CN105384654B - A kind of crystallization purifications of hydroxyalkyl amide - Google Patents
A kind of crystallization purifications of hydroxyalkyl amide Download PDFInfo
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- CN105384654B CN105384654B CN201510911717.6A CN201510911717A CN105384654B CN 105384654 B CN105384654 B CN 105384654B CN 201510911717 A CN201510911717 A CN 201510911717A CN 105384654 B CN105384654 B CN 105384654B
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Abstract
The present invention relates to the crystallization purifications of hydroxyalkyl amide, the hydroxyalkyl amide is formed by the reaction product crystallization purifying of the dialkanol amine under base catalyst existence condition and carboxylic adipate, and crystallization purifications comprise the following steps：a）A certain amount of recrystallisation solvent is added into reaction product；b）Stirring and dissolving backflow is cooled to less than 90 DEG C；c）Water-bath is cooled to 20 30 DEG C, separates out product initial crystallization；d）It is filled with liquid nitrogen and is cooled further to 25 ~ 5 DEG C, separates out target product sufficient crystallising；e）Filtering, drying, obtain the hydroxyalkyl amide product after crystallization purifying；f）The mother liquor after filtering is reclaimed, continuation is used as next group recrystallisation solvent.It is abundant that this method can separate out the product in recrystallisation solvent, and being recycled for multiple times for crystallization Mother liquor can be achieved, and can effectively reduce the deterioration of Recycling Mother Solution product quality, can significantly improve product yield and product quality.
Description
Technical field
The invention belongs to reaction product technical field of purification, it is related to a kind of crystallization purifications of reaction product, especially relates to
And a kind of crystallization purifications of the reaction product of dialkanol amine and carboxylic adipate under base catalyst existence condition.
Background technology
Hydroxyalkyl amide is to carry out amidation process with carboxylic adipate under base catalysis by dialkanol amine and obtain
.Wherein, the dialkanol amine and the base catalyst and other byproducts of residual of residual are typically contained in reaction product, together
When, the crystallization of reaction product is typically based on the method for cold water crystallisation by cooling, and percent crystallization in massecuite is not high, and recovered solvent is participated in after crystallization
When next group is circulated, the change such as xanthochromia can occur for the product remained in solvent, produce influence to subsequent products quality, cause totality
Product yield is not high, and product qualities are bad.
The content of the invention
, should it is an object of the invention to solve the above-mentioned problems in the prior art there is provided a kind of crystallization purifications
It is abundant that method can separate out the product in recrystallisation solvent, being recycled for multiple times for crystallization Mother liquor can be achieved, and can effectively reduce
Recycling Mother Solution product quality deteriorates, and can significantly improve product yield and product quality.
To achieve these goals, the present invention provides following technical scheme：A kind of crystallization purifications of hydroxyalkyl amide,
The hydroxyalkyl amide is crystallized by the reaction product of dialkanol amine and carboxylic adipate under base catalyst existence condition
Purifying is formed, and the crystallization purifications comprise the following steps：
a）A certain amount of recrystallisation solvent is added into the reaction product；
b）Stirring and dissolving backflow is cooled to less than 90 DEG C；
c）Water-bath is cooled to 20-30 DEG C, separates out product initial crystallization；
d）It is filled with liquid nitrogen and is cooled further to -25 ~ -5 DEG C, separates out target product sufficient crystallising；
e）Filtering, drying, obtain the hydroxyalkyl amide product after crystallization purifying；
f）The mother liquor after filtering is reclaimed, continuation is used as next group recrystallisation solvent.
Further, wherein, the base catalyst be sodium methoxide；The formula of the dialkanol amine is HN（ROH）2, its
Middle R be carbon number from 1 to 6 alkyl；The formula of the carboxylic adipate is that R ' OCOR ' ' COOR ', wherein R ' are carbon
Alkyl of the atomicity from 1 to 4, R ' ' be carbon number from 3 to 18 alkyl.
