CN114085372A - Synthesis method of butanol polyether - Google Patents

Synthesis method of butanol polyether Download PDF

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CN114085372A
CN114085372A CN202111479765.4A CN202111479765A CN114085372A CN 114085372 A CN114085372 A CN 114085372A CN 202111479765 A CN202111479765 A CN 202111479765A CN 114085372 A CN114085372 A CN 114085372A
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catalyst
butanol
synthesizing
butanolpolyether
ethylene oxide
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CN114085372B (en
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金一丰
张雨
王马济世
王胜利
周扬
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Zhejiang Huangma Technology Co Ltd
Zhejiang Lvkean Chemical Co Ltd
Zhejiang Huangma Shangyi New Material Co Ltd
Zhejiang Huangma Surfactant Research Institute Co Ltd
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Zhejiang Huangma Technology Co Ltd
Zhejiang Lvkean Chemical Co Ltd
Zhejiang Huangma Shangyi New Material Co Ltd
Zhejiang Huangma Surfactant Research Institute Co Ltd
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    • 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
    • C08G65/2606—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 containing hydroxyl groups
    • C08G65/2609—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 containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2666—Hetero polyacids
    • 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

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

Abstract

The invention relates to the technical field of chemical synthesis, and discloses a method for synthesizing butanol polyether, which comprises the following steps: butanol is used as an initiator, ethylene oxide or propylene oxide or a mixture of the ethylene oxide and the propylene oxide is used as a chain extender, and then heteropolyacid salt is added into the initiator and the chain extender to be used as a catalyst, so that the butanol polyether is prepared under the conditions of normal temperature and normal pressure. The method takes the heteropolyacid salt as the catalyst, synthesizes the butanol polyether by the cation ring-opening polymerization method, changes the method that strong base is taken as the catalyst and can be synthesized only under the conditions of high temperature and pressurization, ensures that the synthesis reaction can be completed at normal temperature and normal pressure, and has high reaction activity, simple process and safety; the invention adopts insoluble acid heteropoly acid salt as the catalyst, can be separated from the material after the synthesis reaction, enables the catalyst to be reused, does not need post-treatment, reduces the cost of post-treatment process links, reduces the product cost, and has good social benefit and economic benefit.

