylene glycol in 1. at 30L reactor, under agitation temperature of charge is raised to 80 ℃, be incubated after 60 minutes, add again 24000g sherwood oil, make temperature of charge in 70 minutes, be raised to gradually 55 ℃, then at 55 ℃, be incubated standing 65 minutes, the material of reactor in has 1. been divided into obvious upper strata feed liquid A and the feed liquid B of lower floor.
Second step: by the upper strata feed liquid A in the first step transfer to clean reactor 2. in, first under 75～85 ℃ of temperature and normal pressure, distill out after 21600g cyclohexane solvent, again the remainder of this upper strata feed liquid A is carried out to decompression step by step distillation, last distillation temperature is 95 ℃, maximum vacuum reaches 90 handkerchiefs, makes bisphenol A with high purity diglycidylether after having distilled.
By the prepared bisphenol A with high purity diglycidylether sample of the above embodiments 1～20 has been carried out to liquid-phase chromatographic analysis, bisphenol A diglycidyl ether content value (%) data in sample are by LC-2010A hplc determination; (23 ℃, mPa.s) Value Data, by LVDV-II Brookfiel viscometer determining, the results are shown in following table 1 to viscosity.
Table 1: the selectivity ratios of the bisphenol A diglycidyl ether in high purity low-viscosity bisphenol A epoxide resin (polymerization degree " n=0 "):
Note: in table 1, the content of bisphenol A diglycidyl ether is mass percentage content.
second section is selected auxiliary agent and is remained the separated of epoxy resin that the polymerization degree is n>=1
Embodiment 21:
By the feed liquid B of lower floor in embodiment 1 get 1900g add reactor 3. in, under room temperature normal pressure, add 2280g toluene and stir 30 minutes, after standing 60 minutes, material is divided into solution layer above and selection auxiliary agent layer below, the selection auxiliary agent layer of isolating below obtains the utilization of ethylene glycol 427g direct circulation, isolate solution layer above, the epoxy resin solution that polymerization degree is n >=1 can be directly used in the glue that glass cloth laminated board and moulding compound are produced in preparation.
Embodiment 22:
By the feed liquid B of lower floor in embodiment 2 get 1900g add reactor 3. in, under room temperature normal pressure, add 950g benzo to stir 30 minutes, after standing 80 minutes, material is divided into solution layer above and selection auxiliary agent layer below, selection auxiliary agent layer the drying isolated below obtain the utilization of silica gel 279g direct circulation, isolate solution layer above, be that the polymerization degree is the epoxy resin solution of n >=1, after distillating recovering solvent, obtain the epoxy resin that the polymerization degree is n >=1.
Embodiment 23:
By the feed liquid B of lower floor in embodiment 3 get 1700g add reactor 3. in, under room temperature normal pressure, add 1360g benzo to stir 40 minutes, after standing 70 minutes, material is divided into solution layer above and selection auxiliary agent layer below, the selection auxiliary agent layer of isolating below obtains the utilization of poly(oxyethylene glycol) 400 auxiliary agent 344g direct circulation, isolate solution layer above, be that the polymerization degree is the epoxy resin solution of n >=1, after distillating recovering solvent, obtain the epoxy resin that the remaining polymerization degree is n >=1.
Embodiment 24:
By the feed liquid B of lower floor in embodiment 4 get 1900g add reactor 3. in, under room temperature normal pressure, add 1140g toluene and stir 35 minutes, after standing 75 minutes, material is divided into solution layer above and selection auxiliary agent layer below, the selection auxiliary agent layer of isolating below obtains the utilization of glycol ether 457g direct circulation, isolate solution layer above, the epoxy resin solution that polymerization degree is n >=1 can be directly used in the glue that glass cloth laminated board and moulding compound are produced in preparation.
Embodiment 25:
By the feed liquid B of lower floor in embodiment 5 get 2000g add reactor 3. in, under room temperature normal pressure, add 2000g diformazan benzo to stir 35 minutes, after standing 60 minutes, material is divided into solution layer above and selection auxiliary agent layer below, selection auxiliary agent layer the drying isolated below obtain the utilization of chromatographic silica gel 345g direct circulation, isolate solution layer above, be that the polymerization degree is the epoxy resin solution of n >=1, after distillating recovering solvent, obtain the epoxy resin that the remaining polymerization degree is n >=1.
