CN103120911A - Colophony/fatty acid sealing end non-ionic surface active agent and preparation method thereof - Google Patents
Colophony/fatty acid sealing end non-ionic surface active agent and preparation method thereof Download PDFInfo
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- CN103120911A CN103120911A CN2012105014622A CN201210501462A CN103120911A CN 103120911 A CN103120911 A CN 103120911A CN 2012105014622 A CN2012105014622 A CN 2012105014622A CN 201210501462 A CN201210501462 A CN 201210501462A CN 103120911 A CN103120911 A CN 103120911A
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Abstract
The invention discloses a colophony/fatty acid sealing end non-ionic surface active agent and a preparation method thereof. Colophony is monocarboxylic acid containing a three-loop diterpene structure, such as common colophony or disproportionated rosin or hydrogenated rosin; and fatty acid is monocarboxylic acid with a linear chain structure, such as stearic acid or palmitinic acid or oleic acid. The one-pot preparation method comprises the following steps of: firstly, performing esterification on fatty acid and polyglycol to form fatty acid polyethylene glycol monoester, and then carrying out reaction on the fatty acid polyethylene glycol monoester and colophony to generate the colophony polyethylene glycol fatty acid ester, wherein the critical micelle concentration of the prepared surface active agent is 0.01-0.1 mmol/L, and the surface tension range of the surface active agent is 40.7-54.8 mN/m. The novel functional green surface active agent provided by the invention has the high activity of a linear chain surface active agent and the high spreading property of a colophony surface active agent.
Description
Technical field
The present invention relates to a kind of novel green surfactant and preparation method thereof, relate in particular to a kind of rosin/aliphatic acid end-blocking non-ionic surface active agent and preparation method thereof.
Background technology
Surfactant is a kind of amphiphile, amphiphilic molecule, namely contains simultaneously hydrophilic group and lipophilic group in molecule.Make the interfacial property generation marked change of material due to their existence.Surfactant is divided into cationic surface active agent, anionic surfactant and nonionic surface active agent etc.Nonionic surface active agent has dissolubility preferably in water He in organic solvent, the variation of solution ion strength and pH value is had higher patience.Have the multiple performances such as dispersion, emulsification, foam, wetting, solubilising due to it, therefore in a lot of fields, important use is being arranged.There is the shortcoming large to the oil interdependency, that environment friendly is poor in China's overwhelming majority emulsifier production take the petrochemical industry resource as raw material.Aspect green emulsifying agent exploitation, natural products is carried out modification often can produce new effect, manifest bright prospects.Biogenic, environmentally friendly, functional form, low aquatile toxicity, easily degraded, do not have the exploitation of virulent new high-efficiency auxiliary agent to rise just at home and abroad to crop.
Polyethylene glycol stearate diester is the important nonionic surface active agent of a class, has high emulsifying capacity, low foam power and good wet performance, is widely used as the viscosity thickener of stamp emulsion, cosmetic emulsions, water-soluble pigment suspension etc.Chen Hong (Chen Hong, synthetic [J] of the two stearic vinegars of polyethylene glycol. chemical industry in Jiangsu Province, 1997,25 (6): 21-22) adopt phosphorous acid and sulfuric acid composite catalyst to synthesize polyethylene glycol stearate diester.Mao Erlin (Mao Erlin. the preparation of polyethylene glycol stearate diester and the mensuration of thickening properties [J] thereof. Perspective of China Washing Product Industry, 2008, (3): 76-80) adopt ester-interchange method, take polyethylene glycol (6000), glyceryl monostearate as base stock, take p-methyl benzenesulfonic acid as catalyst, prepare polyethylene glycol stearate diester under normal pressure, and studied its thickening properties.
Rosin is that a kind of source is abundant, the natural industrial chemicals of low-cost regenerative.Its main component is resin acid, and the active group that utilizes resin acid to have can synthesize a series of and aliphatic acid, fatty amine, the aliphatic alcohols surfactant structure is similar and the product that shows unique characteristics.Simultaneously, rosin acid is natural products, has the tricyclic diterpene structure, generally has plate-out ability energy and ecological performance preferably by its synthetic a series of surfactants.
Summary of the invention
The object of the present invention is to provide a kind of rosin/aliphatic acid end-blocking non-ionic surface active agent, it is characterized in that, general structure is as follows: RCOO-(PEG) n-OOCA,
Described R is rosin, comprises that common rosin or disproportionated rosin or Foral etc. contain the monocarboxylic acid of tricyclic diterpene structure,
Described A is aliphatic acid, comprises the monocarboxylic acid of stearic acid or the linear chain structure such as palmitic acid or oleic acid,
Described PEG is polyethylene glycol, and the molecular weight n of polyethylene glycol is any one in 200,400,600,1000,2000,4000.
The preparation method of rosin/aliphatic acid end-blocking non-ionic surface active agent: adopt the one kettle way preparation, aliphatic acid and polyethylene glycol reaction generate the fatty acid polyglycol ethylene glycol ester, second step, in the fatty acid polyglycol ethylene glycol ester, the reaction of unreacted hydroxyl and rosin generates rosin/aliphatic acid end-blocking non-ionic surface active agent.
The present invention adopts following technical scheme: a kind of rosin/aliphatic acid end-blocking non-ionic surface active agent, R is rosin, comprise that common rosin or disproportionated rosin or Foral etc. contain the monocarboxylic acid of tricyclic diterpene structure, A is aliphatic acid, the monocarboxylic acid that comprises stearic acid or the linear chain structure such as palmitic acid or oleic acid, PEG is polyethylene glycol, and the molecular weight n of polyethylene glycol is any one in 200,400,600,1000,2000,4000.
The preparation method of rosin/aliphatic acid end-blocking non-ionic surface active agent, the catalyst that adopts is the acidic catalysts such as the concentrated sulfuric acid, phosphorous acid, p-methyl benzenesulfonic acid, catalyst amount is the 0.1-0.5% of polyethylene glycol consumption.
The preparation method of rosin/aliphatic acid end-blocking non-ionic surface active agent, it is characterized in that, first step aliphatic acid and polyethylene glycol reaction temperature are 150-220 ℃, and the reaction time is 3-5h, second step fatty acid polyglycol ethylene glycol ester and rosin reaction temperature are 220-280 ℃, and the reaction time is 4-8h.Rosin/aliphatic acid end-blocking non-ionic surface active agent surfactant, its critical micelle concentration is 0.01-0.1mmol/L; Capillary scope is at 40.7-54.8mN/m.
The present invention obtains following technique effect:
1. the lipophilic group of the prepared surfactant of the present invention had both contained the tricyclic diterpene structure of rosin, contained again the linear chain structure of aliphatic acid.Have unique chemical constitution, product toxicity is little, is a kind of novel functional green surfactant.
2. novel rosin/aliphatic acid end-blocking non-ionic surface active agent adopts the one kettle way preparation, and is synthetic through two one pot of step esterification, do not need separation of intermediates.
3. this rosin/aliphatic acid end-blocking non-ionic surface active agent has stronger surface-active, and its critical micelle concentration is 0.01-0.1mmol/L; Capillary scope is at 40.7-54.8mN/m.
The specific embodiment
Embodiment 1
Taking respectively mol ratio is that 1:1 stearic acid and Macrogol 200 are poured in four-hole boiling flask, add wherein again catalyst phosphorous acid (polyethylene glycol quality 0.2%), be heated to 200 ℃, reaction 3-5h, treat that acid number is down to 10 left and right, add common rosin (rosin and Macrogol 200 mol ratio are 1:1), be warmed up to 270 ℃ of reaction 4-8h, treat that acid number is down to 10 left and right reactions and substantially completes.
Embodiment 2
Substantially the same manner as Example 1, wherein stearic acid can be changed to any one in palmitic acid, oleic acid, rosin can be changed to any one in disproportionated rosin, Foral, and Macrogol 200 can be changed to any one in PEG400,600,1000,2000,4000.
Embodiment 3
Substantially the same manner as Example 1, first step reaction aliphatic acid and polyethylene glycol reaction temperature can be 150-220 ℃: reaction temperature can be 150 ℃, 160 ℃, and 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, the reaction temperature of second step reaction fatty acid polyglycol ethylene glycol ester and rosin is 220-280 ℃, for example can choose 220 ℃, 230 ℃, 240 ℃, 250 ℃, 2,60 ℃, 2,70 ℃, 280 ℃.
Embodiment 4
First step reaction aliphatic acid and polyethylene glycol reaction time are 3-5h: the reaction time can be 3 hours, 3.5 hours, and 4 hours, 4.5 hours, 5 hours.The reaction time of second step reaction fatty acid polyglycol ethylene glycol ester and rosin is 4-8h, for example can choose 4 hours, 5 hours, and 6 hours, 7 hours, 8 hours.
Embodiment 5
Substantially the same manner as Example 1, catalyst phosphorous acid can be changed to p-methyl benzenesulfonic acid, or the concentrated sulfuric acid, and catalyst amount is the 0.1-0.5% of polyethylene glycol quality, for example can choose 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%.
Embodiment 6
Product and intermediate carry out the IR Spectral Identification:
The carbonyl characteristic peak of rosin and aliphatic acid is 1690cm
-1, and in product figure, the carbonyl characteristic peak is 1728.7cm
-1, learn that thus rosin and aliphatic acid obtain esterification.-CH
2-wavelength be 2864.9cm
-1, the wavelength of ring is 1353.9cm
-1
Embodiment 7
Adopt film pull-up method to measure surface tension and the CMC of surfactant, measuring temperature is 25 ℃, the surface tension of the aqueous solution when measuring the variable concentrations of series of products.Rosin polyethylene glycol (600) oleic acid surface tension value is 43.8mN/m, and critical micelle concentration is 0.05mmol/L.
Claims (6)
1. rosin/aliphatic acid end-blocking non-ionic surface active agent, is characterized in that, general structure is as follows: RCOO-(PEG) n-OOCA.
2. rosin according to claim 1/aliphatic acid end-blocking non-ionic surface active agent, in formula, R is rosin, comprise that common rosin or disproportionated rosin or Foral etc. contain the monocarboxylic acid of tricyclic diterpene structure, A is aliphatic acid, the monocarboxylic acid that comprises stearic acid or the linear chain structure such as palmitic acid or oleic acid, PEG is polyethylene glycol, and the molecular weight n of polyethylene glycol is any one in 200,400,600,1000,2000,4000.
3. method for preparing rosin claimed in claim 1/aliphatic acid end-blocking non-ionic surface active agent, it is characterized in that, what adopt is one pot reaction, do not separate intermediate product: the first step, aliphatic acid and polyethylene glycol reaction generate the fatty acid polyglycol ethylene glycol ester, second step, in the fatty acid polyglycol ethylene glycol ester, the reaction of unreacted hydroxyl and rosin generates rosin/aliphatic acid end-blocking non-ionic surface active agent.
4. the preparation method of rosin according to claim 3/aliphatic acid end-blocking non-ionic surface active agent, it is characterized in that, the catalyst that adopts is the acidic catalysts such as the concentrated sulfuric acid, phosphorous acid, p-methyl benzenesulfonic acid, and catalyst amount is the 0.1-0.5% of aliphatic acid consumption.
5. the preparation method of rosin according to claim 3/aliphatic acid end-blocking non-ionic surface active agent, it is characterized in that, first step aliphatic acid and polyethylene glycol reaction temperature are 150-220 ℃, reaction time is 3-5h, second step fatty acid polyglycol ethylene glycol ester and rosin reaction temperature are 220-280 ℃, reaction time is 4-8h.
6. rosin according to claim 1/aliphatic acid end-blocking non-ionic surface active agent, its critical micelle concentration is 0.01-0.1mmol/L; Capillary scope is at 40.7-54.8mN/m.
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| CN201210501462.2A CN103120911B (en) | 2012-11-30 | 2012-11-30 | Colophony/fatty acid sealing end non-ionic surface active agent and preparation method thereof |
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| CN201210501462.2A CN103120911B (en) | 2012-11-30 | 2012-11-30 | Colophony/fatty acid sealing end non-ionic surface active agent and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106496078A (en) * | 2016-10-13 | 2017-03-15 | 天津市富特斯科技发展有限公司 | A kind of palmitoleic acid hexahydrobenzoid acid polyethylene glycol sulfonated ester manufacture method |
| CN109867532A (en) * | 2019-04-15 | 2019-06-11 | 梁剑 | A kind of insulating board for building and preparation method thereof |
| CN113461430A (en) * | 2021-07-22 | 2021-10-01 | 江门旭弘磁材有限公司 | Adhesive for dry-pressed magnet and preparation method of magnet |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109867532A (en) * | 2019-04-15 | 2019-06-11 | 梁剑 | A kind of insulating board for building and preparation method thereof |
| CN113461430A (en) * | 2021-07-22 | 2021-10-01 | 江门旭弘磁材有限公司 | Adhesive for dry-pressed magnet and preparation method of magnet |
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| CN103120911B (en) | 2014-08-13 |
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