CN110423340A - A kind of method and reaction unit using micro flow field reaction technology preparation high-quality polyether carboxylation - Google Patents
A kind of method and reaction unit using micro flow field reaction technology preparation high-quality polyether carboxylation Download PDFInfo
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Abstract
The present invention provides a kind of method using micro flow field reaction technology preparation high-quality polyether carboxylation, include the following steps: to react in the first micro-structured reactor for injecting microchannel module reaction unit after the mixing of the first micro-mixer of microchannel module reaction unit after (1) dissolves polyether polyol, catalyst, aqueous sodium hypochlorite solution and inorganic base with solvent；(2) the second micro-structured reactor that microchannel module reaction unit is injected after mixing mixed system obtained in step (1) by the second micro-mixer of microchannel module reaction unit with sodium chlorite buffer solution reacts；(3) mixed system obtained in step (2) is collected in collector, post-processes, obtains high-quality polyether carboxylation.The method of the present invention have many advantages, such as environmentally protective, safe and efficient, raw material be easy to get and it is cheap, without hypertoxic reactant residual, reaction speed it is fast.
Description
Technical field
The invention belongs to polyether carboxylations to prepare synthesis field, in particular to a kind of high using the preparation of micro flow field reaction technology
The method and reaction unit of quality polyether carboxylation.
Background technique
Polyether carboxylation is a kind of novel anionic surfactant, is being modified by nonionic surfactant,
Because it is embedded in the epoxy group of certain adduct number between hydrophobic group and hydrophilic group, such as propylene oxide, ethylene oxide, so tool
The characteristic for thering are other anionic surfactants not have, as temperature-resistant anti-salt performance is strong, small toxicity, easily biological-degradable, surface
Tension is low and the features such as with other surfaces activating agent good compatibility, is a kind of multifunction green surfactant.Due to its spy
Different property, the surfactant of polyether carboxylic acid's salt is in cosmetics, detergent, biochemistry, plastics, leather, pharmacy, food
The fields such as processing and petroleum industry have a wide range of applications.
Although existing preparation method is more, the prior art how is solved when preparing polyether carboxylation, it is existing
Preparation cost is excessively high, the amplification of inefficiency, engineering is difficult, and is still important containing the problems such as violent in toxicity residual wait solve in product
Certainly problem.
Summary of the invention
When the purpose of the present invention is to solve preparing polyether carboxylation in the prior art, existing preparation cost is excessively high,
Inefficiency, engineering amplification are difficult, and are still important problem to be solved containing the problems such as violent in toxicity residual in product, provide
A method of high-quality polyether carboxylation is prepared using micro flow field reaction technology, is included the following steps:
(1) through microchannel module after polyether polyol, catalyst, aqueous sodium hypochlorite solution and inorganic base being dissolved with solvent
Change reaction unit the first micro-mixer mixing after inject microchannel module reaction unit the first micro-structured reactor in into
Row reaction；
(2) mixed system obtained in step (1) and sodium chlorite solution are passed through into microchannel module reaction unit
The second micro-mixer mixing after inject microchannel module reaction unit the second micro-structured reactor reacted；
(3) mixed system obtained in step (2) is imported in the product collector in microchannel module reaction unit,
It is post-processed, obtains polyether carboxylation.
As an improvement, catalyst is precious metal based catalysts, Louis's acid compounds, NO free radical in step (1)
Any in class compound or halogen-based compounds, the dosage of catalyst is the 1~10% of polyether polyol mole.
As an improvement, precious metal based catalysts are one or more of platinum, palladium, ruthenium, rhodium, silver, Louis in step (1)
This acid compounds is one or more of boron trifluoride, sulfur trioxide, ferric trichloride, antimony pentafluoride, NO free radical class
Compound is piperidine NO free radical, in pyrrolidines NO free radical, oxazolidine NO free radical, proxyl NO free radical
One or more, halogen-based compounds be one of sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide or
It is several.
As an improvement, in step (1), sodium hypochlorite is the aqueous solution of available chlorine content 5~10%, polyether polyol and time
The molar ratio of sodium chlorate is 1:(1~10), preferred 1:(1~5).