Embodiment 26:
By the feed liquid B of lower floor in embodiment 6 get 1300g add reactor 3. in, under room temperature normal pressure, add 1170g benzo to stir 45 minutes, after standing 70 minutes, material is divided into solution layer above and selection auxiliary agent layer below, the selection auxiliary agent layer of isolating below obtains the utilization of glycol ether 186g direct circulation, isolate solution layer above, be that the polymerization degree is the epoxy resin solution of n >=1, after distillating recovering solvent, obtain the epoxy resin that the remaining polymerization degree is n >=1.
Embodiment 27:
By the feed liquid B of lower floor in embodiment 7 get 1400g add reactor 3. in, under room temperature normal pressure, add 980g diformazan benzo to stir 50 minutes, after standing 80 minutes, material is divided into solution layer above and selection auxiliary agent layer below, the selection auxiliary agent layer of isolating below obtains the utilization of ethylene glycol 215g direct circulation, isolate solution layer above, be that the polymerization degree is the epoxy resin solution of n >=1, after distillating recovering solvent, obtain the epoxy resin that the remaining polymerization degree is n >=1.
Embodiment 28:
By the feed liquid B of lower floor in embodiment 8 get 1500g add reactor 3. in, under room temperature normal pressure, add 1500g toluene and stir 60 minutes, after standing 60 minutes, material is divided into solution layer above and selection auxiliary agent layer below, selection auxiliary agent layer the drying isolated below obtain the utilization of chromatographic silica gel 165g direct circulation, isolate solution layer above, the epoxy resin solution that polymerization degree is n >=1 can be directly used in the glue that glass cloth laminated board and moulding compound are produced in preparation.
Embodiment 29:
By the feed liquid B of lower floor in embodiment 9 get 1700g add reactor 3. in, under room temperature normal pressure, add 1360g benzo to stir 30 minutes, after standing 70 minutes, material is divided into solution layer above and selection auxiliary agent layer below, selection auxiliary agent layer the drying isolated below obtain the utilization of chromatographic silica gel 308g direct circulation, isolate solution layer above, be that the polymerization degree is the epoxy resin solution of n >=1, after distillating recovering solvent, obtain the epoxy resin that the remaining polymerization degree is n >=1.
Embodiment 30:
By the feed liquid B of lower floor in embodiment 10 get 1300g add reactor 3. in, under room temperature normal pressure, add 1260g toluene and stir 50 minutes, after standing 60 minutes, material is divided into solution layer above and selection auxiliary agent layer below, the selection auxiliary agent layer of isolating below obtains the utilization of ethylene glycol 305g direct circulation, isolate solution layer above, be that the polymerization degree is the epoxy resin solution of n >=1, after distillating recovering solvent, obtain the epoxy resin that the remaining polymerization degree is n >=1.
Embodiment 31:
By the feed liquid B of lower floor in embodiment 11 get 2000g add reactor 3. in, under room temperature normal pressure, add 2200g benzo to stir 30 minutes, after standing 60 minutes, material is divided into solution layer above and selection auxiliary agent layer below, the selection auxiliary agent layer of isolating below obtains the utilization of poly(oxyethylene glycol) 400 auxiliary agent 460g direct circulation, isolate solution layer above, be that the polymerization degree is the epoxy resin solution of n >=1, after distillating recovering solvent, obtain the epoxy resin that the remaining polymerization degree is n >=1.
Embodiment 32:
A method of purification for bisphenol A diglycidyl ether, comprises the following steps:
A, selection separation:
At reactor, add successively in 1. 100 mass parts liquid bisphenol A epoxy resins and 11 mass parts to select auxiliary agent, under agitation heating makes temperature of charge be raised to 85 ℃, be incubated after 45 minutes, add again 750 mass parts solvent I, make material in 50 minutes, be warmed up to gradually 45～75 ℃, and then be incubated standing 70 minutes, the material of reactor in is 1. divided into (significantly) upper strata feed liquid A and the feed liquid B of lower floor, then the upper strata feed liquid A in is 1. separated with the feed liquid B of lower floor and to put into respectively (clean) reactor 2. 3. standby with reactor by reactor;
Described selection auxiliary agent is to contain the compound that hydroxyl and polarity are large, relative density is greater than 1;
Described solvent I is any in sherwood oil, hexanaphthene, normal hexane, isopropyl ether, it is characterized in that molecular polarity is very little, relative density is less than 0.8;
The major ingredient of described upper strata feed liquid A is: the bisphenol A diglycidyl ether of the polymerization degree " n=0 ", solvent I;
The major ingredient of the described feed liquid B of lower floor is: the bisphenol A type epoxy resin of selecting auxiliary agent, polymerization degree n >=1;
B, aftertreatment:
Reactor upper strata feed liquid A 2., first under 65～95 ℃ of temperature and normal pressure, distill out after 70%～90% solvent I, again the remainder of this upper strata feed liquid A is carried out to underpressure distillation, to distillation temperature, be finally that 70～110 ℃, vacuum tightness are while reaching 50～110 handkerchief, distillation completes, and the remaining thing of reactor in is 2. (high purity) bisphenol A diglycidyl ether making.
