CN102746154B - Crystallizing method of solid antioxidant - Google Patents
Crystallizing method of solid antioxidant Download PDFInfo
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- CN102746154B CN102746154B CN201210241524.0A CN201210241524A CN102746154B CN 102746154 B CN102746154 B CN 102746154B CN 201210241524 A CN201210241524 A CN 201210241524A CN 102746154 B CN102746154 B CN 102746154B
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- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 23
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 21
- 239000007787 solid Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 46
- 230000008025 crystallization Effects 0.000 claims abstract description 34
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- 239000000047 product Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 24
- -1 octadecanol ester Chemical class 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000010583 slow cooling Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- 241000237502 Ostreidae Species 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005485 electric heating Methods 0.000 claims description 10
- 235000020636 oyster Nutrition 0.000 claims description 10
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 6
- 229940017219 methyl propionate Drugs 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
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- CAPNUXMLPONECZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-2-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=C(O)C(C(C)(C)C)=C1 CAPNUXMLPONECZ-UHFFFAOYSA-N 0.000 description 4
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Abstract
The invention provides a crystallizing method of a solid antioxidant. Abundant ultrafine crystal grains crystallized in the primary crystallization process are quickly dissolved by a twice quick slight heating method, and large crystal grains are reserved to continue growth in the secondary crystallization process, so that the product crystals can grow bigger and more uniform. The anticaking capacity of the product is greatly enhanced; and meanwhile, since the crystals are more uniform and do not contain abundant fine powder, the subsequent spin-drying can be ensured, and other impurities can be washed out more easily in the washing process, thereby obtaining the product with higher purity.
Description
Technical field
The present invention relates to the crystallization method in a kind of SOLID ORGANIC chemical substance production process, relate in particular to a kind of crystallization method of solid antioxidant.
More particularly, the present invention relates to the crystallization method of the positive octadecanol ester of oxidation inhibitor β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid.
Background technology
Oxidation inhibitor is indispensable additive in polymer production, the course of processing, if there is no oxidation inhibitor, polymkeric substance can oxidative degradation in the course of processing, in use comparatively fast aging.Oxidation inhibitor can not only help polymkeric substance to overcome above problem, and can make polymer product obtain good physical and mechanical properties.And oxidation inhibitor β-(3; 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid is a kind of very important Hinered phenols primary antioxidant; it is a kind of Hinered phenols antioxidant of three-dimensional arrangement; test shows that the positive octadecanol ester of oxidation inhibitor β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid can be widely used in multiple polymers, for example: plastics; synthon; elastomerics, in tamanori and grease, protects these materials that thermooxidative degradation does not occur.Its range of application comprises that polyolefine is as polyethylene, polypropylene, and poly 1-butene and other polymkeric substance are as crystal polystyrene, high-impact polystyrene, ABS and SBS.It can be applied to linear polyester, PVC, polymeric amide and urethane equally; Elastomerics and other synthetic rubber, tamanori, in natural or synthetic gluing resin and other organic materialss.This product is tasteless, has good light stability and remarkable look jail property.Fine with most polymers consistency, have the advantages that volatility is low and high resistance extracts.This product has obtained a lot of authorized by states and has allowed to add in the wrapping material with Food Contact.