As an improvement, the inorganic base is sodium carbonate, sodium bicarbonate, potassium carbonate, sodium chloride or bromination in step (1)
Any in potassium, wherein the additive amount of inorganic base is the 5~20% of polyether polyol mole.
As an improvement, the solvent is ethyl acetate, dimethyl sulfoxide, acetonitrile, dichloroethanes, dichloro in step (1)
It is any in methane or water.
As an improvement, the first micro-structured reactor of the microchannel module reaction unit reacts temperature in step (1)
Degree is 0~90 DEG C, and reaction time is 3~30min, and the flow velocity of the mixed solution obtained after the mixing of the first micro-mixer is
0.5~5mL/min, the first micro-structured reactor volume are 5~50mL.
As an improvement, sodium chlorite solution's the preparation method comprises the following steps: dissolve and fill sodium chlorite solvent in step (2)
Divide stirring, solvent is to appoint in deionized water, sodium bicarbonate solution, sodium chloride solution, phosphate buffer solution or hac buffer
One kind, wherein the molar ratio of sodium chlorite and polyether polyol is 1:(1~10), preferred 1:(1~5).
As an improvement, the second micro-structured reactor of the microchannel module reaction unit reacts temperature in step (2)
Degree is 10~100 DEG C, and reaction time is 3~30min, and mixed system obtained by step (1) and sodium chlorite solution are through second
The mixed flow velocity of micro-mixer is 0.1~10mL/min, and the second micro-structured reactor volume is 5~50mL.
Meanwhile the present invention also provides a kind of device that the above method reacts, including microchannel module reaction unit,
The microchannel module reaction unit include the first micro-mixer being sequentially connected by pipeline, the first micro-structured reactor,
Second micro-mixer, the second micro-structured reactor and product collector；Wherein, the first raw material storage tank and the second raw material storage tank difference
It is connected with the feed inlet of the first micro-mixer, third raw material storage tank is connected with the feed inlet of the second micro-mixer.
The utility model has the advantages that a kind of method using micro flow field reaction technology preparation high-quality polyether carboxylation of method of the invention
And reaction unit, the reaction unit is by setting microchannel module reaction unit, and wherein it includes being sequentially connected by pipeline
First micro-mixer, the first micro-structured reactor, the second micro-mixer, the second micro-structured reactor and product collector；This dress
The first raw material storage tank and the second raw material storage tank are connected with the feed inlet of the first micro-mixer respectively in setting, third raw material storage tank and
The feed inlet of two micro-mixers is connected, and the device is novel, and preparation is simple.It is easy to get with environmentally protective, safe and efficient, raw material
And it is cheap, without hypertoxic reactant residual, reaction speed is fast the advantages that.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of reaction unit of the present invention.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below
Example is not intended to limit the scope of the invention for illustrating the present invention.
Embodiment 1
By the raw material storage tank 1 equipped with catalyst TEMPO and the aqueous solution of polyether polyol and sodium hypochlorite and bromination are housed
The raw material storage tank 2 of the aqueous solution of sodium is injected into the micro-structure of microchannel module reaction unit after micro-mixer 1 is sufficiently mixed
In reactor 1, the content of catalyst is the 5% of polyether polyol mole, and the content of co-catalyst sodium bromide is polyether polyols
The molar ratio of the 5% of alcohol mole, polyether polyol and sodium hypochlorite is 1:5, and 15min is stopped at 10 DEG C, mixed solution
Flow velocity is 0.6mL/min, and the volume of micro-structured reactor 1 is 5mL；The discharging of micro-structured reactor 1 and sodium chlorite phosphoric acid buffer
It is taken up in order of priority after solution mixing by micro-mixer 2, micro-structured reactor 2, wherein control polyether polyol and sodium chlorite
Molar ratio is 1:5, and the flow velocity that micro-structured reactor 1 discharges is 0.9mL/min, and the volume of micro-structured reactor 2 is 5mL.80
5min is stopped at DEG C, the discharging of micro-structured reactor 2 imported into product collector, product is poured into dilute hydrochloric acid solution rapidly,
The acidic aqueous solution is heated, organic phase and aqueous phase separation are promoted；Organic phase is collected, and is repeatedly washed with deionized water, hydrogen-oxygen is used
Changing sodium solution to be neutralized to pH is 8.5~9.5 to get to fatty alcohol ether carboxylic acid sodium product.It is measured after taking a small amount of sample to be acidified
Its acescency is 75.6%, and the conversion ratio of polyether polyol is 88.1%.
