CN113563575B - 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, wherein 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 heteropolyacid as a matrix and adopts a sol-gel method to carry out Zn 2+ And (5) modifying and synthesizing. The supported solid acid catalyst can be used for realizing the reaction of an initiator, tetrahydrofuran, ethylene oxide and propylene oxide under mild conditions, and has high reaction activity and selectivity, so that the content of byproducts 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 R=1.1-1.8, and the process does not need to add a solvent, thereby greatly reducing the reaction steps and the industrialization cost.
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 methylene (-CH) main chain 2 (-) and ether bond (-O-) and the structure breaks the regularity of the macromolecular chain structure, so the structure 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 adhesive of NEPE solid rocket propellant. In addition, the ethylene oxide-propylene oxide-tetrahydrofuran copolymer can be used as a raw material for other plastic materials (such as polyurethane), lubricants, fuel additives, and the like.
However, the applicant found that: as the catalyst for preparing the ethylene oxide-propylene oxide-tetrahydrofuran copolymer, solid acid, boron trifluoride, trifluoromethanesulfonic acid, montmorillonite clay and the like are usually used. For example:
chinese patent CN101942084a describes a method for catalytic synthesis of polytetrahydrofuran with a rare earth triflate compound, which uses the rare earth triflate compound as a catalyst, which is highly prepared, and uses a solvent to separate the catalyst, increasing the complexity of the reaction process.
Chinese patent CN 111072946A adopts boron trifluoride complex as a catalyst and polyol as an initiator, so that the epoxycyclohexane, the epoxyethane and the tetrahydrofuran are subjected to bulk polymerization, tetrahydrofuran, the polyol and the catalyst are added, stirring is carried out, the epoxycyclohexane and the epoxyethane are added, after the reaction is finished, the synthesized crude product is subjected to catalyst removal, micromolecular substances are removed, and finally, the product is obtained through drying and filtering. The boron trifluoride complex adopted in the method has weak reaction activity, and is easy to volatilize, thus being unfavorable for operation.
U.S. patent GB854958 uses montmorillonite clay as a catalyst. The montmorillonite clay is activated by contact with an aqueous solution containing only about 10% by weight or less of a mineral acid. Although this type of montmorillonite clay catalyst is used to copolymerize THF and alkylene oxides for polymerization, the process produces a polycyclic ether by-product in amounts of up to 10% to 15% by weight of the total mass.
Solid acid catalystThe catalyst is an important catalyst in acid-base catalysts, and is widely applied to catalytic reactions of ionic mechanisms. However, the applicant found that: the existing solid acid catalysts in the market at present have higher toxicity and stronger corrosiveness, are difficult to clean from processed products, have the defect of poorer reactivity and selectivity, are complex in production and processing, and have high requirements on production and processing equipment, so that the production cost is high and the production cost is difficult to reduce. For example: phosphotungstic acid (H) 3 PW 12 O 40 ·nH 2 O, HPW) is a solid oxygen-containing heteropoly acid with a Keggin structure, has strong acidity, 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 small specific surface area, is easily dissolved in polar solvents such as water, alcohol and the like, and is difficult to separate from a reaction system.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the alkylene oxide-tetrahydrofuran copolymer synthesized by using the catalyst which has the advantages of low toxicity, no corrosiveness, easy removal, high reaction activity and selectivity and the preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention relates to an alkylene oxide-tetrahydrofuran copolymer, which 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 heteropolyacid as a matrix and adopts a sol-gel method to carry out Zn 2+ And (5) modifying and synthesizing.
Further, the alkylene oxide-tetrahydrofuran copolymer has a reaction equation:
wherein a is greater than or equal to 0, b is greater than or equal to 0, c is greater than or equal to 1, and a+b is greater than or equal to 1..
Further, the supported solid acid catalyst is prepared and synthesized from phosphotungstic acid, zinc nitrate hexahydrate, tetraethyl silicate, absolute ethyl alcohol, nitric acid and Triton X-100; the mass of the tetraethyl silicate is 20-50% of the sum of the masses of the tetraethyl silicate, the phosphotungstic acid and the zinc nitrate hexahydrate, the mol 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 respectively 20-30%, 200-500% and 100-300% of the sum of the volumes of the tetraethyl silicate, the phosphotungstic acid and the zinc nitrate hexahydrate.
Further, 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 ethyl alcohol, 200mL of nitric acid with the concentration of 0.1mol/L and 150mL of Triton X-100.
Further, the supported solid acid catalyst is a powdery 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 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 for three times, and closing the vacuum to start heating;
s200, reaction: heating the reaction kettle to a specified temperature, starting to slowly introduce ethylene oxide and/or propylene oxide into the reaction kettle, controlling the pressure of the reaction kettle, keeping the temperature after the ethylene oxide and/or propylene oxide are added, continuing to react and cure until the pressure is not reduced, and keeping the reaction until the reaction is complete;
s300, removing unreacted substances: after curing, carrying out negative pressure to remove unreacted tetrahydrofuran and ethylene oxide and/or propylene oxide;
s400, discharging: degassing and filtering the product obtained in the step S300 to obtain an alkylene oxide-tetrahydrofuran copolymer finished product;
s500, catalyst removal: and (3) filtering and separating the catalyst in the finished product of the alkylene oxide-tetrahydrofuran copolymer.
Further, the dosage of the supported solid acid catalyst is 0.1 to 100 per mill of the total mass of tetrahydrofuran, the supported solid acid catalyst, an 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 to 10000:0 to 10000:0.1 to 1000, the molar ratio of tetrahydrofuran, propylene oxide and supported solid acid catalyst is 0 to 10000:0 to 10000:0.1 to 1000, the molar ratio of tetrahydrofuran, ethylene oxide and propylene oxide to the supported solid acid catalyst is 0 to 10000:0 to 10000:0 to 10000:0.1 to 1000.
Further, the reaction temperature in the step S200 is-20 to 80 ℃, the temperature for removing unreacted matters in the step S300 is 30 to 120 ℃, and the temperature for removing unreacted matters in a product with the dynamic viscosity of more than 2000cps at the room temperature of 25 ℃ is preferably more than or equal to 50 ℃.
Further, before executing step S100, the supported solid acid catalyst is prepared by the following steps:
(1) Mixing and stirring tetraethyl silicate, absolute ethyl alcohol, nitric acid and Triton X-100 uniformly to obtain a mixed solution;
(2) Oscillating the mixed solution, adding phosphotungstic acid and zinc nitrate hexahydrate, and standing to obtain gel;
(3) Calcining the gel, and heating and drying to obtain xerogel;
(4) The xerogel is ground to obtain the supported solid acid catalyst.
The invention has the following advantages:
the supported solid acid catalyst adopted by the invention can realize the reaction of the initiator, tetrahydrofuran, ethylene oxide and propylene oxide under mild conditionsThe catalyst is prepared by reacting a Lewis metal Zn 2+ Incorporation into H 3 PW 12 O 40 More active sites can be generated in the secondary structure of the catalyst, and the catalyst does not have reducibility, so that the reaction activity and selectivity of the catalyst are improved, the content of byproducts 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 R=1.1-1.8, in addition, the solvent is not required to be added in the process, the reaction steps are greatly reduced, and the industrialization cost is reduced.
Drawings
FIG. 1 is a schematic flow chart of a process for preparing an alkylene oxide-tetrahydrofuran copolymer according to the present invention;
FIG. 2 is a schematic illustration of the preparation process of a supported solid acid catalyst for use in an alkylene oxide-tetrahydrofuran copolymer according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention relates to an alkylene oxide-tetrahydrofuran copolymer, which 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 heteropolyacid as a matrix and adopts a sol-gel method to carry out Zn 2+ Modified and synthesized supported solid acid catalyst Zn 3 (PW 12 O 40 ) 2 /SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Specifically, the catalyst is prepared and synthesized from phosphotungstic acid, zinc nitrate hexahydrate, tetraethyl silicate, absolute ethyl alcohol, nitric acid and Triton X-100, wherein the supported solid acid catalyst is a powdery granular solid, and the particle size is 10-200 meshes; wherein the mass of the tetraethyl silicate is 20-50% of the sum of the masses of the tetraethyl silicate, the phosphotungstic acid and the zinc nitrate hexahydrate, the mol ratio of the phosphotungstic acid to the zinc nitrate hexahydrate is 1:3,the volumes of the absolute ethyl alcohol, the nitric acid and the Triton X-100 are respectively 20-30%, 200-500% and 100-300% of the sum of the volumes of the tetraethyl silicate, the phosphotungstic acid and the zinc nitrate hexahydrate; for example: 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 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 three times), and closing the vacuum to start heating;
step S200, reaction: heating the reaction kettle to a specified temperature, starting to slowly introduce ethylene oxide and/or propylene oxide into the reaction kettle, controlling the pressure of the reaction kettle (preferably controlling the pressure of the reaction kettle to be within 0.4 MPa), keeping the temperature after the ethylene oxide and/or propylene oxide are added for continuous reaction and curing, and keeping the reaction until the pressure is not reduced any more until the reaction is complete (generally, keeping the reaction for about 30 min); the reaction temperature in the reaction process is-20-80 ℃, and the reaction equation is as follows:
wherein a is greater than or equal to 0, b is greater than or equal to 0, c is greater than or equal to 1, and a+b is greater than or equal to 1.
Step S300, removing unreacted substances: after curing, removing unreacted tetrahydrofuran and ethylene oxide and/or propylene oxide under negative pressure, preferably until vacuum is less than or equal to-0.099, and maintaining for 10-30 min to remove oxygen in adverse reaction of air; the temperature for removing unreacted materials is 30-120 ℃, and the temperature for removing unreacted materials from a product with dynamic viscosity of more than 2000cps at 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 an alkylene oxide-tetrahydrofuran copolymer finished product; the filtering can specifically be to filter the degassed product by using spun silk cloth.
Step S500, removing a catalyst: filtering and separating the catalyst in the finished product of the alkylene oxide-tetrahydrofuran copolymer; specifically, the catalyst in the finished 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 to 100 per mill of the total mass of tetrahydrofuran, supported solid acid catalyst, initiator and ethylene oxide and/or propylene oxide, and the molar ratio of the tetrahydrofuran to the ethylene oxide to the supported solid acid catalyst is 0 to 10000:0 to 10000:0.1 to 1000, the molar ratio of tetrahydrofuran, propylene oxide and supported solid acid catalyst is 0 to 10000:0 to 10000:0.1 to 1000, the molar ratio of tetrahydrofuran, ethylene oxide and propylene oxide to the supported solid acid catalyst is 0 to 10000:0 to 10000:0 to 10000:0.1 to 1000.
Wherein, the supported solid acid catalyst is prepared by 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 comprises the following steps: the preparation method comprises the steps of sequentially adding tetraethyl silicate, absolute ethyl alcohol and nitric acid into a container, then adding Triton X-100, and uniformly mixing and stirring.
And 102, carrying out oscillation treatment on the mixed solution (specifically, putting the mixed solution into an ultrasonic oscillator for oscillation treatment for 5 min), adding phosphotungstic acid and zinc nitrate hexahydrate, and standing to obtain gel.
Step 103, calcining the gel, and heating and drying to obtain xerogel; the method comprises the following steps: placing the gel in a drying oven, calcining in an air atmosphere, placing the gel in a muffle furnace, and calcining in a nitrogen atmosphere to obtain xerogel; wherein the calcination temperature of the calcination in the air atmosphere is preferably 120 ℃, the calcination time is preferably 3h, and the heating 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 rising rate is preferably 5 ℃/min.
104, grinding the xerogel to obtain a supported solid acid catalyst Zn 3 (PW 12 O 40 ) 2 /SiO 2 。
For example: in a 1000mL beaker, sequentially adding 25g of tetraethyl silicate, 15mL of absolute ethyl alcohol and 200mL of 0.1mol/L nitric acid, and then adding 150mL of Triton X-100; uniformly stirring the solution formed by mixing the above materials, and placing into an ultrasonic oscillator for oscillation treatment for 5min; 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 oven, and calcining at 120 ℃ for 3 hours in an air atmosphere, wherein the heating rate is 3 ℃/min; placing the gel in a muffle furnace, and calcining at 300 ℃ for 3 hours in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min; grinding xerogel into fine powder with mortar to obtain supported solid acid catalyst Zn 3 (PW 12 O 40 ) 2 /SiO 2 。
The supported solid acid catalyst has the advantages of low toxicity, no corrosiveness and easy removal from products (specifically, 1, after the reaction of phosphotungstic acid and zinc is combined, the acidity of the phosphotungstic acid is obviously reduced, thus the toxicity and corrosiveness are obviously reduced, 2, the supported solid acid catalyst Zn 3 (PW 12 O 40 ) 2 /SiO 2 Is a solid catalyst, is incompatible with the reaction system, and can be separated from the reaction system by simple filtration. ) Meanwhile, the catalyst has higher reactivity and selectivity due to no reducibility, has narrow distribution coefficient, is easy to produce and process, has mild reaction conditions and lower requirements on processing equipment, does not need to add solvent in the preparation process, can greatly reduce reaction steps and effectively reduces production cost.
The alkylene oxide-tetrahydrofuran copolymers and the process for their preparation according to the invention are further illustrated by the following examples.
[ example 1 ]
In the alkylene oxide-tetrahydrofuran copolymer of example 1, a supported solid acid catalyst is used as a catalyst (hereinafter referred to as cat) and ethylene glycol is used as an initiator, the molar ratio of tetrahydrofuran to ethylene oxide to the supported solid acid catalyst is 1000:1000:1 (i.e. THF: EO: cat=1000:1000:1), the reaction temperature is-20 ℃, and the reaction time is 25 hours. The yield was 52%. The molecular weight and molecular weight distribution of the alkylene oxide-tetrahydrofuran copolymer were measured by using a Waters-APC gel permeation chromatograph (polystyrene as a standard, THF as a solvent, 40 ℃, flow rate 0.8 mL/min), and the result was: the molecular weight was 8000 and the molecular weight distribution index was 1.3.
[ example 2 ]
An alkylene oxide-tetrahydrofuran copolymer of example 2, using a supported solid acid catalyst as a catalyst and 1, 4-butanediol as an initiator, wherein the molar ratio of tetrahydrofuran, ethylene oxide and supported solid acid catalyst is 4000:2000:3 (i.e. THF: EO: cat=4000:2000:3), the reaction temperature is 30 ℃, the reaction time is 9h, and the yield is 68%. The molecular weight and molecular weight distribution of the alkylene oxide-tetrahydrofuran copolymer were measured by using a Waters-APC gel permeation chromatograph (polystyrene as a standard, THF as a solvent, 40 ℃, flow rate 0.8 mL/min), and the result was: 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, the molar ratio of tetrahydrofuran to ethylene oxide to the supported solid acid catalyst is 3000:1000:2 (namely THF: EO: CAT=3000:1000:2), the reaction temperature is 80 ℃, the reaction time is 5 hours, and the yield is 89%. The molecular weight and molecular weight distribution of the alkylene oxide-tetrahydrofuran copolymer were measured by using a Waters-APC gel permeation chromatograph (polystyrene as a standard, THF as a solvent, 40 ℃, flow rate 0.8 mL/min), and the result was: the molecular weight was 3000 and the molecular weight distribution index was 1.8.
Examples 4 to 10
An alkylene oxide-tetrahydrofuran copolymer of examples 4 to 10 was prepared by the same method and test method as in examples 1 to 3, and the specific preparation conditions and test results were as follows:
examples 11 to 14
An alkylene oxide-tetrahydrofuran copolymer of examples 11 to 14 was prepared by the same method and test method as in examples 1 to 3, and the specific preparation conditions and test results were as follows:
examples 15 to 18
An alkylene oxide-tetrahydrofuran copolymer of examples 15 to 18 was prepared by the same method and test method as in examples 1 to 3, and the specific preparation conditions and test results were as follows: :
in conclusion, the invention adopts the supported solid acid catalyst Zn 3 (PW 12 O 40 ) 2 /SiO 2 The reaction of the initiator, tetrahydrofuran, ethylene oxide and propylene oxide can be carried out under mild conditions by reacting a Lewis metal Zn 2+ Incorporation into H 3 PW 12 O 40 More active sites can be generated in the secondary structure of the catalyst, and the catalyst has no reducibility, thereby improving the reactivity of the catalystAnd selectivity, and then the by-product content of the synthesized alkylene oxide-tetrahydrofuran copolymer product is reduced, the distribution coefficient is narrowed, so that the distribution coefficient of the alkylene oxide-tetrahydrofuran copolymer product can be controlled to be R=1.1-1.8 (detected by GPC), the distribution index of polytetrahydrofuran obtained by catalysis with other catalysts is generally above 2.0, and the process does not need to add solvents, thereby greatly reducing reaction steps and industrial cost.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (8)
1. The preparation method of the alkylene oxide-tetrahydrofuran copolymer is characterized in that 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 heteropolyacid as a matrix, and adopts a sol-gel method to carry out Zn 2+ The method comprises the following steps of modification and synthesis, wherein the supported solid acid catalyst is prepared by the following steps:
