CN101362711B - High consistency and high purity aqueous solutions of betaine preparation method - Google Patents
High consistency and high purity aqueous solutions of betaine preparation method Download PDFInfo
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- CN101362711B CN101362711B CN2008101980730A CN200810198073A CN101362711B CN 101362711 B CN101362711 B CN 101362711B CN 2008101980730 A CN2008101980730 A CN 2008101980730A CN 200810198073 A CN200810198073 A CN 200810198073A CN 101362711 B CN101362711 B CN 101362711B
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Abstract
The invention relates to a method for preparing beet alkaline aqueous solution with high concentration and high pureness and good fluidity at relatively low temperature (2 DEG C), which is produced according to the steps that: firstly, vegetable oil is amidated with alkyl tertiary amine; then alkyl amido tertiary amine, the amidated product, is quaternized with halogenated carboxylic acid; wherein, during the quaternization period, the pH value of the reaction system is controlled to ensure that the quaternization is more complete and micelle thickener is added during the reaction; a further post-processing reaction is carried out after the quaternization, so that the residue of the halogenated carboxylic acid is less than 20ppm, thus meeting the requirements of high concentration and high pureness.
Description
Technical field
The present invention relates to a kind of preparation method who prepares high dense, high-purity aqueous solutions of betaine, its active matter content is up to more than the 37 weight %.
Background technology
Because trimethyl-glycine is a kind of cosurfactant as mild as a dove; Can with all surface promoting agent compatibility; Have high whipability, fabulous tackifying, the characteristics of clearing power, it has become the frozen composition in the various washing nursing prescriptions in family product, the cosmetic industry at present.In addition, trimethyl-glycine also has good soil removability, and pungency is low, even also can not cause any toxic side effect to sensitive skin, in particular for all kinds of personal cleansing articles for use of cleaning hair and health.
The preparation method of existing aqueous solutions of betaine, fatty amide and halogenated carboxylic acid or its salt that normally will contain the tertiary amine nitrogen atom carry out quaterisation in water.
The used fatty amide that contains the tertiary amine nitrogen atom has following general formula:
R
3-CONH-(CH
2)m-N
+R
1R
2 (I)
R
3For having the natural phant fatty alkyl of 8 to 18 carbon atoms, and the mixture of their natural existence or special adaptations.
R
1R
2Be identical or different alkyl with 1 to 4 carbon atom.
M can be 1 to 3.
In the first step amidate action, utilize the naturally occurring lipid acid of 8 to 18 carbon atoms of carbon chain length, for example cocinic acid or Zoomeric acid, and their hydrogenate carries out condensation reaction with the amine with following general formula down at 130 to 180 ℃:
H
2N-(CH
2)m-NR
1R
2 (II)
R
1, R
2Be identical or different alkyl with 1 to 4 carbon atom,
M can be 1 to 3
Obtain the having general formula fatty amide that contains the tertiary amine nitrogen atom of (I).
Then, in the second step quaterisation, in water medium, carry out quaterisation by fatty amide that contains the tertiary amine nitrogen atom and halogenated carboxylic acid, halogenated carboxylic acid has following general formula:
X-(CH
2)yCOOH (III)
Y can be 1 to 3
X representes halogen atom
Obtain having the trimethyl-glycine of following general formula:
R
3-CONH-(CH
2)m-N
+R
1R
2(CH
2)yCOO
-
R
3For having the natural phant fatty alkyl of 8 to 18 carbon atoms, and the mixture of their natural existence or special adaptations.
R
1, R
2Be identical or different alkyl with 1 to 4 carbon atom.
M can be 1 to 3.
Y can be 1 to 3.
Said quaterisation adds the sodium salt of halogenated carboxylic acid (preferred Mono Chloro Acetic Acid) or halogenated carboxylic acid usually in the fatty amide that contains the tertiary amine nitrogen atom in water medium, and the reaction completion is quaternized down at about 70-100 ℃.
At present, its solid contents of alkali solution of beet that according to said method synthesizes, generally produces and use is about 30%-35% or following.