Embodiment 2
By the raw material storage tank 1 equipped with catalyst TEMPO and the aqueous solution of polyether polyol and sodium hypochlorite and bromination are housed
The raw material storage tank 2 of the aqueous solution of sodium is injected into the micro-structure of microchannel module reaction unit after micro-mixer 1 is sufficiently mixed
In reactor 1, the content of catalyst is the 15% of polyether polyol mole, and the content of co-catalyst sodium bromide is polyether polyols
The molar ratio of the 10% of alcohol mole, polyether polyol and sodium hypochlorite is 1:5, and 15min is stopped at 30 DEG C, mixed solution
Flow velocity is 0.3mL/min, and the volume of micro-structured reactor 1 is 5mL；The discharging of micro-structured reactor 1 and sodium chlorite phosphoric acid buffer
It is taken up in order of priority after solution mixing by micro-mixer 2, micro-structured reactor 2, wherein control polyether polyol and sodium chlorite
Molar ratio is 1:5, and the flow velocity that micro-structured reactor 1 discharges is 0.45mL/min, and the volume of micro-structured reactor 2 is 5mL.80
5min is stopped at DEG C, the discharging of micro-structured reactor 2 imported into product collector, product is poured into dilute hydrochloric acid solution rapidly,
The acidic aqueous solution is heated, organic phase and aqueous phase separation are promoted；Organic phase is collected, and is repeatedly washed with deionized water, hydrogen-oxygen is used
Changing sodium solution to be neutralized to pH is 8.5~9.5 to get to fatty alcohol ether carboxylic acid sodium product.It is measured after taking a small amount of sample to be acidified
Its acescency is 92.6%, and the conversion ratio of polyether polyol is 96.4%.
Embodiment 3
By the raw material storage tank 1 equipped with catalyst TEMPO and the aqueous solution of polyether polyol and sodium hypochlorite and bromination are housed
The raw material storage tank 2 of the aqueous solution of sodium is injected into the micro-structure of microchannel module reaction unit after micro-mixer 1 is sufficiently mixed
In reactor 1, the content of catalyst is the 10% of polyether polyol mole, and the content of co-catalyst sodium bromide is polyether polyols
The molar ratio of the 10% of alcohol mole, polyether polyol and sodium hypochlorite is 1:5, and 30min is stopped at 20 DEG C, mixed solution
Flow velocity is 0.2mL/min, and the volume of micro-structured reactor 1 is 5mL；The discharging of micro-structured reactor 1 and sodium chlorite phosphoric acid buffer
It is taken up in order of priority after solution mixing by micro-mixer 2, micro-structured reactor 2, wherein control polyether polyol and sodium chlorite
Molar ratio is 1:5, and the flow velocity that micro-structured reactor 1 discharges is 0.3mL/min, and the volume of micro-structured reactor 2 is 5mL.50
10min is stopped at DEG C, the discharging of micro-structured reactor 2 imported into product collector, product is poured into dilute hydrochloric acid solution rapidly,
The acidic aqueous solution is heated, organic phase and aqueous phase separation are promoted；Organic phase is collected, and is repeatedly washed with deionized water, hydrogen-oxygen is used
Changing sodium solution to be neutralized to pH is 8.5~9.5 to get to fatty alcohol ether carboxylic acid sodium product.It is measured after taking a small amount of sample to be acidified
Its acescency is 87.5%, and the conversion ratio of polyether polyol is 89.6%.
Embodiment 4
By the raw material storage tank 1 equipped with catalyst TEMPO and the aqueous solution of polyether polyol and sodium hypochlorite and bromination are housed
The raw material storage tank 2 of the aqueous solution of sodium is injected into the micro-structure of microchannel module reaction unit after micro-mixer 1 is sufficiently mixed
In reactor 1, the content of catalyst is the 5% of polyether polyol mole, and the content of co-catalyst sodium bromide is polyether polyols
The molar ratio of the 5% of alcohol mole, polyether polyol and sodium hypochlorite is 1:3, and 5min, the stream of mixed solution are stopped at 50 DEG C
Speed is 0.3mL/min, and the volume of micro-structured reactor 1 is 5mL；The discharging of micro-structured reactor 1 is molten with sodium chlorite phosphoric acid buffer
It is taken up in order of priority after liquid mixing by micro-mixer 2, micro-structured reactor 2, wherein control polyether polyol and sodium chlorite rub
You are than being 1:5, and the flow velocity that micro-structured reactor 1 discharges is 0.45mL/min, and the volume of micro-structured reactor 2 is 5mL.At 50 DEG C
Lower stop 10min, the discharging of micro-structured reactor 2 imported into product collector, product are poured into dilute hydrochloric acid solution rapidly, is added
The hot acidic aqueous solution, promotes organic phase and aqueous phase separation；Organic phase is collected, and is repeatedly washed with deionized water, hydroxide is used
It is 8.5~9.5 to get to fatty alcohol ether carboxylic acid sodium product that sodium solution, which is neutralized to pH,.It is measured after taking a small amount of sample to be acidified
Acescency is 78.5%, and the conversion ratio of polyether polyol is 83.1%.
Embodiment 5
By the raw material storage tank 1 equipped with catalyst TEMPO and the aqueous solution of polyether polyol and sodium hypochlorite and bromination are housed
The raw material storage tank 2 of the aqueous solution of sodium is injected into the micro-structure of microchannel module reaction unit after micro-mixer 1 is sufficiently mixed
In reactor 1, the content of catalyst is the 5% of polyether polyol mole, and the content of co-catalyst sodium bromide is polyether polyols
The molar ratio of the 5% of alcohol mole, polyether polyol and sodium hypochlorite is 1:5, and 10min is stopped at 30 DEG C, mixed solution
Flow velocity is 0.3mL/min, and the volume of micro-structured reactor 1 is 5mL；The discharging of micro-structured reactor 1 and sodium chlorite phosphoric acid buffer
It is taken up in order of priority after solution mixing by micro-mixer 2, micro-structured reactor 2, wherein control polyether polyol and sodium chlorite
Molar ratio is 1:3, and the flow velocity that micro-structured reactor 1 discharges is 0.45mL/min, and the volume of micro-structured reactor 2 is 5mL.80
10min is stopped at DEG C, the discharging of micro-structured reactor 2 imported into product collector, product is poured into dilute hydrochloric acid solution rapidly,
The acidic aqueous solution is heated, organic phase and aqueous phase separation are promoted；Organic phase is collected, and is repeatedly washed with deionized water, hydrogen-oxygen is used
Changing sodium solution to be neutralized to pH is 8.5~9.5 to get to fatty alcohol ether carboxylic acid sodium product.It is measured after taking a small amount of sample to be acidified
Its acescency is 85.7%, and the conversion ratio of polyether polyol is 79.3%.
Embodiment 6
By the raw material storage tank 1 equipped with catalyst TEMPO and the aqueous solution of polyether polyol and sodium hypochlorite and bromination are housed
The raw material storage tank 2 of the aqueous solution of sodium is injected into the micro-structure of microchannel module reaction unit after micro-mixer 1 is sufficiently mixed
In reactor 1, the content of catalyst is the 5% of polyether polyol mole, and the content of co-catalyst sodium bromide is polyether polyols
The molar ratio of the 10% of alcohol mole, polyether polyol and sodium hypochlorite is 1:3, and 10min is stopped at 30 DEG C, mixed solution
Flow velocity is 0.2mL/min, and the volume of micro-structured reactor 1 is 5mL；The discharging of micro-structured reactor 1 and sodium chlorite phosphoric acid buffer
It is taken up in order of priority after solution mixing by micro-mixer 2, micro-structured reactor 2, wherein control polyether polyol and sodium chlorite
Molar ratio is 1:3, and the flow velocity that micro-structured reactor 1 discharges is 0.3mL/min, and the volume of micro-structured reactor 2 is 5mL.80
10min is stopped at DEG C, the discharging of micro-structured reactor 2 imported into product collector, product is poured into dilute hydrochloric acid solution rapidly,
The acidic aqueous solution is heated, organic phase and aqueous phase separation are promoted；Organic phase is collected, and is repeatedly washed with deionized water, hydrogen-oxygen is used
Changing sodium solution to be neutralized to pH is 8.5~9.5 to get to fatty alcohol ether carboxylic acid sodium product.It is measured after taking a small amount of sample to be acidified
Its acescency is 88.5%, and the conversion ratio of polyether polyol is 85.3%.