(1) Mixing and stirring tetraethyl silicate, absolute ethyl alcohol, nitric acid and Triton X-100 uniformly to obtain a mixed solution;
(2) Oscillating the mixed solution, adding phosphotungstic acid and zinc nitrate hexahydrate, and standing to obtain gel;
(3) Calcining the gel, and heating and drying to obtain xerogel;
(4) Grinding the xerogel to obtain a supported solid acid catalyst;
the preparation method of the alkylene oxide-tetrahydrofuran copolymer comprises the following steps:
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, and closing the vacuum to start heating;
s200, reaction: heating the reaction kettle to a specified temperature, starting to slowly introduce ethylene oxide and/or propylene oxide into the reaction kettle, controlling the pressure of the reaction kettle, keeping the temperature after the ethylene oxide and/or propylene oxide are added, continuing to react and cure until the pressure is not reduced, and keeping the reaction until the reaction is complete;
s300, removing unreacted substances: after curing, carrying out negative pressure to remove unreacted tetrahydrofuran and ethylene oxide and/or propylene oxide;
s400, discharging: degassing and filtering the product obtained in the step S300 to obtain an alkylene oxide-tetrahydrofuran copolymer finished product;
s500, catalyst removal: and (3) filtering and separating the catalyst in the finished product of the alkylene oxide-tetrahydrofuran copolymer.
2. The method of claim 1, wherein the reaction equation is:
wherein a is greater than or equal to 0, b is greater than or equal to 0, c is greater than or equal to 1, a+b is greater than or equal to 1, and a and b cannot be 0 at the same time.
3. The preparation method 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 mass of the tetraethyl silicate is 20-50% of the sum of the masses of the tetraethyl silicate, the phosphotungstic acid and the zinc nitrate hexahydrate, the mol 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 respectively 20-30%, 200-500% and 100-300% of the sum of the volumes of the tetraethyl silicate, the phosphotungstic acid and the zinc nitrate hexahydrate.
4. The method according to claim 3, wherein the supported solid acid catalyst is prepared 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 method according to claim 3, wherein the supported solid acid catalyst is a powdery granular solid, and the particles are 10 to 200 mesh.
6. The method according to claim 1, 2, 4 or 5, wherein the initiator is one or more of ethylene glycol, 1, 4-butanediol, diethylene glycol, triethylene glycol, trimethylolpropane, glycerol, pentaerythritol.
7. The preparation method according to claim 1, wherein the amount of the supported solid acid catalyst is 0.1 to 100% by weight of the total mass of tetrahydrofuran, the supported solid acid catalyst, the initiator and ethylene oxide and/or propylene oxide; when the alkylene oxide-tetrahydrofuran copolymer is prepared from tetrahydrofuran, supported solid acid catalyst, initiator and ethylene oxide, the molar ratio of tetrahydrofuran, ethylene oxide and supported solid acid catalyst is 0 to 10000:0 to 10000:0.1 to 1000, and tetrahydrofuran and ethylene oxide cannot be 0; when the alkylene oxide-tetrahydrofuran copolymer is prepared from tetrahydrofuran, supported solid acid catalyst, initiator and propylene oxide, the molar ratio of tetrahydrofuran, propylene oxide and supported solid acid catalyst is 0 to 10000:0 to 10000:0.1 to 1000, and tetrahydrofuran and propylene oxide cannot be 0; when the alkylene oxide-tetrahydrofuran copolymer is prepared from tetrahydrofuran, a supported solid acid catalyst, an initiator, ethylene oxide and propylene oxide, the molar ratio of tetrahydrofuran, ethylene oxide and propylene oxide to the supported solid acid catalyst is 0 to 10000:0 to 10000:0 to 10000:0.1 to 1000, and tetrahydrofuran, ethylene oxide and propylene oxide cannot be 0.
8. The preparation method according to claim 1, wherein the reaction temperature in the step S200 is-20-80 ℃, the temperature for removing unreacted materials in the step S300 is 30-120 ℃, and the temperature for removing unreacted materials in the product with the dynamic viscosity of > 2000cps at room temperature of 25 ℃ is not less than 50 ℃.
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