CN114409888A - Method for preparing high molecular weight polyether polyol by using waste oil - Google Patents

Method for preparing high molecular weight polyether polyol by using waste oil Download PDF

Info

Publication number
CN114409888A
CN114409888A CN202210188515.3A CN202210188515A CN114409888A CN 114409888 A CN114409888 A CN 114409888A CN 202210188515 A CN202210188515 A CN 202210188515A CN 114409888 A CN114409888 A CN 114409888A
Authority
CN
China
Prior art keywords
molecular weight
reaction
high molecular
polyether polyol
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210188515.3A
Other languages
Chinese (zh)
Other versions
CN114409888B (en
Inventor
宿颜彬
金一丰
马定连
高洪军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Huangma Technology Co Ltd
Zhejiang Lvkean Chemical Co Ltd
Zhejiang Huangma Shangyi New Material Co Ltd
Zhejiang Huangma Surfactant Research Institute Co Ltd
Original Assignee
Zhejiang Huangma Technology Co Ltd
Zhejiang Lvkean Chemical Co Ltd
Zhejiang Huangma Shangyi New Material Co Ltd
Zhejiang Huangma Surfactant Research Institute Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Huangma Technology Co Ltd, Zhejiang Lvkean Chemical Co Ltd, Zhejiang Huangma Shangyi New Material Co Ltd, Zhejiang Huangma Surfactant Research Institute Co Ltd filed Critical Zhejiang Huangma Technology Co Ltd
Priority to CN202210188515.3A priority Critical patent/CN114409888B/en
Publication of CN114409888A publication Critical patent/CN114409888A/en
Application granted granted Critical
Publication of CN114409888B publication Critical patent/CN114409888B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2654—Aluminium or boron; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2669—Non-metals or compounds thereof
    • C08G65/2675—Phosphorus or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • Polyethers (AREA)

Abstract

The invention provides a method for preparing high molecular weight polyether polyol by using waste grease, which comprises the following steps: s1, carrying out esterification reaction on the waste oil and the polyhydric alcohol under the action of a Lewis acid catalyst; s2, cooling to 70-80 ℃ after the reaction is finished, carrying out suction filtration to obtain a reaction precursor, and recovering and recycling the Lewis acid catalyst; s3, adding a catalyst into the reaction precursor filtered in the step S2, continuously introducing the EO/PO mixture at the reaction temperature of 140 ℃ and 145 ℃ for polymerization reaction, curing for 10min after the epoxy is introduced, and then cooling and removing moisture and micromolecules to obtain the waste grease high molecular weight polyether. The polyether prepared by the method has the advantages of high molecular weight, narrow distribution, high effective component content and the like.