Embodiment 33:
A method of purification for bisphenol A diglycidyl ether, comprises the following steps:
A, selection separation:
At reactor, add successively in 1. 100 mass parts liquid bisphenol A epoxy resins and 6 mass parts to select auxiliary agent, under agitation heating makes temperature of charge be raised to 90 ℃, be incubated after 30 minutes, add again 500 mass parts solvent I, make material in 30 minutes, be warmed up to gradually 45～75 ℃, and then be incubated standing 60 minutes, the material of reactor in is 1. divided into (significantly) upper strata feed liquid A and the feed liquid B of lower floor, then the upper strata feed liquid A in is 1. separated with the feed liquid B of lower floor and to put into respectively (clean) reactor 2. 3. standby with reactor by reactor;
Described selection auxiliary agent is to contain the compound that hydroxyl and polarity are large, relative density is greater than 1;
Described solvent I is any in sherwood oil, hexanaphthene, normal hexane, isopropyl ether, it is characterized in that molecular polarity is very little, relative density is less than 0.8;
The major ingredient of described upper strata feed liquid A is: the bisphenol A diglycidyl ether of the polymerization degree " n=0 ", solvent I;
The major ingredient of the described feed liquid B of lower floor is: the bisphenol A type epoxy resin of selecting auxiliary agent, polymerization degree n >=1;
B, aftertreatment:
Reactor upper strata feed liquid A 2., first under 65～95 ℃ of temperature and normal pressure, distill out after 70%～90% solvent I, again the remainder of this upper strata feed liquid A is carried out to underpressure distillation, to distillation temperature, be finally that 70～110 ℃, vacuum tightness are while reaching 50～110 handkerchief, distillation completes, and the remaining thing of reactor in is 2. (high purity) bisphenol A diglycidyl ether making.
Embodiment 34:
A method of purification for bisphenol A diglycidyl ether, comprises the following steps:
A, selection separation:
At reactor, add successively in 1. 100 mass parts liquid bisphenol A epoxy resins and 16 mass parts to select auxiliary agent, under agitation heating makes temperature of charge be raised to 80 ℃, be incubated after 60 minutes, add again 950 mass parts solvent I, make material in 80 minutes, be warmed up to gradually 45～75 ℃, and then be incubated standing 80 minutes, the material of reactor in is 1. divided into (significantly) upper strata feed liquid A and the feed liquid B of lower floor, then the upper strata feed liquid A in is 1. separated with the feed liquid B of lower floor and to put into respectively (clean) reactor 2. 3. standby with reactor by reactor;
Described selection auxiliary agent is to contain the compound that hydroxyl and polarity are large, relative density is greater than 1;
Described solvent I is any in sherwood oil, hexanaphthene, normal hexane, isopropyl ether, it is characterized in that molecular polarity is very little, relative density is less than 0.8;
The major ingredient of described upper strata feed liquid A is: the bisphenol A diglycidyl ether of the polymerization degree " n=0 ", solvent I;
The major ingredient of the described feed liquid B of lower floor is: the bisphenol A type epoxy resin of selecting auxiliary agent, polymerization degree n >=1;
B, aftertreatment:
Reactor upper strata feed liquid A 2., first under 65～95 ℃ of temperature and normal pressure, distill out after 70%～90% solvent I, again the remainder of this upper strata feed liquid A is carried out to underpressure distillation, to distillation temperature, be finally that 70～110 ℃, vacuum tightness are while reaching 50～110 handkerchief, distillation completes, and the remaining thing of reactor in is 2. (high purity) bisphenol A diglycidyl ether making.
