阅读说明：本技术 用于仲醇聚氧乙烯醚合成的催化剂及其应用 (Catalyst for synthesizing secondary alcohol polyoxyethylene ether and application thereof ) 是由 张江锋 侯海育 王建臣 李翔 杨健 于 2020-05-29 设计创作，主要内容包括：本发明涉及用于仲醇聚氧乙烯醚合成的催化剂及其应用,主要解决现有技术中存在仲醇转化率低或仲醇聚氧乙烯醚产品中仲醇残留量大的技术问题,通过采用用于仲醇聚氧乙烯醚合成的催化剂,所述催化剂包括组分A和组分B；组分A为哌啶氧化物；组分B包括：(1)茂金属；(2)烷基铝氧烷；茂金属中所述的金属选自IVB族过渡金属元素的技术方案,较好地解决了该技术问题,可用于仲醇聚氧乙烯醚的工业生产中。(The invention relates to a catalyst for synthesizing secondary alcohol polyoxyethylene ether and application thereof, which mainly solves the technical problems of low secondary alcohol conversion rate or large secondary alcohol residue in a secondary alcohol polyoxyethylene ether product in the prior art; the component A is piperidine oxide; the component B comprises: (1) a metallocene; (2) alkylaluminoxane; the technical scheme that the metal in the metallocene is selected from IVB group transition metal elements better solves the technical problem, and can be used in the industrial production of secondary alcohol polyoxyethylene ether.)

1. The catalyst for synthesizing the secondary alcohol polyoxyethylene ether comprises a component A and a component B; the component A is piperidine oxide; the component B comprises:

(1) a metallocene;

(2) alkylaluminoxane;

the metal in the metallocene is selected from group IVB transition metal elements.

2. A catalyst for the synthesis of secondary alcohol polyoxyethylene ethers as claimed in claim 1, wherein said piperidine oxide compound has the following structural formula one:

wherein R1-R10 are independently selected from H or C1-C10 alkyl, but R1-R4 are not H at the same time.

3. A catalyst for synthesis of a secondary alcohol polyoxyethylene ether according to claim 2, characterized in that R1 and R2 are not both H, and R3 and R4 are not both H; further preferably, none of R1 to R4 is H.

4. The catalyst for synthesis of secondary alcohol polyoxyethylene ether according to claim 1, wherein the metallocene is at least one selected from the group consisting of titanocene dichloride, zirconocene dichloride and hafnocene dichloride.

5. A catalyst for synthesizing a secondary alcohol polyoxyethylene ether as claimed in claim 1, wherein the alkyl group of the alkylaluminoxane is at least one selected from the group consisting of C1-C8 alkyl groups.

6. The catalyst for synthesizing secondary alcohol polyoxyethylene ether according to claim 1, wherein the weight ratio of the component A to the component B is 0.01-100, preferably 0.02-50, more preferably 0.05-20, and most preferably 0.1-10.

7. A catalyst for synthesis of a secondary alcohol polyoxyethylene ether according to claim 1, characterized in that the group IVB transition metal element is at least one selected from the group consisting of Ti, Zr and Hf.

8. The catalyst for synthesizing secondary alcohol polyoxyethylene ether according to claim 1, wherein the weight ratio of the alkylaluminoxane to the metallocene is 0.005-0.05.

9. A process for preparing a catalyst as claimed in any one of claims 1 to 8, comprising:

the alkylalumoxane is mixed into the metallocene to obtain an intermediate mixture, and then the piperidine oxide is mixed into the intermediate mixture.

10. Use of the catalyst of any one of claims 1 to 8 or obtained by the preparation method of claim 9 in the synthesis of secondary alcohol polyoxyethylene ethers.

Technical Field

The invention relates to a catalyst for synthesizing secondary alcohol polyoxyethylene ether and application thereof.

Background

The secondary alcohol polyoxyethylene ether is a product obtained by initiating ethylene oxide polymerization by taking a secondary alcohol as an initiator in the presence of a catalyst. The secondary alcohol polyoxyethylene ether has excellent penetration, emulsifying agent, wetting and cleaning agent, does not contain APEO, can be used in combination with other various anionic, nonionic and cationic surfactants, has superior synergistic effect, can greatly reduce the consumption of the auxiliary agent, and achieves good cost performance. At present, the conversion rate of the secondary alcohol polyoxyethylene ether is low, the residual amount of the secondary alcohol is high, and the yield and the productivity of the product are seriously influenced, so that a method for improving the conversion rate of the secondary alcohol polyoxyethylene ether is hopefully found.

