CN113354804A - Fatty alcohol polyoxypropylene ether oxyacid and salt thereof - Google Patents

Fatty alcohol polyoxypropylene ether oxyacid and salt thereof Download PDF

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CN113354804A
CN113354804A CN202011641507.7A CN202011641507A CN113354804A CN 113354804 A CN113354804 A CN 113354804A CN 202011641507 A CN202011641507 A CN 202011641507A CN 113354804 A CN113354804 A CN 113354804A
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fatty alcohol
polyoxypropylene ether
oxyacid
salt
propylene oxide
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CN113354804B (en
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吕明
李禹羲
孟春瑜
张艺晓
尹晓杰
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Shandong Jinzhirui New Material Technology Co ltd
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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
    • C08G65/26—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 from cyclic ethers and other compounds
    • C08G65/2603—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 from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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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
    • C08G65/26—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 from cyclic ethers and other compounds
    • C08G65/2642—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 from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
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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
    • C08G65/26—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 from cyclic ethers and other compounds
    • C08G65/2696—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 from cyclic ethers and other compounds characterised by the process or apparatus used
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Abstract

The invention provides fatty alcohol-polyoxypropylene ether oxyacid or salt thereof and a preparation method thereof, which can greatly reduce irritation and harmful substances in a final product, effectively control the polymerization process of propylene oxide and obtain narrowly distributed fatty alcohol-polyoxypropylene ether oxyacid or salt products thereof, such as fatty alcohol-polyoxypropylene ether sulfate, fatty alcohol-polyoxypropylene ether carbonate, fatty alcohol-polyoxypropylene ether phosphate and the like, so that the quality of the fatty alcohol-polyoxypropylene ether oxyacid or salt thereof is greatly improved, and the fatty alcohol-polyoxypropylene ether oxyacid or salt thereof has great advantages in application.

Description

Fatty alcohol polyoxypropylene ether oxyacid and salt thereof
Technical Field
The invention belongs to the technical field of high molecular surfactants, and particularly relates to fatty alcohol polyoxypropylene ether oxyacid or salt thereof and a related preparation method.
Background
The fatty alcohol ether oxysalt is a novel anionic surfactant, and has wide application in the fields of cosmetics, detergents, biochemistry, pharmacy, food processing, crude oil demulsification, thickened oil viscosity reduction and the like due to the special property of the fatty alcohol ether oxysalt. The multifunctional 'green surfactant' with the characteristics of low surface tension, low toxicity, easy biodegradation and the like is modified by a nonionic surfactant.
At present, the fatty alcohol ether oxysalt surfactant is systematically researched abroad, and is produced in series in batches, while the fatty alcohol ether oxysalt surfactant is trial-sold in China, but the fatty alcohol ether oxysalt surfactant has less varieties and yield and is still in the beginning stage. The fatty alcohol polyoxyethylene ether carboxylate is one of the most widely used fatty alcohol ether oxysalts. It is similar in chemical structure to soap except that an ethylene oxide chain having a certain addition number is added between a hydrophobic group and a hydrophilic group, thereby imparting many excellent properties of anionic and nonionic surfactants. The surface characteristics of the product can be adjusted by changing the length, addition number and pH value of the carbon chain, wherein the acid product is nonionic in nature, and the salt product which is completely neutralized is anionic in nature.
The surfactant is a mixture with various and complicated components, and the molecular weight distribution index of the surfactant is generally wide, so that the performance and the quality of a product cannot meet the use requirement. The oligomerization degree of propylene oxide (PPO) is diversified, and the catalytic polymerization modes of the PPO are mainly cationic polymerization, anionic polymerization and phosphazene organic nonmetal basic catalysts. The cationic polymerization process is not easy to control, the molecular weight is low, the byproducts are more and the like, and the anionic polymerization reaction has the advantages of mild reaction, easy process control and low catalyst cost. However, the disadvantages are also particularly pronounced, such as the easy transfer of the active centers, the low molecular weight of the polymers obtained, the broad molecular weight distribution and the high degree of unsaturation.
Therefore, a fatty alcohol ether oxysalt surfactant with narrow molecular weight distribution, high safety and excellent quality is needed to meet the requirement of practical application.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies, and obtained a class of narrow-distribution fatty alcohol polyoxypropylene ether oxyacids and salts thereof by using fatty alcohols to initiate propylene oxide polymerization, using N-heterocyclic carbenes and N-heterocyclic carbenes as catalysts, and controlling the synthesis conditions, thereby greatly improving the product quality, and thus completed the present invention.
The invention aims at providing fatty alcohol polyoxypropylene ether oxyacid or salt thereof, which is prepared by taking propylene oxide as a raw material, taking fatty alcohol as an initiator and adding an end-capping reagent, wherein the molecular structure of the fatty alcohol polyoxypropylene ether oxyacid comprises a structural part shown as a formula (I):
Figure BDA0002879999540000011
wherein R is1Selected from hydrogen atoms or straight-chain alkyl groups, preferably from hydrogen atoms or C1-C10The linear alkyl group of (1); r2Selected from linear alkyl groups, preferably from C1-C18The linear alkyl group of (1); g is an end group selected from ionic oxyacid group; n is 1 to 15. The ionic oxoacid group is an oxoacid group that ionizes hydrogen ions.
