CN100460384C - Process for synthesizing methyl acryloyl-(N,N-dimethyl propylene diamine) and device therefor - Google Patents
Process for synthesizing methyl acryloyl-(N,N-dimethyl propylene diamine) and device therefor Download PDFInfo
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- CN100460384C CN100460384C CNB2006100504653A CN200610050465A CN100460384C CN 100460384 C CN100460384 C CN 100460384C CN B2006100504653 A CNB2006100504653 A CN B2006100504653A CN 200610050465 A CN200610050465 A CN 200610050465A CN 100460384 C CN100460384 C CN 100460384C
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Abstract
The invention discloses a methacryloyl-(N, N- dimethyl propdiamine) synthesis method and device. which comprises the following steps: putting the beta-(N, N-dimethylin-1, 3-propdiamine)-3-N,N-dimethylamine propyl) propionamide of measuring tank in fixed bed incorporating supported catalyst with the controlling of dosage pump at 100-200 deg.c for 2-10 min; condensing the product; carrying on rectification under vacuum; getting methacryloyl (N, N- dimethyl propdiamine). The invention reduces the cost, which has good safety.
Description
Technical field
The present invention relates to a kind of chemical intermediate---the synthetic method of methacryloyl-(N, N-dimethylated propyl diethylenetriamine), and the used production equipment of this method.
Background technology
Methacryloyl-(N, N-dimethylated propyl diethylenetriamine) is a kind of application functional monomer very widely (DMAPMA), and it belongs to unsaturated tertiary amine, and structural formula is as follows:
Because exist the vinyl group of tertiary amine group and polymerizability in the molecular structure, chemical property is active, homopolymerization, copolymerization and chemical reaction such as quaternary ammoniated can further take place.Product is widely used in the auxiliary agent, leather processing additive in synthetic, the Printing industry of the exploitation of industries such as water treatment, daily use chemicals, papermaking, medicine, fiber, oil and natural gas, photochromics etc.
The method for preparing DMAPMA has multiple, usually all be with methacrylic acid and derivative and N, the N-dimethylated propyl diethylenetriamine makes (US4206143, JP81100749, JP81131555, DE3123970, US4549017, US3652671, JP5976044, JP6270352, JP0267257, DE3128574) by a step or polystep reaction.Wherein, the bibliographical information of single stage method reaction is more concentrated; But the single stage method reaction must relate to the aggregation problem of methacrylic acid and derivative thereof, and in present stage, the poly-technology of main resistance is grasped by several companies of Germany and Japan.The reaction of multistep processes, at first the two keys of blocking group have limited the generation of side reaction in the reaction; But reactions steps is added, and the particularly product of thermo-cracking step loss causes product yield on the low side, and the actual operability of method is not strong.The multistep processes reaction formula is as follows:
Summary of the invention
At problems of the prior art, the invention provides that a kind of cost is low, yield is high, the synthetic method of the good and eco-friendly methacryloyl of security-(N, N-dimethylated propyl diethylenetriamine).
The present invention is for reaching above purpose, be to realize: a kind of methacryloyl-(N is provided by such technical scheme, the N-dimethylated propyl diethylenetriamine) synthetic method: the β in the test tank-(N, N dimethylamine base-1,3-the third two) amine generation-3-(N, N dimethylamine base propyl group) propionic acid amide (being BDMAPA) enters under volume pump control and carries out heat scission reaction in the fixed-bed reactor that loaded catalyst is housed; Reaction times is 2～10min; Temperature of reaction is 100～200 ℃; Carry out rectification under vacuum after the condensation of reaction products therefrom, promptly get methacryloyl-(N, N-dimethylated propyl diethylenetriamine).
A kind of improvement as synthetic method of the present invention: loaded catalyst is made by metal-salt and carrier, and metal-salt is mantoquita, nickel salt or zinc salt, and metal accounts for 5%～20% of loaded catalyst gross weight.
Another kind as synthetic method of the present invention improves: loaded catalyst is made by metal-salt and carrier, metal-salt is at least two kinds in mantoquita, nickel salt and the zinc salt, the metal sum accounts for 15%～40% of loaded catalyst gross weight, and every kind of metal must not be less than 5% of loaded catalyst gross weight.
Further improvement as synthetic method of the present invention: carrier is gama-alumina, activated carbon or zeolite molecular sieve, and metal-salt is a nitrate.Metal-salt and carrier are made loaded catalyst through dipping, drying, calcination steps; Drying step requires 120 ℃ of dry 5h, and calcination steps requires 400 ℃～450 ℃ roasting 4h.
The present invention also provides the reaction unit of realizing above-mentioned synthetic method: comprise β-(N is provided, N dimethylamine base-1,3-the third two) amine generation-3-(N, N dimethylamine base propyl group) test tank 1 of propionic acid amide and the fixed-bed reactor 5 that have heating unit, the upper/lower terminal of these fixed-bed reactor 5 is provided with inert filler 6,10 respectively, and the interlude of fixed-bed reactor 5 is provided with loaded catalyst 9; Test tank 1, pipeline 2, fixed-bed reactor 5, pipeline 11, condenser 12, pipeline 14, rectification under vacuum device 15 link to each other successively, and pipeline 2 is provided with volume pump 4.
