CN107649067B - A kind of abietyl rigid anionic surfactant and its stable foam of formation - Google Patents
A kind of abietyl rigid anionic surfactant and its stable foam of formation Download PDFInfo
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- CN107649067B CN107649067B CN201710827462.4A CN201710827462A CN107649067B CN 107649067 B CN107649067 B CN 107649067B CN 201710827462 A CN201710827462 A CN 201710827462A CN 107649067 B CN107649067 B CN 107649067B
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- C07J73/00—Steroids in which the cyclopenta[a]hydrophenanthrene skeleton has been modified by substitution of one or two carbon atoms by hetero atoms
- C07J73/001—Steroids in which the cyclopenta[a]hydrophenanthrene skeleton has been modified by substitution of one or two carbon atoms by hetero atoms by one hetero atom
- C07J73/005—Steroids in which the cyclopenta[a]hydrophenanthrene skeleton has been modified by substitution of one or two carbon atoms by hetero atoms by one hetero atom by nitrogen as hetero atom
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Abstract
The invention discloses a kind of abietyl rigid anionic surfactant, which is full rigidity structure, and molecular structure is as follows:The invention also discloses the preparation methods of the surfactant: using rosin as starting material, having synthesized abietyl rigid anionic surfactant through D-A addition, imidizate, diazotising, coupling, esterification and acid-base neutralization reaction.The critical micelle concentration of the anionic surfactant of preparation is 0.014 mmol L‑1, show stronger ability of aggregation.Invention additionally discloses the stable foams that the abietyl rigid anionic surfactant is formed, and when its concentration is 0.1%, half-life period is 2238 min.The primary raw material rosin of the surfactant is derived from natural products, meet the development trend of Green Chemistry, it can be applied in the formula of detergent, dispersing agent, emulsifier and foam stabilizer, while the unique rigid structure of the surfactant helps to improve the compressive resistance in oil recovery process.
Description
Technical field
The present invention relates to the stable foam more particularly to a kind of abietyl of a kind of rosin-based surfactant and its formation are rigid
Property anionic surfactant and its stable foam of formation.Using natural products as the green surfactant of Material synthesis and its
The stable foam of formation can be applied in the formula of detergent, dispersing agent, emulsifier and foam stabilizer.Belong to surfactant science
With rosin chemical utilization field.
Background technique
As petroleum resources are increasingly exhausted, the enhancing of people's environmental consciousness, the reproducible biomass resource of green is increasingly
It is taken seriously.Rosin is a kind of natural reproducible resin of pine tree trees secretion, can be used as part with its distinctive chemical structure
The alternate resources of petroleum-based products become increasingly conspicuous in the research of biomass resource.Using rosin as the product of raw material and deep processing
Rich choice of products is widely used in the fields such as ink, coating, adhesive, rubber, pesticide, food.And rosin has unique three
Ring diterpene rigid structure, hydrophobicity with super strength are one of the important source materials of green surfactant preparation.In addition, opening
Hair utilizes Rosin Surfactants, and rosin has also been widened while abundant surfactant product in washing, detergents and cosmetic
The application of product and oil recovery etc..
It is numerous to contain rigid backbone studies have shown that working as in surfactant molecule structure, in emulsion and foam preparation
The relatively stronger interfacial film of mechanical strength can be formed.When colliding between liquid pearl, the surfactant of rigid-skeleton
Molecule can more effectively reduce the mechanical shock between liquid pearl, to prevent the generation of coalescence, keep emulsion and foam more steady
Fixed presence.And compressive resistance of the surfactant in oil recovery process can be improved in rigid structure.Maleopimaric acid is as a kind of
Most widely used Abietyl modified product has two reactive functionalities of carboxyl and acid anhydrides, is easy to chemical modification.And relative to pine
Perfume (or spice), maleopimaric acid have bigger rigid hydrophobic structure, can be applied in the preparation of green surfactant.It is first with rosin
Beginning raw material synthesizes maleopimaric acid through D-A addition, passes through acid imide, diazotising and coupling in the anhydride moiety of maleopimaric acid
Reaction introduces another section of rigid structure, synthesizes abietyl rigid anionic surfactant by acid-base neutralization.Using the rosin
Base rigid anionic surfactant prepares foam, finds its foam stability energy with super strength.It can be applied to detergent, dispersion
In the formula of agent, emulsifier and foam stabilizer.And unique rigid structure is more suitably applied to oil recovery industry.
