WO2018166413A1

WO2018166413A1 - Easily soluble fluorine-containing side chain copolyether glycol copolymerised from perfluoroalkyl glycidyl ether and polycyclic ether

Info

Publication number: WO2018166413A1
Application number: PCT/CN2018/078672
Authority: WO
Inventors: 孔庆刚; 施博文; 王静; 刘飞
Original assignee: 南京信息工程大学
Priority date: 2017-03-16
Filing date: 2018-03-12
Publication date: 2018-09-20
Also published as: CN106832246B; CN106832246A

Abstract

Disclosed is an easily soluble fluorine-containing side chain copolyether glycol copolymerised from a perfluoroalkyl glycidyl ether and a polycyclic ether, prepared by means of a copolymerisation reaction between a perfluoroalkyl glycidyl ether, a substituted propylene oxide and oxetane or tetrahydrofuran. The present invention can synthesise fluorine-containing side chain copolyether glycols with different fluorine contents by changing the raw material ratio, fully utilising the fluorine raw material; furthermore, substituted propylene oxides with different substituent groups may be selected according to the subsequent reaction use of the fluorine-containing side chain copolyether glycol, solving the problem of serious phase separation and inconvenient processing during processing of organic fluorine compounds; in addition, this type of fluorine-containing side chain copolyether glycol is easily soluble in industrially universal and cheap non-toxic or low-toxicity solvents, which can greatly reduce processing costs, and reduce pollution of processing environment. In summary, the fluorine-containing side chain copolyether glycol provided in the present invention is very convenient for various subsequent uses and also expands the usage space of this type of polyether glycol to a considerable degree.

Description

Soluble side chain fluorine-containing copolyether glycol copolymerized by perfluoroalkyl glycidyl ether and polycyclic ether

Technical field

The invention belongs to the technical field of intermediates of polymer materials, and particularly relates to a readily soluble side chain fluorine-containing copolyether glycol copolymerized by a perfluoroalkyl glycidyl ether and a polycyclic ether.

Background technique

As an important intermediate product for the synthesis of polymers such as polyester and polyurethane, the double-end hydroxyl polyether diol has gained many important applications in many aspects of the national economy. The introduction of fluorine-containing side groups can bring many excellent properties of the organic fluorine material into the polyether diol, so that the related materials can graft various properties of the organic fluorine material while retaining the original excellent performance. The preparation and use of such side chain fluoropolyether diols are reported in many literatures and patents. U.S. Patent No. 5,654,450 and U.S. Patent No. 6,472,,,,,,,,,,,,,,,,,,,,, No. 3,591,547 A describes a binary copolyol ether of the following structure C compound with glycerol and propylene oxide. Patent CN201110049906.9 reports a binary copolyether glycol of the following structure D compound and tetrahydrofuran. Patent CN201010022447.0 reports binary copolyether diols of the following structure E compounds and F compounds.

These fluorine-containing homopolymers and binary copolymerized fluorine-containing side chain polyether polyols all exert a special effect of weather resistance, oxidation resistance and corrosion resistance of fluorine elements on the polymer chain. In particular, the fluorine group has an extremely low surface free energy, and if it covers the surface of the polymer, it can impart excellent water repellency, oil repellency, abrasion resistance, low friction coefficient and stain repellency to the polymer. The patent CN2013107367731 and the patent CN201310738875.7 report the multi-ring ring-opening copolymerization of four monomers having a length of a perfluoroalkyl-substituted three-membered cyclic ether and a four- or five-membered cyclic ether.

The above-mentioned various side chain fluorine-containing homopolymerization, binary copolymerization or a plurality of ring-opening polyvalent fluorine-containing copolymers of a plurality of cyclic ether monomers have two disadvantages in different degrees: (1) the prepared side chain The fluorine content control of the fluorine-containing polyether polyol is more or less difficult; (2) the prepared side chain fluorine-containing polyether polyol is not easily dissolved in an industrially versatile, inexpensive non-toxic or low-toxic solvent. in. These two factors lead to: 1) expensive fluorine elements can not be used to the best, resulting in waste of effective resources; 2) such fluorine-containing polyether diols appear in the post-processing mixed with further reacted or mixed raw materials It is difficult to dissolve, and the required solvent is harsh, which leads to an increase in the cost of use and pollution of the processing environment.

