CN1843605A - Anionic oligo surfactant and its preparation method - Google Patents
Anionic oligo surfactant and its preparation method Download PDFInfo
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- CN1843605A CN1843605A CN200610024892.4A CN200610024892A CN1843605A CN 1843605 A CN1843605 A CN 1843605A CN 200610024892 A CN200610024892 A CN 200610024892A CN 1843605 A CN1843605 A CN 1843605A
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Abstract
The invention relates to an anion low-polymer surface activator and relative preparing method. Wherein, said surface activator has the structure as (1). And said preparing method comprises: first processing ring-opening additive reaction between glycerin glycidic alcohol and primary amine to attain ring-opening adduct; than reacting the ring-opening adduct with SOCI2 or Cl3OH2 SOCl2 to attaint the product in alkali condition. And the final product has better surface activity with simple preparation and wider material supply. Wherein, the (1) means: R1 is C10-C16 alkyl; R2 is SO3H, SO3M, or ; M is K or Na.
Description
Technical field
The present invention relates to a kind of anionic surfactant and preparation method thereof, specifically, relate to a kind of anionic oligo surfactant and preparation method thereof.
Background technology
In recent years, oligo surfactant is just becoming the research focus.These surfactants are connected to form by the interval base by two or more conventional surfactant molecules usually, contain many hydrophobic chains and a plurality of hydrophilic group in the molecule.Compare with conventional surfactant, they show unique physicochemical properties, surface of good activity, lower critical micelle concentration (CMC), very low Krafft point, performances such as good calcium soap dispersiveness, foaminess are just becoming surfactant of new generation.
The oligo surfactant of having reported comprises: duplex cationic surfactant, duplex anion surfactant, duplex and duplex non-ionic surface active agent.Wherein duplex anion (said anion comprises carboxyl, sulfonic group and phosphate etc.) surfactant becomes the focus (Yao Zhigang that people pay close attention to, the prune assistant, Dong Fenglan etc. " oligo surfactant synthesis progress ". chemical progress, 2004,16 (3): 340-363.).For example: existing employing ethylenediamine, octyl chloride and chloroacetic acid are feedstock production duplex carboxyl type anion surfactant; Adopting ethylenediamine, lauroyl chloride, sodium chloroacetate is that raw material can prepare duplex carboxyl type anion surfactant and employing contains the diepoxy group material and fatty alcohol is done to react under the catalyst condition at metallic potassium, obtain intermediate product, react the report that makes duplex sulfonic acid fundamental mode anion surfactant with chlorosulfonic acid again.No matter right existing duplex anion surfactant (Gemini) is in performance or in preparation unsatisfactory part to be arranged all, so this area presses for a kind of superior performance of research and development and prepares simple anionic oligo surfactant.
Summary of the invention
The object of the invention is, a kind of superior performance is provided and prepares simple anionic oligo surfactant and preparation method thereof.
The said anionic oligo surfactant of the present invention has structure shown in the formula (1):
In the formula (1): R
1Be C
10-C
16Alkyl, R
2Be SO
3H, SO
3M,
Or
M is K or Na.
The said anionic oligo surfactant of the present invention is with propanetriol-diglycidyl-ether, primary amine (R
1NH
2) and " halosulfonic acid " (or " 3-halogen, 2-hydroxy-propanesulfonic acid ") synthesize for raw material, its synthetic route is as follows:
In the synthetic route, R
1, R
2Implication and preamble put down in writing identical, X is F, Cl, Br or I.
That is: at first by propanetriol-diglycidyl-ether [compound (2)] and primary amine (R
1NH
2) carry out opening and get open loop addition product [compound (3)], and then by compound (3) and " halosulfonic acid " [compound (4)] or " 3-halogen, 2-hydroxy-propanesulfonic acid " [compound (5)] have react under alkali (NaOH or the potassium hydroxide) existence condition object [compound (1)].