The molecular weight distribution index of the fatty alcohol polyoxypropylene ether oxyacid or the salt thereof is 1.05-2.5.
The second aspect of the present invention is to provide a method for preparing fatty alcohol polyoxypropylene ether oxyacid or a salt thereof, wherein propylene oxide is used as a raw material, fatty alcohol is used as an initiator, and an end-capping agent is added to prepare the narrowly distributed fatty alcohol polyoxypropylene ether oxyacid or the salt thereof, specifically comprising the following steps:
step 1, adding fatty alcohol into propylene oxide, and heating for reaction to obtain an intermediate reaction solution;
step 2, adding an end-capping reagent into the intermediate reaction liquid, and reacting to obtain a mixed liquid containing fatty alcohol-polyoxypropylene ether oxyacid;
optionally, further comprising step 2': adding metal hydroxide or oxide into the mixed solution to obtain neutral mixed solution;
and 3, post-treating the mixed solution or the neutral mixed solution containing the fatty alcohol-polyoxypropylene ether oxyacid to obtain the fatty alcohol-polyoxypropylene ether oxyacid or the salt thereof.
The third aspect of the invention aims to provide a preparation method of fatty alcohol polyoxypropylene ether with narrow distribution for preparing fatty alcohol polyoxypropylene ether oxyacid or salt thereof, wherein fatty alcohol is added into propylene oxide, heating and reacting are carried out to obtain intermediate reaction liquid, and the intermediate reaction liquid is purified to prepare the obtained fatty alcohol polyoxypropylene ether. The purification treatment comprises extraction.
The fatty alcohol polyoxypropylene ether oxyacid, the salt thereof and the preparation method provided by the invention have the following beneficial effects:
(1) compared with the conventional product, the fatty alcohol polyoxypropylene ether oxyacid or the salt thereof prepared by the method has the advantages of greatly narrowing the molecular weight distribution, high purity and effectively improved performance.
(2) The fatty alcohol polyoxypropylene ether oxyacid or the salt thereof provided by the invention has low content of free fatty alcohol alkyd products, hardly contains fatty alcohol ether acidification products with high polymerization degree, greatly reduces the irritation and harmful substance content of final products, effectively improves the product quality, and can be applied to the field with high quality requirements.
(3) The preparation method of the fatty alcohol polyoxypropylene ether oxyacid and the salt thereof provided by the invention can effectively control the polymerization process of propylene oxide, obtain the narrow-distribution fatty alcohol polyoxypropylene ether, reduce the adductive compounds in the product and improve the product purity.
(4) The preparation method of the invention adopts a solvent-free or high-concentration system to carry out synthesis reaction, avoids using various organic solvents to cause environmental pollution and realizes green synthesis.
(5) The invention provides a plurality of oxyacids or salts thereof of fatty alcohol polyoxypropylene ether, which enlarges the application range of the product, and simultaneously, the improvement of the product purity can reduce the harm to animals, plants and environment.
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FIG. 1 shows a nuclear magnetic resonance test chart of tetradecanol polyoxypropylene ether sulfuric acid prepared in example 1 of the present invention;
FIG. 2 is a graph showing the molecular weight distribution index of tetradecanol polyoxypropylene ether sulfuric acid obtained in example 1 of the present invention;
FIG. 3 shows a NMR test chart of 2-methyl-1-tridecanol polyoxypropylene ether sulfuric acid obtained in example 2 of the present invention;
FIG. 4 shows a NMR test chart of 2-ethyl-1-dodecanol polyoxypropylene ether sulfuric acid prepared in example 3 of the present invention;
FIG. 5 shows a NMR test chart of 2-propyl-1-undecanol polyoxypropylene ether sulfuric acid obtained in example 4 of the present invention;
FIG. 6 shows a NMR test chart of 2-butyl-1-decanol polyoxypropylene ether sulfuric acid obtained in example 5 of the present invention;
FIG. 7 shows a NMR test chart of 2-pentyl-1-nonanol polyoxypropylene ether sulfuric acid obtained in example 6 of the present invention;
FIG. 8 shows a nuclear magnetic resonance test chart of 2-hexyl-1-octanol polyoxypropylene ether sulfuric acid prepared in example 7 of the present invention;
FIG. 9 shows a nuclear magnetic resonance test chart of 2-butyl-1-octanol polyoxypropylene ether sulfuric acid prepared in example 8 of the present invention;
FIG. 10 shows a nuclear magnetic resonance test chart of 2-butyl-1-octanol polyoxypropylene ether sulfuric acid prepared in example 9 of the present invention;
FIG. 11 is a nuclear magnetic resonance test chart of 2-butyl-1-octanol polyoxypropylene ether sulfuric acid prepared in example 10 of the present invention;
FIG. 12 shows a nuclear magnetic resonance test chart of 2-butyl-1-octanol polyoxypropylene ether sulfuric acid prepared in example 11 of the present invention;
FIG. 13 shows a nuclear magnetic resonance test chart of 2-butyl-1-octanol polyoxypropylene ether sulfuric acid prepared in example 12 of the present invention;
FIG. 14 shows a nuclear magnetic resonance test chart of 2-butyl-1-octanol polyoxypropylene ether sulfuric acid prepared in example 13 of the present invention;
FIG. 15 shows a nuclear magnetic resonance test chart of 2-butyl-1-octanol polyoxypropylene ether sulfuric acid prepared in example 14 of the present invention;
FIG. 16 shows a nuclear magnetic resonance test chart of 2-butyl-1-octanol polyoxypropylene ether carbonic acid prepared in example 15 of the present invention;
FIG. 17 is a nuclear magnetic resonance test chart of 2-butyl-1-octanol polyoxypropylene ether carbonic acid prepared in example 16 of the present invention;
FIG. 18 shows a NMR test chart of 2-butyl-1-octanol polyoxypropylene ether phosphonic acid prepared in example 17 of the present invention;
FIG. 19 shows a nuclear magnetic resonance test chart of 2-butyl-1-octanol polyoxypropylene ether phosphonic acid prepared in example 18 of the present invention.
Detailed Description
The present invention will now be described in detail by way of specific embodiments, and features and advantages of the present invention will become more apparent and apparent from the following description.
The invention provides the fatty alcohol polyoxypropylene ether oxyacid with narrow distribution or the salt thereof, and the preparation method can greatly reduce the content of free fatty alcohol and the acidification product of fatty alcohol ether with high polymerization degree in the final product, thereby obtaining the fatty alcohol polyoxypropylene ether oxyacid with less irritation and higher safety or the salt thereof.
The invention provides fatty alcohol polyoxypropylene ether oxyacid or salt thereof, namely fatty alcohol polyoxypropylene ether oxyacid or fatty alcohol polyoxypropylene ether oxyacid salt, which is a surfactant containing polyoxypropylene groups, is prepared by taking propylene oxide as a raw material, taking fatty alcohol as an initiator and adding an end capping agent, and has a molecular structure comprising a structural part shown as a formula (I):
Figure BDA0002879999540000041
wherein R is1Selected from hydrogen atoms or straight-chain alkyl groups, preferably from hydrogen atoms or C1-C10More preferably a hydrogen atom or C1-C8The linear alkyl group of (1); r2Selected from linear alkyl groups, preferably from C1-C18More preferably C1-C15The linear alkyl group of (1); g is an end group selected from ionic oxyacid group, preferably one selected from ionized carboxyl, sulfonic acid, phosphoric acid or carbonic acid group; n is 1 to 15, preferably 3 to 12, more preferably 4 to 10. The ionic oxoacid group is an oxoacid group that ionizes hydrogen ions.
Preferably, the fatty alcohol polyoxypropylene ether oxy acid or salt thereof comprises one of the following moieties:
Figure BDA0002879999540000042
for example, the fatty alcohol-polyoxypropylene ether oxo acid or salt thereof is fatty alcohol-polyoxypropylene ether sulfuric acid, fatty alcohol-polyoxypropylene ether sulfate, fatty alcohol-polyoxypropylene ether carbonic acid, fatty alcohol-polyoxypropylene ether carbonate, fatty alcohol-polyoxypropylene ether phosphoric acid or fatty alcohol-polyoxypropylene ether phosphate.
The fatty alcohol polyoxypropylene ether oxyacid or the salt thereof is in an acid form or a salt form. Under an acidic environment, the fatty alcohol polyoxypropylene ether oxyacid ionizes hydrogen ions, is in an acid form and is represented as a nonionic surfactant; after the fatty alcohol polyoxypropylene ether oxyacid reacts with metal hydroxide or oxide, the product is in a salt form and is represented as an anionic surfactant in a completely neutralized environment, namely a neutral or alkaline environment.
The molecular weight distribution index of the fatty alcohol polyoxypropylene ether oxyacid or the salt thereof is 1.05-2.5, preferably 1.15-2, and more preferably 1.20-1.55.
The fatty alcohol polyoxypropylene ether oxyacid is fatty alcohol ether prepared by the addition reaction of fatty alcohol and propylene oxide, and is obtained by acidification. Fatty alcohol polyoxypropylene ether oxyacid reacts with metal hydroxide or oxide to obtain fatty alcohol polyoxypropylene ether oxyacid salt.
Conventional fatty alcohol ethers are not single adduct reaction products, wherein propylene oxide adduct number is the average adduct number, and generally have a broad molecular weight distribution of the polymer, resulting in a higher content of free fatty alcohol alkyd products, which are more irritating to the skin, and contain a certain amount of fatty alcohol ether having a high degree of polymerization, which also produces harmful impurities during the acidification process. The addition is the number of moles of propoxy groups bound per mole of fatty alcohol.