Embodiment 7
By the raw material storage tank 1 equipped with catalyst TEMPO and the aqueous solution of polyether polyol and sodium hypochlorite and bromination are housed
The raw material storage tank 2 of the aqueous solution of sodium is injected into the micro-structure of microchannel module reaction unit after micro-mixer 1 is sufficiently mixed
In reactor 1, the content of catalyst is the 10% of polyether polyol mole, and the content of co-catalyst sodium bromide is polyether polyols
The molar ratio of the 5% of alcohol mole, polyether polyol and sodium hypochlorite is 1:5, and 5min, the stream of mixed solution are stopped at 20 DEG C
Speed is 0.3mL/min, and the volume of micro-structured reactor 1 is 5mL；The discharging of micro-structured reactor 1 is molten with sodium chlorite phosphoric acid buffer
It is taken up in order of priority after liquid mixing by micro-mixer 2, micro-structured reactor 2, wherein control polyether polyol and sodium chlorite rub
You are than being 1:5, and the flow velocity that micro-structured reactor 1 discharges is 0.45mL/min, and the volume of micro-structured reactor 2 is 5mL.At 90 DEG C
Lower stop 10min, the discharging of micro-structured reactor 2 imported into product collector, product are poured into dilute hydrochloric acid solution rapidly, is added
The hot acidic aqueous solution, promotes organic phase and aqueous phase separation；Organic phase is collected, and is repeatedly washed with deionized water, hydroxide is used
It is 8.5~9.5 to get to fatty alcohol ether carboxylic acid sodium product that sodium solution, which is neutralized to pH,.It is measured after taking a small amount of sample to be acidified
Acescency is 82.7%, and the conversion ratio of polyether polyol is 85.5%.
Embodiment 8
By the raw material storage tank 1 equipped with catalyst TEMPO and the aqueous solution of polyether polyol and sodium hypochlorite and bromination are housed
The raw material storage tank 2 of the aqueous solution of sodium is injected into the micro-structure of microchannel module reaction unit after micro-mixer 1 is sufficiently mixed
In reactor 1, the content of catalyst is the 5% of polyether polyol mole, and the content of co-catalyst sodium bromide is polyether polyols
The molar ratio of the 5% of alcohol mole, polyether polyol and sodium hypochlorite is 1:3, and 5min, the stream of mixed solution are stopped at 30 DEG C
Speed is 0.4mL/min, and the volume of micro-structured reactor 1 is 5mL；The discharging of micro-structured reactor 1 is molten with sodium chlorite phosphoric acid buffer
It is taken up in order of priority after liquid mixing by micro-mixer 2, micro-structured reactor 2, wherein control polyether polyol and sodium chlorite rub
You are than being 1:5, and the flow velocity that micro-structured reactor 1 discharges is 0.6mL/min, and the volume of micro-structured reactor 2 is 5mL.At 70 DEG C
Lower stop 5min, the discharging of micro-structured reactor 2 imported into product collector, product are poured into dilute hydrochloric acid solution rapidly, is added
The hot acidic aqueous solution, promotes organic phase and aqueous phase separation；Organic phase is collected, and is repeatedly washed with deionized water, hydroxide is used
It is 8.5~9.5 to get to fatty alcohol ether carboxylic acid sodium product that sodium solution, which is neutralized to pH,.It is measured after taking a small amount of sample to be acidified
Acescency is 83.3%, and the conversion ratio of polyether polyol is 85.2%.