Description

Synthesis method of butanol polyether
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a synthetic method of butanol polyether.
Background
Butanol polyether is polyether synthesized by ring-opening copolymerization of butanol serving as an initiator with Ethylene Oxide (EO) and Propylene Oxide (PO) in a catalyst, has the characteristics of good water solubility and viscosity-temperature characteristics, reversible dissolution, better lubrication, heat resistance, antistatic property, surface performance, no coking, low foam and the like, and is widely applied to the fields of spinning, metal processing, equipment lubrication and the like.
The synthesized butanol polyether usually uses strong base as a catalyst, can be synthesized only under the conditions of high temperature and pressurization, and is difficult to control and unsafe in process operation.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the existing preparation process of butanol polyether can be synthesized only under the conditions of high temperature and pressurization, and the process operation is difficult to control and unsafe.
In order to solve the technical problem, the invention provides a method for synthesizing butanol polyether, which comprises the following steps:
butanol is used as an initiator, ethylene oxide or propylene oxide or a mixture of the ethylene oxide and the propylene oxide is used as a chain extender, and then heteropolyacid salt is added into the initiator and the chain extender to be used as a catalyst, so that the butanol polyether is obtained under the conditions of normal temperature and normal pressure.
Preferably, in the mixture of ethylene oxide and propylene oxide, the molar ratio of ethylene oxide to propylene oxide is 1-10: 1 to 10.
Preferably, the catalyst heteropolyacid salt has the general formula: csXH3-XPW12·nH2And O, wherein x represents the atomic number value of Cs, and n represents that the heteropoly acid salt contains n crystal waters.
Preferably, the heteropolyacid salt is Cs1H2PW12·6H2O; the addition amount of the heteropolyacid salt catalyst is 0.1-0.5% of the total mass of the materials.
Preferably, the addition amount of the heteropoly acid salt is 0.35-0.4%.
Preferably, the conditions at normal temperature and normal pressure refer to: the normal temperature is 50-75 ℃, the normal pressure means that the reaction pressure is-0.005 MPa, the polymerization reaction condition under the condition is mild, the conditions of high temperature and high pressure are not needed, the process operation is simple, and the process is safer.
Preferably, the reaction temperature in the step S2 is 60 to 70 ℃.
Preferably, the reaction pressure in the step S2 is 0.003 to 0.045 MPa.
Compared with the prior art, the invention has the following advantages:
1. the synthesis method of the butanol polyether takes the heteropolyacid salt as the catalyst, and synthesizes the butanol polyether by the cation ring-opening polymerization method, so that the synthesis method of the butanol polyether only needs to be synthesized under the conditions of high temperature and pressurization by taking strong base as the catalyst, the synthesis reaction can be completed at normal temperature (50-75 ℃) and normal pressure, the reaction activity is high, and the process is simple and safe;
2. the synthesis method of the butanol polyether adopts insoluble acid heteropoly acid salt as the catalyst, can be easily separated from materials after the synthesis reaction, enables the catalyst to be reused, does not need post-treatment, reduces the cost of the post-treatment process link compared with the conventional method, does not generate waste residue, reduces the disposal cost of the waste residue, reduces the product cost, and has good social benefit and economic benefit.
Detailed Description
The technical solution of the present invention is described in detail and fully below with reference to the following embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, belong to the scope of the present invention.
Example 1: 200g of butanol and heteropoly acid salt Cs are added into a 2.5L reaction kettle1.0H2.0PW12·6H2Stirring O1.75 g, replacing nitrogen for three times, heating, starting to introduce ethylene oxide 1546g when the temperature is raised to 75 ℃, reacting at 0.005MPa, curing until the pressure is unchanged after the addition is finished, degassing and discharging.
Example 2: 200g of butanol and heteropoly acid salt Cs are added into a 2.5L reaction kettle1.0H2.0PW12·6H2Stirring O5.0 g, replacing nitrogen for three times, heating to 50 ℃, introducing 1546g of ethylene oxide, reacting at 0.005MPa, curing until the pressure is unchanged after the addition is finished, degassing and discharging.
Example 3: 200g of butanol and heteropoly acid salt Cs are added into a 2.5L reaction kettle1.0H2.0PW12·6H2Stirring O3.5 g, replacing nitrogen for three times, heating, raising the temperature to 60 ℃, introducing 1546g of ethylene oxide, reacting at 0.005MPa, curing until the pressure is unchanged after the addition is finished, degassing and discharging.
Example 4: 200g of butanol and heteropoly acid salt Cs are added into a 2.5L reaction kettle1.0H2.0PW12·6H2Stirring O5.3 g, replacing nitrogen for three times, heating, raising the temperature to 60 ℃, introducing 1567g of propylene oxide, reacting under 0.005MPa, curing until the pressure is unchanged after the addition is finished, degassing and discharging.
Using example 4 as a reference, a 2.5L reactor was charged with 200g of butanol and 5.3g of sodium hydroxide in the conventional manner, and 1567g of propylene oxide was introduced while maintaining the reaction temperature at 110 ℃ and the reaction pressure at 0.3 MPa. The speed of adding the propylene oxide is 90-110 g/min. Example 4 when the temperature of 60 ℃ and the pressure of 0.005Mpa are maintained, the reaction rate is 150-170 g/min, which is improved by 36.36% -88.88% compared with the reaction rate of the conventional method, which indicates that the catalyst used in the synthesis method of the present invention has higher reaction activity.
Example 5: adding into a 2.5L reaction kettleButanol 200g, heteropolyacid salts Cs1.0H2.0PW12·6H2Stirring O3.1 g, replacing nitrogen for three times, heating, starting to introduce a mixture of 660g of ethylene oxide and 870g of propylene oxide when the temperature is raised to 70 ℃, reacting at 0.004MPa, curing after the addition until the pressure is unchanged, degassing and discharging.
Example 6: 500g of Butanol polyether of example 1, heteropolyacid salt Cs, was charged in a 2.5L reactor1.0H2.0PW12·6H2Stirring O2.7 g, replacing nitrogen for three times, heating, starting to introduce 1364g of ethylene oxide when the temperature is raised to 55 ℃, reacting at 0.003MPa, curing until the pressure is unchanged after the addition is finished, degassing and discharging.
Example 7: A2.5L reactor was charged with 500g of the Butylpolyether of example 4, heteropolyacid salt Cs1.0H2.0PW12·6H20.31g of O, stirring, replacing nitrogen for three times, heating, starting to introduce 1551g of epoxypropane when the temperature is raised to 70 ℃, reacting at the pressure of-0.001 MPa, curing after the addition until the pressure is unchanged, degassing and discharging.
Example 8: A2.5L reactor was charged with 500g of the Butylpolyether of example 5, heteropolyacid salt Cs1.0H2.0PW12·6H2Stirring O2.0 g, replacing nitrogen for three times, heating, starting to introduce a mixture of 660g of ethylene oxide and 870g of propylene oxide when the temperature is raised to 60 ℃, reacting at 0.005MPa, curing until the pressure is unchanged after the addition, degassing and discharging. The yield indexes of the butanol polyether obtained by the reaction are shown in the following table 1:
table 1: comparative table of yields of Butanol polyethers by the synthetic methods of examples 1-8
Figure BDA0003394435870000041
Note: the calculation of the molecular weight is obtained by converting the measured hydroxyl value of the polyether: 56100/measured hydroxyl value; the hydroxyl value detection method is carried out according to the national standard GB/T12008.3-2009.
The yield results in table 1 show that the synthesis method of the butanol polyether has good industrial application prospect, and the product yield is high due to the catalytic production of the heteropolyacid salt catalyst, and the synthesis method is completely suitable for industrial production.
The synthesis method of the butanol polyether takes the heteropolyacid salt as the catalyst, and synthesizes the butanol polyether by the cation ring-opening polymerization method, so that the synthesis method of the butanol polyether only needs to be synthesized under the conditions of high temperature and pressurization by taking strong base as the catalyst, the synthesis reaction can be completed at normal temperature (50-75 ℃) and normal pressure, the reaction activity is high, and the process is simple and safe; insoluble acid heteropoly acid salt is used as catalyst, and after the synthesis reaction, the catalyst can be separated from the material easily, so that the catalyst can be reused. In the conventional method, 50-70 Kg of deionized water, 7-10 Kg of adsorbent (magnesium silicate, etc.), 3-5 Kg of diatomaceous earth are consumed for 1 ton of product, resulting in about 10-15 Kg of waste residue, including heating and labor costs. The method does not need post-treatment, reduces the cost of post-treatment process links, does not generate waste residues, reduces the disposal cost of the waste residues, reduces the product cost, and has good social benefit and economic benefit.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and substitutions can be made without departing from the technical principle of the present invention, and these modifications and substitutions should also be regarded as the protection scope of the present invention.

Claims (10)

1. The synthesis method of butanol polyether is characterized by comprising the following steps:
s1, uniformly mixing butanol and a chain extender to obtain a raw material mixed solution;
s2, adding a heteropolyacid salt catalyst into the raw material mixed solution, and reacting at normal temperature and normal pressure to obtain the butanol polyether.
2. The method of synthesizing the butanolpolyether of claim 1, wherein: the chain extender in step S1 is ethylene oxide or propylene oxide, or a mixture of said ethylene oxide and said propylene oxide.
3. The method of synthesizing the butanolpolyether of claim 2, wherein: in the mixture of the ethylene oxide and the propylene oxide, the mass ratio or the volume ratio of the ethylene oxide to the propylene oxide is as follows.
4. The method of synthesizing the butanolpolyether of any one of claims 1 to 3, wherein: the heteropolyacid salt catalyst is Cs1H2PW12·6H2O。
5. The method of synthesizing the butanolpolyether of claim 4, wherein: the addition amount of the heteropolyacid salt catalyst is 0.1-0.5% of the total mass of the materials.
6. The method of synthesizing the butanolpolyether of claim 5, wherein: the reaction pressure in the step S2 is-0.005 MPa.
7. The method of synthesizing the butanolpolyether of claim 6, wherein: the reaction temperature in the step S2 is 50-75 ℃.
8. The method of synthesizing the butanolpolyether of claim 7, wherein: the reaction temperature in the step S2 is 60-70 ℃.
9. The method of synthesizing the butanolpolyether of claim 4, wherein: the addition amount of the heteropoly acid salt is preferably 0.35-0.4%.
10. The method of synthesizing the butanolpolyether of claim 1, wherein: the reaction pressure in the step S2 is 0.003-0.045 MPa.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6313262B1 (en) * 1999-05-19 2001-11-06 Dairen Chemical Corporation Method for preparing polyether polyol and copolymer thereof
CN101190878A (en) * 2006-11-21 2008-06-04 中国石油化工股份有限公司 Method for preparing propylene glycol ether
CN103113572A (en) * 2013-02-05 2013-05-22 佳化化学股份有限公司 Preparation method of monomer polyether for synthesizing high-efficiency polycarboxylic acid water reducing agent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6313262B1 (en) * 1999-05-19 2001-11-06 Dairen Chemical Corporation Method for preparing polyether polyol and copolymer thereof
CN101190878A (en) * 2006-11-21 2008-06-04 中国石油化工股份有限公司 Method for preparing propylene glycol ether
CN103113572A (en) * 2013-02-05 2013-05-22 佳化化学股份有限公司 Preparation method of monomer polyether for synthesizing high-efficiency polycarboxylic acid water reducing agent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
岳淑美;唐艳茹;丁鹏;高丽娟;: "杂多酸催化合成聚氧丙烯甘油醚" *

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