CN104497295B - Vegetable-fat anionic polymer surfactant and preparation method thereof - Google Patents
Vegetable-fat anionic polymer surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a vegetable-fat anionic polymer surfactant and a preparation method thereof. The preparation method comprises the following steps which are connected in sequence: (1) dissolving epoxy vegetable fats in a solvent, stirring and heating to 30-70 DEG C, dripping initiator solution, reacting for 0.5-2h with heat and then removing the solvent to obtain polymer vegetable fats; (2) mixing the polymer vegetable fats obtained in the step (1) with catalyst aqueous solution with a concentration of 0.2-1.0mol/L according to a ratio that per 1g of the polymer fats is corresponding to 15-30mL of the catalyst aqueous solution, adequately hydrolyzing for 8-24h under the condition of a temperature of 70-100 DEG C, and purifying the obtained product to obtain the vegetable-fat anionic polymer surfactant. According to the preparation method, natural renewable biomass materials are used for replacing industrialized products for the preparation of the polymer surfactant, the preparation process is moderate in reaction conditions and simple in process, and the obtained product has a high surface activity.
Description
Technical field
The invention belongs to the synthesis field of material, be specifically related to a kind of Vegetable oil lipoprotein anionic high molecular surfactant
And preparation method thereof.
Background technology
Surfactant is a kind of amphiphile, amphiphilic molecule, contains hydrophilic group and lipophilic group, due to hydrophilic parent the most simultaneously
The existence of oil base makes the interfacial property of material that notable change occur.Traditional surfactant can be divided into cationic to live
Property agent, anionic surfactant and nonionic surfactant etc..High molecular surfactant refers to that molal weight exists
Thousands of above and there is the material of certain surface activity.Compared with Small molecular surfactant, high molecular surfactant due to
Molecular weight is big, has relatively low reduction surface tension and an ability of interfacial tension, and stability and the less molecule of dispersibility
Surfactant is more preferable.
Vegetable oil lipoprotein is a kind of abundance, reproducible natural resources, either in yield, supply, or cost, property
It is full foot on can and prepare the demand of surfactant.Meanwhile, the natural sex of Vegetable oil lipoprotein so that it is live in a series of surfaces of preparation
Property agent has preferable ecological performance.In recent years due to socioeconomic development, the demand of Surfactant raw material increases
And its price rises steadily, and in order to adhere to sustainable development theory, develop Vegetable oil lipoprotein high molecular surfactant,
There is huge resources advantage undoubtedly.On the one hand surfactant product kind can be enriched, the most also for improving plant
The added value of oils and fats provides an effective approach.
Patent CN 100404117 C discloses a kind of bi-alkyl carboxylate surface activator conduct in tertiary oil recovery
The application of oil displacement agent, synthesizes acyl chlorides with organic acid and thionyl chloride, then product is synthesized with intermediate sodium diacetate
Gemini surface active agent.Patent CN 102266737 B discloses a kind of oil and fat preparation N-fatty acid acylamino acid class surface activity
The method of agent, utilizes the reaction under conditions of catalyst potassium oxide and zeolite exist of oils and fats and amino acid sodium to generate N-fatty acyl group
Amino acid sodium.Patent application CN 103772227 A discloses the preparation side of a kind of fat-based amino acid salts series of surfactants
Method, is with oils and fats or fatty acid and amino acid salts under the effect of pyrovinic acid, through amidation process, separation, post processing etc.
Step makes fat-based amino acid salts.Patent application CN 103191672 A discloses a kind of food stage vegetable oil primary surface activity
Agent and preparation method thereof, food grade lactic acid is carried out polyreaction 1～2h under 90～130 DEG C of vacuum by the method, puts into plant
Oleyl fatty acid and catalyst sodium hydroxide, heating under vacuum to 160～190 DEG C reaction 4～6h, in product and after obtain plant
Oleoyl sodium lactate.In said method, the surfactant of synthesis mostly is Small molecular surfactant, and high-molecular surface active
Agent has relatively low reduction surface tension and an ability of interfacial tension, and stability and dispersibility less molecular surface activity
Agent is more preferable.Though patent application CN 103191672 A is high molecular surfactant, but its preparation process is temperature required higher.
