CN106750237A - A kind of polyether diatomic alcohol containing fluorine and preparation method thereof - Google Patents

A kind of polyether diatomic alcohol containing fluorine and preparation method thereof Download PDF

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CN106750237A
CN106750237A CN201611173231.8A CN201611173231A CN106750237A CN 106750237 A CN106750237 A CN 106750237A CN 201611173231 A CN201611173231 A CN 201611173231A CN 106750237 A CN106750237 A CN 106750237A
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fluorine
polyether
alcohol containing
diatomic alcohol
preparation
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CN106750237B (en
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李战雄
戴礼
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Suzhou University
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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
    • C08G65/04—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 only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
    • C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
    • 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
    • C08G65/2639—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 elements other than oxygen, nitrogen or sulfur
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
    • C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention relates to a kind of polyether diatomic alcohol containing fluorine and preparation method thereof, with perfluoroalkyl iodides as initiation material, after there is single electron addition reaction with acetic acid alkene butyl ester, then oxetanes containing fluoroalkyl is obtained by cyclization；When will contain fluoroalkyl oxetanes and dimethyl oxygen azetidine copolymerization, because two kinds of epoxy monomer polymerisation reactivities are close, therefore can obtain fluoroalkyl well-proportioned polyether products are distributed on polyethers macromolecular main chain；Regulation and control comonomer ratio has obtained the different polyether Glycols of Oil repellent, beneficial to the various fluoro containing polymerses product of processability；By adding non-fluorine-containing oxetane monomer copolymerization, the production cost of fluorochemical polyether product is reduced.When the fluorine-containing alkyl, polyether dihydroxylic alcohols of pendant type that the present invention is provided is used to prepare macromolecular material, side chain fluoroalkyl can provide strong-hydrophobicity；Meanwhile, the polyether diatomic alcohol containing fluorine preparation technology for being provided is easy, and reaction condition is gentle, and production only needs conventional equipment, is adapted to industrialized production.

Description

A kind of polyether diatomic alcohol containing fluorine and preparation method thereof
Technical field
The present invention relates to a kind of polyether diatomic alcohol containing fluorine and preparation method thereof, belong to catalyst preparation and macromolecule material Material field.
Background technology
PPG is the critical materials of synthesis of polyurethane, is to be obtained by open loop of epoxy compound polymerization.Conventional ring Oxygen compound has oxirane, expoxy propane, oxetanes and tetrahydrofuran etc..Synthesized by a kind of epoxide monomer Referred to as equal polyethers, copolyether is then can obtain by two kinds of epoxide copolymerization.
With oxirane as raw material, polymerization obtains polyoxyethylene in the presence of water and base catalyst（Also known as polyoxyethylene Alkene ether）.Under conditions of base catalyst presence, Polymerization of Propylene Oxide generation polyoxypropylene, product terminal hydroxy group is secondary hydroxyl, its Reactivity ratio's primary hydroxyl is poor.During synthesis, base catalyst easily causes propylene oxide isomerization to be reacted, and generates allyl alcohol and third Enol.Allyl alcohol and propenyl belong to monohydroxy ether all containing only a hydroxyl, and molecule one end is hydroxyl, and the other end is allyl Base and acrylic.When 1,2- expoxy propane synthesizing polyethers are used in this explanation, it is easy to generate undersaturated monohydroxy ether accessory substance, this meeting Influence the chain of polyethers to increase, therefore be difficult to produce high molecular weight polyether with base catalyst.For example, using the poly- propyl alcohol of base catalysis Mean molecule quantity highest is only up to 4000.
The content of the invention
, to provide a kind of polyether diatomic alcohol containing fluorine, it is by oxetanes containing fluoroalkyl and dimethyl oxygen for the purpose of the present invention Azetidine monomer copolymerization is formed, and the hydrophobicity that side chain fluoroalkyl is provided is strong, and Oil repellent is adjustable, and preparation technology simplicity, reaction Mild condition, is adapted to industrialized production.
The invention discloses a kind of polyether diatomic alcohol containing fluorine, with following structure：
Wherein, w is 2~7；M is 10~100；N is 10~100.
The polarity and hydrophily of PTMEG are reduced with the reduction of ethylene oxide and hydroxy radical content, in pendant polyether group The polarity and hydrophily that polyethers can be then greatly reduced containing fluoroalkyl are introduced, thus can be obtained with the poly- ammonia for refusing water-proof function Ester product；Therefore the application the invention also discloses above-mentioned polyether diatomic alcohol containing fluorine in fluorochemical urethane is prepared.
The present invention further discloses the preparation method of above-mentioned polyether diatomic alcohol containing fluorine, by a kind of ring fourth of oxa- containing fluoroalkyl Alkane is formed with dimethyl oxygen azetidine ring opening copolymer, is comprised the following steps：
（1）Acetic acid alkene butyl ester, sodium acid carbonate, sodium dithionite, organic solvent and water are added in the reactor；Then In at -20~5 DEG C, perfluoroalkyl iodides are added dropwise；Then synthetic reaction is carried out；It is subsequently adding alkali lye and carries out cyclization and obtains fluorine-containing Oxetanes；
（2）Halogenated alkanes solvents and butanediol are added in the reactor；Then in BFEE is added at 0~5 DEG C, instead Initiator should be obtained；Then mix monomer is added dropwise in initiator, carries out ring-opening polymerization, obtain fluorochemical polyether binary Alcohol；The mix monomer is made up of fluorine-containing oxetanes with 3,3- dimethyl oxygen azetidines.
In above-mentioned technical proposal, step（1）In, after the completion of synthetic reaction, with aromatic hydrocarbon solvent extractive reaction liquid；Then exist Alkali lye is added in the extract for obtaining carries out cyclization.
In above-mentioned technical proposal, step（1）In, the time that perfluoroalkyl iodides are added dropwise is 0.5~2 hour；The conjunction It is in being reacted 1~12 hour at -20~5 DEG C, then at room temperature reaction 1~12 hour into reaction；The cyclization is in 5~30 DEG C reaction 1~12 hour.
In above-mentioned technical proposal, step（1）In, acetic acid alkene butyl ester, sodium acid carbonate, sodium dithionite, organic solvent, Water, perfluoroalkyl iodides, the mass ratio of alkali lye are（1~3）∶（2~3）∶（4~7）∶（10~30）∶（10~30）∶（3~10）∶ （10~60）；The mass concentration of the alkali lye is 5~20%.
In above-mentioned technical proposal, step（2）In, halogenated alkanes solvents, butanediol, BFEE, fluorine-containing oxa- Cyclobutane is with the mass ratio of 3,3- dimethyl oxygen azetidines（2~120）∶（0.1~4）∶（0.1~4）∶（10~100）∶（5 ~50）.
In above-mentioned technical proposal, step（2）In, reaction obtains initiator in 0.5~2 hour；Mix monomer is added dropwise to starting The time of agent is 0.5~3 hour；The temperature of ring-opening polymerization is 20~40 DEG C, and the time is 1~48 hour.
In above-mentioned technical proposal, post-processed after the completion of reaction, specifically, step（1）In, after cyclization terminates, Organic layer in reaction solution obtains fluorine-containing oxetanes by washing, dry, vacuum distillation；Step（1）In, ring-opening polymerisation is anti- After should terminating, aqueous alkali carbonate solution is added in polymerization liquid, stirred 0.5~6 hour；Then alkyl chloride hydro carbons is used Solvent extraction, then extract is washed to neutrality, then dry, filtering, vacuum distillation obtain polyether diatomic alcohol containing fluorine.
In above-mentioned technical proposal, the perfluoroalkyl iodides are seven fluorine iodopropanes, nine fluorine iodobutanes, ten trifluoro iodohexanes, ten Any one in five fluorine iodine heptane, 17 fluorine iodo-octanes；The halogenated alkanes solvents are dichloromethane, dichloroethanes, three Any one in chloromethanes；The organic solvent is N,N-dimethylformamide；The butanediol is BDO；It is described Alkali lye is any one in the NaOH aqueous solution, the KOH aqueous solution.
The preparation method of the polyether diatomic alcohol containing fluorine that the present invention is provided, it includes that oxetane monomer containing fluoroalkyl synthesizes With polymerization two-step reaction, specially：
（1）Fluorine-containing oxetanes synthesis
A. addition：By weight, 10 ~ 30 parts of acetic acid alkene butyl esters, 20 ~ 30 parts of sodium acid carbonates, 40 ~ 70 are put into the reactor Part sodium dithionite, 100 ~ 300 parts of DMFs, 100 ~ 300 parts of water.Control temperature for -20 ~ -5 DEG C, be added dropwise 30 ~ 100 parts of perfluoroalkyl iodides, time for adding is 30 minutes ~ 2 hours；Add rear insulation reaction 1 ~ 12 hour, then be slowly increased to room Temperature reaction 1 ~ 12 hour；
B. extract：With 3 ~ 5 extractive reaction liquid of aromatic hydrocarbon solvent point, 15 ~ 60 parts of aromatic hydrocarbon solvent is used every time；Merge, washing Extract 3 ~ 5 times；
C. it is cyclized：100 ~ 600 parts of alkali lye are added in extract, is reacted 1 ~ 12 hour in 5 ~ 30 DEG C；
D. post-process：Organic layer in extracting reaction solution, washes 3 ~ 5 times, 0.5 ~ 3 part of addition desiccant dryness 1 ~ 12 hour；Decompression Distill to obtain fluorine-containing oxetane monomer；
（2）Copolyreaction
A. prepared by initiator：By weight, 20 ~ 120 parts of halogenated alkanes solvents and 0.1 ~ 4.0 part 1 are put into the reactor, 4- butanediols, add 0.1 ~ 4.0 part of BFEE after being cooled to 0 ~ 5 DEG C（BF3.Et2O）, react 30 minutes ~ 2 hours, obtain To initiator；
B. monomer mixing：By weight, by 10 ~ 100 parts of fluorine-containing oxetane monomers and 5 ~ 50 parts of 3,3- dimethyl oxygen heterocycles Butane mixes in a reservoir, stirs, and obtains mix monomer；
C. ring-opening polymerisation：Mix monomer is added dropwise in initiator, control is added for 30 minutes ~ 3 hours.After adding, 20 are warming up to ~ 40 DEG C are reacted 1 ~ 48 hour；
D. reaction is quenched：2 ~ 20 parts of aqueous alkali carbonate solutions are added in polymerization liquid, is stirred 30 minutes ~ 6 hours；
E. extract：With alkyl chloride hydro carbons solvent extraction 3 ~ 5 times, 20 ~ 60 parts of extractants are used every time；
F. post-process：Combining extraction liquid, is fully washed to neutrality, adds desiccant dryness 30 minutes ~ 6 hours, is filtered to remove dry After drying prescription, vacuum distillation obtains polyether diatomic alcohol containing fluorine.
In above-mentioned technical proposal, the aromatic hydrocarbon solvent is toluene, dimethylbenzene, benzotrifluoride, two（Trifluoromethyl）In benzene Any one；Described alkali carbonate is NaHCO3、Na2CO3、K2CO3In any one；Its mass concentration is 1.0% ~10%；Described drying is any one in anhydrous sodium sulfate, anhydrous magnesium sulfate, Anhydrous potassium carbonate；Described vacuum distillation Condition is 40 ~ 80 DEG C of temperature, 10 ~ 20mmHg of vacuum.
The preparation method of the polyether diatomic alcohol containing fluorine that the present invention is provided, is passed through using perfluoroalkyl iodides with acetic acid alkene butyl ester Single electron addition and cyclization are obtained oxetanes containing fluoroalkyl, then will contain fluoroalkyl oxetanes and dimethyl oxa- Cyclobutane ring opening copolymer, is obtained polyether diatomic alcohol containing fluorine.Reaction equation is as follows：
Compared with prior art, the advantage of the invention is that：
1st, the polyether diatomic alcohol containing fluorine of present invention synthesis is total to by oxetanes containing fluoroalkyl and dimethyl oxetane monomer Poly- to obtain, two kinds of epoxy monomer ring-opening polymerizations are approached during copolymerization, be can obtain fluoroalkyl and are divided on polyethers macromolecular main chain The uniform polyether products of cloth；
2nd, the polyether diatomic alcohol containing fluorine of present invention synthesis is the fluorine-containing alkyl, polyether dihydroxylic alcohols of pendant type, and it is used to prepare macromolecule material During material, the hydrophobicity that side chain fluoroalkyl is provided is strong；And prepared by fluorine-containing epoxy monomer and non-fluorine-containing epoxy monomer copolymerization fluorine-containing During polyether Glycols, regulation and control comonomer ratio can obtain the adjustable product of Oil repellent, be conducive to various fluorine-containing of processability Macromolecule product；
3rd, the preparation method of polyether diatomic alcohol containing fluorine disclosed by the invention introduces non-fluorine-containing epoxy monomer copolymerization, gained polyether products Fusing point is low, with good strand compliance, excellent cryogenic property and film forming can be provided for synthesis of polyurethane；Add Non- fluorine-containing epoxy monomer copolymerization prepares polyether diatomic alcohol containing fluorine can also reduce production cost；
4th, the number-average molecular weight of polyether diatomic alcohol containing fluorine product disclosed by the invention can reach 10000, be conducive to preparing surface The fluorochemical urethane of superior performance；And preparation method technique is easy, reaction condition is gentle, and preparation only needs conventional equipment, is adapted to Industrialized production.
Brief description of the drawings
Fig. 1 is the FT-IR figures of polyether diatomic alcohol containing fluorine prepared by embodiment 1；
Fig. 2 is polyether diatomic alcohol containing fluorine prepared by embodiment 11H NMR scheme.
Specific embodiment
Technical solution of the present invention is further described with reference to embodiment and accompanying drawing.
Embodiment 1
（1）Nine fluorine oxetanes synthesize
In the 1000mL there-necked flasks protected equipped with thermometer, ice-water bath and magnetic stirring apparatus, 16.1g acetic acid alkene butyl is added Ester, 26.2g sodium acid carbonates, 55.8g sodium dithionites, 227g DMFs, 202g water is added dropwise 55.3g perfluors Butyl iodide alkane, -13 DEG C of reaction 3h, is slowly increased to room temperature, insulation reaction 2h.After reaction terminates, with 3 extractions of 180g toluene point. Combining extraction liquid, is washed 3 times, and the fluorine butyl -3- iodine butyl acetate solutions of 4- nine are obtained, and solution is direct plungeed into down without treatment One step cyclization.
The above-mentioned ester solution of butylacetic acid containing halothane test is added directly into 1000mL there-necked flasks, 310g mass is added dropwise Concentration is 20% sodium hydroxide solution, is incubated and reacts 3h in 12 DEG C.Reaction is layered after terminating.Organic layer is washed 3 times, is dried, is subtracted Pressure distillation, obtains 3-（The fluorine amyl group of 1H, 1H- nine）Oxetanes 32.6g, yield is 73.2%.
（2）Copolyreaction
In the there-necked flask equipped with thermometer, agitator and constant pressure funnel, add under nitrogen protection, add 41g bis- Chloromethanes and 0.26g1,4- butanediol, ice-water bath are cooled to 2 DEG C, are slowly added into 0.26gBF3.Et2O, after reacting 30 minutes, drop Plus by the 3- of 28.1g（The fluorine amyl group of 1H, 1H- nine）The mixing of the 3,3- dimethyl oxygens azetidine composition of oxetanes and 8.9g Monomer.Control is added for 35 minutes.After adding, 30 DEG C are warming up to, continue to react 24h.Stop reaction.Add 7g mass concentrations be 2.5% NaHCO3The aqueous solution, stirring reaction is extracted 3 times after 1 hour with 105g dichloromethane, merges organic layer, adds drying Agent anhydrous magnesium sulfate is dried 1 hour, and after being filtered to remove drier, filtrate decompression boils off solvent and obtains product 29.6g, yield 84.6%.The number-average molecular weight for measuring product by GPC is 9800.The structural formula of product is as follows：
Wherein, m is 10~30；N is 10~30；
Fig. 1 is the FT-IR figures of above-mentioned polyether diatomic alcohol containing fluorine；Fig. 2 is above-mentioned polyether diatomic alcohol containing fluorine1H NMR scheme；Product FT-IR：ν3454.7（-OH）, 2928.9,2870.8（-CH3,-CH2-）, 1112.6（C-O）, 731.6 (C-F) cm-1。1H NMR δ：3.412~3.649（12H）；1.627（4H）ppm.
Ketones solvent adds dibutyl tin laurate after mixing with above-mentioned fluorine-containing alkyl, polyether dihydroxylic alcohols；Then in 65 Diisocyanate is added dropwise at DEG C；Then react 8 hours；Chain extender is subsequently adding, continues to react 10 hours；It is subsequently adding amino silicone Alkane coupling agent, continues to react 10 hours, obtains fluorochemical urethane, can be used for water repellency polyurethane coating.
Embodiment 2
（1）Nine fluorine oxetanes synthesize
In the 1000mL there-necked flasks protected equipped with thermometer, ice-water bath and magnetic stirring apparatus, 16.0g acetic acid alkene butyl is added Ester, 26.6g sodium acid carbonates, 55.5g sodium dithionites, 231g DMFs, 208g water is added dropwise 55.9g perfluors Butyl iodide alkane, -14 DEG C of reaction 3h, is slowly increased to room temperature, insulation reaction 4h.After reaction terminates, with 3 extractions of 200g benzotrifluorides point Take.Combining extraction liquid, is washed 3 times, and the fluorine butyl -3- iodine butyl acetate solutions of 4- nine are obtained, and solution is direct plungeed into without treatment Next step cyclization.
The above-mentioned ester solution of butylacetic acid containing halothane test is added directly into 1000mL there-necked flasks, 385g mass is added dropwise Concentration is 15% sodium hydroxide solution, is incubated and reacts 3h in 12 DEG C.Reaction is layered after terminating.Organic layer is washed 3 times, is dried, is subtracted Pressure distillation, obtains 3-（The fluorine amyl group of 1H, 1H- nine）Oxetanes 34.1g, yield is 76.6%.
（2）Copolyreaction
In the there-necked flask equipped with thermometer, agitator and constant pressure funnel, add under nitrogen protection, add 45g bis- Chloromethanes and 0.19g1,4- butanediol, ice-water bath are cooled to 2 DEG C, are slowly added into 0.20gBF3.Et2O, after reacting 30 minutes, drop Plus by the 3- of 28.5g（The fluorine amyl group of 1H, 1H- nine）It is mixed that the 3,3- dimethyl oxygens azetidine of oxetanes and 17.5g is constituted Close monomer.Control is added for 45 minutes.After adding, 30 DEG C are warming up to, continue to react 36h.Stop reaction.Add 9g mass concentrations be 2.5% NaHCO3The aqueous solution, stirring reaction is extracted 3 times after 1 hour with 135g dichloroethanes, merges organic layer, adds drying Agent anhydrous magnesium sulfate is dried 1 hour, and after being filtered to remove drier, filtrate boils off solvent and obtains product 39.7g, yield 85.2%.By The number-average molecular weight that GPC measures product is 10800.The structural formula of product is as follows：
Wherein, m is 12~32；N is 10~30.
Embodiment 3
In the 3000mL there-necked flasks equipped with thermometer, mechanical agitator and constant pressure funnel, add under nitrogen protection, 565g dichloromethane and 6.2g1,4- butanediol, ice-water bath is added to be cooled to 1 DEG C, be slowly added into 5.5 gBF3.Et2O, temperature is about Rise 6 DEG C, after reacting 1 hour, be added dropwise by the 3- of 292g（The fluorine amyl group of 1H, 1H- nine）The 3,3- diformazans of oxetanes and 185g The mix monomer of base oxetanes composition.Control is added for 2 hours.After adding, 30 DEG C are warming up to, continue to react 36h.Stop anti- Should.Add the NaHCO that 102g mass concentrations are 2.5%3The aqueous solution, stirring reaction extracts 3 after 3 hours with 1500g dichloromethane It is secondary, merge organic layer, add drier anhydrous magnesium sulfate to dry 1 hour, after being filtered to remove drier, filtrate boils off solvent and must produce Thing 412.2g, yield 86.4%.
The number-average molecular weight for measuring product by GPC is 8800.The structural formula of product is as follows：
Wherein, m is 8~30；N is 10~30.
Embodiment 4
（1）Ten trifluoro oxetanes synthesize
In the 1000mL there-necked flasks protected equipped with thermometer, ice-water bath and magnetic stirring apparatus, 16.5g acetic acid alkene butyl is added Ester, 28.2g sodium acid carbonates, 55.5g sodium dithionites, 221g DMFs, 230g water is added dropwise 73.0g perfluors Hexyl iodide alkane, adds for 50 minutes, adds and reacts 6h after -12 DEG C, is slowly increased to room temperature, insulation reaction 3h.After reaction terminates, with 3 extractions of 180g benzotrifluorides point.Combining extraction liquid, washes 3 times, and the trifluoro hexyl -3- iodine butyl acetate solutions of 4- ten are obtained, Solution direct plunges into next step cyclization without treatment.
The above-mentioned ester solution of butylacetic acid containing halothane test is added directly into 1000mL there-necked flasks, 550g mass is added dropwise Concentration is 10% sodium hydroxide solution, is incubated and reacts 8h in 13 DEG C.Reaction is layered after terminating.Organic layer is washed 3 times, is dried, is subtracted Pressure distillation, obtains 3-（The trifluoro heptyl of 1H, 1H- ten）Oxetanes 35.6g, yield is 59.3%.
（2）Copolyreaction
In the there-necked flask equipped with thermometer, agitator and constant pressure funnel, add under nitrogen protection, add 61g bis- Chloromethanes and 0.51g1,4- butanediol, ice-water bath are cooled to 2 DEG C, are slowly added into 0.49gBF3.Et2O, after reacting 50 minutes, drop Plus by the 3- of 36.3g（The trifluoro heptyl of 1H, 1H- ten）It is mixed that the 3,3- dimethyl oxygens azetidine of oxetanes and 8.1g is constituted Close monomer.Add within 1 hour.After adding, 25 DEG C are warming up to, continue to react 24h.Stop reaction.Add 16.5g mass concentrations be 2.5% Na2CO3The aqueous solution, terminating reaction, stirring reaction is extracted 3 times after 2 hours with 185g dichloromethane, merges organic layer, Neutrality is fully washed to, drier anhydrous sodium sulfate drying is added 1 hour, after being filtered to remove drier, filtrate boils off solvent and obtains Product 29.3g, yield 87.7%.The number-average molecular weight for measuring product by GPC is 10200.The structural formula of product is as follows：
Wherein, m is 5~20；N is 10~30.
Embodiment 5
（1）Ten trifluoro oxetanes synthesize
In the 1000mL there-necked flasks protected equipped with thermometer, ice-water bath and magnetic stirring apparatus, 16.6g acetic acid alkene butyl is added Ester, 28.1g sodium acid carbonates, 55.2g sodium dithionites, 209g DMFs, 230g water is added dropwise 73.4g perfluors Hexyl iodide alkane, adds for 45 minutes, adds and reacts 6h after -12 DEG C, is slowly increased to room temperature, insulation reaction 3h.After reaction terminates, with 3 extractions of 180g benzotrifluorides point.Combining extraction liquid, washes 3 times, and the trifluoro hexyl -3- iodine butyl acetate solutions of 4- ten are obtained, Solution direct plunges into next step cyclization without treatment.
The above-mentioned ester solution of butylacetic acid containing halothane test is added directly into 1000mL there-necked flasks, 310g mass is added dropwise Concentration is 20% sodium hydroxide solution, is incubated and reacts 6h in 12 DEG C.Reaction is layered after terminating.Organic layer is washed 3 times, is dried, is subtracted Pressure distillation, obtains 3-（The trifluoro heptyl of 1H, 1H- ten）Oxetanes 37.5g, yield is 62.5%.
（2）Copolyreaction
In the there-necked flask equipped with thermometer, agitator and constant pressure funnel, add under nitrogen protection, add 120g bis- Chloromethanes and 0.18g1,4- butanediol, ice-water bath are cooled to 3 DEG C, are slowly added into 0.62gBF3.Et2O, after reacting 1 hour, is added dropwise By the 3- of 37.6g（The trifluoro heptyl of 1H, 1H- ten）It is mixed that the 3,3- dimethyl oxygens azetidine of oxetanes and 34.5g is constituted Close monomer.Add within 2 hours.After adding, 25 DEG C are warming up to, continue to react 36h.Stop reaction.It is 5% to add 32.1g mass concentrations Na2CO3The aqueous solution, terminating reaction, stirring reaction is extracted 3 times after 4 hours with 240g dichloromethane, merges organic layer, is added Drier anhydrous sodium sulfate drying 3 hours, after being filtered to remove drier, filtrate boils off solvent and obtains product 63.6g, yield 88.2%. The number-average molecular weight for measuring product by GPC is 12050.The structural formula of product is as follows：
Wherein, m is 5~20；N is 15~35.

Claims (10)

1. a kind of polyether diatomic alcohol containing fluorine, it is characterised in that：The polyether diatomic alcohol containing fluorine has following structure：
Wherein, w is 2~7；M is 10~100；N is 10~100.
2. the preparation method of polyether diatomic alcohol containing fluorine described in claim 1, it is characterised in that comprise the following steps：
（1）Acetic acid alkene butyl ester, sodium acid carbonate, sodium dithionite, organic solvent and water are added in the reactor；Then In at -20~5 DEG C, perfluoroalkyl iodides are added dropwise；Then synthetic reaction is carried out；It is subsequently adding alkali lye and carries out cyclization and obtains fluorine-containing Oxetanes；
（2）Halogenated alkanes solvents and butanediol are added in the reactor；Then in BFEE is added at 0~5 DEG C, instead Initiator should be obtained；Then mix monomer is added dropwise in initiator, carries out ring-opening polymerization, obtain fluorochemical polyether binary Alcohol；The mix monomer is made up of fluorine-containing oxetanes with 3,3- dimethyl oxygen azetidines.
3. the preparation method of polyether diatomic alcohol containing fluorine according to claim 2, it is characterised in that：Step（1）In, synthetic reaction After the completion of, with aromatic hydrocarbon solvent extractive reaction liquid；Then alkali lye is added in the extract for obtaining carries out cyclization.
4. the preparation method of polyether diatomic alcohol containing fluorine according to claim 2, it is characterised in that：Step（1）In, the dropwise addition The time of perfluoroalkyl iodides is 0.5~2 hour；The synthetic reaction is in being reacted 1~12 hour at -20~5 DEG C, then at room temperature Reaction 1~12 hour；The cyclization is to be reacted 1~12 hour in 5~30 DEG C.
5. the preparation method of polyether diatomic alcohol containing fluorine according to claim 2, it is characterised in that：Step（1）In, acetic acid alkene fourth Base ester, sodium acid carbonate, sodium dithionite, organic solvent, water, perfluoroalkyl iodides, the mass ratio of alkali lye are（1~3）∶（2~3） ∶（4~7）∶（10~30）∶（10~30）∶（3~10）∶（10~60）；The mass concentration of the alkali lye is 5~20%.
6. the preparation method of polyether diatomic alcohol containing fluorine according to claim 2, it is characterised in that：Step（2）In, halogenated alkane The mass ratio of class solvent, butanediol, BFEE, fluorine-containing oxetanes and 3,3- dimethyl oxygen azetidines is（2~ 120）∶（0.1~4）∶（0.1~4）∶（10~100）∶（5~50）.
7. the preparation method of polyether diatomic alcohol containing fluorine according to claim 2, it is characterised in that：Step（2）In, reaction 0.5 Obtain initiator within~2 hours；The time that mix monomer is added dropwise to initiator is 0.5~3 hour；The temperature of ring-opening polymerization is 20~40 DEG C, the time is 1~48 hour.
8. the preparation method of polyether diatomic alcohol containing fluorine according to claim 2, it is characterised in that：Step（1）In, cyclization After end, the organic layer in reaction solution obtains fluorine-containing oxetanes by washing, dry, vacuum distillation；Step（2）In, open After cyclopolymerization reaction terminates, aqueous alkali carbonate solution is added in polymerization liquid, stirred 0.5~6 hour；Then chlorine is used For alkane solvents extraction, then extract is washed to neutrality, then dry, filtering, vacuum distillation obtain fluorochemical polyether binary Alcohol.
9. the preparation method of polyether diatomic alcohol containing fluorine according to claim 8, it is characterised in that：The perfluoroalkyl iodides are seven Any one in fluorine iodopropane, nine fluorine iodobutanes, ten trifluoro iodohexanes, 15 fluorine iodine heptane, 17 fluorine iodo-octanes；The halogen It is any one in dichloromethane, dichloroethanes, chloroform for alkane solvents；The organic solvent is N, N- dimethyl Formamide；The butanediol is BDO；The alkali lye is any one in the NaOH aqueous solution, the KOH aqueous solution.
10. application of the polyether diatomic alcohol containing fluorine described in claim 1 in fluorochemical urethane is prepared.
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