CN107759482A - DMAE and DMAEE integrated preparation method in micro-pipe reactor - Google Patents
DMAE and DMAEE integrated preparation method in micro-pipe reactor Download PDFInfo
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- CN107759482A CN107759482A CN201711167802.1A CN201711167802A CN107759482A CN 107759482 A CN107759482 A CN 107759482A CN 201711167802 A CN201711167802 A CN 201711167802A CN 107759482 A CN107759482 A CN 107759482A
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- dmaee
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- dimethylamine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
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Abstract
The invention discloses the integrated preparation method of DMAE and DMAEE in micro-pipe reactor a kind of, comprise the following steps successively：It is pumped into respectively in micro-pipe reactor as material using oxirane and by dimethylamine with the dimethylamine agueous solution being mixed to form as the water of catalyst, it is 1~2 to control the mol ratio of oxirane and dimethylamine:1；It is 1.3 ± 0.2Pa that the reaction temperature in micro-pipe reactor, which is set, as 60~90 DEG C, pressure, and residence time of the control material in micro-pipe reactor is 15~90s；The aqueous solution for DMAE and DMAEE flowed out from micro-pipe reactor.The method of the present invention has the advantages that Atom economy height, good reaction selectivity, reaction condition is gentle, the reaction time is short, catalyst is simple, product separation is simple.
Description
Technical field
The present invention relates to organic compound dimethylaminoethoxyethanol (DMAEE) and N, N- dimethylethanolamine (DMAE)
Micro-pipe reactive synthesis technique and product integrated technique.
Background technology
DMAE be mainly used in ion exchange resin, catalysts for polyurethanes, medicine (local anesthetic tetracaine hydrochloride, anti-group
Amine agent, antispastic and drug for hypertension etc.), emulsifying agent, textile auxiliary, corrosion inhibitor, scale preventative, dyestuff and paint solvent, conjunction
Into 763 resins and its curing agent etc.；Fuel oil additive is additionally operable to, the wadding of city water purification field is used as acrylic acid derivative
Solidifying agent.
Synthetic method main at present DMAE has：
(1), monoethanolamine N- methylation methods (Salvatore R N, Yoon C H, Jung K W.Synthesis of
Secondary amines [J] .Tetrahedron, 2001,57 (37)：7785-7811)：It is original using monoethanolamine and methanol
Material, N- is alkylated sintetics in the presence of catalyst, and this method has the reaction time longer, and yield is relatively low, catalyst into
The shortcomings that this is higher.
(2), dimethyl suflfate N- methylation methods (Choji Kashima, Kazuo Harada, Yoshimoki
Omote.The influence of a base on the methylation of aminoalcohols[J]
.Can.J.Chem,.1985,63:288-290)：It is that Material synthesis has gone out N- methyl ethanols using dimethyl suflfate and monoethanolamine
Amine product.It is using alkali compounds induction dimethyl sulfate ester hydrolysis attack amine alcohol amine, the catalysis of hydride in active metal
The generation N- methyl ethanol amine products of the lower high selectivity of effect.But party's law limitation is quite prominent, dimethyl suflfate category high poison
Class, should not largely it be used in industrialization, only 60% or so conversion per pass, reaction process is complicated in addition, and needs
Reacted under THF solvent conditions, cause cost of equipment and energy consumption to greatly improve.
(3), dimethyl carbonate N- methylation methods (Chen Mingyuan, Yu Hongyan, Wang Xingli .N- methyl diethanolamine green syts
Study [J] .2007,36 (1)：1-3)：The N- methyl ethanol amine products using dimethyl carbonate and hydramine as Material synthesis, research
The optimum charging ratio for obtaining alcohol and ester is 1:1.2, reaction time 3h, it is 100 DEG C to answer temperature, on this condition the yield of product
96% can be reached.But the price of dimethyl carbonate is very high, Atom economy is also worst, has only used the feelings of a methyl
By-product carbinol and carbon dioxide are just generated under condition.Because the reaction is a reversible reaction, the residual of dimethyl carbonate is caused,
And the presence of by-product methanol brings sizable material consumption and energy consumption to subsequent products separation.