It is known that metallocene catalysts are mainly referred to as IVAn organometallic complex compound of a group B transition metal (e.g., Ti, Zr, Hf) bonded to at least one Cp (cyclopentadienyl anion ligand) or Cp derivative, metallocene as a main component, and an alkylaluminoxane or an organoboride (e.g., B (C)₆F₅)₃) As an auxiliary component. Among the above metallocenes, titanocene dichloride, zirconocene dichloride and the like are common. The alkylaluminoxane is widely used, and examples thereof include methylaluminoxane (abbreviated to MAO), ethyl-modified MAO (abbreviated to MMAO-Et), and isobutyl-modified MAO (MMAO-i-Bu). Metallocene catalysts are commonly used in olefin polymerization reactions, but have not found application in the ring-opening polymerization of alkylene oxides using secondary alcohols as initiators.

2,2,6, 6-tetramethylpiperidine oxide (TEMPO for short) can be used as an oxidation catalyst in the selective oxidation reaction of oxidizing a primary alcohol to an aldehyde and a secondary alcohol to a ketone in the presence of an oxidizing agent, but is not reported to be used in the ring-opening polymerization reaction of alkylene oxide using a secondary alcohol as an initiator.

Disclosure of Invention

One of the technical problems to be solved by the invention is the technical problem that the secondary alcohol residue in a secondary alcohol polyoxyethylene ether product obtained by the reaction of a secondary alcohol and ethylene oxide under the condition of a catalyst in the prior art is large, and the catalyst for synthesizing the secondary alcohol polyoxyethylene ether is provided.

The second technical problem to be solved by the invention is the preparation method of the catalyst.

The third technical problem to be solved by the invention is the application of the catalyst.

In order to solve one of the above technical problems, the technical solution of the present invention is as follows:

the catalyst for synthesizing the secondary alcohol polyoxyethylene ether comprises a component A and a component B; the component A is piperidine oxide; the component B comprises:

(1) a metallocene;

(2) alkylaluminoxane;

the metal in the metallocene is selected from group IVB transition metal elements.

The catalyst is used for synthesizing secondary alcohol polyoxyethylene ether, has the advantage of low secondary alcohol residue in a secondary alcohol polyoxyethylene ether product, and the component A and the component B are mutually enhanced in the aspect of reducing the secondary alcohol residue.

In the above technical solution, preferably, the piperidine oxide has the following structural formula one:

wherein R1-R10 are independently selected from H or C1-C10 alkyl, but R1-R4 are not H at the same time; it is further preferred that R1 and R2 are not both H, and R3 and R4 are not both H; it is further preferred that none of R1-R4 is H, and the piperidine oxide in this case may be, for example only, a 2,2,6, 6-tetraalkylpiperidine oxide. Preferably, the hydrocarbyl group is an alkyl or aryl group. Examples of the alkyl group include, but are not limited to, a C1 alkyl group, a C2 alkyl group, a C3 alkyl group, a C4 alkyl group, a C5 alkyl group, a C6 alkyl group, a C7 alkyl group, a C8 alkyl group, a C9 alkyl group, and a C10 alkyl group. In a specific embodiment, 2,6, 6-tetramethylpiperidine oxide is used as piperidine oxide, just by analogy.

In the above technical scheme, the metallocene of component (1) is a complex of IVB group transition metals (such as Ti, Zr, Hf) and the ligand contains at least one Cp (short for cyclopentadiene anion ligand) or Cp derivative. By way of example only, the metallocene is selected from the group consisting of titanocene dichloride (formula Cp)₂TiCl₂) Zirconocene dichloride (molecular formula is Cp)₂ZrCl₂) And hafnocene dichloride (formula Cp)₂HfCl₂) At least one of the group of substances. In terms of equivalents only, the metallocene used in the specific embodiment is titanocene dichloride.