Summary of the invention

The object of the present invention is to overcome the deficiencies of the prior art and to provide a soluble side chain fluorine-containing copolyether glycol which is substituted by propylene oxide and a perfluoroalkyl group. A ternary cationic copolymerization of a glyceryl ether and a four-membered cyclic oxetane or a five-membered cyclic tetrahydrofuran can obtain a side chain fluorine-containing copolyether diol having a desired fluorine content, and the side chain fluorine-containing copolyether The diol has excellent solubility and is easily soluble in general-purpose, non-toxic or low-toxic solvents.

The above object of the present invention is achieved by the following technical solutions:

A side chain fluorine-containing copolyether glycol obtained by substituting propylene oxide, perfluoroalkyl glycidyl ether and oxetane or tetrahydrofuran to have a molecular structure as shown in Structural Formula I:

among them:

p is any number of 1 or 2; n is any number of 1 or 2; m is any natural number from 4 to 13; q is any of 0 or 3; x, y and z are 1 Any one of ~100;

y:(x+z) is in the range of 5 to 1:1; x:z is in the range of 20 to 1:1;

R is any one of hydrogen, a saturated alkyl group, a saturated alkoxy group, a phenoxy group, and a benzyloxy group.

The number average molecular weight is from 1000 to 10000 g/mol, and is a colorless or light yellow transparent viscous liquid.

The preparation method of the above copolyether diol is prepared by copolymerization of perfluoroalkyl glycidyl ether, substituted propylene oxide and oxetane or tetrahydrofuran, and the reaction formula is represented by the following formula:

among them:

y:(x+z) is in the range of 5 to 1:1; x:z is in the range of 20 to 1:1;

Preferably, the perfluoroalkyl glycidyl ether is selected from any one of the following structural compounds:

Wherein n is any one of 1 or 2; m is any one of 4 to 13.

Preferably, the substituted propylene oxide is selected from any one of the following structural compounds:

Where L is any natural number from 0 to 10.

The above preparation method specifically includes the following steps:

(1) Preparation of raw materials: replacing propylene oxide and perfluoroalkyl glycidyl ether, the ratio of the sum of the moles of the two to the molar ratio of one of oxetane or tetrahydrofuran is in the range of 1:5 to 1 Wherein the molar ratio of the substituted propylene oxide to the perfluoroalkyl glycidyl ether is from 20 to 1:1, and the amount of the cationic material released by the cationic initiator is from 2% to 7% of the total amount of the total monomer, the diol The initiator accounts for 2.5% to 7% of the total monomeric substance; the substituted propylene oxide and the perfluoroalkyl glycidyl ether are dissolved in a solvent, and the solute concentration in the solution is 1 to 20 moles/liter;

(2) adding a solvent, oxetane or tetrahydrofuran, a cationic initiator and a diol initiator in a waterless and oxygen-free reactor equipped with a stirrer, at a temperature of -10 ° C to 15 ° C, into the kettle At the same time, the substituted propylene oxide and perfluoroalkyl glycidyl ether solution in the above step (1) is slowly added dropwise, and then at -10 ° C to 15 ° C, the polymerization reaction is carried out for 5 to 15 hours, and then 3 to 10 times of diol is added. The amount of the starting material is deionized water to terminate the reaction;

(3) After terminating the reaction, the organic solvent in the reaction vessel is distilled off and recovered, and then 1.5 to 2.5 volumes of distilled water of the mixture after distillation is added, using sodium carbonate, sodium hydrogencarbonate, ammonium carbonate, ammonium hydrogencarbonate or sodium hydroxide. The alkaline compound was neutralized to a pH of 7, the mixture was stirred and washed, and the mixture was allowed to stand for separation. The aqueous phase was separated, and the oil phase was washed once again with distilled water, and allowed to stand for stratification. After the oil phase is dehydrated and dried, the solvent is removed to obtain a side chain fluorine-containing copolyether glycol.

