CN110903476A - Preparation method of polyoxyalkylene ether sulfate surfactant - Google Patents
Preparation method of polyoxyalkylene ether sulfate surfactant Download PDFInfo
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- CN110903476A CN110903476A CN201911366623.XA CN201911366623A CN110903476A CN 110903476 A CN110903476 A CN 110903476A CN 201911366623 A CN201911366623 A CN 201911366623A CN 110903476 A CN110903476 A CN 110903476A
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
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- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
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Abstract
The invention discloses a preparation method of a polyoxyalkylene ether sulfate surfactant, which comprises the following steps of 1) providing a polyoxyalkylene ether nonionic surfactant shown in a formula (II) and sulfamic acid; 2) reacting a polyoxyalkylene ether nonionic active agent with sulfamate in the presence of a rare earth-metal heterobinuclear complex catalyst; 3) adding water or alkali metal hydroxide aqueous solution, and separating to obtain the polyoxyalkylene ether sulfate surfactant product. Compared with the known method, the preparation method disclosed by the invention has the advantages that the reaction temperature is reduced, the reaction time is shortened, the reaction yield is improved, the dosage of urea in the conventional method can be obviously reduced, and the preparation method is more environment-friendly.
Description
Technical Field
The invention relates to a preparation method of a surfactant, and particularly relates to a preparation method of a polyoxyalkylene ether sulfate surfactant.
Background
The surfactant, as an important product of fine chemical engineering, has the name of industrial monosodium glutamate, is rapidly developed since the 50 th century in the 20 th century, is almost applied to various industries, and has important function and significance for the whole industrial economy of China. Surfactants can be classified into anionic, cationic, nonionic and amphoteric surfactants according to their ionic properties, and have different performance advantages. The polyoxyalkylene ether sulfate surfactant has the advantages of both anionic and nonionic surfactants, better solubility and stability, good compatibility, salt and temperature resistance and higher efficiency due to the structure containing both anionic and nonionic hydrophilic groups, so that the polyoxyalkylene ether sulfate surfactant is widely concerned and researched.
At present, the preparation of polyoxyalkylene ether sulfate surfactants is based on the reaction of polyoxyalkylene ether nonionic surfactants with sulfating agents. The sulfating agent mainly comprises chlorosulfonic acid, oleum, sulfur trioxide and sulfamic acid; wherein, chlorosulfonic acid and fuming sulfuric acid have active properties and fast reaction rate, but the reaction process needs to maintain high concentration, the dosage is high, and a large amount of waste acid is generated, so that equipment is corroded, and a large amount of inorganic salt is generated in the later period of neutralization, thereby influencing the product quality and being gradually eliminated. Sulfur trioxide reacts quickly, has high conversion rate, but is easy to sublimate into gas at the temperature of more than 16.8 ℃, is easy to self-polymerize at normal temperature and is difficult to control, and the patent 'production process of nonylphenol polyoxyethylene ether sulfate surfactant' (publication number: CN 10434132A) adopts a special multi-tube membrane type reactor to control the reaction and improve the product quality, but also has the problems of large reaction heat release, complex operation and difficult control. Sulfamic acid has moderate reactivity, mild reaction process, can directly generate ammonium sulfate salt, is easy to be converted into other salts, and has good product quality, so that the sulfamic acid is researched more in recent years.
However, sulfamic acid has high requirements on synthetic environment when participating in reaction, and because the sulfamic acid is decomposed to generate toxic ammonium sulfate when meeting water during the reaction and loses the sulfation, raw materials and reaction equipment are required to be fully dried before the reaction; sulfamic acid can also react with carbon dioxide in the air at a higher temperature to generate urea and fuming sulfuric acid to generate waste acid; in addition, sulfamic acid is solid, is in heterogeneous reaction, is not fully contacted with raw materials, has moderate activity, and has low reaction efficiency, high required temperature, long time, excessive sulfamic acid, aggravated decomposition of sulfamic acid at high temperature, further increased dosage and low utilization rate of raw materials. In the patent polystyrol phenol polyoxyethylene ether sulfate dispersing agent and the preparation method and application thereof (publication number: CN109400869A), sulfamic acid is used as a sulfating reagent, urea is added to inhibit the decomposition of sulfamic acid to generate fuming sulfuric acid, but the urea has large dosage and the nitrogen content is up to 46.6 percent, which is not beneficial to environmental protection, and the problems of water decomposition and heterogeneous reaction, low efficiency and the like cannot be solved.