Summary of the invention
The present invention provides a kind of Vegetable oil lipoprotein anionic high molecular surfactant and preparation method thereof, plants with renewable
The epoxidation product of thing oils and fats is as raw material, it is provided that the system of the high molecular surfactant of design entirely different with prior art
Preparation Method, enriches the kind of surfactant product, improves the added value of Vegetable oil lipoprotein.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is as follows:
The preparation method of a kind of Vegetable oil lipoprotein anionic high molecular surfactant, including following step connected in order
Rapid:
(1), epoxidized vegetable oil fat is dissolved in solvent, is heated with stirring to 30～70 DEG C, drip initiator solution, insulation
Reaction 0.5～2h after remove solvent, obtain polymerized vegetable oils and fats, initiator quality consumption be epoxidized vegetable oil lipid amount 0.1～
5%；
(2), by aqueous catalyst solution that the polymerized vegetable oils and fats of step (1) gained and concentration are 0.2～1.0mol/L by
The ratio mixing of every 1 gram of corresponding 15～30mL aqueous catalyst solution of polymerization oils and fats, under conditions of temperature is 70～100 DEG C fully
After hydrolysis 8～24h, products therefrom is purified, obtains Vegetable oil lipoprotein anionic high molecular surfactant.
Above-mentioned preparation method substitutes industrialization product for high molecular surfactant with natural reproducible biological material
Preparation, preparation process reaction condition is gentle, and technique is simple, and the product obtained has stronger surface activity.
Preferably, initiator quality consumption is the 0.2～0.5% of epoxidized vegetable oil lipid amount.
In above-mentioned steps (2), purify and include following steps connected in order:
A, step (2) being reacted gained material filtering, after the distillation of gained filtrate, the solid product ethyl acetate that obtains is washed
Wash deglycerizin and unhydrolysed oils and fats；
B, washing gained solid is scattered in distilled water again with dilute acid soln regulation pH value to 4～6, floating oil slick lead to
Cross solvent extraction and wash；
C, washing gained organic layer is distilled off solvent after, be again dispersed in water, with alkali liquor regulation pH value to 8～
11, after distillation dehydration, obtain Vegetable oil lipoprotein anionic high molecular surfactant.
In step (1), epoxidized vegetable oil fat mass fraction in the solution is 5～60%, the epoxy of epoxidized vegetable oil fat
Value scope is 4～7%.So can improve the surface activity of products obtained therefrom further.Epoxidized vegetable oil fat quality in the solution
Mark refers to the concentration before initiator solution dropping.
Epoxidized vegetable oil fat in step (1) is soybean oil, Oleum Ricini, olive oil, Oleum Verniciae fordii, Oleum Gossypii semen, Oleum Arachidis hypogaeae semen, Xiang
Certain herbaceous plants with big flowers oil and tea-seed oil epoxidation product in any one or a few arbitrarily than mixture.The most not only enrich surface to live
The kind of property agent product, improves the added value of Vegetable oil lipoprotein, and ensure that the surface activity of products obtained therefrom.
Solvent in step (1), initiator solution solvent for use be ethyl acetate or dichloromethane or both arbitrarily than
Mixture.
Initiator in step (1) is concentrated sulphuric acid, trifluoroacetic acid, amberlyst 15 ion exchange resin, SnCl4、
ZnCl2、AlCl3、TiCl4And SbCl5In any one or two or more arbitrarily ratio mixture, initiator in initiator solution
Mass content be 0.1～5%.This further ensures that being smoothed out of polyreaction, and then further ensure that gained
The surface activity of product.Preferably, in initiator solution, the mass content of initiator is 0.2～1.5%.
In step (1), the time for adding of initiator solution is 2～20min.This further ensures that extent of polymerization.
Catalyst in step (2) is the mixture of one or more any ratios in NaOH, KOH or LiOH；Institute
Stating acid used by regulation pH value is any one in hydrochloric acid, sulphuric acid, phosphoric acid or acetic acid or the mixture of two or more any ratio, institute
It is any one or the mixture of two or more any ratio in NaOH, KOH, LiOH, triethylamine or tripropyl amine (TPA) with alkali.So enter
One step ensure that the mildness of reaction efficiency and reaction condition.
By the Vegetable oil lipoprotein prepared by the preparation method of above-mentioned Vegetable oil lipoprotein anionic high molecular surfactant cloudy from
Subtype high molecular surfactant, its critical micelle concentration scope is 0.01～2g/L；Surface tension range be 15.6～
28.2mN/m。
Above-mentioned Vegetable oil lipoprotein anionic high molecular surfactant, its weight average molecular weight range is 1000～8000；HLB
Value scope is 8～14；Krafft point range is 30～55 DEG C.