The positive octadecanol ester of oxidation inhibitor β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid is because melting range is 50-55 DEG C, and melt temperature is lower, if crystalline state is bad, and easily caking.Oxidation inhibitor β-(3 in the market, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid be generally packaged as 25 kilograms packed, for Powdered, crystalline particle is thinner, in storage transportation, easily lump, particularly in storage process in order effectively to utilize storage space, generally that bagged product hit-gain trust or piling are deposited, when hit-gain trust, a common holder is one ton, 40 totally bags of points of 8 layers of block pattern row pattern hit-gain trusts, therefore the pressure that the suffered upper strata of orlop product product gravity produces is larger, more easily accelerates caking.If transport lorry runs into summer blazing sun and irradiates in transportation, goods the temperature inside the box is conventionally up to 40-50 DEG C, if added, crystallization is thin, to pile up the number of plies more, easily causes that product in transportation is heated, pressurized caking.After caking, conventionally destroyed original crystal habit, sometimes form a monoblock for one bag, be difficult to pulverize evenly again, the product of caking in use has the following disadvantages: the one, and use procedure trouble, after caking, normally one whole bag of product formation is a bulk of, is difficult to pour out in packing bag, also cannot directly use, conventionally need physical pulverization or return factory and office's reason, increase product loss and processing cost, the 2nd, even if the antioxidant product after caking is through the fragmentation of physical action external force, conventionally also inhomogeneous, there are some pieces not of uniform size, and polymeric articles normally compared with uniform powder or diameter 5mm with interior single-size, these antioxidant product morphological inhomogeneities after crushed, too large with the morphological differentiation of polymeric articles, cause adding in the process of polymeric articles and be difficult to mix with polymer beads, there is subregion oxidation inhibitor excessive concentration, cause autooxidation, subregion oxidation inhibitor concentration is too low, do not reach due antioxidant effect, thereby cause overall antioxidant effect to be affected.Therefore oxidation inhibitor downstream user can refuse to use the product of caking conventionally.
The antioxidant product that the crystallization method of the solid antioxidant the present invention relates to can make to produce in crystallisation process, allow crystallization look more greatly, more even, not only make the anti-caking ability of product greatly improve, and can make product purity higher.
At present, find no and relate to the bibliographical information that improves the large submethod of antioxidant product crystalline particle.
Summary of the invention
The invention provides a kind of crystallization method of solid antioxidant, can effectively improve the easy agglomeration problems that oxidation inhibitor too carefully causes because of crystallization, and can make product purity higher simultaneously, effectively overcome the easy agglomeration problems that above-mentioned currently available products crystalline state exists.
Technical scheme of the present invention is: a kind of crystallization method of solid antioxidant, finish in the reaction solution of gained in transesterification reaction, add certain lower alcohol solvent, heat up reaction solution is fully dissolved, then make antioxidant product crystallization from solution by controlling temperature-fall period, then obtain oxidation inhibitor crystalline product after filtration.It is characterized in that: slow cooling after fully dissolving, be on the increase to crystal seed again to separating out a small amount of crystal seed, crystal grain is constantly grown up, now both some crystallizations of having grown up in mixture, also there are a large amount of harsh longer small grains, occur being rapidly heated again when mass crystallization to part small grains and dissolve, and have little time to dissolve and retained compared with large crystallization, carry out again slow cooling, the xln remaining is further grown up, during to mass crystallization again, slow cooling is to about 30-40 DEG C, logical refrigerated water fast cooling to 20 DEG C filters below again, obtain xln crystalline product greatly and uniformly.
Described solid antioxidant is Hinered phenols antioxidant.
Described solid antioxidant is the positive octadecanol ester of β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid.
Described lower alcohol is industrial methanol, ethanol or Virahol.
Described solid antioxidant and the feed ratio of lower alcohol are 1: 1-5 (mass ratio), preferably feed ratio is 1: 2-4 (mass ratio), particularly preferred feed ratio is 1: 3 (mass ratio).
Described dissolution process condition is normal pressure, boiling, dissolution time 5-30 minute.
Described slow cooling refers to that it is to be cooled to a small amount of crystallization in the air of 25 DEG C that the flask that fills mixture is put to room temperature.
Described mass crystallization refers to the product crystallization of about 50%-80%.
Described being rapidly heated refers to and in 1-2 minute, heats up approximately 2 DEG C.
Described partial crystallization dissolves, refer in temperature-rise period and can obviously see that in the interior material system of flask, thin crystallization is partly dissolved very soon, thicker crystallization is not dissolved substantially, and material system can be by opaque bleach, and can see that flask intercrystalline particle obviously becomes evenly.
The present invention has following remarkable advantage: the one, and the present invention uses economy, the lower alcohol of easily buying is made the solvent of solid antioxidant, raw material is easy to get, the 2nd, the present invention adopts the quick microlitre warm therapy of secondary that a large amount of utmost point small grains that crystallize out in one time of crystallization are dissolved fast, effectively control nucleus quantity, retain larger crystal grain continues to grow up in secondary crystal process, make product grains grow greatlyr, more even, simultaneously because crystallization is more even, a large amount of fine powders undope, ensure that lower step dries, in washing process, can more contained other impurity washing be removed, product purity is improved.
