CN113563575A - Alkylene oxide-tetrahydrofuran copolymer and preparation method thereof - Google Patents
Alkylene oxide-tetrahydrofuran copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an alkylene oxide-tetrahydrofuran copolymer and a preparation method thereof, the alkylene oxide-tetrahydrofuran copolymer is prepared by tetrahydrofuran, a supported solid acid catalyst, an initiator and ethylene oxide and/or propylene oxide, wherein the supported solid acid catalyst takes dodecaphosphotungstic heteropoly acid as a matrix and adopts a sol-gel method to carry out Zn2+Modification and synthesis. The supported solid acid catalyst can realize the reaction of the initiator, tetrahydrofuran, ethylene oxide and propylene oxide under mild conditions, and has high reaction activity and selectivity, so that the content of by-products of the synthesized alkylene oxide-tetrahydrofuran copolymer product is reduced, the distribution coefficient is narrowed, the distribution coefficient of the alkylene oxide-tetrahydrofuran copolymer product can be controlled to be 1.1-1.8, no solvent is required to be added in the process, the reaction steps can be greatly reduced, and the industrialization cost can be reduced.
Description
Technical Field
The invention belongs to the technical field of fine chemical synthesis, and particularly relates to an alkylene oxide-tetrahydrofuran copolymer and a preparation method thereof.
Background
Ethylene oxide-propylene oxide-tetrahydrofuran copolymer with main chain comprising methylene (-CH)2-) and ether bond (-O-), and the structure destroys the regularity of the macromolecular chain structure, so that the product is not easy to crystallize, has the characteristics of good flexibility, low-temperature performance, strong cohesiveness, good mechanical property and the like, and is a new generation of binder of the NEPE solid rocket propellant. In addition, the ethylene oxide-propylene oxide-tetrahydrofuran copolymer can be used as a raw material for other plastic materials (e.g., polyurethane) as well as lubricant and fuel additives.
However, the applicant found that: as the catalyst for producing the ethylene oxide-propylene oxide-tetrahydrofuran copolymer, a solid acid, boron trifluoride, trifluoromethanesulfonic acid, montmorillonite clay, etc. are usually used. For example:
chinese patent CN101942084A describes a method for synthesizing polytetrahydrofuran by using trifluoromethanesulfonic acid rare earth metal compound as catalyst, the catalyst has high finished product preparation, and the catalyst is separated by using solvent, which increases the complexity of the reaction process.
Chinese patent CN 111072946A adopts boron trifluoride complex as catalyst and polyalcohol as initiator to make cyclohexene oxide, ethylene oxide and tetrahydrofuran undergo the process of bulk polymerization, firstly adds tetrahydrofuran, polyalcohol and catalyst, stirs them, then adds cyclohexene oxide and ethylene oxide, after the reaction is completed, the synthesized crude product is passed through the processes of removing catalyst, removing small molecular substance, drying and filtering so as to obtain the invented product. The boron trifluoride complex compound adopted in the method has weak reaction activity, and is easy to volatilize, thus being not beneficial to operation.
Us patent GB854958, using montmorillonite clay as catalyst. The smectite clay is activated by contacting it with an aqueous solution containing only about 10% by weight or less of an inorganic acid. Although this type of montmorillonite clay catalyst is used to copolymerize THF and alkylene oxide polymerizations, this process produces a poly cyclic ether by-product, which can be present in amounts of up to 10% to 15% of the total mass.
The solid acid catalyst is one important kind of acid-base catalyst and is used widely in ionic catalytic reaction. However, the applicant found that: the existing solid acid catalysts on the market at present have high toxicity and strong corrosivity, are difficult to clean from processed products, and have the defects of poor reaction activity and selectivity. For example: phosphotungstic acid (H)3PW12O40·nH2O, HPW) is a solid oxygen-containing heteropoly acid with a Keggin structure, has strong acidity and higher catalytic activity and stability, and is widely applied to reactions such as olefin hydration, dehydration, esterification, alkylation, epoxidation and the like; however, the phosphotungstic acid catalyst has a small specific surface area, is easily dissolved in polar solvents such as water and alcohol, and is difficult to separate from the reaction system.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an alkylene oxide-tetrahydrofuran copolymer synthesized by using a catalyst with low toxicity, no corrosion, easy removal, high reaction activity and high selectivity and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the alkylene oxide-tetrahydrofuran copolymer is prepared from tetrahydrofuran, a supported solid acid catalyst, an initiator and ethylene oxide and/or propylene oxide, wherein the supported solid acid catalyst takes dodecaphosphotungstic heteropoly acid as a matrix and adopts a sol-gel method to perform Zn2+Modification and synthesis.
