CN111138655B - Polyether ester nonionic surfactant and preparation method thereof - Google Patents
Polyether ester nonionic surfactant and preparation method thereof Download PDFInfo
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- CN111138655B CN111138655B CN201911297159.3A CN201911297159A CN111138655B CN 111138655 B CN111138655 B CN 111138655B CN 201911297159 A CN201911297159 A CN 201911297159A CN 111138655 B CN111138655 B CN 111138655B
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- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
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- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/34—Polyoxyalkylenes of two or more specified different types
Abstract
The invention relates to the technical field of lubricants, in particular to a polyether ester nonionic surfactant and a preparation method thereof. The preparation method at least comprises the following steps: polyether and fatty acid are mixed, added with a catalyst and subjected to a reduced pressure reaction to obtain the polyether ester nonionic surfactant. The polyether ester nonionic surfactant disclosed by the invention is excellent in water solubility, good in intersolubility with other additives, free of the phenomenon of direct 'repulsion' of the additives, good in biodegradability, non-toxic, good in stability and alkali resistance, free of the problem of 'precipitation' of a polyether lubricant in a cutting fluid, far superior in lubricating performance to the traditional polyether lubricant, and the polyether ester nonionic surfactant is the most outstanding product in the lubricating performance of the water-soluble cutting fluid additives at present.
Description
Technical Field
The invention relates to the technical field of lubricants, in particular to a polyether ester nonionic surfactant and a preparation method thereof.
Background
The metal machining industry occupies a great position in the national basic industrial field, and the annual output value is about hundreds of billions of yuan. In the metal machining industry, corresponding lubricating fluid, namely cutting fluid, can not be separated always. The cutting fluid is an essential additive in the metal machining industry, mainly plays roles in lubrication, cooling, rust prevention and the like, and can greatly improve the metal machining efficiency. In the past decades, the cutting fluid mainly uses an emulsion of mineral oil as one of main cutting fluid products, but with the gradual enhancement of environmental protection awareness of people, the national environmental protection is becoming stricter, and the product using the mineral oil emulsion as the cutting fluid can not meet the environmental protection requirement gradually, the reason for this is mainly that the product contains a large amount of mineral oil and an emulsifier, which causes great pollution to water, and in the later-stage wastewater treatment, the efficient treatment and solution are difficult, the cost is extremely high, the treatment process is complex, and the problem always puzzles related personnel of the metal processing industry and the wastewater treatment.
Over the last decade, many researchers have attempted to replace traditional mineral oil emulsions with fully synthetic cutting fluids. The total-synthesis type cutting fluid is mainly prepared from water and a small amount of additives with lubricating and antirust effects, and has the characteristics of low price and simple sewage treatment, and belongs to a more environment-friendly cutting fluid product. The fully synthetic cutting fluid has become the mainstream in recent years abroad, but the technical level of the domestic cutting fluid is a distance away from that of the foreign cutting fluid. The main component of the fully synthetic cutting fluid is water, so that the lubrication is poor, and the lubricating additive which has excellent lubricating property, good water intersolubility and standard environmental protection property is lacking in China at present, so that the fully synthetic cutting fluid cannot be used under the condition of metal machining with harsh requirements or complex process, the precision of a machined workpiece is often insufficient, the abrasion of a machining cutter is serious, and the fully synthetic cutting fluid is slowly developed in China.
In the current domestic market, common lubricants with good water-miscible property mainly include several types, i.e., glycerin type, polyethylene glycol type, oleic acid soap type, borate type, and polyether type. Although glycerol type and polyethylene glycol type lubricating additives have good water intersolubility and belong to environment-friendly additives, the lubricating properties are very limited, and the high-precision metal machining is difficult to meet. The oleic soap type and borate type lubricants are slightly stronger in lubricating properties than the glycerin type and polyethylene glycol type lubricants, but are still unsatisfactory. The polyether type is one of the more popular lubricating products in nearly ten years, and has the characteristics of good water intersolubility, easy biodegradation, no toxicity and the like. Although the polyether lubricant is greatly improved in lubricating performance compared with lubricants such as glycerin type, polyethylene glycol type and borate type, the high-precision metal machining cannot be met, and the polyether lubricant is not resistant to an alkaline system, so that the polyether lubricant cannot be effectively popularized and used.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention provides a method for preparing a novel polyether ester nonionic surfactant, comprising at least the following steps: polyether and fatty acid are mixed, added with a catalyst and subjected to a pressure reduction reaction to obtain the novel polyether ester nonionic surfactant.
As a preferred technical solution, the molar ratio of the polyether to the fatty acid is (1.1-1.5): 1.
as a preferable technical scheme, the polyether is selected from one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, fatty acid polyoxyethylene ether, block polymer of ethylene oxide and propylene oxide, castor oil polyoxyethylene ether and allyl alcohol polyoxyethylene ether.
As a preferred embodiment, the block polymer of ethylene oxide and propylene oxide has a molecular weight of 2000 to 4100; the fatty alcohol-polyoxyethylene ether is a condensation product of isomeric alcohol and ethylene oxide and/or a condensation product of fatty alcohol and ethylene oxide.
As a preferred technical solution, the fatty acid is a saturated fatty acid; the saturated fatty acid is selected from one or more of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and palmitic acid.
As a preferred technical solution, the molar ratio of the saturated fatty acid to the catalyst is 1: (0.01-0.05).
As a preferred technical scheme, the catalyst is a basic catalyst; the alkaline catalyst is selected from Ca (OH) 2 One or more of activated white mud, diatomite, naOH, KOH, sodium carbonate, sodium bicarbonate, sodium methoxide, sodium ethoxide, potassium carbonate, sodium phenolate, potassium methoxide, triethylamine, tributylamine, trimethylamine, tripropylamine, tributylamine, diisopropylamine, diisopropylethylamine, tetramethylammonium hydroxide, benzyltrialkylammonium hydroxide, and tetraalkylammonium hydroxide.
As a preferred technical scheme, the temperature of the decompression reaction is 100-130 ℃; the pressure of the reduced pressure reaction is 0.15-0.25MPa.
In a second aspect, the present invention provides a novel polyetherester nonionic surfactant prepared by the above-mentioned preparation method.
The third aspect of the invention provides a lubricating fluid which contains the novel polyether ester nonionic surfactant; the content of the novel polyether ester nonionic surfactant in the lubricating liquid is 20-60wt%.
Has the advantages that: the invention provides a preparation method of a novel polyether ester nonionic surfactant, which is characterized in that a polyether lubricant and fatty acid are grafted together to form a novel polyether ester nonionic lubricant, the novel polyether ester nonionic lubricant has excellent water solubility, good intersolubility with other additives, no direct additive rejection phenomenon, good biodegradability, no toxicity, environmental protection products, good stability and good alkali resistance, the problem of 'precipitation' of the polyether lubricant in a cutting fluid can not occur, the lubricating property is far superior to that of the conventional polyether lubricant, the novel polyether ester nonionic surfactant is a product with the most outstanding lubricating property in the water-soluble cutting fluid additive at present, the defect of the domestic fully-synthetic cutting fluid can be greatly overcome, and the blank of the domestic fully-synthetic cutting fluid in the high-precision metal machining industry can be filled up.
Drawings
FIG. 1 is a nuclear magnetic spectrum of the novel polyether ester nonionic surfactant prepared in example 3.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
The term "prepared from …" as used herein is synonymous with "comprising". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject of the claims rather than immediately after the subject matter, it defines only the elements described in that clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 to 5" is disclosed, the described range should be construed as including the ranges "1 to 4", "1 to 3", "1 to 2", "2 to 3" and "3 to 4", "4 to 5" and "3 to 5", etc. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The invention provides a preparation method of a novel polyether ester nonionic surfactant, which at least comprises the following steps: polyether and fatty acid are mixed, added with a catalyst and subjected to a pressure reduction reaction to obtain the novel polyether ester nonionic surfactant.
In one embodiment, the molar ratio of polyether to fatty acid is (1.1-1.5): 1.
in a preferred embodiment, the molar ratio of polyether to fatty acid is 1.3:1.
polyether
In the invention, the polyether is a linear polymer prepared by ring opening homopolymerization or copolymerization under the action of a catalyst by using ethylene oxide, propylene oxide, butylene oxide and the like as raw materials.
In one embodiment, the polyether is selected from one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, fatty acid polyoxyethylene ether, block polymer of ethylene oxide and propylene oxide, castor oil polyoxyethylene ether, and allyl alcohol polyoxyethylene ether.
In one embodiment, the fatty alcohol-polyoxyethylene ether is a condensate of an isomeric alcohol and ethylene oxide and/or a condensate of a fatty alcohol and ethylene oxide.
The condensates of isomeric alcohols with ethylene oxide may be exemplified by: emulsifier E-1302, emulsifier E-1306, emulsifier E-1310, emulsifier E-1312, emulsifier E-1308 and emulsifier E-1304.
As the condensates of aliphatic alcohol with ethylene oxide, there can be exemplified: emulsifier AEO-3, emulsifier AEO-5, emulsifier AEO-7, emulsifier AEO-9, peregal OS-15, peregal O-20, peregal O-3, peregal O-5, peregal O-8, peregal O-9, peregal O-10, peregal O-15, peregal O-30, emulsifier MOA-3, emulsifier MOA-4, emulsifier MOA-5, emulsifier MOA-7, emulsifier MOA-9, emulsifier MOA-15, emulsifier MOA-20, and emulsifier MOA-23.
In a preferred embodiment, the fatty alcohol-polyoxyethylene ether is a condensate of an isomeric alcohol and ethylene oxide.
The alkylphenol ethoxylates can be enumerated by: emulsifier NP-4, emulsifier NP-6, emulsifier NP-7, emulsifier NP-9, emulsifier NP-10, emulsifier NP-15, emulsifier NP-20, emulsifier NP-21, emulsifier NP-30, emulsifier NP-40.
The fatty amine polyoxyethylene ethers include, for example: AC-1210, AC-1215, AC-1810, AC-1815, AC-1820, AC-1860, and a leveling agent AN.
The fatty acid polyoxyethylene ethers include, for example: emulsifier LAE-9, emulsifier SE-10 and softener SG.
As said block polymer of ethylene oxide and propylene oxide, there may be enumerated: RPE 1720, RPE 1740, RPE 2035, RPE 2520, RPE 2525, RPE 3110, L31, L35, F38, L42, L43, L44, L45, L61, L62, L63, L64, P65, F68, F127.
The polyoxyethylene castor oil ether may be exemplified by: emulsifier EL-10, emulsifier EL-20, emulsifier EL-40, emulsifier EL-80, emulsifier C-125 and emulsifier EL-90.
As the allyl alcohol polyoxyethylene ether, there can be exemplified: APEG-700, APEG-800, APEG-1000, APEG-2000, APEG-2400, APEG-3000, and APEG-4000.
In a preferred embodiment, the polyether is a block polymer of ethylene oxide and propylene oxide, a blend of fatty alcohol polyoxyethylene ethers.
In a preferred embodiment, the molar ratio of the block polymer of ethylene oxide and propylene oxide to the fatty alcohol polyoxyethylene ether is (0.8-1.2): 1.
more preferably, the molar ratio of the block polymer of ethylene oxide and propylene oxide to the fatty alcohol-polyoxyethylene ether is 1:1.
in a preferred embodiment, the polyether is a block polymer of ethylene oxide and propylene oxide, a complex of an isomeric alcohol and an ethylene oxide condensate.
In a preferred embodiment, the molar ratio of the block polymer of ethylene oxide and propylene oxide, the isomeric alcohol and ethylene oxide condensate is (0.8 to 1.2): 1.
more preferably, the molar ratio of the block polymer of ethylene oxide and propylene oxide, the isomeric alcohol and the ethylene oxide condensate is 1:1.
in a preferred embodiment, the block polymer of ethylene oxide and propylene oxide has a molecular weight of 2000 to 4100.
More preferably, the block polymer of ethylene oxide and propylene oxide has a molecular weight of 2650.
In the present invention, the molecular weight means an average molecular weight, and the unit is 1.
In a preferred embodiment, the isomeric alcohol and ethylene oxide condensate has a hydroxyl number of 83 to 175mgKOH/g.
More preferably, the condensate of the isomeric alcohol and ethylene oxide has a hydroxyl value of from 115 to 125mgKOH/g.
In the present invention, the hydroxyl value is the content or concentration of hydroxyl group and refers to the amount of hydroxyl value contained in a sample per unit weight, and mgKOH/g is the unit of hydroxyl value, wherein mgKOH is the unit of measurement of hydroxyl group; in the present invention, the hydroxyl group is converted to KOH, and 1 mol of OH is converted to 1 mol of KOH, which means that 56100mgKOH and 1mgKOH are 156100 mol of hydroxyl groups.
In view of the preferred technical effect of the present invention, the block polymer of ethylene oxide and propylene oxide is Pluronic RPE 1740 having a molecular weight of 2650, available from basf (china) ltd; the condensate of isomeric alcohol and epoxy ethane is emulsifier E-1306, hydroxyl value is 115-125mgKOH/g, and the condensate is purchased from the petrochemical industry of Haian in Jiangsu province.
The ethylene oxide/propylene oxide copolyether used in the invention is composed of a hydrophilic group-CH 2 CH 2 O-and a hydrophobic group-C 3 H 6 The amphiphilic block copolymer formed by O-adopts a single ethylene oxide/propylene oxide copolyether, only one chain end group is adsorbed to form a tail chain on an interface reacting with saturated fatty acid, which is not beneficial to the complete conversion of the saturated fatty acid, thereby reducing the water solubility of the whole system. The inventor finds that in the research process, when the isomerol and ethylene oxide condensate are added to be compounded with the propylene oxide-ethylene oxide block polyether, and the hydroxyl value of the isomerol and ethylene oxide condensate is 83-175mgKOH/g, the water solubility of the system is improved, and the inventor believes that the reason is probably that the isomerol and ethylene oxide condensate contain isomerol, so that the isomerol and ethylene oxide block polyether are beneficial to conversion between isomers of neodecanoic acid, the conversion rate is increased, the water solubility of the system is improved, and different isomerol and ethylene oxide condensates have different hydroxyl values, so that the intermolecular action is different, and the intersolubility of polyether ester and other substances is influenced. The inventors have surprisingly found that when the molar ratio of the block polymer of ethylene oxide and propylene oxide and the isomeric alcohol to ethylene oxide condensate is (0.8 to 1.2): 1, and the ethylene oxide-propylene oxide block polyether is Pluronic RPE 1740, and the condensate of isomeric alcohol and ethylene oxide is milkThe best stability of the system was obtained with the reagent E-1306, and the reason the inventors thought was probably due to the use of the condensate of the isomeric alcohol with ethylene oxide as emulsifier E-1306 for the-CH in the polyetherester 2 CH 2 Increasing the proportion of O-chain segment to produce-CH 2 CH 2 Complex chain entanglement between O-chain segments is easy to occur to make-CH 2 CH 2 The more the O-chain segment is condensed, the stability of the polyether ester is obviously improved.
Fatty acids
In the invention, the fatty acid is a compound consisting of three elements of carbon, hydrogen and oxygen, and is the main component of neutral fat, phospholipid and glycolipid. Fatty acids refer to long aliphatic hydrocarbon chains containing a carboxyl group at one end. Fatty acids can be divided into two classes: one is saturated fatty acid without carbon-carbon double bond in the molecule, such as stearic acid, palmitic acid, etc.; another class is saturated fatty acids with one or several carbon-carbon double bonds in the molecule, most commonly oleic acid.
In one embodiment, the fatty acid is a saturated fatty acid and/or an unsaturated fatty acid.
The saturated fatty acid is selected from one or more of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and palmitic acid.
The unsaturated fatty acid includes, but is not limited to, any one of alpha-linolenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, conjugated linoleic acid, gamma-linolenic acid, eicosatrienoic acid, arachidonic acid, oleic acid, trans-oleic acid, eicosenoic acid, eicosatrienoic acid, erucic acid, nervonic acid.
In a preferred embodiment, the fatty acid is a saturated fatty acid.
In a preferred embodiment, the saturated fatty acid is a complex of capric acid and palmitic acid.
In a preferred embodiment, the molar ratio of capric acid to palmitic acid is (1.2-1.8): 1.
more preferably, the molar ratio of capric acid to palmitic acid is 1.5:1.
in a preferred embodiment, the decanoic acid is selected from one or more of n-decanoic acid, isodecanoic acid, neodecanoic acid.
More preferably, the decanoic acid is neodecanoic acid.
In a preferred embodiment, the molar ratio of neodecanoic acid to palmitic acid is (1.2-1.8): 1.
more preferably, the molar ratio of neodecanoic acid (CAS number 26896-20-8) to palmitic acid (CAS number 57-10-3) is 1.5:1.
in a preferred embodiment, the molar ratio of polyether to saturated fatty acid is (1.1-1.5): 1.
more preferably, the molar ratio of the polyether to the saturated fatty acid is 1.3:1.
in the invention, saturated fatty acid and polyether are reacted to synthesize polyether ester, but since the saturated fatty acid belongs to oily products, is easy to oxidize and harden in air and is insoluble in water, the inventor finds that when the molar ratio of the polyether to the saturated fatty acid is (1.1-1.5): 1, when the saturated fatty acid is a compound of neodecanoic acid and palmitic acid, the water solubility and the lubricity of the system are the best. The reason the inventor believes is probably because the polar end-COOH of palmitic acid is towards the-OH end of polyether under the action of foam generated by KOH, the steric reaction steric hindrance between the polar end-COOH of saturated fatty acid and polyether is reduced, the reaction rate is improved, and in the case of excessive polyether, water generated in the reaction is continuously sucked out in the reaction process, so that the saturated fatty acid is completely converted into polyether ester, and the water solubility of polyether ester with branched neodecanoic acid is obviously improved due to the existence of isomerization phenomenon. The inventors have surprisingly found that when the molar ratio of polyether to saturated fatty acid is 1.3:1, and the polyether is a compound of Pluronic RPE 1740 and emulsifier E-1306, the lubricity of the resulting system is best, and the inventor believes that the reason is probably that the product obtained by the reaction under the conditions of high temperature of 120 ℃ and reduced pressure is a mixture of polyether ester, polyether Pluronic RPE 1740 and emulsifier E-1306, and-CH in polyether ester 2 CH 2 O-segment and-CH in polyether 2 CH 2 The O-segments overlap each other and are solvated by binding to water molecules to form hydrogen bondsHigh system stability and lubricity.
Catalyst and process for producing the same
In the present invention, the catalyst is a substance that alters the rate of reaction without altering the overall standard gibbs free energy of reaction.
In one embodiment, the catalyst is an acidic catalyst and/or a basic catalyst.
The acidic catalyst includes, but is not limited to, any one of concentrated sulfuric acid, aluminum silicate, molecular sieve, acidic ion exchange resin, phosphoric acid, boric acid.
The basic catalyst is selected from Ca (OH) 2 One or more of activated white mud, diatomite, naOH, KOH, sodium carbonate, sodium bicarbonate, sodium methoxide, sodium ethoxide, potassium carbonate, sodium phenolate, potassium methoxide, triethylamine, tributylamine, trimethylamine, tripropylamine, tributylamine, diisopropylamine, diisopropylethylamine, tetramethylammonium hydroxide, benzyltrialkylammonium hydroxide, and tetraalkylammonium hydroxide.
In a preferred embodiment, the catalyst is a basic catalyst.
In a preferred embodiment, the basic catalyst is a combination of KOH and diatomaceous earth.
In a preferred embodiment, the molar ratio of KOH to diatomaceous earth is (2-4): 1.
more preferably, the molar ratio of KOH to diatomaceous earth is 3:1.
the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xu mineral products Co.
In a preferred embodiment, the molar ratio of saturated fatty acids to catalyst is 1: (0.01-0.05).
More preferably, the molar ratio of saturated fatty acids to catalyst is 1:0.03.
the invention adopts the alkaline catalyst to prepare the polyether ester, can solve the problem that the polyether lubricant is not resistant to an alkaline system, and the inventor finds that when the alkaline catalyst is potassium hydroxide and kieselguhr, and the molar ratio of KOH to the kieselguhr is (2-4): 1, the polyether ester prepared by the invention does not have the problem of 'precipitation' in cutting fluid, and the polyether ester has the best alkali resistance. The reason the inventor thinks is probably that the dispersion degree of the catalyst is improved due to the special porous structure of the diatomite, the effective collision between the polyether and the saturated fatty acid molecules reaches an equilibrium state, and the KOH generates certain foam, so that the problem of 'precipitation' in the cutting fluid can be inhibited. The inventors have surprisingly found that when the molar ratio of basic catalyst to saturated fatty acid is (0.01-0.05): 1, the lubricity of the polyether ester can be improved at the same time, and the reason considered by the inventor is probably that potassium ions are beneficial to isomerization of neodecanoic acid in saturated fatty acid, close packing between chain segments is hindered, and the lubricity of the polyether ester is improved.
In one embodiment, the temperature of the reduced pressure reaction is from 100 to 130 ℃; the pressure of the reduced pressure reaction is 0.15-0.25MPa, and the reduced pressure reaction time is 2-10h.
In a preferred embodiment, the temperature of the reduced pressure reaction is 120 ℃; the pressure of the decompression reaction is 0.2Mpa; the reduced pressure reaction time is 5h.
The invention adopts the decompression reaction to discharge the water generated by the reaction of polyether and fatty acid in time, and the inventor finds that the lubricating property of polyether ester is best when the temperature of the decompression reaction is 120 ℃ and the pressure of the decompression reaction is 0.2MPa in the research process. The reason the inventors thought might be that when the pressure of the reduced pressure reaction was too small, the reaction of polyether Pluronic RPE 1740, emulsifier E-1306 and saturated fatty acid was too vigorous, increasing the viscosity of the system and decreasing the lubricity of the system; and when the pressure is higher, the saturated fatty acid can not be completely converted, so that the water solubility and the stability of the system are reduced.
In the nuclear magnetic spectrum disclosed by the invention, a signal peak belonging to an ester bond at 4.2ppm indicates that the polyether and the fatty acid form a good ester bond, and the polyether ester is successfully synthesized.
In a second aspect, the present invention provides a novel polyetherester nonionic surfactant prepared by the above-mentioned preparation method.
The third aspect of the invention provides a lubricating fluid which contains the novel polyether ester nonionic surfactant; the content of the novel polyether ester nonionic surfactant in the lubricating liquid is 20-60wt%.
In a preferred embodiment, the novel polyetherester nonionic surfactant is present in the lubricating fluid in an amount of 40wt%.
The present invention is described in detail below with reference to examples, which are provided for the purpose of further illustration only and are not to be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations thereof by those skilled in the art based on the teachings of the present invention will still fall within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
Example 1 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 10 hours at 100 ℃ under the pressure of 0.15MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.1:1; the molar ratio of the fatty acid to the catalyst is 1:0.01;
the polyether is a compound of a block polymer Pluronic RPE 1740 and an emulsifier E-1310 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1310 is 0.8:1; the Pluronic RPE 1740 has a molecular weight of 2650, available from Pasteur (China) Inc.; the emulsifier E-1310 has a hydroxyl value of 83-93mgKOH/g, and is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.2:1;
the catalyst is a compound of KOH and kieselguhr, and the molar ratio of the KOH to the kieselguhr is 2:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xu mineral products Co.
Example 2
Example 2 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 10 hours at 130 ℃ under the pressure of 0.25MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.5:1; the molar ratio of the fatty acid to the catalyst is 1:0.05;
the polyether is a compound of a block polymer Pluronic RPE 1740 and an emulsifier E-1303 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1303 is 1.2:1; the Pluronic RPE 1740 has a molecular weight of 2650, and is available from Pasteur (China) Inc.; the emulsifier E-1303, with a hydroxyl value of 165-175mgKOH/g, is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.8:1;
the catalyst is a compound of KOH and kieselguhr, and the molar ratio of the KOH to the kieselguhr is 4:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xuxu mineral products, inc.
Example 3
Example 3 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a block polymer Pluronic RPE 1740 and an emulsifier E-1306 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1306 is 1:1; the Pluronic RPE 1740 has a molecular weight of 2650, and is available from Pasteur (China) Inc.; the emulsifier E-1306 has a hydroxyl value of 115-125mgKOH/g, and is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.5:1;
the catalyst is a compound of KOH and kieselguhr, and the molar ratio of the KOH to the kieselguhr is 3:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xu mineral products Co.
Example 4
Example 4 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a block polymer Pluronic RPE 2525 of ethylene oxide and propylene oxide and an emulsifier E-1306, and the molar ratio of the Pluronic RPE 2525 to the emulsifier E-1306 is 1:1; the Pluronic RPE 2525 has a molecular weight of 2000, purchased from Pasteur (China) Inc.; the hydroxyl value of the emulsifier E-1306 is 115-125mgKOH/g, and the emulsifier E-1306 is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.5:1;
the catalyst is a compound of KOH and diatomite, and the molar ratio of the KOH to the diatomite is 3:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xu mineral products Co.
Example 5
Example 5 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a block polymer Pluronic RPE 2035 of ethylene oxide and propylene oxide and an emulsifier E-1306, and the molar ratio of the Pluronic RPE 2035 to the emulsifier E-1306 is 1:1; the Pluronic RPE 2035 has a molecular weight of 4100, and is purchased from Pasteur (China) Inc.; the hydroxyl value of the emulsifier E-1306 is 115-125mgKOH/g, and the emulsifier E-1306 is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.5:1;
the catalyst is a compound of KOH and diatomite, and the molar ratio of the KOH to the diatomite is 3:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xuxu mineral products, inc.
Example 6
Example 6 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a pressure reduction reaction for 5 hours at 120 ℃ under 0.02MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a block polymer Pluronic RPE 1740 and an emulsifier E-1306 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1306 is 1:1; the Pluronic RPE 1740 has a molecular weight of 2650, available from Pasteur (China) Inc.; the emulsifier E-1306 has a hydroxyl value of 115-125mgKOH/g, and is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.5:1;
the catalyst is a compound of KOH and diatomite, and the molar ratio of the KOH to the diatomite is 3:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xu mineral products Co.
Example 7
Example 7 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 5 hours at 120 ℃ under the pressure of 0.8MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a segmented polymer Pluronic RPE 1740 and an emulsifier E-1306 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1306 is 1:1; the Pluronic RPE 1740 has a molecular weight of 2650, available from Pasteur (China) Inc.; the emulsifier E-1306 has a hydroxyl value of 115-125mgKOH/g, and is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.5:1;
the catalyst is a compound of KOH and kieselguhr, and the molar ratio of the KOH to the kieselguhr is 3:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xu mineral products Co.
Example 8
Example 8 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 0.5:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a block polymer Pluronic RPE 1740 and an emulsifier E-1306 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1306 is 1:1; the Pluronic RPE 1740 has a molecular weight of 2650, and is available from Pasteur (China) Inc.; the emulsifier E-1306 has a hydroxyl value of 115-125mgKOH/g, and is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.5:1;
the catalyst is a compound of KOH and kieselguhr, and the molar ratio of the KOH to the kieselguhr is 3:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xu mineral products Co.
Example 9
Example 9 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a segmented polymer Pluronic RPE 1740 and an emulsifier E-1306 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1306 is 1:1; the Pluronic RPE 1740 has a molecular weight of 2650, available from Pasteur (China) Inc.; the emulsifier E-1306 has a hydroxyl value of 115-125mgKOH/g, and is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.5:1;
the catalyst is a compound of KOH and kieselguhr, and the molar ratio of the KOH to the kieselguhr is 3:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xuxu mineral products, inc.
Example 10
Example 10 provides a method of making a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a block polymer Pluronic RPE 1740 and an emulsifier E-1306 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1306 is 1:1; the Pluronic RPE 1740 has a molecular weight of 2650, available from Pasteur (China) Inc.; the emulsifier E-1306 has a hydroxyl value of 115-125mgKOH/g, and is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is palmitic acid (CAS number 57-10-3);
the catalyst is a compound of KOH and kieselguhr, and the molar ratio of the KOH to the kieselguhr is 3:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xu mineral products Co.
Example 11
Example 11 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a block polymer Pluronic RPE 1740 and an emulsifier E-1306 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1306 is 1:1; the Pluronic RPE 1740 has a molecular weight of 2650, available from Pasteur (China) Inc.; the emulsifier E-1306 has a hydroxyl value of 115-125mgKOH/g, and is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is neodecanoic acid (CAS number 26896-20-8);
the catalyst is a compound of KOH and kieselguhr, and the molar ratio of the KOH to the kieselguhr is 3:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xu mineral products Co.
Example 12
Example 12 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a segmented polymer Pluronic RPE 1740 and an emulsifier E-1306 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1306 is 1:1; the Pluronic RPE 1740 has a molecular weight of 2650, and is available from Pasteur (China) Inc.; the emulsifier E-1306 has a hydroxyl value of 115-125mgKOH/g, and is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is oleic acid;
the catalyst is a compound of KOH and kieselguhr, and the molar ratio of the KOH to the kieselguhr is 3:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xu mineral products Co.
Example 13
Example 13 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a pressure reduction reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a block polymer Pluronic RPE 1740 and fatty alcohol polyoxyethylene ether OE-2 of ethylene oxide and propylene oxide, and the molar ratio of Pluronic RPE 1740 to fatty alcohol polyoxyethylene ether OE-2 is 1:1; the Pluronic RPE 1740 has a molecular weight of 2650, available from Pasteur (China) Inc.; the hydroxyl value of the fatty alcohol-polyoxyethylene ether OE-2 is 220-260mgKOH/g, and the fatty alcohol-polyoxyethylene ether OE-2 is purchased from Haian petrochemical engineering in Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.5:1;
the catalyst is a compound of KOH and kieselguhr, and the molar ratio of the KOH to the kieselguhr is 3:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xu mineral products Co.
Example 14
Example 14 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a pressure reduction reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a block polymer Pluronic RPE 1740 of ethylene oxide and propylene oxide; the Pluronic RPE 1740 has a molecular weight of 2650, available from Pasteur (China) Inc.;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.5:1;
the catalyst is a compound of KOH and kieselguhr, and the molar ratio of the KOH to the kieselguhr is 3:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xuxu mineral products, inc.
Example 15
Example 15 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a block polymer Pluronic RPE 1740 and an emulsifier E-1306 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1306 is 1:1; the Pluronic RPE 1740 has a molecular weight of 2650, available from Pasteur (China) Inc.; the emulsifier E-1306 has a hydroxyl value of 115-125mgKOH/g, and is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.5:1;
the catalyst is a compound of KOH and kieselguhr, and the molar ratio of the KOH to the kieselguhr is 3:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xu mineral products Co.
Example 16
Example 16 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.2;
the polyether is a compound of a segmented polymer Pluronic RPE 1740 and an emulsifier E-1306 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1306 is 1:1; the Pluronic RPE 1740 has a molecular weight of 2650, available from Pasteur (China) Inc.; the emulsifier E-1306 has a hydroxyl value of 115-125mgKOH/g, and is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.5:1;
the catalyst is a compound of KOH and kieselguhr, and the molar ratio of the KOH to the kieselguhr is 3:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xu mineral products Co.
Example 17
Example 17 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a block polymer Pluronic RPE 1740 and an emulsifier E-1306 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1306 is 1:1; the Pluronic RPE 1740 has a molecular weight of 2650, available from Pasteur (China) Inc.; the emulsifier E-1306 has a hydroxyl value of 115-125mgKOH/g, and is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.5:1;
the catalyst is a compound of KOH and diatomite, and the molar ratio of the KOH to the diatomite is 0.5:1; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xuxu mineral products, inc.
Example 18
Example 18 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a block polymer Pluronic RPE 1740 and an emulsifier E-1306 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1306 is 1:1; the Pluronic RPE 1740 has a molecular weight of 2650, available from Pasteur (China) Inc.; the emulsifier E-1306 has a hydroxyl value of 115-125mgKOH/g, and is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.5:1;
the catalyst is diatomite; the diatomaceous earth has a mesh size of 200 meshes and is purchased from Hebeixin Xu mineral products Co.
Example 19
Example 19 provides a method for preparing a novel polyetherester nonionic surfactant, comprising the steps of: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction for 5 hours at 120 ℃ under the pressure of 0.2MPa to obtain a novel polyether ester nonionic surfactant;
the molar ratio of the polyether to the fatty acid is 1.3:1; the molar ratio of the fatty acid to the catalyst is 1:0.03;
the polyether is a compound of a block polymer Pluronic RPE 1740 and an emulsifier E-1306 of ethylene oxide and propylene oxide, and the molar ratio of the Pluronic RPE 1740 to the emulsifier E-1306 is 1:1; the Pluronic RPE 1740 has a molecular weight of 2650, available from Pasteur (China) Inc.; the emulsifier E-1306 has a hydroxyl value of 115-125mgKOH/g, and is purchased from Haian petrochemical engineering of Jiangsu province;
the fatty acid is a compound of neodecanoic acid (CAS number 26896-20-8) and palmitic acid (CAS number 57-10-3), and the molar ratio of neodecanoic acid to palmitic acid is 1.5:1;
the catalyst is concentrated sulfuric acid; the mass fraction of sulfuric acid in the concentrated sulfuric acid is 98wt%.
Performance testing
1. Lubricating property: the PB values of the novel polyetherester nonionic surfactants obtained in examples 1 to 19 and the common commercially available lubricating products (soap oleate, trans-polyether 1740) were measured by means of a four-ball mill with reference to SH/T0202-1992 standard, and the results are shown in Table 1.
2. Stability: 20g of the novel polyetherester nonionic surfactants obtained in examples 1 to 19 were taken and left at room temperature (25 ℃ C.) for 24 hours to observe whether or not delamination occurred, and the experimental results are shown in Table 1.
3. Water solubility: 5g of the novel polyether ester nonionic surfactants obtained in examples 1 to 19 were added with 20g of distilled water, and the dissolution of the novel polyether ester nonionic surfactants obtained in examples 1 to 19 was observed, and the experimental results are shown in Table 1.
4. Alkali resistance: 5g of the novel polyether ester nonionic surfactant obtained in examples 1 to 19 was put into 50mL of a 1% NaOH aqueous solution at room temperature (25 ℃ C.) for 2 hours, and it was observed whether the NaOH aqueous solution was turbid.
Table 1 results of performance testing
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (3)
1. A preparation method of polyether ester nonionic surfactant is characterized by at least comprising the following steps: mixing polyether and fatty acid, adding a catalyst, and carrying out a reduced pressure reaction to obtain a polyether ester nonionic surfactant;
the polyether is a compound of a block polymer of ethylene oxide and propylene oxide, and a condensation product of isomeric alcohol and ethylene oxide; the molar ratio of the block polymer of ethylene oxide and propylene oxide, the isomeric alcohol and the ethylene oxide condensate is (0.8-1.2): 1;
the fatty acid is saturated fatty acid, and the saturated fatty acid is a compound of neodecanoic acid and palmitic acid; the molar ratio of the polyether to the saturated fatty acid is (1.1-1.5): 1;
the molecular weight of the block polymer of ethylene oxide and propylene oxide is 2000-4100;
the molar ratio of the saturated fatty acid to the catalyst is 1: (0.01-0.05);
the catalyst is a basic catalyst; the alkaline catalyst is a compound of KOH and diatomite; the molar ratio of the KOH to the diatomite is (2-4): 1;
the temperature of the reduced pressure reaction is 100-130 ℃; the pressure of the reduced pressure reaction was 0.02MPa.
2. A polyether ester nonionic surfactant, wherein the polyether ester nonionic surfactant is prepared according to the preparation method of claim 1.
3. A lubricating fluid comprising the polyether ester nonionic surfactant according to claim 2; the content of the polyether ester nonionic surfactant in the lubricating liquid is 20-60wt%.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4950420A (en) * | 1988-08-31 | 1990-08-21 | Nalco Chemical Company | Antifoam/defoamer composition |
| US5576451A (en) * | 1991-11-13 | 1996-11-19 | Henkel Kommanditgesellschaft Auf Aktien | Esters of fatty acids with ethoxylated polyols |
| CN102634005A (en) * | 2012-03-15 | 2012-08-15 | 上海多纶化工有限公司 | Synthesis method of isomeric alcohol polyethenoxy ether |
| CN103509633A (en) * | 2012-06-21 | 2014-01-15 | 中国石油天然气股份有限公司 | Water-soluble poly ether ester lubrication additive and preparation method thereof |
| CN104059783A (en) * | 2014-06-10 | 2014-09-24 | 深圳市新纶科技股份有限公司 | Preparation method of surfactant for detergents and detergent composition |
| JP2016175898A (en) * | 2015-03-20 | 2016-10-06 | 三洋化成工業株式会社 | Cyclic polyether-ester, lubricant composition including the same, and production method of cyclic polyether-ester |
| CN106554492A (en) * | 2015-09-28 | 2017-04-05 | 上海东大化学有限公司 | A kind of isomery alcohol alkoxy polyether and preparation method thereof |
| CN106975247A (en) * | 2017-05-25 | 2017-07-25 | 济宁南天农科化工有限公司 | A kind of novel polyether ester defoamer and preparation method thereof |
-
2019
- 2019-12-16 CN CN201911297159.3A patent/CN111138655B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4950420A (en) * | 1988-08-31 | 1990-08-21 | Nalco Chemical Company | Antifoam/defoamer composition |
| US5576451A (en) * | 1991-11-13 | 1996-11-19 | Henkel Kommanditgesellschaft Auf Aktien | Esters of fatty acids with ethoxylated polyols |
| CN102634005A (en) * | 2012-03-15 | 2012-08-15 | 上海多纶化工有限公司 | Synthesis method of isomeric alcohol polyethenoxy ether |
| CN103509633A (en) * | 2012-06-21 | 2014-01-15 | 中国石油天然气股份有限公司 | Water-soluble poly ether ester lubrication additive and preparation method thereof |
| CN104059783A (en) * | 2014-06-10 | 2014-09-24 | 深圳市新纶科技股份有限公司 | Preparation method of surfactant for detergents and detergent composition |
| JP2016175898A (en) * | 2015-03-20 | 2016-10-06 | 三洋化成工業株式会社 | Cyclic polyether-ester, lubricant composition including the same, and production method of cyclic polyether-ester |
| CN106554492A (en) * | 2015-09-28 | 2017-04-05 | 上海东大化学有限公司 | A kind of isomery alcohol alkoxy polyether and preparation method thereof |
| CN106975247A (en) * | 2017-05-25 | 2017-07-25 | 济宁南天农科化工有限公司 | A kind of novel polyether ester defoamer and preparation method thereof |
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