阅读说明：本技术 一种双（2-二甲基胺基乙基）醚的制备方法 (A kind of preparation method of bis- (2- dimethyl amido ethyl) ethers ) 是由 方旺旺 刘帅 应钱晶 于 2019-04-15 设计创作，主要内容包括：本发明公开了一种双(2-二甲基胺基乙基)醚的制备方法,以二甲胺和二甘醇为原料,在催化剂作用下一步反应得到,所述催化剂包括活性组分和载体,所述载体为经水热处理脱铝改性后的γ-Al<Sub>2</Sub>O<Sub>3</Sub>。本发明通过对催化剂的载体进行水热处理脱铝改性,以实现提升催化剂的酸性活性的目的,大大提高了二甘醇周围局部的二甲胺浓度,进而大大提高了目标产物的选择性及收率,同时原料的转化率也可达99％以上。(The invention discloses a kind of preparation methods of bis- (2- dimethyl amido ethyl) ethers, using dimethylamine and diethylene glycol (DEG) as raw material, single step reaction obtains under the action of catalyst, and the catalyst includes active component and carrier, and the carrier is the γ-Al after hydrothermal treatment Dealumination 2 O 3 .The present invention carries out hydro-thermal process Dealumination by the carrier to catalyst, to realize the active purpose of acidity for promoting catalyst, substantially increase dimethylamine concentration local around diethylene glycol (DEG), and then the selectivity and yield of target product are substantially increased, while the conversion ratio of raw material is also up to 99% or more.)

1. a kind of preparation method of bis- (2- dimethyl amido ethyl) ethers is made using dimethylamine and diethylene glycol (DEG) as raw material in catalyst It is obtained with next step reaction, which is characterized in that the catalyst includes active component and carrier, and the carrier is hydrothermal treatment γ-Al after Dealumination₂O₃。

2. the preparation method of bis- (2- dimethyl amido ethyl) ethers according to claim 1, which is characterized in that the hydro-thermal Dealumination is handled, specifically:

By γ-Al₂O₃It is placed under high-pressure water vapor and purges certain time to get modified γ-Al is arrived₂O₃；

The pressure of the high-pressure water vapor is 0.1~0.8MPa, and purge time is 1~12h.

3. the preparation method of bis- (2- dimethyl amido ethyl) ethers according to claim 2, which is characterized in that the high pressure The pressure of water vapour is 0.3~0.5MPa, and purge time is 6~12h.

4. the preparation method of bis- (2- dimethyl amido ethyl) ethers according to claim 1, which is characterized in that the activity Component includes main active component and alternative addition ground Supplementary active compounds；

The main active component is Cu and/or Ni and their oxide；

The Supplementary active compounds are selected from least one of Cr, Co, Fe, La, Mn, Zn.

5. the preparation method of bis- (2- dimethyl amido ethyl) ethers according to claim 1, which is characterized in that the activity Component includes Cu and/or Ni and Co.

6. the preparation method of bis- (2- dimethyl amido ethyl) ethers according to claim 1, which is characterized in that the activity Component includes Cu, Cr and Co.

7. the preparation method of bis- (2- dimethyl amido ethyl) ethers according to claim 1, which is characterized in that with catalyst Gross mass meter, the quality accounting of the active component are 10~30%, and the quality accounting of carrier is 50~70%.

8. the preparation method of bis- (2- dimethyl amido ethyl) ethers according to claim 1, which is characterized in that specifically:

The catalyst, dimethylamine and diethylene glycol (DEG) after Hydrogen activation is added in reactor, under hydrogen atmosphere, control reaction Pressure is 1.0~4.0MPa, and reaction temperature is 150~210 DEG C, post-treated after reaction to obtain bis- (2- diformazans Base amido ethyl) ether.The dimethylamine includes dimethylamine gas, and the solution comprising dimethylamine, for example diformazan amine alcohol is molten Liquid, dimethylamine agueous solution etc..

9. the preparation method of bis- (2- dimethyl amido ethyl) ethers according to claim 1 or claim 7, which is characterized in that described Reaction temperature is 150~210 DEG C.

10. the preparation method of bis- (2- dimethyl amido ethyl) ethers according to claim 1 or claim 7, which is characterized in that described The mass ratio of dimethylamine and diethylene glycol (DEG) is 1:1~3:1.

Technical field

The present invention relates to Polyurethane foaming agent fields, and in particular to a kind of bis- (2- dimethyl amido ethyl) ethers of foaming agent Preparation method.

Background technique

Bis- (2- dimethyl amido ethyl) ethers are a kind of common Polyurethane foaming agent, referred to as diamine ether, abbreviation BDMAEE, usually uses its 70% ethylene glycol solution, which is also referred to as A-1.It is mainly used for flexible polyether type Polyurethane The production of foamed plastics, it can also be used to be packed for hard bubble.A-1 is especially strong to the catalytic effect of water, therefore foam density can be made to drop It is low.It is used to control the effect of reaction for producing gas and accounts for about 80%, and for controlling gel reaction the effect of accounts for about 20%.It is led It wants feature: 1) retardance A-1: extending cream time, foam is made to possess better mobility.2) low smell A-1: contain in structure Active hydrogen can participate in reacting, and product possesses lower amine taste.

Data shows that the catalytic activity of BDMAEE (A-1) is very high, it divides the catalytic efficiency of foaming and gel reaction It is not 1.5 times and 1.1 times of triethylene diamine (A-33), is suitable for almost the production of all foam plastic products, is particularly suitable for Height rebound and reaction injection molding (RIM) product.

Currently, the main technique of production BDMAEE has:

(1) with N, N- dimethylethanolamine is raw material, the dehydration production BDMAEE under the catalysis of the concentrated sulfuric acid.The process recovery ratio It is low, and a large amount of spent acid is generated, it has been not suitable with the requirement of current environmental protection.

(2) in the gas phase, N is catalyzed using basic zeolite, N- dimethylethanolamine is dehydrated into ether technique.The technique is Richard Paul et al. was reported in 1999.Although the technique uses solid catalyst and carries out catalytic dehydration, acid is avoided Pollution, but the conversion ratio of raw material N, N- dimethylethanolamine is only 56%, BDMAEE selectively about 50%, and yield is only 28%.

(3) a kind of applied metal catalyst is disclosed in the Chinese patent literature of 105837457 A of Publication No. CN The method for synthesizing bis- (dimethylamino ethyl) ethers, metal oxide is first prepared in this method, then is prepared by metal oxide Metallic catalyst is obtained, using the catalytic action of metallic catalyst, using dimethylamine and dimethylamino ethoxy ethyl alcohol as raw material, system It is standby to obtain BDMAEE.The raw material of the process route is dimethylamino ethoxy ethyl alcohol, and not only price is relatively high for the raw material, and not It easily obtains, is unfavorable for the industrialization of the process route.

(4) a kind of method for continuously preparing amine is disclosed in the Chinese patent literature of 1984873 A of Publication No. CN, In describe the technique for preparing BDMAEE through catalytic dehydration using diethylene glycol (DEG) and dimethylamine as raw material.Catalyst uses 55%CuO/ 45% γ-Al₂O₃, catalyst is before filling first at 200 DEG C using hydrogen stream progress reductive heat treatment.Reaction system operation For pressure between 2.0~2.5MPa, reaction temperature is 210 DEG C.The process route avoids raw material problem, and reaction process is only Water is generated, is polluted low.But it having a defect that, the BDMAEE prepared using the catalyst system, yield is low, and only 40%.

Summary of the invention

In view of the above technical problems, the present invention is used using diethylene glycol (DEG) and dimethylamine as raw material, is prepared through catalytic dehydration The process route of BDMAEE substantially increases the conversion ratio of raw material and the selectivity of BDMAEE by optimizing catalyst system And yield.

Inventor is directed to the prior art, using diethylene glycol (DEG) and dimethylamine as raw material, the technique for preparing BDMAEE through catalytic dehydration The lower problem of the selectivity and yield of target product present in route, has carried out deep mechanism study, has found the work The reaction equation of skill route is as follows:

I.e. diethylene glycol (DEG) is first and dimethylamine reaction generates dimethylamino ethoxy ethyl alcohol, and then dimethylamino ethoxy ethyl alcohol is again It is reacted with a molecule dimethylamine, finally obtains BDMAEE.And dimethylamino ethoxy ethyl alcohol is under the effect of the catalyst, being can be with Cyclization reaction occurs, cyclization process reaction formula is as follows:

I.e. itself cyclization occurs for dimethylamino ethoxy ethyl alcohol, after methyl is transferred on a molecule dimethylamine, is formed N-methylmorpholine by-product and trimethylamine by-product.

According to the generation process of N-methylmorpholine, inventor's analysis, when being reacted with diethylene glycol (DEG), if the concentration of dimethylamine is not Local dimethylamine concentration is inadequate around enough or diethylene glycol (DEG), it is possible to cause dimethylamino ethoxy ethyl alcohol that itself occurs Cyclization.Inventor increases dimethylamine concentration thus, and when dimethylamine concentration is much higher than diethylene glycol (DEG), test discovery results change is simultaneously Less, in reaction solution the ratio of N-methylmorpholine still 20% or more.And with the raising of dimethylamine concentration, this ratio It is almost stable.That is, simple increase dimethylamine concentration, can not improve the dimethylamine concentration to react.

Based on above-mentioned conclusion, inventor has found after further study again, and in the reaction process, dimethylamine is first by catalyst After absorption, then with equally by the diethylene glycol (DEG) of Catalyst Adsorption anti-life react, therefore, inventor have also been proposed by raising catalyst The mode of the dimethylamine concentration of absorption promotes dimethylamine concentration local around diethylene glycol (DEG).The aobvious alkalinity of dimethylamine, thus improve The acidity activity of catalyst becomes key of the invention.

Based on the above analysis, it is as follows to inventors herein propose specific technical solution:

A kind of preparation method of bis- (2- dimethyl amido ethyl) ethers, using dimethylamine and diethylene glycol (DEG) as raw material, in catalyst Reaction obtains in next step for effect, and the catalyst includes active component and carrier, and the carrier is hydrothermal treatment Dealumination γ-Al afterwards₂O₃。

The present invention carries out hydro-thermal process by the carrier to catalyst and is modified, to realize that the acidity for improving catalyst is active Purpose substantially increases dimethylamine concentration local around diethylene glycol (DEG), and then substantially increases the selectivity and receipts of target product Rate, while the conversion ratio of raw material also may be up to 99% or more.

The hydro-thermal process Dealumination, specifically:

By γ-Al₂O₃It is placed under high-pressure water vapor and purges certain time to get modified γ-Al is arrived₂O₃；

The pressure of the high-pressure water vapor is 0.1~0.8MPa, and purge time is 1~12h.

Hydro-thermal process Dealumination can be real by regulating and controlling different water vapor pressures and different modification time Now to the regulation of acidity of catalyst range.

Preferably, the pressure of the high-pressure water vapor is 0.3~0.5MPa, and purge time is 6~12h.It is found through experiment that When using the modified obtained γ-Al of technological parameter by above-mentioned optimization₂O₃The catalyst of carrier preparation, can will be in catalyst Acid field of activity control in suitable range, further tested discovery, urged with the suitable acidity field of activity Agent carries out catalysis reaction, and the selectivity of (2- dimethyl amido ethyl) ethers bis- in product can be improved, reduce the content of by-product.

The catalyst, active component include main active component and alternative addition ground Supplementary active compounds；

The main active component is Cu and/or Ni and their oxide；

The Supplementary active compounds are selected from least one of Cr, Co, Fe, La, Mn, Zn.

In the present invention, as necessary component, function is to be catalyzed the generation of de-/hydrogenation reaction main active component.And it is auxiliary Help active component as optional Component, the property of can choose is added.In addition, in the present invention, it is also that Supplementary active compounds are further Three classes are divided into, one kind stablizes main active component to play, and the second component for preventing it to be lost is selected from Cr, Co, Fe；One kind is For the third component of regulation system Acid and basic sites, it is selected from Co, Fe, La, Mn, Zn；

Preferably, the active component of the catalyst includes Cu and/or Ni and Co.It is found through experiment that the addition of Co can To further increase the selectivity of BDMAEE.Analyzing reason may be the γ-Al of Co and hydrothermal treatment Dealumination₂O₃It generates Mutual collaboration, by the acid Active Regulation of catalyst to more particularly suitable range.

Preferably, Cr can also be added in active component, on the one hand the addition of Cr can disperse main active component, can also be with The loss of inhibitory activity component improves the service life of catalyst.

Further preferably, the active component includes Cu, Cr and Co.It is found through experiment that the active component of the special composition In conjunction with the γ-Al after special modification₂O₃Carrier has optimal catalytic effect.

In terms of the gross mass of catalyst, main active component accounting is 15~30%, and the second component accounting is 5~10%, the Three component accountings are 0~5%, and the 4th component accounting is 0~5%.

In terms of catalyst gross mass, the quality accounting of the active component is 20~50%, and the quality accounting of carrier is 50 ~80%.

The catalyst can be prepared using conventional technique, such as infusion process, kneading extrusion method.

Kneading extrusion method is used in the present invention, specifically:

The band water nitrate crystallization heating of active component is turned into aqueous solution, then by modified carrier until dissolution It is proportionally added into above-mentioned solution, mediates extrusion after mixing evenly, then obtain catalyst after drying, roasting.

The preparation method of bis- (2- dimethyl amido ethyl) ethers, specifically:

The catalyst, dimethylamine and diethylene glycol (DEG) after Hydrogen activation is added in reactor, under hydrogen atmosphere, control Reaction pressure is 1.0~4.0MPa, and reaction temperature is 150~210 DEG C, post-treated after reaction to obtain bis- (2- Dimethyl amido ethyl) ether.

The temperature of the Hydrogen activation is 250~320 DEG C, and the time is 1~10h；

The mass ratio of the dimethylamine and diethylene glycol (DEG) is 1:1~3:1, and the mode of being passed through can be dimethylamine, diethylene glycol (DEG) and solvent With 0.1~2h^-1Air speed be passed through fixed bed, preferably 0.5h^-1。

Further preferably, the reaction temperature is 170~190 DEG C.It is found through experiment that compared to the reaction for being higher than 190 DEG C Temperature under the preferred range, can be further improved the selectivity of BDMAEE, reduce containing for by-product N-methylmorpholine Amount.

Further preferably, the group of the catalyst becomes Cu-20%/Cr-7%/Co-5%/modification γ-Al₂O₃Carrier 68%.

Reaction temperature is 170 DEG C, reaction pressure 3.0Mpa, and the mass ratio of dimethylamine and diethylene glycol (DEG) is 2.5:1, diethylene glycol (DEG) Intake per minute is the 1/200 of catalyst quality.

Compared with prior art, the present invention has the advantage that

The present invention is used using diethylene glycol (DEG) and dimethylamine as raw material, and the process route of BDMAEE is prepared through catalytic dehydration, is passed through Hydro-thermal process Dealumination is carried out to the carrier of catalyst, to realize the active purpose of acidity for promoting catalyst, is greatly improved Local dimethylamine concentration around diethylene glycol (DEG), and then substantially increase the selectivity and yield of target product, while raw material Conversion ratio also may be up to 99% or more.

Specific embodiment

Hydrothermal modification γ-Al₂O₃The preparation of carrier, by γ-Al₂O₃Be placed under high-pressure water vapor purge certain time to get To modified γ-Al₂O₃, the carrier being prepared under different modified techniques is listed in the table below in 1.

Table 1

Serial number	Pressure/MPa	Time/h	Bearer number
				1	0.1	12	Carrier -1
2	0.3	6	Carrier -2
				3	0.5	12	Carrier -3
4	0.6	6	Carrier -4
				5	0.8	12	Carrier -5