CN111732525B - Method for preparing non-aqueous system fatty alcohol ether sulfuric acid organic alkanolamine salt product - Google Patents
Method for preparing non-aqueous system fatty alcohol ether sulfuric acid organic alkanolamine salt product Download PDFInfo
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Abstract
The invention relates to a method for preparing a non-aqueous fatty alcohol ether sulfate organic alcohol amine salt product, which mainly solves the technical problems that in the prior art, the subsequent product is influenced by the need of adding a metal complexing agent, a preservative, a pH stabilizer and the like due to the existence of water in a fatty alcohol polyoxyethylene ether sulfate organic amine salt product, and the fatty alcohol polyoxyethylene ether sulfate organic alcohol amine salt containing a large amount of water is difficult to use in an anhydrous or low-water formula, and the method for preparing the non-aqueous fatty alcohol polyoxyethylene ether sulfate organic alcohol amine salt product comprises the following steps: (1) reacting an organic material with a sulfonating agent in a sulfonation reactor to obtain sulfate, wherein the organic material comprises fatty alcohol-polyoxyethylene ether; (2) in a non-aqueous organic diluent, organic alcohol amine is taken as a neutralizer to neutralize the sulfate to obtain the non-aqueous fatty alcohol polyoxyethylene ether sulfate organic alcohol amine salt product, so that the technical problem is better solved.
Description
Technical Field
The invention relates to a method for preparing a non-aqueous fatty alcohol ether sulfate organic alkanolamine salt product.
Background
At present, almost all fatty alcohol ether sulfate products obtained by sulfonating fatty alcohol or fatty alcohol ether take water as a solvent, and the lowest water content in the sulfonated products reaches about 30 percent, so that almost all liquid sulfonated products cannot be used in anhydrous formulas or anhydrous application environments. The field of surfactants is currently evolving more and more towards high active, highly concentrated formulations. In addition, in the product using water as a solvent, the risk of microorganisms for bacterial reproduction is inevitable all the time, and various preservatives and bactericides must be added in the formula to ensure the stability of the product quality. The metal ion complexing agent is also a necessary component, and although the additives provide guarantee for the quality of the product, the additives have many uncontrollable influences on downstream manufacturers and even cause quality accidents of the product. Therefore, according to the market demand, the development of a fatty alcohol ether sulfate product sulfonated from non-aqueous fatty alcohol ether is needed.
The prior production of fatty alcohol-polyoxyethylene ether sulfate organic alcohol amine salt products adopts a multi-tube membrane type sulfonator to sulfonate fatty alcohol-polyoxyethylene ether, and then adopts organic alcohol amine (such as triethanolamine) aqueous solution to neutralize immediately. Because of the use of water, in order to prevent the influence of metal ions on products, a metal ion complexing agent such as EDTA is required to be added, and because the existence of water easily causes decomposition in the storage process, the pH value is adjusted and stabilized between 6.0 and 8.0 by using phosphoric acid or citric acid. Because of the existence of water, microorganisms are easy to grow in the product during storage and transportation, and preservatives such as common kaempferol and the like are added according to needs. Metal ion complexing agents such as EDTA can deactivate and discolor some functional effective substances of downstream products such as ZPT antidandruff agents, thereby causing quality problems. And the added phosphoric acid, Kethon and the like can cause the violation of environmental protection, forbidden substances of cosmetics and the like mixed in downstream products. The addition of a dioxane removal unit increases equipment investment and operating cost. The active matter content of the product is about 40 percent generally.
Disclosure of Invention
In order to solve the technical problems that in the prior art, due to the existence of water in a fatty alcohol-polyoxyethylene ether sulfuric acid organic amine salt product, a metal complexing agent, a preservative, a pH stabilizer and the like are required to be added to influence subsequent products, and the fatty alcohol-polyoxyethylene ether sulfuric acid organic amine salt containing a large amount of water is difficult to apply to the anhydrous or low-water field, a novel method for preparing the non-aqueous fatty alcohol-polyoxyethylene ether sulfuric acid organic amine salt is provided.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the method for preparing the non-aqueous system fatty alcohol-polyoxyethylene ether sulfate organic alcohol amine salt product comprises the following steps:
(1) reacting an organic material with a sulfonating agent in a sulfonation reactor to obtain a sulfate, wherein the organic material comprises fatty alcohol-polyoxyethylene ether;
(2) and neutralizing the sulfate in a non-aqueous organic diluent by taking organic alcohol amine as a neutralizer to obtain the non-aqueous system fatty alcohol-polyoxyethylene ether sulfate organic alcohol amine salt product.
Because of the existence of the organic solvent, the viscosity is low in the neutralization process, the neutralization is sufficient, and no water or almost no water exists in the neutralization process, so that the local hydrolysis of the system is prevented, and the corrosion of the materials to equipment is greatly reduced. In the product, no other auxiliary agent is added, the content of effective substances of the product even reaches more than 90 percent, the content of active substances reaches 75 to 90 percent, the product has good fluidity, and is not bleached, and the product only contains the active substances, a small amount of unsulfonated substances, sulfate and dihydric alcohol solvents. Because no addition agent is added, the adjusting time can be greatly shortened, and the production efficiency is improved. The product has stable quality in the storage process, no risk of bacterial pollution and propagation, and no component which has influence on the formula performance of downstream products. Furthermore, we have found that the production of dioxane during the neutralisation process is also significantly reduced, with levels below 10ppm, due to the non-aqueous organic diluent used in place of water.
In the above technical scheme, preferably, the fatty alcohol-polyoxyethylene ether is in accordance with the following structural formula 1:
R1(OCH2CH2)nOH, structural formula 1;
wherein R is1Is selected from C8-C18 aliphatic hydrocarbon groups, and n is more than 0 and less than 10.
In the above technical solution, n can be, for example, but not limited to, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, and the like, as non-limiting examples. For the sake of comparison, all of the embodiments of the present invention have n of 3.
In the above technical solution, preferably, the non-aqueous organic diluent comprises one or more selected from ethanol, ethylene glycol, propylene glycol and polyethylene glycol.
Ethylene glycol, propylene glycol and polyethylene glycol are less volatile than ethanol, have low flash points, are not easy to deflagrate, and are therefore safer than ethanol solvent systems.
In the above technical solution, the propylene glycol is preferably 1, 2-propylene glycol, and for convenience of comparison, 1, 2-propylene glycol is used as the propylene glycol in the embodiment of the present invention.
Polyethylene glycol is referred to in the art as PEG for short.
In the above technical solution, the molecular weight of PEG is preferably 150 to 450, for example, but not limited thereto, the molecular weight may be 160, 170, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, and the like.
The molecular weight of PEG is determined according to a method for determining the molecular weight of PEG400 in the pharmacopoeia of 2015 edition, which comprises the following steps: taking about 1.2g of PEG, accurately weighing, placing the PEG into a dry 250ml conical flask with a plug, accurately adding 25ml of pyridine solution of phthalic anhydride (taking 14g of phthalic anhydride, dissolving in 100ml of anhydrous pyridine, placing overnight for later use), shaking, adding a small amount of anhydrous pyridine to the edge of the conical flask, placing the conical flask in a boiling water bath, heating for 30-60 minutes, taking out and cooling, accurately adding 50ml of sodium hydroxide titration solution (0.5mol/L), taking the pyridine solution of phenolphthalein with the weight concentration of 1% as an indicator, titrating the solution to be red by using the sodium hydroxide titration solution (0.5mol/L), and correcting the titration result by using a blank test. The product of the test amount (g) and 4000 is divided by the volume (ml) of the sodium hydroxide titration solution (0.5mol/L) consumed, thus obtaining the average molecular weight of the test sample.
In the above technical solution, the operation manner of step (2) can be, but not limited to, dissolving organic amine in non-aqueous organic diluent, and neutralizing the sulfate ester with the obtained organic amine non-aqueous organic diluent solution; in this case, the mole number of the organic amine contained in 100 g of the organic amine non-aqueous organic diluent solution is preferably 0.2 to 0.5, for example, but not limited to, 0.25, 0.30, 0.35, 0.40, 0.45, and the like.