In addition, during the reaction of the polyoxyalkylene ether with the sulfating agent, the viscosity of the reaction system rapidly increases and gradually increases as the reaction proceeds. For example, in the sulfation of polyoxyethylene lauryl ether (EO ═ 3), after a certain period of reaction time, the viscosity of the system rapidly increases from 45mpa.s to about 1500mpa.s and gradually increases, which seriously hinders the reaction, reduces the reaction rate, greatly prolongs the reaction time, and also reduces the yield, while sulfamic acid, which is a solid, is more affected. In the patent of production process of high-quality fatty alcohol-polyoxyethylene ether sulfate (publication number: CN 107915837), fatty acid and esterified derivatives thereof are added to reduce the viscosity of a reaction system, but the reduction degree is small, and the later separation is difficult, so that impurities are increased, and the product quality and the application performance are reduced.
Therefore, the preparation method of the polyoxyalkylene ether sulfate surfactant, which has the advantages of mild reaction, low requirements on synthesis conditions and equipment, simple process, energy conservation, easy control, high conversion rate and high product purity, is provided, and has very important practical significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a polyoxyalkylene ether sulfate surfactant shown as a formula I,
wherein: r is C6-C18Aliphatic hydrocarbon radical or C6-C30An aromatic hydrocarbon group; m is 0-15, n is 0-15, m + n is 2-30;
M+is H, Na+、K+、NH4 +；
The method comprises the following steps:
1) providing a polyoxyalkylene ether nonionic active agent represented by formula (II) and sulfamic acid represented by formula (III);
wherein: r is C6-C18Aliphatic hydrocarbon radical or C6-C30An aromatic hydrocarbon group; m is 0-15, n is 0-15, m + n is 2-30;
2) reacting a polyoxyalkylene ether nonionic active agent with sulfamic acid in the presence of a rare earth-metal heterobinuclear complex catalyst;
3) adding water or alkali metal hydroxide aqueous solution to obtain the polyoxyalkylene ether sulfate surfactant product.
Compared with the known method, the preparation method disclosed by the invention has the advantages that the reaction temperature is reduced, the reaction time is shortened, the reaction yield is improved, the dosage of urea in the conventional method can be obviously reduced, and the preparation method is more environment-friendly.
Detailed Description
In a preferred embodiment, the polyoxyalkylene ether sulfate surfactant is represented by the following formula (I):
wherein: r is C6-C18Aliphatic hydrocarbon radical or C6-C30An aromatic hydrocarbon group; m is 0-15, n is 0-15, m + n is 2-30;
M+is H, Na+、K+、NH4 +；
In a more preferred embodiment, C6-C18The aliphatic hydrocarbon group is preferably C10-C18An aliphatic hydrocarbon group. Specific examples include hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, decynyl, dodecylynyl, tetradecynyl, hexadecylynyl, octadecynyl, dodecylynyl, tetradecynyl, hexadecylynyl, octadecynylAn alkynyl group, a dodecadienyl group, a tetradecadidienyl group, a hexadecadidienyl group, an octadecadienyl group, or a combination thereof.
In a particularly preferred embodiment, C6-C18Specific examples of aliphatic hydrocarbon groups include octyl, decyl, dodecyl, hexadecyl, octadecyl, or combinations thereof.