Summary of the invention
The purpose of the present invention is to provide a kind of abietyl rigid anionic surfactants and preparation method thereof, with pine
Perfume, maleic anhydride, p-phenylenediamine, phenol, bromoethane and sodium hydroxide are primary raw material, using D-A addition, imidizate, again
The method of nitridation, coupling, esterification and acid-base neutralization reaction, obtains a kind of abietyl rigid female for meeting green chemistry trend
Ionic surface active agent.And the foam system of first stability is constructed with the surfactant.
In order to achieve the above object, the present invention adopts the following technical scheme:
Using a kind of abietyl rigid anionic surfactant that rosin is prepared as initial feed, molecular structural formula is such as
Under:
Its specific synthesis step is as follows: the ratio between amount of substance of the first step, rosin and maleic anhydride be 1:(1.05~
1.10) 1:1.05,1:1.08,1:1.10, can be chosen, acetic acid makees solvent, reacts 3~4 h under 140~155 °C, such as react
Temperature is 140 °C, 145 °C, 150 °C, 155 °C；Reaction time is 3 h, 3.5h, 4 h, obtains maleopimaric acid.Second step,
The ratio between amount of substance of maleopimaric acid and p-phenylenediamine is 1:(1.10~1.30), 1:1.10,1:1.15,1:1.20 can be chosen,
1:1.25,1:1.30, DMF make solvent, and 3~4 h are reacted under 75~85 °C, such as reaction temperature is 75 °C, 80 °C, 85 °
C；Reaction time be 3 h, 3.5h, 4 h, 155-165 °C of 4~6 h of reaction, such as reaction temperature be 155 °C, 160 °C, 165
°C；Reaction time is 4 h, 5h, 6h, obtains intermediate 4- maleopimaric acid base aniline.Third step, 4- maleopimaric acid base aniline and
The ratio between amount of substance of sodium nitrite is 1:(1.25~1.50), 1:1.25,1:1.35,1:1.45,1:1.50 can be chosen, by nitrous
The aqueous solution of sour sodium is added to the mixed solution of 4- maleopimaric acid base aniline and appropriate 18%~30% hydrochloric acid, such as hydrochloric acid is dense
Degree can be chosen: 18%, 25%, 30%, reaction temperature is -5~5 °C, such as reaction temperature is -5 °C, 0 °C, 5 °C, is dripped
Cheng Hou, reaction time are 1~2 h, can choose 1 h, 1.5 h, 2 h；The amount of substance of 4- maleopimaric acid base aniline and phenol it
Than for 1:(1.00~1.10), 1:1.00,1:1.05,1:1.10 can be chosen, by the sodium hydroxide solution (PH=9~11) of phenol
Instill above-mentioned reaction solution, such as PH adjustable are as follows: 9,10,11, reaction temperature is -5~5 °C, and the reaction time is 1~2 h, such as
Reaction temperature is -5 °C, 0 °C, 5 °C；Reaction time is 1 h, 1.5 h, 2 h, obtains intermediate 4- maleopimaric acid base azo
Phenol.4th step, 4- maleopimaric acid base azophenol with to the ratio between the amount of substance of bromoethane 1:(1.15~1.35), can choose
1:1.15,1:1.20,1:1.25,1:1.30,1:1.35, the Anhydrous potassium carbonate that amount of substance is 5~7 times are acid binding agent, anhydrous carbon
The amount of substance of sour potassium can choose 5 times, and 6 times, 7 times, DMF makees solvent, react 12-24 h under 75~85 °C, such as reaction temperature is
75 °C, 80 °C, 85 °C；Reaction time is 12 h, 16 h, 20 h, 24 h, and it is even to obtain intermediate 4- maleopimaric acid ethoxycarbonyl
Pyridine phenol.The ratio between amount of substance of 5th step, 4- maleopimaric acid ethoxycarbonyl azophenol and sodium hydroxide be 1:(1.10~
1.25) 1:1.10,1:1.20,1:1.25, ethanol as solvent, can be chosen, reaction temperature is 60~80 °C, such as reaction temperature
It is 60 °C, 70 °C, 80 °C, the reaction time is 8~12 h, such as the reaction time is 8 h, 9h, 10 h, and 11 h, 12 h are obtained
Abietyl rigid anionic surfactant.
