CN101695641A - Cationic surfactant and preparation method thereof - Google Patents

Cationic surfactant and preparation method thereof Download PDF

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CN101695641A
CN101695641A CN200910210747A CN200910210747A CN101695641A CN 101695641 A CN101695641 A CN 101695641A CN 200910210747 A CN200910210747 A CN 200910210747A CN 200910210747 A CN200910210747 A CN 200910210747A CN 101695641 A CN101695641 A CN 101695641A
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acid
cationic surfactant
methyl
surfactant according
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CN101695641B (en
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徐荣明
陈文婕
韦亚锋
江立新
赵辉
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BANGBU FENGYUAN MEDICINE SCI-TECH DEVELOPMENT Co Ltd
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BANGBU FENGYUAN MEDICINE SCI-TECH DEVELOPMENT Co Ltd
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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

A kind of cationic surfactant and preparation method thereof
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 TE.The cationic surfactant of this structure than be easier to be adsorbed in the fabric face and 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 pi-allyl are introduced in the molecular structure, strengthen the electropositive of molecule.The easier fabric face that is adsorbed on of molecule 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 introduces ester group in the quaternary ammonium salt molecular structure.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 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:
Figure G2009102107479D0000021
Wherein n is 10~14 integer; X is F, Cl, Br or I.
In the described 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
Figure G2009102107479D0000031
Second step: dodecanoic acid methacrylic diethanol amine ester ammonium chloride synthetic
Figure G2009102107479D0000032
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 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: 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 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: 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, magnetic stirring apparatus heating stirring and refluxing reaction down.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
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, 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, magnetic stirring apparatus heating stirring and refluxing reaction down.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 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 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, magnetic stirring apparatus heating stirring and refluxing reaction down.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 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 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, magnetic stirring apparatus heating stirring and refluxing reaction down.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%.
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 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 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 improvements and modifications; for example reactant bromo dodecanoic acid is changed into bromo n-teradecanoic acid or the acid of bromo hexadecane, these improvements and modifications 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 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 3 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 or ethyl acetate.
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