Embodiment 35:
A method of purification for bisphenol A diglycidyl ether, comprises the following steps:
A, selection separation:
At reactor, add successively in 1. 100 mass parts liquid bisphenol A epoxy resins and 6～16 mass parts to select auxiliary agent, under agitation heating makes temperature of charge be raised to 80～90 ℃, be incubated after 30～60 minutes, add again 500～950 mass parts solvent I, make material in 30～80 minutes, be warmed up to gradually 45～75 ℃, and then be incubated standing 60～80 minutes, the material of reactor in is 1. divided into (significantly) upper strata feed liquid A and the feed liquid B of lower floor, by reactor, the upper strata feed liquid A in is 1. separated with the feed liquid B of lower floor and to put into respectively (clean) reactor 2. 3. standby with reactor again,
Described selection auxiliary agent is to contain the compound that hydroxyl and polarity are large, relative density is greater than 1;
Described solvent I is any in sherwood oil, hexanaphthene, normal hexane, isopropyl ether, it is characterized in that molecular polarity is very little, relative density is less than 0.8;
The major ingredient of described upper strata feed liquid A is: the bisphenol A diglycidyl ether of the polymerization degree " n=0 ", solvent I;
The major ingredient of the described feed liquid B of lower floor is: the bisphenol A type epoxy resin of selecting auxiliary agent, polymerization degree n >=1;
B, aftertreatment:
Reactor upper strata feed liquid A 2., first under 65～95 ℃ of temperature and normal pressure, distill out after 70%～90% solvent I, again the remainder of this upper strata feed liquid A is carried out to underpressure distillation, to distillation temperature, be finally that 70～110 ℃, vacuum tightness are while reaching 50～110 handkerchief, distillation completes, and the remaining thing of reactor in is 2. (high purity) bisphenol A diglycidyl ether making.
Embodiment 36-42:
A method of purification for bisphenol A diglycidyl ether, comprises the following steps:
A, selection separation:
At reactor, add successively in 1. 100 mass parts liquid bisphenol A epoxy resins and 6～16 mass parts to select auxiliary agent, under agitation heating makes temperature of charge be raised to 80～90 ℃, be incubated after 30～60 minutes, add again 500～950 mass parts solvent I, make material in 30～80 minutes, be warmed up to gradually 45～75 ℃, and then be incubated standing 60～80 minutes, the material of reactor in is 1. divided into (significantly) upper strata feed liquid A and the feed liquid B of lower floor, by reactor, the upper strata feed liquid A in is 1. separated with the feed liquid B of lower floor and to put into respectively (clean) reactor 2. 3. standby with reactor again, the composition of the material component of each embodiment and mass parts see the following form 2:
Table 2:
Described selection auxiliary agent is to contain the compound that hydroxyl and polarity are large, relative density is greater than 1;
Described solvent I is any in sherwood oil, hexanaphthene, normal hexane, isopropyl ether, it is characterized in that molecular polarity is very little, relative density is less than 0.8;
The major ingredient of described upper strata feed liquid A is: the bisphenol A diglycidyl ether of the polymerization degree " n=0 ", solvent I;
The major ingredient of the described feed liquid B of lower floor is: the bisphenol A type epoxy resin of selecting auxiliary agent, polymerization degree n >=1;
B, aftertreatment:
Reactor upper strata feed liquid A 2., first under 65～95 ℃ of temperature and normal pressure, distill out after 70%～90% solvent I, again the remainder of this upper strata feed liquid A is carried out to underpressure distillation, to distillation temperature, be finally that 70～110 ℃, vacuum tightness are while reaching 50～110 handkerchief, distillation completes, and the remaining thing of reactor in is 2. (high purity) bisphenol A diglycidyl ether making.
Embodiment 42:
A method of purification for bisphenol A diglycidyl ether, also comprises the following steps:
Auxiliary agent is selected in c, recovery:
At room temperature, at the reactor that the feed liquid B of lower floor is housed, add in 3. and be easy to dissolve bisphenol A type epoxy resin and the single solvent II insoluble to the selection auxiliary agent described in step a adds the amount of solvent II to be: the mass ratio=100:85 of the feed liquid B of lower floor and solvent II; Stir at normal temperatures and pressures 45 minutes, then standing 70 minutes, separation (obviously) is divided into containing the upper strata solvent II layer of bisphenol A type epoxy resin and containing the lower floor of bisphenol A type epoxy resin, does not select auxiliary agent layer, thereby realizes recovery and the recycle of selecting auxiliary agent.