The polymerization reaction mechanism of the application step (1) is (with SnCl4As a example by initiator) as follows:
Representing the arbitrary epoxide group in epoxidized vegetable oil fat, wave key is the Vegetable oil lipoprotein structure omitted.
Chain causes by SnCl4Initiator (exists in the hydroxyl of epoxidized vegetable oil fat existence itself or solvent with coinitiator
Trace alcohol) formed complex, be then transformed into ion pair, it is provided that proton.Chain increases and causes epoxide group open loop, shape for proton
Become oxonium ion positively charged, its neighbouring alpha-carbon atom electron deficiency, cause bond fission, form the most again ion pair form,
Increase the most always.It is that counter ion nucleophilicity is too strong during chain termination, is easily combined with cationic species and terminates.
The application reaction process (as a example by epoxy soybean oil) is as follows:
Epoxy soybean oil, under catalyst action, by foregoing polymerization reaction mechanism ring-opening polymerisation, is polymerized
Soybean oil product.Then polymerization soybean oil is hydrolyzed in the basic conditions, obtain Vegetable oil lipoprotein anionic macromolecule after purification
Surfactant.Prepared Vegetable oil lipoprotein anionic high molecular surfactant can be used for leather, pesticide, papermaking, printing and dyeing
With industrial departments such as oil.
The NM technology of the present invention is all with reference to prior art.
The preparation method of Vegetable oil lipoprotein anionic high molecular surfactant of the present invention, with the ring of renewable Vegetable oil lipoprotein
Oxidation product is as raw material, it is provided that the preparation method of the high molecular surfactant of design entirely different with prior art, rich
The rich kind of surfactant product, improves the added value of Vegetable oil lipoprotein；The application substitutes traditional with renewable raw materials
Industrial products raw material, the most with low cost, and meet sustainable development requirement；The application preparation method reaction condition is gentle,
Technique is simple, and the product obtained has stronger surface activity.
Accompanying drawing explanation
Fig. 1 is epoxy soybean oil raw material in embodiment 1, polymerization soybean oil product and Vegetable oil lipoprotein anionic macromolecule
The FT-IR figure of surfactant.
Fig. 2 is the concentration of Vegetable oil lipoprotein anionic high molecular surfactant and surface tension relationship figure in embodiment 1.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but the present invention
Content is not limited solely to the following examples.
Method of testing in each example:
Vegetable oil lipoprotein anionic high molecular surfactant CMC value method of testing: the surface activity of preparation series concentration
Agent solution, is automatically determined in Sigma 701 surface tension instrument by Wilhelmy board test method.
Vegetable oil lipoprotein anionic high molecular surfactant Krafft point method of testing: preparation mass fraction is 1%
Aqueous solution, heating, recording solution is this Vegetable oil lipoprotein anionic high-molecular surface active by muddiness to temperature time transparent
The Krafft point of agent, each sample is repeated 3 times, and takes its meansigma methods.
The method of testing of Vegetable oil lipoprotein anionic high molecular surfactant molecular weight: sample is placed in chromatographic grade DMSO
And fully dissolve under the conditions of 80 DEG C, DMSO is flowing phase, and flow velocity is 1mL/min, and column temperature is 60 DEG C, passes through Malvern
Viscotek HT-GPC Module 350A high temperature gel chromatograph records.
The method of testing of Vegetable oil lipoprotein anionic high molecular surfactant HLB value: select a pair HLB value difference bigger
Emulsifying agent: span-80 (HLB=4.3) and Tween-60 (HLB=14.9).Have not by different quality proportions is a series of
Blended emulsifier with HLB value.With this blended emulsifier, the Vegetable oil lipoprotein high molecular surfactant of the 1g/L of preparation is made
Series emulsion, it is thus achieved that corresponding to the emulsion that emulsion stability is best, the HLB value of emulsifying agent is the HLB value of product.
