CN101695641B - Cationic surfactant and preparation method thereof - Google Patents
Cationic surfactant and preparation method thereof Download PDFInfo
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- CN101695641B CN101695641B CN200910210747A CN200910210747A CN101695641B CN 101695641 B CN101695641 B CN 101695641B CN 200910210747 A CN200910210747 A CN 200910210747A CN 200910210747 A CN200910210747 A CN 200910210747A CN 101695641 B CN101695641 B CN 101695641B
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Abstract
The invention relates to a cationic surfactant and a preparation method thereof. The structural general formula of the cationic surfactant is expressed as follows: n is an integer from 10 to 14; and X is F, Cl, Br or I. The cationic surfactant and the preparation method thereof have the advantages of easily obtained raw materials, mild reaction conditions, simple operation, high yield, reclaimable solvent and no three wastes.
Description
Technical field
The present invention relates to field of fine chemical, particularly relate to a kind of cationic surfactant and preparation method thereof.
Background technology
Surfactant is one type of fine chemicals; Every field such as extensive use commercial production, washing cosmetic, agricultural chemicals, medicine, printing and dyeing, tertiary oil recovery, sterilizing, sewage disposal; Along with the surfactant industrial expansion, cationic surfactant receives much attention aspect fabric softening at present.General fabrics softener cationoid surfactant structure characteristics are: the quaternary ammonium salt product that contains two chain alkyls in the molecular structure simultaneously.Typical representation compound is VARISOFT TA100 (D1821).The enhancing of Along with people's environmental consciousness, replace biological degradation rate height, production operation easily quaternary ammonium salt occur in succession, wherein most representative is ester based quaternary ammonium salt, its full name is dialkyl dimethyl hydroxyethyl sulfate methyl ammonium TE.The cationic surfactant of this structure than be easier to be adsorbed in the fabric face with fabric on negative electrical charge.
People such as the Zhang Changhui of Shaanxi Tech Univ have synthesized the dodecyl dimethyl allyl ammonium chloride, in molecular structure, introduce pi-allyl in the molecular structure, strengthen the electropositive of molecule.Molecule more is prone to be adsorbed on fabric face and forms film, intercepts extraneous negative electrical charge.The China chemical dairy industry graduate king people such as dimension grade that wears successfully uses aliphatic acid and monoethanolamine to react, and in the quaternary ammonium salt molecular structure, introduces ester group.But existing problems still, be exactly how to make surfactant as fabric softening agent the time, not only have favorable biological degradability but also adsorptivity with in stronger with the negative electrical charge ability.
Summary of the invention
The purpose of this invention is to provide a kind of cationic surfactant and preparation method thereof, to solve the problems referred to above that prior art exists.
The present invention provides a kind of cationic surfactant, and its general structure is as follows:
Wherein n is 10～14 integer; X is F, Cl, Br or I.
In the said general structure, when n is 10, the name of the cationic surfactant when X is Cl is called dodecanoic acid methacrylic diethanol amine ester ammonium chloride;
The name of the cationic surfactant when n is 12 is called; N-teradecanoic acid methacrylic diethanol amine ester ammonium chloride;
The name of the cationic surfactant when n is 14 is called hexadecane acid methyl pi-allyl diethanol amine ester ammonium chloride.
The present invention also prepares the method for above-mentioned cationic surfactant, comprises the steps:
1) esterification
Aliphatic acid and methyl diethanolamine are carried out esterification in 120 ℃～150 ℃ obtain intermediate (I) fatty acid methyl diethanol amine ester in the presence of acidic catalyst, wherein the mol ratio of aliphatic acid and methyl diethanolamine is 2.2～2.5: 1, preferred 2.4: 1;
2) quaternary amine salinization reaction
Intermediate (I) and 3-halogen propylene are carried out the target product that quaternary amine salinization reaction obtains in organic solvent, wherein intermediate (I) is 1: 1.2～1.5 with the mol ratio of 3-halogen propylene, preferred 1: 1.2.
Wherein, acidic catalyst described in the step 1) is selected from inorganic acid such as phosphoric acid or organic acid such as p-methyl benzenesulfonic acid, preferred p-methyl benzenesulfonic acid.