Further, wherein, the mol ratio of the carboxylic adipate and the dialkanol amine is 1：2~1：2.1；
The mass ratio of the carboxylic adipate and the base catalyst is 1：0.00001~1：0.05.
Yet further, wherein, the recrystallisation solvent be methanol, acetone, isopropanol in one or more；The carboxylic two
The mass ratio of acid dialkyl ester and the recrystallisation solvent is 1：3~1：5.
The crystallization purifications of the hydroxyalkyl amide of the present invention employ that to be filled with liquid nitrogen further cold after conventional chilling
But to the mode of low temperature crystallization, i.e. completely reacted reaction product is first dissolved by heating in recrystallisation solvent, then conventional chilling is extremely
Room temperature initial crystallization, is re-filled with liquid nitrogen and is cooled further to low temperature, while having crystallized inertia protective effect to product, produces target
Product sufficient crystallising is separated out, and is filtered out after product, and by disposing mother liquor, the mother liquor after recovery continues to circulate as next group recrystallisation solvent
Use.Therefore, the crystallization purifications of hydroxyalkyl amide of the invention can be such that the product in recrystallisation solvent separates out fully, can be achieved
Being recycled for multiple times for Mother liquor is crystallized, and can effectively reduce the deterioration of Recycling Mother Solution product quality, product yield can be significantly improved
With product quality.
Embodiment
With reference to embodiment, the present invention is further described, and the content of embodiment is not as to protection scope of the present invention
Limitation.
Embodiment【1】
（1）In distilling flask bottle, diethanol amine 315g is added（3mol）, 30% sodium methoxide 5g, then put up distillation dress
Put, at 100 DEG C, agitation and dropping hexanedioic acid dimethyl ester 261g（1.5mol）, about 2h is added, and insulation reaction 2h, -0.05MPa
Distillating carbinol.After 2h, 104 DEG C are warming up to, vacuum is decompressed to for -0.09MPa, keeping temperature and vacuum, stirring reaction 1h,
Stop heating, release after vacuum, obtain reaction product.Reaction product is put into reflux, it is careful that 1000g isopropanols are added dropwise, stir
Mix dissolving backflow be cooled to less than 90 DEG C, water-bath is cooled to 25 DEG C, makes product initial crystallization, be filled with liquid nitrogen be further cooled to-
15 DEG C, filter, drying obtains crystallized product 450.6g, reclaims filtrate；
（2）With step（1）Recovery filtrate be used as recrystallisation solvent, repeat step（1）Operation, obtains crystallized product 484.12g,
Reclaim filtrate；
（3）With step（2）Recovery filtrate be used as recrystallisation solvent, repeat（2）Operation, obtains crystallized product 488.71g.
Comparative example【1】
（1）In distilling flask, diethanol amine 315g is added（3mol）, 30% sodium methoxide 5g, then put up distilling apparatus,
At 100 DEG C, agitation and dropping hexanedioic acid dimethyl ester 261g（1.5mol）, about 2h is added, and insulation reaction 2h, -0.05MPa distillation first
Alcohol.After 2h, 104 DEG C are warming up to, vacuum is decompressed to for -0.09MPa, keeping temperature and vacuum, stirring reaction 1h stops adding
Heat, releases after vacuum, obtains reaction product.Reaction product is put into reflux, it is careful that 1000g isopropanols, stirring and dissolving is added dropwise
Backflow is cooled to less than 90 DEG C, is crystallized using cold water Slow cooling, is further cooled to 20 DEG C, filters, and drying obtains crystallized product
421g, reclaims filtrate；
（2）With step（1）Reclaim filtrate and be used as recrystallisation solvent, repeat step（1）Operation, obtains crystallized product 466.65g, returns
Receive filtrate；
（3）With step（2）Reclaim filtrate and be used as recrystallisation solvent, repeat step（2）Operation, obtains crystallized product 482.1g.