Embodiment 1
Weigh the epoxy soybean oil that 20g epoxide number is 6.4% be dissolved in 15g ethyl acetate and pour the there-necked flask of 200mL into
In, magnetic agitation is heated to 60 DEG C, is leaked by constant voltage as initiator with 5g ethyl acetate mixture by 0.06g butter of tin
Bucket is slowly added dropwise, a length of 15min during dropping, and the response time is 1h.Product removes ethyl acetate, obtains being polymerized soybean oil.Weigh
10g above-mentioned polymerization soybean oil, in the there-necked flask of 500mL, adds 0.8mol/L NaOH solution 280mL, at temperature 100 DEG C
Stirring makes it be fully hydrolyzed 24h.It is cooled to room temperature, reaction mixture is filtered, to obtain after ethyl acetate washing distillation filtrate
Solid product, deglycerizin and unhydrolysed oils and fats；Gained solid after washing is scattered in distilled water again with dilute hydrochloric acid
Solution regulation pH value is to 4～6, and after floating oil slick is extracted by ethyl acetate and washed, the decompression of gained organic layer is distilled off second
Polymerized vegetable fatty acid oil is obtained after acetoacetic ester；Above-mentioned product is dispersed in water again, is 9 by KOH solution regulation pH value,
Distillation dehydration, i.e. obtains Vegetable oil lipoprotein anionic high molecular surfactant.
Product and intermediate carry out IR spectroscopic identification:
1740cm-1For carbonyl C=O stretching vibration absworption peak, 822cm in epoxy soybean oil-1Locate to inhale for epoxide group feature
Receive peak.After epoxy soybean oil polymerization, 822cm in polymerization soybean oil product-1Place's epoxide group characteristic absorption peak disappears, and occurs in that
1044cm-1Locate as the eigen vibration absworption peak of C-O in the secondary hydroxyl of epoxy ring-opening generation.After polymerization soybean oil hydrolysis, alkali tune is produced
Thing occurs 1561cm-1The characteristic absorption peak of the carboxylate at place, illustrates to have obtained polymerization soybean oil carboxylate, i.e. Vegetable oil lipoprotein cloudy
Ion-type high molecular surfactant.
The surface tension value of embodiment 1 gained Vegetable oil lipoprotein anionic high molecular surfactant is 22.1mN/m, faces
Boundary's micellar concentration is 0.265g/L；Weight average molecular weight is 5400；HLB value is 10.66；Krafft point is 37 DEG C.
Embodiment 2
Weigh the epoxy castor oil that 20g epoxide number is 4.1% be dissolved in 20g ethyl acetate and pour the there-necked flask of 200mL into
In, magnetic agitation is heated to 50 DEG C, is leaked by constant voltage as initiator with 3g ethyl acetate mixture by 0.07g trifluoroacetic acid
Bucket is slowly added dropwise, a length of 10min during dropping, and the response time is 1.5h.Product removes ethyl acetate, obtains polymerized castor oil.Claim
Take the above-mentioned polymerized castor oil of 8g in the there-necked flask of 500mL, add 1.0mol/L NaOH solution 180mL, under temperature 70 C
Stirring makes it be fully hydrolyzed 20h.It is cooled to room temperature, reaction mixture is filtered, to obtain after ethyl acetate washing distillation filtrate
Solid product, deglycerizin and unhydrolysed oils and fats；Gained solid after washing is scattered in distilled water again with dilute sulfuric acid
Solution regulation pH value is to 4～6, and after floating oil slick is extracted by ethyl acetate and washed, the decompression of gained organic layer is distilled off second
Polymerized vegetable fatty acid oil is obtained after acetoacetic ester；Again it is dispersed in water, is 10 by NaOH regulation pH value, distillation dehydration, i.e.
Obtain Vegetable oil lipoprotein anionic high molecular surfactant.
The surface tension value of embodiment 2 gained Vegetable oil lipoprotein anionic high molecular surfactant is 19.8mN/m, faces
Boundary's micellar concentration is 0.178g/L；Weight average molecular weight is 6200；HLB value is 11.2；Krafft point is 42 DEG C.
Embodiment 3
Weigh the epoxy Oleum Verniciae fordii that 20g epoxide number is 4.3% be dissolved in 30g ethyl acetate and pour 200mL into there-necked flask in,
Magnetic agitation is heated to 60 DEG C, and as initiator, 0.05g titanium tetrachloride and 2g ethyl acetate mixture are passed through constant pressure funnel
Being slowly added dropwise, a length of 5min during dropping, the response time is 0.5h.Product removes ethyl acetate, obtains polymerized tung oil.Weigh 10g
Above-mentioned polymerized tung oil, in the there-necked flask of 500mL, adds 0.6mol/L NaOH solution 250mL, stirs and make at temperature 80 DEG C
It is fully hydrolyzed 16h.It is cooled to room temperature, reaction mixture is filtered, with the solid obtained after ethyl acetate washing distillation filtrate
Product, deglycerizin and unhydrolysed oils and fats；Gained solid after washing is scattered in distilled water again and adjusts with dilute phosphoric acid solution
Joint pH value is to 4～6, and after floating oil slick is extracted by ethyl acetate and washed, the decompression of gained organic layer is distilled off ethyl acetate
After obtain polymerized vegetable fatty acid oil；Again it is dispersed in water, is 11 by KOH regulation pH value, distillation dehydration, i.e. obtain plant
Oils and fats anionic high molecular surfactant.