Brief description of the drawings
Fig. 1 is 20 times of magnifying glass enlarged photographs that make product by 1 crystallization method of embodiment in this specification sheets;
Fig. 2 is 20 times of magnifying glass enlarged photographs that make product by 1 crystallization method of comparative example in this specification sheets.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but be not intended to limit scope of patent protection of the present invention.Any change that those of ordinary skill in the art made for the present invention easily realize do not exceeding under the prerequisite of technical solution of the present invention, within all will fall into scope of patent protection of the present invention.
Embodiment 1
Electric stirring is being housed, thermometer, vacuum control unit, condenser, in the 500ml there-necked flask of cold-trap, add 60 grams of (0.205 moles) 3, 5-di-tert-butyl-hydroxy phenyl methyl propionate (3, 5-methyl esters), 55 grams of (0.203 mole) octadecanols, 0.1 gram of Dibutyltin oxide, adjust vacuum to 50-100mmHg, be warming up to 100-120 DEG C, keep stirring, the methyl alcohol that reaction process is generated is constantly extracted out, be collected in cold-trap, under this condition, keep reaction approximately 2 hours, be warming up to again 125-135 DEG C, the methyl alcohol that reaction process is generated is constantly extracted out, be collected in cold-trap, under this condition, keep reaction approximately 1 hour, be evacuated to vacuum tightness be less than 2mmHg finish below reaction.Be cooled to 60-70 DEG C, in reaction flask, add 300 milliliters of (239.28 grams) methyl alcohol, keep stirring, be heated to boiling, dissolve approximately 10 minutes, obtain water white mixing liquid, keep stirring, the flask that fills reaction mixture is dropped a hint to middle natural slow cooling to 45-47 DEG C, muddy by as clear as crystal change gradually in flask, finally present oyster white, and engender crystallization, when temperature is down to approximately 43 while spending, in flask, there are a large amount of inhomogeneous crystallizations, liquid portion is creamy white, in the time that temperature is down to approximately 42 DEG C, be rapidly heated with electric heating cover, in about 1-2 minute, be warming up to 44 DEG C, can observe in temperature-rise period the muddy solidliquid mixture liquid portion of oyster white in flask and become gradually as clear as crystal, can clearly see in flask more even, thick xln, remove electric heating cover, flask is put and in air, is naturally cooled to 35-38 degree, be cooled to below 20 DEG C with 5 DEG C of cold water again, by gained solidliquid mixture suction filtration, and with 50ml washed with methanol filter cake suction filtration again, gained filter residue is put under heat lamp and obtained 100.3 grams of white products after oven dry, yield 92.94%.Can observe obvious white needles homogeneously crystallized, can observe xln by magnifying glass and be thicker needle-like, and more even, be 99.69% by chromatogram testing product purity.
Embodiment 2
Electric stirring is being housed, thermometer, vacuum control unit, condenser, in the 500ml there-necked flask of cold-trap, add 60 grams of (0.205 moles) 3, 5-di-tert-butyl-hydroxy phenyl methyl propionate (3, 5-methyl esters), 55 grams of (0.203 mole) octadecanols, 0.1 gram of Dibutyltin oxide, adjust vacuum to 50-100mmHg, be warming up to 100-120 DEG C, keep stirring, the methyl alcohol that reaction process is generated is constantly extracted out, be collected in cold-trap, under this condition, keep reaction approximately 2 hours, be warming up to again 125-135 DEG C, the methyl alcohol that reaction process is generated is constantly extracted out, be collected in cold-trap, under this condition, keep reaction approximately 1 hour, be less than 2mmHg to vacuum tightness and finish below reaction.Be cooled to 60-70 DEG C, in reaction flask, add 400 milliliters of (322.48 grams) ethanol, keep stirring, be heated to boiling, dissolve approximately 5 minutes, obtain water white mixing liquid, keep stirring, the flask that fills reaction mixture is dropped a hint to middle natural slow cooling to 41-43 DEG C, muddy by as clear as crystal change gradually in flask, finally present oyster white, and engender crystallization, when temperature is down to approximately 39 while spending, in flask, there are a large amount of inhomogeneous crystallizations, liquid portion is creamy white, in the time that temperature is down to approximately 38 DEG C, be rapidly heated with electric heating cover, in about 1-2 minute, be warming up to 40 DEG C, can observe in temperature-rise period the muddy solidliquid mixture liquid portion of oyster white in flask and become gradually as clear as crystal, can clearly see in flask more even, thick xln, remove electric heating cover, flask is put and in air, is naturally cooled to 33-35 degree, be cooled to below 20 DEG C with 5 DEG C of cold water again, by gained solidliquid mixture suction filtration, and with 50ml alcohol flushing filter cake suction filtration again, gained filter residue is put under heat lamp and obtained 99.1 grams of white products after oven dry, yield 91.83%.Can observe obvious white needles homogeneously crystallized, can observe xln by magnifying glass and be thicker needle-like, and more even, be 99.69% by chromatogram testing product purity.