Using the rigid anionic surfactant of the reproducible biomass resource rosin synthesis of green, meet Green Chemistry
Development trend, alternative part petrochemical use.The critical micelle concentration of the abietyl rigid anionic surfactant
For 0.014 mmol L-1；Say it with preferable ability of aggregation.Due to the molecular structure of its full rigidity, the rosin rigid female from
Sub- surfactant has preferable foam stability energy, and the stable foam half-life period formed is 2238 min.The surfactant
It can be applied in the formula of detergent, dispersing agent, emulsifier and foam stabilizer.
The present invention obtains following technical effect:
1. the present invention combines the design feature of rosin, by D-A addition, imidizate, diazotising, coupling, esterification and acid
Alkali neutralization, which is reacted, is made abietyl rigid anionic surfactant, and product has compared with high added value, has widened the application of rosin.
2. the abietyl rigid anionic surfactant has stronger ability of aggregation, critical micelle concentration is
0.014 mmol L-1。
3. the abietyl rigid anionic surfactant has good foam stability energy, when its concentration is 0.1%, shape
At half-life period of stable foam be 2238 min.It can be used for the formula of detergent, dispersing agent, emulsifier and foam stabilizer
In.
4. present invention process uses biomass resource rosin for raw material, principle is spliced using active group, by abietyl three
Ring diterpene structure is introduced into synthesis abietyl rigid anionic surfactant in surfactant structure, has preferable biofacies
Capacitive and degradability.It can be used as a kind of environmentally-friendly surfactant of function admirable, be applied to daily cleaning agent, foam stabilizing
The fields such as agent, dispersing agent, wetting agent.And the structure of its full rigidity is applied to oil recovery industry, can be improved in oil recovery process
Compressive resistance.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic spectrogram of abietyl rigid anionic surfactant.
Fig. 2 is the surface tension value of abietyl rigid anionic aqueous surfactant solution with the variation relation figure of concentration
(25 °C)。
Fig. 3 is the foam volume versus time curve (room of abietyl rigid anionic surfactant (0.1%)
Temperature).
Specific embodiment
Embodiment 1
A kind of molecular structural formula of abietyl rigid anionic surfactant is as follows:
。
Embodiment 2
(1) synthesis of maleopimaric acid accurately weighs horse hair rosin (300 g, 1.00 mol), maleic anhydride (131.5
G, 1.37 mol) and 120g acetic acid be added equipped in churned mechanically four-hole boiling flask, chain connects reflux unit.Temperature is risen to
150 °C, react 4 h, end of reaction.It is cooled to room temperature to reaction solution, reaction solution is added in 350 g acetic acid, recrystallization 2
It is secondary.Obtaining white solid is maleopimaric acid, purity 95.2%.
(2) synthesis of 4- maleopimaric acid base aniline accurately weighs maleopimaric acid (40 g, 0.10 mol), to benzene two
The DMF of amine (12.0 g, 0.11 mol) and 120 g are added in the 500 mL three-necked flasks equipped with magnetic rotor, connect reflux
Device.Temperature is risen to 80 °C, reacts 3 h.165 °C are continuously heating to, 5 h, end of reaction are stirred.It is cooled to reaction solution
Reaction solution is added in 400 mL water, there is brown-red solid precipitation by room temperature.After filtering, being dry, with DMF and water recrystallization two
It is secondary to obtain brown solid, i.e. 4- maleopimaric acid base aniline (37.4 g), yield: 76.3%.
(3) 4- maleopimaric acid base benzene is added in the synthesis of 4- maleopimaric acid base azophenol in the beaker of 600 mL
Amine (30.0 g, 0.061 mol), 40 mL of water and concentrated hydrochloric acid (45.0 g), stirring is to being uniformly mixed, and system is in paste after cooling
Shape places it in ice salt bath.Sodium nitrite (5.59 g, 0.81 mol) is dissolved in 20 mL water, it, will when being lower than 0 °C
Sodium nitrite solution instills in above-mentioned 4- maleopimaric acid base aniline and concentrated hydrochloric acid system, and system is gradually clarified, and forms yellow
Solution.Guarantee that reaction system is acid with the detection of pH test paper in reaction process.