Institute's recovered solvent II layer (mixing solutions of the bisphenol A type epoxy resin that the polymerization degree is n >=1 and solvent II) can be directly used in the glue that glass cloth laminated board and moulding compound are produced in preparation, also can pass through distillating recovering solvent II, the epoxy resin that the polymerization degree that obtains higher molecular weight is n >=1.
Embodiment 43:
A method of purification for bisphenol A diglycidyl ether, also comprises the following steps:
Auxiliary agent is selected in c, recovery:
At room temperature, at the reactor that the feed liquid B of lower floor is housed, add in 3. and be easy to dissolve bisphenol A type epoxy resin and the single solvent II insoluble to the selection auxiliary agent described in step a adds the amount of solvent II to be: the mass ratio=100:50 of the feed liquid B of lower floor and solvent II; Stir at normal temperatures and pressures 30 minutes, then standing 60 minutes, separation (obviously) is divided into containing the upper strata solvent II layer of bisphenol A type epoxy resin and containing the lower floor of bisphenol A type epoxy resin, does not select auxiliary agent layer, thereby realizes recovery and the recycle of selecting auxiliary agent.
Institute's recovered solvent II layer (mixing solutions of the bisphenol A type epoxy resin that the polymerization degree is n >=1 and solvent II) can be directly used in the glue that glass cloth laminated board and moulding compound are produced in preparation, also can pass through distillating recovering solvent II, the epoxy resin that the polymerization degree that obtains higher molecular weight is n >=1.
Embodiment 44:
A method of purification for bisphenol A diglycidyl ether, also comprises the following steps:
Auxiliary agent is selected in c, recovery:
At room temperature, at the reactor that the feed liquid B of lower floor is housed, add in 3. and be easy to dissolve bisphenol A type epoxy resin and the single solvent II insoluble to the selection auxiliary agent described in step a adds the amount of solvent II to be: the mass ratio=100:120 of the feed liquid B of lower floor and solvent II; Stir at normal temperatures and pressures 60 minutes, then standing 80 minutes, separation (obviously) is divided into containing the upper strata solvent II layer of bisphenol A type epoxy resin and containing the lower floor of bisphenol A type epoxy resin, does not select auxiliary agent layer, thereby realizes recovery and the recycle of selecting auxiliary agent.
Institute's recovered solvent II layer (mixing solutions of the bisphenol A type epoxy resin that the polymerization degree is n >=1 and solvent II) can be directly used in the glue that glass cloth laminated board and moulding compound are produced in preparation, also can pass through distillating recovering solvent II, the epoxy resin that the polymerization degree that obtains higher molecular weight is n >=1.
Embodiment 45-50:
A method of purification for bisphenol A diglycidyl ether, also comprises the following steps:
Auxiliary agent is selected in c, recovery:
At room temperature, at the reactor that the feed liquid B of lower floor is housed, add in 3. and be easy to dissolve bisphenol A type epoxy resin and the single solvent II insoluble to the selection auxiliary agent described in step a adds the amount of solvent II to be: mass ratio=100:50～120 of the feed liquid B of lower floor and solvent II; Stir at normal temperatures and pressures 30～60 minutes, then standing 60～80 minutes, separation (obviously) is divided into containing the upper strata solvent II layer of bisphenol A type epoxy resin and containing the lower floor of bisphenol A type epoxy resin, does not select auxiliary agent layer, thereby realizes recovery and the recycle of selecting auxiliary agent; The material component of each embodiment and mass ratio see the following form 3:
Table 3:
Institute's recovered solvent II layer (mixing solutions of the bisphenol A type epoxy resin that the polymerization degree is n >=1 and solvent II) can be directly used in the glue that glass cloth laminated board and moulding compound are produced in preparation, also can pass through distillating recovering solvent II, the epoxy resin that the polymerization degree that obtains higher molecular weight is n >=1.
In above-described embodiment 32-50: liquid bisphenol A epoxy resin described in step a is oxirane value eq/100g at 0.51～0.56 bisphenol A type epoxy resin, wherein: the viscosity when content of the bisphenol A diglycidyl ether of the polymerization degree " n=0 " is 70%～82%, 23 ℃ is 11000～15000mPa.s.
In above-described embodiment 32-50: select described in step a that auxiliary agent can (all can in the polymerization degree≤1000 for ethylene glycol, poly(oxyethylene glycol) 400, preferably the polymerization degree is 400), any in glycol ether, the granularity chromatographic silica gel that is 200～500, all have and in molecule, contain hydroxyl so polarity is large, relative density is greater than 1 feature.
