CN115536829A - Method for synthesizing fatty acid monoethanolamide polyoxyethylene ether - Google Patents
Method for synthesizing fatty acid monoethanolamide polyoxyethylene ether Download PDFInfo
- Publication number
- CN115536829A CN115536829A CN202211283695.XA CN202211283695A CN115536829A CN 115536829 A CN115536829 A CN 115536829A CN 202211283695 A CN202211283695 A CN 202211283695A CN 115536829 A CN115536829 A CN 115536829A
- Authority
- CN
- China
- Prior art keywords
- fatty acid
- acid monoethanolamide
- phosphate
- polyoxyethylene ether
- ethylene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 71
- 239000000194 fatty acid Substances 0.000 title claims abstract description 71
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 71
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 70
- 229940051841 polyoxyethylene ether Drugs 0.000 title claims abstract description 40
- 229920000056 polyoxyethylene ether Polymers 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910000319 transition metal phosphate Inorganic materials 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims abstract description 18
- -1 alkali metal alkoxide Chemical class 0.000 claims abstract description 11
- 229910000159 nickel phosphate Inorganic materials 0.000 claims abstract description 11
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000007514 bases Chemical class 0.000 claims abstract description 9
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims abstract description 9
- 229910000165 zinc phosphate Inorganic materials 0.000 claims abstract description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims abstract description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 238000010438 heat treatment Methods 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- BOWVQLFMWHZBEF-KTKRTIGZSA-N oleoyl ethanolamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCO BOWVQLFMWHZBEF-KTKRTIGZSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 238000009489 vacuum treatment Methods 0.000 description 20
- 241001550224 Apha Species 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 238000005485 electric heating Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 4
- 235000002867 manganese chloride Nutrition 0.000 description 4
- 239000011565 manganese chloride Substances 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229940043237 diethanolamine Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000005480 straight-chain fatty acid group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G65/2618—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 nitrogen
- C08G65/2633—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 nitrogen the other compounds containing amide groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
Abstract
The invention relates to a method for synthesizing fatty acid monoethanolamide polyoxyethylene ether, which mainly solves the problem of high product chromaticity in the prior art, and adopts the method for synthesizing the fatty acid monoethanolamide polyoxyethylene ether, and comprises the following steps: in the presence of a catalyst, fatty acid monoethanolamide is used as an initiator, and ethylene oxide is subjected to ring-opening polymerization reaction to obtain fatty acid monoethanolamide polyoxyethylene ether; the catalyst comprises a basic compound and a transition metal phosphate; the alkaline compound comprises an alkali metal alkoxide or an alkali metal hydroxide; the transition metal phosphate is at least one selected from the group consisting of zinc phosphate, nickel phosphate and manganese phosphate.
Description
Technical Field
The invention relates to a method for synthesizing fatty acid monoethanolamide polyoxyethylene ether, in particular to a polymerization reaction of fatty acid monoethanolamide and ethylene oxide serving as raw materials, belonging to the technical field of synthesis of organic compounds.
Background
The fatty acid alkanolamide is a novel green and efficient surfactant, the raw material of the fatty acid alkanolamide is derived from natural fatty acid, and the surfactant has good foaming, thickening, emulsifying and other performances, but recent researches show that the fatty acid diethanolamide has more diethanol amine residues, and the diethanol amine has a certain carcinogenic effect on human bodies, so that the fatty acid monoethanolamide product without the diethanol amine is one of better substitutes. Because the hydrophilic property of the fatty acid monoethanolamide is poor, the application of the fatty acid monoethanolamide is limited to a great extent. At present, more hydrophilic modified derivatives of fatty acid monoethanolamide appear. Among the numerous hydrophilic modified derivatives, the properties of fatty acid monoethanolamide polyoxyethylene ether are closest to those of fatty acid monoethanolamide.
The existing synthesis method of fatty acid monoethanolamide polyoxyethylene ether comprises the following steps: fatty acid monoethanolamide is polymerized with ethylene oxide under the action of an alkaline catalyst to prepare fatty acid monoethanolamide polyoxyethylene ether; however, the fatty acid monoethanolamide polyoxyethylene ether synthesized by the existing synthesis method has a dark color and a limited application range.
CN110845716A provides a synthesis method of low-chroma fatty acid monoethanolamide polyoxyethylene ether, which mainly reduces chroma by adding borohydride to reduce and decolor after synthesis reaction is finished.
Disclosure of Invention
The invention aims to solve the technical problem that fatty acid monoethanolamide polyoxyethylene ether synthesized by the prior art has deep chroma, and provides a method for synthesizing the fatty acid monoethanolamide polyoxyethylene ether.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the synthesis method of fatty acid monoethanolamide polyoxyethylene ether comprises the following steps:
in the presence of a catalyst, fatty acid monoethanolamide is used as an initiator, and ethylene oxide is subjected to ring-opening polymerization reaction to obtain fatty acid monoethanolamide polyoxyethylene ether; the catalyst comprises a basic compound and a transition metal phosphate; the alkaline compound comprises an alkali metal alkoxide or an alkali metal hydroxide; the transition metal phosphate is at least one selected from the group consisting of zinc phosphate, nickel phosphate and manganese phosphate.
Compared with the method of singly adopting the alkali metal alkoxy compound or the alkali metal hydroxide, the chroma of the fatty acid monoethanolamide polyoxyethylene ether product is reduced due to the use of the zinc phosphate, the nickel phosphate or the manganese phosphate.
In the above technical solution, the mass ratio of the transition metal phosphate to the basic compound is preferably 0.05 to 10. For example, but not limited to, the transition metal phosphate to basic compound mass ratio is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and the like. The mass ratio of the transition metal phosphate to the basic compound is more preferably 0.2 to 0.9.
In the above technical solution, it is preferable that the alkali metal in the alkali metal alkoxide and the alkali metal hydroxide is independently potassium or sodium.
In the above technical solution, the alkoxy group in the alkali metal alkoxide is preferably a methoxy group or an ethoxy group.
In the above technical solution, it is preferable that the fatty acid in the fatty acid monoethanolamide is C 8 ～C 18 The fatty acid of (2). That is, the fatty acid is selected from the group consisting of C 8 Fatty acid of (2), C 9 Fatty acid of (2), C 10 Fatty acid of (2), C 11 Fatty acid of (2), C 12 Fatty acid of (2), C 13 Fatty acid of (2), C 14 Fatty acid of (2), C 15 Fatty acid of (2), C 16 Fatty acid of (2), C 17 Fatty acid and C 18 At least one member of the substance group consisting of fatty acids.
In the technical scheme, the fatty acid is saturated or unsaturated fatty acid.
The key point of the invention is the selection of the catalyst components, and related to the dosage of the catalyst, the reaction temperature, the total feeding molar ratio of the ethylene oxide and the fatty acid monoethanolamine, the reaction pressure and the like, a person skilled in the art can reasonably select the catalyst components to obtain comparable technical effects without creative labor.
In the technical scheme, the dosage of the catalyst is preferably 0.05-1% of the total mass of the theoretical product. For example, but not limited to, the catalyst is used in an amount of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, etc., based on the total mass of the theoretical product, and more preferably the catalyst is used in an amount of 0.1 to 0.7% based on the total mass of the theoretical product.
In the above technical scheme, the reaction temperature is preferably 110-170 ℃, for example, but not limited to, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃ and the like. More preferably 120 to 160 ℃.
In the above technical solutions, the total feeding molar ratio of ethylene oxide to fatty acid monoethanolamide is preferably 2 to 20, for example, but not limited to, the total feeding molar ratio of ethylene oxide to fatty acid monoethanolamide is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and the like. More preferably, the feed molar ratio of ethylene oxide to fatty acid monoethanolamide is from 5 to 18.
In the above technical scheme, the reaction pressure is preferably-0.04 MPa to 0.6MPa. Examples of the reaction pressure include, but are not limited to, -0.04MPa, -0.03MPa, -0.02MPa, -0.01MPa, 0MPa, 0.01MPa, 0.02MPa, 0.03MPa, 0.04MPa, 0.05MPa, 0.06MPa, 0.07MPa, 0.08MPa, 0.09MPa, 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, and the like.
In the technical scheme, the transition metal phosphates are all phosphates of positive 2-valent metal.
In the above technical solution, preferably, the transition metal salt includes two transition metal phosphates at the same time, the 1 st transition metal phosphate is manganese phosphate, and the 2 nd transition metal phosphate is nickel phosphate or zinc phosphate. The 1 st transition metal phosphate and the 2 nd transition metal phosphate have an interaction promoting effect on reducing the chromaticity of the fatty acid monoethanolamide polyoxyethylene ether product.
In the above-mentioned embodiment, the mass ratio of the 2 nd transition metal phosphate to the 1 st transition metal phosphate is preferably 0.1 to 3.0, and for example, but not limited thereto, the mass ratio of the 2 nd transition metal phosphate to the 1 st transition metal phosphate is 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, or the like. More preferably, the mass ratio is 0.2 to 0.5.
In the present invention, the technical effects comparable to those of the present invention can be obtained regardless of whether the transition metal phosphate is an anhydrate (i.e., does not contain crystal water) or a crystal hydrate, but the anhydrate is preferred. In the examples of the present invention and the comparative examples, the transition metal salts were used as an anhydride only, and the amounts and the amount ratios were calculated as an anhydride.
The particle size of the transition metal phosphate is not particularly limited and may be reasonably selected by one skilled in the art, for example, the particle size is expressed in mesh. As non-limiting examples, the particle size of the transition metal phosphate is 100 to 2000 mesh in terms of mesh number, and further non-limiting examples are 100 mesh, 120 mesh, 150 mesh, 180 mesh, 200 mesh, 400 mesh, 600 mesh, 800 mesh, 1000 mesh, 2000 mesh, and the like. However, the fine particles are advantageous for the performance of the catalyst, and for the same reason, the components of the catalyst in the examples of the present embodiment are further ground based on a commercially available transition metal phosphate, and the powder passing through a 180-mesh sieve is used. Only by the same ratio, manganese sulfate and manganese dichloride used in the specification of the invention are also ground and taken up as powder passing through a 180-mesh sieve.
When the catalyst comprises the basic compound and the transition metal phosphate, the order of adding the two components to the polymerization reaction system separately or mixing the two components and then adding the two components to the polymerization reaction system is not particularly limited, and comparable technical effects can be obtained.
When the transition metal phosphate contains more than 2 phosphates, the sequence of adding the two phosphate components and the alkaline compound into the polymerization reaction system separately or adding the components into the polymerization reaction system separately after mixing the components, and adding the components into the polymerization reaction system separately is not particularly limited, and comparable technical effects can be obtained.
In the above technical solutions, the fatty acid may be a straight-chain fatty acid or a fatty acid having a branched chain, and the fatty acid is not particularly limited and can achieve comparable technical effects. For comparison only, straight chain fatty acids were used in the examples and comparative examples of the present embodiment.
The pressures in the present invention are gauge pressures.
Compared with the prior ethoxylation synthesis technology, the method of the invention can obviously reduce the chroma of the fatty acid monoethanolamide polyoxyethylene ether product.
In the specific embodiment of the invention, the chromaticity value is measured by a Lovibond PFxi195/1 full-automatic colorimetric analyzer to obtain the platinum-cobalt chromaticity of the product.
The present invention will be further described with reference to the following examples.
Detailed Description
[ example 1 ]
200.0g of oleic acid monoethanolamide and 0.34g of a catalyst (consisting of sodium methoxide and manganese phosphate, wherein the mass ratio of manganese phosphate to sodium methoxide is 0.2, and the manganese phosphate is added first and then sodium methoxide are added sequentially) are added into a 2L reaction kettle with a stirring and electric heating jacket and an internal water-cooling coil, and the reaction kettle is sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of minus 0.09MPa, then heating to 160 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when the total amount of the ethylene oxide is 135.4g, carrying out curing reaction at 160 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of minus 0.09MPa, and then reducing the temperature to 60 ℃ to obtain the oleic acid monoethanolamide polyoxyethylene ether product.
The detection proves that the chroma (APHA) value of the fatty acid monoethanolamide polyoxyethylene ether product is 135.
[ example 2 ]
200.0g of oleic monoethanolamide and 4.81g of a catalyst (consisting of sodium methoxide and manganese phosphate, wherein the mass ratio of manganese phosphate to sodium methoxide is 0.9, and the manganese phosphate is added first and then sodium methoxide are added sequentially) are added into a 2L reaction kettle with a stirring and electric heating jacket and an internal water-cooling coil, and the reaction kettle is sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of minus 0.09MPa, then heating to 120 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 487.4g of the ethylene oxide is introduced, carrying out curing reaction at 120 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of minus 0.09MPa, and then reducing the temperature to 60 ℃ to obtain the oleic acid monoethanolamide polyoxyethylene ether product.
The detection proves that the chromaticity (APHA) value of the fatty acid monoethanolamide polyoxyethylene ether product is 116.
[ example 3 ] A method for producing a polycarbonate
200.0g of oleic acid monoethanolamide and 1.57g of a catalyst (consisting of sodium methoxide and manganese phosphate, the mass ratio of manganese phosphate to sodium methoxide being 0.5, and the manganese phosphate being added first and the sodium methoxide being added subsequently) were put into a 2L reactor equipped with a stirring and electric heating jacket and an internal water-cooling coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of minus 0.09MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 324.9g of the ethylene oxide is introduced in total, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of minus 0.09MPa, and then reducing the temperature to 60 ℃ to obtain the oleic acid monoethanolamide polyoxyethylene ether product.
The detection proves that the chromaticity (APHA) value of the fatty acid monoethanolamide polyoxyethylene ether product is 85.
[ example 4 ]
A2L reactor equipped with a stirring and electric heating jacket and an internal water-cooled coil was charged with 200.0g of oleic acid monoethanolamide, 1.57g of a catalyst (consisting of sodium methoxide and zinc phosphate, the mass ratio of zinc phosphate to sodium methoxide being 0.5, and the zinc phosphate and sodium methoxide were added in this order), and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introduction speed of the ethylene oxide, stopping introducing materials when 324.9g of the ethylene oxide is introduced in total, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 60 ℃ to obtain the oleic acid monoethanolamide polyoxyethylene ether product.
The detection proves that the chromaticity (APHA) value of the fatty acid monoethanolamide polyoxyethylene ether product is 121.
[ example 5 ] A method for producing a polycarbonate
200.0g of oleic acid monoethanolamide and 1.57g of a catalyst (consisting of sodium methoxide and nickel phosphate, the mass ratio of nickel phosphate to sodium methoxide being 0.5, and the contents being added in the order of nickel phosphate addition followed by sodium methoxide) were put into a 2L reactor equipped with a stirring and electric heating jacket and an internal water-cooling coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of minus 0.09MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 324.9g of the ethylene oxide is introduced in total, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of minus 0.09MPa, and then reducing the temperature to 60 ℃ to obtain the oleic acid monoethanolamide polyoxyethylene ether product.
The detection proves that the chroma (APHA) value of the fatty acid monoethanolamide polyoxyethylene ether product is 102.
[ example 6 ]
200.0g of oleic acid monoethanolamide and 1.57g of a catalyst (consisting of sodium methoxide and transition metal phosphate, the mass ratio of the transition metal phosphate to the sodium methoxide being 0.5, the mass ratio of the transition metal phosphate to the nickel phosphate being manganese phosphate and nickel phosphate, the mass ratio of the nickel phosphate to the manganese phosphate being 0.35) were put into a 2L reactor equipped with a stirring and electric heating jacket and an internal water-cooling coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of minus 0.09MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 324.9g of the ethylene oxide is introduced in total, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of minus 0.09MPa, and then reducing the temperature to 60 ℃ to obtain the oleic acid monoethanolamide polyoxyethylene ether product.
The detection proves that the chroma (APHA) value of the fatty acid monoethanolamide polyoxyethylene ether product is 43.
[ example 7 ] A method for producing a polycarbonate
200.0g of oleic acid monoethanolamide and 1.57g of a catalyst (consisting of sodium methoxide and a transition metal phosphate, the mass ratio of the transition metal phosphate to the sodium methoxide being 0.5, the mass ratio of the transition metal phosphate to the manganese phosphate being 0.35, and the zinc phosphate to the manganese phosphate being 0.35) were put into a 2L reactor equipped with a stirring and electric heating jacket and an internal water-cooling coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of-0.09 MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introduction speed of the ethylene oxide, stopping introducing materials when 324.9g of the ethylene oxide is introduced in total, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of-0.09 MPa, and then reducing the temperature to 60 ℃ to obtain the oleic acid monoethanolamide polyoxyethylene ether product.
The detection proves that the chroma (APHA) value of the fatty acid monoethanolamide polyoxyethylene ether product is 59.
[ COMPARATIVE EXAMPLE 1 ]
200.0g of oleic acid monoethanolamide and 1.57g of sodium methoxide are put into a 2L reaction kettle with a stirring and electric heating jacket and an internal water-cooling coil, and the reaction kettle is sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of minus 0.09MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 324.9g of the ethylene oxide is introduced in total, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of minus 0.09MPa, and then reducing the temperature to 60 ℃ to obtain the oleic acid monoethanolamide polyoxyethylene ether product.
The detection proves that the chroma (APHA) value of the fatty acid monoethanolamide polyoxyethylene ether product is 420.
[ COMPARATIVE EXAMPLE 2 ]
200.0g of oleic acid monoethanolamide and 1.57g of a catalyst (consisting of sodium methoxide and manganese sulfate, the mass ratio of manganese sulfate to sodium methoxide being 0.5, and the manganese sulfate being added first and the sodium methoxide being added later) were put into a 2L reactor equipped with a stirring and electric heating jacket and an internal water-cooling coil, and the reactor was sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of minus 0.09MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 324.9g of the ethylene oxide is introduced in total, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of minus 0.09MPa, and then reducing the temperature to 60 ℃ to obtain the oleic acid monoethanolamide polyoxyethylene ether product.
The detection proves that the chroma (APHA) value of the fatty acid monoethanolamide polyoxyethylene ether product is 432.
[ COMPARATIVE EXAMPLE 3 ]
200.0g of oleic acid monoethanolamide and 1.57g of a catalyst (consisting of sodium methoxide and manganese dichloride, wherein the mass ratio of the manganese dichloride to the sodium methoxide is 0.5, and the manganese dichloride and the sodium methoxide are added in sequence) are added into a 2L reaction kettle with a stirring and electric heating jacket and an internal water-cooling coil, and the reaction kettle is sealed. Replacing nitrogen in the reaction kettle with nitrogen for three times, starting stirring, heating to 90 ℃, carrying out vacuum treatment for 60min at the pressure of minus 0.09MPa, then heating to 140 ℃, maintaining the temperature, introducing ethylene oxide, keeping the reaction pressure at 0.3MPa by controlling the introducing speed of the ethylene oxide, stopping introducing materials when 324.9g of the ethylene oxide is introduced in total, carrying out curing reaction at 140 ℃ until the pressure is not reduced (indicating that the curing reaction is finished), carrying out vacuum treatment for 30min at the pressure of minus 0.09MPa, and then reducing the temperature to 60 ℃ to obtain the oleic acid monoethanolamide polyoxyethylene ether product.
The detection proves that the chroma (APHA) value of the fatty acid monoethanolamide polyoxyethylene ether product is 435.
For comparison, the main process conditions and results of the above examples and comparative examples are summarized in Table 1.
TABLE 1
(ii) the following: in the table, EO is an abbreviation for ethylene oxide.
Claims (9)
1. The synthesis method of fatty acid monoethanolamide polyoxyethylene ether comprises the following steps:
in the presence of a catalyst, fatty acid monoethanolamide is used as an initiator, and ethylene oxide is subjected to ring-opening polymerization reaction to obtain fatty acid monoethanolamide polyoxyethylene ether; the catalyst comprises a basic compound and a transition metal phosphate; the alkaline compound comprises an alkali metal alkoxide or an alkali metal hydroxide; the transition metal phosphate is at least one selected from the group consisting of zinc phosphate, nickel phosphate and manganese phosphate.
2. The synthesis method according to claim 1, wherein the mass ratio of the transition metal phosphate to the basic compound is 0.05 to 10. The mass ratio of the transition metal phosphate to the basic compound is more preferably 0.2 to 0.9.
3. The method of claim 1, wherein the alkali metal of the alkali metal alkoxide and the alkali metal hydroxide is independently potassium or sodium.
4. The method of claim 1, wherein the alkoxy group of the alkali metal alkoxide is a methoxy group or an ethoxy group.
5. The method of claim 1, wherein the fatty acid in the fatty acid monoethanolamide is C 8 ～C 18 The fatty acid of (2). The fatty acid is saturated or unsaturated fatty acid.
6. The synthesis process according to claim 1, wherein the catalyst is used in an amount of 0.05 to 1% based on the total mass of the theoretical product. More preferably, the amount of catalyst is 0.1 to 0.7% of the total mass of the theoretical product.
7. The synthesis process according to claim 1, wherein the reaction temperature is 110 to 170 ℃. More preferably 120 to 160 ℃.
8. The synthesis process according to claim 1, characterized in that the total feed molar ratio of ethylene oxide to fatty acid monoethanolamide ranges from 2 to 20. More preferably, the feed molar ratio of ethylene oxide to fatty acid monoethanolamide is from 5 to 18.
9. The synthesis process according to claim 1, wherein the reaction pressure is from-0.04 MPa to 0.6MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211283695.XA CN115536829A (en) | 2022-10-20 | 2022-10-20 | Method for synthesizing fatty acid monoethanolamide polyoxyethylene ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211283695.XA CN115536829A (en) | 2022-10-20 | 2022-10-20 | Method for synthesizing fatty acid monoethanolamide polyoxyethylene ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115536829A true CN115536829A (en) | 2022-12-30 |
Family
ID=84736498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211283695.XA Pending CN115536829A (en) | 2022-10-20 | 2022-10-20 | Method for synthesizing fatty acid monoethanolamide polyoxyethylene ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115536829A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1264102A (en) * | 1969-03-29 | 1972-02-16 | ||
| WO2004054958A1 (en) * | 2002-12-16 | 2004-07-01 | Basf Aktiengesellschaft | Hydroxyalkylation method |
| CN102321238A (en) * | 2011-08-04 | 2012-01-18 | 浙江皇马科技股份有限公司 | The preparation method of fatty amide Soxylat A 25-7 |
| CN110845716A (en) * | 2019-11-26 | 2020-02-28 | 上海东大化学有限公司 | Fatty acid monoethanolamide polyoxyethylene ether and preparation method thereof |
-
2022
- 2022-10-20 CN CN202211283695.XA patent/CN115536829A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1264102A (en) * | 1969-03-29 | 1972-02-16 | ||
| WO2004054958A1 (en) * | 2002-12-16 | 2004-07-01 | Basf Aktiengesellschaft | Hydroxyalkylation method |
| CN102321238A (en) * | 2011-08-04 | 2012-01-18 | 浙江皇马科技股份有限公司 | The preparation method of fatty amide Soxylat A 25-7 |
| CN110845716A (en) * | 2019-11-26 | 2020-02-28 | 上海东大化学有限公司 | Fatty acid monoethanolamide polyoxyethylene ether and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| BRITTA M. FOLMER ET AL.: ""Fatty Amide Ethoxylates: Synthesis and Self-Assembly"", 《JOURNAL OF SURFACTANTS AND DETERGENTS》, vol. 4, no. 2, pages 175 - 183, XP055443002 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101440074B (en) | Synthesizing method of C12/14 alkyl glycidyl ether | |
| CN101928389B (en) | Method for preparing glycidol ether terminated propenol polyoxyethylene ether | |
| JP2008540080A (en) | Method for producing double metal cyanide complex catalyst | |
| CN107674195B (en) | Catalyst for synthesizing polyethylene oxide polymer and synthesis method thereof | |
| CN115536829A (en) | Method for synthesizing fatty acid monoethanolamide polyoxyethylene ether | |
| CN102363645A (en) | Method for synthesizing tetramethylolmethane polyoxyethylene ether | |
| CN109776786B (en) | Preparation method of monomer-terminated amine ether for synthesizing early-strength polycarboxylate superplasticizer | |
| CN113527067A (en) | Preparation method of initiator for polycarboxylate superplasticizer polyether macromonomer | |
| EP0087298A2 (en) | Process for producing benzaldehydes | |
| CN111087597A (en) | Preparation method of high-activity polyether polyol | |
| CN106699702B (en) | A kind of preparation method of Span series product | |
| CN112517039B (en) | Nitrogen modified composite metal oxide insertion type catalyst and application thereof | |
| CN114015034A (en) | Preparation method and application of sodium alkoxide catalyst for synthesizing water reducer polyether | |
| CN109317187B (en) | Catalyst for synthesis of fatty acid ester alkoxylates and application thereof | |
| CN110713595A (en) | Application of DMC (dimethyl formamide) bimetallic complex in preparation of hydroxyl-terminated polyether quaternary ammonium salt | |
| CN115678001A (en) | Method for synthesizing fatty acid monoethanolamide polyoxyethylene ether | |
| CN113912752A (en) | Composite polymerization inhibitor and application thereof, high-stability polyether for polycarboxylate superplasticizer and preparation method thereof | |
| CN107903221B (en) | Preparation method of TBSI | |
| CN105111427A (en) | Preparation method for polyether alkyl hydroxyl acrylate | |
| JP2009280543A (en) | Method for producing polyoxyalkylene alkyl ether | |
| CN115814800B (en) | Preparation method and application of fatty acid methyl ester ethoxylation catalyst | |
| CN113045617B (en) | Preparation method of 3, 5-estradiene-3, 17 beta-diacetate | |
| CN109337061B (en) | Preparation method and application of catalyst for synthesizing polycarboxylate-type water reducer macromonomer | |
| CN114773167B (en) | Pentaerythritol polyoxyethylene ether with low addition number and high conversion rate preparation method thereof | |
| KR102356046B1 (en) | Method for preparing dibutyl tetrahydrophthalate and dibutyl tetrahydrophthalate prepared by the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |