CN103120911B - 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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- CN103120911B CN103120911B CN201210501462.2A CN201210501462A CN103120911B CN 103120911 B CN103120911 B CN 103120911B CN 201210501462 A CN201210501462 A CN 201210501462A CN 103120911 B CN103120911 B CN 103120911B
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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, in molecule, contains hydrophilic group and lipophilic group simultaneously.Because their existence makes the interfacial property generation marked change of material.Surfactant is divided into cationic surface active agent, anionic surfactant and nonionic surface active agent etc.Nonionic surface active agent has good dissolubility in water He in organic solvent, and the variation of solution ion strength and pH value is had to higher patience.There is the multiple performances such as dispersion, emulsification, foam, wetting, solubilising due to it, therefore in a lot of fields, have important use.Taking petrochemical industry resource as raw material, there is the shortcoming large to oil interdependency, environment friendly is poor in China's overwhelming majority emulsifier production.Aspect green emulsifying agent exploitation, natural products is carried out to modification and 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, taking polyethylene glycol (6000), glyceryl monostearate as base stock, taking p-methyl benzenesulfonic acid as catalyst, under normal pressure, prepare polyethylene glycol stearate diester, 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 the product that a series of and aliphatic acid, fatty amine, aliphatic alcohols surfactant structure are similar and show unique characteristics.Meanwhile, rosin acid is natural products, has tricyclic diterpene structure, generally has good plate-out ability energy and ecological performance 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 the monocarboxylic acid that common rosin or disproportionated rosin or Foral etc. contain tricyclic diterpene structure,
Described A is aliphatic acid, comprises the monocarboxylic acid of the linear chain structure such as stearic acid or 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 one kettle way preparation, aliphatic acid reacts with polyethylene glycol and generates fatty acid polyglycol ethylene glycol ester, second step, in fatty acid polyglycol ethylene glycol ester, unreacted hydroxyl reacts with rosin and 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 the monocarboxylic acid that common rosin or disproportionated rosin or Foral etc. contain tricyclic diterpene structure, A is aliphatic acid, comprise the monocarboxylic acid of the linear chain structure such as stearic acid or 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 adopting 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 DEG C, and the reaction time is 3-5h, second step fatty acid polyglycol ethylene glycol ester and rosin reaction temperature are 220-280 DEG C, 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 one kettle way preparation, synthetic through one pot of two step esterification, does 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.
Detailed description of the invention
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 DEG C, 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 DEG C 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 DEG C: reaction temperature can be 150 DEG C, 160 DEG C, and 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, the reaction temperature of second step reaction fatty acid polyglycol ethylene glycol ester and rosin is 220-280 DEG C, for example can choose 220 DEG C, 230 DEG C, 240 DEG C, 250 DEG C, 2,60 DEG C, 2,70 DEG C, 280 DEG C.
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 IR Spectral Identification:
The carbonyl characteristic peak of rosin and aliphatic acid is 1690cm
-1, and in product figure, 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 DEG C, 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 (2)
1. rosin/aliphatic acid end-blocking non-ionic surface active agent, it is characterized in that, general structure is as follows: RCOO-(PEG) n-OOCA, in formula, R is rosin, is the one in common rosin or disproportionated rosin or Foral, and A is aliphatic acid, for the one in stearic acid or palmitic acid or oleic acid, PEG is polyethylene glycol, the molecular weight that n is polyethylene glycol, and wherein n is any one in 200,400,600,1000,2000,4000.
2. prepare the method for rosin/aliphatic acid end-blocking non-ionic surface active agent claimed in claim 1 for one kind, it is characterized in that, what adopt is one pot reaction, not isolation of intermediate products: the first step, aliphatic acid reacts with polyethylene glycol and generates fatty acid polyglycol ethylene glycol ester, second step, in fatty acid polyglycol ethylene glycol ester, unreacted hydroxyl reacts with rosin and generates rosin/aliphatic acid end-blocking non-ionic surface active agent.
3. the preparation method of rosin/aliphatic acid end-blocking non-ionic surface active agent according to claim 2, it is characterized in that, the catalyst adopting is the one in the concentrated sulfuric acid, phosphorous acid, p-methyl benzenesulfonic acid, and catalyst amount is the 0.1-0.5% of polyethylene glycol consumption.
4. the preparation method of rosin/aliphatic acid end-blocking non-ionic surface active agent according to claim 2, it is characterized in that, first step aliphatic acid and polyethylene glycol reaction temperature are 150-220 DEG C, reaction time is 3-5h, second step fatty acid polyglycol ethylene glycol ester and rosin reaction temperature are 220-280 DEG C, and the reaction time is 4-8h.
5. rosin/aliphatic acid end-blocking non-ionic surface active agent according to claim 1, its critical micelle concentration is 0.01-0.1mmol/L; Capillary scope is at 40.7-54.8mN/m.
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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 |
| CN109867532B (en) * | 2019-04-15 | 2022-01-28 | 大庆悦众塑料制品有限公司 | Building insulation board and preparation method thereof |
| CN113461430B (en) * | 2021-07-22 | 2022-09-27 | 江门旭弘磁材有限公司 | Adhesive for dry-pressed magnet and preparation method of magnet |
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