In the raw material and reagent involved in the present invention, remove " 3-halogen, 2-hydroxy-propanesulfonic acid " outer commercially available product that is.And the preparation of " 3-halogen, 2-hydroxy-propanesulfonic acid " can be referring to " colloid and polymer " .2003,21 (2): and 17-18 or " chemical reagent " .2003,25 (2): 95-97, or according to existing methods instruction self-control.
Description of drawings
Fig. 1 is the infrared spectrogram of the anionic oligo surfactant of embodiment 1 preparation.
Fig. 2 is that the surface tension of embodiment 1 anionic oligo surfactant preparation, not purified is with concentration curve (25 ℃).
Fig. 3 is that the surface tension of low anionic oligo surfactant embodiment 1 preparation, purified is with concentration curve (25 ℃).
Fig. 4 is the change curve (25 ℃) of sodium dodecyl benzene sulfonate aqueous solution surface tension with concentration.
The specific embodiment
The method for preparing the said anionic oligo surfactant of the present invention comprises the steps:
(1) with primary amine (R
1NH
2) and solvent (recommend use solvent be the 95v/v% ethanol water) place reactor, under 50～65 ℃ and stirring condition, add propanetriol-diglycidyl-ether [compound (2)] reaction 5～6 hours, in this reactor, add compound (4) or compound (5) again, and with the pH value of NaOH or potassium hydroxide aqueous solution conditioned reaction system greater than 7, reacted 2～10 hours, and filtered the gained reactant mixture and promptly obtain thick object [compound (1)] crude product;
(2) crude product of the compound (1) that will be made by step (1) is dissolved in the deionized water, with the pH value of hydrochloric acid regulation system less than 2, have sediment to separate out in the system, filter, sediment also obtains the sulfonic acid type oligo-anion surfactant after drying through washing to neutrality.
Under 60 ℃～80 ℃, with sulfonic acid type oligo-anion surfactant and the neutralization of equimolar NaOH deionized water solution, system is thickness transparence liquid; Excessive moisture is removed in decompression distillation, obtains the oligomeric anionic surfactant of paste (sulfonate type).
The present invention's anionic oligo surfactant designed and preparation has excellent surface activity, and its preparation method is simple, and raw material sources are extensive.
The invention will be further described below by embodiment, and its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention:
The specification that relates to primary raw material and reagent in an embodiment is as follows:
Propanetriol-diglycidyl-ether (epoxide number: 0.55～0.71, technical grade, sharpening worker Co., Ltd is striven in Shanghai);
Lauryl amine (technical grade, Chinese Xinghua, Tianjin worker Co., Ltd);
3-chloro-2-hydroxypropyl azochlorosulfonate acid sodium (self-control, method is referring to " colloid and polymer " .2003, and 21 (2): 17-18 or " chemical reagent " .2003,25 (2): 95-97);
NaOH, chemical pure;
95v/v% ethanol, chemical pure;
Hydrochloric acid, chemical pure;
Embodiment
The preparation of structure anionic oligo surfactant [hereinafter to be referred as compound (6)] as the formula (6):
Take by weighing lauryl amine 55.6g (0.3mol), solvent (95v/v% ethanol 40ml, deionized water 20ml) joins in the flask with three necks,round bottom of 1000ml.Under 60 ℃, drip propanetriol-diglycidyl-ether (26g is dissolved in the 15ml95v/v% ethanol) while stirring, drip half an hour, reacted 6 hours, make thick transparency liquid.Under 60 ℃, in above-mentioned product, add 59g 3-chloro-hydroxypropyl-sodium sulfonate (being dissolved in the 160ml deionized water), system muddiness.In course of reaction, need to divide and add alkali adjusting pH value for three times: for the first time, add 5ml 50%NaOH solution, reacted 5 hours; For the second time, add 10ml 50%NaOH, reacted 2 hours; For the third time, add 10ml50%NaOH, reacted 2 hours; Obtain thick transparent oligo-anion surfactant alcohol solution.With above-mentioned solution standing over night at room temperature, isolated by filtration then obtains compound (6) crude product of white thickness.
Take by weighing 13g compound (6) crude product and be dissolved in the 100ml deionized water, add 1mol/1L hydrochloric acid and regulate pH＜2, separating and filtering, sediment deionized water cyclic washing, remove excessive hydrochloric acid, under 60 ℃,, obtain the sulfonic acid type oligo-anion surfactant the sediment oven dry.
Take by weighing 2 gram NaOH and be dissolved in the 50ml deionized water, add the sulfonic acid type oligo-anion surfactant, adjust pH=13～14, added thermal agitation 1 hour under 60 ℃, system is thickness transparence liquid; Excessive moisture is removed in decompression distillation, obtains the oligomeric anionic surfactant of paste (sulfonate type).
Structural confirmation, performance test and the comparison of compound (6)
I. structural confirmation
The infrared spectrum of compound (6) as shown in Figure 1.As shown in Figure 1,2954.92cm
-1Be the asymmetric stretching vibration peak of methyl C-H, 1465.41cm
-1Asymmetrical deformation vibration peak for methyl; 2923.32cm
-1With 2853.19cm
-1Be asymmetric stretching vibration peak and the symmetrical stretching vibration peak of methylene C-H, 1465.41cm
-1Be the deformation vibration peak of methylene, 721.26cm
-1Rocking vibration peak for the plane of methylene contains (CH in the molecule
2)
nDuring the methene chain of (n＞4), its rocking vibration is at 721cm
-1Near absworption peak appears.
3341.26cm
-1Form the absworption peak that forms behind the hydrogen bond for-OH; 1033.42cm
-1The strong peak at place is a C-O absworption peak in the primary alconol.
For the S=O in the sulfonate, 1250～1140cm
-1A wide and very strong absorption is arranged in the scope, have several submaximums, so 1215.41cm among the figure
-1, 1157.31cm
-1Absworption peak for S=O.At 810cm
-1And 880cm
-1Be the absworption peak of epoxide group, but 810cm among the figure
-1And 880cm
-1Two places illustrate that all less than very strong absworption peak the epoxide group base reacts.
Fat primary amine with secondary alpha-carbon atom is at 1140～1080cm
-1Stronger bands of a spectrum appear, and in the spectrogram at 1190～1170cm
-1Do not have corresponding bands of a spectrum, illustrate that primary amine transforms; Fatty primary secondary amine with secondary alpha-carbon atom is at 1190～1170cm
-1Strong bands of a spectrum in the appearance, and in the spectrogram at 1190～1170cm
-1Do not have corresponding bands of a spectrum, illustrate that secondary amine is converted into tertiary amine.
II. performance test and comparison
1) active matter content of compound (6)
Adopt the JIS method to measure compound (6) active matter content, anion-content is 84.3% before the purifying, and anion-content is 96.2% behind the purifying.
2) dissolubility of compound (6)
When pH＜2, the said surfactant of the present invention does not dissolve, and produces white casse; When pH 〉=3, the said surfactant clear of the present invention.
Compound (6) is made into 1% solution, under 0 ℃, can dissolves.Owing to contain a plurality of sulfonate radicals, a plurality of ehter bond and hydroxyl in this oligo-anion surfactant molecule, these groups can both have strong water and effect with water, so favorable solubility.
3) the surface tension curve and the critical micelle concentration of compound (6)
Measure purifying front and back compound (6) surface tension with change in concentration (25 ℃), respectively as Fig. 2, shown in Figure 3 with surface tension instrument (Contact Angle-Surface Tension, RADIAN Series 300).
As shown in Figure 2, when concentration be 1.3 * 10
-5(g/mL) time, the surface tension of purifying compounds (6) does not reach minimum of a value (γ=35.2dyn/cm) is so CMC=1.3 * 10
-5(g/mL).
As shown in Figure 3, when concentration be 6.5 * 10
-5(g/mL) time, the surface tension of purifying compounds (6) reaches minimum of a value, and (γ=38.7 (dyn/cm) is so its critical micelle concentration CMC=6.5 * 10
-5(g/mL).