Description

Method for preparing high molecular weight polyether polyol by using waste oil
Technical Field
The invention relates to the technical field of polyether polyol preparation, and particularly relates to a method for preparing high molecular weight polyether polyol from waste grease.
Background
At present, polyether polyol is mainly prepared from petroleum nonrenewable resources and low molecular alcohols, and the production process is complex, so that the actual demand of polyether polyol in the market can not be met. The polyether polyol prepared by utilizing renewable resources such as waste grease and the like is a good relief to the shortage of petroleum, and the prepared polyether polyol can be used as a defoaming agent in textile assistants and papermaking assistants, as an additive in lubricating oil and lubricating grease, as a grinding assistant in coating, printing ink and dye, and the like. The waste grease polyether has the other advantages that the structure contains ester bonds, the waste grease polyether has good compatibility with a foaming agent and an auxiliary agent, and the waste grease polyether can be stored for a long time. Therefore, the waste grease polyether is an excellent direction for recycling waste oil, and has good social and economic benefits.
For example, chinese patent CN110951067A reports a method for preparing polyether polyol from high acid value waste oil, i.e. firstly, the high acid value waste oil and polyol are esterified and deacidified under the catalysis of Lewis acid to obtain a reaction precursor, and then the reaction precursor is polymerized with PO under the action of alkali catalyst to obtain a crude product of polyether polyol. Although the process has excellent effect on the high-acid-value waste oil raw material, the prepared polyether polyol has low molecular weight which is generally about 700-. In addition, in order to obtain refined waste grease polyether, acid and adsorbent post-treatment is needed to remove the alkali catalyst in the crude polyether product, so that the production cost is further increased, and the environment is not favorable.
Chinese patents CN104974340A and CN106700058A disclose a method for preparing polyether from waste grease by an acid-base two-step method, respectively, that is, polyether polyol is prepared by catalytic esterification with acid and catalytic polymerization with a base catalyst. However, the polyether polyol prepared by the method has the defect of low molecular weight (about 1500), a large amount of water is needed to wash the acid catalyst after esterification, the water resource loss is large, the production cost is further increased by treating waste acid water, and the method is also a threat to the environment.
Therefore, it is necessary to develop a preparation process of waste grease polyether polyol, which has the advantages of simple preparation process, stable production, high polyether molecular weight, safety and environmental protection.
Disclosure of Invention
In view of the background, it is desirable to provide a novel method for preparing high molecular weight polyether polyol from waste oil.
The purpose of the invention is realized by the following technical scheme:
a method for preparing high molecular weight polyether polyol by using waste grease comprises the following steps:
s1, carrying out esterification reaction on the waste oil and the polyhydric alcohol under the action of a Lewis acid catalyst;
s2, cooling to 70-80 ℃ after the reaction is finished, carrying out suction filtration to obtain a reaction precursor, and recovering and recycling the Lewis acid catalyst;
s3, adding a catalyst into the reaction precursor filtered in the step S2, continuously introducing the EO/PO mixture at the reaction temperature of 140 ℃ and 145 ℃ for polymerization, curing for 10min after the epoxy is introduced, and then cooling and removing water and small molecules to obtain the waste grease high molecular weight polyether polyol.
In a preferred embodiment of the present invention, the mass ratio of the polyol to the waste oil and fat in step S1 is 1:1 to 10, and the amount of the Lewis acid catalyst added is 0.05% to 1% of the mass of the waste oil and fat.
In a preferred embodiment of the present invention, the acid value of the waste oil or fat in the step S1 is 0.5 to 1.0 mgKOH/g.
In a preferred embodiment of the present invention, the waste oil and fat in step S1 is one or a mixture of any two or more of rapeseed oil, peanut oil, palm oil, soybean oil, coconut oil, and castor oil.
In a preferred embodiment of the present invention, the polyol in step S1 is one or a mixture of two or more selected from ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, 1, 4-butanediol, pentaerythritol, and sorbitol.
As a preferred embodiment of the present invention, the Lewis acid catalyst in step S1 is selected from one or a mixture of any two or more of AlCl3, ZnCl2, ZnO, TiCl4, zn (ac)2, SnCl 4.
In a preferred embodiment of the present invention, the mass ratio of the reaction precursor to the EO/PO mixture in step S3 is 1:10 to 20.
In a preferred embodiment of the present invention, the ratio of PO in the EO/PO mixture in step S3 is 50% to 100%.
In a preferred embodiment of the present invention, the amount of the catalyst added in step S3 is 0.05 to 2% by mass of the reaction precursor.
As a preferred embodiment of the present invention, the catalyst in step S3 is selected from one of DMC, MMC, boron trifluoride diethyl etherate, triphenylphosphine, etc.
Compared with the prior art, the invention has the beneficial effects that:
in the process of preparing polyether polyol, Lewis acid is adopted to catalyze the esterification reaction between the waste grease and the polyol. Compared with acid catalysts such as sulfuric acid and methyl benzenesulfonic acid, the Lewis acid catalyst is safer and more environment-friendly, can be directly recovered and recycled after suction filtration, does not need water to wash the catalyst and treat the generated waste acid water, further saves the production cost, and is safe and efficient.
And continuously polymerizing the reaction precursor obtained after esterification with an epoxy mixture under the action of catalysts such as DMC, MMC and the like to obtain the high-molecular-weight waste grease polyether. Compared with the conventional alkali catalysis process, the catalyst has higher reaction activity and selectivity, and can reduce the probability of isomerizing PO into allyl or allyl, so that the prepared polyether has high molecular weight, narrow distribution, high effective component content and less impurities.
In conclusion, the polyether prepared by the method has the advantages of high molecular weight, narrow distribution, high effective component content and the like.
In addition, the process has the advantages of low production cost, high efficiency, stable product, energy conservation, environmental protection and the like.
Detailed Description
In the description of the present invention, it is to be noted that those whose specific conditions are not specified in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
A method for preparing high molecular weight polyether polyol by using waste grease comprises the following steps:
s1, carrying out esterification reaction on the waste oil and the polyhydric alcohol under a Lewis acid catalyst, placing nitrogen for 3 times, and then reacting for 0.5-1.5 h under the conditions that the reaction temperature is 150-180 ℃ and the vacuum degree is-0.08-0.098 MPa; wherein the acid value of the waste oil is 0.5-1.0 mgKOH/g; the mass ratio of the polyhydric alcohol to the waste oil is 1: 1-10, and the addition amount of the Lewis acid catalyst is 0.05-1% of the mass of the waste oil;
s2, cooling to 70-80 ℃ after the reaction is finished, carrying out suction filtration to obtain a reaction precursor, and recovering and recycling the Lewis acid catalyst;
s3, adding a catalyst into the reaction precursor filtered in the step S2, continuously introducing the EO/PO mixture at the reaction temperature of 140 ℃ and 145 ℃ for polymerization reaction, curing for 10min after the epoxy is introduced, and then cooling and removing moisture and micromolecules to obtain the waste grease high molecular weight polyether.
In the method, the waste oil in the step S1 is one or a mixture of more than two of rapeseed oil, peanut oil, palm oil, soybean oil, coconut oil and castor oil; the polyalcohol is one or mixture of more than two of ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, 1, 4-butanediol, pentaerythritol and sorbitol; the Lewis acid catalyst is selected from AlCl3、ZnCl2、ZnO、TiCl4、Zn(AC)2、 SnCl4One or more ofA mixture of any two or more. The catalyst in the step S3 is selected from one of DMC, MMC, boron trifluoride ether, triphenylphosphine and the like, and the adding amount of the catalyst is 0.05-2 per mill of the mass of the reaction precursor; in the step S3, the mass ratio of the reaction precursor to the epoxy mixture is 1: 3-10, and the proportion of PO in the EO/PO mixture is 50% -100%.
Example 1:
a method for preparing high molecular weight polyether polyol by using waste grease comprises the following steps:
s1, mixing propylene glycol, soybean oil and ZnCl2According to the mass ratio of propylene glycol to soybean oil to ZnCl2Putting 100:500:0.05 into a reaction kettle, adding nitrogen for 3 times, heating, and esterifying for 1.5 hours at 150 ℃ under the vacuum degree of-0.08 to-0.098 MPa;
s2, after the esterification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a clean reaction kettle, adding a DMC catalyst with the mass of 0.06 per thousand of that of the reaction precursor, placing nitrogen for 3 times, heating, when the temperature is raised to 140 ℃, continuously introducing an EO/PO mixture according to the mass ratio of EO to PO of 500:750:750 as the reaction precursor to carry out polymerization reaction, controlling the pressure to be below 0.35MPa, after the epoxy mixture is introduced, keeping the temperature at 140 ℃ for continuous reaction for 10min, and finally cooling and removing water and micromolecules to obtain the waste grease high molecular weight polyether.
The product indexes of the polyether polyol prepared by the embodiment are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 67.3 mgKOH/g; moisture content: 0.03 percent; polyether molecular weight: 2503 of a paper substrate; distribution coefficient: 1.12; the product yield is as follows: 96.5 percent.
Example 2:
a method for preparing high molecular weight polyether polyol by using waste grease comprises the following steps:
s1, mixing glycerol, palm oil and AlCl3According to the mass ratio of glycerol to palm oil to AlCl3Putting 100:800:0.1 into a reaction kettle, adding nitrogen for 3 times, heating, and esterifying for 1.0h at 180 ℃ and under the vacuum degree of-0.08 to-0.098 MPa;
s2, after the esterification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a clean reaction kettle, adding an MMC catalyst with the mass of 0.08 per thousand of that of the reaction precursor, placing nitrogen for 3 times, heating, when the temperature is raised to 143 ℃, continuously introducing an EO/PO mixture into the reaction precursor according to the mass ratio of EO to PO 300:600:1200 to perform polymerization reaction, controlling the pressure to be below 0.35MPa, after the epoxy mixture is introduced, keeping the temperature at 140 ℃ to continue the reaction for 10min, and finally cooling and removing water and micromolecules to obtain the waste grease high molecular weight polyether.