Comparative result is analyzed：When being cooled down when reaction product is crystallized by being filled with liquid nitrogen, three batch reaction product yields difference
For 93.87%, 100.85%, 101.81%；The batch reaction product yield of cold water crystallisation by cooling three is respectively 87.71%,
97.22%th, 100.44%, it is seen that be filled with liquid nitrogen cooling, reaction product yield is significantly improved.And according to state of Chinese name republic
Family's standard GB/T 27807-2001 " measure of appendix C hydroxyalkyl amide content " method determines embodiment【1】Three batch reactions production
Thing purity is respectively 93%, 92.7%, 92.5%, the batch reaction product purity of cold water crystallisation by cooling three is respectively 93.5%,
89.6%th, 86.7%.It can be seen that, after liquid nitrogen is filled with, reaction product yield is significantly improved with purity.
Embodiment【2】
（1）In distilling flask bottle, diisopropanolamine (DIPA) 402g is added（3mol）, 30% sodium methoxide 5g, then put up distillation dress
Put, at 100 DEG C, agitation and dropping Isosorbide-5-Nitrae-cyclohexyldicarboxylic acids dimethyl ester 300g（1.5mol）, about 2h is added, and insulation reaction
2h, -0.05MPa distillating carbinol.After 2h, 104 DEG C are warming up to, vacuum is decompressed to for -0.09MPa, keeping temperature and vacuum,
Stirring reaction 1h, stops heating, releases after vacuum, obtains reaction product.Reaction product is put into reflux, it is careful to be added dropwise
1200g methanol, stirring and dissolving backflow is cooled to less than 90 DEG C, and water-bath is cooled to 25 DEG C, makes product initial crystallization, is filled with liquid nitrogen and enters
One step is cooled to -15 DEG C, filters, and drying obtains crystallized product 508.12g, reclaims filtrate；
（2）With step（1）Recovery filtrate be used as recrystallisation solvent, repeat step（1）Operation, obtains crystallized product 547.5g,
Reclaim filtrate；
（3）With step（2）Recovery filtrate be used as recrystallisation solvent, repeat step（2）Operation, obtains crystallized product 554.71g.
Comparative example【2】
（1）In distilling flask, diisopropanolamine (DIPA) 402g is added（3mol）, 30% sodium methoxide 5g, then put up distillation dress
Put, at 100 DEG C, agitation and dropping hexanedioic acid dimethyl ester 300g（1.5mol）, about 2h is added, and insulation reaction 2h, -0.05MPa steaming
Evaporate methanol.After 2h, 104 DEG C are warming up to, vacuum is decompressed to for -0.09MPa, keeping temperature and vacuum, stirring reaction 1h stops
Only heat, release after vacuum, obtain reaction product.Reaction product is put into reflux, it is careful that 1200g methanol is added dropwise, stir molten
Solution backflow is cooled to less than 90 DEG C, is crystallized using cold water Slow cooling, is further cooled to 20 DEG C, filters, and drying must crystallize production
Thing 472.74g, reclaims filtrate；
（2）With step（1）Recovery filtrate be used as recrystallisation solvent, repeat step（1）Operation, obtains crystallized product 528.04g,
Reclaim filtrate；
（3）With step（2）Recovery filtrate be used as recrystallisation solvent, repeat step（2）Operation, obtains crystallized product 544.46g.
Comparative result is analyzed：When being cooled down when product is crystallized by being filled with liquid nitrogen, three batches of product yields are respectively
88.77%th, 95.65%, 96.91%；Three batches of product yields of cold water crystallisation by cooling are respectively 82.59%, 92.25%,
95.12%, it is seen that be filled with liquid nitrogen cooling, product yield is significantly improved.And according to Chinese name republic standard GB/T/T
27807-2001 " measure of appendix C hydroxyalkyl amide content " method determines embodiment【2】Three batches of product purities be respectively
93.4%th, 93.1%, 92.6%, three batches of product purities of cold water crystallisation by cooling are respectively 93.7%, 91.6%, 86.7%.It can be seen that,
After liquid nitrogen is filled with, product yield is significantly improved with purity.
The crystallization purifications of the hydroxyalkyl amide of the present invention employ that to be filled with liquid nitrogen further cold after conventional chilling
But to the mode of low temperature crystallization, i.e. completely reacted reaction product is first dissolved by heating in recrystallisation solvent, then conventional chilling is extremely
Room temperature initial crystallization, is re-filled with liquid nitrogen and is cooled further to low temperature, while having crystallized inertia protective effect to product, produces target
Product sufficient crystallising is separated out, and is filtered out after product, and by disposing mother liquor, the mother liquor after recovery continues to circulate as next group recrystallisation solvent
Use.Therefore, the crystallization purifications of hydroxyalkyl amide of the invention can be such that the product in recrystallisation solvent separates out fully, can be achieved
Being recycled for multiple times for Mother liquor is crystallized, and can effectively reduce the deterioration of Recycling Mother Solution product quality, product yield can be significantly improved
With product quality.
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention
Embodiment restriction.For those of ordinary skill in the field, it can also make on the basis of the above description
Other various forms of changes or variation.Here all embodiments can not be exhaustive.Every skill for belonging to the present invention
Row of the obvious changes or variations that art scheme is extended out still in protection scope of the present invention.
Claims (1)
1. a kind of crystallization purifications of hydroxyalkyl amide, the hydroxyalkyl amide is by the dioxane under base catalyst existence condition
The reaction product crystallization purifying of hydramine and carboxylic adipate is formed, and the crystallization purifications comprise the following steps：
A) a certain amount of recrystallisation solvent is added into the reaction product；
B) stirring and dissolving backflow is cooled to less than 90 DEG C；
C) water-bath is cooled to 20-30 DEG C, separates out product initial crystallization；
D) it is filled with liquid nitrogen and is cooled further to -25~-5 DEG C, separates out target product sufficient crystallising；
E) filter, dry, obtain the hydroxyalkyl amide product after crystallization purifying；
F) mother liquor after filtering is reclaimed, continuation is used as next group recrystallisation solvent;
The recrystallisation solvent is the one or more in methanol, acetone, isopropanol, the carboxylic adipate and the crystallization
The mass ratio of solvent is 1：3~1：5；The base catalyst is sodium methoxide, and the formula of the dialkanol amine is HN (ROH)2, its
Middle R be carbon number from 1 to 6 alkyl, the formula of the carboxylic adipate is that carbon is former for R ' OCOR " COOR ', wherein R '
Alkyl of the subnumber from 1 to 4, R " be carbon number from 3 to 18 alkyl；The carboxylic adipate and the dialkanol amine
Mol ratio is 1：2~1：2.1；The mass ratio of the carboxylic adipate and the base catalyst is 1：0.00001~1：
0.05。
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| CN109553547B (en) * | 2018-12-03 | 2021-07-09 | 南京红宝丽醇胺化学有限公司 | Preparation method of N, N, N ', N' -tetra (beta-hydroxypropyl) adipamide |
| CN115960011A (en) * | 2022-12-22 | 2023-04-14 | 南京红宝丽醇胺化学有限公司 | Method for purifying N, N, N ', N' -tetra (beta-hydroxypropyl) adipamide |
Family Cites Families (4)
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| DE2509237A1 (en) * | 1974-03-25 | 1975-10-09 | Rohm & Haas | PROCESS FOR CURING POLYMERS AND CURABLE POLYMER COMPOSITIONS |
| US5101073A (en) * | 1990-08-27 | 1992-03-31 | Rohm And Haas Company | Production of β-hydroxyalkylamides |
| DE19823925C2 (en) * | 1998-05-28 | 2001-01-11 | Inventa Ag | Process for the preparation of beta-hydroxyalkylamides |
| CN102633667B (en) * | 2012-03-13 | 2013-12-25 | 黄山华惠科技有限公司 | Preparation technique of beta-hydroxyalkylamide |
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Address after: 237000 Anhui city in Lu'an Province, Beijiao, ten Patentee after: Lu'an Jietongda new materials Co. Ltd. Address before: 237000 Anhui city in Lu'an Province, Beijiao, ten Patentee before: Liu'an Jietongda Chemical Co., Ltd. |