CN109503395A - A kind of stable choline solution and preparation method thereof - Google Patents
A kind of stable choline solution and preparation method thereof Download PDFInfo
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- CN109503395A CN109503395A CN201811594587.8A CN201811594587A CN109503395A CN 109503395 A CN109503395 A CN 109503395A CN 201811594587 A CN201811594587 A CN 201811594587A CN 109503395 A CN109503395 A CN 109503395A
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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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- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/40—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton with quaternised nitrogen atoms bound to carbon atoms of the carbon skeleton
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Abstract
The present invention relates to a kind of stable choline solutions and preparation method thereof, belong to technical field of chemical synthesis.Stable choline solution of the present invention includes bursine, water and carbonic acid choline, and metal ion, property are not stablized, and is a kind of excellent nonmetallic highly basic of wiring board cleaning.Trimethylamine is first added to the water by preparation method to be stirred and evenly mixed, and a certain amount of carbon dioxide is passed through, stirring while adding, obtains the solution of the ammonium carbonate containing trimethyl；Ethylene oxide is added into above-mentioned solution, cools down, stable choline solution of the invention is obtained by filtration.Preparation method does not use poisonous and harmful substance, has prevented the discharge of volatile organic matter in production process (VOC), does not use catalyst, and reaction condition is mild.Using choline carbonate as stabilizer, side reaction is eliminated obviously, and do not introduce other materials, stable production process safety, the fields such as assist side cleaning agent, material preparation, electrochemistry, organic synthesis have a wide range of applications.
Description
Technical field
The present invention relates to a kind of choline solutions and preparation method thereof, and in particular to a kind of stable choline solution and its preparation
Method belongs to technical field of chemical synthesis.
Background technique
Bursine, (CH3)3N(OH)CH2CH2OH also known as hydroxide ethoxy trimethylamine or (2- hydroxyethyl) three
Ammonium hydroxide is a kind of organic alkali, is widely used in the fields such as material preparation, electrochemistry, organic synthesis.In electric wire
Cleaning agent is needed in road plate manufacture cleaning process to dispose the rosin based scaling powder on surface-pasted component and packaging part, lack
The residue of remaining scaling powder, water-soluble flux, uncured welding paste and component is measured, bursine is as a kind of inorganic non-
Metal overbase will not generate volatile contaminant as cleaning agent in application process, and will not because of metal ion and
Wiring board quality is had an impact.
Bursine is a kind of unstable Huffman alkali, and Huffman elimination is easy to happen in water environment, is resolved into
Many by-products such as olefine aldehydr quasi polymer cause such as to darken, form precipitating, volatility, strong gas in choline solution
The variation such as taste.Degradation reaction reduces the quality of choline hydroxide solutions, therefore how to prepare a kind of stable bursine
Solution is the key technology for improving its application.
The prior art uses addition stabilizer to overcome side reaction bring adverse effect, and stabilizer is generally used for processing suddenly
The acetaldehyde that the graceful elimination reaction of husband is discharged, it is required that " removing " of acetaldehyde eliminates the subsequent aldol condensation institute for generating colored polymeric
Reactant.It reacted with acetaldehyde, be easy to restore acetaldehyde or the devastatingly substance with acetaldehyde combined polymerization, such as formaldehyde, azanol, amino
Urea and sulphite are the good stabilizers of choline hydroxide solutions.
United States Patent (USP) US 4686002 is disclosed, and the stabilization concentrate of formaldehyde is added in aqueous choline hydroxide composition,
It prepares and stablizes choline hydroxide composition.Due to toxicity and problem of environmental pollution, the application of formaldehyde, azanol and semicarbazides is limited
System.United States Patent (USP) US 429491 is disclosed, and the stabilization concentrate of sulphite is added in aqueous choline hydroxide composition, system
It is standby to stablize choline hydroxide composition.Since solubility of the sodium sulfite in dense choline solution is lower, dense choline solution still exists
Blackening in the shorter time, therefore sulphite usually requires at higher concentrations effectively.
In addition, boron hydride and alanate can be by acetaldehyde reductions at corresponding alcohol, and it can will be conjugated olefine aldehydr polymer also
Original is at corresponding alcohol, also along with some reduction that conjugated polyene function occurs.But a large amount of hydrogen can be discharged when in reaction process
Gas, there are security risks.
Therefore need to add it is a kind of safe and non-toxic for choline hydroxide solutions and preparation method thereof, to reduce as far as possible
Or eliminate the adverse effect that side reaction generates.
Summary of the invention
In order to overcome the drawbacks of the prior art, the present invention provides a kind of raw material and is easy to get, is stable reaction, environmentally protective, safe
Property high stable choline solution and preparation method thereof, prepared stable choline solution is applied to wiring board cleaning, material
The fields such as preparation, electrochemistry.