The product indexes of the polyether polyol prepared by the embodiment are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 38.4 mgKOH/g; moisture content: 0.05 percent; polyether molecular weight: 4380; distribution coefficient: 1.16; the product yield is as follows: 97.4 percent.
Example 3:
a method for preparing high molecular weight polyether polyol by using waste grease comprises the following steps:
s1, mixing ethylene glycol, castor oil and ZnO according to the mass ratio of ethylene glycol: castor oil: putting 100:600:0.3 ZnO into a reaction kettle, adding nitrogen for 3 times, heating, and esterifying for 1.0h at 160 ℃ and under the vacuum degree of-0.08 to-0.098 MPa;
s2, after the esterification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a clean reaction kettle, adding a boron trifluoride diethyl etherate catalyst with the mass of 1.5 per mill of the reaction precursor, placing nitrogen for 3 times, heating, when the temperature is raised to 142 ℃, continuously introducing an EO/PO mixture into the reaction precursor according to the mass ratio of EO to PO 300:300:700 to perform polymerization reaction, controlling the pressure to be below 0.35MPa, after the epoxy mixture is introduced, keeping the temperature at 140 ℃ to continue the reaction for 10min, and finally cooling and removing water and small molecules to obtain the waste grease high molecular weight polyether.
The product indexes of the polyether polyol prepared by the embodiment are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 63.9 mgKOH/g; moisture content: 0.03 percent; polyether molecular weight: 2630; distribution coefficient: 1.14; the product yield is as follows: 97.0 percent.
Example 4:
a method for preparing high molecular weight polyether polyol by using waste grease comprises the following steps:
s1, mixing triethylene glycol, rapeseed oil and TiCl4Triethylene glycol according to the mass ratio: rapeseed oil: TiCl (titanium dioxide)4Putting 100:800:0.5 into a reaction kettle, adding nitrogen for 3 times, heating, and esterifying for 1.0h at 180 ℃ and under the vacuum degree of-0.08 to-0.098 MPa;
s2, after the esterification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a clean reaction kettle, adding a DMC catalyst with the mass of 0.07 thousandth of that of the reaction precursor, placing nitrogen for 3 times, heating, when the temperature is raised to 145 ℃, continuously introducing an EO/PO mixture into the reaction precursor according to the mass ratio of EO to PO (200: 400: 1600) to carry out polymerization reaction, controlling the pressure to be below 0.35MPa, after the epoxy mixture is introduced, keeping the temperature at 140 ℃ to continue the reaction for 10min, and finally cooling and removing water and micromolecules to obtain the waste grease high molecular weight polyether.
The product indexes of the polyether polyol prepared by the embodiment are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 27.1 mgKOH/g; moisture content: 0.03 percent; polyether molecular weight: 6210; distribution coefficient: 1.19; the product yield is as follows: 96.0 percent.
Example 5:
a method for preparing high molecular weight polyether polyol by using waste grease comprises the following steps:
s1, mixing 1, 4-butanediol, peanut oil, Zn (AC)21, 4-butanediol by mass ratio: peanut oil: zn (AC) 2-100: 500:1.0 is put into a reaction kettle, nitrogen is put into the reaction kettle for 3 times, then the temperature is raised, and esterification is carried out for 1.5 hours under the conditions of 180 ℃ and the vacuum degree of-0.08 to-0.098 MPa;
s2, after the esterification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a clean reaction kettle, adding a triphenylphosphine catalyst with the mass of 2.0 per thousand of that of the reaction precursor, placing nitrogen for 3 times, heating, when the temperature is raised to 141 ℃, continuously introducing an EO/PO mixture into the reaction precursor according to the mass ratio of EO to PO (200: 0: 600) for polymerization reaction, controlling the pressure to be below 0.35MPa, after the epoxy mixture is introduced, keeping the temperature at 140 ℃ for continuous reaction for 10min, and finally cooling and removing water and micromolecules to obtain the waste grease high molecular weight polyether.
The product indexes of the polyether polyol prepared by the embodiment are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 67.0 mgKOH/g; moisture content: 0.05 percent; polyether molecular weight: 2505 of a water-soluble polymer; distribution coefficient: 1.11; the product yield is as follows: 96.7 percent.
Example 6:
a method for preparing high molecular weight polyether polyol by using waste grease comprises the following steps:
s1, putting propylene glycol, rapeseed oil and ZnO into a reaction kettle according to the mass ratio of propylene glycol to soybean oil to ZnO of 100:500:0.25, adding nitrogen for 3 times, heating, and esterifying for 1.5 hours at 150 ℃ under the vacuum degree of-0.08 to-0.098 MPa;
s2, after the esterification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a clean reaction kettle, adding a DMC catalyst with the mass of 0.08 per thousand of that of the reaction precursor, placing nitrogen for 3 times, heating, when the temperature is raised to 144 ℃, continuously introducing an EO/PO mixture according to the mass ratio of EO to PO of 500:750:1250 as the reaction precursor to carry out polymerization reaction, controlling the pressure to be below 0.35MPa, after the epoxy mixture is introduced, keeping the temperature at 140 ℃ for continuous reaction for 10min, and finally cooling and removing water and micromolecules to obtain the waste grease high molecular weight polyether.