In a more preferred embodiment, C6-C30The aromatic hydrocarbon group is preferably C12-C30An aromatic hydrocarbon group. C6-C30Specific examples of the aromatic hydrocarbon group include a phenyl group, an aliphatic alkylphenyl group, an aliphatic alkenylphenyl group, an aliphatic alkynylphenyl group, a naphthyl group, a biphenyl group, a phenethylphenyl group, a diphenylethylphenyl group, or a triphenylethylphenyl group.
In a particularly preferred embodiment, C6-C30Examples of the aromatic hydrocarbon group include C15Alkenylphenyl or triphenylethylphenyl.
In a more preferred embodiment, M is 1-15, n is 1-15, M + n is 2-25, M+Is NH4 +Or Na+。
In a particularly preferred embodiment, M is 2 to 10, n is 3 to 12, M + n is 5 to 22, M+Is NH4 +Or Na+。
In a particularly preferred embodiment, specific examples of the polyoxyalkylene ether sulfate include polyoxyethylene ether sulfate, polyoxypropylene ether sulfate, polyoxyethylene oxypropylene ether sulfate.
In a preferred embodiment, the polyoxyalkylene ether nonionic active agent has the structure shown in formula (II);
wherein: r is C6-C18Aliphatic hydrocarbon radical or C6-C30An aromatic hydrocarbon group; m is 0-15, n is 0-15, m + n is 2-30;
in a more preferred embodiment, C6-C18An aliphatic hydrocarbon group,C6-C30The preferred ranges of the aromatic hydrocarbon group, m, n and m + n are the same as those in the formula (I).
In a particularly preferred embodiment, specific examples of the polyoxyalkylene ether nonionic active agent include polyoxyethylene ether nonionic active agents, polyoxypropylene ether nonionic active agents, polyoxyethylene oxypropylene ether nonionic active agents.
In a preferred embodiment, the sulfamic acid is represented by the following formula (III):
in a preferred embodiment, the molar ratio of the polyoxyalkylene ether nonionic active agent to sulfamic acid is: 1:1-1: 1.5, preferably 1:1 to 1: 1.3.
In a preferred embodiment, the reaction of the polyoxyalkylene ether nonionic active agent with sulfamic acid is carried out at a temperature of from 70 to 120 ℃, preferably at a temperature of from 70 to 105 ℃, more preferably at a temperature of from 75 to 100 ℃.
In a preferred embodiment, the reaction of the polyoxyalkylene ether nonionic surfactant and sulfamic acid is carried out in the presence of a rare earth-metal heterodinuclear complex catalyst.
In a more preferred embodiment, the rare earth-metal heterobinuclear complex catalyst is a lanthanide-zinc heterobinuclear complex.
In a more preferred embodiment, the lanthanide-zinc heterobinuclear complex is selected from europium-zinc heterobinuclear complexes, terbium-zinc heterobinuclear complexes, or combinations thereof.
In a particularly preferred embodiment, the lanthanide-zinc heterobinuclear complex is selected from: Zn-Eu (ALPHA) (acac)3、Zn-Eu(NO3)3(L1)2、Zn-Tb(L2)2(NO3)3Py, wherein ALPHA represents N, N-bis (salicylidene) ethylenediamine, Acac represents acetylacetone group, and L is1Represents 2- [2- (4-benzoic acid) ethenyl]-8-hydroxyQuinolines, L2Represents (2-hydroxy-3-methoxyphenyl) benzimidazole, and Py represents pyridine.
In a more preferred embodiment, the rare earth-metal heterodinuclear complex catalyst is used in an amount of: 0.5 to 3% by weight, preferably 0.5 to 2% by weight, based on the total weight of polyoxyalkylene ether and sulfamic acid.
In a preferred embodiment, a diluent, preferably a fluorocarbon inert liquid, may also be added in step 2).
In a more preferred embodiment, the fluorocarbon inert liquid is selected from the group consisting of: one or more of perfluoronaphthalene, perfluorodecalin, perfluoromethyldecalin, perfluorotributylamine, perfluorotripentylamine and fluorinated polyether.
