CN101869813A - Preparation method for gemini surfactant with double bonds - Google Patents
Preparation method for gemini surfactant with double bonds Download PDFInfo
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- CN101869813A CN101869813A CN200910059039A CN200910059039A CN101869813A CN 101869813 A CN101869813 A CN 101869813A CN 200910059039 A CN200910059039 A CN 200910059039A CN 200910059039 A CN200910059039 A CN 200910059039A CN 101869813 A CN101869813 A CN 101869813A
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Abstract
The invention discloses a preparation method for a gemini surfactant with double bonds. The method includes the following steps that: (A) prepared tertiary amine with a long alkyl chain and epoxy chloropropane are dissolved in alcohol solution, and after reaction, gemini surfactant with a hydroxyl group is prepared; (B) the gemini surfactant with the hydroxyl group reacts with newly prepared acryloyl chloride, so that the gemini surfactant with the double bonds is prepared.
Description
Technical field
The present invention relates to a kind of preparation method of the Shuangzi cationic surfactant with two keys.Belong to chemical technology field.
Background technology
Gemini surface active agent is with two amphiphilic compositions, and a class novel surfactant that is connected together and forms by chemical bond-linking by spacer group at its base or near a Ji Chu when if its hydrophilic group is quaternary ammonium salt, then is the Shuangzi cationic surfactant.Compare with traditional surfactant, it has high surface-active, very low Krafft (Kraft) point and well water-soluble, and some also has the thickening property that compares favourably with high molecular surfactant.Gemini surface active agent on the molecular weight usually between conventional surfactant and high molecular surfactant, bridge has between the two been set up in its appearance, be described as surfactant of new generation, most possibly become a class surfactant of 21 century extensive use.But conventional method needs trivial step, can not be used for a large amount of productions, and need use many organic solvents, and is unfriendly to environment.In recent years the Shuangzi cationic surfactant of Chu Xianing has been subjected to the extensive concern of Chinese scholars.Unique premium properties of Gemini surface active agent makes it have very wide application prospect in weaving, biology and material field.
Polymerisable surfactant also is the research focus of colloid and Surface Science, and it is by two keys are incorporated in the surfactant molecule structure, make its in emulsion polymerization process by radical polymerization, surfactant molecule for good and all is keyed on the micelle.This class surfactant not only has all character of conventional surfactants, as formation micella and reduction interfacial tension, and the irreplaceable advantage of conventional surfactants is arranged.At first, the desorb of surfactant is difficulty more, and stability is better; The second, when latex film forming, the use of polymerisable surfactant can reduce even suppress the migration in surfactant hydrophily field in film surface or film; The 3rd, the surfactant of part embedding can be used as the performance that coalescent improves formed film; At last, with the prepared emulsion applications of polymerisable surfactant in rubber industry,, will simplify as the processing of the water that condenses or wash so emulsion condensation as elder generation before use, in other words this water be carried out the amount minimizing that needed oxygen is handled in decontamination.
Since application polymerisable surfactants such as Bistline in 1956 carried out polymerisation, through the development of decades, the kind of polymerisable surfactant was more and more now, and U.S. chemical abstract only 1997 yearly correlation patents just reaches 20 multinomial.Abroad, particularly there is the patent of widely applying polymerisable surfactant in Japan.In the surfactant of being studied, what be used for emulsion polymerisation mainly contains acrylic acid and polymerisable surfactants such as methacrylic acid, acrylamide and styrene, the allylic that reactivity is lower also can be used for emulsion polymerisation, what research was many at present is the maleic acid type polymerisable surfactant, because compare with other polymerisable surfactant, its maximum characteristics be can only copolymerization can not homopolymerization.
But the polymerisable surfactant of bibliographical information all is to be made of a hydrophilic group and a hydrophobic group at present, has the polymerisable surfactant of two hydrophilic groups and two hydrophobic groups also not report.The high-performance of the functional and Gemini surface active agent of polymerisable surfactant is combined, for the synthesizing new surfactant has been created opportunity.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who has the Shuangzi cationic surfactant of two keys, this Gemini surface active agent is a kind of polymerisable surfactant, has the characteristics of Gemini surface active agent high surface again simultaneously.In achieving the above object, according to the invention provides a kind of method that has the Shuangzi cationic surfactant of two keys, this method comprises a kind of preparation method who has the Shuangzi cationic surfactant of two keys, it is characterized in that it comprises the steps:
(A) in the alcohols and hydrochloric acid of metering, add long alkyl chain tertiary amine and epoxychloropropane simultaneously by a certain percentage, reaction makes the Gemini surface active agent that has hydroxyl;
(B) reaction makes the Gemini surface active agent that has two keys: in the solvent of metering, add Gemini surface active agent and the new system acryloyl chloride that has hydroxyl in (A) by a certain percentage, add a spot of polymerization inhibitor reaction simultaneously and make the Gemini surface active agent that has two keys.
The purpose that adds a spot of polymerization inhibitor is to prevent double-bond polymerization in reaction.
Alcohols in the step among the present invention (A) comprises
(a) ethanol
(b) normal propyl alcohol
(c) isopropyl alcohol
(d) n-butanol
(e) isoamyl alcohol
In the step (A), the ratio of hydrochloric acid, long alkyl chain tertiary amine and epoxychloropropane amount of substance is that 1: 2.5: 1 o'clock effect is better.Epoxychloropropane concentration is 0.0001～0.1 mol preferably in reactant liquor, and is more preferably 0.0025～0.025 mol.
Solvent comprises in the step among the present invention (B)
(a) chloroform
(b) oxolane
(c) pyridine
In the step (B), having the Gemini surface active agent of hydroxyl and the ratio of new system acryloyl chloride amount of substance is that 1: 1 o'clock effect is better.New system acryloyl chloride concentration is 0.0001～0.1 mol preferably in reactant liquor, and is more preferably 0.0025～0.025 mol.
The Gemini surface active agent that has two keys that the present invention synthesizes, its aqueous solution demonstrates higher viscosity and high surface, and because polymerisable character is arranged, will have good application prospects in fields such as emulsion polymerisation, nano material preparation
The specific embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
(1) take by weighing 20.6 gram 12 tertiary amines and 10 gram hydrochloric acid fully mix, add 60 gram ethanol and 20.6 grams, 12 tertiary amines again, after stirring, Dropwise 5 gram epoxychloropropane in 1h, treat titration after, continue reaction 12h down at 60 ℃, constantly stir.After question response finished, purified product obtained hydroxyl Gemini surface active agent A.
(2) take by weighing 8.5 gram A and be dissolved in 30 gram chloroforms, after stirring, add 0.05 gram hydroquinones, and in 1h, drip 1.5 gram new system acryloyl chlorides, treat titration after, continue reaction 12h down at 45 ℃, constantly stir.After question response finished, purified product obtained the Gemini surface active agent B with two keys.
Embodiment 2
(1) take by weighing 26.5 gram 14 tertiary amines and 12 gram hydrochloric acid fully mix, add 50 gram normal propyl alcohols and 26.5 grams, 12 tertiary amines again, after stirring, Dropwise 5 gram epoxychloropropane in 1h, treat titration after, continue reaction 6h down at 70 ℃, constantly stir.After question response finished, purified product obtained hydroxyl Gemini surface active agent A.
(2) take by weighing 8.5 gram A and be dissolved in 30 gram chloroforms, after stirring, add 0.05 gram hydroquinones, and in 1h, drip 1.2 gram new system acryloyl chlorides, treat titration after, continue reaction 14h down at 40 ℃, constantly stir.After question response finished, purified product obtained the Gemini surface active agent B with two keys.
Embodiment 3
(1) take by weighing 35 gram 16 tertiary amines and 14 gram hydrochloric acid fully mix, add 75 gram normal propyl alcohols and 26.5 grams, 16 tertiary amines again, after stirring, Dropwise 5 gram epoxychloropropane in 1h, treat titration after, continue reaction 8h down at 80 ℃, constantly stir.After question response finished, purified product obtained hydroxyl Gemini surface active agent A.
(2) take by weighing 12 gram A and be dissolved in 35 gram chloroforms, after stirring, add 0.1 gram hydroquinones, and in 1h, drip 1.5 gram new system acryloyl chlorides, treat titration after, continue reaction 16h down at 60 ℃, constantly stir.After question response finished, purified product obtained the Gemini surface active agent B with two keys.
Claims (6)
1. a preparation method who has two key Gemini surface active agents is characterized in that it comprises the steps:
(A) reaction makes the Gemini surface active agent that has hydroxyl: in the there-necked flask of the strap clamp cover that backflow is housed, add the ethanol and the hydrochloric acid of metering, add long alkyl chain tertiary amine and epoxychloropropane simultaneously by a certain percentage, the heating that refluxes, reaction 4～24h;
(B) reaction makes the Gemini surface active agent that has two keys: in the there-necked flask of the strap clamp cover that backflow is housed, the chloroform that adds metering, add above-mentioned Gemini surface active agent and the new system acryloyl chloride that has hydroxyl by a certain percentage, add a spot of hydroquinone of polymerization retarder or phenthazine simultaneously, reaction 4～12h.
2. by the described preparation method of claim 1, it is characterized in that, its Chinese style 1 is the described Gemini surface active agent that has hydroxyl of claim 1 (A), and formula 2 is the described Gemini surface active agent that has two keys of claim 1 (A), and wherein R is that the n value is 4～24 long alkyl chains; Its counter ion is Cl
-Anion,
Formula 1
Formula 2.
