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CN109134530A - A kind of pair of hydrophobic based surfactants and preparation method thereof - Google Patents

A kind of pair of hydrophobic based surfactants and preparation method thereof Download PDF

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CN109134530A
CN109134530A CN201810863612.1A CN201810863612A CN109134530A CN 109134530 A CN109134530 A CN 109134530A CN 201810863612 A CN201810863612 A CN 201810863612A CN 109134530 A CN109134530 A CN 109134530A
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hydrophobic based
based surfactants
double
surfactant
double hydrophobic
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李云峰
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Zhejiang Kefeng Silicone Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/14—Derivatives of phosphoric acid

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Abstract

The present invention relates to a kind of surfactant, in particular to a kind of double hydrophobic based surfactants and preparation method thereof.A kind of double hydrophobic based surfactants, the molecular structural formula of this pair of hydrophobic based surfactants are as follows:Wherein R=CnH2n+1, n >=5.A kind of preparation method of double hydrophobic based surfactants, the reaction equation of this method are

Description

A kind of pair of hydrophobic based surfactants and preparation method thereof
Technical field
The present invention relates to a kind of surfactant, in particular to a kind of double hydrophobic based surfactants and preparation method thereof.
Background technique
Surfactant has the performances such as emulsification, solubilising, wetting, dispersion, foaming, decontamination, sterilization, antistatic and inhibition, It is widely used in each industrial circle, such as weaving, leather, papermaking, cosmetics, articles for washing, medicine, food, printing, agriculture Medicine, metallurgy, petrochemical industry, bioengineering etc..Due to the rapid development of modern industry, cause the whole world that will consume daily a large amount of Surfactant, this causes very big burden to natural environment, while also to the raw material for manufacturing surfactant, such as stone The increasingly depleted resource such as oil, coal brings huge pressure.It explores and there is high performance surface activating agent to have become table for research The research hotspot of face activating agent industry.Gemini (meaning of Gemini) surfactant that early 1970s rise is due to it Just there is very high surface-active under lower concentration, attracts people's extensive concern.
Bunton in 1971 etc. has synthesized a series of double alkyl chain surfactants of dication head bases for the first time, and by they Phase transfer catalyst as nucleophilic substitution.However, really system carry out this kind of surfactant research work be from The early 1990s.Nineteen ninety, Okahara etc. have synthesized the anionic type Gemini surface active agent with flexible connected base.It arrives 1991, the Menger and Littau of Emory university of the U.S. synthesized the Gemini surface active with rigid attachment group, And to this kind of novel surfactant it is named as Gemini surfactant, this kind of novel surfactant of figurative expression The design feature of molecule.The same year, Rosen group of New York city,U.S state university adopt the name of " Gemini ", and system It synthesizes, have studied the anionic type Gemini surface active agent coupled with ethylene oxide or oxypropylene flexible group, no longer distich It connects base and does any additional restriction.By 1994, the ion head base that Q.Huo etc. connects spacer group was different with alkyl chain Gemini surface active is studied, and is investigated to their application value.2004, Zana professor recorded with the summer Ancient cooking vessel professor has collaborateed " Gemini surfactants, synthesis, interfacial and solution-phase Behavior, and application " book, outline the synthesis of Gemini surface active, interfacial property, solution are mutually gone For and application.At present to the report of the surface property of Gemini surface active, interface performance, aggregation number and solubilization etc. Road occurs in succession, and a large amount of research work has been done to Gemini surface active by various countries, and has synthesized many novel Gemini surface active, such as the both sexes of asymmetrical type, nuisanceless disaccharide type, cation (quaternary ammonium salt) and anion (phosphate) Type.Research of the China in terms of Gemini surface active is started late, and 1997, Dalian University of Technology Wang Jiang etc. took the lead in synthesizing A kind of amphoteric ionic Gemini surfactant is simultaneously applied in agriculture breast agent, achieves preferable effect.Foochow in 1999 University's Zhao Jian sunlight has delivered the research overview in relation to external Gemini surface active, has caused the very big emerging of Chinese scholar Interest.Hereafter, surface of the prune of the Zhao Jian sunlight research group and Shandong University assistant research group to some Gemini surface actives Performance has carried out research report.Some synthesis and performance study in relation to Gemini surface active are relevant at present is reported in state Interior magazine starts to occur in succession, such as: quaternary ammonium salt Gemini cationic surfactant, the cation form of Gemini containing ester based quaternary ammonium salt Face activating agent, dinonyl phenol condensation and glycine derivative Quaternary ammonium gemini surfactants, but the research of this respect It still needs further improvement for work.It can be seen that the research of Gemini surface active starts from 1970s Bunton etc. A kind of bi-quaternary ammonium salt phase transfer catalyst of synthesis.Since such surfactant has many conventional surfactants can not The performance to compare favourably such as characterizes micelle formation ability and reduces by two characteristic indexs of surface tension efficiency: critical micelle concentration (cmc) and C20Reduce two to three orders of magnitude respectively than conventional surfactant.1991, F.M.Menger etc. was used first Gemini is named to this kind of surfactant, and hereafter this kind of new structural surfactant causes people in worldwide Extensive concern.The field has become a popular domain of international cross discipline and related fields research at present.