(4), epoxyethane method, BASF AG, JP. Mel morals et al. urging in only water using oxirane and alkylamine
Synthesized corresponding AEOA under change effect, this method reaction is simple but product scope is very big, alkyl can be C1~
C8 long chain alkane.
DMAEE is low smell alcamines kicker, the not only catalytic action with alcamines and the low smell of product
Feature, and than the excellent catalytic effect of dimethylethanolamine and dimethyl triethylene glycol amine, it is mainly used in hard packing foamed plastics,
High resilience toy foam, it can also be used to mold soft bubble and the soft bubble of polyether-polyurethane, there is special result to the curing of foam epidermis.
Synthetic method main at present DMAEE has：
(1), two chloroethoxyethanol methods (Ruberg L A, Shriner R L.The Local Anesthetic
Action of Dialkylaminoethoxyethyl p-Aminobenzoates[J].J.Am.Chem.Soc,1935(9):
1581-1583)：Two chloroethoxyethanols and dimethylamine are Material synthesis DMAEE, and this method needs to be fractionated to separate DMAEE
Reaction solution, and the cut containing DMAEE is dissolved in the absolute ether of hydrogen chloride saturation and obtains hydrochloride, hydrochloride is in alcohol-nothing
Recrystallize and precipitate in the mixture system of water ether, obtained DMAEE yields are very low.
(2), diglycolamine method (Kordas Imre, et al.Process for the preparation of N-
methylated amines by metal-catalyzed reductive methylation[P]:Hungary,
9701207.1999-06-28)：Using diglycolamine as raw material, formaldehyde is alkylating reagent, and formic acid makees reducing agent, in reflux temperature
Reaction obtains DMAEE, and this reaction scheme is simple, mild condition, but often has residues of formaldehyde in product, is easily reacted with DMAEE, institute
Must add KOH backflows before vacuum distillation, consumption alkali number is larger, and cost is higher.
(3), epoxyethane method, the shortcomings that this method as epoxyethane method synthesis DMAE, product scope is big.It is specific and
Speech：United States Patent (USP) US3853818, by 89gN, N- dimethylethanolamines, 5mL water and the mixing of a small amount of sodium hydroxide, at 80~90 DEG C
Under conditions of be gradually passed through 44g oxirane, obtain 25gDMAEE, yield 18.8% through atmospheric distillation.Accessory substance is mainly
The long-chain hydramine that oxirane further reacts with DMAEE.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of Atom economy height, DMAEE good reaction selectivities, reaction bar
Part is gentle, the reaction time is short, the product integrated technology using DMAE and DMAEE as target product.
In order to solve the above-mentioned technical problem, the present invention provides the integrated preparation of DMAE and DMAEE in micro-pipe reactor a kind of
Method, comprise the following steps successively：
Using oxirane and by dimethylamine with dividing as the dimethylamine agueous solution that the water of catalyst is mixed to form as material
It is not pumped into micro-pipe reactor, it is 1~2 to control the mol ratio of oxirane and dimethylamine:1；
It is 1.3 ± 0.2Pa that the reaction temperature in micro-pipe reactor, which is set, as 60~90 DEG C, pressure, and control material is in micro-pipe
Residence time in reactor is 15~90s；
The aqueous solution for DMAE and DMAEE flowed out from micro-pipe reactor.
Improvement as DMAE and DMAEE integrated preparation method in the micro-pipe reactor of the present invention：The DMAE with
The DMAEE aqueous solution passes through rectifying, respectively obtains DMAE and DMAEE.
Further improvement as DMAE and DMAEE integrated preparation method in the micro-pipe reactor of the present invention：The water
Mass ratio with dimethylamine is 0~3：1 (preferably 2~3:1).
