CN106140006A - A kind of Dehydroabietic acid anion surfactant and the stable foam of formation thereof - Google Patents
A kind of Dehydroabietic acid anion surfactant and the stable foam of formation thereof Download PDFInfo
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- CN106140006A CN106140006A CN201610480581.2A CN201610480581A CN106140006A CN 106140006 A CN106140006 A CN 106140006A CN 201610480581 A CN201610480581 A CN 201610480581A CN 106140006 A CN106140006 A CN 106140006A
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- dehydroabietic acid
- surfactant
- amide groups
- acid anion
- anion surfactant
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
Abstract
The present invention relates to a kind of Dehydroabietic acid anion surfactant 6 dehydrogenation fir amide groups Sodium caproate and the stable foam of formation thereof.The main synthesis material dehydroabietic acid of this surfactant and aminoacid are all from natural product, are a kind of green surfactants.6 dehydrogenation fir amide groups Sodium caproates dissolubility at room temperature is more than 0.8mol/L, has the ability compounding with Multiple components；Its critical micelle concentration value is 1.26mmol/L, shows stronger ability of aggregation.Additionally, 6 dehydrogenation fir amide groups Sodium caproates also have good foam stability energy.This surfactant can be applied in daily cleaning agent, detergent, dispersant, household chemicals and foam stabilizer formula as the environmentally friendly product of a kind of function admirable.
Description
Technical field
The present invention relates to a kind of novel Dehydroabietic acid anion surfactant, particularly to a kind of Dehydroabietic acid ammonia
Base acids anion surfactant, belongs to surfactant science and Colophonium chemical utilization field.
Background technology
Colophonium is the renewable forest products resource of a kind of abundance.Product or deep processed product with Colophonium as raw material are the widest
In the general every field being applied to the industry such as rubber, ink, coating, pesticide, medicine, food, electronics and life.Along with people couple
The growing interest of environmental problem, seeks the target that natural and green raw materials for production are chemical industry every profession and trades, surfactant industry
Also it is such.And Colophonium has renewable, biodegradable, abundance, structure and is prone to the advantages such as modification, it is to live in green surface
One of important source material source of property agent.Due to the rigid-skeleton that main part is tricyclic diterpene type of rosin acid, volume is relatively
Greatly, therefore, the ability of aggregation of tradition rosin-based surfactant is the strongest；Meanwhile, rosin acid also contains a large amount of ethylene linkages etc. easily
The group of oxidation, makes the rosin-based surfactant application in some field be restricted.
Dehydroabietic acid is a kind of important rosin derivative, and compared with the resinic acid common with Colophonium, dehydroabietic acid has
More stable chemical property.In the present invention, in order to strengthen the self-organizing performance of surfactant, in dehydroabietic acid intramolecular
Introduce the omega-amino acid containing flexible chain, synthesize the anion surfactant of a kind of Dehydroabietic acid amino acid pattern, and structure
Build a kind of stable foam system.Owing to dehydroabietic acid used and aminoacid all can obtain from natural reproducible resource,
Surfactant with them as Material synthesis is the surfactant that a class meets that " Green Chemistry " requires.
Summary of the invention
It is an object of the invention to the main component dehydroabietic acid in disproportionated rosin as raw material, contain flexible hydrophobic with one
The aminoacid 6-aminocaprolc acid reaction of segment, it is thus achieved that a kind of surfactant 6-dehydrogenation fir amide groups meeting Green Chemistry requirement
Sodium caproate.And based on this surfactant, construct a kind of stable foam system.
For achieving the above object, the present invention adopts the following technical scheme that
With the main component dehydroabietic acid in disproportionated rosin as raw material, a kind of Dehydroabietic acid aminoacid anionic surface of synthesis is lived
Property agent 6-dehydrogenation fir amide groups Sodium caproate, its structural formula is as follows:
The synthetic route of 6-dehydrogenation fir amide groups Sodium caproate is as follows:
Its concrete synthesis step is as follows:
The synthesis of dehydrogenation fir acyl chlorides: be equipped with preparing the device for absorbing tail gas of alkali liquor and reflux condensing tube by dehydroabietic acid solid
There-necked flask in, add the DMAP of catalytic amount.When temperature is raised to 60 DEG C, start to be slowly added dropwise protochloride
Sulfone, has a large amount of gas to generate.After thionyl chloride completion of dropwise addition, react 3h when temperature is 72 DEG C.Reactant mixture is cooled down, subtracts
Pressure removes excess thionyl chloride, obtains the dehydrogenation thick product of fir acyl chlorides.
The synthesis of 6-dehydrogenation fir amide groups Sodium caproate: add a certain amount of 6-aminocaprolc acid in there-necked flask, adds appropriate
Acetone and the mixed solvent (volume ratio of acetone and water is 1:1) of water.It is sufficiently stirred for down, drips the third of dehydrogenation fir acyl chlorides respectively
Ketone solution and NaOH solution, control the pH value of reaction system in about 8-10, reaction temperature 10-20 DEG C.After reaction terminates, will produce
Thing is transferred in the beaker of 1000mL, is 1-2 with the pH value of hydrochloric acid regulation system, has faint yellow solid to produce.With water and oil
Ether carries out three washings respectively to product, adds the sodium hydrate solid little over amount.Fully after reaction, add ethanol in proper amount, then
Add anhydrous Na2SO4It is dried, then standing, sucking filtration.Remove solvent under filtrate decompression, the solid acetone obtained and ethanol are mixed
Bonding solvent recrystallization, obtains 6-dehydrogenation fir amide groups Sodium caproate after vacuum drying.
Surfactant 6-dehydrogenation fir amide groups Sodium caproate by acquisition is made into the solution of series concentration, carries out surface and opens
The measurement of power, dissolubility and foaming properties.
Beneficial effect
Rosin derivative dehydroabietic acid and 6-aminocaprolc acid just can be met by simple synthesis step " greenization
Learn " the abietyl anion surfactant 6-dehydrogenation fir amide groups Sodium caproate that requires, alternative part oil product plays to be made
With, alleviate the situation that petroleum-based energy is nervous.6-dehydrogenation fir amide groups Sodium caproate dissolubility at room temperature is more than 0.8mol/L, tool
There is the ability compounding with Multiple components；Its critical micelle concentration value is 1.26mmol/L, illustrates that it has stronger ability of aggregation.
6-dehydrogenation fir amide groups Sodium caproate has good foam stability energy, and the half-life forming foam is 1928 minutes.This surface activity
Agent can be applied to daily cleaning agent, detergent, dispersant, detergents and cosmetic as the environmentally friendly product of a kind of function admirable
In product and foam stabilizer formula.
Accompanying drawing explanation
The molecular structure of Fig. 1 6-dehydrogenation fir amide groups Sodium caproate
The hydrogen nuclear magnetic resonance spectrogram of Fig. 2 6-dehydrogenation fir amide groups Sodium caproate
Surface tension γ of Fig. 3 6-dehydrogenation fir amide groups Sodium caproate is with the change curve (25 DEG C) of concentration C
The foam volume of Fig. 4 6-dehydrogenation fir amide groups Sodium caproate (4mmol/L) (room temperature) over time
Detailed description of the invention
Embodiment 1: the synthesis of dehydrogenation fir acyl chlorides.Dehydroabietic acid solid (10.6g, 0.05mol) is equipped with tail gas inhale
Receiving apparatus, reflux condensing tube there-necked flask in, add a small amount of DMAP (DMAP) as catalyst, be raised in temperature
When 60 DEG C, start to be slowly added dropwise thionyl chloride (10g, 0.08mol).This process has a large amount of sour gas to generate, and uses tail gas absorption
Device absorbs.After dropping, arranging temperature is 72 DEG C, continues reaction 3h.After reaction terminates, vacuum rotary steam removes the chlorine of excess
Change sulfoxide, prepare dehydrogenation fir crude acid chloride.
The synthesis of embodiment 2:6-dehydrogenation fir amide groups Sodium caproate.In there-necked flask add 6-aminocaprolc acid (5.5g,
0.04mol), adding the mixed solvent of appropriate acetone and water, acetone is 1:1 with the volume ratio of water.Under being sufficiently stirred for, point
Di Jia not contain the acetone soln of dehydrogenation fir acyl chlorides 0.04mol and the aqueous solution containing sodium hydroxide 0.12mol, control reaction temperature
10-20 DEG C, control the pH value of reaction system at about 8-10, reaction 2-3h.After reaction terminates, product is transferred to 1000mL's
In beaker, with the pH value of the hydrochloric acid regulation system of 6mol/L to 1-2, produce faint yellow solid.With water and petroleum ether respectively to product
Thing carries out three washings, adds excessive sodium hydrate solid and makes product become sodium salt, fully adds 100mL ethanol after reaction.To
Mixture adds anhydrous sodium sulfate and is dried except water, stand, after sucking filtration, filtrate is under reduced pressure removed solvent, solid acetone/
Ethyl alcohol recrystallization three times, obtains finished product 6-dehydrogenation fir amide groups Sodium caproate, and productivity is 52.6%.
Embodiment 3: capillary mensuration.Prepare the aqueous surfactant solution of a series of variable concentrations, at 25 DEG C
Measure its surface tension by suspension ring method, draw concentration and the relation curve of surface tension value of sample aqueous solution.
Embodiment 4: solubility test.Take 5mL deionized water, be gradually added into 6-dehydrogenation fir amide groups Sodium caproate wherein,
At room temperature stand, observe solution state.Solution is defined as surface by surfactant concentration corresponding when clarifying change muddiness
The dissolubility of activating agent.
Embodiment 5: foaming properties measures.The 6-dehydrogenation fir amide groups Sodium caproate solution 10mL of preparation 4mmol/L, is placed in
In the tool plug graduated cylinder of 100mL.Firmly being stood after vibration 20 times the most up and down by solution, at room temperature record foam volume is with time of repose
Change.
Claims (5)
1. a Dehydroabietic acid anion surfactant 6-dehydrogenation fir amide groups Sodium caproate, its molecular structure is as follows:
A kind of Dehydroabietic acid anion surfactant the most according to claim 1, it is characterised in that be to be disproportionated pine
Main component dehydroabietic acid in perfume (or spice) is primary raw material, and reaction obtains as the following formula:
A kind of Dehydroabietic acid anion surfactant the most according to claim 1, it is characterised in that it is at room temperature
Dissolubility more than 0.8mol/L, critical micelle concentration is 1.26mmol/L.
4. the stable foam formed by the Dehydroabietic acid anion surfactant described in claim 1, is by necessarily
The surfactant of amount obtains with forced oscillation after being dissolved in water, and wherein the concentration range of surfactant is 2-500mmol/L.
Stable foam the most according to claim 4, it is characterised in that half foam life period is more than 1500 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610480581.2A CN106140006A (en) | 2016-06-28 | 2016-06-28 | A kind of Dehydroabietic acid anion surfactant and the stable foam of formation thereof |
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| CN201610480581.2A CN106140006A (en) | 2016-06-28 | 2016-06-28 | A kind of Dehydroabietic acid anion surfactant and the stable foam of formation thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107311882A (en) * | 2017-06-16 | 2017-11-03 | 江南大学 | A kind of Dehydroabietic acid dipeptides surfactant and its performance |
| CN107308883A (en) * | 2017-06-26 | 2017-11-03 | 江南大学 | A kind of stable foam formed by abietyl amino acid surfactant |
| CN107321261A (en) * | 2017-06-26 | 2017-11-07 | 江南大学 | A kind of abietyl sulfated surfactant and its performance |
| CN108863836A (en) * | 2018-06-27 | 2018-11-23 | 江南大学 | A kind of abietyl grape sugar surfactant and its application |
| CN109772226A (en) * | 2019-01-23 | 2019-05-21 | 江南大学 | One kind by abietyl stabilized with amine oxide surfactant gel emulsion |
| CN112028767A (en) * | 2020-08-18 | 2020-12-04 | 江南大学 | Rosin-based antioxidant surfactant and preparation and performance thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1644610A (en) * | 2004-12-14 | 2005-07-27 | 林敬文 | High performance light adjusting additive |
| CN105413577A (en) * | 2015-11-16 | 2016-03-23 | 江南大学 | Viscous and elastic solution constructed by rosin-based amino acid surfactant |
-
2016
- 2016-06-28 CN CN201610480581.2A patent/CN106140006A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1644610A (en) * | 2004-12-14 | 2005-07-27 | 林敬文 | High performance light adjusting additive |
| CN105413577A (en) * | 2015-11-16 | 2016-03-23 | 江南大学 | Viscous and elastic solution constructed by rosin-based amino acid surfactant |
Non-Patent Citations (2)
| Title |
|---|
| 宋冰蕾 等: ""含酰胺基团松香基双子表面活性剂的合成与性能"", 《林产化学与工业》 * |
| 王世荣等编: "《表面活性剂化学 第二版》", 30 April 2010, 北京：化学工业出版社 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107311882A (en) * | 2017-06-16 | 2017-11-03 | 江南大学 | A kind of Dehydroabietic acid dipeptides surfactant and its performance |
| CN107308883A (en) * | 2017-06-26 | 2017-11-03 | 江南大学 | A kind of stable foam formed by abietyl amino acid surfactant |
| CN107321261A (en) * | 2017-06-26 | 2017-11-07 | 江南大学 | A kind of abietyl sulfated surfactant and its performance |
| CN107321261B (en) * | 2017-06-26 | 2019-10-25 | 江南大学 | A kind of abietyl sulfated surfactant and its performance |
| CN108863836A (en) * | 2018-06-27 | 2018-11-23 | 江南大学 | A kind of abietyl grape sugar surfactant and its application |
| CN108863836B (en) * | 2018-06-27 | 2019-10-08 | 江南大学 | A kind of abietyl grape sugar surfactant and its application |
| CN109772226A (en) * | 2019-01-23 | 2019-05-21 | 江南大学 | One kind by abietyl stabilized with amine oxide surfactant gel emulsion |
| CN109772226B (en) * | 2019-01-23 | 2020-06-09 | 江南大学 | Gel emulsion stabilized by rosin-based amine oxide surfactant |
| CN112028767A (en) * | 2020-08-18 | 2020-12-04 | 江南大学 | Rosin-based antioxidant surfactant and preparation and performance thereof |
| CN112028767B (en) * | 2020-08-18 | 2021-09-28 | 江南大学 | Rosin-based antioxidant surfactant and preparation and performance thereof |
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Application publication date: 20161123 |