The product indexes of the polyether polyol prepared by the embodiment are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 30.5 mgKOH/g; moisture content: 0.03 percent; polyether molecular weight: 5500; distribution coefficient: 1.09; the product yield is as follows: 97.5 percent.
Example 7:
a method for preparing high molecular weight polyether polyol by using waste grease comprises the following steps:
s1, mixing propylene glycol, castor oil and ZnCl2Putting propylene glycol, soybean oil and ZnCl3 into a reaction kettle according to the mass ratio of 100:500:0.55, adding nitrogen for 3 times, heating, and esterifying for 1.5 hours at the temperature of 150 ℃ and the vacuum degree of-0.08 to-0.098 MPa;
s2, after the esterification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a clean reaction kettle, adding a boron trifluoride diethyl etherate catalyst with the mass of 0.1 per mill of the reaction precursor, placing nitrogen for 3 times, heating, when the temperature is raised to 144 ℃, continuously introducing an EO/PO mixture according to the mass ratio of EO to PO (500: 750: 1000) of the reaction precursor to carry out polymerization reaction, controlling the pressure below 0.35MPa, after the epoxy mixture is introduced, keeping the temperature at 140 ℃ for continuous reaction for 10min, and finally cooling and removing water and small molecules to obtain the waste grease high molecular weight polyether.
The product indexes of the polyether polyol prepared by the embodiment are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 26.5 mgKOH/g; moisture content: 0.05 percent; polyether molecular weight: 6300; distribution coefficient: 1.08; the product yield is as follows: 97.7 percent.
Example 8:
a method for preparing high molecular weight polyether polyol by using waste grease comprises the following steps:
s1, mixing propylene glycol, peanut oil and TiCl4Putting propylene glycol, soybean oil and TiCl4 in a mass ratio of 100:500:0.75 into a reaction kettle, adding nitrogen for 3 times, heating, and esterifying for 1.5h at 150 ℃ and under the vacuum degree of-0.08 to-0.098 MPa;
s2, after the esterification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a clean reaction kettle, adding an MMC catalyst with the mass of 1.0 per mill of the reaction precursor, placing nitrogen for 3 times, heating, when the temperature is raised to 143 ℃, continuously introducing an EO/PO mixture into the reaction precursor according to the mass ratio of EO to PO of 500:750:1000 for polymerization reaction, controlling the pressure to be below 0.35MPa, after the epoxy mixture is introduced, keeping the temperature at 140 ℃ for continuous reaction for 10min, and finally cooling and removing water and small molecules to obtain the waste grease high molecular weight polyether.
The product indexes of the polyether polyol prepared by the embodiment are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 32.7 mgKOH/g; moisture content: 0.04 percent; polyether molecular weight: 5100, adding water; distribution coefficient: 1.08; the product yield is as follows: 97.1 percent.
Example 9:
a method for preparing high molecular weight polyether polyol by using waste grease comprises the following steps:
s1, mixing propylene glycol, palm oil and SnCl4According to the mass ratio of propylene glycol to soybean oil to SnCl4Putting 100:500:0.50 into a reaction kettle, adding nitrogen for 3 times, heating, and esterifying for 1.5 hours at 150 ℃ under the vacuum degree of-0.08 to-0.098 MPa;
s2, after the esterification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a clean reaction kettle, adding an MMC catalyst with the mass of 0.5 per mill of the reaction precursor, placing nitrogen for 3 times, heating, when the temperature rises to 143 ℃, continuously introducing an EO/PO mixture into the reaction precursor according to the mass ratio of EO to PO of 500:550:1000 for polymerization reaction, controlling the pressure below 0.35MPa, after the epoxy mixture is introduced, keeping the temperature at 140 ℃ for continuous reaction for 10min, and finally cooling and removing water and micromolecules to obtain the waste grease high molecular weight polyether.
The product indexes of the polyether polyol prepared by the embodiment are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 28.4 mgKOH/g; moisture content: 0.04 percent; polyether molecular weight: 5800; distribution coefficient: 1.10; the product yield is as follows: 97.6 percent.
Comparative example 1:
a method for preparing polyether polyol by using waste grease comprises the following steps:
s1, mixing triethylene glycol, castor oil and ZnCl2 in a mass ratio of triethylene glycol: castor oil: putting ZnCl 2-200: 500:0.5 into a four-neck flask, adding nitrogen for 3 times, heating, and esterifying for 2.5 hours at the temperature of 120-130 ℃ and the vacuum degree of-0.08-0.098 MPa;
s2, after the reaction is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a reaction kettle, adding a potassium methoxide catalyst with the mass being 2 per thousand of that of the reaction precursor, placing nitrogen for 3 times, heating, keeping the reaction precursor EO and PO at 500:750:750 by mass ratio to perform polymerization reaction when the temperature is increased to 110-115 ℃, keeping the temperature of 115-120 ℃ after the propylene oxide is introduced until the pressure is lowest and does not change any more, continuing the reaction for 1 hour, and finally removing water and small molecules to obtain the crude product of the waste grease polyether polyol.
The product indexes of the polyether polyol prepared by the comparative example are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 127.5 mgKOH/g; moisture content: 0.1 percent; polyether molecular weight: 1320; distribution coefficient: 1.23; the product yield is as follows: 85.9 percent.
Comparative example 2:
a method for preparing polyether polyol by using waste grease comprises the following steps:
s1, mixing glycerol, rapeseed oil, palm oil and TiCl4 in a mass ratio of glycerol: rapeseed oil: palm oil: putting TiCl 4-200: 250:1.5 into a four-neck flask, adding nitrogen for 3 times, heating, and esterifying for 2.5h at 120-130 ℃ under the vacuum degree of-0.08-0.098 MPa;
s2, after the esterification is finished, cooling the reactant to 70-80 ℃, and performing suction filtration to obtain a reaction precursor;
s3, putting the reaction precursor into a reaction kettle, adding a NaOH catalyst with the mass of 3.5 per mill of the reaction precursor, placing nitrogen for 3 times, heating, and heating to 115-120 ℃ according to the mass ratio of EO to PO of the reaction precursor to 500: 400: and (2) continuously introducing propylene oxide into the reactor 400 for polymerization reaction, controlling the pressure to be below 0.35MPa, keeping the temperature of 120-125 ℃ after the propylene oxide is introduced, reacting for 1 hour after the pressure is lowest and is not changed any more, and finally removing water and small molecules to obtain the crude product of the waste grease polyether polyol.
The product indexes of the polyether polyol prepared by the comparative example are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 103.2 mgKOH/g; moisture content: 0.04 percent; polyether molecular weight: 1630; distribution coefficient: 1.26; the product yield is as follows: 87.4 percent.
Comparative example 3:
a method for preparing polyether polyol by using waste grease comprises the following steps:
s1, mixing glycerol, soybean oil and concentrated sulfuric acid in a mass ratio of glycerol: soybean oil: putting concentrated sulfuric acid at a ratio of 200:500:2.5 into a four-neck flask, adding nitrogen for 3 times, heating, and esterifying at 240 ℃ and under the vacuum degree of-0.08 to-0.098 MPa for 5 hours;
s2, washing the substance after the S1 reaction to be neutral by a large amount of deionized water, and removing water at 110-115 ℃ to obtain a reaction precursor.
S3, 200g of reaction precursor and 2.5g of potassium hydroxide are put into a reaction kettle, nitrogen is placed for 3 times, and then the temperature is raised. When the temperature reaches 140 ℃, 500g of ethylene oxide and 500g of propylene oxide are introduced in an equivalent circulation manner, and after each time of epoxy introduction, the reaction is carried out for 40min under the conditions of 140 ℃ and 0.8MP until the reaction is finished after the epoxy introduction. The reaction was stopped and evacuated. And (3) vacuumizing under reduced pressure at the temperature of 110 ℃/10mmHg for 30min to obtain a crude product of the fatty acid polyether polyol.
The product indexes of the polyether polyol prepared by the comparative example are as follows: appearance: a light yellow transparent liquid; hydroxyl value: 146.2 mgKOH/g; moisture content: 0.06 percent; polyether molecular weight: 1150; distribution coefficient: 1.29; the product yield is as follows: 73.5 percent.
TABLE 1
Hydroxyl value (mgKOH/g) Water content% Molecular weight Coefficient of distribution The product yield is%
Example 1 67.3 0.03 2503 1.12 96.5
Example 2 38.4 0.05 4380 1.16 97.4
Example 3 63.9 0.03 2630 1.14 97.0
Example 4 27.1 0.03 6210 1.19 96.0
Example 5 67.0 0.05 2505 1.11 96.7
Example 6 30.5 0.03 5500 1.09 97.5
Example 7 26.5 0.05 6300 1.08 97.7
Example 8 32.7 0.04 5100 1.08 97.1
Example 9 28.4 0.04 5800 1.10 97.6
Comparative example 1 127.5 0.1 1320 1.23 85.9
Comparative example 2 103.2 0.04 1630 1.26 87.4
Comparative example 3 146.2 0.06 1150 1.29 73.5
From the comparison of the data of examples 1 to 5 with comparative examples 1 to 2, it can be found that: the reaction precursor is obtained by using Lewis acid for catalysis and esterification, and then the reaction precursor is further polymerized with the epoxy mixture to obtain the waste grease polyether, and the yield of the polyether is about 10 percent higher than that of the waste grease polyether obtained by using an alkali-catalyzed epoxy polymerization process; the molecular weight of the obtained polyether is 2500-6200, which is higher than that of the alkali-catalyzed polymerization process, and the polyether has the advantages of small distribution coefficient, narrow product distribution and high effective component.
As can be seen from the comparison of the data of examples 1-5 with the data of comparative example 3: the invention not only has the product yield 25 percent higher than that of the acid catalysis esterification-alkali catalysis polymerization process, but also has the polyether with excellent molecular weight and distribution. In addition, the Lewis acid catalyst used in the process can be directly recycled and reused after being filtered, so that the cost can be saved, the generation of waste acid water in acid catalytic esterification is avoided, the cost can be further reduced, and the process is more environment-friendly.
In conclusion, the polyether prepared by the method has the advantages of high molecular weight, narrow distribution, high effective component content and the like. In addition, the process has the advantages of low production cost, high efficiency, stable product, energy conservation, environmental protection and the like.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.