To achieve the above object, the technical solution adopted by the present invention to solve the technical problems is:
A kind of stable choline solution, it is characterised in that: include bursine, water and carbonic acid choline.
Preferably, carbonic acid choline concentration is 15 ~ 20% in the choline solution.
A kind of preparation method of stable choline solution, comprising the following steps:
1), trimethylamine is added to the water and is stirred and evenly mixed, carbon dioxide is passed through, stirring while adding, pressure is less than 2kgf/cm2, temperature
10 ~ 40 DEG C, obtain the aqueous solution containing trimethylamine and trimethyl ammonium carbonate；
2) ethylene oxide, is added into aqueous solution made from above-mentioned steps, trimethylamine, ethylene oxide and water reaction generate hydroxide
Choline；Trimethyl ammonium carbonate, ethylene oxide and water reaction generate carbonic acid choline；Cooling, filtering, obtains stable choline solution.
Preferably, the molar ratio of trimethylamine described in step 1) and carbon dioxide is trimethylamine: carbon dioxide=8.5 ~
10:1。
Preferably, trimethylamine described in step 1) is the trimethylamine aqueous solution of concentration 40 ~ 50% or the liquefaction of purity 99%
Trimethylamine.
Preferably, the molar ratio of trimethylamine described in ethylene oxide described in step 2 and step 1) is ethylene oxide:
Trimethylamine=1:1.
Preferably, 30 ~ 60 DEG C are down to described in step 2.
Preferably, cooling described in step 2 is that cooling water temperature or ice water circulation cool.
Preferably, ethylene oxide is added when 30 ~ 60 DEG C of temperature in step 2.
Preferably, ethylene oxide described in step 2 is the liquefaction ethylene oxide of concentration 99%.
Advantageous effects of the invention:
(1) stable choline solution of the invention and preparation method thereof does not use poisonous and harmful substance, has prevented in production process
The discharge of volatile organic matter (VOC), does not use catalyst, and reaction condition is mild.
(2) stable choline solution of the invention and preparation method thereof is using choline carbonate as stabilizer, to side reaction
It eliminates obviously, and does not introduce other materials, process stablizes safety.
(3) stable choline solution of the invention and preparation method thereof economic security, environmentally protective, obtained choline is molten
Liquid stability is good, and there is extensive potential using value in the fields such as assist side cleaning agent, material preparation, electrochemistry, organic synthesis.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiments are some of the embodiments of the present invention, without
It is whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not before making creative work
Every other embodiment obtained is put, shall fall within the protection scope of the present invention, specific embodiment does not limit the present invention.
Embodiment 1:
The liquefaction trimethylamine and 105.24kg water that 75.83kg purity is 99% are added into reaction kettle, is passed through 5.94kg titanium dioxide
Carbon, stirring while adding, pressure is less than 2kgf/cm2, temperature is 10 DEG C, obtains the aqueous solution containing trimethylamine and trimethyl ammonium carbonate；
The liquefaction ethylene oxide of 56.44kg 99% is added when 30 DEG C of temperature, trimethylamine, ethylene oxide and water reaction generate hydroxide gallbladder
Alkali；Trimethyl ammonium carbonate, ethylene oxide and water reaction generate carbonic acid choline；To 30 DEG C, filtering obtains stable cooling water temperature
Choline solution.Carbonic acid choline concentration is 15% in gained choline solution, and bursine concentration is 50%.
Embodiment 2:
The liquefaction trimethylamine and 143.25kg water that 86.58kg purity is 99% are added into reaction kettle, is passed through 9.94kg titanium dioxide
Carbon, stirring while adding, pressure is less than 2kgf/cm2, temperature is 20 DEG C, obtains the aqueous solution containing trimethylamine and trimethyl ammonium carbonate；
The liquefaction ethylene oxide of 64.44 kg 99% is added when 40 DEG C of temperature, trimethylamine, ethylene oxide and water reaction generate hydroxide
Choline；Trimethyl ammonium carbonate, ethylene oxide and water reaction generate carbonic acid choline；Ice water circulation cools to 35 DEG C, and filtering obtains
To stable choline solution.Carbonic acid choline concentration is 20% in gained choline solution, and bursine concentration is 40 %.
Embodiment 3:
The trimethylamine aqueous solution that 189.58kg concentration is 40% is added into reaction kettle, is passed through 5.94kg carbon dioxide, side edged stirs
It mixes, pressure is less than 2kgf/cm2, temperature is 30 DEG C, obtains the aqueous solution containing trimethylamine and trimethyl ammonium carbonate；Work as temperature 50 C
When be added 56.44kg 99% liquefaction ethylene oxide, trimethylamine, ethylene oxide and water reaction generate bursine；Trimethyl
Ammonium carbonate, ethylene oxide and water reaction generate carbonic acid choline；For cooling water temperature to 40 DEG C, filtering obtains stable choline solution.