Gemini surface active is otherwise known as Anionic Gemini Surfactant, coupled surfaces activating agent or twin surface-active Agent is a kind of novel surfactant of oligomerization with high surface.This kind of surfactant is coupled by one Two same or similar surfactant monomers are passed through chamical binding near its hydrophilic head base or hydrophilic head base by group A kind of novel surfactant for connecing and being formed, so that the property of controllable head base, generates quite high surface-active.Gemini The amphipathic of surfactant molecule structure allows them to spontaneously assemble in adsorbed on interfaces and in the solution.By its parent Head base type, Gemini surface active can be divided into cationic, anionic, amphoteric ion type and non-ionic Gemini surface active.In Gemini surface active, Recent study development is cationic Gemini table faster Face activating agent, it is the compound containing N that they are most of, also known as quaternary Gemini cationic surfactant.
Gemini surface active is because its novel structure and excellent performance worldwide cause people's Extensive concern.The molecular structure of Gemini surface active is generally made of three parts.First is that two same or similar The hydrophobic group of long-chain fat chain composition, is normally at the both ends of molecule, can introduce the functions such as ester group, amide groups on hydrophobic group Group；Second is that hydrophilic group, that is, ion head base；Third is that connection base plays anastomosis positioned at the centre of molecule.Gemini surface active Molecular structural formula be
The superiority of Gemini surface active is mostly derived from: being on the one hand because in Gemini surface active two A ion head base passes through by spacer group to be chemically bonded, therefore it is close to cause two surfactant monomer ions Connection, so that hydrocarbon interchain is more prone to produce strong interaction, strengthens the hydrophobic binding power of hydrocarbon interchain.Chemical bond simultaneously Power largely reduced the tendency of the repulsion between ion head base, so that Gemini surface active is easier aggregation in the solution and forms glue Beam.In Gemini surface active solution, two hydrophobic chains enter in solution micella from water phase simultaneously, result in it is biggish from By that can change, to reduce the critical micelle concentration of solution, make Gemini surface active than traditional single-stranded single head base table Face activating agent has higher surface-active.On the other hand, it is hydrophilic will not to destroy its for being chemically bonded between two ion head bases Property, so that the extensive use for Gemini surface active provides the foundation.It can be seen that passing through the above-mentioned side being chemically bonded Method is not identical to improve surface-active and previous usually used physical method, is one in the research field of surfactant It breaks through.
Summary of the invention
The purpose of the present invention is to provide a kind of double hydrophobic based surfactants, this pair of hydrophobic based surfactants have height Emulsifiability,
The present invention also provides a kind of preparation methods of double hydrophobic based surfactants.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of double hydrophobic based surfactants, the molecular structural formula of this pair of hydrophobic based surfactants are as follows:Wherein R=CnH2n+1, n >=5.
A kind of preparation method of double hydrophobic based surfactants, the reaction equation of this method areSpecific steps are as follows: with alcohol (ROH) and ring Oxygen chloropropane is raw material, and phase transfer catalyst is added, and is reacted under the conditions of stirring, reflux condensation mode, and reaction temperature is 45 DEG C ~65 DEG C, the reaction time is 2h~8h, and the molar ratio of alcohol (ROH), epoxychloropropane and phase transfer catalyst is 1:2.2~3.5: 0.03~0.15；Product after reaction filters the salt for removing and generating through decompression, and saturated sodium-chloride water solution is washed to neutrality, dry (desiccant generally uses anhydrous sodium sulfate), being evaporated under reduced pressure to transparent micro- thick liquid is product.Reaction rises in order to prevent It is warm acutely when raw material is added to need that epoxychloropropane is added dropwise while stirring, reacted system heating after dripping.
The structure of double hydrophobic based surfactants of the invention is different from typical Gemini surface active structure, only One ion head base, dual link base, structure is simpler, can such as be applied to as emulsifier directly as surfactant application Emulsion polymerization, emulsion dispersion etc. also can be used as the series such as exploitation Sulfonates, phosphoric acid salt, polyethenoxy ether class The intermediate of Gemini surface active.
The present invention provides several double hydrophobic based surfactants, their general formula of molecular structure are as follows:
In surfactant provided by the invention, the intervention of spacer group and its chemical structure, coupled position, degree of rigidity And the variation of the factors such as chain length, the structure for making this surfactant is had into diversified feature, and then to its solution and boundary The properties such as face have an impact, and are allowed to the performance for having more excellent.
Surfactant provided by the invention reduces the principle of surface tension as conventional surfactant, all passes through Surfactant is in aqueous solution adsorption thus to reduce surface tension.But this surfactant is easier to be adsorbed on Gas/liquid surface, to more effectively reduce the surface tension of aqueous solution.Meanwhile connection the passing through of base in active agent molecule It learns key to connect two hydrophobic groups, weakens the repulsion of the electrostatic repulsion and its aquation interlayer between hydrophobic group, promote this Absorption and autohemagglutination in aqueous solution of the kind surfactant molecule on aqueous solution surface, thus there is very high adsorption energy Power.
Surfactant provided by the invention is easier autohemagglutination in aqueous solution than conventional surfactant, and tends to shape At the aggregation of lower curvature.It can form a series of aggregation in aqueous solution: globular micelle, ellipsoid micella, rodlike Micella, branch shape micella, linear micella, double-layer structure, liquid crystal, vesica etc..Surface-active is excellent, especially there is good emulsifying power Power can be used as emulsifier and directly use；Other can also further be developed as Sulfonates, phosphoric acid salt, polyethenoxy ether class are double Hydrophobic based surfactants.
Preferably, the alcohol is selected from amylalcohol, enanthol, isooctanol, lauryl alcohol, tetradecyl alchohol or hexadecanol, phase transfer is urged Agent is tetrabutylammonium bromide.
A kind of double hydrophobic based surfactants of Sulfonates, the molecular structural formula of this pair of hydrophobic based surfactants are as follows:Wherein R=CnH2n+1, n >=5.
A kind of preparation method of the double hydrophobic based surfactants of the Sulfonates, the reaction equation of this method are
, step includes:
A, the double hydrophobic based products of hydroxyl, i.e., described double hydrophobic based surfactants are prepared；
B, it in four mouthfuls of reaction flasks that electric mixer, thermometer, dropping funel, HCl gas absorbing device are housed, is added The double hydrophobic based products of hydroxyl made from step a are added dropwise by the quality of double 1~4 times of the hydrophobic based products of hydroxyl under vigorous stirring HSO3Cl (chlorosulfonic acid), time for adding control in 0.5~3h, and reaction temperature is controlled at 10~45 DEG C, are absorbed with NaOH solution The dosage of the HCl of releasing, NaOH are HSO3The 5~35% of Cl mass；After charging, 1~5h is reacted, the abundant sulphur of product is made Change；1~8h is placed, the HCl generated is discharged as much as possible；Then, equipped with electric mixer, thermometer, dropping funel In four mouthfuls of reaction flasks, NaOH solution is added, the dosage of NaOH is equivalent to HSO3The 5~25% of Cl mass；At 15~60 DEG C At a temperature of be added dropwise aryl sulfonic acid into system, the time controls after 0.5~2.5h, completion of dropwise addition, adjusts the pH value of whole system To 7~8, product is the double hydrophobic based surfactants of Sulfonates.Aryl sulfonic acid is common agents, in the present invention, ability Field technique personnel can select according to the prior art.