Preferably, the substituted propylene oxide and perfluoroalkyl glycidyl ether solution in step (2) should be added dropwise within 1 to 6 hours.

Preferably, the solvent for dissolving the substituted propylene oxide and the perfluoroalkyl glycidyl ether in the step (1) is selected from the group consisting of dichloromethane, 1,4-dioxane, diethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, dibutyl ether One of them.

Preferably, the cationic initiator is selected from the group consisting of 20% by mass of fuming sulfuric acid, perchloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, boron trifluoride etherate, trichloroacetic acid, phosphoric acid, trichlorination One of aluminum, titanium tetrachloride, tin tetrachloride, zinc chloride, and antimony pentachloride.

Preferably, the diol initiator is selected from one of ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, and 1,4-butanediol.

The beneficial effects of the invention:

The present invention employs a substituted propylene oxide and a perfluoro-substituted alkyl glycidyl ether to copolymerize with one of a four-membered cyclic ether or a five-membered cyclic ether, and has the beneficial effects of: (1) by changing the perfluoro group The ratio of the substituted alkyl glycidyl ether to the three raw materials of one of the substituted propylene oxide and the four-membered cyclic ether or the five-membered cyclic ether, to synthesize the desired side chain fluorine-containing copolyether glycol with different fluorine content, Make full use of expensive fluorine raw materials; (2) because a variety of structural groups can be substituted on propylene oxide, so that the raw material structure can be selected according to the next reaction with the side chain fluorine-containing copolyether diol, One step is to copolymerize the propylene oxide monomer with the same solubility parameter or the similar substituent group in the reaction, so that when the synthesized side chain fluoropolyether diol is reacted with the next raw material, the organic fluorine compound processing can be easily solved. The problem of severe phase separation and incompatibility; (3) The side chain fluorine-containing copolyether glycol is easily dissolved in a non-toxic or low-toxic solvent which is industrially versatile and inexpensive, which can be largely Low processing costs, reduce pollution processing environment. In summary, the side chain fluorine-containing copolyether diols provided by the present invention are extremely convenient in various subsequent uses, and the space for the use of such polyether diols is also expanded to a considerable extent.

detailed description

The substantial content of the present invention will be specifically described below with reference to the embodiments, but the scope of the present invention is not limited thereto. Test procedures not detailed in the experiments are routine test operations well known to those skilled in the art.

Example 1

A solution of 0.05 mol of 2-(taptycafluorotridecyl)ethyl glycidyl ether and 0.95 mol of 2-methylphenyl glycidyl ether was dissolved in a dichloromethane solution formed with 100 mL of dichloromethane.

Then, in a 1000 mL autoclave, the air in the autoclave was replaced with pure nitrogen, and then the temperature was lowered to -10 ° C, and 5 mol of oxetane, 50 mL of dichloromethane, 0.15 mol of 98% concentrated sulfuric acid, and 0.18 mol of ethylene glycol were added. After cooling to -10 ° C for 20 minutes and maintaining this temperature, add 0.05 mol of 2-(heptadecafluorotridecyl)ethyl glycidyl ether and 0.95 mol of 2-methylphenyl glycidyl ether. The methane solution was controlled to drip within 2 hours. The reaction was maintained at -10 ° C for 10 hours. The reaction was quenched by the addition of 20 ml of deionized water, and the solvent was evaporated and neutralized to neutral with sodium carbonate. It was washed with 100 mL of deionized water for 20 minutes and allowed to stand for stratification. The oil phase was again washed once with distilled water and allowed to stand for stratification. The oil phase was passed through a rotary evaporator to remove the residual solvent to obtain a crude polyether diol having a side chain fluorine-containing phase. Then, it was vacuum dried at 120 ° C under a pressure of 5 mmHg to obtain a colorless viscous liquid of the product, and the yield was 73.5%, which was measured by a GPC analyzer.

g/mol,

The fluorine content was 6.8%, and the side chain fluorine-containing polyether glycol was numbered CFJM-1.

Example 2

0.1 mol of 2-(heptadecafluorooctyl)ethyl glycidyl ether and 0.5 mol of benzyl glycidyl ether were dissolved together in 200 ml of diethyl ether to form a diethyl ether solution.

In a 1000 mL autoclave equipped with a stirrer, the air in the autoclave was replaced with pure nitrogen, and then the temperature was lowered to -5 ° C. 100 mL of diethyl ether was added as a solvent, and 1.8 mol of oxetane, 0.072 mol of perchloric acid and 0.12 mol of butyl were added. Glycol. The above ternary diethyl ether solution obtained by dissolving 0.1 mol of 2-(heptadecafluorooctyl)ethyl glycidyl ether and 0.5 mol of benzyl glycidyl ether and 200 mL of diethyl ether was added dropwise, and the dropwise addition was controlled to complete in 3 hours. The reaction was maintained at -5 ° C for 8 hours. The reaction was quenched by the addition of 30 mL of deionized water. The solvent was evaporated and neutralized to neutral with sodium bicarbonate. After adding 200 mL of deionized water and stirring for 20 minutes, the mixture was allowed to stand for stratification, and the oil phase was washed once again with distilled water, and allowed to stand for stratification. The oil phase was removed by a rotary evaporator to give a crude polyether diol having a side chain of fluorine. Then, it was vacuum dried at 120 ° C under a pressure of 5 mmHg to obtain a colorless viscous liquid of the product, and the yield was 82%, which was measured by a GPC analyzer.

g/mol,

The fluorine content was 16.6%, and the side chain fluorine-containing polyether glycol was numbered CFJM-2.

Example 3

0.15 mol of 1-(nonafluorobutyl)methyl glycidyl ether and 0.3 mol of benzyl glycidyl ether were dissolved together in 250 mL of acetone to form a triacetone solution.

After replacing the air in the autoclave with a pure nitrogen gas in a 1000 mL autoclave equipped with a stirrer, the mixture was cooled to -0 ° C, and 100 mL of acetone was added as a solvent, and 0.45 mol of tetrahydrofuran, 0.0225 mol of perchloric acid, and 0.027 mol of butanediol were added. The above acetone solution of 0.15 mol of 1-(nonafluorobutyl)methyl glycidyl ether and 0.3 mol of benzyl glycidyl ether dissolved in 250 mL of acetone was added dropwise, and the dropwise addition was controlled to complete in 3 hours. The reaction was maintained at 0 ° C for 10 hours, and the reaction was quenched by the addition of 50 ml of deionized water. The solvent was evaporated and neutralized to neutral with aqueous amine carbonate. After adding 200 mL of deionized water for 20 minutes, the mixture was allowed to stand for stratification, and the oil phase was washed once again with distilled water, and allowed to stand for stratification. The oil phase was vacuum dried at 120 ° C under a pressure of 5 mm Hg to obtain a colorless viscous liquid with a yield of 89%, which was determined by a GPC analyzer.

g/mol,

The fluorine content was 24.7%, and the side chain fluorine-containing polyether glycol was numbered CFJM-3.

Example 4

A solution of 0.1 mol of 2-(pentadecafluoroheptyl)ethyl glycidyl ether and 0.2 mol of butyl glycidyl ether was dissolved in a tetrahydrofuran solution formed using 200 mL of tetrahydrofuran.

After replacing the air in the autoclave with a pure nitrogen gas in a 1000 mL autoclave equipped with a stirrer, the mixture was cooled to 5 ° C and 0.9 mol of oxetane, 0.024 mol of trifluoroacetic acid and 0.072 mol of 1,2-propanediol were added. The above solution of 0.1 mol of 2-(hexadecafluoroheptyl)ethyl glycidyl ether and 0.2 mol of butyl glycidyl ether was dissolved in a solution of 200 mL of tetrahydrofuran, and the dropwise addition was controlled to complete in 2 hours. The reaction was maintained at 5 ° C for 6 hours, the reaction was terminated by the addition of 30 ml of deionized water, the solvent was distilled off, and neutralized with a sodium carbonate solution. After adding 200 mL of deionized water and stirring for 20 minutes, the mixture was allowed to stand for stratification, and the oil phase was washed once again with distilled water, and allowed to stand for stratification. The oil phase was vacuum dried at 120 ° C under a pressure of 5 mm Hg to obtain a colorless viscous liquid in a yield of 72%, which was determined by a GPC analyzer.

g/mol,

The fluorine content was 38.8%, and the side chain fluorine-containing polyether glycol was numbered CFJM-4.

Example 5

A solution of 0.25 mol of 2-(heptadecafluorooctyl)ethyl glycidyl ether and 1 mol of butyl glycidyl ether was dissolved in a tetrahydrofuran solution formed using 150 mL of tetrahydrofuran.

After replacing the air in the autoclave with a pure nitrogen gas in a 1000 mL autoclave equipped with a stirrer, the mixture was cooled to 2 ° C, and 1.9 mol of tetrahydrofuran, 0.25 mol of boron trifluoride etherate and 0.25 mol of 1,2-propanediol were added. The above solution of 0.25 mol of 2-(heptadecafluorooctyl)ethyl glycidyl ether and 1 mol of butyl glycidyl ether dissolved in 150 mL of tetrahydrofuran was added dropwise, and the dropwise addition was controlled to complete in 3 hours. The reaction was maintained at 2 ° C for 5 hours, and the reaction was quenched by the addition of 50 ml of deionized water. The solvent was evaporated and neutralized with sodium bicarbonate solution to neutral. After adding 250 mL of deionized water and stirring for 20 minutes, the mixture was allowed to stand for stratification, and the oil phase was again washed once with distilled water, and allowed to stand for stratification. A crude polyether diol having a side chain fluorine-containing phase is obtained. The oil phase was vacuum dried at 120 ° C under a pressure of 5 mm Hg to obtain a colorless viscous liquid with a yield of 79%, which was determined by a GPC analyzer.

g/mol,

The fluorine content was 17.5%, and the side chain fluorine-containing polyether glycol was numbered CFJM-5.

Example 6

0.1 mol of 1-(decafluoroheptyl)methyl glycidyl ether and 0.5 mol of 1,2-epoxycyclohexane were dissolved together in 1,4-dioxane with 200 mL of 1,4-dioxane. Oxyhexane solution.

In a 1000 mL autoclave equipped with a stirrer, the air in the autoclave was replaced with pure nitrogen, then the temperature was lowered to 10 ° C, 100 mL of 1,4-dioxane was added as a solvent, 2.4 mol of oxetane was added, and trifluoronation was carried out. Boron ether 0.09 moles and 0.165 moles of ethylene glycol. The above-mentioned 1,4-formed by 0.1 mol of 1-(decafluoroheptyl)methyl glycidyl ether and 0.5 mol of 1,2-epoxycyclohexane and 200 mL of 1,4-dioxane were added dropwise. The dioxane solution was controlled to complete in 5 hours. The reaction was maintained at 10 ° C for 15 hours, and the reaction was quenched by the addition of 60 ml of deionized water. The solvent was evaporated and neutralized to neutral with sodium bicarbonate. After adding 200 mL of deionized water and stirring for 20 minutes, the mixture was allowed to stand for stratification, and the oil phase was washed once again with distilled water, and the layers were allowed to stand to obtain a side chain fluorine-containing crude polyether diol. The oil phase was vacuum dried at 120 ° C under a pressure of 5 mm Hg to obtain a colorless viscous liquid with a yield of 79%, which was determined by a GPC analyzer.

g/mol,

The fluorine content was 13.7%, and the side chain fluorine-containing polyether glycol was numbered CFJM-6.

Comparative Example 7 is synthesized according to the embodiment of the granted patent ZL201310738875.7

150 mL of dichloromethane was added as a solvent in a stirred 500 mL autoclave, and the air in the kettle was replaced with pure nitrogen for 20 minutes. Then according to tetrahydrofuran: 2-(heptafluoro-n-propyl)methyl glycidyl ether: 2-(undecfluoro-n-pentyl)methyl glycidyl ether: 2-(pentadecafluoro-n-heptyl)methyl glycidyl ether The respective reactants were prepared in a molar ratio of boron trifluoride diethyl ether complex: 1,4-butanediol of 0.35:0.15:0.2:0.3:0.07:0.07. Weigh 0.35 moles of tetrahydrofuran, 0.15 moles of 2-(heptafluoro-n-propyl)methyl glycidyl ether, 0.2 moles of 2-(undecfluoro-n-pentyl)methyl glycidyl ether, and 0.3 moles of 2-(pentadecyl fluoride) N-heptyl) methyl glycidyl ether. The latter three were dissolved together with 70 mL of dichloromethane for use. When the temperature in the reaction vessel was controlled to 5 ° C, boron trifluoride diethyl etherate complex and 1,4-butanediol were added to the kettle, and 0.35 mol of tetrahydrofuran was added in one portion, followed by stirring for 20 minutes. Then, a solution of three fluorine-containing methyl glycidyl ether in dichloromethane was added dropwise, and the dropwise addition was completed within three hours. The temperature was raised to reflux temperature for 24 hours. The reaction was stopped by the addition of 20 ml of deionized water. Lower the temperature of the reaction system to ambient temperature. After adding 100 mL of deionized water and stirring for 20 minutes, the mixture was allowed to stand for stratification, and the oil phase was again washed once with distilled water, and allowed to stand for stratification. The oil phase was again subjected to removal of impurities at a pressure of 2 ° C and 2 mm Hg at 120 ° C to obtain a polyether diol having a side chain containing different perfluoro-substituted alkyl groups. Yield 78%, determined by GPC analyzer,

g/mol,

The fluorine content was 43.2%. The side chain fluoropolyether diol is numbered CFJM-7.

Embodiment 8 effect embodiment

Different solvent dissolution experiments were carried out on the side chain fluorine-containing copolyether glycol synthesized in Examples 1-7. The specific experimental method was as follows: eight 50 mL single-mouth flasks were used, and 40 mL of diethyl ether and 40 mL of dibutyl were respectively added to eight flasks. Ether, 40 mL of acetone, 40 mL of methyl ethyl ketone, 40 mL of cyclohexanone, 40 mL of dichloromethane, 40 mL of ethyl acetate, 40 mL of butyl acetate and 40 mL of tetrahydrofuran, and then weighed 10 g of the side chain fluorine-containing copolyether glycol of the above examples. It was added to each of the solvent bottles, and the magnetizer was stirred for 30 minutes, and then ultrasonically dispersed for 10 minutes, and allowed to stand for 24 hours, and the dissolution state in each sample flask was observed. The experimental results are shown in Table 1.

Table 1 Table of dissolution results of samples of various examples in common solvents

The above embodiments are intended to specifically describe the substantial content of the present invention, but those skilled in the art should understand that the scope of the present invention should not be limited to the specific embodiments.

Claims

A side chain fluorine-containing copolyether glycol obtained by substituting propylene oxide, perfluoroalkyl glycidyl ether, and oxetane or tetrahydrofuran, and having a molecular structure as shown in Structural Formula I:

among them:

p is any number of 1 or 2; n is any number of 1 or 2; m is any natural number from 4 to 13; q is any of 0 or 3; x, y and z are 1 Any one of ~100;

y:(x+z) is in the range of 5 to 1:1; x:z is in the range of 20 to 1:1;

R is any one of hydrogen, a saturated alkyl group, a saturated alkoxy group, a phenoxy group, and a benzyloxy group.
The copolyether glycol according to claim 1, which has a number average molecular weight of from 1,000 to 10,000 g/mol.
The method for preparing a copolyether diol according to claim 1 or 2, which is prepared by copolymerization of perfluoroalkyl glycidyl ether, substituted propylene oxide and oxetane or tetrahydrofuran, and the reaction formula thereof It is represented by the following formula:

among them:

p is any number of 1 or 2; n is any number of 1 or 2; m is any natural number from 4 to 13; q is any of 0 or 3; x, y and z are 1 Any one of ~100;

y:(x+z) is in the range of 5 to 1:1; x:z is in the range of 20 to 1:1;

R is any one of hydrogen, a saturated alkyl group, a saturated alkoxy group, a phenoxy group, and a benzyloxy group.
The process according to claim 3, wherein the perfluoroalkyl glycidyl ether is selected from any one of the following structural compounds:

Wherein n is any one of 1 or 2; m is any one of 4 to 13.
The method according to claim 3, wherein the substituted propylene oxide is selected from any one of the following structural compounds:

Where L is any natural number from 0 to 10.
The preparation method according to claim 3, comprising the steps of:

(1) Preparation of raw materials: replacing propylene oxide and perfluoroalkyl glycidyl ether, the ratio of the sum of the moles of the two to the molar ratio of one of oxetane or tetrahydrofuran is in the range of 1:5 to 1 Wherein the molar ratio of the substituted propylene oxide to the perfluoroalkyl glycidyl ether is from 20 to 1:1, and the amount of the cationic material released by the cationic initiator is from 2% to 7% of the total amount of the total monomer, the diol The initiator accounts for 2.5% to 7% of the total monomeric substance; the substituted propylene oxide and the perfluoroalkyl glycidyl ether are dissolved in a solvent, and the solute concentration in the solution is 1 to 20 moles/liter;

(2) adding a solvent, oxetane or tetrahydrofuran, a cationic initiator and a diol initiator in a waterless and oxygen-free reactor equipped with a stirrer, at a temperature of -10 ° C to 15 ° C, into the kettle At the same time, the substituted propylene oxide and perfluoroalkyl glycidyl ether solution in the above step (1) is slowly added dropwise, and then at -10 ° C to 15 ° C, the polymerization reaction is carried out for 5 to 15 hours, and then 3 to 10 times of diol is added. The amount of the starting material is deionized water to terminate the reaction;

(3) After terminating the reaction, the organic solvent in the reaction vessel is distilled off and recovered, and then 1.5 to 2.5 volumes of distilled water of the mixture after distillation is added, and the pH is adjusted to 7 with a basic compound, stirred and washed, and allowed to stand for stratification. The aqueous phase is separated, and the oil phase is washed once again with distilled water, and the layer is allowed to stand. After the oil phase is dehydrated and dried, the solvent is removed to obtain a side chain fluorine-containing copolyether glycol.
The process according to claim 6, wherein the substituted propylene oxide and perfluoroalkyl glycidyl ether solution in the step (2) is added dropwise within 1 to 6 hours.
The preparation method according to claim 6, wherein the solvent for dissolving the substituted propylene oxide and the perfluoroalkyl glycidyl ether in the step (1) is selected from the group consisting of dichloromethane, 1,4-dioxane, and diethyl ether. One or more of tetrahydrofuran, acetone, methyl ethyl ketone, and dibutyl ether.
The preparation method according to claim 6, wherein the cationic initiator is selected from the group consisting of 20% by mass of fuming sulfuric acid, perchloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid and boron trifluoride etherate. And one of trichloroacetic acid, phosphoric acid, aluminum trichloride, titanium tetrachloride, tin tetrachloride, zinc chloride, antimony pentachloride; the basic compound in the step (3) is selected from the group consisting of sodium carbonate, Sodium bicarbonate, ammonium carbonate, ammonium bicarbonate or sodium hydroxide.
The preparation method according to claim 6, wherein the diol initiator is one selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, and 1,4-butanediol. .