Claims (10)

1. A method for preparing high molecular weight polyether polyol by using waste grease is characterized by comprising the following steps:
s1, carrying out esterification reaction on the waste oil and the polyhydric alcohol under the action of a Lewis acid catalyst;
s2, cooling to 70-80 ℃ after the reaction is finished, carrying out suction filtration to obtain a reaction precursor, and recovering and recycling the Lewis acid catalyst;
s3, adding a catalyst into the reaction precursor filtered in the step S2, continuously introducing the EO/PO mixture at the reaction temperature of 140 ℃ and 145 ℃ for polymerization reaction, curing after the epoxy is introduced till the epoxy reaction is complete, and then cooling and removing moisture and small molecules to obtain the waste grease high molecular weight polyether.
2. The method for preparing the high molecular weight polyether polyol by using the waste oil and fat according to claim 1, wherein the mass ratio of the polyol to the waste oil and fat in the step S1 is 1: 1-10, and the addition amount of the Lewis acid catalyst is 0.05-1% of the mass of the waste oil and fat.
3. The method for preparing high molecular weight polyether polyol from waste oil and fat according to claim 1, wherein the acid value of the waste oil and fat in the step S1 is 0.5 to 1.0mgKOH/g, and the method for measuring the acid value is GB 5009.229-2016.
4. The method for preparing polyether polyol with high molecular weight using waste oil and fat according to claim 3, wherein the waste oil and fat in step S1 is one or a mixture of any two or more of rapeseed oil, peanut oil, palm oil, soybean oil, coconut oil and castor oil.
5. The method for preparing high molecular weight polyether polyol using waste oil and fat according to claim 1, wherein the polyol in the step S1 is one or a mixture of two or more of ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, 1, 4-butanediol, pentaerythritol, and sorbitol.
6. The method for preparing polyether polyol with high molecular weight by using waste grease as claimed in any one of claims 1 to 5, wherein the Lewis acid catalyst in the step S1 is selected from AlCl3、ZnCl2、ZnO、TiCl4、Zn(AC)2、SnCl4One or a mixture of any two or more of them.
7. The method for preparing high molecular weight polyether polyol from waste grease as claimed in claim 1, wherein the S1 specifically comprises: waste grease, polyhydric alcohol and a Lewis acid catalyst are put into a reaction kettle, nitrogen is replaced for 3 times, and then the reaction is carried out for 1 to 1.5 hours under the conditions that the reaction temperature is 150 to 180 ℃ and the vacuum degree is minus 0.08 to minus 0.098 MPa.
8. The method for preparing high molecular weight polyether polyol by using waste grease as claimed in claim 1, wherein the mass ratio of the reaction precursor to the EO/PO mixture in the step S3 is 1: 10-20; the PO accounts for 50 to 100 percent of the EO/PO mixture.
9. The method for preparing high molecular weight polyether polyol from waste grease as claimed in claim 1, wherein the amount of the catalyst added in the step S3 is 0.05 to 2% by mass of the reaction precursor.
10. The method for preparing high molecular weight polyether polyol using waste grease as claimed in claim 9, wherein the catalyst in the step S3 is one selected from DMC, MMC, boron trifluoride diethyl etherate, triphenylphosphine, etc.
CN202210188515.3A 2022-02-28 2022-02-28 Method for preparing high molecular weight polyether polyol by using waste grease Active CN114409888B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210188515.3A CN114409888B (en) 2022-02-28 2022-02-28 Method for preparing high molecular weight polyether polyol by using waste grease