Preferably, the aryl sulfonic acid is selected from toluenesulfonic acid, dodecyl alkyl benzene sulphonate, myristyl alkyl One of benzene sulfonic acid or methyl naphthalene sulfonic acid.
A kind of double hydrophobic based surfactants of polyethenoxy ether class, the molecular structural formula of this pair of hydrophobic based surfactants Are as follows:Wherein R=CnH2n+1, n >=5.
A kind of preparation method of the double hydrophobic based surfactants of the polyethenoxy ether class, it is characterised in that: this method Reaction equation be
, step includes:
A, the double hydrophobic based products of hydroxyl, i.e., described double hydrophobic based surfactants are prepared；
B, by the double hydrophobic based products of hydroxyl made from 0.02~0.10mol step a and 0.0025~0.02mol sodium hydroxide It is added in autoclave, obtains compound n, vacuumize, be passed through high pure nitrogen, and replaced 2~4 times with high pure nitrogen, then lead to Entering ethylene oxide makes molar ratio 1:20~30 of compound n and ethylene oxide, 100~160 DEG C is warming up under stirring, 120 DEG C~180 DEG C at react 1~3h；Reaction kettle is cooled to room temperature, reaction solution neutralizes through acid, obtains polyoxy second after active carbon decoloring The double hydrophobic based surfactants of alkene ethers.
A kind of double hydrophobic based surfactants of phosphoric acid salt, the molecular structural formula of this pair of hydrophobic based surfactants are as follows:Wherein R=CnH2n+1, n >=5.
A kind of preparation method of the double hydrophobic based surfactants of the phosphoric acid salt, it is characterised in that: this method it is anti- Ying Shiwei
, step includes: a, prepares the double hydrophobic based products of hydroxyl, i.e., described double hydrophobic based surfactants；
B, by solvent C Cl4、POCl3Heating water bath produces the double hydrophobic groups of hydroxyl made from step a to 10~35 DEG C after mixing Object is added dropwise in dicyandiamide solution, wherein the double hydrophobic based products of hydroxyl and POCl3Molar ratio is 1:1~2, CCl4It is double hydrophobic for hydroxyl Based products and POCl3The 70%~100% of gross mass；The insulation reaction 1-1.5h at 15~35 DEG C, then it is warming up to 80~100 DEG C The reaction was continued 8~10h, the hydrogen chloride gas for reacting generation are absorbed with sodium hydroxide solution, obtain intermediate product 2- (O- phosphinylidyne two Chlorine) two hydrophobic based products；Then the intermediate product is instilled in excessive cold water, obtains the double hydrophobic group surface-actives of phosphoric acid salt Agent.
The beneficial effects of the present invention are: double hydrophobic based surfactants of the invention have high emulsibility energy, can directly use In cosmetics, organosilicon, weaving, leather, articles for washing, medicine, food, papermaking, printing, pesticide, metallurgy, petrochemical industry, life The fields such as object engineering, the intermediate also developed as high performance surface activating agent.
Specific embodiment
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.It should be appreciated that this hair Bright implementation is not limited by the following examples, and the accommodation in any form made to the present invention and/or changed will all be fallen Enter the scope of the present invention.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc. It is commercially available or commonly used in the art.Method in following embodiments is unless otherwise instructed the normal of this field Rule method.