Esterification finishes back vacuum distillation recovered solvent and excess fats acid, and intermediate is used for quaternary ammonium reaction behind washing, extraction separation purification.
Step 2) salinization of quaternary amine described in is carried out under being reflected at and refluxing in the low boiling point solvent.
Described low boiling point solvent is acetone or ethyl acetate.
Be initiation material with dodecyl acid and allyl chloride etc. below, preparation method's of the present invention reaction principle be described:
The first step: fatty acid methyl diethanol amine ester synthetic
Second step: dodecanoic acid methacrylic diethanol amine ester ammonium chloride synthetic
Existing two long alkane chains have been introduced ester group and pi-allyl again in the molecular structure of cationic surfactant of the present invention.This structure make surfactant as fabric softening agent the time, not only have favorable biological degradability but also adsorptivity with in stronger with the negative electrical charge ability.
Cationic surfactant of the present invention and preparation method thereof has following beneficial effect: the method raw material is easy to get, reaction condition gentle, and is simple to operate, and yield is high, recycled solvent, the no three wastes.
The specific embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.
Embodiment 1
The first step: fatty acid methyl diethanol amine ester synthetic
In the reaction bulb of rectifying column is housed; Add methyl diethanolamine 35.7g (0.30mol), dodecanoic acid 132g (0.66mol) and catalyst p-methyl benzenesulfonic acid 0.5g respectively; 120 ℃～150 ℃ following fusions, stirring reaction then is through dividing the content monitoring reaction process of water outlet in the water knockout drum.Behind about 8～10h, the water yield of telling reaches 95% o'clock of theoretical the branchs water yield and stops to react.Be dissolved in CHCl at the gained reactant
3, boiling off organic facies after the washing, anhydrous sodium sulfate drying gets product laurate methyl diethanolamine ester weak yellow liquid, receives heavy 122g, and it is 97% that gas-chromatography normalization detects purity, yield 81%.
Second step: dodecanoic acid methacrylic diethanol amine ester ammonium chloride synthetic
In the reaction bulb of condenser pipe is housed, add laurate methyl diethanolamine ester 20.0g (0.04mol), chlorallylene 3.67g (0.048mol) and acetone 35mL, heated and stirred back flow reaction under the magnetic stirring apparatus.Gas chromatography monitoring reaction terminal point.About 16h reaction finishes.Pressurization boils off solvent, obtains faint yellow thickness lotion.In the mixed solvent of acetone and acetonitrile (V (acetone): V (acetonitrile))=20: 1.0) recrystallization, white powder solid 20.5g.Solid content is not less than 98%, and the bromophenol blue diphasic titration is calculated amine value effective content 96.5%, yield 85.75%.
1HNMR chemical shift ppm:0.9～0.96 (6H), 1.29～1.68 (36H), 2.25 (4H), 2.9 (3H), 3.52 (4H), 3.91 (4H), 4.52 (2H), 4.97～5.03 (2H), 5.7 (1H).
In methyl diethanolamine, total recovery 69.46%.
Embodiment 2
Press embodiment 1 and operate equally, only change use therein dodecanoic acid 132g (0.66mol) into dodecanoic acid 144g (0.72mol), other are constant; Get product laurate methyl diethanolamine ester weak yellow liquid; Receive heavy 126g, it is 97% that gas-chromatography normalization detects purity, yield 83.6%.
In methyl diethanolamine, total recovery 71.69%.
Embodiment 3
Pressing embodiment 1 operates equally; The chlorallylene 3.67g (0.048mol) that only will be wherein uses in the synthetic method in second step changes chlorallylene 4.59g (0.06mol) into; Other are constant, get the quaternary ammonium salt product, receive heavy 21.8g; It is 97%, the second step synthesis yield 91.6% that gas-chromatography normalization detects purity.
In methyl diethanolamine, total recovery 74.2%.
Embodiment 4
Press embodiment 2 and operate equally, carry out the first step and synthesize.Carrying out for second step according to embodiment 3 same behaviour synthesizes.
In methyl diethanolamine, total recovery 76.57%.
Embodiment 5 dodecanoic acid methacrylic diethanol amine ester ammonium iodides
The first step: fatty acid methyl diethanol amine ester synthetic
Operate equally by embodiment one first step.
Second step: dodecanoic acid methacrylic diethanol amine ester ammonium iodide synthetic
In the reaction bulb of condenser pipe is housed, add laurate methyl diethanolamine ester 20.0g (0.04mol), 3-iodopropylene 8.11g (0.048mol) and ethyl acetate 35mL, heated and stirred back flow reaction under the magnetic stirring apparatus.Gas chromatography monitoring reaction terminal point.About 16h reaction finishes.The pressure reducing and steaming solvent obtains faint yellow thickness lotion.In the mixed solvent of acetone and acetonitrile (V (acetone): V (acetonitrile))=20: 1.0) recrystallization, white powder solid 22.5g.The bromophenol blue diphasic titration is calculated amine value effective content 96.0%, yield 82.95%.
In methyl diethanolamine, total recovery 67.19%.
Embodiment 6
The first step: fatty acid methyl diethanol amine ester synthetic
In the reaction bulb of rectifying column is housed; Add methyl diethanolamine 35.7g (0.30mol), n-teradecanoic acid 150.48g (0.66mol) and catalyst p-methyl benzenesulfonic acid 0.5g respectively; 120 ℃～150 ℃ following fusions; Stirring reaction then is through dividing the content monitoring reaction process of water outlet in the water knockout drum.Behind about 8～10h, the water yield of telling reaches 95% o'clock of theoretical the branchs water yield and stops to react.Be dissolved in CHCl at the gained reactant
3, boiling off organic facies after the washing, anhydrous sodium sulfate drying gets product tetradecanoic acid methyl diethanolamine ester weak yellow liquid, receives heavy 138g, and it is 97.2% that gas-chromatography normalization detects purity, yield 83%.
Second step: n-teradecanoic acid methacrylic diethanol amine ester ammonium chloride synthetic
In the reaction bulb of condenser pipe is housed, add tetradecanoic acid methyl diethanolamine ester 22.18g (0.04mol), chlorallylene 3.67g (0.048mol) and acetone 35mL, heated and stirred back flow reaction under the magnetic stirring apparatus.Gas chromatography monitoring reaction terminal point.About 16h reaction finishes.Pressurization boils off solvent, obtains faint yellow thickness lotion.In the mixed solvent of acetone and acetonitrile (V (acetone): V (acetonitrile))=20: 1.0) recrystallization, white powder solid 22.5g.The bromophenol blue diphasic titration is calculated amine value effective content 96.5%, yield 88.2%.
In methyl diethanolamine, total recovery 73.2%.
Embodiment 7
The first step: fatty acid methyl diethanol amine ester synthetic
In the reaction bulb of rectifying column is housed; Add methyl diethanolamine 35.7g (0.30mol), hexadecane acid 169g (0.66mol) and catalyst p-methyl benzenesulfonic acid 0.5g respectively; 120 ℃～150 ℃ following fusions, stirring reaction then is through dividing the content monitoring reaction process of water outlet in the water knockout drum.Behind about 8～10h, the water yield of telling reaches 95% o'clock of theoretical the branchs water yield and stops to react.Be dissolved in CHCl at the gained reactant
3, boiling off organic facies after the washing, anhydrous sodium sulfate drying gets product hexadecanoic acid methyl diethanolamine ester weak yellow liquid, receives heavy 140g, and it is 97% that gas-chromatography normalization detects purity, yield 76.07%.
Second step: hexadecane acid methyl pi-allyl diethanol amine ester ammonium chloride synthetic
In the reaction bulb of condenser pipe is housed, add hexadecanoic acid methyl diethanolamine ester 27.7g (0.04mol), chlorallylene 3.67g (0.048mol) and acetone 35mL, heated and stirred back flow reaction under the magnetic stirring apparatus.Gas chromatography monitoring reaction terminal point.About 16h reaction finishes.The pressure reducing and steaming solvent obtains faint yellow thickness lotion.In the mixed solvent of acetone and acetonitrile (V (acetone): V (acetonitrile))=20: 1.0) recrystallization, white powder solid 22.5g.The bromophenol blue diphasic titration is calculated amine value effective content 96.5%, yield 80.8%.
In methyl diethanolamine, total recovery 61.5%.
Can be found out that by above embodiment the synthesis route of the double long-chain alkyl ester group cationic surfactant that the embodiment of the invention provides is short, not have harsh reaction condition, raw material is easy to get, recycled solvent, the no three wastes.This method is about 76.57% in the total recovery of methyl diethanolamine dodecanoic acid methacrylic diethanol amine ester ammonium chloride.Be fit to suitability for industrialized production; Existing two long alkane chains have been introduced ester group and pi-allyl again in the molecular structure of the cationic surfactant of embodiment 1-7.This structure make surfactant as fabric softening agent the time, not only have favorable biological degradability but also adsorptivity with in stronger with the negative electrical charge ability.
The above only is a preferred implementation of the present invention; Should be understood that; For those skilled in the art, under the prerequisite that does not break away from know-why of the present invention, can also make some improvement and retouching; For example change reactant bromo dodecanoic acid into bromo n-teradecanoic acid or the acid of bromo hexadecane, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (7)
1. a cationic surfactant is characterized in that, its general structure is as follows:
Wherein n is 10～14 integer; X is F, Cl, Br or I.
2. cationic surfactant according to claim 1 is characterized in that, in the said general structure, n is 10; X is Cl.
3. prepare the method for claim 1 or 2 described cationic surfactants, it is characterized in that, comprise the steps:
1) esterification
Methyl diethanolamine and aliphatic acid are carried out esterification in 120 ℃～150 ℃ obtain intermediate (I) fatty acid methyl diethanol amine ester in the presence of acidic catalyst, wherein the mol ratio of aliphatic acid and methyl diethanolamine is 2.2～2.5: 1;
2) quaternary amine salinization reaction
Intermediate (I) and 3-halogen propylene are carried out the target product that quaternary amine salinization reaction obtains in organic solvent, wherein intermediate (I) is 1: 1.2～1.5 with the mol ratio of 3-halogen propylene.
4. the method for preparing cationic surfactant according to claim 3 is characterized in that acidic catalyst described in the step 1) is selected from organic acid or inorganic acid.
5. the method for preparing cationic surfactant according to claim 4 is characterized in that, organic acid described in the step 1) is a p-methyl benzenesulfonic acid, and said inorganic acid is the phosphoric acid or the concentrated sulfuric acid.
6. the method for preparing cationic surfactant according to claim 3 is characterized in that step 2) described in the quaternary amine salinization be reflected in the low boiling point solvent and carry out under refluxing.
7. the method for preparing cationic surfactant according to claim 6 is characterized in that, described low boiling point solvent is acetone or ethyl acetate.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557535A (en) * | 2004-01-13 | 2004-12-29 | ����ʦ����ѧ | Gemini quaternary surfactant containing pyridine rings and preparing method thereof |
| WO2005096711A2 (en) * | 2004-04-05 | 2005-10-20 | Kanagawa University | Emulsifying dispersants, method for emusification and dispersion with the same, emulsions, and emulsion fuels |
| CN101185867A (en) * | 2006-11-17 | 2008-05-28 | 天津科技大学 | Gemini quaternary ammonium salt cationic surfactant and preparation method thereof |
| US7390432B2 (en) * | 1998-06-30 | 2008-06-24 | Sandia Corporation | Enhanced formulations for neutralization of chemical, biological and industrial toxants |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7390432B2 (en) * | 1998-06-30 | 2008-06-24 | Sandia Corporation | Enhanced formulations for neutralization of chemical, biological and industrial toxants |
| CN1557535A (en) * | 2004-01-13 | 2004-12-29 | ����ʦ����ѧ | Gemini quaternary surfactant containing pyridine rings and preparing method thereof |
| WO2005096711A2 (en) * | 2004-04-05 | 2005-10-20 | Kanagawa University | Emulsifying dispersants, method for emusification and dispersion with the same, emulsions, and emulsion fuels |
| CN101185867A (en) * | 2006-11-17 | 2008-05-28 | 天津科技大学 | Gemini quaternary ammonium salt cationic surfactant and preparation method thereof |
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