Further, the alkylene oxide-tetrahydrofuran copolymer has the reaction equation:
wherein a is more than or equal to 0, b is more than or equal to 0, c is more than or equal to 1, and a + b is more than or equal to 1. .
Further, the supported solid acid catalyst is prepared and synthesized by phosphotungstic acid, zinc nitrate hexahydrate, tetraethyl silicate, absolute ethyl alcohol, nitric acid and Triton X-100; the weight of the tetraethyl silicate is 20-50% of the total weight of the tetraethyl silicate, the phosphotungstic acid and the zinc nitrate hexahydrate, the molar ratio of the phosphotungstic acid to the zinc nitrate hexahydrate is 1:3, and the volumes of the absolute ethyl alcohol, the nitric acid and the Triton X-100 are 20-30%, 200-500% and 100-300% of the total weight of the tetraethyl silicate, the phosphotungstic acid and the zinc nitrate hexahydrate respectively.
Further, the supported solid acid catalyst was prepared and synthesized from 40.0g of phosphotungstic acid, 6.2g of zinc nitrate hexahydrate, 25g of tetraethyl silicate, 15mL of anhydrous ethanol, 200mL of nitric acid with a concentration of 0.1mol/L, and 150mL of Triton X-100.
Further, the supported solid acid catalyst is a powder granular solid, and the particle size is 10-200 meshes.
Further, the initiator is one or more of ethylene glycol, 1, 4-butanediol, diethylene glycol, triethylene glycol, trimethylolpropane, glycerol and pentaerythritol.
The invention also provides a preparation method of the alkylene oxide-tetrahydrofuran copolymer, which comprises the following steps:
s100, feeding and nitrogen replacement: sequentially adding an initiator, tetrahydrofuran and a supported solid acid catalyst into a reaction kettle, starting stirring, vacuumizing under the protection of nitrogen, repeatedly replacing for three times, closing vacuum, and starting heating;
s200, reaction: raising the temperature in the reaction kettle to a specified temperature, starting to slowly introduce the ethylene oxide and/or the propylene oxide into the reaction kettle, simultaneously controlling the pressure of the reaction kettle, keeping the temperature after the ethylene oxide and/or the propylene oxide are added, continuing to react and slake until the pressure is not reduced any more, and then keeping the reaction till the reaction is thorough;
s300, removing unreacted substances: after the ripening is finished, removing unreacted tetrahydrofuran, ethylene oxide and/or propylene oxide under negative pressure;
s400, discharging: degassing and filtering the product obtained in the step S300 to obtain a finished product of the alkylene oxide-tetrahydrofuran copolymer;
s500, catalyst removal: and (3) filtering and separating the catalyst in the finished product of the alkylene oxide-tetrahydrofuran copolymer.
Furthermore, the dosage of the supported solid acid catalyst is 0.1-100 per mill of the total mass of the tetrahydrofuran, the supported solid acid catalyst, the initiator and the ethylene oxide and/or the propylene oxide, and the molar ratio of the tetrahydrofuran to the ethylene oxide to the supported solid acid catalyst is 0-10000: 0 to 10000: 0.1-1000, wherein the molar ratio of tetrahydrofuran to propylene oxide to the supported solid acid catalyst is 0-10000: 0 to 10000: 0.1-1000, wherein the molar ratio of tetrahydrofuran, ethylene oxide, propylene oxide and a supported solid acid catalyst is 0-10000: 0 to 10000: 0 to 10000: 0.1 to 1000.
Further, the reaction temperature in the step S200 is-20-80 ℃, the temperature for removing the unreacted reactant in the step S300 is 30-120 ℃, and the temperature for removing the unreacted reactant in the product with the dynamic viscosity of more than 2000cps at room temperature of 25 ℃ is preferably more than or equal to 50 ℃.