Embodiment 3
Electric stirring is being housed, thermometer, vacuum control unit, condenser, in the 500ml there-necked flask of cold-trap, add 60 grams of (0.205 moles) 3, 5-di-tert-butyl-hydroxy phenyl methyl propionate (3, 5-methyl esters), 55 grams of (0.203 mole) octadecanols, 0.1 gram of Dibutyltin oxide, adjust vacuum to 50-100mmHg, be warming up to 100-120 DEG C, keep stirring, the methyl alcohol that reaction process is generated is constantly extracted out, be collected in cold-trap, under this condition, keep reaction approximately 2 hours, be warming up to again 125-135 DEG C, the methyl alcohol that reaction process is generated is constantly extracted out, be collected in cold-trap, under this condition, keep reaction approximately 1 hour, be less than 2mmHg to vacuum tightness and finish below reaction.Be cooled to 60-70 DEG C, in reaction flask, add 150 milliliters of (117.77 grams) Virahols, keep stirring, be heated to boiling, dissolve approximately 20 minutes, obtain water white mixing liquid, keep stirring, the flask that fills reaction mixture is dropped a hint to middle natural slow cooling to 48-50 DEG C, muddy by as clear as crystal change gradually in flask, finally present oyster white, and engender crystallization, when temperature is down to approximately 46 while spending, in flask, there are a large amount of inhomogeneous crystallizations, liquid portion is creamy white, in the time that temperature is down to approximately 42 DEG C, be rapidly heated with electric heating cover, in about 1-2 minute, be warming up to 47 DEG C, can observe in temperature-rise period the muddy solidliquid mixture liquid portion of oyster white in flask and become gradually as clear as crystal, can clearly see in flask more even, thick xln, remove electric heating cover, flask is put and in air, is naturally cooled to 38-40 degree, be cooled to below 20 DEG C with 5 DEG C of cold water again, by gained solidliquid mixture suction filtration, and with 50ml Virahol flush cake suction filtration again, gained filter residue is put under heat lamp and obtained 99.7 grams of white products after oven dry, yield 92.39%.Can observe obvious white needles homogeneously crystallized, can observe xln by magnifying glass and be thicker needle-like, and more even, be 99.51% by chromatogram testing product purity.