It is the detection method that the present invention uses below:
1. surface property measures
The ability that surfactant forms micella in the solution is to characterize a key property parameter of surface-active height. The micellization concentration of surfactant is indicated with cmc, refers to surfactant when gas water interface reaches saturation absorption, in solution Surfactant molecule forms the concentration of aggregation by diffusion contact.Cmc value is smaller, and surfactant forms the ability of micella Higher, surface-active is also higher.
The present invention surveys surface property using drop-volume method.The surface tension of aqueous surfactant solution is measured at 25 DEG C. Principle is when liquid is slowly dripped from nozzle, and the size of drop is related with the density of liquid and surface tension, when the weight of drop When power and surface tension balance, mg=2 π R γ.Since drop has a part residual when nozzle drips, must introduce correction because Sub- F, according to the actual situation with introduce error correction coefficient(pure water correction), finally obtains formula:Wherein, m: the quality of drop；R: drop volume pipe water dropper cross-sectional area.
At 25 DEG C, the surface tension of pure water is 71.5m N/m, when product is dissolved in water, generation molecular surface absorption first Phenomenon, at this moment surface tension declines with the increase of concentration, when absorption reaches saturation, will assemble plastic in the inside of water The surface tension of beam, solution is no longer widely varied with concentration, and the concentration of solution is the critical micelle concentration of product at this time (cmc).Critical micelle concentration (cmc) value of surfactant is found out according to the inflection point on γ-lgc curve.
2. emulsifiability measures
Emulsion is that a kind of liquid is scattered in another not miscible liquid, a kind of stability of formation it is less big and point The divergence liquid-liquid dispersions system lower than colloidal dispersion degree.The interface of system increases in dispersion process, need to do work system to increase The gross energy of system, this is a kind of nonspontaneous process；And liquid pearl condenses, system median surface is reduced, the mistake that system free energy reduces Journey is spontaneous.Therefore emulsion is thermodynamically unstable system, there is biggish Gibbs free energy.In order to reduce not Surfactant can be added as emulsifier to reduce interfacial tension in degree of stability, to reduce because of caused by emulsification The thermodynamic phase of interfacial area increase bring system.Meanwhile according to Gibbs adsorption theorem, surfactant is on boundary Face is adsorbed, and tough and tensile interfacial film is formed, and can reduce the coalescence speed of dispersed phase drop, to prevent or delay dispersion liquid The coagulation and condensation that the mutual collision of pearl is formed.But anyway still with the presence of interface and interfacial tension, therefore system is still not Stable, always try hard to reduce interfacial area, final grease is incompatible, and lamination occurs.Emulsifiability test will be seen that Whether designated surface activating agent has excellent emulsifying capacity, so extremely important.
The present invention emulsifies measuring method: having the surfactant solution that 20m L 0.1% is added in plug graduated cylinder to 100m L With 20m L atoleine (chemistry is pure), plug is covered, is stood after fiercely vibrating 50 times up and down, record is since standing to water phase Separate the time of 10m L.Each sample experiments in triplicate, take its average value.Every 40s records a water-oil separating feelings later Emulsifiability is calculated as follows in condition: emulsifying ability=emulsion layer volume/total liquid volume.
Oil phase drop and aqueous phase droplets are taken respectively, then the emulsifier on the interface ambient absorption of these drops, observe water The speed of phase and oily phase coalescence speed, and thus judge the type of emulsion, i.e., O/W is formed when water phase coalescence speed is greater than oil phase Type emulsion, on the contrary form w/o type emulsion.
Embodiment 1
Raw material enanthol, epoxychloropropane and tetrabutylammonium bromide are added to electric mixing device, reflux condensation mode dress It sets, in the three-necked flask of thermometer.Wherein, enanthol, epoxychloropropane molar ratio n (enanthol): n (epoxychloropropane) be 1: 3.5, phase transfer catalyst tetrabutylammonium bromide dosage is 0.05 (molar ratio of opposite alcohol).Reaction temperature is 50 DEG C, when reaction Between be 3.5h.Acutely, epoxychloropropane is added dropwise in reaction heating while stirring in order to prevent, temperature reaction after dripping, gained Mixture filters the salt for removing and generating by decompression, then is washed to neutrality with saturated sodium-chloride water solution, dry with anhydrous sodium sulfate After dry, it is evaporated under reduced pressure to transparent micro- thick liquid.Its surface-active parameter and emulsifiability are tested, the result is shown in tables 1.