In the above technical scheme, the pH of the non-aqueous system fatty alcohol polyoxyethylene ether sulfate organic alkanolamine salt product is 6 to 8, for example, but not limited to, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, and the like, and more preferably, the pH is 6.5 to 7.5.
In the above technical solution, preferably, the organic alcohol amine has a structure shown in the following structural formula 2:
wherein R is2Is methyl or H; r is3And R4Independently selected from H or a group represented by the following structural formula 3:
wherein R is5Is H or methyl.
By way of non-limiting example, the organic alcohol amine may be monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine.
In the above technical solution, the sulfonating agent may be at least one of fuming sulfuric acid, sulfur trioxide, chlorosulfonic acid and sulfamic acid, and preferably the sulfonating agent is sulfur trioxide.
In the above technical solution, preferably, the sulfur trioxide is used in a form diluted with a gaseous diluent.
In the above technical solution, preferably, the gaseous diluent is air or nitrogen.
In the above technical scheme, preferably, the sulfur trioxide accounts for 0.1-10% of the total weight of the sulfur trioxide and the gaseous diluent. By way of non-limiting example, sulfur trioxide can be 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc., based on the total weight of the sulfur trioxide and the gaseous diluent.
In the technical scheme, the molar ratio of the sulfonating agent to the organic material is preferably 1.01-1.03. In the present invention, the mole number of the organic material in the mole ratio of the sulfonating agent to the organic material is calculated by the mole number of the hydroxyl group contained therein.
In the above technical scheme, the sulfonation reactor may be a stirred bubbling reactor, a membrane reactor or a jet reactor. More preferably a membrane reactor, most preferably a falling film reactor in a membrane reactor.
In the above technical scheme, the reaction temperature is preferably 40-50 ℃, such as but not limited to 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃ and the like.
In the above technical solution, further, the organic material simultaneously includes fatty alcohol-polyoxyethylene ether and an organic carbonyl compound, wherein a molecule of the carbonyl compound contains a carboxylic ester bond or a carboxylic amide bond.
When the organic carbonyl compound is added into fatty alcohol polyoxyethylene ether to be used as an organic material for sulfonation reaction, the content of dioxane in the obtained sulfonated product is obviously lower than that in the sulfonated product which is prepared by only using fatty alcohol polyoxyethylene ether as the organic material without adding the organic carbonyl compound.
In the above technical solutions, it is preferable that the carbonyl compound corresponds to the following structural formula 4:
wherein R is6Is aliphatic hydrocarbon radical of C8-C20, R7Is methyl or H, R8Is H or a group of formula 4:
wherein R is9Is H or methyl.
In the above technical solution, preferably, the ratio of the organic carbonyl compound to the organic material is more than 0 and less than 0.1 by weight.
In the above embodiment, as non-limiting examples of the ratio of the organic carbonyl compound to the organic material, for example, but not limited to, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09, 0.095, etc. can be given.
In the above technical solution, when the ratio of the organic carbonyl compound to the organic material is greater than 0 and less than 0.009, the effect of reducing dioxane becomes more obvious as the addition amount of the organic carbonyl compound increases; however, from the viewpoint of obtaining a stable low level of dioxane and not excessively increasing the amount of the organic carbonyl compound added, the ratio of the organic carbonyl compound to the organic material is preferably 0.015 to 0.090.
In the above technical scheme, R1 and R6 are independently selected from linear hydrocarbon groups or hydrocarbon groups having a branched chain.
In the above schemes, R1 and R6 are independently primary or secondary hydrocarbyl groups, but primary hydrocarbyl groups are preferred.
In the above technical scheme, R6 is selected from saturated hydrocarbon group or unsaturated hydrocarbon group, preferably alkyl.