Embodiment 4
Electric stirring is being housed, thermometer, vacuum control unit, condenser, in the 500ml there-necked flask of cold-trap, add 60 grams of (0.205 moles) 3, 5-di-tert-butyl-hydroxy phenyl methyl propionate (3, 5-methyl esters), 55 grams of (0.203 mole) octadecanols, 0.1 gram of Dibutyltin oxide, adjust vacuum to 50-100mmHg, be warming up to 100-120 DEG C, keep stirring, the methyl alcohol that reaction process is generated is constantly extracted out, be collected in cold-trap, under this condition, keep reaction approximately 2 hours, be warming up to again 125-135 DEG C, the methyl alcohol that reaction process is generated is constantly extracted out, be collected in cold-trap, under this condition, keep reaction approximately 1 hour, be less than 2mmHg to vacuum tightness and finish below reaction.Be cooled to 60-70 DEG C, in reaction flask, add 500 milliliters of (400.25 grams) methyl alcohol, keep stirring, be heated to boiling, dissolve approximately 30 minutes, obtain water white mixing liquid, keep stirring, the flask that fills reaction mixture is dropped a hint to middle natural slow cooling to 43-45 DEG C, muddy by as clear as crystal change gradually in flask, finally present oyster white, and engender crystallization, when temperature is down to approximately 41 while spending, in flask, there are a large amount of inhomogeneous crystallizations, liquid portion is creamy white, in the time that temperature is down to approximately 40 DEG C, be rapidly heated with electric heating cover, in about 1-2 minute, be warming up to 42 DEG C, can observe in temperature-rise period the muddy solidliquid mixture liquid portion of oyster white in flask and become gradually as clear as crystal, can clearly see in flask more even, thick xln, remove electric heating cover, flask is put and in air, is naturally cooled to 33-35 degree, be cooled to below 15 DEG C with 5 DEG C of cold water again, by gained solidliquid mixture suction filtration, and with 50ml washed with methanol filter cake suction filtration again, gained filter residue is put under heat lamp and obtained 98.6 grams of white products after oven dry, yield 91.37%.Can observe obvious white needles homogeneously crystallized, can observe xln by magnifying glass and be thicker needle-like, and more even, be 99.82% by chromatogram testing product purity.
Comparative example 1
Electric stirring is being housed, thermometer, vacuum control unit, condenser, in the 500ml there-necked flask of cold-trap, add 60 grams of (0.205 moles) 3, 5-di-tert-butyl-hydroxy phenyl methyl propionate (3, 5-methyl esters), 55 grams of (0.203 mole) octadecanols, 0.1 gram of Dibutyltin oxide, adjust vacuum to 50-100mmHg, be warming up to 100-120 DEG C, keep stirring, the methyl alcohol that reaction process is generated is constantly extracted out, be collected in cold-trap, under this condition, keep reaction approximately 2 hours, be warming up to again 125-135 DEG C, the methyl alcohol that reaction process is generated is constantly extracted out, be collected in cold-trap, under this condition, keep reaction approximately 1 hour, be less than 2mmHg to vacuum tightness and finish below reaction.Be cooled to 60-70 DEG C, in reaction flask, add 300 ml methanol, keep stirring, be heated to boiling, dissolve approximately 10 minutes, obtain water white mixing liquid, keep stirring, the flask that fills reaction mixture is dropped a hint to middle natural slow cooling to 35-38 degree, be cooled to below 15 DEG C with 5 DEG C of cold water again, by gained solidliquid mixture suction filtration, and with 50ml washed with methanol filter cake suction filtration again, gained filter residue is put under heat lamp and obtained 97.7 grams of white products, yield 90.53% after oven dry.Can observe products obtained therefrom crystallization thinner, and inhomogeneous, be 99.07% by chromatogram testing product purity.
Claims (2)
1. solid antioxidant β-(3,5 di-tert-butyl-hydroxy phenyls) crystallization method of the positive octadecanol ester of propionic acid, it is characterized in that: the β-(3 that finishes gained in transesterification reaction, 5 di-tert-butyl-hydroxy phenyls) in the reaction solution of the positive octadecanol ester of propionic acid, be 1 by the mass ratio of oxidation inhibitor and lower alcohol: the charging capacity of 1-5 adds industrial methanol, ethanol or Virahol, under normal pressure, boiling, dissolving 5-30 minute, fully dissolve reaction solution; Then slow cooling, start insulation when soon separating out a small amount of crystallization, insulation, to separating out a small amount of crystal seed while arriving the crystallization of 50%-80% product, was rapidly heated 2 DEG C in 1-2 minute again, part small grains is dissolved, and have little time to dissolve and retained compared with large crystallization; And then while carrying out slow cooling to mass crystallization again, slow cooling is to 30-40 DEG C, more logical refrigerated water fast cooling to 20 DEG C filters below, obtains the large and crystalline product uniformly of xln.
