阅读说明：本技术 脂肪酸聚乙二醇酯的合成方法 (Method for synthesizing fatty acid polyglycol ester ) 是由 张怀哲 李翔 钟敏 王建臣 张江锋 侯海育 于 2021-10-08 设计创作，主要内容包括：本发明涉及脂肪酸聚乙二醇酯的合成方法,主要解决脂肪酸聚乙二醇酯现有合成方法得到的产品色度高的问题,通过采用脂肪酸聚乙二醇酯的合成方法,包括在酸性催化剂和其他反应助剂存在下,聚乙二醇与原料脂肪酸发生酯化反应得到脂肪酸聚乙二醇酯,所述其它反应助剂包括选自次磷酸化合物和脂肪酸亚锡中的至少一种的技术方案,较好地解决了该技术问题,可用于脂肪酸聚乙二醇酯的生产中。(The invention relates to a synthesis method of fatty acid polyglycol ester, mainly solve the problem that the product chroma obtained by existing synthesis method of fatty acid polyglycol ester is high, through adopting the synthesis method of fatty acid polyglycol ester, including in presence of acid catalyst and other reaction auxiliary agent, polyglycol takes place the esterification reaction with raw materials fatty acid to get fatty acid polyglycol ester, the said other reaction auxiliary agent includes the technical scheme of at least one selected from hypophosphorous acid compound and fatty acid stannous, has solved this technical matter well, can be used in the production of fatty acid polyglycol ester.)

1. The synthesis method of the fatty acid polyglycol ester comprises the step of carrying out esterification reaction on polyethylene glycol and raw material fatty acid in the presence of an acid catalyst and other reaction aids to obtain the fatty acid polyglycol ester, wherein the other reaction aids comprise at least one selected from hypophosphorous acid compounds and fatty acid stannous.

2. The method according to claim 1, wherein the acidic catalyst comprises at least one member selected from the group consisting of arylsulfonic acid, sulfuric acid, and acid sulfate. And/or preferably, the feeding amount of the catalyst accounts for 0.2-1% of the weight of the polyethylene glycol. And/or preferably the aromatic sulfonic acid corresponds to the following formula 1:

wherein R is₁And R₂Is independently selected from H or alkyl of C1-C3.

3. The method according to claim 1, wherein said hypophosphite compound comprises hypophosphorous acid and/or hypophosphite salt. And/or said hypophosphite salt is preferably an alkali metal hypophosphite salt, said alkali metal more preferably being potassium or sodium.

4. The synthesis method according to claim 1, wherein the fatty acid stannous is represented by the following structural formula 2:

wherein R is₃And R₄Independently selected from C9-C20 hydrocarbyl, and/or R₃And R₄Independently preferably a linear hydrocarbon group, and/or R₃And R₄Independently preferably a primary hydrocarbyl group, and/or R₃And R₄Independently, alkenyl or alkyl groups are preferred.

5. The method as set forth in claim 1, wherein the amount of the other reaction auxiliary is 0.2-1% by weight based on the weight of the polyethylene glycol.

6. The method according to claim 1, wherein the temperature of the esterification reaction is 110 to 160 ℃.

7. The method according to claim 1, wherein the esterification reaction time is 3 to 6 hours.

8. The method according to claim 1, wherein the starting fatty acid is a C8-C20 monobasic acid.

9. The method according to claim 1, wherein the polyethylene glycol has a number average molecular weight of 200 to 1000.

10. The method according to claim 1, wherein the molar ratio of the raw material fatty acid to the polyethylene glycol is 0.9 to 2.2.

Technical Field

The invention relates to a synthetic method of fatty acid polyglycol ester.

Background

The fatty acid polyglycol ester is a nonionic surfactant and has wide application in various spinning oil, chemical auxiliary, daily chemical and other fields.

The fatty acid polyglycol ester can be obtained by an esterification reaction between a fatty acid and polyethylene glycol in the presence of an acid catalyst, for example, a synthesis study of a polyethylene glycol oleate catalyst (dawn, heavy waves, anyongfang, a catalytic synthesis study of polyethylene glycol oleate [ J ]. university of shanxi science and technology, 2008, 26 (2): 50-52) conducted by dawn, etc., but the product of the fatty acid polyglycol ester obtained by such a method has a dark color, and is limited in market popularization in a field where the requirement for low color of the product is high.

Disclosure of Invention

The invention mainly solves the technical problem that the product obtained by the existing synthesis method of the fatty acid polyglycol ester has high chromaticity, and provides a novel synthesis method of the fatty acid polyglycol ester, which has the advantage of reducing the chromaticity of the fatty acid polyglycol ester product.

In order to solve the technical problems, the technical scheme of the invention is as follows:

the synthesis method of the fatty acid polyglycol ester comprises the step of carrying out esterification reaction on polyethylene glycol and raw material fatty acid in the presence of an acid catalyst and other reaction aids to obtain the fatty acid polyglycol ester, wherein the other reaction aids comprise at least one selected from hypophosphorous acid compounds and fatty acid stannous.

The presence of the other reaction aids reduces the color of the product during the esterification reaction.

In the above technical solution, preferably, the acidic catalyst includes at least one selected from the group consisting of an aromatic sulfonic acid, a sulfuric acid, and an acid sulfate.

In the technical scheme, preferably, the feeding amount of the catalyst accounts for 0.2-1% of the weight of the polyethylene glycol. For example, but not limited to, catalyst loading of 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, etc., by weight of the polyethylene glycol.

In the above technical solution, preferably, the aromatic sulfonic acid corresponds to the following formula 1:

wherein R is₁And R₂Independently selected from H or alkyl of C1-C3, such as but not limited to, said aryl sulfonic acid is benzene sulfonic acid, p-toluene sulfonic acid, isopropyl benzene sulfonic acid, xylene sulfonic acidAnd so on.

In the above technical solution, preferably, the hypophosphite compound comprises hypophosphorous acid and/or hypophosphite. The hypophosphorous acid salt is preferably an alkali metal salt of hypophosphorous acid, and the alkali metal salt is more preferably potassium or sodium.

In the above technical solution, preferably, the fatty acid stannous is in accordance with the following structural formula 2:

wherein R is₃And R₄Independently selected from C9-C20 hydrocarbyl groups (such as but not limited to R)₃And R₄Independently selected from C10 hydrocarbyl, C11 hydrocarbyl, C12 hydrocarbyl, C13 hydrocarbyl, C14 hydrocarbyl, C15 hydrocarbyl, C16 hydrocarbyl, C17 hydrocarbyl, C18 hydrocarbyl, C19 hydrocarbyl).

In the above technical scheme, R₃And R₄Independently, linear hydrocarbon groups are preferred.

In the above technical scheme, R₃And R₄Independently, primary hydrocarbyl groups are preferred.

In the above technical scheme, R₃And R₄Independently, alkenyl or alkyl groups are preferred.

In the above technical scheme, preferably, the feeding amount of the other reaction auxiliary agent accounts for 0.2-1% of the weight of the polyethylene glycol. For example, but not limited to, the other reaction auxiliary agents are added in an amount of 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95% by weight of the polyethylene glycol, and the like.

In the above technical solution, preferably, the other reaction auxiliary agent includes a hypophosphorous acid compound and fatty acid stannous. The hypophosphorous acid compound and the fatty acid stannous have mutual promotion effect on the aspect of reducing the chromaticity of the product.

In the above technical solution, the weight ratio of the fatty acid stannous to the hypophosphorous acid compound is preferably greater than 0 and less than 0.5, and further non-limiting specific examples are: the weight ratio of fatty acid stannous to hypophosphorous acid compound is 0.01, 0.02, 0.03, 0.04, 0.05, 0.08, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, etc. Most preferably 0.10 to 0.45.

In the above technical scheme, preferably, the temperature of the esterification reaction is 110-160 ℃. For example, but not limited to, the esterification reaction temperature is 115 deg.C, 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C, 145 deg.C, 150 deg.C, 155 deg.C, etc.

In the above technical scheme, preferably, the esterification reaction time is 3-6 hours. Such as, but not limited to, esterification reaction times of 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, and the like.

In the above technical scheme, those skilled in the art know that, in order to reduce the color of the product, a nitrogen atmosphere is preferably used in the esterification reaction process, and the continuous introduction of nitrogen is more preferred. The nitrogen atmosphere is favorable for reducing the chroma of the product, and the continuous introduction of nitrogen is also favorable for taking the water generated by the esterification reaction out of the reaction system by using nitrogen, so that the esterification reaction is favorable for increasing the esterification degree. The space velocity of the nitrogen gas is preferably 0.2-0.5 ml of nitrogen gas per gram of polyethylene glycol per minute relative to the weight of polyethylene glycol.

In the above technical solution, preferably, the raw material fatty acid is a C8 to C20 monobasic acid. Such as, but not limited to, C9 monoacids, C10 monoacids, C11 monoacids, C12 monoacids, C13 monoacids, C14 monoacids, C15 monoacids, C16 monoacids, C17 monoacids, C18 monoacids, and the like. More preferably straight chain fatty acids; optionally saturated or unsaturated fatty acids. For comparison, oleic acid is used in the specific embodiments.

In the technical scheme, the number average molecular weight of the polyethylene glycol is preferably 200-1000. For example, but not limited to, the polyethylene glycol has a number average molecular weight of 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, and the like. For comparison, polyethylene glycol 400 (abbreviated as PEG400) is used in the examples and comparative examples.

In the above technical scheme, preferably, the molar ratio of the raw material fatty acid to the polyethylene glycol is 0.9-2.2. For example, but not limited to, a molar ratio of fatty acid to polyethylene glycol of 0.95, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.95, 2, 2.05, 2.1, 2.15, and the like.

In the above technical solution, the esterification reaction preferably adopts a two-stage esterification reaction, that is, the esterification reaction includes:

a first esterification reaction: the method comprises the steps of carrying out first esterification reaction on a first esterification raw material mixture in the presence of an acid catalyst and other reaction auxiliary agents to obtain a first esterification product mixture, wherein the first esterification raw material mixture comprises polyethylene glycol and a first part of raw material fatty acid;

second esterification reaction: and subjecting a second esterification raw material mixture to a second esterification reaction to obtain a fatty acid polyethylene glycol ester product, wherein the second esterification raw material mixture comprises the first esterification product mixture and a second part of raw material fatty acid.

In the technical scheme, the reaction temperature of the first esterification reaction and the reaction temperature of the second esterification reaction are preferably 110-160 ℃ independently.

In the above technical solution, preferably, the reaction time of the first esterification reaction and the second esterification reaction is independently 1 to 5 hours (for example, but not limited to, the reaction time of the first esterification reaction and the reaction time of the second esterification reaction are independently 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours, 3.5 hours, 4.0 hours, 4.5 hours, and the like), and the sum of the first esterification reaction time and the second esterification reaction time is 3 to 6 hours.

In the above technical solution, preferably, the molar ratio of the first part of raw material fatty acid to the polyethylene glycol is 0.05-0.8. For example, but not limited to, the weight ratio of the first portion of raw fatty acids to the second portion of raw fatty acids is 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.6, 0.65, 0.7, 0.75, and the like. More preferably, the weight ratio of the first portion of raw fatty acids to the second portion of raw fatty acids is 0.1 to 0.5.

In the above technical solution, preferably, the molar ratio of (the first part of raw material fatty acids + the second part of raw material fatty acids) to the polyethylene glycol is 0.9 to 2.2. For example, but not limited to, a molar ratio of (first portion of feedstock fatty acids + second portion of feedstock fatty acids) to polyethylene glycol of 0.95, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.95, 2, 2.05, 2.1, 2.15, and the like.

Compared with the one-stage esterification reaction process adopting the esterification reaction of all the polyethylene glycol and all the raw material fatty acid under the same ratio condition, the product chroma value obtained by the two-stage esterification process adopting the two-stage esterification reaction of all the polyethylene glycol and the first part of the raw material fatty acid and then adding the rest raw material fatty acid for the second esterification reaction is lower.

The chromaticity of the fatty acid polyglycol ester product is measured according to a standard method (GB/T605-2006 chemical reagent chromaticity determination general method).

The acid value of the fatty acid polyglycol ester product is measured by a standard method (GB/T6365-2006, a titration method for measuring the free alkalinity or free acidity of a surfactant).

Detailed Description

Example 1

Adding 400 g of polyethylene glycol 400, 560 g of oleic acid, 2.0 g of p-toluenesulfonic acid and 2.0 g of hypophosphorous acid into a 2L reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port passing through an air reflux condenser pipe), starting and maintaining stirring, replacing air in the reaction kettle with nitrogen for three times, continuously introducing nitrogen, increasing the temperature of the kettle to 150 ℃ for reaction for 5 hours, cooling to 60 ℃, stopping stirring, stopping introducing nitrogen, and discharging to obtain a fatty acid polyethylene glycol ester product.

For comparison, the main process parameters and the product test results are listed in table 1.

Comparative example 1

Adding 400 g of polyethylene glycol 400, 560 g of oleic acid and 2.0 g of p-toluenesulfonic acid into a 2L reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port passing through an air reflux condenser pipe), starting and maintaining stirring, replacing air in the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃ for reaction for 5 hours, cooling to 60 ℃, stopping stirring, stopping introducing nitrogen, and discharging to obtain the fatty acid polyethylene glycol ester product.

For comparison, the main process parameters and the product test results are listed in table 1.

Example 2

Adding 400 g of polyethylene glycol 400, 560 g of oleic acid, 2.0 g of p-toluenesulfonic acid and 2.0 g of stannous oleate into a 2L reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port passing through an air reflux condenser pipe), starting and maintaining stirring, replacing air in the reaction kettle with nitrogen for three times, continuously introducing nitrogen, increasing the temperature of the kettle to 150 ℃ for reaction for 5 hours, cooling to 60 ℃, stopping stirring, stopping introducing nitrogen, and discharging to obtain a fatty acid polyethylene glycol ester product.

For comparison, the main process parameters and the product test results are listed in table 1.

Example 3

Adding 400 g of polyethylene glycol 400, 560 g of oleic acid, 2.0 g of p-toluenesulfonic acid, 0.2 g of stannous oleate and 1.8 g of hypophosphorous acid into a 2L reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port passing through an air reflux condenser pipe), starting and maintaining stirring, replacing air in the reaction kettle with nitrogen for three times, continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 5 hours, cooling to 60 ℃, stopping stirring and introducing nitrogen, and discharging to obtain the fatty acid polyglycol ester product.

For comparison, the main process parameters and the product test results are listed in table 1.

Example 4

Adding 400 g of polyethylene glycol 400, 560 g of oleic acid, 2.0 g of p-toluenesulfonic acid, 0.6 g of stannous oleate and 1.4 g of hypophosphorous acid into a 2L reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port passing through an air reflux condenser pipe), starting and maintaining stirring, replacing air in the reaction kettle with nitrogen for three times, continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 5 hours, cooling to 60 ℃, stopping stirring and introducing nitrogen, and discharging to obtain the fatty acid polyglycol ester product.

For comparison, the main process parameters and the product test results are listed in table 1.

Example 5

Adding 400 g of polyethylene glycol 400, 70 g of oleic acid, 2.0 g of p-toluenesulfonic acid and 2.0 g of hypophosphorous acid into a 2L reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port passing through an air reflux condenser pipe), starting and maintaining stirring, replacing the space in the reaction kettle with nitrogen for three times, then continuously introducing nitrogen, wherein the flow of the nitrogen is 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 2 hours, and cooling to 60 ℃; and stopping continuously introducing nitrogen, adding 490 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 3 hours, cooling to 60 ℃, stopping stirring, stopping introducing nitrogen, and discharging to obtain the fatty acid polyethylene glycol ester product.

For comparison, the main process parameters and the product test results are listed in table 1.

Comparative example 2

Adding 400 g of polyethylene glycol 400, 70 g of oleic acid and 2.0 g of p-toluenesulfonic acid into a 2L reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port passing through an air reflux condenser pipe), starting and maintaining stirring, replacing the space in the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 2 hours, and cooling to 60 ℃; and stopping continuously introducing nitrogen, adding 490 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 3 hours, cooling to 60 ℃, stopping stirring, stopping introducing nitrogen, and discharging to obtain the fatty acid polyethylene glycol ester product.

For comparison, the main process parameters and the product test results are listed in table 1.

Comparative example 3

Adding 400 g of polyethylene glycol 400, 140 g of oleic acid and 2.0 g of p-toluenesulfonic acid into a 2L reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port passing through an air reflux condenser pipe), starting and maintaining stirring, replacing the space in the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 2 hours, and cooling to 60 ℃; and stopping continuously introducing nitrogen, adding 420 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 3 hours, cooling to 60 ℃, stopping stirring, stopping introducing nitrogen, and discharging to obtain the fatty acid polyethylene glycol ester product.

For comparison, the main process parameters and the product test results are listed in table 1.

Comparative example 4

Adding 400 g of polyethylene glycol 400, 280 g of oleic acid and 2.0 g of p-toluenesulfonic acid into a 2L reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port passing through an air reflux condenser pipe), starting and maintaining stirring, replacing the space in the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 2 hours, and cooling to 60 ℃; and stopping continuously introducing nitrogen, adding 280 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the reaction kettle to 150 ℃, reacting for 3 hours, cooling to 60 ℃, stopping stirring, stopping introducing nitrogen, and discharging to obtain the fatty acid polyethylene glycol ester product.

For comparison, the main process parameters and the product test results are listed in table 1.

Example 6

Adding 400 g of polyethylene glycol 400, 70 g of oleic acid, 2.0 g of p-toluenesulfonic acid and 2.0 g of stannous linoleate into a 2L reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port passing through an air reflux condenser pipe), starting and maintaining stirring, replacing the space in the reaction kettle with nitrogen for three times, continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the reaction kettle to 150 ℃, reacting for 2 hours, and cooling to 60 ℃; and stopping continuously introducing nitrogen, adding 490 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 3 hours, cooling to 60 ℃, stopping stirring, stopping introducing nitrogen, and discharging to obtain the fatty acid polyethylene glycol ester product.

For comparison, the main process parameters and the product test results are listed in table 1.

Example 7

Adding 400 g of polyethylene glycol 400, 70 g of oleic acid, 2.0 g of p-toluenesulfonic acid, 0.2 g of stannous oleate and 1.8 g of hypophosphorous acid into a 2L reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port of an air reflux condenser pipe), starting and maintaining stirring, replacing the space in the reaction kettle with nitrogen for three times, then continuously introducing nitrogen, wherein the flow of the nitrogen is 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 2 hours, and cooling to 60 ℃; and stopping continuously introducing nitrogen, adding 490 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 3 hours, cooling to 60 ℃, stopping stirring, stopping introducing nitrogen, and discharging to obtain the fatty acid polyethylene glycol ester product.

For comparison, the main process parameters and the product test results are listed in table 1.

Example 8

Adding 400 g of polyethylene glycol 400, 70 g of oleic acid, 2.0 g of p-toluenesulfonic acid, 0.6 g of stannous oleate and 1.4 g of hypophosphorous acid into a 2L reaction kettle (provided with a kettle body heating device, a kettle body water circulation cooling device, a stirring device and a tail gas discharge port of an air reflux condenser pipe), starting and maintaining stirring, replacing the space in the reaction kettle with nitrogen for three times, then continuously introducing nitrogen, wherein the flow of the nitrogen is 100 ml/min, raising the temperature of the kettle to 150 ℃, reacting for 2 hours, and cooling to 60 ℃; stopping continuously introducing nitrogen, adding 490 g of oleic acid into the reaction kettle, replacing the space of the reaction kettle with nitrogen for three times, then continuously introducing nitrogen with the flow of 100 ml/min, raising the temperature of the reaction kettle to 150 ℃, reacting for 3 hours, cooling to 60 DEG C

Stopping stirring, stopping introducing nitrogen, and discharging to obtain the fatty acid polyglycol ester product.

For comparison, the main process parameters and the product test results are listed in table 1.

TABLE 1

In the table: TsOH is p-toluenesulfonic acid, T is reaction temperature, T is reaction time, T is₁Is the first esterification reaction temperature, t₁For the first esterification reaction time, T₂Is the second esterification reaction temperature, t₂For a second esterification reaction time; a represents stannous oleate, B represents stannous oleate and hypophosphorous acid, and the value in () behind B is the weight ratio of stannous oleate to hypophosphorous acid; d is the molar ratio of the first part of raw material fatty acid to the polyethylene glycol.