In a particularly preferred embodiment, the diluent is used in an amount such as: 0 to 6% by weight, preferably 0.1 to 6% by weight, more preferably 4 to 6% by weight, based on the total weight of polyoxyalkylene ether and sulfamic acid.
In a preferred embodiment, a stabilizer, such as urea, an azocyclic compound or a mixture thereof, preferably an azocyclic compound, such as one or more of N-methylpyrrolidone, N-ethylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and 1, 3-dimethyl-tetrahydro-2-pyrimidinone, may also be added in step 2).
In a particularly preferred embodiment, the stabilizers are used in amounts such as: 0 to 2% by weight, preferably 0.1 to 1.5% by weight, more preferably 0.5 to 1.2% by weight, based on the total weight of polyoxyalkylene ether and sulfamic acid.
In a preferred embodiment, an adsorbent can also be added in step 2). The adsorbent is used for adsorbing water generated in a reaction kettle, raw materials and a reaction process. The adsorbent is preferably a microporous molecular sieve adsorbent, and preferably one or more of a 4A type molecular sieve and a 5A type molecular sieve.
In a particularly preferred embodiment, the adsorbent is used in an amount such as: 0 to 1% by weight, preferably 0.1 to 1% by weight, more preferably 0.5 to 1% by weight, based on the total weight of polyoxyalkylene ether and sulfamic acid.
In a particularly preferred embodiment, the process for the preparation of the polyoxyalkylene ether sulfate according to the present invention comprises the steps of:
1) sequentially adding a polyoxy alkenyl ether nonionic active agent shown in the formula (II) and optional diluent and adsorbent into a reaction kettle, stirring at room temperature for 5-30 minutes, and then stirring and heating to 50-70 ℃;
2) adding optional stabilizer, stirring for 5-20 min under heat preservation, adding rare earth-metal heterobinuclear complex catalyst and sulfamic acid, and stirring for 5-35 min under heat preservation;
3) heating to 70-120 ℃, keeping the temperature and stirring for 1.5-3.5h, cooling to 25-60 ℃, adding water and an alkali metal hydroxide aqueous solution, stirring for 10-30 min, cooling to room temperature, and finishing the reaction;
4) filtering and centrifuging to separate out the diluent and the adsorbent, thus obtaining the polyoxyalkylene ether sulfate surfactant product.
In a particularly preferred embodiment, the alkali metal hydroxide is, for example, sodium hydroxide, potassium hydroxide or a mixture thereof.
In a particularly preferred embodiment, the polyoxyalkylene ether sulfate surfactant product is, for example, a polyoxyalkylene ether sulfate surfactant, a polyoxyalkylene ether sulfate sodium salt surfactant, a polyoxyalkylene ether sulfate potassium salt surfactant, a polyoxyalkylene ether sulfate ammonium salt surfactant, or mixtures thereof.
The originality of the preparation method of the polyoxyalkylene ether sulfate surfactant is shown in the following aspects: 1) according to the invention, the rare earth-metal heterobinuclear complex is used as a catalyst, so that the activation energy required by the reaction is reduced, the reaction is easier to carry out, the reaction temperature is reduced, the raw material decomposition is reduced, and the yield is improved; 2) the introduced diluent can obviously reduce the viscosity of a reaction system, increase the contact reaction among raw materials, facilitate the full reaction, shorten the reaction time and improve the reaction efficiency and yield; 3) the addition of the adsorbent and the stabilizer avoids sulfamic acid decomposition caused by moisture and carbon dioxide, improves the utilization rate of raw materials and solves the problem of harsh reaction conditions; 4) the preparation method provided by the invention has the advantages of low reaction temperature, short time, high yield, mild reaction, simple process, low requirements on synthesis conditions and equipment, energy conservation and easy control.
Compared with the conventional method, the preparation method of the polyoxyalkylene ether sulfate can reduce the reaction temperature by about 20 ℃, save the time by about 1.5h and ensure that the synthesis condition is milder; the dosage of urea in the conventional method can be obviously reduced, and the method is more environment-friendly; in the synthesis process, decomposition of sulfamic acid caused by moisture and carbon dioxide is avoided, the utilization rate of raw materials is improved, the process is simple, the operation is convenient, and the requirements on synthesis conditions and equipment are low; and the viscosity of a reaction system can be effectively reduced, so that the reaction is rapidly and fully carried out, the conversion rate of the polyoxyalkylene ether nonionic surfactant is improved by about 25 percent, and the method is far better than the conventional method on the whole.
Examples
The present invention will be described in detail and specifically with reference to the following examples to facilitate better understanding of the present invention, but the following examples do not limit the scope of the present invention.
By adopting the preparation method, the method for measuring the performance of the prepared sample comprises the following steps:
1) and (3) viscosity measurement:
the viscosity is determined according to GB/T5561-2012 method for determining viscosity and flow properties by using a viscometer through rotation of surfactants, and the smaller the viscosity value is, the better the fluidity is, and the easier the operation is.
2) Determination of the yield:
according to GB/T5173-2018 direct two-phase titration method for measuring surface active agent and detergent anion active matter, the content (mmol/g) of the polyoxyalkylene ether sulfate surface active agent in the product is calculated according to the formula (a):
examples
Comparative example 1
Adding 119.0g (0.10mol) of triphenylethylphenol polyoxypropylene ether polyoxyethylene ether (PO-9, EO-6) into a four-neck flask, stirring at room temperature for 10min, heating to 70 ℃, adding 7.78g (6.0%) of urea and 10.7g (0.11mol) of sulfamic acid respectively, stirring at constant temperature for 25min, continuing heating to 115 ℃, stirring at constant temperature for 4.0h, cooling to 60 ℃, adding 18.1g of water, stirring for 20min, and cooling to room temperature; 153.2g of a reddish brown viscous liquid was obtained (sampling test, content of triphenylethylphenol polyoxypropylene ether polyoxyethylene ether sulfate: 0.48 mmol/g).
Example 1
119.0g (0.10mol) of triphenylethylphenol polyoxypropylene ether polyoxyethylene ether (PO 9, EO 6) was added to a four-necked flask, the mixture was stirred at room temperature for 10min, the temperature was raised to 70 ℃, and Zn-Eu (ALPHA) (acac) was added thereto31.95g (1.5%), 1.94g (1.5%) of urea and 10.7g (0.11mol) of sulfamic acid, keeping the temperature and stirring for 25min, continuing to heat to 95 ℃, keeping the temperature and stirring for 4.0h, then cooling to 70 ℃, adding 18.1g of water, stirring for 20min, and then cooling to room temperature to obtain 150.2g of yellow-brown viscous liquid (the content of triphenylethylphenol polyoxypropylene ether polyoxyethylene ether sulfate is 0.60mmol/g by sampling test).
Example 2
119.0g (0.10mol) of triphenylethylphenol polyoxypropylene ether polyoxyethylene ether (PO 9, EO 6) was added to a four-necked flask, the mixture was stirred at room temperature for 10min, the temperature was raised to 70 ℃, and Zn-Tb (L) was added thereto2)2(NO3)31.55g of Py (1.2%), 1.94g of urea (1.5%) and 10.7g of sulfamic acid (0.11mol), keeping the temperature and stirring for 25min, continuously heating to 95 ℃, keeping the temperature and stirring for 4.0h, then cooling to 60 ℃, adding 18.1g of water, stirring for 20min, and cooling to room temperature; 149.1g of a yellow-brown viscous liquid was obtained (sampling test, content of sulfate salt of triphenylethylphenol polyoxypropylene ether polyoxyethylene ether: 0.60 mmol/g).
Example 3
119.0g (0.10mol) of triphenylethylphenol polyoxypropylene ether polyoxyethylene ether (PO. RTM.9, EO. RTM.6) and fluorinated polyether E were sequentially added to a four-necked flask47.1g (5.5%), stirring at room temperature for 10min, heating to 70 ℃, adding 7.78g (6.0%) of urea and 10.7g (0.11mol) of sulfamic acid respectively, stirring at the constant temperature for 25min, continuing to heat to 115 ℃, keeping the temperature and stirring for 2.5h, then cooling to 60 ℃, adding 18.1g of water, stirring for 20min, and then cooling to room temperature; 161.4g of yellow brown liquid is obtained (sampling test, the content of the triphenylethylphenol polyoxypropylene ether polyoxyethylene ether ammonium sulfate salt is 0.51 mmol/g); filtering, and centrifuging to obtain yellow brown extremely viscous liquid.
Example 4
119.0g (0.10mol) of triphenylethylphenol polyoxypropylene ether polyoxyethylene ether (PO 9, EO 6) and 7.1g (5.5 mol) of perfluoromethyldecalin were sequentially added to a four-necked flask, stirred at room temperature for 10min, heated to 70 ℃, and added with Zn-Eu (NO: 6) respectively3)3(L1)21.68g (1.3%), 1.94g (1.5%) of urea and 10.7g (0.11mol) of sulfamic acid, keeping the temperature and stirring for 25min, continuously heating to 95 ℃, keeping the temperature and stirring for 2.5h, then cooling to 60 ℃, adding 18.1g of water, stirring for 20min, and then cooling to room temperature; 157.7g of yellow brown liquid is obtained (sampling test, the content of triphenylethylphenol polyoxypropylene ether polyoxyethylene ether sulfate is 0.59 mmol/g); filtering and centrifuging to obtain yellow-brown extremely viscous liquid.
Example 5
119.0g (0.10mol) of triphenylethylphenol polyoxypropylene ether polyoxyethylene ether (PO. RTM.9, EO. RTM.6) and fluorinated polyether E were sequentially added to a four-necked flask45.8g (4.5%), stirring at room temperature for 10min, heating to 70 deg.C, adding Zn-Tb (L)2)2(NO3)31.30g (1.0%) of Py, 1.30g (1.0%) of stabilizer 1, 3-dimethyl-2-imidazolidinone, 10.7g (0.11mol) of sulfamic acid, keeping the temperature and stirring for 25min, continuously heating to 95 ℃, keeping the temperature and stirring for 2.5h, cooling to 60 ℃, adding 18.1g of water, stirring for 20min, and cooling to room temperature; 155.7g of yellow-brown liquid is obtained (sampling test, the content of the triphenylethylphenol polyoxypropylene ether polyoxyethylene ether sulfate is 0.61 mmol/g); filtering and centrifuging to obtain yellow-brown extremely viscous liquid.
Example 6
119.0g (0.10mol) of triphenylethylphenol polyoxypropylene ether polyoxyethylene ether (PO ═ 9, EO ═ 6), 5.2g (4.0%) of perfluorotripentylamine, 0.78g (0.6%) of 5A molecular sieve, and a four-necked flask were placed in this orderStirring for 10min, heating to 70 deg.C, and adding Zn-Eu (NO) respectively3)3(L1)21.43g (1.1%) of 1, 3-dimethyl-tetrahydro-2-pyrimidone and 1.04g (0.8%) of sulfamic acid, 10.7g (0.11mol) of sulfamic acid, keeping the temperature and stirring for 25min, continuously heating to 95 ℃, keeping the temperature and stirring for 2.5h, cooling to 60 ℃, adding 18.1g of water, stirring for 20min, and cooling to room temperature; 155.6g of yellow-brown liquid is obtained (sampling test, the content of the triphenylethylphenol polyoxypropylene ether polyoxyethylene ether sulfate is 0.62 mmol/g); filtering and centrifuging to obtain yellow-brown extremely viscous liquid.
The examples and comparative examples were compared in performance tests, as shown in Table 1
TABLE 1 comparison of the results of measurements of product properties
From the test results of the examples and comparative examples in table 1, it can be seen that: compared with a comparative example (a conventional method), the preparation method of the polyoxyalkylene ether sulfate provided by the invention has the advantages that the reaction temperature can be reduced by 20 ℃, the reaction time is shortened by 1.5h (37.5%), and the synthesis condition is milder; the dosage of urea in the conventional method can be obviously reduced (6%), so that the method is more environment-friendly; in the synthesis process, the viscosity of the reaction system is obviously reduced, the operation is more convenient, the reaction is rapidly and fully carried out, the utilization rate of raw materials is obviously improved, the yield of the polyoxyalkylene ether nonionic surfactant is improved by about 25 percent, and the method is far better than that of a comparative example (a conventional method) on the whole.
Example 7
In a four-neck flask, 95.7g (0.3mol) of polyoxyethylene lauryl ether (EO ═ 3), 6.86g (5.5%) of perfluoromethyldecalin, 0.75g (0.6%) of 5A molecular sieve were sequentially added, and the mixture was stirred at room temperature for 10min, warmed to 50 ℃, added with 0.87g (0.7%) of N-methylpyrrolidone, stirred for 5min, and then added with Zn-Eu (ALPHA) (Acac)31.0g (0.8%) of sulfamic acid and 29.1g (0.3mol) of sulfamic acid, keeping the temperature and stirring for 15min, and continuing to stirHeating to 75 ℃, keeping the temperature and stirring for 2h, cooling to 40 ℃, adding 24g of 50% sodium hydroxide aqueous solution, stirring for 40min, and cooling to room temperature; 152.4g of white liquid is obtained (sampling test shows that the content of the sodium laureth sulfate is 1.89 mmol/g); filtering, centrifuging and separating to obtain white viscous paste product.
Comparative example 2
Adding 95.7g (0.3mol) of lauryl alcohol polyoxyethylene ether (EO & lt3 & gt) into a four-neck flask, stirring for 10min at room temperature, heating to 50 ℃, adding 6.24gg (5%) of urea and 29.1g (0.3mol) of sulfamic acid, keeping the temperature and stirring for 15min, continuing heating to 95 ℃, keeping the temperature and stirring for 3h, cooling to 40 ℃, adding 24g of 50% sodium hydroxide aqueous solution, stirring for 40min, and cooling to room temperature; 148.5g of a yellow viscous pasty product are obtained (sampling test, the content of sodium laureth sulfate is 1.44 mmol/g).
Example 8
In a four-neck flask, 104.5g (0.15mol) of cardanol polyoxyethylene ether (EO ═ 9), 4.9g (4.0%) of perfluorotripentylamine, and 1.1g (0.9%) of 5A molecular sieve were sequentially added, and the mixture was stirred at room temperature for 15min, heated to 60 ℃, 1.34g (1.1%) of 1, 3-dimethyl-tetrahydro-2-pyrimidinone was added, and after stirring for 10min, Zn-Tb (L-Tb) was added, respectively2)2(NO3)31.2g of Py (1.0%) and 17.5g of sulfamic acid (0.18mol), keeping the temperature and stirring for 20min, continuously heating to 80 ℃, keeping the temperature and stirring for 2h, cooling to 50 ℃, adding 17g of water, stirring for 30min, and cooling to room temperature; 146.8g of red brown liquid is obtained (sampling test shows that the content of the cardanol polyoxyethylene ether sodium sulfate is 0.97 mmol/g); filtering and centrifuging to obtain reddish brown extremely viscous liquid.