In above-described embodiment 32-50: the II of solvent described in step c can be any in benzene,toluene,xylene.
In above-described embodiment: each raw material adopting is commercially available prod.
In above-described embodiment: in the percentage adopting, do not indicate especially, be quality (weight) percentage; Described quality (weight) part can be all gram or kilogram.
In above-described embodiment: the processing parameter in each step (temperature, time, pressure etc.) and each amounts of components numerical value etc. are scope, and any point is all applicable.
The not concrete same prior art of technology contents of narrating in content of the present invention and above-described embodiment.
The invention is not restricted to above-described embodiment, all can implement and have described good result described in content of the present invention.
Claims (3)
1. a method of purification for bisphenol A diglycidyl ether, is characterized in that comprising the following steps:
A, selection separation:
At reactor, add successively in 1. 100 mass parts liquid bisphenol A epoxy resins and 6～16 mass parts to select auxiliary agent, under agitation heating makes temperature of charge be raised to 80～90 ℃, be incubated after 30～60 minutes, add again 500～950 mass parts solvent I, make material in 30～80 minutes, be warmed up to gradually 45～75 ℃, and then be incubated standing 60～80 minutes, the material of reactor in is 1. divided into upper strata feed liquid A and the feed liquid B of lower floor, then the upper strata feed liquid A in is 1. separated with the feed liquid B of lower floor and to put into respectively reactor 2. 3. standby with reactor by reactor;
Described selection auxiliary agent is any in ethylene glycol, poly(oxyethylene glycol) 400, glycol ether, the granularity chromatographic silica gel that is 200～500;
Described solvent I is any in sherwood oil, hexanaphthene, normal hexane, isopropyl ether;
B, aftertreatment:
Reactor upper strata feed liquid A 2., first under 65～95 ℃ of temperature and normal pressure, distill out after 70%～90% solvent I, again the remainder of this upper strata feed liquid A is carried out to underpressure distillation, to distillation temperature, be finally that 70～110 ℃, vacuum tightness are while reaching 50～110 handkerchief, distillation completes, and the remaining thing of reactor in is 2. the bisphenol A diglycidyl ether making.
2. by the method for purification of bisphenol A diglycidyl ether claimed in claim 1, it is characterized in that also comprising the following steps:
Auxiliary agent is selected in c, recovery:
At room temperature, at the reactor that the feed liquid B of lower floor is housed, add solvent II in 3., add the amount of solvent II to be: mass ratio=100:50～120 of the feed liquid B of lower floor and solvent II; Stir at normal temperatures and pressures 30～60 minutes, then standing 60～80 minutes, separation has been divided into containing the upper strata solvent II layer of bisphenol A type epoxy resin and containing the lower floor of bisphenol A type epoxy resin, has not selected auxiliary agent layer, thereby realizes recovery and the recycle of selecting auxiliary agent;
Described solvent II is any in benzene,toluene,xylene.
3. by the method for purification of the bisphenol A diglycidyl ether described in claim 1 or 2, it is characterized in that: liquid bisphenol A epoxy resin described in step a is oxirane value eq/100g at 0.51～0.56 bisphenol A type epoxy resin.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066648A (en) * | 1991-05-16 | 1992-12-02 | 时明水 | Purifying bisphenol a solvent by chemical extraction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066648A (en) * | 1991-05-16 | 1992-12-02 | 时明水 | Purifying bisphenol a solvent by chemical extraction |
Non-Patent Citations (4)
| Title |
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| 梁平辉.高纯低粘度环氧树脂制备工艺研究.《第五次全国环氧树脂应用技术学术交流会论文集》.1993,32-44页，特别是39-40页. |
| 梁平辉.高纯度双酚A二缩水甘油醚的分离制备.《第七次全国环氧树脂应用技术学术交流会论文集》.1997,163-172页，特别是162页第3段，164页1-4段，表1-2，165页1-2段. |
| 高纯低粘度环氧树脂制备工艺研究;梁平辉;《第五次全国环氧树脂应用技术学术交流会论文集》;19931231;32-44页，特别是39-40页 * |
| 高纯度双酚A二缩水甘油醚的分离制备;梁平辉;《第七次全国环氧树脂应用技术学术交流会论文集》;19971231;163-172页，特别是162页第3段，164页1-4段，表1-2，165页1-2段 * |
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