Carbonic acid choline concentration is 15% in gained choline solution, and bursine concentration is 50%.
Embodiment 4:
The trimethylamine aqueous solution and 29.41kg water that 151.66kg concentration is 50% are added into reaction kettle, is passed through 5.94kg titanium dioxide
Carbon, stirring while adding, pressure is less than 2kgf/cm2, temperature is 40 DEG C, obtains the aqueous solution containing trimethylamine and trimethyl ammonium carbonate；
The liquefaction ethylene oxide of 56.44kg 99% is added when temperature 60 C, trimethylamine, ethylene oxide and water reaction generate hydroxide gallbladder
Alkali；Trimethyl ammonium carbonate, ethylene oxide and water reaction generate carbonic acid choline；To 50 DEG C, filtering obtains stable cooling water temperature
Choline solution.Carbonic acid choline concentration is 15% in gained choline solution, and bursine concentration is 50%.
Embodiment 5:
The trimethylamine aqueous solution that 155.24kg concentration is 50% is added into reaction kettle, is passed through 6.6kg carbon dioxide, side edged stirs
It mixes, pressure is less than 2kgf/cm2, temperature is 40 DEG C, obtains the aqueous solution containing trimethylamine and trimethyl ammonium carbonate；Work as temperature 60 C
When the liquefaction ethylene oxide of 57.78 kg 99% is added, trimethylamine, ethylene oxide and water reaction generate bursine；Trimethyl
Ammonium carbonate, ethylene oxide and water reaction generate carbonic acid choline；Ice water circulation cools to 60 DEG C, and filtering obtains stable gallbladder
Aqueous slkali.Carbonic acid choline concentration is 18.5% in gained choline solution, and bursine concentration is 55%.
Embodiment 6:
The liquefaction trimethylamine and 70.52kg water that 73.20kg purity is 99% are added into reaction kettle, is passed through 4.97kg carbon dioxide,
Stirring while adding, pressure is less than 2kgf/cm2, temperature is 10 DEG C, obtains the aqueous solution containing trimethylamine and trimethyl ammonium carbonate；When
The liquefaction ethylene oxide of 54.49kg 99% is added when temperature 50 C, trimethylamine, ethylene oxide and water reaction generate hydroxide gallbladder
Alkali；Trimethyl ammonium carbonate, ethylene oxide and water reaction generate carbonic acid choline；To 50 DEG C, filtering obtains stable cooling water temperature
Choline solution.Carbonic acid choline concentration is 15% in gained choline solution, and bursine concentration is 60%.
As a result it compares:
The stability of the stable choline solution of the present invention is tested
The stability of choline solution made from above-described embodiment 1~6 is tested respectively, and respectively with: be not added with stabilization
Choline hydroxide solutions that agent concentration is 50% are not added with the choline hydroxide solutions that stabilizer concentration is 60%, addition 1000ppm
The hydroxide gallbladder that choline hydroxide solutions that hydrosulfurous acid na concn is 60%, addition 1000ppm concentration of sodium sulfite are 60%
Aqueous slkali, addition 1000ppm benzaldehyde concentration 60% are that pure cerium hydroxide choline solution 1~5 carries out stability pair as a comparison case
Than.
Test method includes: the choline solution that above-described embodiment 1~6 and the preparation of comparative example 1~5 are covered with nitrogen, is passed through
The Lovibond colorimeter of quartz colorimetric utensil with 5cm path length carries out APHA measurement.
Coloration is judged by the visual assessment across 4cm path length of the grade based on 0~4, and 0 be clarification and water white
(APHA<20)；1 is clear slightly colored appearance (APHA < 100)；2 be clear micro- amber (APHA < 500)；3 be almost
Opaque depth is amber (APHA > 500)；4 be opaque aterrimus (APHA > 500).Specific test result see the table below 1.
1 stability test result of table
Testing result shows:
Slightly to change colour after sample 7 days of stable choline solution Examples 1 to 5 prepared by the present invention, kept in 30~60 days
It is constant, it was demonstrated that choline solution property prepared by the present invention is stablized, and the duration is long.6 sample of embodiment slightly changes colour after 7 days, and 30
Become within~60 days clear micro- amber.Relative to the comparative example 1~2 for being not added with stabilizer, effectively Huffman is inhibited to eliminate.
Being not added with comparative example 1~2 of stabilizer, to begin to change within the 2nd day almost opaque depth amber, becomes within the 4th day
Bright aterrimus, it was demonstrated that the choline hydroxide solutions for addition stabilizer are unstable, are easy to happen Huffman elimination, resolve into alkene
Many by-products such as aldehyde polymer, cause to darken.
The 60% pure cerium hydroxide choline solution of concentration of comparative example 3 plus 1000ppm sodium dithionite slightly changes colour after 7 days, and 30
It is remained unchanged in~60 days, is reaching equi-stable effect with the present invention to a certain degree.
Comparative example 4 adds the 60% pure cerium hydroxide choline solution of concentration of 1000ppm sodium sulfite and comparative example 5 is added
The 60% pure cerium hydroxide choline solution of concentration of 1000ppm benzaldehyde slightly changes colour after 1 day, becomes clear micro- amber after 7 days,
The depth for becoming almost opaque after 30 days is amber.
In conclusion stable choline solution of the invention and preparation method thereof is using choline carbonate as stabilizer,
Side reaction is eliminated obviously, it is permanent to stablize the retention time, and do not introduce other materials, process stablizes safety.
It is pointed out that the technical concepts and features of above-mentioned preferred embodiment only to illustrate the invention, its object is to
Those skilled in the art can understand the contents of the present invention and implements accordingly, and protection of the invention can not be limited with this
Range.Any equivalent change or modification in accordance with the spirit of the invention should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of stable choline solution, it is characterised in that: include bursine, water and carbonic acid choline.
2. a kind of stable choline solution as described in claim 1, it is characterised in that: carbonic acid choline is dense in the choline solution
Degree is 15 ~ 20%.
3. a kind of preparation method of stable choline solution as described in claim 1, it is characterised in that the following steps are included:
1), trimethylamine is added to the water and is stirred and evenly mixed, carbon dioxide is passed through, stirring while adding, pressure is less than 2kgf/cm2, temperature
10 ~ 40 DEG C, obtain the solution containing trimethylamine and trimethyl ammonium carbonate；
2) ethylene oxide, is added into solution made from above-mentioned steps, trimethylamine, ethylene oxide and water reaction generate hydroxide gallbladder
Alkali；Trimethyl ammonium carbonate, ethylene oxide and water reaction generate carbonic acid choline；Cooling, filtering, obtains stable choline solution.
4. a kind of preparation method of stable choline solution as claimed in claim 3, it is characterised in that: described in step 1)
The molar ratio of trimethylamine and carbon dioxide is trimethylamine: carbon dioxide=8.5 ~ 10:1.
5. a kind of preparation method of stable choline solution as claimed in claim 3, it is characterised in that: described in step 1)
Trimethylamine is the trimethylamine aqueous solution of concentration 40 ~ 50% or the liquefaction trimethylamine of purity 99%.
6. a kind of preparation method of stable choline solution as claimed in claim 3, it is characterised in that: described in step 2
The molar ratio of trimethylamine described in ethylene oxide and step 1) is ethylene oxide: trimethylamine=1:1.
7. a kind of preparation method of stable choline solution as claimed in claim 3, it is characterised in that: dropped described in step 2
Temperature drop is to 30 ~ 60 DEG C.
8. a kind of preparation method of stable choline solution as claimed in claim 3, it is characterised in that: described in step 2
Cooling is that cooling water temperature or ice water circulation cool.
9. a kind of preparation method of stable choline solution as claimed in claim 3, it is characterised in that: work as temperature in step 2
Ethylene oxide is added at 30 ~ 60 DEG C.
10. a kind of preparation method of stable choline solution as claimed in claim 3, it is characterised in that: described in step 2
Ethylene oxide be concentration 99% liquefaction ethylene oxide.
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| CN201811594587.8A CN109503395B (en) | 2018-12-26 | 2018-12-26 | Stable choline solution and preparation method thereof |
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| CN201811594587.8A CN109503395B (en) | 2018-12-26 | 2018-12-26 | Stable choline solution and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999051796A1 (en) * | 1998-04-06 | 1999-10-14 | Olin Microelectronic Chemicals, Inc. | Method for removing photoresist and plasma etch residues |
| CN1984875A (en) * | 2004-07-09 | 2007-06-20 | 阿克佐诺贝尔股份有限公司 | Composition comprising choline hydroxide and process for preparing the same |
| CN103874679A (en) * | 2012-04-13 | 2014-06-18 | 亨斯迈石油化学有限责任公司 | Using novel amines to stabilize quaternary trialkylalkanolamines |
-
2018
- 2018-12-26 CN CN201811594587.8A patent/CN109503395B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999051796A1 (en) * | 1998-04-06 | 1999-10-14 | Olin Microelectronic Chemicals, Inc. | Method for removing photoresist and plasma etch residues |
| CN1984875A (en) * | 2004-07-09 | 2007-06-20 | 阿克佐诺贝尔股份有限公司 | Composition comprising choline hydroxide and process for preparing the same |
| CN103874679A (en) * | 2012-04-13 | 2014-06-18 | 亨斯迈石油化学有限责任公司 | Using novel amines to stabilize quaternary trialkylalkanolamines |
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