Comparative example 3
Adding 104.5g (0.15mol) of cardanol polyoxyethylene ether (EO ═ 9) into a four-neck flask, stirring for 10min at room temperature, heating to 60 ℃, adding 6.1g (5%) of urea and 17.5g (0.18mol) of sulfamic acid respectively, keeping the temperature and stirring for 20min, continuing heating to 95 ℃, keeping the temperature and stirring for 3h, cooling to 50 ℃, adding 17g of water, stirring for 30min, and cooling to room temperature; 144.2g of a reddish brown highly viscous liquid was obtained (sampled and tested, the content of cardanol polyoxyethylene ether sulfate was 0.71 mmol/g).
Table 2 comparison of results of measurements of product properties
Claims (10)
1. A preparation method of polyoxy alkenyl ether sulfate surfactant shown as formula I,
wherein: r is C6-C18Aliphatic hydrocarbon radical or C6-C30An aromatic hydrocarbon group; m is 0-15, n is 0-15, m + n is 2-30;
M+is H, Na+、K+、NH4 +；
The method comprises the following steps:
1) providing a polyoxyalkylene ether nonionic active agent represented by formula (II) and sulfamic acid represented by formula (III);
wherein: r is C6-C18Aliphatic hydrocarbon radical or C6-C30An aromatic hydrocarbon group; m is 0-155, n is 0-15, m + n is 2-30;
2) reacting a polyoxyalkylene ether nonionic active agent with sulfamic acid in the presence of a rare earth-metal heterobinuclear complex catalyst;
3) adding water and alkali metal hydroxide aqueous solution to obtain the polyoxyalkylene ether sulfate surfactant product.
2. The method of preparing a polyoxyalkylene ether sulfate surfactant according to claim 1, wherein the molar ratio of the polyoxyalkylene ether nonionic active agent to the sulfamic acid is: 1:1-1: 1.5.
3. the method of claim 1, wherein the rare earth-metal heterobinuclear complex catalyst is a lanthanide-zinc heterobinuclear complex.
4. The method of preparing a polyoxyalkylene ether sulfate surfactant according to claim 3, wherein the lanthanide-zinc heterobinuclear complex is selected from the group consisting of: Zn-Eu (ALPHA) (acac)3、Zn-Eu(NO3)3(L1)2、Zn-Tb(L2)2(NO3)3Py, wherein ALPHA represents N, N-bis (salicylidene) ethylenediamine, Acac represents acetylacetone group, and L is1Represents 2- [2- (4-benzoic acid) ethenyl]-8-hydroxyquinoline, L2Represents (2-hydroxy-3-methoxyphenyl) benzimidazole, and Py represents pyridine.
5. The method for preparing polyoxyalkylene ether sulfate surfactant according to claim 1, wherein the amount of the rare earth-metal heterobinuclear complex catalyst is: 0.5 to 3% by weight, based on the total weight of polyoxyalkylene ether and sulfamic acid.
6. The method of claim 1, wherein a diluent is further added in step 2), wherein the diluent is a fluorocarbon inert liquid.
7. The method of claim 6 wherein said fluorocarbon inert liquid is selected from the group consisting of: one or more of perfluoronaphthalene, perfluorodecalin, perfluoromethyldecalin, perfluorotributylamine, perfluorotripentylamine and fluorinated polyether.
8. The method of claim 6, wherein the diluent is present in an amount of: 0-6 wt.%, based on the total weight of polyoxyalkylene ether and sulfamic acid.
9. The method for preparing polyoxyalkylene ether sulfate surfactant according to claim 1, wherein a stabilizer is further added in step 2), wherein the stabilizer is one or more of nitrogen heterocyclic ketone compounds, preferably N-methyl pyrrolidone, N-ethyl pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and 1, 3-dimethyl-tetrahydro-2-pyrimidinone.
10. The method for preparing the polyoxyalkylene ether sulfate surfactant according to claim 1, wherein an adsorbent is further added in the step 2), wherein the adsorbent is a microporous molecular sieve adsorbent, preferably one or more of a 4A type molecular sieve and a 5A type molecular sieve.
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