The surface tension value of embodiment 3 gained Vegetable oil lipoprotein anionic high molecular surfactant is 24.4mN/m, faces
Boundary's micellar concentration is 0.583g/L；Weight average molecular weight is 2460；HLB value is 9.5；Krafft point is 48 DEG C.
Embodiment 4
Weigh the epoxy soybean oil that 20g epoxide number is 6.4% be dissolved in 25g ethyl acetate and pour the there-necked flask of 200mL into
In, magnetic agitation is heated to 40 DEG C, is leaked by constant voltage as initiator with 5g ethyl acetate mixture by 0.06g Antimony pentachloride
Bucket is slowly added dropwise, a length of 20min during dropping, and the response time is 2h.Product removes ethyl acetate, obtains being polymerized soybean oil.Weigh
6g above-mentioned polymerization soybean oil, in the there-necked flask of 500mL, adds 0.5mol/L NaOH solution 150mL, stirs at temperature 90 DEG C
Mix and make it be fully hydrolyzed 10h.It is cooled to room temperature, reaction mixture is filtered, with obtain after ethyl acetate washing distillation filtrate
Solid product, deglycerizin and unhydrolysed oils and fats；Gained solid after washing is scattered in distilled water again with acetum
Regulation pH value is to 4～6, and after floating oil slick is extracted by ethyl acetate and washed, the decompression of gained organic layer is distilled off acetic acid second
Polymerized vegetable fatty acid oil is obtained after ester；Again it is dispersed in water, is 9 by triethylamine regulation pH value, i.e. obtains Vegetable oil lipoprotein
Anionic high molecular surfactant.
The surface tension value of gained Vegetable oil lipoprotein anionic high molecular surfactant is 18.2mN/m, and critical micell is dense
Degree is 0.362g/L；Weight average molecular weight is 4270；HLB value is 10.2；Krafft point is 35 DEG C.
Embodiment 5
Weigh the epoxy olive oil that 20g epoxide number is 3.7% be dissolved in 20g ethyl acetate and pour the there-necked flask of 200mL into
In, magnetic agitation is heated to 60 DEG C, is leaked by constant voltage as initiator with 2g ethyl acetate mixture by 0.05g butter of tin
Bucket is slowly added dropwise, a length of 15min during dropping, and the response time is 1h.Product removes ethyl acetate, obtains being polymerized olive oil.Weigh
10g above-mentioned polymerization olive oil, in the there-necked flask of 500mL, adds 0.8mol/L NaOH solution 250mL, at temperature 100 DEG C
Stirring makes it be fully hydrolyzed 10h.It is cooled to room temperature, reaction mixture is filtered, to obtain after ethyl acetate washing distillation filtrate
Solid product, deglycerizin and unhydrolysed oils and fats；Gained solid after washing is scattered in distilled water again with dilute sulfuric acid
Solution regulation pH value is to 4～6, and after floating oil slick is extracted by ethyl acetate and washed, the decompression of gained organic layer is distilled off second
Polymerized vegetable fatty acid oil is obtained after acetoacetic ester；Again it is dispersed in water, is 10 by NaOH regulation pH value, i.e. obtains vegetable oil
Fat anionic high molecular surfactant.
The surface tension value of gained Vegetable oil lipoprotein anionic high molecular surfactant is 27.5mN/m, and critical micell is dense
Degree is 0.682g/L；Weight average molecular weight is 6700；HLB value is 12.5；Krafft point is 50 DEG C.
Application examples 1
Vegetable oil lipoprotein anionic high molecular surfactant prepared by this patent, not only has reduction surface more by force and opens
The ability of power, and oil water interfacial tension can be significantly reduced, meet the requirement for tertiary oil production in oil field surfactant.With
In embodiment 1 as a example by the Vegetable oil lipoprotein anionic high molecular surfactant of preparation, by the table that concentration is 0.5～1.5g/L
Face activating agent is 1.2 with mass concentration～the sodium hydrate aqueous solution of 1.8% and mass concentration are that 0.012% molecular weight is
The polyacrylamide solution of 17000000 is made into ternary oil displacement system, with crude oil equilibrium interfacial tension up to 4 × 10-3mN/m with
Under ultralow value, oil displacement efficiency than water drive improve more than 22%OOIP.