Further improvement as DMAE and DMAEE integrated preparation method in the micro-pipe reactor of the present invention：The system
The principal product of Preparation Method is DMAEE.
Further improvement as DMAE and DMAEE integrated preparation method in the micro-pipe reactor of the present invention：Epoxy second
The mol ratio of alkane and dimethylamine is 1.8：1, the optimum quality ratio of water and dimethylamine is 2：1, reaction temperature is 80 DEG C, the residence time
For 90s.
The present invention has larger specific surface area, good mass-and heat-transfer performance, can accurately controlled using micro-pipe reactor
The characteristic of reaction condition processed, applied in the reaction of oxirane and dimethylamine so that oxirane and dimethylamine, DMAE
And DMAEE consecutive reaction on a microscopic scale can be with precisely controlled, so as to farthest avoid the hair of subsequent reactions
It is raw, and make that price is higher, brings up to more than 85% using wider array of DMAEE selectivity, and control DMAEEE (2- [2- [2-
(dimethylamino) ethyoxyl] ethyoxyl] ethanol) and selectivity below 1.5%.
The present invention mixes dimethylamine with the water as catalyst, is led to oxirane and dimethylamine agueous solution with flow pump
In a subtle way in pipe reactor, reacted under conditions of heating is pressurizeed, obtain DMAE and the DMAEE aqueous solution, by rectifying, obtain
DMAE and DMAEE.
The reaction equation that the DMAE of the present invention synthesizes with DMAEE is as follows：
The characteristics of present invention utilizes micro-pipe reactor good mixing effect, and back-mixing is small improves reaction rate and selecting response
Property.The method of the present invention has Atom economy high, and good reaction selectivity, reaction condition is gentle, and the reaction time is short, catalyst cartridge
Single, product separates the advantages that simple.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the structural representation of equipment therefor of the present invention.
Embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
Fig. 1 gives a kind of reaction unit with micro-pipe reactor, including for storing the storage tank I 11 of water, for depositing
Store up storage tank II 12, the storage tank III 13 for storing oxirane of dimethylamine.Storage tank I 11 passes through flow pump I 21 and diformazan aqueous amine
The import of solution mixer 6 is connected, another import phase that storage tank II 12 passes through flow pump II 22 and dimethylamine agueous solution blender 6
Even；The outlet of dimethylamine agueous solution blender 6 after flow pump IV 24 with the import of micro-pipe reactor 3 by being connected；Storage tank III 13
It is connected by import of the flow pump III 23 also with micro-pipe reactor 3；The outlet of micro-pipe reactor 3 pass sequentially through stop valve III 73,
It is connected after counterbalance valve 4 with reaction liquid storage tank 5.Stop valve I 71 is provided between the import of flow pump III 23 and micro-pipe reactor 3,
Stop valve II 72 also is provided between the import of flow pump IV 24 and micro-pipe reactor 3.
In the apparatus：
Flow pump I 21 is used for the flow for controlling water, and flow pump II 22 is used for the flow for controlling dimethylamine, dimethylamine agueous solution
Blender 6 is used to uniformly mix water and dimethylamine so as to form dimethylamine agueous solution；Flow pump III 23 is used to control into a subtle way
The flow of oxirane in pipe reactor 3, flow pump IV 24 are used to control the dimethylamine agueous solution entered in micro-pipe reactor 3
Flow；
It can prevent that reaction solution is countercurrently after reacting stopping by closing stop valve I 71, stop valve II 72 and stop valve III 73
(that is, working condition when, stop valve I 71, stop valve II 72 and stop valve III 73 are in open mode；After stopping reaction, close and cut
Only valve I 71, stop valve II 72 and stop valve III be 73)；Residence time of the material in micro-pipe reactor 3 is by charging rate and micro-
The volume of pipe reactor determines.
Following case uses the reaction unit.And the caliber of micro-pipe reactor 3 is set as 500 μm, length 255cm.
The density of oxirane is 0.87g/mL, and the density of dimethylamine is 0.65g/mL.