A kind of improvement as reaction unit of the present invention: heating unit is the heating jacket 8 that is enclosed within fixed-bed reactor 5 outside surfaces, and heating jacket 8 is provided with thermometer 7.
Further improvement as reaction unit of the present invention: pipeline 2 is provided with stopping valve 3, and pipeline 14 is provided with stopping valve 13.
Synthetic method of the present invention is utilized β-(N, N dimethylamine base-1,3-the third two) amine generation-3-(N, N dimethylamine base propyl group) propionic acid amide, promptly BDMAPA is as raw material, under the effect of loaded catalyst, carry out the thermo-cracking building-up reactions, improved the yield of thermo-cracking step greatly.And utilizing reaction unit of the present invention, can be the fixed bed continuous production processes with existing single still batch production process reform.Therefore, advantage of the present invention is as follows: equipment is simple, and is easy to operate, easy control of reaction conditions, and the productive rate height, product quality is good, and industrial a small amount of investment of needs just can realize scale operation.
Description of drawings
Fig. 1 is the annexation synoptic diagram of reaction unit of the present invention.
Embodiment
With reference to above-mentioned accompanying drawing, the specific embodiment of the present invention is elaborated.Fig. 1 has provided a kind of reaction unit that is used to realize the synthetic method of methacryloyl-(N, N-dimethylated propyl diethylenetriamine), comprises test tank 1 that BDMAPA is provided and the fixed-bed reactor 5 that carry out the thermo-cracking building-up reactions; The upper end of these fixed-bed reactor 5 (being entrance end) is provided with inert filler 6, the lower end of fixed-bed reactor 5 (being exit end) is provided with inert filler 10, and the interlude of fixed-bed reactor 5 (be between inert filler 6 and the inert filler 10 institute have living space) is provided with loaded catalyst 9.The outside surface of fixed-bed reactor 5 is with heating jacket 8, is used for fixed-bed reactor 5 are heated, and this heating jacket 8 is provided with thermometer 7.Test tank 1, pipeline 2, fixed-bed reactor 5, pipeline 11, condenser 12, pipeline 14, rectification under vacuum device 15 link to each other successively.Be provided with stopping valve 3 and volume pump 4 successively according to flowing on the pipeline 2, pipeline 14 is provided with stopping valve 13.
Fixed-bed reactor 5 can be selected a stainless steel reaction pipe for use, its internal diameter Φ=7.5mm, useful length 600mm, effective volume 110～120ml (representing the interlude of fixed-bed reactor 5), loading catalyst 100 grams generally speaking.
Utilize above-mentioned reaction unit, the synthetic method of methacryloyl of the present invention-(N, N-dimethylated propyl diethylenetriamine) is carried out following steps successively:
The preparation of step 1, β-(3-the third two for N, N dimethylamine base-1) amine generation-3-(N, N dimethylamine base propyl group) propionic acid amide (BDMAPA):
In the 500ml there-necked flask that magnetic stirring apparatus, thermometer, connection vacuum pump are housed, add methyl methacrylate, 10g magnesium dichloride that 107ml (about 0.1mol) heavily steams through decompression, carry out nitrogen replacement, slowly put into 224g (about 2.2mol) N then, N dimethylamine base propylene diamine, exothermic heat of reaction, treat that heat release stops after, under agitation be heated to 40 ℃ of reaction 4h, be warming up to 90 ℃ of reaction 6h then gradually.Cooled and filtered, with small amount of methanol washing, then at 90 ℃, rectification under vacuum under the 650Pa pressure, 288.2g β-(3-the third two for N, N dimethylamine base-1) amine generation-3-(N, N dimethylamine base propyl group) propionic acid amide (BDMAPA).
Step 2: thermal cracking catalyst (being loaded catalyst) preparation (following percentage number average refers to weight percent).
With the nitrate mixed solution thorough mixing dipping of molecular sieve and Cu and Ni, room temperature is dried the back at 120 ℃ of dry 5h, and again at 400 ℃～450 ℃ roasting 4h, cooling promptly gets required loaded catalyst A naturally.This loaded catalyst A contains 18% Cu and 16% Ni.
With the nitrate mixed solution thorough mixing dipping of gac and Cu and Zn, room temperature is dried the back at 120 ℃ of dry 5h, and again at 400 ℃～450 ℃ roasting 4h, cooling promptly gets required loaded catalyst B naturally.This loaded catalyst B contains 20% Cu and 18% Zn.
With gama-alumina (specific surface area 220-250m
2g
-1) with the nitrate mixed solution thorough mixing dipping of Cu, Ni and Zn, room temperature is dried the back at 120 ℃ of dry 5h, again at 400 ℃～450 ℃ roasting 4h, lowering the temperature naturally promptly gets required loaded catalyst C, D, E.Wherein loaded catalyst C contains 19% Cu, 10% Ni and 9%Zn; Loaded catalyst D contains 19% Cu, 5% Ni and 5%Zn; Loaded catalyst E contains 5% Cu, 5% Ni and 19%Zn.