The fatty alcohol polyoxypropylene ether oxyacid or the salt thereof prepared by the method has narrow molecular weight distribution, wherein the contents of free fatty alcohol acidification products and fatty alcohol ether acidification products with high polymerization degree are very low, and the prepared fatty alcohol polyoxypropylene ether oxyacid or the salt thereof has small irritation and is safer, so that the fatty alcohol polyoxypropylene ether oxyacid or the salt thereof is greatly improved in quality as an upgraded product and has great advantages in application.
The invention also provides a preparation method of the fatty alcohol polyoxypropylene ether oxyacid or the salt thereof, the method takes propylene oxide as a raw material, fatty alcohol as an initiator and an end-capping reagent as well as the initiator to react, and the narrowly distributed fatty alcohol polyoxypropylene ether oxyacid or the salt thereof is prepared and specifically comprises the following steps:
step 1, adding fatty alcohol into propylene oxide, and heating for reaction to obtain an intermediate reaction solution.
The fatty alcohol is selected from saturated monoalcohols, preferably from saturated linear monoalcohols or saturated branched monoalcohols, more preferably saturated monoalcohols having the following structure:
Figure BDA0002879999540000051
wherein R is1And R2As defined above: r1Selected from hydrogen atoms or straight-chain alkyl groups, preferably from hydrogen atoms or C1-C10More preferably a hydrogen atom or C1-C8The linear alkyl group of (1); r2Selected from linear alkyl groups, preferably from C1-C18More preferably C1-C15Linear alkyl group of (1).
Preferably, the fatty alcohol is selected from the group consisting of 1-tetradecanol, 2-methyl-1-tridecanol, 2-ethyl-1-dodecanol, 2-propyl-1-undecanol, 2-butyl-1-decanol, 2-pentyl-1-nonanol, 2-butyl-1-octanol and 2-hexyl-1-octanol.
The reaction is carried out in the presence of a catalyst, the catalyst comprises a main catalyst which is selected from N-heterocyclic carbene or N-heterocyclic carbene alkene, the N-heterocyclic carbene is a compound with a structure shown in a formula (II), and the N-heterocyclic carbene is a compound with a structure shown in a formula (III).
Figure BDA0002879999540000052
Wherein X, X 'are each independently a nitrogen atom or a carbon atom, Y, Y' are each independently a nitrogen atom or a sulfur atom, R3、R4、R5、R6、R7、R8、R9、R10Each independently selected from a hydrogen atom or an alkyl group, said alkyl group being C1-C5Alkyl group of (1).
Preferably, the procatalyst is selected from one or more of NHC1, NHC2, NHO1 and NHO2, more preferably the procatalyst is selected from NHC1 and/or NHO 1. The structures of NHC1, NHC2, NHO1, and NHO2 are shown below, respectively:
Figure BDA0002879999540000061
NHC1 is a compound shown as a formula (II), wherein X, Y is all compoundsNitrogen atom, R3、R4Are each methyl, R5、R6Are all hydrogen atoms.
NHC2 is a compound shown as a formula (II), wherein X is a carbon atom, Y is a sulfur atom, and R is4Is methyl, R3、R5、R6Are all hydrogen atoms.
NHO1 is a compound shown as a formula (III), wherein X 'and Y' are nitrogen atoms, and R7、R8、R10Are each methyl, R9Is a hydrogen atom.
NHO2 is a compound shown as a formula (III), wherein X is a carbon atom, Y is a sulfur atom, and R is8Is methyl, R7、R9、R10Are all hydrogen atoms.
Preferably, the catalyst further comprises a promoter selected from metal halides, preferably from metal iodides or metal chlorides, more preferably from LiI, NaI, MgI2、LiCl、MgCl2And AlCl3One or more of them, e.g. LiI, NaI, MgI2、LiCl。
In a preferred embodiment of the present invention, the main catalyst is used in combination with a cocatalyst.
Preferably, when the main catalyst is N-heterocyclic carbene, the catalyst promoter is metal iodide or metal chloride; when the main catalyst is N-heterocyclic carbene olefin, the catalyst promoter is metal iodide.
When the main catalyst is NHC1, the cocatalyst is LiI or MgI2Or one or more of LiCl; when the main catalyst is NHO1, the cocatalyst is LiI and/or MgI2。
The organic catalyst and inorganic salt catalytic system adopted in the invention can effectively control the alcohol initiator to initiate monomer polymerization and inhibit chain transfer reaction, and the catalytic ring-opening polymerization reaction can be carried out according to the ratio of the concentration of the initial monomer to the concentration of the initiator, namely, the polymerization degree n is the ratio of the concentration of the initial monomer to the concentration of the initiator, so that the fatty alcohol polyoxypropylene ether with controllable molecular weight and molecular weight distribution is synthesized, the raw material residue is reduced, and the generation of impurities such as polypropylene oxide and the like and the residue of free fatty alcohol are further reduced.
In one embodiment of the present invention, the reaction is carried out in the presence of an organic solvent selected from one or more of toluene, dichloromethane, tetrahydrofuran, dimethyl sulfoxide and N, N-dimethylformamide. In this case, the concentration of the propylene oxide after dissolution is 5mol/L to 25mol/L, preferably 10mol/L to 20 mol/L.
In a preferred embodiment of the present invention, propylene oxide is used as a reaction raw material and also as a reaction solvent, and no additional solvent is added, so that the post-treatment process can be simplified, and the residue of the organic solvent in the final product can be reduced.
The molar ratio of the fatty alcohol to the propylene oxide is 1 (1-15), preferably 1 (4-12), and more preferably 1 (4-10). In the invention, under the action of the catalyst, the polymerization degree of the target product can be realized by controlling the molar ratio of the initiator fatty alcohol to the propylene oxide, so that final products in different application directions are obtained.
The molar ratio of the fatty alcohol to the catalyst is 1.25 (0.01-2.0), preferably 1 (0.6-1.8), and more preferably 1.25 (1.3-1.6).
The molar ratio of the main catalyst to the cocatalyst is 0.5 (0.2-3.0), preferably 0.5 (0.6-2.1), and more preferably 0.5 (0.8-1.2).
Researches show that under the condition of the using amount and the proportion of the catalyst, the reaction can be regulated and controlled to be carried out towards the direction of the target polymerization degree on the premise of not wasting the catalyst, and harmful impurities in the product are reduced.
The reaction temperature is 35 to 75 ℃, preferably 45 to 65 ℃, more preferably 55 to 65 ℃. The reaction time is 30-85h, preferably 40-75 h. The reaction is preferably carried out under anhydrous and oxygen-free conditions. After the reaction is finished, an intermediate reaction solution containing the fatty alcohol polyoxypropylene ether is obtained.
The invention also provides a preparation method of the fatty alcohol polyoxypropylene ether with narrow distribution, which comprises the step 1, and then the intermediate reaction liquid obtained in the step 1 is purified to obtain the fatty alcohol polyoxypropylene ether.
The purification treatment comprises extraction. And standing the intermediate reaction solution, and separating after layering to obtain a crude fatty alcohol polyoxypropylene ether product.
The extraction is to add the crude product of the fatty alcohol polyoxypropylene ether into an extracting agent, fully stir the mixture, and then stand the mixture for layering to obtain the fatty alcohol polyoxypropylene ether. The extraction can be performed several times. The extractant is selected from inorganic salt solution and/or ether solvent, preferably saturated sodium chloride and/or petroleum ether.
In a preferred embodiment of the invention, the extraction is carried out twice, the first extraction uses a composition of saturated sodium chloride and petroleum ether as an extracting agent, the volume ratio of the saturated sodium chloride to the petroleum ether is (0.5-1.5):1, and the second extraction uses the saturated sodium chloride as an extracting agent to obtain an organic phase of the fatty alcohol polyoxypropylene ether after extraction.
The purification treatment also includes distillation and drying. The organic phase containing the fatty alcohol polyoxypropylene ether is subjected to rotary evaporation to remove the petroleum ether, and then is dried. The drying method and conditions are not particularly limited in the present invention, and the drying purpose can be achieved.
And 2, adding an end-capping reagent into the intermediate reaction liquid, and reacting to obtain a mixed liquid containing fatty alcohol-polyoxypropylene ether oxyacid.
Adding a blocking agent into the intermediate reaction liquid, and adding the blocking agent into the original catalytic reaction system to carry out blocking reaction. The end capping agent is selected from one or more of carboxylic acid compounds, carbonic acid compounds, hexavalent sulfur compounds or pentavalent phosphorus compounds, and preferably chloroacetic acid, sulfur trioxide-triethylamine complex, propyl carbonate, cesium bicarbonate or phosphorus oxychloride.
The molar ratio of the blocking agent to the fatty alcohol is (0.6-3.5):1, preferably (0.8-3.0):1, more preferably (1-2.5): 1. When the using amount of the end-capping agent is too small, the end-capping structure of the obtained product is more complex, and a uniform end-capping structure of the ionic oxyacid group is difficult to form; when the amount of the end-capping agent is too large, the difficulty of purification increases and the cost of purification increases.
The reaction temperature is 8 to 75 ℃, preferably 30 to 65 ℃, more preferably 55 to 65 ℃. The reaction time is 8-15h, preferably 10-12 h.
After the reaction is finished, adding an alcohol solvent into the reaction system, and quenching the reaction to obtain a mixed solution containing the fatty alcohol polyoxypropylene ether oxyacid. The alcohol solvent is selected from methanol, ethanol or propanol, preferably methanol. The reaction is carried out in a protective gas atmosphere, such as nitrogen or argon.
Optionally, further comprising step 2': adding metal hydroxide or oxide into the mixed solution to obtain a neutral mixed solution.