2. solid antioxidant β-(3 according to claim 1, 5 di-tert-butyl-hydroxy phenyls) crystallization method of the positive octadecanol ester of propionic acid, it is characterized in that said concrete crystallization processes operational condition is as follows: electric stirring is being housed, thermometer, vacuum control unit, condenser, in the 500ml there-necked flask of cold-trap, add 60 gram 3, 5-di-tert-butyl-hydroxy phenyl methyl propionate, 55 grams of octadecanols, 0.1 gram of Dibutyltin oxide, adjust vacuum to 50-100mmHg, be warming up to 100-120 DEG C, keep stirring, the methyl alcohol that reaction process is generated is constantly extracted out, be collected in cold-trap, under this condition, keep reaction 2 hours, be warming up to again 125-135 DEG C, the methyl alcohol that reaction process is generated is constantly extracted out, be collected in cold-trap, under this condition, keep reaction 1 hour, be evacuated to vacuum tightness be less than 2mmHg finish below reaction, be cooled to 60-70 DEG C, in reaction flask, add 239.28 grams of methyl alcohol, keep stirring, be heated to boiling, dissolve 10 minutes, obtain water white mixing liquid, keep stirring, the flask that fills reaction mixture is placed on to natural slow cooling in air, to 45-47 DEG C, gradually by as clear as crystal change muddiness, finally to be presented oyster white, and engenders crystallization in flask, when temperature is down to 43 while spending, in flask, occur that a large amount of inhomogeneous crystallizations, liquid portion are creamy white, in the time that temperature is down to 42 DEG C, be rapidly heated with electric heating cover, in 1-2 minute, be warming up to 44 DEG C, can observe in temperature-rise period the muddy solidliquid mixture liquid portion of oyster white in flask and become gradually as clear as crystal, can clearly see in flask more even, thick xln, remove electric heating cover, flask is put and in air, is naturally cooled to 35-38 degree, be cooled to below 20 DEG C with 5 DEG C of cold water again, by gained solidliquid mixture suction filtration, and with 50ml washed with methanol filter cake suction filtration again, after gained filter residue is put under heat lamp and to be dried, obtain 100.3 grams of white crystals products, yield is 92.94%, observe xln by magnifying glass and be thicker needle-like, and more even, be 99.69% by chromatogram testing product purity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210241524.0A CN102746154B (en) | 2012-07-03 | 2012-07-03 | Crystallizing method of solid antioxidant |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210241524.0A CN102746154B (en) | 2012-07-03 | 2012-07-03 | Crystallizing method of solid antioxidant |
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| Publication Number | Publication Date |
|---|---|
| CN102746154A CN102746154A (en) | 2012-10-24 |
| CN102746154B true CN102746154B (en) | 2014-07-30 |
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| CN201210241524.0A Active CN102746154B (en) | 2012-07-03 | 2012-07-03 | Crystallizing method of solid antioxidant |
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| CN107417528A (en) * | 2017-05-02 | 2017-12-01 | 沈阳化工大学 | A kind of method that antioxidant 1076 obtains the crystallization of needle-like crystalline form in methanol solvate |
| CN107693362A (en) * | 2017-09-26 | 2018-02-16 | 侯马高知新生物科技有限公司 | A kind of method for increasing mannitol particles granularity |
| CN115160179A (en) * | 2022-08-04 | 2022-10-11 | 湖南方盛堂制药有限公司 | Preparation process of ezetimibe intermediate |
| CN115160138B (en) * | 2022-08-16 | 2024-01-02 | 宁波市鼎瑞翔新材料科技有限公司 | Method for preparing antioxidant 1076 |
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| EP0421928B1 (en) * | 1989-10-02 | 1994-06-15 | Ciba-Geigy Ag | Hydroxyphenylcarboxylic acid esters as stabilizers |
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| US4594444A (en) * | 1983-12-22 | 1986-06-10 | Ciba-Geigy Corporation | Process for the preparation of sterically hindered hydroxyphenylcarboxylic acid esters |
| EP0421928B1 (en) * | 1989-10-02 | 1994-06-15 | Ciba-Geigy Ag | Hydroxyphenylcarboxylic acid esters as stabilizers |
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