Further, before performing step S100, the supported solid acid catalyst is prepared by the following steps:
(1) tetraethyl silicate, absolute ethyl alcohol, nitric acid and Triton X-100 are mixed and stirred uniformly to obtain a mixed solution;
(2) after oscillating the mixed solution, adding phosphotungstic acid and zinc nitrate hexahydrate, and standing to obtain gel;
(3) calcining the gel, heating and drying to obtain dry gel;
(4) and grinding the xerogel to obtain the supported solid acid catalyst.
The invention mainly has the following beneficial effects:
the supported solid acid catalyst adopted by the invention can realize the reaction of an initiator, tetrahydrofuran, ethylene oxide and propylene oxide under mild conditions, and the catalyst is prepared by adding Lewis metal Zn2+Incorporation into H3PW12O40The secondary structure of the catalyst can generate more active sites, and meanwhile, the catalyst has no reducibility, so that the reaction activity and selectivity of the catalyst are improved, the content of by-products of the synthesized alkylene oxide-tetrahydrofuran copolymer product is reduced, the distribution coefficient is narrowed, the distribution coefficient of the alkylene oxide-tetrahydrofuran copolymer product can be controlled to be 1.1-1.8, no solvent is required to be added in the process, the reaction steps can be greatly reduced, and the industrialization cost is reduced.
Drawings
FIG. 1 is a schematic flow diagram of a process for preparing an alkylene oxide-tetrahydrofuran copolymer according to the present invention;
FIG. 2 is a schematic diagram of a preparation process of a supported solid acid catalyst used for an alkylene oxide-tetrahydrofuran copolymer according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention relates to an alkylene oxide-tetrahydrofuran copolymer, which is prepared from tetrahydrofuranA supported solid acid catalyst and an initiator, and ethylene oxide and/or propylene oxide. Wherein the supported solid acid catalyst takes dodecaphosphotungstic heteropoly acid as a matrix and adopts a sol-gel method to perform Zn2+Modified and synthesized supported solid acid catalyst Zn3(PW12O40)2/SiO2(ii) a The supported solid acid catalyst is a powder granular solid with the particle size of 10-200 meshes; the weight of the tetraethyl silicate is 20-50% of the total weight of tetraethyl silicate, phosphotungstic acid and zinc nitrate hexahydrate, the molar ratio of the phosphotungstic acid to the zinc nitrate hexahydrate is 1:3, and the volumes of the absolute ethyl alcohol, the nitric acid and the Triton X-100 are 20-30%, 200-500% and 100-300% of the total weight of the tetraethyl silicate, the phosphotungstic acid and the zinc nitrate hexahydrate respectively; for example: the supported solid acid catalyst is prepared and synthesized by 40.0g of phosphotungstic acid, 6.2g of zinc nitrate hexahydrate, 25g of tetraethyl silicate, 15mL of absolute ethyl alcohol, 200mL of nitric acid with the concentration of 0.1mol/L and 150mL of Triton X-100. The initiator is one or more of ethylene glycol, 1, 4-butanediol, diethylene glycol, triethylene glycol, trimethylolpropane, glycerol and pentaerythritol.
As shown in fig. 1, the present invention also provides a method for preparing an alkylene oxide-tetrahydrofuran copolymer, comprising the steps of:
s100, feeding and replacing nitrogen: sequentially adding an initiator, tetrahydrofuran and a supported solid acid catalyst into a reaction kettle, starting stirring, vacuumizing under the protection of nitrogen, repeatedly replacing (preferably repeatedly replacing for three times), closing vacuum, and starting heating;
step S200, reaction: raising the temperature in the reaction kettle to a specified temperature, starting to slowly introduce the ethylene oxide and/or the propylene oxide into the reaction kettle, controlling the pressure of the reaction kettle (preferably controlling the pressure of the reaction kettle within 0.4 MPa), keeping the temperature after the ethylene oxide and/or the propylene oxide is added, continuing to react and slake until the pressure is not reduced any more, and then keeping the reaction to be complete (generally keeping the time for about 30 min); the reaction temperature in the reaction process is-20-80 ℃, and the reaction equation is as follows:
wherein a is more than or equal to 0, b is more than or equal to 0, c is more than or equal to 1, and a + b is more than or equal to 1.
S300, removing unreacted substances: after the ripening is finished, removing unreacted tetrahydrofuran and ethylene oxide and/or propylene oxide under negative pressure, preferably until the vacuum is less than or equal to-0.099, and keeping for 10-30 min to remove oxygen in adverse reactions of air; the temperature for removing the unreacted reactant is 30-120 ℃, and the temperature for removing the unreacted reactant in the product with the dynamic viscosity of more than 2000cps at the room temperature of 25 ℃ is preferably more than or equal to 50 ℃ (namely 50-120 ℃).
S400, discharging: degassing and filtering the product obtained in the step S300 to obtain a finished product of the alkylene oxide-tetrahydrofuran copolymer; wherein, the filtering can be specifically to filter the degassed product by adopting spun silk cloth.
S500, catalyst removal: filtering and separating the catalyst in the finished product of the alkylene oxide-tetrahydrofuran copolymer; specifically, the catalyst in the final product of the alkylene oxide-tetrahydrofuran copolymer can be filtered and separated by using 200-mesh spun silk cloth or 200-mesh copper mesh.
In the preparation method of the alkylene oxide-tetrahydrofuran copolymer, the dosage of the supported solid acid catalyst is 0.1-100 per mill of the total mass of tetrahydrofuran, the supported solid acid catalyst, the initiator and ethylene oxide and/or propylene oxide, and the molar ratio of the tetrahydrofuran, the ethylene oxide and the supported solid acid catalyst is 0-10000: 0 to 10000: 0.1-1000, wherein the molar ratio of tetrahydrofuran to propylene oxide to the supported solid acid catalyst is 0-10000: 0 to 10000: 0.1-1000, wherein the molar ratio of tetrahydrofuran, ethylene oxide, propylene oxide and a supported solid acid catalyst is 0-10000: 0 to 10000: 0 to 10000: 0.1 to 1000.
The supported solid acid catalyst is prepared by adopting a method shown in figure 2, and comprises the following steps:
step 101, mixing and stirring tetraethyl silicate, absolute ethyl alcohol, nitric acid and Triton X-100 uniformly to obtain a mixed solution; the method specifically comprises the following steps: sequentially adding tetraethyl silicate, absolute ethyl alcohol and nitric acid into a container, then adding Triton X-100, and uniformly mixing and stirring.
And step 102, carrying out oscillation treatment on the mixed solution (specifically, putting the mixed solution into an ultrasonic oscillator for oscillation treatment for 5min), adding phosphotungstic acid and zinc nitrate hexahydrate, and standing to obtain the gel.
103, calcining the gel, heating and drying to obtain dry gel; the method specifically comprises the following steps: placing the gel in a drying box, calcining the gel in the air atmosphere, then placing the gel in a muffle furnace, and calcining the gel in the nitrogen atmosphere to obtain dry gel; wherein the calcination temperature of the calcination in the air atmosphere is preferably 120 ℃, the calcination time is preferably 3h, and the temperature rise rate is preferably 3 ℃/min; the calcination temperature of the "calcination under nitrogen atmosphere" is preferably 300 ℃, the calcination time is preferably 3 hours, and the temperature rise rate is preferably 5 ℃/min.
Step 104, grinding the xerogel to obtain the supported solid acid catalyst Zn3(PW12O40)2/SiO2。
For example: sequentially adding 25g of tetraethyl silicate, 15mL of absolute ethyl alcohol and 200mL of 0.1mol/L nitric acid into a 1000mL beaker, and then adding 150mL of Triton X-100; uniformly stirring the solution formed by mixing the substances, and placing the solution into an ultrasonic oscillator for oscillation treatment for 5 min; adding 40.0g of phosphotungstic acid and 6.2g of zinc nitrate hexahydrate into the solution after ultrasonic treatment, and standing until gel appears; placing the gel in a drying box, calcining for 3h at 120 ℃ in the air atmosphere, and raising the temperature at a rate of 3 ℃/min; placing the gel in a muffle furnace, and calcining for 3h at 300 ℃ in a nitrogen atmosphere at the heating rate of 5 ℃/min; grinding the dry gel into fine powder by using a mortar to obtain the supported solid acid catalyst Zn3(PW12O40)2/SiO2。
The supported solid acid catalyst has the advantages of low toxicity, no corrosiveness and easy removal from productsIts advantages are 1, combination of phosphotungstic acid with Zn, obvious decrease in acidity and toxicity and corrosivity, 2, supported solid acid catalyst Zn3(PW12O40)2/SiO2Is a solid catalyst, is incompatible with the reaction system, and can be separated from the reaction system by simple filtration. ) Meanwhile, the catalyst has high reaction activity and selectivity due to no reducibility, is narrow in distribution coefficient, easy to produce and process, mild in reaction condition, low in requirement on processing equipment, free of adding a solvent in the preparation process, capable of greatly reducing reaction steps and effectively reducing production cost.
The alkylene oxide-tetrahydrofuran copolymer and the preparation method of the present invention are further illustrated by the following examples.
[ example 1 ]
An alkylene oxide-tetrahydrofuran copolymer of example 1 was prepared by using a supported solid acid catalyst (hereinafter abbreviated as Cat.) as a catalyst, ethylene glycol as a starter, and tetrahydrofuran, ethylene oxide and the supported solid acid catalyst in a molar ratio of 1000:1000:1 (i.e., THF: EO: Cat.: 1000:1), at a reaction temperature of-20 ℃ and for a reaction time of 25 hours. The yield was 52%. The molecular weight and molecular weight distribution of the alkylene oxide-tetrahydrofuran copolymer were measured by a Waters-APC gel permeation chromatograph (polystyrene as a standard, THF as a solvent, 40 ℃, flow rate 0.8 mL/min), and the results were: the molecular weight is 8000 and the molecular weight distribution index is 1.3.
[ example 2 ]
An alkylene oxide-tetrahydrofuran copolymer of example 2 was prepared using a supported solid acid catalyst as a catalyst and 1, 4-butanediol as an initiator, and the molar ratio of tetrahydrofuran, ethylene oxide and the supported solid acid catalyst was 4000:2000:3 (i.e., THF: EO: cat 4000:2000:3), the reaction temperature was 30 ℃, the reaction time was 9 hours, and the yield was 68%. The molecular weight and molecular weight distribution of the alkylene oxide-tetrahydrofuran copolymer were measured by a Waters-APC gel permeation chromatograph (polystyrene as a standard, THF as a solvent, 40 ℃, flow rate 0.8 mL/min), and the results were: the molecular weight was 12000 and the molecular weight distribution index was 1.5.
[ example 3 ]
An alkylene oxide-tetrahydrofuran copolymer takes a supported solid acid catalyst as a catalyst, trimethylolpropane as an initiator, tetrahydrofuran, ethylene oxide and the supported solid acid catalyst are mixed according to a molar ratio of 3000:1000:2 (namely THF: EO: CAT.: 3000:1000:2), the reaction temperature is 80 ℃, the reaction time is 5h, and the yield is 89%. The molecular weight and molecular weight distribution of the alkylene oxide-tetrahydrofuran copolymer were measured by a Waters-APC gel permeation chromatograph (polystyrene as a standard, THF as a solvent, 40 ℃, flow rate 0.8 mL/min), and the results were: the molecular weight is 3000, and the molecular weight distribution index is 1.8.
[ examples 4-10 ]
The alkylene oxide-tetrahydrofuran copolymers of examples 4 to 10 were prepared and tested in the same manner as in examples 1 to 3, and the specific preparation conditions and test results were as follows:
[ examples 11 to 14 ]
The alkylene oxide-tetrahydrofuran copolymers of examples 11 to 14 were prepared and tested in the same manner as in examples 1 to 3, and the specific preparation conditions and test results were as follows:
[ examples 15 to 18 ]
The alkylene oxide-tetrahydrofuran copolymers of examples 15 to 18 were prepared and tested in the same manner as in examples 1 to 3, and the specific preparation conditions and test results were as follows: :
in conclusion, the supported solid acid catalyst Zn adopted by the invention3(PW12O40)2/SiO2The reaction of the initiator, tetrahydrofuran, ethylene oxide and propylene oxide can be carried out under mild conditions by reacting the Lewis metal Zn2+Incorporation into H3PW12O40The secondary structure of the catalyst can generate more active sites, and the catalyst has no reducibility, so that the reaction activity and selectivity of the catalyst are improved, the content of by-products of a synthesized alkylene oxide-tetrahydrofuran copolymer product is reduced, the distribution coefficient is narrowed, the distribution coefficient of the alkylene oxide-tetrahydrofuran copolymer product can be controlled to be 1.1-1.8 (GPC detection), the distribution index of polytetrahydrofuran catalyzed by other catalysts is generally over 2.0, no solvent is required to be added in the process, the reaction steps can be greatly reduced, and the industrialization cost is reduced.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. The alkylene oxide-tetrahydrofuran copolymer is characterized by being prepared from tetrahydrofuran, a supported solid acid catalyst, an initiator and ethylene oxide and/or propylene oxide, wherein the supported solid acid catalyst takes dodecaphosphotungstic heteropoly acid as a matrix and adopts a sol-gel method to perform Zn2+Modification and synthesis.
2. The alkylene oxide-tetrahydrofuran copolymer according to claim 1, wherein the reaction equation is:
wherein a is more than or equal to 0, b is more than or equal to 0, c is more than or equal to 1, and a + b is more than or equal to 1.
3. The alkylene oxide-tetrahydrofuran copolymer according to claim 1 or 2, wherein the supported solid acid catalyst is prepared and synthesized from phosphotungstic acid, zinc nitrate hexahydrate, tetraethyl silicate, absolute ethanol, nitric acid, Triton X-100; the weight of the tetraethyl silicate is 20-50% of the total weight of the tetraethyl silicate, the phosphotungstic acid and the zinc nitrate hexahydrate, the molar ratio of the phosphotungstic acid to the zinc nitrate hexahydrate is 1:3, and the volumes of the absolute ethyl alcohol, the nitric acid and the Triton X-100 are 20-30%, 200-500% and 100-300% of the total weight of the tetraethyl silicate, the phosphotungstic acid and the zinc nitrate hexahydrate respectively.
4. The alkylene oxide-tetrahydrofuran copolymer according to claim 3, wherein the supported solid acid catalyst is prepared and synthesized from 40.0g of phosphotungstic acid, 6.2g of zinc nitrate hexahydrate, 25g of tetraethyl silicate, 15mL of absolute ethanol, 200mL of nitric acid with a concentration of 0.1mol/L, and 150mL of Triton X-100.
5. The alkylene oxide-tetrahydrofuran copolymer according to claim 3, wherein the supported solid acid catalyst is a powdery granular solid having a particle size of 10 to 200 mesh.
6. The alkylene oxide-tetrahydrofuran copolymer according to claim 1 or 2 or 4 or 5, wherein the initiator is one or more of ethylene glycol, 1, 4-butanediol, diethylene glycol, triethylene glycol, trimethylolpropane, glycerol, pentaerythritol.
7. A method for preparing the alkylene oxide-tetrahydrofuran copolymer according to any one of claims 1 to 5, comprising the steps of:
s100, feeding and nitrogen replacement: sequentially adding an initiator, tetrahydrofuran and a supported solid acid catalyst into a reaction kettle, starting stirring, vacuumizing under the protection of nitrogen, repeatedly replacing, closing vacuum, and starting heating;
s200, reaction: raising the temperature in the reaction kettle to a specified temperature, starting to slowly introduce the ethylene oxide and/or the propylene oxide into the reaction kettle, simultaneously controlling the pressure of the reaction kettle, keeping the temperature after the ethylene oxide and/or the propylene oxide are added, continuing to react and slake until the pressure is not reduced any more, and then keeping the reaction till the reaction is thorough;
s300, removing unreacted substances: after the ripening is finished, removing unreacted tetrahydrofuran, ethylene oxide and/or propylene oxide under negative pressure;
s400, discharging: degassing and filtering the product obtained in the step S300 to obtain a finished product of the alkylene oxide-tetrahydrofuran copolymer;
s500, catalyst removal: and (3) filtering and separating the catalyst in the finished product of the alkylene oxide-tetrahydrofuran copolymer.
8. The preparation method according to claim 7, wherein the amount of the supported solid acid catalyst is 0.1 to 100 ‰ of the total mass of the tetrahydrofuran, the supported solid acid catalyst, the initiator and the ethylene oxide and/or propylene oxide, and the molar ratio of the tetrahydrofuran, the ethylene oxide and the supported solid acid catalyst is 0 to 10000: 0 to 10000: 0.1-1000, wherein the molar ratio of tetrahydrofuran to propylene oxide to the supported solid acid catalyst is 0-10000: 0 to 10000: 0.1-1000, wherein the molar ratio of tetrahydrofuran, ethylene oxide, propylene oxide and a supported solid acid catalyst is 0-10000: 0 to 10000: 0 to 10000: 0.1 to 1000.
9. The preparation method according to claim 7, wherein the reaction temperature in the step S200 is-20 to 80 ℃, the temperature for removing the unreacted reactant in the step S300 is 30 to 120 ℃, and the temperature for removing the unreacted reactant in the product with the kinetic viscosity of more than 2000cps at room temperature of 25 ℃ is preferably not less than 50 ℃.
10. The method according to claim 7, wherein the supported solid acid catalyst is prepared by the following steps before the step S100 is performed:
(1) tetraethyl silicate, absolute ethyl alcohol, nitric acid and Triton X-100 are mixed and stirred uniformly to obtain a mixed solution;
(2) after oscillating the mixed solution, adding phosphotungstic acid and zinc nitrate hexahydrate, and standing to obtain gel;
(3) calcining the gel, heating and drying to obtain dry gel;
(4) and grinding the xerogel to obtain the supported solid acid catalyst.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5099074A (en) * | 1989-11-14 | 1992-03-24 | Basf Aktiengesellschaft | Process for the preparation of polyether glycols |
| CN1161684A (en) * | 1994-10-27 | 1997-10-08 | 美孚石油公司 | Polyether lubricant |
| JPH09291144A (en) * | 1995-08-31 | 1997-11-11 | Hodogaya Chem Co Ltd | Production of polyether |
| CN1226570A (en) * | 1998-11-26 | 1999-08-25 | 北京大学 | Preparation of polyether by polymerization of tetramethylene oxide |
| CN101302290A (en) * | 2007-05-07 | 2008-11-12 | 株式会社晓星 | Method for preparing polytetramethylene terephthalat ether glycol using heteropolyacid catalyst |
| CN102516554A (en) * | 2011-11-23 | 2012-06-27 | 中北大学 | Method for preparing hydroxyl-terminated polytetrahydrofuran polypropylene oxide block copolyether |
| CN106061932A (en) * | 2014-03-10 | 2016-10-26 | 竹本油脂株式会社 | Process for producing alkylene oxide adduct and alkylene oxide adduct |
-
2021
- 2021-07-29 CN CN202110864760.7A patent/CN113563575B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5099074A (en) * | 1989-11-14 | 1992-03-24 | Basf Aktiengesellschaft | Process for the preparation of polyether glycols |
| CN1161684A (en) * | 1994-10-27 | 1997-10-08 | 美孚石油公司 | Polyether lubricant |
| JPH09291144A (en) * | 1995-08-31 | 1997-11-11 | Hodogaya Chem Co Ltd | Production of polyether |
| CN1226570A (en) * | 1998-11-26 | 1999-08-25 | 北京大学 | Preparation of polyether by polymerization of tetramethylene oxide |
| CN101302290A (en) * | 2007-05-07 | 2008-11-12 | 株式会社晓星 | Method for preparing polytetramethylene terephthalat ether glycol using heteropolyacid catalyst |
| CN102516554A (en) * | 2011-11-23 | 2012-06-27 | 中北大学 | Method for preparing hydroxyl-terminated polytetrahydrofuran polypropylene oxide block copolyether |
| CN106061932A (en) * | 2014-03-10 | 2016-10-26 | 竹本油脂株式会社 | Process for producing alkylene oxide adduct and alkylene oxide adduct |
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