The metal is selected from sodium, potassium, calcium, magnesium, barium, zinc, aluminum or iron. Adding solid or solution of metal hydroxide or oxide, such as solid hydroxide or oxide of calcium, magnesium, barium, zinc, aluminum or iron, and aqueous or alcoholic solution of sodium hydroxide and potassium hydroxide.
Gradually adding metal hydroxide or oxide, heating to form uniform solution, and adjusting pH to 7-8 to obtain neutral mixed solution. The reaction is carried out in a protective gas atmosphere, such as nitrogen or argon.
And 3, post-treating the mixed solution or the neutral mixed solution containing the fatty alcohol-polyoxypropylene ether oxyacid to obtain the fatty alcohol-polyoxypropylene ether oxyacid or the salt thereof.
The post-treatment comprises purification, filtration and drying. The purification is that organic or inorganic solvent and residual small amount of propylene oxide in the mixed solution or the neutral mixed solution are removed by rotary evaporation, and then organic solvent such as normal hexane is added for washing. The polymer was obtained by filtration and dried.
The drying is preferably vacuum drying, the drying temperature is 20-30 ℃, the vacuum degree is 0.1-0.001mbar, and the drying is carried out until the weight is constant, so as to obtain the fatty alcohol polyoxypropylene ether oxyacid ester or the salt thereof.
The fatty alcohol polyoxypropylene ether oxyacid or the salt thereof in the invention is prepared by taking the fatty alcohol polyoxypropylene ether as a raw material through the steps 2 and 3 of the method, and optionally further comprises the step 2'.
The fatty alcohol polyoxypropylene ether oxyacid or the salt thereof provided by the invention is narrow in molecular weight distribution, and the content of free fatty alcohol and the acidification product of fatty alcohol ether with high polymerization degree in a final product is greatly reduced by controlling the synthesis process, so that the fatty alcohol polyoxypropylene ether oxyacid or the salt thereof with low irritation and higher safety is obtained, the product quality is greatly improved, the synthesis method is easy to control, and the large-scale production is favorably realized.
Examples
Example 1
The addition of material was carried out in a glove box, 0.5mmol of NHC1, 1mmol of MgI21.25mmol of 1-tetradecanol was sequentially added to a 10mL Schlenk reaction tube. The reaction tube is removed from the glove box, 10mmol of propylene oxide is injected and heated to 60 ℃ for reaction under the condition of stirring, and the timing is started to utilize1H NMR monitored the progress of the monomer polymerization, and after 48H, the reaction was stopped.
Adding 3.125mmol of sulfur trioxide-triethylamine complex into a Schlenk reaction tube, reacting for 12h, and adding methanol for quenching reaction. And (2) performing rotary evaporation to remove the methanol solvent and a small amount of residual monomers, adding n-hexane, filtering to separate out a polymer, and drying to constant weight under the condition of room temperature and a vacuum degree of 0.1-0.001mbar to obtain tetradecanol polyoxypropylene ether sulfuric acid, wherein the structure is presumed to be shown as formula (1), and the conversion rate of the propylene oxide is 98%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum is shown in FIG. 1, and the degree of polymerization n is about 10.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝1100g·mmol-1And the molecular weight distribution index is PDI 1.44, the molecular weight distribution test curve is shown in fig. 2.
Example 2
2-methyl-1-tridecanol polyoxypropylene ether sulfuric acid was synthesized in accordance with the procedure of example 1, and the structure thereof was presumed to be shown in the formula (2). The only difference is that: 1.25mmol of 1-tetradecanol was replaced with 1.25mmol of 2-methyl-1-tridecanol. The propylene oxide conversion was 95%.
By passing1H NMR measurementThe structure of the product was determined by trial,1the H NMR spectrum is shown in FIG. 3, and the degree of polymerization n is about 5.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝720g·mmol-1And a molecular weight distribution index PDI of 1.39.
Example 3
2-Ethyl-1-dodecanol polyoxypropylene ether sulfuric acid was synthesized according to the procedure of example 1, and the structure thereof was presumed to be shown in the formula (3). The only difference is that: 1.25mmol of 1-tetradecanol was replaced with 1.25mmol of 2-ethyl-1-dodecanol. The propylene oxide conversion was 97%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum is shown in FIG. 4, and the degree of polymerization n is about 10.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝970g·mmol-1And a molecular weight distribution index PDI of 1.43.
Example 4
2-propyl-1-undecanol polyoxypropylene ether sulfuric acid was synthesized in the same manner as in example 1, and the structure thereof was estimated to be shown in the formula (4). The only difference is that: 1mmol of MgI was replaced by 1mmol of LiI and 1.25mmol of 1-tetradecanol by 1.25mmol of 2-propyl-1-undecanol. The propylene oxide conversion was 98%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum is shown in FIG. 5, and the degree of polymerization n is about 9.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝950g·mmol-1And a molecular weight distribution index PDI of 1.53.