In the above technical solution, the alkyl group in the alkylaluminoxane is preferably at least one selected from the group consisting of C1 to C8 alkyl groups. Such as, but not limited to, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, and C8 alkyl. As examples of the specific substance, alkylaluminoxane may be, but not limited to, methylaluminoxane (abbreviated to MAO), ethyl-modified MAO (abbreviated to MMAO-Et), isobutyl-modified MAO (MMAO-i-Bu), and the like. In terms of ratios only, methylaluminoxane is used in the specific embodiment.

In the above technical solution, the catalyst preferably comprises the component a and the component B at the same time, and the weight ratio of the component a to the component B is 0.01 to 100, such as but not limited to 0.01, 0.02, 0.05, 0.08, 0.1, 0.2, 0.5, 1, 2, 5, 8, 10, 20, 50, 80, 100, and the like, preferably 0.02 to 50, more preferably 0.05 to 20, most preferably 0.1 to 10, and most preferably 0.1 to 5.

In the above aspect, the group IVB transition metal element is preferably at least one selected from the group consisting of Ti, Zr, and Hf, and more preferably the group IVB transition metal element includes Ti.

In the above technical solution, the weight ratio of the alkylaluminoxane to the metallocene is preferably 0.005-0.05. Such as but not limited to 0.01, 0.02, 0.03, 0.04, and the like. In one embodiment, the weight ratio of the alkylaluminoxane to the metallocene is 0.01, and the alkylaluminoxane and the metallocene are collectively referred to as "metallocene catalyst".

The order of mixing the catalysts, and whether they are mixed before or in situ with the polymerization system, are not particularly limited and achieve comparable technical results. However, in order to solve the second technical problem, it is recommended to add a polymerization system after mixing in advance, that is, a method for preparing the catalyst, which comprises:

the alkylalumoxane is mixed into the metallocene to obtain an intermediate mixture, i.e., the metallocene catalyst described above, and then the piperidine oxide is mixed into the intermediate mixture. That is, a mixing sequence of adding (2) to (1) and then adding component A is employed. The examples in the embodiments of the present invention all employ this method for preparing the catalyst.

For convenience of comparison, the embodiment of the present invention relates to a comparative example using only a metallocene catalyst, which is obtained by previously adding alkylaluminoxane to a mixing order of metallocenes and mixing.

To solve the third technical problem, the technical scheme of the invention is as follows:

use of a catalyst according to any one of the preceding technical problems or of a catalyst obtained by the preparation process according to the second technical problem for the synthesis of secondary alcohols polyoxyethylene ethers.

The technical key of the invention is the selection of the catalyst components, and the technical conditions of the specific application can be reasonably selected by a person skilled in the art without creative work and can achieve comparable technical effects. However:

in the above technical solution, preferably, in the process of initiating ethylene oxide polymerization to obtain a secondary alcohol polyoxyethylene ether product by using a secondary alcohol as an initiator, the secondary alcohol is at least one of the group consisting of a secondary alcohol of C8, a secondary alcohol of C9, a secondary alcohol of C10, a secondary alcohol of C11, a secondary alcohol of C12, a secondary alcohol of C13, a secondary alcohol of C14, a secondary alcohol of C15, a secondary alcohol of C16, a secondary alcohol of C17 and a secondary alcohol of C18.

In the technical scheme, only preferably, in the process of initiating ethylene oxide polymerization to obtain a secondary alcohol polyoxyethylene ether product by using a secondary alcohol as an initiator, the molar ratio of the total feeding amount of the polymerization ethylene oxide to the feeding amount of the secondary alcohol is 3-10. Such as, but not limited to, a molar ratio of 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, and the like.

In the above technical solution, preferably, in the process of initiating ethylene oxide polymerization to obtain a secondary alcohol polyoxyethylene ether product by using a secondary alcohol as an initiator, the reaction temperature is 50-150 ℃, for example, but not limited to, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, and the like. And/or the pressure of the reaction is 0.05 to 0.5MPa, such as but not limited to 0.06MPa, 0.07MPa, 0.08MPa, 0.09MPa, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, and the like.

The key to the process of the invention is the choice of catalyst, which can be reasonably chosen by the person skilled in the art without any inventive effort with regard to the amount of catalyst used and the relevant process conditions. By way of example only, the catalyst may be used in an amount of 0.05 to 0.8% by weight, specifically 0.06%, 0.07%, 0.08%, 0.09%, 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.35%, 0.40%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75% and the like, more preferably 0.05 to 5% by weight, based on the total weight of the secondary alcohol polyoxyethylene ether product.

Unless otherwise specified, the pressures described herein are in terms of gauge pressure.

The secondary alcohol residue in the secondary alcohol polyoxyethylene ether product is determined by gas chromatography.

The inventors have experimentally found that, using the catalyst described herein, the conversion of secondary alcohols is high or the amount of secondary alcohols in the secondary alcohol polyoxyethylene ether product is low, and that in the catalyst, component a and component B have an interactive promoting effect in increasing the conversion of secondary alcohols or reducing the amount of secondary alcohols in the secondary alcohol polyoxyethylene ether product.

The present invention will be further described with reference to the following examples.

Detailed Description

[ COMPARATIVE EXAMPLE 1 ]

Adding 200g of sec-tridecanol and 1g of potassium hydroxide into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, sealing the high-pressure reaction kettle, starting stirring, replacing with nitrogen for three times, evacuating and dehydrating at the temperature of 100 ℃ and the pressure of-0.096 MPa for 30 minutes, then slowly introducing ethylene oxide into the reactor kettle, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.20MPa until the total amount of the introduced ethylene oxide is 264g, stopping introducing the ethylene oxide, then maintaining the reaction temperature until the pressure of the reactor does not drop any more, indicating that the curing reaction is finished, cooling to 60 ℃, adding 1g of lactic acid for neutralization, and obtaining a secondary alcohol polyoxyethylene (6) ether product.

The secondary alcohol residue in the product was measured by gas chromatography to find that the secondary alcohol residue was 45% by weight.

[ COMPARATIVE EXAMPLE 2 ]

Adding 200g of sec-tridecanol and 0.5g of metallocene catalyst into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, sealing the high-pressure reaction kettle, starting stirring, replacing nitrogen for three times, evacuating and dehydrating at the temperature of 100 ℃ and the pressure of-0.096 MPa for 30 minutes, then slowly introducing ethylene oxide into the reactor kettle, controlling the reaction temperature to 120 ℃ and the reaction pressure to 0.20MPa until the total amount of the introduced ethylene oxide is 264g, stopping introducing the ethylene oxide, then maintaining the reaction temperature until the pressure of the reactor does not drop any more, indicating that the curing reaction is finished, cooling to 60 ℃, adding 1g of lactic acid for neutralization, and obtaining a secondary alcohol polyoxyethylene (6) ether product.

The secondary alcohol residue in the product was measured by gas chromatography to find that the secondary alcohol residue was 26% by weight.

[ COMPARATIVE EXAMPLE 3 ]

Adding 200g of sec-tridecanol and 1g of metallocene catalyst into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, sealing the high-pressure reaction kettle, starting stirring, replacing with nitrogen for three times, evacuating and dehydrating at the temperature of 100 ℃ and the pressure of-0.096 MPa for 30 minutes, then slowly introducing ethylene oxide into the reactor kettle, controlling the reaction temperature to 120 ℃ and the reaction pressure to 0.20MPa until the total amount of the introduced ethylene oxide is 264g, stopping introducing the ethylene oxide, then maintaining the reaction temperature until the pressure of the reactor does not drop any more, indicating that the curing reaction is finished, cooling to 60 ℃, adding 1g of lactic acid for neutralization, and obtaining a secondary alcohol polyoxyethylene (6) ether product.

The secondary alcohol residue in the product was measured by gas chromatography, and was found to be 15% by weight.

[ COMPARATIVE EXAMPLE 4 ]

Adding 200g of sec-tridecanol and 1.5g of metallocene catalyst into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, sealing the high-pressure reaction kettle, starting stirring, replacing nitrogen for three times, evacuating and dehydrating at the temperature of 100 ℃ and the pressure of-0.096 MPa for 30 minutes, then slowly introducing ethylene oxide into the reactor kettle, controlling the reaction temperature to 120 ℃ and the reaction pressure to 0.20MPa until the total amount of the introduced ethylene oxide is 264g, stopping introducing the ethylene oxide, then maintaining the reaction temperature until the pressure of the reactor does not drop any more, indicating that the curing reaction is finished, cooling to 60 ℃, adding 1g of lactic acid for neutralization, and obtaining a secondary alcohol polyoxyethylene (6) ether product.

The secondary alcohol residue in the product was measured by gas chromatography, and found to be 10% by weight.

[ COMPARATIVE EXAMPLE 5 ]

200g of secondary tridecanol and 0.5g of 2,2,6, 6-tetramethylpiperidine oxide are put into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, the high-pressure reaction kettle is sealed, the stirring is started, nitrogen is replaced for three times, the reaction kettle is evacuated and dehydrated for 30 minutes at the temperature of 100 ℃ and the pressure of-0.096 MPa, then ethylene oxide is slowly introduced into the reaction kettle, the reaction temperature of 120 ℃ and the reaction pressure of 0.20MPa are controlled until the total amount of the introduced ethylene oxide is 264g, the introduction of the ethylene oxide is stopped, the reaction temperature is maintained until the pressure of the reaction kettle does not drop any more, the curing reaction is finished, 1g of lactic acid is added for neutralization when the cooling temperature reaches 60 ℃, and a secondary alcohol polyoxyethylene (6) ether product is obtained.

The secondary alcohol residue in the product was measured by gas chromatography, and found to be 32% by weight.

[ COMPARATIVE EXAMPLE 6 ]

200g of sec-tridecanol and 1g of 2,2,6, 6-tetramethyl piperidine oxide are put into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, the high-pressure reaction kettle is sealed, the stirring is started, nitrogen is replaced for three times, the reaction kettle is pumped out and dehydrated for 30 minutes at the temperature of 100 ℃ and the pressure of-0.096 MPa, then ethylene oxide is slowly introduced into the reaction kettle, the reaction temperature is controlled to be 120 ℃ and the reaction pressure to be 0.20MPa until the total amount of the introduced ethylene oxide is 264g, the introduction of the ethylene oxide is stopped, the reaction temperature is maintained until the pressure of the reaction kettle does not drop any more, the curing reaction is finished, and 1g of lactic acid is added for neutralization when the cooling temperature is 60 ℃, so as to obtain the secondary alcohol polyoxyethylene (6) ether.

The secondary alcohol residue in the product was measured by gas chromatography, and found to be 24% by weight.

[ COMPARATIVE EXAMPLE 7 ]

200g of secondary tridecanol and 1.5g of 2,2,6, 6-tetramethylpiperidine oxide are put into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, the high-pressure reaction kettle is sealed, the stirring is started, nitrogen is replaced for three times, the reaction kettle is evacuated and dehydrated for 30 minutes at the temperature of 100 ℃ and the pressure of-0.096 MPa, then ethylene oxide is slowly introduced into the reaction kettle, the reaction temperature of 120 ℃ and the reaction pressure of 0.20MPa are controlled until the total amount of the introduced ethylene oxide is 264g, the introduction of the ethylene oxide is stopped, the reaction temperature is maintained until the pressure of the reaction kettle does not drop any more, the curing reaction is finished, 1g of lactic acid is added for neutralization when the cooling temperature reaches 60 ℃, and a secondary alcohol polyoxyethylene (6) ether product is obtained.

The secondary alcohol residue in the product was measured by gas chromatography to find that the secondary alcohol residue was 19% by weight.

[ example 1 ]

200g of sec-tridecanol and 1g of catalyst (consisting of 0.5g of metallocene catalyst and 0.5g of 2,2,6, 6-tetramethylpiperidine oxide) are put into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, the high-pressure reaction kettle is sealed, the stirring is started, nitrogen is replaced for three times, the high-pressure reaction kettle is evacuated and dehydrated for 30 minutes at the temperature of 100 ℃ and the pressure of-0.096 MPa, then ethylene oxide is slowly introduced into the reaction kettle, the reaction temperature is controlled to be 120 ℃ and the reaction pressure is controlled to be 0.20MPa until the total amount of the introduced ethylene oxide is 264g, the introduction of the ethylene oxide is stopped, the reaction temperature is maintained until the pressure of the reaction kettle does not drop any more to indicate that the curing reaction is finished, 1g of lactic acid is added for neutralization when the cooling temperature reaches 60 ℃, and the secondary alcohol polyoxyethylene.

The secondary alcohol residue in the product was measured by gas chromatography to find that the secondary alcohol residue was 7% by weight.