Table 1
*γcmcReach surface tension when critical micelle concentration for surfactant；ΓmaxFor maximal absorptive capacity, that is, it is saturated Adsorbance
The preparation of the double hydrophobic based surfactants of 2 sodium sulfonate of embodiment
With molar ratio n (lauryl alcohol): n (epoxychloropropane) is 1:2.6, and phase transfer catalyst tetrabutylammonium bromide dosage is 0.075 molar ratio of alcohol (opposite) be added to electric mixing device, reflux condensate device, thermometer three-necked flask in. Reaction temperature is 50 DEG C, reaction time 3h.Acutely, epoxychloropropane is added dropwise in reaction heating while stirring in order to prevent, is added dropwise Temperature reaction after complete, gained mixture filters the salt for removing and generating by decompression, then is washed to saturated sodium-chloride water solution Neutrality is evaporated under reduced pressure to transparent micro- thick liquid after anhydrous sodium sulfate drying.
In four mouthfuls of reaction flasks that electric mixer, thermometer, dropping funel, HCl gas absorbing device are housed, hydroxyl is added HSO is added dropwise by the quality of double 2 times of the hydrophobic based products of hydroxyl under vigorous stirring in the double hydrophobic based products of base3Cl, time for adding are 1h, reaction temperature are controlled at 20~25 DEG C, are equivalent to HSO with containing3The NaOH solution of the NaOH of Cl mass 15%, which absorbs, releases HCl, after charging, react 2h, make the abundant sulfonation of product.3h is placed, the HCl of generation is discharged as much as possible.Then, it is filling In four mouthfuls of reaction flasks for having electric mixer, thermometer, dropping funel, add containing being equivalent to HSO3Cl mass 15% The NaOH solution of NaOH, is placed in water bath with thermostatic control, and reaction temperature is controlled at 35~40 DEG C, is slowly added to methylbenzene with dropping funel 1h is added dropwise in sulfonic acid, after completion of dropwise addition, adjusts whole system pH value in 7~8, and product is that the double hydrophobic primary surfaces of sodium sulfonate are living Property agent.Its surface-active parameter and emulsifiability are tested, the result is shown in tables 2.
Table 2
*γcmcReach surface tension when critical micelle concentration for surfactant；ΓmaxFor maximal absorptive capacity, that is, it is saturated Adsorbance
The preparation of the double hydrophobic based surfactants of 3 polyoxyethylene ether of embodiment
With molar ratio n (tetradecyl alchohol): n (epoxychloropropane) is 1:3.2, and phase transfer catalyst tetrabutylammonium bromide dosage is 0.05 molar ratio of alcohol (opposite) be added to electric mixing device, reflux condensate device, thermometer three-necked flask in.Instead Answering temperature is 50 DEG C, reaction time 4h.Reaction heating acutely, epoxychloropropane is added dropwise while stirring, drips in order to prevent Temperature reaction later, gained mixture filter the salt for removing and generating by decompression, then are washed to saturated sodium-chloride water solution Property, after anhydrous sodium sulfate drying, it is evaporated under reduced pressure to transparent micro- thick liquid.
The double hydrophobic based products of hydroxyl 0.05mol prepared above and 0.01mol sodium hydroxide are added in autoclave, are obtained It to compound n, vacuumizes, is passed through high pure nitrogen, and replaced 3 times with high pure nitrogen, then passes to 1.00mol (46mL) epoxy second Alkane, i.e. compound n and molar ratio are 1:20), it is warming up to 120 DEG C under stirring, reacts 2h at 130 DEG C.It will reaction Kettle is cooled to room temperature, and reaction solution neutralizes through acid, obtains the surfactant of the double hydrophobic groups of polyoxyethylene ether after active carbon decoloring.It surveys Its surface-active parameter and emulsifiability are tried, the result is shown in tables 3.
Table 3
*γcmcReach surface tension when critical micelle concentration for surfactant；ΓmaxFor maximal absorptive capacity, that is, it is saturated Adsorbance
The preparation of the double hydrophobic based surfactants of 4 phosphoric acid salt of embodiment
With molar ratio n (hexadecanol): n (epoxychloropropane) is 1:3.0, and phase transfer catalyst tetrabutylammonium bromide dosage is 0.05 molar ratio of alcohol (opposite) be added to electric mixing device, reflux condensate device, thermometer three-necked flask in.Instead Answering temperature is 55 DEG C, reaction time 3h.Reaction heating acutely, epoxychloropropane is added dropwise while stirring, drips in order to prevent Temperature reaction later, gained mixture filter the salt for removing and generating by decompression, then are washed to saturated sodium-chloride water solution Property, after anhydrous sodium sulfate drying, it is evaporated under reduced pressure to transparent micro- thick liquid.
Solvent C Cl is sequentially added in three-necked flask4、POCl3, heating water bath dredges to 25 DEG C, by hydroxyl prepared above is double Water base product slowly drips in flask, wherein the double hydrophobic based products of hydroxyl and POCl3Molar ratio is 1:1.2, CCl4For hydroxyl Double hydrophobic based products and POCl3The 70% of gross mass.The insulation reaction 1h at 750mmHg, 25 DEG C, then be warming up to 80 DEG C and continue instead 8h is answered, the hydrogen chloride gas for reacting generation is absorbed with sodium hydroxide solution, obtains 2- (O- phosphinylidyne dichloro) two hydrophobic based products.Then The intermediate product is instilled in excessive cold water, the double hydrophobic based surfactants of phosphoric acid salt are obtained.Test its surface-active parameter And emulsifiability, the result is shown in tables 4.
Table 4
*γcmcReach surface tension when critical micelle concentration for surfactant；ΓmaxFor maximal absorptive capacity, that is, it is saturated Adsorbance
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.

Claims (2)

1. a kind of double hydrophobic based surfactants of phosphoric acid salt, it is characterised in that: the molecule knot of this pair of hydrophobic based surfactants Structure formula are as follows:Wherein R=CnH2n+1, n >=5.
2. a kind of preparation method of the double hydrophobic based surfactants of phosphoric acid salt described in claim 1, it is characterised in that: the party The reaction equation of method is
,
Step includes:
A, the double hydrophobic based products of hydroxyl are prepared, i.e., double hydrophobic based surfactants described in claim 1；
B, by solvent C Cl4、POCl3Heating water bath drips the double hydrophobic based products of hydroxyl made from step a to 10~35 DEG C after mixing It adds in dicyandiamide solution, wherein the double hydrophobic based products of hydroxyl and POCl3Molar ratio is 1:1~2, CCl4It is produced for the double hydrophobic groups of hydroxyl Object and POCl3The 70%~100% of gross mass；The insulation reaction 1-1.5h at 15~35 DEG C, then it is warming up to 80~100 DEG C of continuation 8~10h is reacted, the hydrogen chloride gas for reacting generation is absorbed with sodium hydroxide solution, obtains intermediate product 2- (O- phosphinylidyne dichloro) two Hydrophobic based products；Then the intermediate product is instilled in excessive cold water, obtains the double hydrophobic based surfactants of phosphoric acid salt.
CN201810863612.1A 2017-05-24 2017-05-24 A kind of pair of hydrophobic based surfactants and preparation method thereof Pending CN109134530A (en)

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CN113548985B (en) * 2021-08-25 2023-04-11 成都理工大学 Preparation method of shale fracturing fluid cleanup additive gemini hybrid fluorinated surfactant
CN115305073B (en) * 2022-07-14 2024-07-09 江苏海洋大学 Gemini surfactant for preparing water-resistant water from stratum brine and preparation method thereof
CN118562121B (en) * 2024-06-18 2025-04-11 广州敏峰高新材料有限公司 A method for producing functional surfactant

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