DMAE and DMAEE preparation method in embodiment 1, a kind of micro-pipe reactor, using oxirane and dimethylamine as original
Material, using water as catalyst, is followed the steps below successively：
By adjusting flow pump I 21, flow pump II 22, flow pump III 23 and the (flow of flow pump IV 24 of flow pump IV 24
Size be flow pump I 21 and flow pump III 22 plus and), so that the flow of water, oxirane and dimethylamine is respectively
0.433mL/min, 0.435mL/min, 0.333mL/min, so that the mass ratio of water and dimethylamine is 2:1, oxirane with
The mol ratio of dimethylamine is 1.8:1, it is passed through in the micro-pipe reactor 3 being placed in 80 DEG C of water-baths, reaction time 25s,
DMAE the and DMAEE aqueous solution is obtained, DMAE and DMAEE are obtained after rectifying, purity is respectively 99.7% and 99.8%.In product
DMAE accounts for 26.1mol%, and DMAEE accounts for 73.9mol%, and DMAEEE accounts for 0mol%, and oxirane conversion ratio is 94.1%, dimethylamine
Conversion ratio is 97.4%.
Remarks explanation：To ensure that reaction is homogeneous liquid phase reactor, regulation counterbalance valve makes the micro-pipe reactor pressure be
1.3Pa。
Above-mentioned distillation operation is under conditions of vacuum is 10mmHg, 80.5 DEG C of cut is DMAE, and 103.5 DEG C evaporate
It is divided into DMAEE.
2~embodiment of embodiment 244, change oxirane (EO) and the mol ratio of dimethylamine (DMA), water and dimethylamine
It is mass ratio, reaction temperature and residence time, specific such as Tables 1 and 2 so as to obtain corresponding case.
Remarks：All cases in table 1, water and DMA rate of charge are 2:1.The display water of table 2 and DMA rate of charge are to anti-
The influence answered.
Table 1
Table 2
Finally, it is also necessary to it is noted that listed above is only several specific embodiments of the invention.Obviously, this hair
It is bright to be not limited to above example, there can also be many deformations.One of ordinary skill in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (5)
1. DMAE and DMAEE integrated preparation method in micro-pipe reactor, it is characterized in that comprising the following steps successively：
Using oxirane and by dimethylamine with distinguishing pump as material as the dimethylamine agueous solution that the water of catalyst is mixed to form
In a subtle way in pipe reactor, it is 1~2 to control the mol ratio of oxirane and dimethylamine:1；
It is 1.3 ± 0.2Pa that the reaction temperature in micro-pipe reactor, which is set, as 60~90 DEG C, pressure, and control material is reacted in micro-pipe
Residence time in device is 15~90s；
The aqueous solution for DMAE and DMAEE flowed out from micro-pipe reactor.
2. DMAE and DMAEE integrated preparation method in micro-pipe reactor according to claim 1, it is characterized in that：It is described
The DMAE and DMAEE aqueous solution passes through rectifying, respectively obtains DMAE and DMAEE.
3. DMAE and DMAEE integrated preparation method in micro-pipe reactor according to claim 1 or 2, it is characterized in that：Institute
The mass ratio for stating water and dimethylamine is 0~3：1.
4. DMAE and DMAEE integrated preparation method in micro-pipe reactor according to claim 3, it is characterized in that：It is described
The principal product of preparation method is DMAEE.
5. DMAE and DMAEE integrated preparation method in micro-pipe reactor according to claim 4, it is characterized in that：
The mol ratio of oxirane and dimethylamine is 1.8：1, the optimum quality ratio of water and dimethylamine is 2：1, reaction temperature 80
DEG C, residence time 90s.