3. by the described preparation method of claim 1, it is characterized in that, (A) in the step
(1) wherein saidly contain the long alkyl chain tertiary amine and the epoxychloropropane solution concentration is 0.0001～0.1 mol, mol ratio is 2.5: 1;
(2) consumption of hydrochloric acid is 1/2～1 times of long alkyl chain tertiary amine;
(3) solvent for use is ethanol or normal propyl alcohol.
4. by the described preparation method of claim 1, it is characterized in that, (B) in the step
(1) wherein said to contain the Gemini surface active agent and the new system acryloyl chloride solution concentration that have hydroxyl be 0.0001～0.1 mol, and mol ratio is 1: 1;
(2) polymerization inhibitor consumption: 0～100ppm;
(3) solvent for use is chloroform or pyridine.
5. by the described preparation method of claim 1, it is characterized in that, (A) in the step
Product decompression distillation after the reaction end except that desolvating, is obtained yellow jelly matter, use acetone recrystallization, remove impurity component, vacuum drying obtains crystal powder.
6. by the described preparation method of claim 1, it is characterized in that, (B) in the step
Product decompression distillation after the reaction end except that desolvating, is obtained faint yellow gluey material, with the acetoneand ethyl acetate recrystallization, remove impurity component, vacuum drying obtains crystal powder.
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| CN200910059039A CN101869813A (en) | 2009-04-23 | 2009-04-23 | Preparation method for gemini surfactant with double bonds |
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| CN200910059039A CN101869813A (en) | 2009-04-23 | 2009-04-23 | Preparation method for gemini surfactant with double bonds |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151514A (en) * | 2011-01-20 | 2011-08-17 | 天津市职业大学 | Synthetic method of gemini quaternary ammonium salt surfactant and application as drag reduction agent |
| CN103406063A (en) * | 2013-08-08 | 2013-11-27 | 上海发凯化工有限公司 | Cationic gemini surfactant preparation method |
| CN104128120A (en) * | 2014-07-22 | 2014-11-05 | 武汉工程大学 | Preparation method of cationic gemini surfactant with connection chain containing hydroxy group |
| CN105037176A (en) * | 2015-07-07 | 2015-11-11 | 西北大学 | Preparation method for quaternary ammonium salt dimeric surfactant containing hydroxyl group and application of quaternary ammonium salt dimeric surfactant containing hydroxyl group in tertiary oil recovery |
| CN109575234A (en) * | 2018-11-13 | 2019-04-05 | 沈阳新意石油化工厂 | A kind of preparation method of nonionic surfactant |
| CN111233680A (en) * | 2019-04-29 | 2020-06-05 | 河南省科学院高新技术研究中心 | Acrylic acid biquaternary ammonium salt monomer and preparation method thereof |
| CN114195927A (en) * | 2020-09-18 | 2022-03-18 | 中国石油天然气集团有限公司 | Thickening agent, composition for forming same, emulsion polymer, fracturing fluid system and application thereof |
-
2009
- 2009-04-23 CN CN200910059039A patent/CN101869813A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151514A (en) * | 2011-01-20 | 2011-08-17 | 天津市职业大学 | Synthetic method of gemini quaternary ammonium salt surfactant and application as drag reduction agent |
| CN103406063A (en) * | 2013-08-08 | 2013-11-27 | 上海发凯化工有限公司 | Cationic gemini surfactant preparation method |
| CN104128120A (en) * | 2014-07-22 | 2014-11-05 | 武汉工程大学 | Preparation method of cationic gemini surfactant with connection chain containing hydroxy group |
| CN105037176A (en) * | 2015-07-07 | 2015-11-11 | 西北大学 | Preparation method for quaternary ammonium salt dimeric surfactant containing hydroxyl group and application of quaternary ammonium salt dimeric surfactant containing hydroxyl group in tertiary oil recovery |
| CN109575234A (en) * | 2018-11-13 | 2019-04-05 | 沈阳新意石油化工厂 | A kind of preparation method of nonionic surfactant |
| CN111233680A (en) * | 2019-04-29 | 2020-06-05 | 河南省科学院高新技术研究中心 | Acrylic acid biquaternary ammonium salt monomer and preparation method thereof |
| CN114195927A (en) * | 2020-09-18 | 2022-03-18 | 中国石油天然气集团有限公司 | Thickening agent, composition for forming same, emulsion polymer, fracturing fluid system and application thereof |
| CN114195927B (en) * | 2020-09-18 | 2023-08-22 | 中国石油天然气集团有限公司 | Thickening agent, composition for forming thickening agent, emulsion polymer, fracturing fluid system and application of fracturing fluid system |
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Application publication date: 20101027 |