Embodiment 9
By the raw material storage tank 1 equipped with catalyst TEMPO and the aqueous solution of polyether polyol and sodium hypochlorite and bromination are housed
The raw material storage tank 2 of the aqueous solution of sodium is injected into the micro-structure of microchannel module reaction unit after micro-mixer 1 is sufficiently mixed
In reactor 1, the content of catalyst is the 10% of polyether polyol mole, and the content of co-catalyst sodium bromide is polyether polyols
The molar ratio of the 10% of alcohol mole, polyether polyol and sodium hypochlorite is 1:4, and 5min is stopped at 10 DEG C, mixed solution
Flow velocity is 0.2mL/min, and the volume of micro-structured reactor 1 is 5mL；The discharging of micro-structured reactor 1 and sodium chlorite phosphoric acid buffer
It is taken up in order of priority after solution mixing by micro-mixer 2, micro-structured reactor 2, wherein control polyether polyol and sodium chlorite
Molar ratio is 1:4, and the flow velocity that micro-structured reactor 1 discharges is 0.3mL/min, and the volume of micro-structured reactor 2 is 5mL.80
5min is stopped at DEG C, the discharging of micro-structured reactor 2 imported into product collector, product is poured into dilute hydrochloric acid solution rapidly,
The acidic aqueous solution is heated, organic phase and aqueous phase separation are promoted；Organic phase is collected, and is repeatedly washed with deionized water, hydrogen-oxygen is used
Changing sodium solution to be neutralized to pH is 8.5~9.5 to get to fatty alcohol ether carboxylic acid sodium product.It is measured after taking a small amount of sample to be acidified
Its acescency is 86.6%, and the conversion ratio of polyether polyol is 85.1%.
Embodiment 10
By the raw material storage tank 1 equipped with catalyst TEMPO and the aqueous solution of polyether polyol and sodium hypochlorite and bromination are housed
The raw material storage tank 2 of the aqueous solution of sodium is injected into the micro-structure of microchannel module reaction unit after micro-mixer 1 is sufficiently mixed
In reactor 1, the content of catalyst is the 5% of polyether polyol mole, and the content of co-catalyst sodium bromide is polyether polyols
The molar ratio of the 10% of alcohol mole, polyether polyol and sodium hypochlorite is 1:5, and 5min is stopped at 30 DEG C, mixed solution
Flow velocity is 0.6mL/min, and the volume of micro-structured reactor 1 is 5mL；The discharging of micro-structured reactor 1 and sodium chlorite phosphoric acid buffer
It is taken up in order of priority after solution mixing by micro-mixer 2, micro-structured reactor 2, wherein control polyether polyol and sodium chlorite
Molar ratio is 1:3, and the flow velocity that micro-structured reactor 1 discharges is 0.9mL/min, and the volume of micro-structured reactor 2 is 5mL.70
10min is stopped at DEG C, the discharging of micro-structured reactor 2 imported into product collector, product is poured into dilute hydrochloric acid solution rapidly,
The acidic aqueous solution is heated, organic phase and aqueous phase separation are promoted；Organic phase is collected, and is repeatedly washed with deionized water, hydrogen-oxygen is used
Changing sodium solution to be neutralized to pH is 8.5~9.5 to get to fatty alcohol ether carboxylic acid sodium product.It is measured after taking a small amount of sample to be acidified
Its acescency is 83.7%, and the conversion ratio of polyether polyol is 82.8%.
Embodiment 11
By the raw material storage tank 1 equipped with catalyst TEMPO and the aqueous solution of polyether polyol and sodium hypochlorite and bromination are housed
The raw material storage tank 2 of the aqueous solution of sodium is injected into the micro-structure of microchannel module reaction unit after micro-mixer 1 is sufficiently mixed
In reactor 1, the content of catalyst is the 5% of polyether polyol mole, and the content of co-catalyst sodium bromide is polyether polyols
The molar ratio of the 5% of alcohol mole, polyether polyol and sodium hypochlorite is 1:3, and 3min, the stream of mixed solution are stopped at 20 DEG C
Speed is 0.3mL/min, and the volume of micro-structured reactor 1 is 5mL；The discharging of micro-structured reactor 1 is molten with sodium chlorite phosphoric acid buffer
It is taken up in order of priority after liquid mixing by micro-mixer 2, micro-structured reactor 2, wherein control polyether polyol and sodium chlorite rub
You are than being 1:5, and the flow velocity that micro-structured reactor 1 discharges is 0.45mL/min, and the volume of micro-structured reactor 2 is 5mL.At 80 DEG C
Lower stop 5min, the discharging of micro-structured reactor 2 imported into product collector, product are poured into dilute hydrochloric acid solution rapidly, is added
The hot acidic aqueous solution, promotes organic phase and aqueous phase separation；Organic phase is collected, and is repeatedly washed with deionized water, hydroxide is used
It is 8.5~9.5 to get to fatty alcohol ether carboxylic acid sodium product that sodium solution, which is neutralized to pH,.It is measured after taking a small amount of sample to be acidified
Acescency is 87.7%, and the conversion ratio of polyether polyol is 80.6%.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of method using micro flow field reaction technology preparation high-quality polyether carboxylation, which is characterized in that including walking as follows
It is rapid:
(1) anti-through microchannel moduleization after dissolving polyether polyol, catalyst, aqueous sodium hypochlorite solution and inorganic base with solvent
It injects in the first micro-structured reactor of microchannel module reaction unit and is carried out instead after answering the first micro-mixer of device to mix
It answers；
(2) mixed system obtained in step (1) and sodium chlorite solution are passed through the second of microchannel module reaction unit
The second micro-structured reactor that microchannel module reaction unit is injected after micro-mixer mixing is reacted；
(3) mixed system obtained in step (2) is imported in the product collector in microchannel module reaction unit, is carried out
Post-processing, obtains polyether carboxylation.
2. the method according to claim 1, wherein catalyst is precious metal based catalysts, road in step (1)
Any in Lewis acid class compound, NO free radical class compound or halogen-based compounds, the dosage of catalyst is that polyethers is more
The 1~10% of first alcohol mole.
3. according to the method described in claim 2, it is characterized in that, in step (1), precious metal based catalysts be platinum, palladium, ruthenium,
One or more of rhodium, silver, Louis's acid compounds are boron trifluoride, in sulfur trioxide, ferric trichloride, antimony pentafluoride
One or more, NO free radical class compound are piperidine NO free radical, pyrrolidines NO free radical, oxazolidine nitrogen oxygen freedom
One or more of base, proxyl NO free radical, halogen-based compounds be sodium chloride, sodium bromide, sodium iodide, potassium chloride,
One or more of potassium bromide, potassium iodide.
4. the method according to claim 1, wherein in step (1), sodium hypochlorite be available chlorine content 5~
The molar ratio of 10% aqueous solution, polyether polyol and sodium hypochlorite is 1:(1~10).
5. the method according to claim 1, wherein the inorganic base is sodium carbonate, carbonic acid in step (1)
It is any in hydrogen sodium, potassium carbonate, sodium chloride or potassium bromide, wherein the additive amount of inorganic base be polyether polyol mole 5~
20%.
6. the method according to claim 1, wherein the solvent is ethyl acetate, diformazan in step (1)
Base sulfoxide, acetonitrile, dichloroethanes, methylene chloride or water kind are any.
7. the method according to claim 1, wherein in step (1), the microchannel module reaction unit
The first micro-structured reactor reaction temperature be 0~90 DEG C, reaction time be 3~30min, through the first micro-mixer mix
The flow velocity of the mixed solution obtained afterwards is 0.5~5mL/min, and the first micro-structured reactor volume is 5~50mL.
8. the method according to claim 1, wherein in step (2), sodium chlorite solution's the preparation method comprises the following steps:
Sodium chlorite solvent is dissolved and is sufficiently stirred, solvent is deionized water, sodium bicarbonate solution, sodium chloride solution, phosphoric acid are slow
Rush it is any in solution or hac buffer, wherein the molar ratio of sodium chlorite and polyether polyol be 1:(1~10).
9. the method according to claim 1, wherein in step (2), the microchannel module reaction unit
The second micro-structured reactor reaction temperature be 10~100 DEG C, reaction time is 3~30min, mixing obtained by step (1)
System and sodium chlorite solution are 0.1~10mL/min through the mixed flow velocity of the second micro-mixer, and second micro-structure is anti-
Answering body product is 5~50mL.
10. the device that a kind of any one of claim 1-9 reacts, which is characterized in that reacted including microchannel module
Device, the microchannel module reaction unit include that the first micro-mixer being sequentially connected by pipeline, the first micro-structure are anti-
Answer device, the second micro-mixer, the second micro-structured reactor and product collector；Wherein, the first raw material storage tank and the storage of the second raw material
Tank is connected with the feed inlet of the first micro-mixer respectively, and third raw material storage tank is connected with the feed inlet of the second micro-mixer.
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