CN101695642B - Cationic surfactant and preparation method thereof - Google Patents
Cationic surfactant and preparation method thereof Download PDFInfo
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- CN101695642B CN101695642B CN2009102107483A CN200910210748A CN101695642B CN 101695642 B CN101695642 B CN 101695642B CN 2009102107483 A CN2009102107483 A CN 2009102107483A CN 200910210748 A CN200910210748 A CN 200910210748A CN 101695642 B CN101695642 B CN 101695642B
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Abstract
The invention relates to a cationic surfactant and a preparation method thereof. The structural 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 a class fine chemicals, every field such as extensive use industrial 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).
Along with the enhancing of 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 EQDMS.The cationic surfactant of this structure than be easier to be adsorbed in the fabric face and fabric on 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 introduces ester group in the quaternary ammonium salt molecular structure.But still have problems, be exactly how to make the easier fabric face that is adsorbed on of molecule form film, intercept extraneous negative electrical charge, and make surfactant as fabric softening agent the time, not only have favorable biological degradability but also adsorptivity and in and the negative electrical charge ability stronger.
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 invention provides a kind of cationic surfactant, its general structure is as follows:
Wherein n is 10～14 integer; X is F, Cl, Br or I.Preferred n is 10; X is Cl.
The name of the cationic surfactant when n is 10 is called two dodecylic acid diethylester methyl-benzyl ammonium chlorides;
The name of the cationic surfactant when n is 12 is called two tetradecanoic acid diethylester methyl-benzyl ammonium chlorides;
The name of the cationic surfactant when n is 14 is called two hexadecanoic acid diethylester methyl-benzyl ammonium chlorides.
The present invention also provides the method for the above-mentioned cationic surfactant of preparation, comprises 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 methyl diethanolamine and aliphatic acid is 1: 2.2～2.5, preferred 1: 2.4;
2) quaternary amine salinization reaction
Intermediate (I) and benzyl halogen 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 benzyl halogen, preferred 1: 1.2.
Wherein, acidic catalyst described in the step 1) is selected from organic acid (as p-methyl benzenesulfonic acid) or inorganic acid (as the phosphoric acid and the concentrated sulfuric acid), preferred p-methyl benzenesulfonic acid.
Wherein, quaternary amine salinization step 2) is carried out under being reflected at and refluxing in the low boiling point solvent.
Described low boiling point solvent is acetone, ethyl acetate or isopropyl alcohol.
Be initiation material with dodecyl acid and benzyl 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: two dodecylic acid diethylester methyl-benzyl ammonium chlorides synthetic
Cationic surfactant of the present invention is introduced benzyl in the molecular structure, strengthens the electropositive of molecule.The easier fabric face that is adsorbed on of molecule forms film, intercepts extraneous negative electrical charge.In cationic surfactant structure of the present invention, existing two long alkane chains have been introduced ester group and benzyl again in the molecular structure of surfactant.This structure make surfactant as fabric softening agent the time, not only have favorable biological degradability but also adsorptivity and in and the negative electrical charge ability stronger.
Cationic surfactant of the present invention and preparation method thereof has following beneficial effect: the method raw material is easy to get, the reaction condition gentleness, and is simple to operate, yield height, recycled solvent, the no three wastes.
The specific embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
The first step: laurate methyl diethanolamine 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 by 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: two dodecylic acid diethylester methyl-benzyl ammonium chlorides synthetic
In the reaction bulb of condenser pipe is housed, add laurate methyl diethanolamine ester 20.0g (0.04mol), benzyl chlorine 5.40g (0.048mol) and acetone 35mL, magnetic stirring apparatus heating stirring and refluxing reaction down.Gas chromatography monitoring reaction terminal point.About 12h 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, pale yellow powder shape solid 20.0g.Solid content is not less than 98%, and the bromophenol blue diphasic titration is calculated effective content 92.5%, yield 77.3%.
1HNMR chemical shift ppm:0.96 (6H), 1.29～1.68 (36H), 2.25 (4H), 2.30 (3H), 3.52 (4H), 4.48 (2H), 4.52～4.58 (4H), 7.06～7.14 (5H).
In methyl diethanolamine, the total recovery 62.6% of two dodecylic acid diethylester methyl-benzyl ammonium chlorides.
Embodiment 2
Pressing embodiment 1 operates 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, the total recovery 64.6% of two dodecylic acid diethylester methyl-benzyl ammonium chlorides.
Embodiment 3
Pressing embodiment 1 operates equally, the benzyl chlorine 5.40g (0.048mol) that only will be wherein uses in the synthetic method in second step changes benzyl chlorine 6.75g (0.06mol) into, other are constant, get the quaternary ammonium salt product, receive heavy 21.5g, it is 94.0%, the second step synthesis yield 84.4% that the bromophenol blue diphasic titration detects purity.