But, in order to reduce production, storage and transportation cost, and follow-up use or reason such as composite, under many circumstances,, hope that all it has higher concentration no matter be manufacturer or applying unit.Therefore, many solution to this problem had been proposed up till now.But some can only bring up to 40% the solid content of the aqueous solutions of betaine that these methods are prepared; And solid content reaches or near 50% product, or unusual thickness, and is mobile poor; Use inconvenient; Or in reaction system, added too much viscosity modifier, like nonionogenic tenside (polyethenoxy ether class etc.), both sexes glycinate, Trimethyl glycine, Schardinger dextrins, VISOSE etc., but being added in when reducing trimethyl-glycine viscosity of these materials; Formula system viscosity is reduced greatly, bigger to the use influence of product; Also having certain methods is in reaction system, to add organic solvent, contains organic solvent and causes the potential negative impact then maybe be bigger to user's prescription.So the certain methods that has proposed at present still is unsafty for addressing this problem.
In addition, with regard to the trimethyl-glycine that generally uses at present, generally all there is the residual too much problem of alkylamide and halogenated carboxylic acid (mainly being Monochloro Acetic Acid, dichloro acetic acid).And alkylamide and halogenated carboxylic acid all are to have big pungency and toxic chemical substance, and they too much remain in the various washing care productss and directly contact with human body, certainly will people's skin be worked the mischief, even influence the healthy of people.Therefore, have the lower residual and irritating alkali solution of beet product of objectionable impurities, can satisfy the human consumer better and protect nontoxic, the non-stimulated requirement that product proposes to washing, this also is the trend of the times of technical development.
Summary of the invention
The object of the invention just provides a kind of preparation method of aqueous solutions of betaine of high dense, high-purity, good fluidity, and need not to add various viscosity adjustment materials, and can reduce residues of harmful substances.
The preparation method of aqueous solutions of betaine of the present invention, it may further comprise the steps successively:
I. amidation
1) 1: 3.0 in molar ratio～5.0 get the raw materials ready vegetables oil and alkyl tertiary amines;
2) respectively material plant oil, alkyl tertiary amine and basic catalyst are joined in the flask; Lead to rare gas element (nitrogen); Be warming up to 130 ℃～180 ℃; And carried out amidate action in 5 hours～10 hours 130 ℃～180 ℃ refluxed, wherein the basic catalyst add-on is 0.1%～2% of a vegetables oil weight;
3) after amidate action finishes, under 130 ℃-180 ℃, be decompressed to negative 0.05-0.1Mpa, distill and to cross quantity tertiary amine in 1-4 hour and steam, promptly get intermediate product alkylamidoalkyl tertiary amine;
Ii. quaternized and aftertreatment
1) 1: 1.0 in molar ratio～1.5 get the raw materials ready alkylamidoalkyl tertiary amine and halogenated carboxylic acids;
2) with halogenated carboxylic acid with alkali 1:1 neutralization in molar ratio;
3) the alkylamidoalkyl tertiary amine adds water and stirs, and adds the halogenated carboxylic acid after the neutralization, is warming up to 70-100 ℃, insulation reaction 6-12 hour;
4) during the quaterisation, make reacting system PH value maintain 8-12 through adding alkali;
5) after quaterisation is accomplished, add sulphite or the hydrosulphite of weight of material 0.1-1%, be incubated 2-10 hour and carry out the aftertreatment reaction.
6) be incubated after sulphite in molar ratio: ydrogen peroxide 50=1:1 adds ydrogen peroxide 50, is incubated 1 hour.
In the said quaternized and aftertreatment; The alkylamidoalkyl tertiary amine adds water and stirs, and the amount of the adding of water can be regulated according to alkylamidoalkyl tertiary amine consumption, uses different alkylamidoalkyl tertiary amines; Can have influence on the solid content and the active matter content of product; Thereby the consumption of water also changes naturally thereupon, and the consumption of Gu Shui can only be according to formula calculation, and this is the general knowledge of the industry.
The said basic catalyst of amidation is sodium hydroxide, Pottasium Hydroxide, sodium methylate, potassium methylate, yellow soda ash, salt of wormwood, particular methanol sodium, potassium methylate.
The said vegetables oil of amidation comprises plam oil, palm-kernel oil, Oleum Cocois, VT 18, vegetable seed wet goods and hydrogenate thereof.
The said alkyl tertiary amine of amidation has following general formula:
H
2N-(CH
2)m-NR
1R
2
R
1R
2Be identical or different alkyl with 1 to 4 carbon atom,
M can be 1 to 3
Quaternized said halogenated carboxylic acid has following general formula:
X-(CH
2)yCOOH
Y can be 1 to 3
X representes halogen atom.(like Cl.Br)
Quaternized said be used for halogenated carboxylic acid alkali be sodium hydroxide, Pottasium Hydroxide, calcium hydroxide, Marinco H etc., preferred sodium hydroxide, Pottasium Hydroxide; Being used to keep the used alkali of reacting system PH value is sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, preferred sodium hydroxide, Pottasium Hydroxide.
Said rare gas element is argon gas, helium, neon or xenon.
Sulfurous acid (hydrogen) salt that said aftertreatment reaction is adopted is S-WAT, potassium sulfite, sodium sulfite anhy 96, Potassium hydrogen sulfite, preferred sodium sulfite anhy 96, Potassium hydrogen sulfite.
The aqueous solutions of betaine for preparing gained according to above-mentioned steps:
R
3-CONH-(CH
2)m-N
+R
1R
2(CH
2)yCOO
-
R
3For having the natural phant fatty alkyl of 8 to 18 carbon atoms, and the mixture of their natural existence or special adaptations;
R
1R
2Be identical or different alkyl with 1 to 4 carbon atom;
M can be 1 to 3;
Y can be 1 to 3;
Its trimethyl-glycine solid content be at least aqueous solutions of betaine weight 45%, active matter content is at least 37% of aqueous solutions of betaine weight, high dense, high-purity and good fluidity.
The aqueous solutions of betaine of gained is used to prepare household, industry and personal care product, plays washing and cleaning action.
The alkali solution of beet that the present invention makes need not to add various viscosity adjustment materials (micelle thickening agent); In addition, the present invention uses naturally occurring vegetables oil, like Oleum Cocois, plam oil, palm-kernel oil, VT 18, vegetable seed wet goods and hydrogenate thereof; Preferred Oleum Cocois and plam oil and hydrogenate thereof, preferred especially Oleum Cocois and hydrogenate thereof carry out amidate action with alkyl tertiary amine in the presence of alkaline catalysts; Gained midbody alkylamidoalkyl tertiary amine; Through the resulting alkylamidoalkyl tertiary amine of this method, wherein contain the glycerine of certainweight per-cent, carry out that quaterisation can be avoided during reaction gel occurring and the phenomenon that can't stir with itself and halogenated carboxylic acid; Gained trimethyl-glycine viscosity when solid content reaches 45-55% is still very low; Even also can unrestricted flow when temperature is low to moderate 2 ℃, can gel, can not become turbid at subzero 15 ℃ yet; High dense trimethyl-glycine difference with other method preparation is that also it can not make the formula system viscosity degradation.
The present invention carries out quaterisation with currently known methods by fatty amide that contains the tertiary amine nitrogen atom and halogenated carboxylic acid to obtain in water medium; During quaterisation; Make reacting system PH value maintain 8-12 through adding alkali; Make reaction system more help the generation of quaterisation, thereby make the alkylamidoalkyl reactive tertiary amine more thorough, residual lower; Through adding sulfurous acid (hydrogen) salt, preferred hydrosulphite is through reacting reduction or eliminating the content of halogenated carboxylic acid in alkali solution of beet during the quaterisation aftertreatment.
The present invention carries out according to the step of present prior art, and its basic difference is to be to adopt vegetables oil rather than alkyl fatty acid and amino tertiary amine to carry out amidate action in amidate action; During quaterisation, need not add viscosity modifier (micelle thickening agent); Behind quaterisation, alkali solution of beet has been increased postprocessing working procedures, effectively reduction or elimination tool severe toxicity spinoff material (being mainly halogenated carboxylic acid) is residual.
When technology of the present invention is included in amidate action,, at the extremely negative 0.05-0.1Mpa of 130 ℃ of-180 ℃ of following underpressure distillation, will crosses quantity tertiary amine and steam again at 130 ℃～180 ℃ refluxed some hrs; Before 70-100 ℃ of insulation reaction some hrs carries out quaterisation, should be earlier with the oxyhydroxide neutralization of halogenated carboxylic acid and at least a basic metal or earth alkali metal, and keep reacting system PH value at 8-12 through the oxyhydroxide that adds preferred as alkali; It is sulfurous acid (hydrogen) salt that post-processing stages adds post-treatment agent, preferred sodium sulfite anhy 96, Potassium hydrogen sulfite.
Compared with prior art; The invention has the beneficial effects as follows: aqueous solutions of betaine of the present invention need not to add under the situation of various viscosity adjustment materials (micelle thickening agent); Also can realize alkali solution of beet high solids content and high reactivity thing content, and gained alkali solution of beet good fluidity; In addition, the present invention also through having improved quaternized technology and having increased postprocessing working procedures, has reduced residues of harmful substances.Aqueous solutions of betaine of the present invention can be used for preparing among household and the personal care product, is a kind of cosurfactant as mild as a dove, can with all surface promoting agent compatibility, be applicable to all kinds of personal cleansing articles for use and cosmetic formulations.
Embodiment
Combine specific embodiment that the present invention is further specified as follows at present:
Embodiment 1
May further comprise the steps successively:
I. amidation
1) 1: 3.0 in molar ratio～5.0 get the raw materials ready vegetables oil-gently change Oleum Cocois 600g and alkyl tertiary amine-N.N-dimethyl-1.3-tn 310g;
2) in 1 liter of four-hole boiling flask that whisking appliance, return line, TM and nitrogen tube are housed, add lightization Oleum Cocois and catalyzer sodium methylate 6.0g earlier in flask; Feed nitrogen protection; Add N.N-dimethyl-1.3-tn again; Be warming up to 170 ℃, and carried out amidate action in 8 hours 170 ℃ of refluxed;
3) after amidate action finishes,, will cross quantity tertiary amine and steam, promptly get intermediate product alkylamidoalkyl tertiary amine-cocamidopropyl propyl-dimethyl tertiary amine at 2 hours extremely negative 0.05-0.1Mpa of 170 ℃ of following underpressure distillation;
Ii. quaternized and aftertreatment
1) 1: 1.0 in molar ratio～1.5 get the raw materials ready cocamidopropyl propyl-dimethyl tertiary amine 250 grams and halogenated carboxylic acid-Monochloro Acetic Acids;
2) Monochloro Acetic Acid being used sodium hydroxide 1:1 neutralization in molar ratio is 200 grams, 50% Monochloro Acetic Acid sodium water solutions;
3) in 1 liter of four-hole boiling flask that return line, TM, whisking appliance and tap funnel are housed, add cocamidopropyl propyl-dimethyl tertiary amine and 278 gram water, be warming up to 60 ℃; From tap funnel, be added dropwise to the Monochloro Acetic Acid sodium water solution then, the dropping time is 30 minutes, is warming up to 95 ℃, insulation reaction 8 hours;
4) during the quaterisation, make reacting system PH value maintain 9-10 through being added dropwise to 50% aqueous sodium hydroxide solution;
5) after quaterisation is accomplished, add S-WAT 3.64 grams of weight of material 0.1-1%, be incubated 4 hours and carry out the aftertreatment reaction.
6) be incubated after sulphite in molar ratio: ydrogen peroxide 50=1:1 adds ydrogen peroxide 50 2.38 grams, is incubated 1 hour and promptly gets product.
Gained alkali solution of beet technical indicator detected result is following:
Solid content: 47.9%
Active matter content: 38.2%
Free acid amides: 0.03%
Monochloro Acetic Acid: 0
Dichloro acetic acid: 5ppm.
Embodiment 2
1. amidation prepares the alkylamidoalkyl tertiary amine
With example 1;
2. quaternized and aftertreatment prepares aqueous solutions of betaine
In 1 liter of four-hole boiling flask that return line, TM, whisking appliance and tap funnel are housed, add 250 grams 1 earlier) go on foot the cocamidopropyl propyl-dimethyl tertiary amine and the 250 gram water that make, stir and be warming up to 60 ℃; From tap funnel, be added dropwise to 200 grams, 50% Monochloro Acetic Acid sodium water solution then; The dropping time is 30 minutes; Then reaction mixture is warming up to 95 ℃, insulation reaction is 8 hours under this temperature, and to keep reaction system PH be 9-10 through being added dropwise to 50% aqueous sodium hydroxide solution between the reaction period; After quaterisation is intact, add sodium sulfite anhy 96 3.64 grams, be incubated 4 hours again; Add 2.38 grams, 50% ydrogen peroxide 50, be incubated 1 hour.
Gained alkali solution of beet technical indicator detected result is following:
Solid content: 49.5%
Active matter content: 39.7%
Free acid amides: 0.02%
Monochloro Acetic Acid: 0
Dichloro acetic acid: 4ppm
Embodiment 3
1. amidation prepares the alkylamidoalkyl tertiary amine
In 1 liter of four-hole boiling flask that whisking appliance, return line, TM and nitrogen tube are housed; Add 600g earlier and gently change Oleum Cocois and catalyzer 6.0g sodium hydroxide, feed nitrogen protection, add 310gN.N-dimethyl-1.3-tn again; Be warming up to 170 ℃ then, and 170 ℃ of refluxed reactions 8 hours; Be decompressed to negative 0.08Mpa at last, distill down at 170 ℃ and removed excessive N .N-dimethyl-1.3-tn in 2 hours;
2. quaternized and aftertreatment prepares aqueous solutions of betaine
In 1 liter of four-hole boiling flask that return line, TM, whisking appliance and tap funnel are housed, add earlier 250 grams 1) the cocamidopropyl propyl-dimethyl tertiary amine and the 278 gram water that make of step.
Stirring is warming up to 60 ℃; From tap funnel, be added dropwise to 200 grams, 50% Monochloro Acetic Acid sodium water solution then; The dropping time is 30 minutes; Then reaction mixture is warming up to 95 ℃, insulation reaction is 6 hours under this temperature, and to keep reaction system PH be 10-12 through being added dropwise to 50% aqueous sodium hydroxide solution between the reaction period.
3) after quaterisation finishes, add sodium sulfite anhy 96 7.30 grams, be incubated 4 hours again; Add 4.76 grams, 50% ydrogen peroxide 50, be incubated 1 hour.
Gained alkali solution of beet technical indicator detected result is following:
Solid content: 48.4%
Active matter content: 38.4%
Free acid amides: 0.01%
Monochloro Acetic Acid: 0
Dichloro acetic acid: 0
Embodiment 4
1. amidation prepares the alkylamidoalkyl tertiary amine
In 1 liter of four-hole boiling flask that whisking appliance, return line, TM and nitrogen tube are housed; Add 600g earlier and gently change Oleum Cocois and catalyzer 6.0g sodium methylate, feed nitrogen protection, add 410gN.N-dimethyl-1.3-tn again; Be warming up to 160 ℃ then, and 160 ℃ of refluxed reactions 6 hours; Be decompressed to negative 0.095Mpa at last, distill down at 160 ℃ and removed excessive N .N-dimethyl-1.3-tn in 2 hours.
2. quaternized and aftertreatment prepares aqueous solutions of betaine
In 1 liter of four-hole boiling flask that return line, TM, whisking appliance and tap funnel are housed, add earlier 250 grams 1) the cocamidopropyl propyl-dimethyl tertiary amine and the 278 gram water that make of step.
Stirring is warming up to 60 ℃; From tap funnel, be added dropwise to 200 grams, 50% Monochloro Acetic Acid sodium water solution then; The dropping time is 30 minutes; Then reaction mixture is warming up to 85 ℃, insulation reaction is 8 hours under this temperature, and to keep reaction system PH be 9-10 through being added dropwise to 50% aqueous sodium hydroxide solution between the reaction period.
3) after quaterisation finishes, add sodium sulfite anhy 96 3.64 grams, be incubated 4 hours again; Add 2.38 grams, 50% ydrogen peroxide 50, be incubated 1 hour.
Gained alkali solution of beet technical indicator detected result is following:
Solid content: 47.9%
Active matter content: 38.0%
Free acid amides: 0.06%
Monochloro Acetic Acid: 0
Dichloro acetic acid: 6ppm
Embodiment 5
1) preparation of alkylamidoalkyl tertiary amine: in 1 liter of four-hole boiling flask that whisking appliance, return line, TM and nitrogen tube are housed; Add 600g earlier and gently change Oleum Cocois and catalyzer 9.0g sodium methylate; Feed nitrogen protection; Add 310gN.N-dimethyl-1.3-tn again, be warming up to 170 ℃ then, and 170 ℃ of refluxed reactions 6 hours; Be decompressed to negative 0.08Mpa at last, distill down at 170 ℃ and removed excessive N .N-dimethyl-1.3-tn in 2 hours.
2) elder generation's adding 250 grams 1 in 1 liter of four-hole boiling flask that return line, TM, whisking appliance and tap funnel are housed) go on foot the cocamidopropyl propyl-dimethyl tertiary amine and the 250 gram water that make.
Stirring is warming up to 60 ℃; From tap funnel, be added dropwise to 210 grams, 50% Monochloro Acetic Acid sodium water solution then; The dropping time is 30 minutes; Then reaction mixture is warming up to 95 ℃, insulation reaction is 8 hours under this temperature, and to keep reaction system PH be 9-10 through being added dropwise to 50% aqueous sodium hydroxide solution between the reaction period.
3) after quaterisation finishes, add sodium sulfite anhy 96 3.64 grams, be incubated 4 hours again; Add 2.38 grams, 50% ydrogen peroxide 50, be incubated 1 hour.
Gained alkali solution of beet technical indicator detected result is following:
Solid content: 49.3%
Active matter content: 39.2%
Free acid amides: 0.01%
Monochloro Acetic Acid: 0
Dichloro acetic acid; : 9ppm
Embodiment 6
1) preparation of alkylamidoalkyl tertiary amine: in 1 liter of four-hole boiling flask that whisking appliance, return line, TM and nitrogen tube are housed; Add 600g earlier and gently change Oleum Cocois and catalyzer 6.0g sodium methylate; Feed nitrogen protection; Add 234gN.N-dimethyl-1.3-tn again, be warming up to 170 ℃ then, and 170 ℃ of refluxed reactions 8 hours; Be decompressed to negative 0.08Mpa at last, distill down at 170 ℃ and removed excessive N .N-dimethyl-1.3-tn in 2 hours.
2) elder generation's adding 250 grams 1 in 1 liter of four-hole boiling flask that return line, TM, whisking appliance and tap funnel are housed) go on foot the lightization Oleum Cocois amidopropyl dimethyl tertiary amine and the 278 gram water that make.
Stirring is warming up to 60 ℃; From tap funnel, be added dropwise to 200 grams, 50% Monochloro Acetic Acid sodium water solution then; The dropping time is 30 minutes; Then reaction mixture is warming up to 95 ℃, insulation reaction is 8 hours under this temperature, and to keep reaction system PH be 9-10 through being added dropwise to 50% aqueous sodium hydroxide solution between the reaction period.
3) after quaterisation finishes, add S-WAT 3.64 grams, be incubated 4 hours again; Add 1.96 grams, 50% ydrogen peroxide 50, be incubated 1 hour.
Gained alkali solution of beet technical indicator detected result is following:
Solid content: 48.0%
Active matter content: 38.2%
Free acid amides: 0.03%
Monochloro Acetic Acid: 3ppm
Dichloro acetic acid; 12ppm
Embodiment 7
1) preparation of alkylamidoalkyl tertiary amine: in 1 liter of four-hole boiling flask that whisking appliance, return line, TM and nitrogen tube are housed; Add 600g palm-kernel oil and catalyzer 6.0g sodium methylate earlier; Feed nitrogen protection; Add 295gN.N-dimethyl-1.3-tn again, be warming up to 170 ℃ then, and 170 ℃ of refluxed reactions 8 hours; Be decompressed to negative 0.08Mpa at last, distill down at 170 ℃ and removed excessive N .N-dimethyl-1.3-tn in 2 hours.
2) elder generation's adding 250 grams 1 in 1 liter of four-hole boiling flask that return line, TM, whisking appliance and tap funnel are housed) go on foot the palmitoleoyl aminocarbonyl propyl dimethyl tertiary amine and the 263 gram water that make.
Stirring is warming up to 60 ℃; From tap funnel, be added dropwise to 168 grams, 50% Monochloro Acetic Acid sodium water solution then; The dropping time is 30 minutes; Then reaction mixture is warming up to 95 ℃, insulation reaction is 8 hours under this temperature, and to keep reaction system PH be 9-10 through being added dropwise to 50% aqueous sodium hydroxide solution between the reaction period.
3) after quaterisation finishes, add sodium sulfite anhy 96 3.40 grams, be incubated 4 hours again; Add 2.22 grams, 50% ydrogen peroxide 50, be incubated 1 hour.
Gained alkali solution of beet technical indicator detected result is following:
Solid content: 48.9%
Active matter content: 39.8%
Free acid amides: 0.04%
Monochloro Acetic Acid: 0
Dichloro acetic acid: 6ppm
Embodiment 8
1) preparation of alkylamidoalkyl tertiary amine: in 1 liter of four-hole boiling flask that whisking appliance, return line, TM and nitrogen tube are housed; Add 600g rapeseed oil and catalyzer 6.0g sodium methylate earlier; Feed nitrogen protection; Add 210gN.N-dimethyl-1.3-tn again, be warming up to 170 ℃ then, and 170 ℃ of refluxed reactions 8 hours; Be decompressed to negative 0.08Mpa at last, distill down at 170 ℃ and removed excessive N .N-dimethyl-1.3-tn in 2 hours.
2) elder generation's adding 250 grams 1 in 1 liter of four-hole boiling flask that return line, TM, whisking appliance and tap funnel are housed) go on foot the palm-kernel oil amidopropyl dimethyl tertiary amine and the 250 gram water that make.
Stirring is warming up to 60 ℃; From tap funnel, be added dropwise to 196 grams, 50% Monochloro Acetic Acid sodium water solution then; The dropping time is 30 minutes; Then reaction mixture is warming up to 95 ℃, insulation reaction is 8 hours under this temperature, and to keep reaction system PH be 9-10 through being added dropwise to 50% aqueous sodium hydroxide solution between the reaction period.
3) after quaterisation finishes, add sodium sulfite anhy 96 3.48 grams, be incubated 4 hours again; Add 2.27 grams, 50% ydrogen peroxide 50, be incubated 1 hour.
Gained alkali solution of beet technical indicator detected result is following:
Solid content: 49.1%
Active matter content: 39.2%
Free acid amides: 0.05%
Monochloro Acetic Acid: 0
Dichloro acetic acid; 6ppm.
Claims (8)
1. the preparation method of a high consistency and high purity aqueous solutions of betaine is characterized in that may further comprise the steps successively:
I. amidation
1) in molar ratio 1: 3. 0～5.0 is equipped with material plant oil and alkyl tertiary amine;
2) raw material and basic catalyst are joined in the flask, carried out amidate action in 5 hours～10 hours 130 ℃～180 ℃ refluxed, wherein the basic catalyst add-on is 0.1%～2% of a vegetables oil weight;
3) after amidate action finishes, under 130 ℃-180 ℃, be decompressed to negative 0.05-0.1Mpa, distill and excessive alkyl tertiary amine steamed in 1-4 hour, promptly get intermediate product alkylamidoalkyl tertiary amine;
Ii. quaternized and aftertreatment
1) in molar ratio 1: 1. 0～1.5 get the raw materials ready alkylamidoalkyl tertiary amine and halogenated carboxylic acid;
2) with halogenated carboxylic acid with alkali 1:1 neutralization in molar ratio;
3) the alkylamidoalkyl tertiary amine adds water and stirs, and adds the halogenated carboxylic acid after the neutralization, is warming up to 70-100 ℃, insulation reaction 6-12 hour;
4) during the quaterisation, make reacting system PH value maintain 8-12 through adding alkali;
5) after quaterisation is accomplished, add sulphite or the hydrosulphite of the solution weight 0.1-1% of reaction back gained, be incubated 2-10 hour;
6) be incubated after sulphite or hydrosulphite in molar ratio: ydrogen peroxide 50=1:1 adds ydrogen peroxide 50, is incubated 1 hour and promptly gets product.
2. the preparation method of high consistency and high purity aqueous solutions of betaine according to claim 1, it is characterized in that: amidation is carried out under protection of inert gas, and described rare gas element has nitrogen, argon gas, helium, neon or xenon.
3. the preparation method of high consistency and high purity aqueous solutions of betaine according to claim 2, it is characterized in that: the said basic catalyst of amidation is sodium hydroxide, Pottasium Hydroxide, sodium methylate, potassium methylate, yellow soda ash or salt of wormwood.
4. the preparation method of high consistency and high purity aqueous solutions of betaine according to claim 3 is characterized in that: the said vegetables oil of amidation be plam oil, palm-kernel oil, Oleum Cocois, VT 18 or rapeseed oil with and hydrogenate.
5. the preparation method of high consistency and high purity aqueous solutions of betaine according to claim 4, it is characterized in that: the said alkyl tertiary amine of amidation has following general formula:
H
2N-(CH
2)m-NR
1R
2
R
1, R
2Be identical or different alkyl with 1 to 4 carbon atom,
M is 1 to 3.
6. the preparation method of high consistency and high purity aqueous solutions of betaine according to claim 5, it is characterized in that: quaternized said halogenated carboxylic acid has following general formula:
X-(CH
2)yCOOH
Y is 1 to 3
X representes halogen atom.
7. the preparation method of high consistency and high purity aqueous solutions of betaine according to claim 6 is characterized in that: quaternized said be used for halogenated carboxylic acid alkali be sodium hydroxide, Pottasium Hydroxide, calcium hydroxide or Marinco H; Being used to keep the used alkali of reacting system PH value is sodium hydroxide, Pottasium Hydroxide, yellow soda ash or salt of wormwood.
8. the preparation method of high consistency and high purity aqueous solutions of betaine according to claim 7 is characterized in that: sulphite or hydrosulphite that said aftertreatment reaction is adopted are S-WAT, potassium sulfite, sodium sulfite anhy 96 or Potassium hydrogen sulfite.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101980730A CN101362711B (en) | 2008-08-28 | 2008-08-28 | High consistency and high purity aqueous solutions of betaine preparation method |
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| CN2008101980730A CN101362711B (en) | 2008-08-28 | 2008-08-28 | High consistency and high purity aqueous solutions of betaine preparation method |
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| Publication Number | Publication Date |
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| CN101362711A CN101362711A (en) | 2009-02-11 |
| CN101362711B true CN101362711B (en) | 2012-07-04 |
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| US8894726B2 (en) * | 2012-06-13 | 2014-11-25 | Afton Chemical Corporation | Fuel additive for improved performance in fuel injected engines |
| US9017431B2 (en) * | 2013-01-16 | 2015-04-28 | Afton Chemical Corporation | Gasoline fuel composition for improved performance in fuel injected engines |
| CN104447388B (en) * | 2014-11-19 | 2016-05-11 | 广州花语精细化工有限公司 | Residual chloroacetic improvement technique in a kind of processing amido propyl betaine |
| CN106496059B (en) * | 2016-08-31 | 2018-07-17 | 四川花语精细化工有限公司 | The process of free acid in a kind of reduction glycine betaine |
| CN106622015B (en) * | 2016-12-20 | 2018-09-18 | 福州大学 | One vegetable oil base zwitterionic surfactant and preparation method thereof |
| CN107382762A (en) * | 2017-07-18 | 2017-11-24 | 钟千里 | A kind of synthetic method of fatty diglycollic amide |
| CN114507152B (en) * | 2022-02-28 | 2023-05-05 | 山东大学 | Synthesis process and optimization method of cocamidopropyl betaine |
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