Example 5
2-butyl-1-decanol polyoxypropylene ether sulfuric acid was synthesized in accordance with the procedure of example 1, and the structure thereof was presumed to be shown in the formula (5). The only difference is that: 1mmol of MgI was replaced with 1mmol of LiI, and 1.25mmol of 1-tetradecanol was replaced with 1.25mmol of 2-butyl-1-decanol. The propylene oxide conversion was 99%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum is shown in FIG. 6, and the degree of polymerization n is about 7.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝830g·mmol-1And a molecular weight distribution index PDI of 1.50.
Example 6
2-pentyl-1-nonanol polyoxypropylene ether sulfuric acid was synthesized in the same manner as in example 1, and the structure thereof was estimated to be shown in the formula (6). The only difference is that: 1mmol of MgI was replaced with 1mmol of LiI and 1.25mmol of 1-tetradecanol with 1.25mmol of 2-pentyl-1-nonanol. The propylene oxide conversion was 96%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum is shown in FIG. 7, and the degree of polymerization n is about 7.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝860g·mmol-1And a molecular weight distribution index PDI of 1.50.
Example 7
2-hexyl-1-octanol polyoxypropylene ether sulfuric acid was synthesized according to the method of example 1, and the structure thereof was presumed to be represented by the formula (7). The only difference is that: 1.25mmol of 1-tetradecanol was replaced with 1.25mmol of 2-hexyl-1-octanol. The propylene oxide conversion was 90%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum is shown in FIG. 8, and the degree of polymerization n is about 4.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝660g·mmol-1And a molecular weight distribution index PDI of 1.36.
Example 8
2-butyl-1-octanol polyoxypropylene ether sulfuric acid was synthesized according to the method of example 1, and the structure thereof was presumed to be represented by the formula (8). The only difference is that: 1.25mmol of 1-tetradecanol was replaced with 1.25mmol of 2-butyl-1-octanol. The propylene oxide conversion was 98%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum is shown in FIG. 9, and the degree of polymerization n is about 5.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝920g·mmol-1And a molecular weight distribution index PDI of 1.39.
Example 9
2-butyl-1-octanol polyoxypropylene ether sulfuric acid was synthesized according to the procedure of example 8. The only difference is that: the addition amount of 2-butyl-1-octanol was 0.8mmol, and the addition amount of sulfur trioxide-triethylamine complex was 1.6 mmol. The propylene oxide conversion was 95%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum is shown in FIG. 10, and the degree of polymerization n is about 6.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝940g·mmol-1And a molecular weight distribution index PDI of 1.39.
Example 10
2-butyl-1-octanol polyoxypropylene ether sulfuric acid was synthesized according to the procedure of example 8. The only difference is that: the addition amount of 2-butyl-1-octanol was 1mmol, and the addition amount of sulfur trioxide-triethylamine complex was 2.0 mmol. The propylene oxide conversion was 98%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum is shown in FIG. 11, and the degree of polymerization n is about 7.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝1200g·mmol-1And a molecular weight distribution index PDI of 1.32.
Example 11
2-butyl-1-octanol polyoxypropylene ether sulfuric acid was synthesized according to the procedure of example 8. The only difference is that: the addition amount of 2-butyl-1-octanol was 0.4mmol, and the addition amount of sulfur trioxide-triethylamine complex was 0.4 mmol. The propylene oxide conversion was 86%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum is shown in FIG. 12, and the degree of polymerization n is about 6.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝900g·mmol-1And a molecular weight distribution index PDI of 1.36.
Example 12
2-butyl-1-octanol polyoxypropylene ether sulfuric acid was synthesized according to the procedure of example 8. The only difference is that: the addition of 0.5mmol of NHC1 was replaced with 0.5mmol of NHC 2. The propylene oxide conversion was 80%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum of the sample is shown in FIG. 13, and the degree of polymerization n is about 4.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝680g·mmol-1And a molecular weight distribution index PDI of 1.39.
Example 13
2-butyl-1-octanol polyoxypropylene ether sulfuric acid was synthesized according to the procedure of example 8. The only difference is that: the addition of 0.5mmol of NHC1 was replaced with 0.5mmol of NHO 1. The propylene oxide conversion was 97%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum is shown in FIG. 14, and the degree of polymerization n is about 10.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝2400g·mmol-1And a molecular weight distribution index PDI of 1.27.
Example 14
2-butyl-1-octanol polyoxypropylene ether sulfuric acid was synthesized according to the procedure of example 8. The only difference is that: the addition of 0.5mmol of NHC1 was replaced with 0.5mmol of NHO 2. The propylene oxide conversion was 85%.
By passing1H NMR test to determine yieldThe structure of the object is that the object is provided with a plurality of grooves,1the H NMR spectrum was as shown in FIG. 15, and the degree of polymerization n was about 5.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝690g·mmol-1And the molecular weight distribution index is PDI 1.42.
Example 15
2-butyl-1-octanol polyoxypropylene ether carbonate was synthesized according to the procedure of example 8, and its structure was presumed to be represented by the formula (9). The only difference is that: 3.125mmol of sulfur trioxide-triethylamine complex was replaced by 5mmol of propyl carbonate. The propylene oxide conversion was 98%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum was as shown in FIG. 16, and the degree of polymerization n was about 7.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝1100g·mmol-1And a molecular weight distribution index PDI of 1.47.
Example 16
2-butyl-1-octanol polyoxypropylene ether carbonate was synthesized according to the procedure in example 15. The only difference is that: the addition of 0.5mmol of NHC1 was replaced with 0.5mmol of NHO 1. The propylene oxide conversion was 92%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum was as shown in FIG. 17, and the degree of polymerization n was about 8.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝830g·mmol-1And a molecular weight distribution index PDI of 1.34.
Example 17
2-butyl-1-octanol polyoxypropylene ether phosphonic acid was synthesized according to the procedure of example 8, and its structure was presumed to be shown in formula (10). The only difference is that: adding 1mmol of MgI2Replacement was with 1mmol LiCl; 3.125mmol of sulfur trioxide-triethylamine complex was replaced with 3.125mmol of phosphorus oxychloride. The propylene oxide conversion was 95%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum was as shown in FIG. 18, and the degree of polymerization n was about 5.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝560g·mmol-1And a molecular weight distribution index PDI of 1.53.
Example 18
2-butyl-1-octanol polyoxypropylene ether phosphonic acid was synthesized according to the procedure for example 17. The only difference is that: the addition of 0.5mmol of NHC1 was replaced with 0.5mmol of NHO 1; after adding phosphorus oxychloride, reacting for 72 h. The propylene oxide conversion was 80%.
By passing1H NMR testing determines the structure of the product,1the H NMR spectrum was as shown in FIG. 19, and the degree of polymerization n was about 8.
The molecular weight of the product, M, was determined by gel permeation chromatography in combination with laser light scattering (GPC)n＝560g·mmol-1And a molecular weight distribution index PDI of 1.34.
The invention has been described in detail with reference to specific embodiments and/or illustrative examples and the accompanying drawings, which, however, should not be construed as limiting the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (10)

1. The fatty alcohol polyoxypropylene ether oxyacid or salt thereof is characterized by being prepared by taking propylene oxide as a raw material, taking fatty alcohol as an initiator and adding an end-capping agent.
2. The oxo acid or a salt thereof according to claim 1, wherein the molecular structure of the fatty alcohol polyoxypropylene ether oxo acid or a salt thereof comprises a structural moiety according to formula (i):
Figure FDA0002879999530000011
wherein R is1Selected from hydrogen atoms or straight chain alkyl groups; r2Selected from straight chain alkyl; g is an end group selected from ionic oxyacid group; n is 1 to 15.
3. The fatty alcohol polyoxypropylene ether oxo acid or a salt thereof according to claim 1 or 2, wherein the oxo acid or salt thereof has a molecular weight distribution index of 1.05-2.5.
4. A method for preparing fatty alcohol polyoxypropylene ether oxyacid or salt thereof according to any one of claims 1-3, wherein propylene oxide is used as raw material, fatty alcohol is used as initiator, and end capping agent is added for reaction.
5. The method according to claim 4, characterized in that it comprises in particular the steps of:
step 1, adding fatty alcohol into propylene oxide, and heating for reaction to obtain an intermediate reaction solution;
step 2, adding an end-capping reagent into the intermediate reaction liquid, and reacting to obtain a mixed liquid containing fatty alcohol-polyoxypropylene ether oxyacid;
optionally, further comprising step 2': adding metal hydroxide or oxide into the mixed solution to obtain neutral mixed solution;
and 3, post-treating the mixed solution or the neutral mixed solution containing the fatty alcohol-polyoxypropylene ether oxyacid to obtain the fatty alcohol-polyoxypropylene ether oxyacid or the salt thereof.
6. The method according to claim 5, wherein in step 1, the fatty alcohol is selected from saturated monoalcohols having the following structure:
Figure FDA0002879999530000021
wherein the content of the first and second substances,R1selected from hydrogen atoms or straight chain alkyl groups; r2Selected from linear alkyl groups.
7. The process of claim 5 or 6, wherein in step 1, the reaction is carried out in the presence of a catalyst comprising a procatalyst selected from the group consisting of an N-heterocyclic carbene or an N-heterocyclic carbene ene.
8. The process according to any one of claims 5 to 7, wherein in step 1, the catalyst further comprises a promoter selected from metal halides, preferably from metal iodides or metal chlorides.
9. The process according to any one of claims 5 to 8, wherein the molar ratio of fatty alcohol to propylene oxide is 1 (1-15), preferably 1 (4-12).
10. The method of any one of claims 5 to 9, wherein in step 2, the capping agent is selected from one or more of carboxylic acid compounds, carbonic acid compounds, hexavalent sulfur compounds, or pentavalent phosphorus compounds.
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Denomination of invention: A fatty alcohol polyoxypropylene ether oxygen-containing acid and its salt

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