Experiment records sodium dodecyl benzene sulfonate aqueous solution surface tension curve as shown in Figure 4.As seen from Figure 4, under 25 degree, the critical micelle concentration of neopelex is 3.5 * 10
-4(g/mL) time, surface tension reaches minimum of a value, and (γ=31.8 (dyn/cm) is so CMC=3.5 * 10
-4(g/mL).
Compare with neopelex, purifying compounds (6) does not all reduce greatly with the critical micelle concentration of purifying compounds (6), has shown higher surface activity.
Claims (6)
1, a kind of anionic oligo surfactant, it has structure shown in the formula (1):
In the formula (1): R
1Be C
10-C
16Alkyl, R
2Be SO
3H, SO
3M,
Or
M is K or Na.
2, surfactant as claimed in claim 1 is characterized in that, R
2Be CH
2CHOHCH
2SO
3Na.
3, surfactant as claimed in claim 2 is characterized in that, described surfactant has structure shown in the formula (6):
4, preparation is characterized in that said preparation method's key step is: at first by compound (2) and R as the method for any described surfactant in the claim 1～3
1NH
2Carry out opening and get compound (3), and then by compound (3) and compound (4) or compound (5) have react under NaOH or the potassium hydroxide existence condition object; Its reactional equation is as follows:
Wherein: R
1, R
2Implication and claim 1 in record identical, X is F, Cl, Br or I.
5, preparation method as claimed in claim 4 is characterized in that, described preparation method comprises the steps:
(1) with R
1NH
2Place reactor with solvent, under 50～65 ℃ and stirring condition, add compound (2) reaction 5～6 hours, in this reactor, add compound (4) or compound (5) again, and with the pH value of NaOH or potassium hydroxide aqueous solution conditioned reaction system greater than 7, and reacted 2～10 hours, filter the gained reactant mixture and promptly obtain thick crude product object;
(2) will be dissolved in the deionized water by the crude product object that step (1) makes, with the pH value of hydrochloric acid regulation system less than 2, there is sediment to separate out in the system, filter, sediment also obtains the sulfonic acid type oligo-anion surfactant after drying through washing to neutrality, under 60 ℃～80 ℃, with sulfonic acid type oligo-anion surfactant and the neutralization of equimolar NaOH deionized water solution, system is thickness transparence liquid; Excessive moisture is removed in decompression distillation, obtains the paste target product.
6, preparation method as claimed in claim 5 is characterized in that, said solvent is the 95v/v% ethanol water in the step (1).
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|---|---|---|---|
| CN200610024892.4A CN1843605A (en) | 2006-03-21 | 2006-03-21 | Anionic oligo surfactant and its preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955767A (en) * | 2010-08-16 | 2011-01-26 | 大庆高新区华龙祥化工有限公司 | Gemini surfactant for tertiary oil recovery chemical oil-displacing agent and preparation method thereof |
| CN105732442A (en) * | 2016-01-27 | 2016-07-06 | 江苏苏博特新材料股份有限公司 | Oligomer surfactant, and preparation method and application thereof |
-
2006
- 2006-03-21 CN CN200610024892.4A patent/CN1843605A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955767A (en) * | 2010-08-16 | 2011-01-26 | 大庆高新区华龙祥化工有限公司 | Gemini surfactant for tertiary oil recovery chemical oil-displacing agent and preparation method thereof |
| CN101955767B (en) * | 2010-08-16 | 2013-01-09 | 大庆高新区华龙祥化工有限公司 | Gemini surfactant for tertiary oil recovery chemical oil-displacing agent and preparation method thereof |
| CN105732442A (en) * | 2016-01-27 | 2016-07-06 | 江苏苏博特新材料股份有限公司 | Oligomer surfactant, and preparation method and application thereof |
| CN105732442B (en) * | 2016-01-27 | 2017-11-03 | 江苏苏博特新材料股份有限公司 | Oligomeric-type surfactant, its preparation method and application |
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