Priority Applications (1)
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| CN201711167802.1A CN107759482A (en) | 2017-11-21 | 2017-11-21 | DMAE and DMAEE integrated preparation method in micro-pipe reactor |
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| CN201711167802.1A CN107759482A (en) | 2017-11-21 | 2017-11-21 | DMAE and DMAEE integrated preparation method in micro-pipe reactor |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824529A (en) * | 2019-01-29 | 2019-05-31 | 江苏奥斯佳材料科技股份有限公司 | The preparation method of 2- [2- [2- (dimethylamino) ethyoxyl] ethyoxyl] ethyl alcohol |
| CN110683962A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Method for preparing N-methyldiethanolamine by micro-reaction synthesis |
| CN113666978A (en) * | 2020-05-14 | 2021-11-19 | 洛阳惠中兽药有限公司 | Preparation method of macrolide compound and intermediate used by same |
| CN114105789A (en) * | 2021-12-17 | 2022-03-01 | 南通恒光大聚氨酯材料有限公司 | Synthesis method of dimethylamino propylamine diisopropanol |
| CN115350679A (en) * | 2022-08-17 | 2022-11-18 | 沈阳工业大学 | Device and method for preparing dimethyl carbonate by high-speed jet flow impact tubular reactor |
| CN115490604A (en) * | 2022-09-29 | 2022-12-20 | 南通恒光大聚氨酯材料有限公司 | Pipeline synthesis method of 3-dimethylaminopropyl-2-hydroxypropyl amine |
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| WO2011096729A2 (en) * | 2010-02-04 | 2011-08-11 | University-Industry Cooperation Group Of Kyunghee University | Novel method of preparing secondary amine compound using microflow reactor |
| CN106061932A (en) * | 2014-03-10 | 2016-10-26 | 竹本油脂株式会社 | Process for producing alkylene oxide adduct and alkylene oxide adduct |
| CN107011191A (en) * | 2017-04-06 | 2017-08-04 | 浙江大学 | Produce N, the method for N dimethyldiglycolamine co-production N, N dimethylethanolamines |
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| WO2011056929A1 (en) * | 2009-11-04 | 2011-05-12 | Massachusetts Institute Of Technology | Continuous flow synthesis of amino alcohols using microreactors |
| WO2011096729A2 (en) * | 2010-02-04 | 2011-08-11 | University-Industry Cooperation Group Of Kyunghee University | Novel method of preparing secondary amine compound using microflow reactor |
| CN106061932A (en) * | 2014-03-10 | 2016-10-26 | 竹本油脂株式会社 | Process for producing alkylene oxide adduct and alkylene oxide adduct |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110683962A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Method for preparing N-methyldiethanolamine by micro-reaction synthesis |
| CN109824529A (en) * | 2019-01-29 | 2019-05-31 | 江苏奥斯佳材料科技股份有限公司 | The preparation method of 2- [2- [2- (dimethylamino) ethyoxyl] ethyoxyl] ethyl alcohol |
| CN113666978A (en) * | 2020-05-14 | 2021-11-19 | 洛阳惠中兽药有限公司 | Preparation method of macrolide compound and intermediate used by same |
| CN114105789A (en) * | 2021-12-17 | 2022-03-01 | 南通恒光大聚氨酯材料有限公司 | Synthesis method of dimethylamino propylamine diisopropanol |
| CN114105789B (en) * | 2021-12-17 | 2023-09-01 | 恒光新材料(江苏)股份有限公司 | Synthesis method of dimethylaminopropylamine diisopropyl alcohol |
| CN115350679A (en) * | 2022-08-17 | 2022-11-18 | 沈阳工业大学 | Device and method for preparing dimethyl carbonate by high-speed jet flow impact tubular reactor |
| CN115490604A (en) * | 2022-09-29 | 2022-12-20 | 南通恒光大聚氨酯材料有限公司 | Pipeline synthesis method of 3-dimethylaminopropyl-2-hydroxypropyl amine |
| CN115490604B (en) * | 2022-09-29 | 2023-09-01 | 恒光新材料(江苏)股份有限公司 | 3-dimethylaminopropyl-2-hydroxypropyl amine pipelining synthesis method |
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