The preparation of step 3, methacryloyl-(N, N-dimethylated propyl diethylenetriamine):
Change the loaded catalyst kind of using in the foregoing description 1, the temperature of reaction and the reaction time (the sample introduction flow according to BDMAPA is controlled) of thermo-cracking building-up reactions, obtain embodiment 2～6, concrete implementation content and corresponding yield see Table 1.
Table 1
| Sequence number | The loaded catalyst kind | Temperature of reaction (℃) | Reaction time (min) | Yield (%) |
| Embodiment 1 | C | 160 | 10 | 70 |
| Embodiment 2 | A | 100 | 2 | 63 |
| Embodiment 3 | B | 150 | 5 | 84 |
| Embodiment 4 | D | 150 | 2 | 65 |
| Embodiment 5 | C | 170 | 5 | 62 |
| Embodiment 6 | E | 200 | 3 | 55 |
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. methacryloyl-(N, the N-dimethylated propyl diethylenetriamine) synthetic method, it is characterized in that: the β in the test tank-(N, N dimethylamine base-1,3-the third two) amine generation-3-(N, N dimethylamine base propyl group) propionic acid amide enters and carries out heat scission reaction in the fixed-bed reactor that loaded catalyst is housed under volume pump control; Reaction times is 2～10min; Temperature of reaction is 100～200 ℃; Carry out rectification under vacuum after the condensation of reaction products therefrom, promptly get methacryloyl-(N, N-dimethylated propyl diethylenetriamine);
Described loaded catalyst is made by metal-salt and carrier, and metal-salt is at least two kinds in mantoquita, nickel salt and the zinc salt; The metal sum accounts for 15%～40% of loaded catalyst gross weight, and every kind of metal must not be less than 5% of loaded catalyst gross weight.
2. the synthetic method of methacryloyl according to claim 1-(N, N-dimethylated propyl diethylenetriamine), it is characterized in that: described carrier is gama-alumina, activated carbon or zeolite molecular sieve.
3. the synthetic method of methacryloyl according to claim 2-(N, N-dimethylated propyl diethylenetriamine), it is characterized in that: described metal-salt is a nitrate.
4. the synthetic method of methacryloyl according to claim 3-(N, N-dimethylated propyl diethylenetriamine) is characterized in that: described metal-salt and carrier are made loaded catalyst through dipping, drying, calcination steps; Drying step requires 120 ℃ of dry 5h, and calcination steps requires 400 ℃～450 ℃ roasting 4h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101177403B (en) * | 2007-04-12 | 2011-01-26 | 本溪万哈特化工有限公司 | Method for preparing N-dimethylamino propyl methyl acrylamide |
| CN101362706B (en) * | 2008-05-09 | 2012-07-18 | 沈阳万哈特化工有限公司 | Catalytic cracking method for preparing N-(3-dimethylamino propyl) methacrylamide |
| DE102009002239A1 (en) | 2009-04-07 | 2010-10-14 | Evonik Röhm Gmbh | Process for the continuous production of alkylamino (meth) acrylamides |
| CN108047057B (en) * | 2017-12-28 | 2020-06-02 | 山东铂源药业有限公司 | Synthesis method of butenafine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3652671A (en) * | 1970-06-01 | 1972-03-28 | Dow Chemical Co | Process for making a cationic methacrylamide |
| US4287363A (en) * | 1980-09-02 | 1981-09-01 | Texaco Inc. | Preparation of N-(alkylaminoalkyl)acrylamides |
| US4549017A (en) * | 1983-09-23 | 1985-10-22 | Texaco Inc. | Process for the production of N-substituted (meth)acrylamides from (meth)acrylates and amines over a metal oxide or alkoxide catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3652671A (en) * | 1970-06-01 | 1972-03-28 | Dow Chemical Co | Process for making a cationic methacrylamide |
| US4287363A (en) * | 1980-09-02 | 1981-09-01 | Texaco Inc. | Preparation of N-(alkylaminoalkyl)acrylamides |
| US4549017A (en) * | 1983-09-23 | 1985-10-22 | Texaco Inc. | Process for the production of N-substituted (meth)acrylamides from (meth)acrylates and amines over a metal oxide or alkoxide catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 二甲胺基丙撑丙烯酰胺的合成与纸张增强. 周仲实，朱敏.中华纸业，第2期. 2004 |
| 二甲胺基丙撑丙烯酰胺的合成与纸张增强. 周仲实，朱敏.中华纸业，第2期. 2004 * |
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Owner name: JIANGSU FEYMER TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: FEIXIANG CHEMICAL CO., LTD., JIANGSU Effective date: 20120620 |
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Effective date of registration: 20120620 Address after: Phoenix yangjiaqiao town of Zhangjiagang city 215613 Suzhou city in Jiangsu Province Co-patentee after: Zhejiang University Patentee after: Jiangsu Feymer Technology Co., Ltd. Address before: 215613, No. 8 slip road, Fenghuang Town, Zhangjiagang, Jiangsu, Suzhou Co-patentee before: Zhejiang University Patentee before: Feixiang Chemical Co., Ltd., Jiangsu |