[ example 2 ]

200g of sec-tridecanol and 1.5g of catalyst (consisting of 0.5g of metallocene catalyst and 1g of 2,2,6, 6-tetramethylpiperidine oxide) are put into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, the high-pressure reaction kettle is sealed, the stirring is started, nitrogen is replaced for three times, the high-pressure reaction kettle is evacuated and dehydrated for 30 minutes at the temperature of 100 ℃ and the pressure of-0.096 MPa, then ethylene oxide is introduced into a slow reaction kettle, the reaction temperature is controlled to be 120 ℃ and the reaction pressure is controlled to be 0.20MPa until the total amount of the introduced ethylene oxide is 264g, the introduction of the ethylene oxide is stopped, the reaction temperature is maintained until the pressure of the reaction kettle does not drop any more to indicate that the curing reaction is finished, 1g of lactic acid is added for neutralization when the cooling temperature reaches 60 ℃, and a secondary alcohol polyoxyethylene.

The secondary alcohol residue in the product was measured by gas chromatography to find that the secondary alcohol residue was 4% by weight.

[ example 3 ]

Adding 200g of sec-tridecanol and 2g of catalyst (consisting of 0.5g of metallocene catalyst and 1.5g of 2,2,6, 6-tetramethylpiperidine oxide) into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil pipe, sealing the high-pressure reaction kettle, starting stirring, replacing nitrogen for three times, evacuating and dehydrating at the temperature of 100 ℃ and the pressure of-0.096 MPa for 30 minutes, then slowly introducing ethylene oxide into the reactor kettle, controlling the reaction temperature of 120 ℃ and the reaction pressure of 0.20MPa until the total amount of the introduced ethylene oxide is 264g, stopping introducing the ethylene oxide, maintaining the reaction temperature until the pressure of the reaction kettle does not drop any more to indicate that the curing reaction is finished, and adding 1g of lactic acid for neutralization when the cooling temperature reaches 60 ℃ to obtain the secondary alcohol polyoxyethylene (6) ether product.

The secondary alcohol residue in the product was measured by gas chromatography, and was found to be 2% by weight.

[ example 4 ]

200g of sec-tridecanol and 1.5g of catalyst (consisting of 1g of metallocene catalyst and 0.5g of 2,2,6, 6-tetramethylpiperidine oxide) are put into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil, the high-pressure reaction kettle is sealed, the stirring is started, nitrogen is replaced for three times, the high-pressure reaction kettle is evacuated and dehydrated for 30 minutes at the temperature of 100 ℃ and the pressure of-0.096 MPa, then ethylene oxide is slowly introduced into the reaction kettle, the reaction temperature is controlled to be 120 ℃ and the reaction pressure is controlled to be 0.20MPa until the total amount of the introduced ethylene oxide is 264g, the introduction of the ethylene oxide is stopped, the reaction temperature is maintained until the pressure of the reaction kettle does not drop any more to indicate that the curing reaction is finished, 1g of lactic acid is added for neutralization when the cooling temperature reaches 60 ℃, and the secondary alcohol polyoxyethylene.

The secondary alcohol residue in the product was measured by gas chromatography to find that the secondary alcohol residue was 5% by weight.

[ example 5 ]

Adding 200g of sec-tridecanol and 2g of catalyst (consisting of 1.5g of metallocene catalyst and 0.5g of 2,2,6, 6-tetramethylpiperidine oxide) into a 1-pressure-rising reaction kettle with a stirring, electric heating jacket and an internal water-cooling coil pipe, sealing the high-pressure reaction kettle, starting stirring, replacing nitrogen for three times, evacuating and dehydrating at the temperature of 100 ℃ and the pressure of-0.096 MPa for 30 minutes, then slowly introducing ethylene oxide into the reactor kettle, controlling the reaction temperature of 120 ℃ and the reaction pressure of 0.20MPa until the total amount of the introduced ethylene oxide is 264g, stopping introducing the ethylene oxide, maintaining the reaction temperature until the pressure of the reaction kettle does not drop any more to indicate that the curing reaction is finished, and adding 1g of lactic acid for neutralization when the cooling temperature reaches 60 ℃ to obtain the secondary alcohol polyoxyethylene (6) ether product.

The secondary alcohol residue in the product was measured by gas chromatography, and found to be 3% by weight.