In the above technical schemes, as a non-limiting example, R1 and R6 are each independently a C8 hydrocarbon group, a C9 hydrocarbon group, a C10 hydrocarbon group, a C11 hydrocarbon group, a C12 hydrocarbon group, a C13 hydrocarbon group, a C14 hydrocarbon group, a C15 hydrocarbon group, a C16 hydrocarbon group, a C17 hydrocarbon group, a C18 hydrocarbon group, or the like.
R in the embodiments of the present invention is merely for comparison1Are all 1-dodecyl, R6Are each 1-undecyl, R2 and R5 are each methyl, R7And R9Are all H.
In order to achieve comparable technical effects, the specific embodiment of the invention adopts a multi-tube falling film reactor manufactured by Ballestra, Italy, wherein each reaction tube is 6 meters high, the inner diameter of the reaction tube is 25.4mm, each reaction tube adopts upper and lower sections for cooling, and a tube for cooling SO is arranged above all the reaction tubes3And air, said organic material being fed using an annular gap.
Once the form and size of the reactor are determined, the skilled person can rationally select the feed rate of the organic material and achieve the technical effect of the invention of comparably reducing the amount of dioxane in the sulfonated product. For example, for the reactor employed in the embodiments of the present invention, the feed rate of the organic material, expressed as the average feed rate per reaction tube, may be, but is not limited to, 10 to 60 kg/hour, as non-limiting examples of feed rate point values, such as, but not limited to, 10 kg/hour, 20 kg/hour, 30 kg/hour, 40 kg/hour, 50 kg/hour, 60 kg/hour, and the like. In order to achieve comparable results in the examples and comparative examples, the feed rate of the organic material described in the examples or of the fatty alcohol polyoxyethylene ether in the comparative examples was 30 kg/h.
In the specific embodiment of the invention, the method for measuring the content of the dioxane in the non-aqueous system fatty alcohol polyoxyethylene ether sulfate organic alcohol amine salt product sample is carried out according to a standard addition method specified in 7.2.1 in GB/T26388-2011 gas chromatography for measuring the residual amount of the dioxane in a surfactant.
The invention is further illustrated by the following specific embodiments:
Detailed Description
[ COMPARATIVE EXAMPLE 1 ]
Step 1, obtaining organic materials
The lauryl polyoxyethylene (3) ether is used directly as the organic material for sulfonation as described in step 2 below.
Step 2, sulfonation in a sulfonation reactor
Introducing the organic material and sulfur trioxide dry air mixed gas with the sulfur trioxide content of 4% from the top of a sulfonation reactor, wherein the feeding speed of the organic material is 30 kg/h, the feeding molar ratio of sulfur trioxide to the organic material is 1.03, and the temperature of the sulfonation reaction is 45 ℃. After the sulfonation reaction is finished, the sulfonated product in the form of sulfonate is obtained, and then:
step 3, neutralization of sulfonate ester
The sulfonated product in the form of the sulfonic acid ester is neutralized by aqueous solution with the weight concentration of 15% (equivalent to 0.38mol of sodium hydroxide in each 100 g of aqueous sodium hydroxide solution) until the pH value is 7, and the neutralization temperature is 58 ℃, so that the water system sodium alcohol ether sulfate product is obtained.
Step 4, analysis and characterization of sulfonated products
And (4) measuring the content of the dioxane in the water system fatty alcohol polyoxyethylene ether sodium sulfate product obtained in the step (3). And (3) determining that each kilogram of the water system fatty alcohol polyoxyethylene ether sodium sulfate product obtained in the step (3) contains 72 mg of dioxane.
For comparison, the main process conditions and test results are listed in table 1.
[ example 1 ]
Step 1, obtaining organic materials
The lauryl polyoxyethylene (3) ether is used directly as the organic material for sulfonation as described in step 2 below.
Step 2, sulfonation in a sulfonation reactor
Introducing the organic material and sulfur trioxide dry air mixed gas with the sulfur trioxide content of 4% from the top of a sulfonation reactor, wherein the feeding speed of the organic material is 30 kg/h, the feeding molar ratio of sulfur trioxide to the organic material is 1.03, and the temperature of the sulfonation reaction is 45 ℃. After the sulfonation reaction is finished, the sulfonated product is obtained in the form of sulfonate ester, and then:
step 3, neutralization of sulfonate ester
And neutralizing the sulfonated product in the form of the sulfonic acid ester by using a triisopropanolamine propylene glycol solution with the weight concentration of 72% (equivalent to 0.38mol of triisopropanolamine in every 100 g of triisopropanolamine propylene glycol solution) until the pH value is 7, and neutralizing the temperature at 58 ℃ to obtain the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product.
Step 4, analysis and characterization of sulfonated products
And (4) measuring the content of the dioxane in the non-aqueous system fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3). And (3) determining that each kilogram of the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3) contains 31 mg of dioxane.
For comparison, the main process conditions and test results are listed in table 1.
[ example 2 ]
Step 1, obtaining organic materials
The lauryl polyoxyethylene (3) ether is used directly as the organic material for sulfonation as described in step 2 below.
Step 2, sulfonation in a sulfonation reactor
Introducing the organic material and sulfur trioxide dry air mixed gas with the sulfur trioxide content of 4% from the top of a sulfonation reactor, wherein the feeding speed of the organic material is 30 kg/h, the feeding molar ratio of sulfur trioxide to the organic material is 1.03, and the temperature of the sulfonation reaction is 45 ℃. After the sulfonation reaction is finished, the sulfonated product is obtained in the form of sulfonate ester, and then:
step 3, neutralization of sulfonate ester
And neutralizing the sulfonated product in the form of the sulfonic acid ester by using a triisopropanolamine propylene glycol solution with the weight concentration of 81% (equivalent to 0.42mol of triisopropanolamine in every 100 g of the triisopropanolamine propylene glycol solution) until the pH value is 7, and neutralizing at the temperature of 58 ℃ to obtain the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product.
Step 4, analysis and characterization of sulfonated products
And (4) measuring the content of the dioxane in the non-aqueous system fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3). And (3) measuring that each kilogram of the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3) contains 29 milligrams of dioxane.
For comparison, the main process conditions and test results are listed in table 1.
[ example 3 ]
Step 1, obtaining organic materials
The organic material is obtained by uniformly mixing ammonium n-dodecanol polyoxyethylene (3) ether sulfate and dodecanol polyoxyethylene (3) ether according to the weight ratio of the ammonium n-dodecanol polyoxyethylene (3) ether sulfate to the dodecanol polyoxyethylene (3) ether of 0.005.
Step 2, sulfonation in a sulfonation reactor
Introducing the organic material and sulfur trioxide dry air mixed gas with the sulfur trioxide content of 4% from the top of a sulfonation reactor, wherein the feeding speed of the organic material is 30 kg/h, the feeding molar ratio of sulfur trioxide to the organic material is 1.03, and the temperature of the sulfonation reaction is 45 ℃. After the sulfonation reaction is finished, the sulfonated product is obtained in the form of sulfonate ester, and then:
step 3, neutralization of sulfonate ester
And neutralizing the sulfonated product in the form of the sulfonic acid ester by using a triisopropanolamine propylene glycol solution with the weight concentration of 81% (equivalent to 0.42mol of triisopropanolamine in every 100 g of the triisopropanolamine propylene glycol solution) until the pH value is 7, and neutralizing at the temperature of 58 ℃ to obtain the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product.
Step 4, analysis and characterization of sulfonated products
And (4) measuring the content of the dioxane in the non-aqueous system fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3). And (3) determining that each kilogram of the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3) contains 27 milligrams of dioxane.
For comparison, the main process conditions and test results are listed in table 1.
[ example 4 ]
Step 1, obtaining organic materials
And uniformly mixing the lauric acid monoethanolamide and the lauryl polyoxyethylene (3) ether according to the weight ratio of the lauric acid monoethanolamide to the lauryl polyoxyethylene (3) ether of 0.005 to obtain the organic material.
Step 2, sulfonation in a sulfonation reactor
Introducing the organic material and sulfur trioxide dry air mixed gas with the sulfur trioxide content of 4% from the top of a sulfonation reactor, wherein the feeding speed of the organic material is 30 kg/h, the feeding molar ratio of sulfur trioxide to the organic material is 1.03, and the temperature of the sulfonation reaction is 45 ℃. After the sulfonation reaction is finished, the sulfonated product is obtained in the form of sulfonate ester, and then:
step 3, neutralization of sulfonate ester
And neutralizing the sulfonated product in the form of the sulfonic acid ester by using a triisopropanolamine propylene glycol solution with the weight concentration of 81% (equivalent to 0.42mol of triisopropanolamine in every 100 g of the triisopropanolamine propylene glycol solution) until the pH value is 7, and neutralizing at the temperature of 58 ℃ to obtain the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product.
Step 4, analysis and characterization of sulfonated products
And (4) measuring the content of the dioxane in the non-aqueous system fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3). And (3) measuring that each kilogram of the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3) contains 11 mg of dioxane.
For comparison, the main process conditions and test results are listed in table 1.
[ example 5 ]
Step 1, obtaining organic materials
And (3) uniformly mixing the dodecanoic acid diethanolamide and the dodecanol polyoxyethylene (3) ether according to the weight ratio of the dodecanoic acid diethanolamide to the dodecanol polyoxyethylene (3) ether of 0.005 to obtain the organic material.
Step 2, sulfonation in a sulfonation reactor
Introducing the organic material and sulfur trioxide dry air mixed gas with the sulfur trioxide content of 4% from the top of a sulfonation reactor, wherein the feeding speed of the organic material is 30 kg/h, the feeding molar ratio of sulfur trioxide to the organic material is 1.03, and the temperature of the sulfonation reaction is 45 ℃. After the sulfonation reaction is finished, the sulfonated product is obtained in the form of sulfonate ester, and then:
step 3, neutralization of sulfonate ester
And neutralizing the sulfonated product in the form of the sulfonic acid ester by using a triisopropanolamine propylene glycol solution with the weight concentration of 81% (equivalent to 0.42mol of triisopropanolamine in every 100 g of the triisopropanolamine propylene glycol solution) until the pH value is 7, and neutralizing at the temperature of 58 ℃ to obtain the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product.
Step 4, analysis and characterization of sulfonated products
And (4) measuring the content of the dioxane in the non-aqueous system fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3). And (3) measuring that each kilogram of the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3) contains 15 mg of dioxane.
For comparison, the main process conditions and test results are listed in table 1.
[ example 6 ]
Step 1, obtaining organic materials
And uniformly mixing the lauric acid monoethanolamide and the lauryl polyoxyethylene (3) ether according to the weight ratio of the lauric acid monoethanolamide to the lauryl polyoxyethylene (3) ether of 0.002 to obtain the organic material.
Step 2, sulfonation in a sulfonation reactor
Introducing the organic material and sulfur trioxide dry air mixed gas with the sulfur trioxide content of 4% from the top of a sulfonation reactor, wherein the feeding speed of the organic material is 30 kg/h, the feeding molar ratio of sulfur trioxide to the organic material is 1.03, and the temperature of the sulfonation reaction is 45 ℃. After the sulfonation reaction is finished, the sulfonated product is obtained in the form of sulfonate ester, and then:
step 3, neutralization of sulfonate ester
And neutralizing the sulfonated product in the form of the sulfonic acid ester by using a triisopropanolamine propylene glycol solution with the weight concentration of 81% (equivalent to 0.42mol of triisopropanolamine in every 100 g of the triisopropanolamine propylene glycol solution) until the pH value is 7, and neutralizing at the temperature of 58 ℃ to obtain the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product.
Step 4, analysis and characterization of sulfonated products
And (4) measuring the content of the dioxane in the non-aqueous system fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3). And (3) measuring that each kilogram of the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3) contains 18 milligrams of dioxane.
For comparison, the main process conditions and test results are listed in table 1.
[ example 7 ]
Step 1, obtaining organic materials
And uniformly mixing the lauric acid monoethanolamide and the lauryl polyoxyethylene (3) ether according to the weight ratio of the lauric acid monoethanolamide to the lauryl polyoxyethylene (3) ether of 0.009 to obtain the organic material.
Step 2, sulfonation in a sulfonation reactor
Introducing the organic material and sulfur trioxide dry air mixed gas with the sulfur trioxide content of 4% from the top of a sulfonation reactor, wherein the feeding speed of the organic material is 30 kg/h, the feeding molar ratio of sulfur trioxide to the organic material is 1.03, and the temperature of the sulfonation reaction is 45 ℃. After the sulfonation reaction is finished, the sulfonated product is obtained in the form of sulfonate ester, and then:
step 3, neutralization of sulfonate ester
And neutralizing the sulfonated product in the form of the sulfonic acid ester by using a triisopropanolamine propylene glycol solution with the weight concentration of 81% (equivalent to 0.42mol of triisopropanolamine in every 100 g of the triisopropanolamine propylene glycol solution) until the pH value is 7, and neutralizing at the temperature of 58 ℃ to obtain the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product.
Step 4, analysis and characterization of sulfonated products
And (4) measuring the content of the dioxane in the non-aqueous system fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3). And (3) measuring that each kilogram of the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3) contains 10 milligrams of dioxane.
For comparison, the main process conditions and test results are listed in table 1.
[ example 8 ]
Step 1, obtaining organic materials
And uniformly mixing the lauric acid monoethanolamide and the lauryl polyoxyethylene (3) ether according to the weight ratio of the lauric acid monoethanolamide to the lauryl polyoxyethylene (3) ether of 0.015 to obtain the organic material.
Step 2, sulfonation in a sulfonation reactor
Introducing the organic material and sulfur trioxide dry air mixed gas with the sulfur trioxide content of 4% from the top of a sulfonation reactor, wherein the feeding speed of the organic material is 30 kg/h, the feeding molar ratio of sulfur trioxide to the organic material is 1.03, and the temperature of the sulfonation reaction is 45 ℃. After the sulfonation reaction is finished, the sulfonated product is obtained in the form of sulfonate ester, and then:
step 3, neutralization of sulfonate ester
And neutralizing the sulfonated product in the form of the sulfonic acid ester by using a triisopropanolamine propylene glycol solution with the weight concentration of 81% (equivalent to 0.42mol of triisopropanolamine in every 100 g of the triisopropanolamine propylene glycol solution) until the pH value is 7, and neutralizing at the temperature of 58 ℃ to obtain the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product.
Step 4, analysis and characterization of sulfonated products
And (4) measuring the content of the dioxane in the non-aqueous system fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3). And (3) measuring that each kilogram of the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3) contains 8 mg of dioxane.
For comparison, the main process conditions and test results are listed in table 1.
[ example 9 ]
Step 1, obtaining organic materials
And uniformly mixing the lauric acid monoethanolamide and the lauryl polyoxyethylene (3) ether according to the weight ratio of the lauric acid monoethanolamide to the lauryl polyoxyethylene (3) ether of 0.050 to obtain the organic material.
Step 2, sulfonation in a sulfonation reactor
Introducing the organic material and sulfur trioxide dry air mixed gas with the sulfur trioxide content of 4% from the top of a sulfonation reactor, wherein the feeding speed of the organic material is 30 kg/h, the feeding molar ratio of sulfur trioxide to the organic material is 1.03, and the temperature of the sulfonation reaction is 45 ℃. After the sulfonation reaction is finished, the sulfonated product in the form of sulfonate is obtained, and then:
step 3, neutralization of sulfonate ester
And neutralizing the sulfonated product in the form of the sulfonic acid ester by using a triisopropanolamine propylene glycol solution with the weight concentration of 81% (equivalent to 0.42mol of triisopropanolamine in every 100 g of the triisopropanolamine propylene glycol solution) until the pH value is 7, and neutralizing at the temperature of 58 ℃ to obtain the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product.
Step 4, analysis and characterization of sulfonated products
And (4) measuring the content of the dioxane in the non-aqueous system fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3). And (3) measuring that each kilogram of the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3) contains 8 mg of dioxane.
For comparison, the main process conditions and test results are listed in table 1.
[ example 10 ]
Step 1, obtaining organic materials
And uniformly mixing the lauric acid monoethanolamide and the lauryl polyoxyethylene (3) ether according to the weight ratio of the lauric acid monoethanolamide to the lauryl polyoxyethylene (3) ether of 0.090 to obtain the organic material.
Step 2, sulfonation in a sulfonation reactor
Introducing the organic material and sulfur trioxide dry air mixed gas with 4 percent of sulfur trioxide content from the top of a sulfonation reactor, wherein the feeding speed of the organic material is 30 kg/h, the feeding molar ratio of the sulfur trioxide to the organic material is 1.03, and the temperature of the sulfonation reaction is 45 ℃. After the sulfonation reaction is finished, the sulfonated product in the form of sulfonate is obtained, and then:
step 3, neutralization of sulfonate ester
And neutralizing the sulfonated product in the form of the sulfonic acid ester by using a triisopropanolamine propylene glycol solution with the weight concentration of 81% (equivalent to 0.42mol of triisopropanolamine in every 100 g of the triisopropanolamine propylene glycol solution) until the pH value is 7, and neutralizing at the temperature of 58 ℃ to obtain the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product.
Step 4, analysis and characterization of sulfonated products
And (4) measuring the content of the dioxane in the non-aqueous system fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3). And (3) determining that each kilogram of the non-aqueous fatty alcohol polyoxyethylene ether triisopropanolamine sulfate product obtained in the step (3) contains 7 milligrams of dioxane.
For comparison, the main process conditions and test results are listed in table 1.
TABLE 1
Claims (9)
1. The method for preparing the non-aqueous system fatty alcohol-polyoxyethylene ether sulfate organic alcohol amine salt product comprises the following steps:
(1) reacting an organic material with a sulfonating agent in a sulfonation reactor to obtain sulfate, wherein the organic material comprises fatty alcohol-polyoxyethylene ether and an organic carbonyl compound, and the molecule of the carbonyl compound contains a carboxylic ester bond or a carboxylic amide bond;
(2) neutralizing the sulfate in a non-aqueous organic diluent by taking organic alcohol amine as a neutralizer to obtain the non-aqueous system fatty alcohol-polyoxyethylene ether sulfate organic alcohol amine salt product;
the fatty alcohol-polyoxyethylene ether conforms to the following structural formula 1:
R1(OCH2CH2)nOH, structural formula 1;
wherein R is1Selected from C8-C18 aliphatic hydrocarbon groups, n is more than 0 and less than 10;
the organic alcohol amine conforms to the structure shown as follows:
Wherein R2 is methyl or H; r3 and R4 are independently selected from H or a group represented by the following structural formula 3:
wherein R5 is H or methyl;
the carbonyl compound corresponds to the following structural formula 4:
wherein R is6Is aliphatic hydrocarbon radical of C8-C20, R7Is methyl or H, R8Is H or the following group:
wherein R is9Is H or methyl;
the ratio of organic carbonyl compound to the organic material is greater than 0 and less than 0.1 by weight.
2. The method of claim 1, wherein the non-aqueous organic diluent comprises a compound selected from the group consisting of ethanol, ethylene glycol, propylene glycol, and polyethylene glycol.
3. The process as set forth in claim 1 characterized in that the sulfonating agent is sulfur trioxide.
4. The process as set forth in claim 3 characterized in that the sulfur trioxide is used in a form diluted with a gaseous diluent.
5. The method according to claim 4, wherein the gaseous diluent is air or nitrogen.
6. The process as set forth in claim 4, characterized in that sulfur trioxide represents 0.1 to 10% by weight of the total weight of sulfur trioxide and gaseous diluent.
7. The method according to claim 1, wherein the molar ratio of the sulfonating agent to the organic material is 1.01 to 1.03.
8. The method according to claim 1, wherein the reaction temperature is 40 to 50 ℃.
9. The method of claim 1, wherein the ratio of organic carbonyl compound to organic material is greater than 0 and less than 0.009.
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