Claims (10)
1. the preparation method of a Vegetable oil lipoprotein anionic high molecular surfactant, it is characterised in that: include connected in order
Following steps:
(1), epoxidized vegetable oil fat is dissolved in solvent, is heated with stirring to 30～70 DEG C, drip initiator solution, insulation reaction
Removing solvent after 0.5～2h, obtain polymerized vegetable oils and fats, initiator quality consumption is the 0.1～5% of epoxidized vegetable oil lipid amount；
(2) it is, that the aqueous catalyst solution of 0.2～1.0mol/L is by every 1 gram by the polymerized vegetable oils and fats of step (1) gained and concentration
The ratio mixing of the corresponding 15～30mL aqueous catalyst solutions of polymerization oils and fats, is fully hydrolyzed 8 under conditions of temperature is 70～100 DEG C
～after 24h, products therefrom is purified, obtains Vegetable oil lipoprotein anionic high molecular surfactant, wherein, catalyst is
The mixture of one or more any ratios in NaOH, KOH or LiOH.
2. the preparation method of Vegetable oil lipoprotein anionic high molecular surfactant as claimed in claim 1, it is characterised in that:
In step (2), purify and include following steps connected in order:
A, by step (2) react gained material filtering, gained filtrate distillation after obtain solid product ethyl acetate washing remove
Remove glycerol and unhydrolysed oils and fats；
B, being again scattered in distilled water by washing gained solid with dilute acid soln regulation pH value to 4～6, floating oil slick is by molten
Agent extracts and washes；
C, washing gained organic layer is distilled off solvent after, be again dispersed in water, with alkali liquor regulation pH value to 8～11, steam
After evaporating dehydration, obtain Vegetable oil lipoprotein anionic high molecular surfactant.
3. the preparation method of Vegetable oil lipoprotein anionic high molecular surfactant as claimed in claim 1 or 2, its feature exists
In: in step (1), epoxidized vegetable oil fat mass fraction in the solution is 5～60%, and the epoxide number of epoxidized vegetable oil fat is 4
～7%.
4. the preparation method of Vegetable oil lipoprotein anionic high molecular surfactant as claimed in claim 1 or 2, its feature exists
In: the epoxidized vegetable oil fat in step (1) is soybean oil, Oleum Ricini, olive oil, Oleum Verniciae fordii, Oleum Gossypii semen, Oleum Arachidis hypogaeae semen, Oleum helianthi
With in the epoxidation product of tea-seed oil any one or a few arbitrarily than mixture.
5. the preparation method of Vegetable oil lipoprotein anionic high molecular surfactant as claimed in claim 1 or 2, its feature exists
In: the solvent described in step (1) and initiator solution solvent for use be ethyl acetate or dichloromethane or both arbitrarily than
Mixture.
6. the preparation method of Vegetable oil lipoprotein anionic high molecular surfactant as claimed in claim 1 or 2, its feature exists
In: the initiator in step (1) is concentrated sulphuric acid, trifluoroacetic acid, amberlyst 15 ion exchange resin, SnCl4、 ZnCl2、
AlCl3、TiCl4Or SbCl5In one or more arbitrarily ratio mixture, mass content of initiator in initiator solution
It is 0.1～5%.
7. the preparation method of Vegetable oil lipoprotein anionic high molecular surfactant as claimed in claim 1 or 2, its feature exists
In: in step (1), the time for adding of initiator solution is 2～20min.
8. the preparation method of Vegetable oil lipoprotein anionic high molecular surfactant as claimed in claim 2, it is characterised in that:
Acid used by described regulation pH value is any one or the mixture of two or more any ratio in hydrochloric acid, sulphuric acid, phosphoric acid or acetic acid,
Alkali used is any one or the mixture of two or more any ratio in NaOH, KOH, LiOH, triethylamine or tripropyl amine (TPA).
9. by the preparation method institute of the Vegetable oil lipoprotein anionic high molecular surfactant described in claim 1-8 any one
Preparation Vegetable oil lipoprotein anionic high molecular surfactant, it is characterised in that: its critical micelle concentration scope be 0.01～
2g/L；Surface tension range is 15.6～28.2mN/m.
10. Vegetable oil lipoprotein anionic high molecular surfactant as claimed in claim 9, its weight average molecular weight range is
1000～8000；HLB value scope is 8～14；Krafft point range is 30～55 DEG C.
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