Phenol (5.90 g, 0.063 mol) is added in the beaker of 800 mL, 100 mL water are added, it is dense with sodium hydroxide
The pH value of solution is adjusted to 11 by solution.Above-mentioned diazonium salt solution is slowly added dropwise, it is same to be kept for 0 °C of temperature or less (process is added dropwise
In by be added dropwise sodium hydroxide aqueous solution guarantee system pH value be 9-11).It waits a period of time, it is heavy that brown color is generated in solution
It forms sediment.Continue to stir 1 h after being added dropwise to complete, reaction terminates, and HCl, which is added dropwise, makes system in acidity.Above-mentioned reaction solution is filtered, distilled water
It washes twice, obtains khaki powder.Orange/yellow solid is obtained twice with second alcohol and water recrystallization.That is 4- maleopimaric acid base azo
Phenol (23.7 g) yield 62.4%.
(4) synthesis of 4- maleopimaric acid ethoxycarbonyl azophenol is in N2Under protection, by K2CO3 (26.58 g, 0.19
Mol it) is added in the 500 mL three-necked flasks equipped with magnetic rotor with 100 mL DMF, connects reflux unit.0.5 h is stirred,
The DMF solution of 4- maleopimaric acid ethoxycarbonyl azophenol (19.2 g, 0.032 mol) is added, is warming up to 80 °C, again
Property be added bromoethane (3.67 g, 0.034 mol) DMF solution, be stirred to react 24 h, reaction terminates.Room temperature is cooled to,
It filtering, collects filtrate, add 100 mL ice water into filtrate under stiring, liquid separation extracts (methylene chloride) three times, collected organic layer,
And it is washed with deionized three times.Anhydrous MgSO4It is dry, it filters, collects filtrate, distillation (removes methylene chloride), obtains brown solid.
Petroleum ether and re-crystallizing in ethyl acetate 3 times are used again, obtain orange/yellow solid, i.e. 4- maleopimaric acid ethoxycarbonyl azophenol (13.6
G), yield: 68.2%.
(5) synthesis of abietyl rigid anionic surfactant is by obtained 4- maleopimaric acid ethoxycarbonyl azophenol
The dehydrated alcohol of (10.0 g, 0.016 mol), sodium hydroxide (0.67 g, 0.017 mol) and 80 g are added to be turned equipped with magnetic force
In 250 mL single bottles of son, reflux unit is connected.Temperature is risen to 70 °C, reacts 12 h.Reaction solution is cooling after reaction was completed
To room temperature, revolving removes ethyl alcohol.With ethyl alcohol and acetone recrystallization 2 times, orange/yellow solid, as abietyl rigid anionic table are obtained
Face activating agent (7.5 g), yield 72.5%.
Embodiment 3
The measurement critical micelle concentration of critical micelle concentration is the important parameter for characterizing surfactant ability of aggregation, is originally ground
Study carefully using 701 type surface tension instrument of Sigma hang Wilhelmy plate method measurement surfactant critical micelle concentration (cmc),
Measuring temperature is 25 °C, and Wilhelmy plate width is 19.44 mm, and it is highly 65 mm that thickness, which is 0.1 mm,.Each replication 3
Secondary, the evaluated error of each point is set as 0.05 mN m-1.The surface tension of surfactant is drawn with the change curve of concentration.
The critical micelle concentration of abietyl rigid anionic surfactant is 0.014 mmol L-1。
Embodiment 4
The water-soluble of the abietyl rigid anionic surfactant that 10 mL concentration are 0.1% is prepared in the measurement of foaming properties
Liquid places it in the tool plug graduated cylinder of 100 mL, and solution is exerted oneself uniform vertical tremor 20 times, is stood at room temperature, record bubble
The volume of foam changes with time.Draw the foam volume versus time curve of surfactant.The pine that concentration is 0.1%
The half-life period that perfume base rigid anionic surfactant solution forms foam is 2238 min.
Claims (3)
1. a kind of abietyl rigid anionic surfactant, which is characterized in that the hydrophobic group of surfactant is full rigidity, point
Minor structure is as follows:
2. a kind of prepare abietyl rigid anionic surface-active agent method described in claim 1, which is characterized in that use D-
A addition, imidizate, diazotising, the method for coupling, esterification and acid-base neutralization reaction: the object of the first step, rosin and maleic anhydride
Mass ratio is 1:(1.05~1.10), acetic acid makees solvent, reacts 3~4h at 140~155 DEG C, obtains maleopimaric acid；Second
The ratio between amount of substance of step, maleopimaric acid and p-phenylenediamine is 1:(1.10~1.30), DMF makees solvent, reacts 3 at 75~85 DEG C
~4h, 155~165 DEG C of 4~6h of reaction obtain intermediate 4- maleopimaric acid base aniline；Third step, 4- maleopimaric acid base aniline
It is 1:(1.25~1.50 with the ratio between the amount of substance of sodium nitrite), the aqueous solution of sodium nitrite is added to 4- maleopimaric acid base
In the mixed solution of aniline and appropriate 18%~30% hydrochloric acid, reaction temperature is -5~5 DEG C, after being added dropwise to complete, the reaction was continued 1~
The ratio between amount of substance of 2h, 4- maleopimaric acid base aniline and phenol is 1:(1.0~1.1), by the phenol hydroxide of pH=9~11
Sodium solution instills above-mentioned reaction solution, and reaction temperature is -5~5 DEG C, and the reaction time is 1~2h, obtains intermediate 4- maleopimaric acid base
Azophenol；The ratio between the amount of substance of 4th step, 4- maleopimaric acid base azophenol and bromoethane 1:(1.15~1.35), substance
The Anhydrous potassium carbonate that amount is 5~7 times of azophenol of 4- maleopimaric acid base is acid binding agent, and DMF makees solvent, reacts at 80~85 DEG C
12~for 24 hours, obtain intermediate 4- maleopimaric acid ethoxycarbonyl azophenol；5th step, 4- maleopimaric acid ethoxycarbonyl azophenol
It is 1:(1.10~1.25 with the ratio between the amount of substance of sodium hydroxide), ethanol as solvent, reaction temperature is 60~80 DEG C, the reaction time
For 8~12h, abietyl rigid anionic surfactant is obtained.
3. the stable foam that a kind of abietyl rigid anionic surfactant according to claim 1 is formed, is by one
Quantitative abietyl rigid anionic surfactant is soluble in water, and firmly concussion obtains up and down, the concentration range of surfactant
Longest half-life period for 0.1%-0.5%, stable foam is greater than 2000min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109173921B (en) * | 2018-08-28 | 2020-09-04 | 中国林业科学研究院林产化学工业研究所 | PH-responsive rosin-based rigid surfactant and preparation method and application thereof |
| CN108997994B (en) * | 2018-09-05 | 2021-01-05 | 石家庄长宏能源科技有限公司 | Foaming agent for oil displacement and channeling prevention in oil field and preparation method thereof |
| CN111606967B (en) * | 2020-06-02 | 2023-03-14 | 中国林业科学研究院林产化学工业研究所 | Maleopimaric acid radical azobenzene monomer and preparation method thereof |
| JP7021446B1 (en) * | 2020-09-24 | 2022-02-17 | 千住金属工業株式会社 | Flux and solder paste |
| CN112110980B (en) * | 2020-09-29 | 2023-01-17 | 中国林业科学研究院林产化学工业研究所 | Photoresponse type rosinyl anionic surfactant, preparation method thereof and photoresponse type viscoelastic liquid |
| CN113735933B (en) * | 2021-09-13 | 2022-10-18 | 中国林业科学研究院林产化学工业研究所 | PH-responsive rosin-based surfactant, preparation method thereof and pseudo-gemini surfactant constructed by same |
| CN113956463B (en) * | 2021-10-22 | 2024-04-05 | 中国林业科学研究院林产化学工业研究所 | Application of photoresponsive end-group rosin-based azobenzene polymer |
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