In methyl diethanolamine, two dodecylic acid diethylester methyl-benzyl ammonium chloride total recoverys 68.4%.
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, two dodecylic acid diethylester methyl-benzyl ammonium chloride total recoverys 70.56%.
Embodiment 5
The first step: dodecylic acid methyl diethanolamine ester synthetic
Synthesize according to embodiment 1 first step method.
Second step: two dodecylic acid diethylester methyl-benzyl ammonium iodides synthetic
In the reaction bulb of condenser pipe is housed, add dodecylic acid methyl diethanolamine ester 24.5g (0.04mol), benzyl iodine 10.46g (0.048mol) and isopropyl alcohol 30mL, magnetic stirring apparatus heating stirring and refluxing reaction down.Gas chromatography monitoring reaction terminal point.About 12h 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, pale yellow powder shape solid 24.5g.The bromophenol blue diphasic titration is calculated effective content 92.0%, yield 80.4%.
In methyl diethanolamine, the total recovery 65.1% of two dodecylic acid diethylester methyl-benzyl ammonium iodides.
Embodiment 6
The first step: tetradecanoic acid methyl diethanolamine ester synthetic
In the reaction bulb of rectifying column is housed, add methyl diethanolamine 35.7g (0.30mol), n-teradecanoic acid 171g (0.75mol) and catalyst phosphoric acid 0.8g respectively, 120 ℃～150 ℃ following fusions, stirring reaction then is by dividing the content monitoring reaction process of water outlet in the water knockout drum.Approximately behind the 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 tetradecylic acid methyl diethanolamine ester weak yellow liquid, receives 124g, and it is 98% that gas-chromatography normalization detects purity, yield 75.2%.
Second step: two tetradecanoic acid diethylester methyl-benzyl ammonium chlorides synthetic
In the reaction bulb of condenser pipe is housed, add tetradecanoic acid methyl diethanolamine ester 22.2g (0.04mol), benzyl chlorine 6.07g (0.048mol) and ethyl acetate 40mL, magnetic stirring apparatus heating stirring and refluxing reaction down.Gas chromatography monitoring reaction terminal point.About 12h 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, pale yellow powder shape solid 24.0g.The bromophenol blue diphasic titration is calculated effective content 92.5%, yield 83.4%.
In methyl diethanolamine, the total recovery 62.7% of two hexadecanoic acid diethylester methyl-benzyl ammonium chlorides.
Embodiment 7
The first step: hexadecanoic acid methyl diethanolamine 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 concentrated sulfuric acid 1.0g respectively, 120 ℃～150 ℃ following fusions, stirring reaction then is by dividing the content monitoring reaction process of water outlet in the water knockout drum.Approximately behind the 8h, 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 146g, and it is 98.0% that gas-chromatography normalization detects purity, yield 80.2%.
Second step: two hexadecanoic acid diethylester methyl-benzyl ammonium chlorides synthetic
In the reaction bulb of condenser pipe is housed, add hexadecanoic acid methyl diethanolamine ester 24.3g (0.04mol), benzyl chlorine 6.07g (0.048mol) and isopropyl alcohol 30mL, magnetic stirring apparatus heating stirring and refluxing reaction down.Gas chromatography monitoring reaction terminal point.About 12h 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, pale yellow powder shape solid 22.5g.The bromophenol blue diphasic titration is calculated effective content 92.5%, yield 72.1%.
In methyl diethanolamine, the total recovery 57.8% of two hexadecanoic acid diethylester methyl-benzyl ammonium chlorides.
As can be seen from the above embodiments, the synthesis route of the double long-chain alkyl ester group cationic surfactant that the embodiment of the invention provides is short, does not have harsh reaction condition, and raw material is easy to get, recycled solvent, the no three wastes.This method is about 70.58% in the total recovery of the two dodecylic acid diethylester methyl-benzyl ammonium chlorides of methyl diethanolamine.Be fit to suitability for industrialized production; Compared with prior art, the resulting cationic surfactant of embodiment 1-7 is introduced benzyl in the molecular structure, strengthens the electropositive of molecule.The easier fabric face that is adsorbed on of molecule forms film, intercepts extraneous negative electrical charge.In cationic surfactant structure of the present invention, existing two long alkane chains have been introduced ester group and benzyl again in the molecular structure of surfactant.This structure make surfactant as fabric softening agent the time, not only have favorable biological degradability but also adsorptivity and in and the negative electrical charge ability stronger.
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 the technology of the present invention principle; can also make some improvement and variation; for example reactant bromo dodecanoic acid is changed into bromo n-teradecanoic acid or the acid of bromo hexadecane, these improvement and variation also should be considered 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 described 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 methyl diethanolamine and aliphatic acid is 1: 2.2～2.5;
2) quaternary amine salinization reaction
Intermediate (I) and benzyl halogen 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 benzyl halogen.
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 described 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, ethyl acetate or isopropyl alcohol.
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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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