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210188515.3A CN114409888B (en) 2022-02-28 2022-02-28 Method for preparing high molecular weight polyether polyol by using waste grease

Publications (2)

Publication Number Publication Date
CN114409888A true CN114409888A (en) 2022-04-29
CN114409888B CN114409888B (en) 2023-11-14

Family

ID=81262252

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210188515.3A Active CN114409888B (en) 2022-02-28 2022-02-28 Method for preparing high molecular weight polyether polyol by using waste grease

Country Status (1)

Country Link
CN (1) CN114409888B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8933191B1 (en) * 2010-05-19 2015-01-13 Thomas M. Garrett Method for synthesizing high molecular weight natural oil polyols
CN109593190A (en) * 2018-12-07 2019-04-09 浙江绿科安化学有限公司 A kind of synthetic method of low unsaturation degree and high molecular weight high activity butylol polyether
CN110951067A (en) * 2019-12-11 2020-04-03 浙江皇马新材料科技有限公司 Method for preparing polyether polyol by using high-acid-value waste oil

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8933191B1 (en) * 2010-05-19 2015-01-13 Thomas M. Garrett Method for synthesizing high molecular weight natural oil polyols
CN109593190A (en) * 2018-12-07 2019-04-09 浙江绿科安化学有限公司 A kind of synthetic method of low unsaturation degree and high molecular weight high activity butylol polyether
CN110951067A (en) * 2019-12-11 2020-04-03 浙江皇马新材料科技有限公司 Method for preparing polyether polyol by using high-acid-value waste oil

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
刘艳春,邓剑如,许晖,蒋卫和: "新型环氧环己烷-四氢呋喃共聚醚的合成与应用" *
周志勇等: "窄分子量分布端羟基环氧乙烷-四氢呋喃共聚醚的合成及表征" *
王胜利等: "UV固化涂料单体用多元醇聚醚系列产品的制备工艺研究" *

Also Published As

Publication number Publication date
CN114409888B (en) 2023-11-14

Similar Documents

Publication Publication Date Title
CN100390128C (en) Bio-based polyhydric alcohol prepared by using rape seed oil
KR101980744B1 (en) A method for circulating a polyether polyol using a DMC catalyst
US20060194974A1 (en) Novel triglycerides and method of preparation thereof
CN101851329A (en) Starter feed stream acidification in dmc-catalyzed process for the production of polyether polyols
CN109970964B (en) Preparation method of tertiary alkynol polyether
CN107177034B (en) Allyl alcohol polyoxypropylene ether and preparation method thereof
CN101959931A (en) Process for preparing polyols
CN107474229A (en) A kind of fatty poly-ester carbonate copolyesters and preparation method thereof
CN114409888A (en) Method for preparing high molecular weight polyether polyol by using waste oil
CN110951067A (en) Method for preparing polyether polyol by using high-acid-value waste oil
CN110591070A (en) Castor oil-based flame-retardant polyether polyol for polyurethane elastomer and preparation method thereof
CN110669583B (en) Vegetable insulating oil refining process with rapeseed oil as raw material
CN106748767A (en) A kind of low hydroxyl value plant oil polylol and preparation method thereof
CN100396353C (en) Process for suppressing the foaming of an aqueous system
CN109467691A (en) A kind of preparation method of low unsaturation degree and high molecular weight polyoxyalkylene polyol
CN111138278A (en) Preparation method of butanediol caprylate
CN108059717B (en) Refining method and application of low-odor polyether polyol
CN107151680A (en) A kind of tung oil polylol and preparation method
CN112457480B (en) Preparation method of bio-based modified high-activity polyether polyol
CN112724394B (en) Preparation method of cellulose polyether polyol
CN110951066A (en) Preparation method of polyether polyol
CN106957241A (en) A kind of high hydroxyl value tung oil polyalcohol and preparation method thereof
CN106957229A (en) A kind of tung oil polyalcohol and preparation method thereof
CN115572385B (en) Preparation method of plant-based polyether polyol
CN117487153B (en) Alkynol polyether for industrial defoaming and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant