CN106832246B - A kind of fluorine-containing copolyether glycol of readily soluble side chain by perfluoroalkyl glycidol ether and the copolymerization of polynary cyclic ethers - Google Patents
A kind of fluorine-containing copolyether glycol of readily soluble side chain by perfluoroalkyl glycidol ether and the copolymerization of polynary cyclic ethers Download PDFInfo
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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
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/18—Oxetanes
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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
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/20—Tetrahydrofuran
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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
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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
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Abstract
The invention discloses a kind of fluorine-containing copolyether glycols of readily soluble side chain by perfluoroalkyl glycidol ether and the copolymerization of polynary cyclic ethers, and carrying out copolyreaction by perfluoroalkyl glycidol ether, subsituted oxirane and oxetanes or tetrahydrofuran is prepared.The present invention can synthesize the fluorine-containing copolyether glycol of side chain of different fluorine contents by feed change ratio, make full use of fluorine raw material；The subsituted oxirane that can select different substituents according to the fluorine-containing copolyether glycol subsequent reactions purposes of side chain simultaneously, solves the defect of the serious inconvenient processing of organofluorine compound process split-phase；Furthermore the fluorine-containing copolyether glycol of such side chain is soluble in industrial general, cheap non-toxic or low-toxic solvent, this can largely reduce processing cost, reduces processing environment pollution.In short, the fluorine-containing copolyether glycol of side chain provided by the invention is extremely convenient in follow-up various uses, the use space of such polyetherdiol has also been expanded to a great extent.
Description
Technical field
The invention belongs to the intermediate technical fields of high molecular material, and in particular to one kind is by perfluoroalkyl glycidol ether
With the fluorine-containing copolyether glycol of readily soluble side chain of polynary cyclic ethers copolymerization.
Background technology
Important intermediate of the both-end hydroxy polyethers glycol as polymer such as synthesizing polyester and polyurethane, in national economy
All various aspects obtained many important applications.And the introducing of fluorine-containing side group then can be many excellent properties of organic fluorine material
It is brought into polyetherdiol so that relevant material is grafted on the basis of retaining original excellent properties organic fluorine material
Various performances.Many documents and the patent report preparation and its application of such side chain fluorochemical polyether glycol.United States Patent (USP)
US5654450 and US6479623B1 report respectively homopolymerization such as two kinds of structures of following A and B and the two respectively with tetrahydrochysene furan
It mutters copolymerization product.Patent US3591547A describes following structure C compounds and glycerine and the binary copolymerization of propylene oxide
Polyol ethers.Patent CN201110049906.9 reports the binary copolymerization ether glycol of following structure D compounds and tetrahydrofuran.
Patent CN201010022447.0 then reports the binary copolymerization ether glycol of following structure E compounds and F compound.
These fluorine-containing homopolymers and the fluorine-containing pendant polyether polyalcohol of binary copolymerization have all played fluorine element and have polymerize well
Weatherability, inoxidizability on object chain and corrosion resistance special role.Especially fluorin radical has extremely low surface free energy, such as
It is covered in the surface of polymer to fruit, can assign polymer with excellent water repellency, oil repellent, wearability, low-friction coefficient and
Soil repellency energy.Patent CN2013107367731 and patent CN201310738875.7 is reported with perfluor alkane different in size
The ternary cyclic ethers of base substitution and quaternary or the polynary ring opening copolymer of four kinds of monomers of five-membered ring ether.
The above-mentioned fluorine-containing homopolymerization of various side chains, the polynary fluorinated copolymer of the open loop of binary copolymerization or a variety of cyclic ether monomers,
There is the deficiency for making two aspects to some extent：(1) the side chain fluorine-containing polyether glycol prepared by fluorine content control have or
More or few difficulties；(2) the side chain fluorine-containing polyether glycol prepared by is not easily dissolved industrially general, cheap nothing
In the solvent of poison or low toxicity.The factor of these two aspects results in：1) expensive fluorine element cannot make the best use of everything, and cause effectively
The waste of resource；2) this kind of fluorochemical polyether glycol occurs further reacting with it in post-processing or mixed raw material is miscible tired
It is difficult, harsh to required solvent, and then use cost is caused to rise and bring the pollution of processing environment.
Invention content
The purpose of the present invention is to overcome the deficiency in the prior art, provide a kind of fluorine-containing copolyether glycol of readily soluble side chain and its
Preparation method, the fluorine-containing copolyether glycol of the side chain are miscellaneous by subsituted oxirane, perfluoroalkyl glycidol ether and four-membered ring ether oxygen
Cyclobutane or five-membered ring ether tetrahydrofuran carry out triple cationic and are copolymerized, and the side chain that can obtain expected different fluorine contents contains
Fluorine copolyether glycol, and the fluorine-containing copolyether glycol dissolubility of the side chain is outstanding, it is readily soluble in general, non-toxic or low-toxic solvent.
The above-mentioned purpose of the present invention is achieved by following technical solution：
The side that a kind of subsituted oxirane, perfluoroalkyl glycidol ether and oxetanes or tetrahydrofuran copolymerization obtain
The fluorine-containing copolyether glycol of chain has the molecular structure as shown in structural formula I：
Wherein：
P is any number in 1 or 2；N is any number in 1 or 2；M is any one natural number in 4~13；Q is 0 or 3 liang
Any number in person；X, y and z are any one natural number in 1~100；
y：(x+z) it is 5~1：In 1 range；x：Z is 20~1：In 1 range；
R is any one in hydrogen, saturated alkyl, saturation alkoxy, phenoxy group, benzyloxy.
Its number-average molecular weight is 1000~10000g/mol, is colourless or pale yellow transparent viscous liquid.
The preparation method of above-mentioned copolyether glycol, by perfluoroalkyl glycidol ether, subsituted oxirane and oxa- ring fourth
Alkane or tetrahydrofuran carry out copolyreaction and are prepared, and reaction equation is expressed from the next：
Wherein：
P is any number in 1 or 2；N is any number in 1 or 2；M is any one natural number in 4~13；Q is 0 or 3 liang
Any number in person；X, y and z are any one natural number in 1~100；
y：(x+z) it is 5~1：In 1 range；x：Z is 20~1：In 1 range；
R is any one in hydrogen, saturated alkyl, saturation alkoxy, phenoxy group, benzyloxy.
Preferably, any one of the perfluoroalkyl glycidol ether in following structural compounds：
Wherein, n is any number in 1 or 2；M is any one natural number in 4~13.
Preferably, any one of the subsituted oxirane in following structural compounds：
Wherein, L is any natural number in 0 to 10.
Above-mentioned preparation method specifically includes the following steps：
(1) raw material preparation：Subsituted oxirane and perfluoroalkyl glycidol ether, the sum of molal quantity of the two and oxa- ring
The ratio between molal quantity of one of butane or tetrahydrofuran is 1：In 5~1 ranges, wherein subsituted oxirane and perfluoroalkyl contract
Water glycerin ether molar ratio is 20~1：1, the amount of the released cationic substance of cationic initiator accounts for the amount of total monomer total material
2%~7%, glycol initiator accounts for the 2.5%~7% of the amount of total monomer substance；Subsituted oxirane and perfluoroalkyl are contracted
Water glycerin ether is dissolved into solvent, and solute concentration is 1~20 mol/L in solution；
(2) solvent, oxetanes or tetrahydrofuran, cation are added in reaction kettle of the anhydrous and oxygen-free equipped with blender
Initiator and glycol initiator are slowly added dropwise in above-mentioned steps (1) into kettle at a temperature of -10 DEG C~15 DEG C and replace ring simultaneously
Ethylene Oxide and perfluoroalkyl glycidol ethereal solution, then at -10 DEG C~15 DEG C, polymerisation is added 3 after 5~15 hours
The deionized water of the amount of~10 times of glycol starter substances terminates reaction；
(3) it after terminating reaction, steams and recycles the organic solvent in reaction kettle, 1.5 of mixture after distilling then are added
The distilled water of~2.5 times of volumes, in the alkali compounds such as sodium carbonate, sodium bicarbonate, ammonium carbonate, Ammonium bicarbonate food grade or sodium hydroxide
With pH value to 7, agitator treating, stratification separate water phase, and oil phase is washed with distilled water once again, stratification.Oil phase is de-
After water drying, through removing solvent up to the fluorine-containing copolyether glycol of side chain.
Preferably, subsituted oxirane and perfluoroalkyl glycidol ethereal solution should drip in 1~6 hour in step (2)
It adds into.
Preferably, step (1) dissolving subsituted oxirane and perfluoroalkyl glycidol ether solvent be selected from dichloromethane,
One kind in Isosorbide-5-Nitrae-dioxane, ether, tetrahydrofuran, acetone, butanone, dibutyl ethers.
Preferably, the cationic initiator is selected from the oleum of mass fraction 20%, perchloric acid, trifluoroacetic acid, three
Methyl fluoride sulfonic acid, boron trifluoride ether, trichloroacetic acid, phosphoric acid, alchlor, titanium tetrachloride, butter of tin, zinc chloride, five
One kind in antimony chloride.
Preferably, the one kind of glycol initiator in ethylene glycol, 1,2-PD, 1,3-PD, 1,4-butanediol.
Beneficial effects of the present invention：
The present invention is using subsituted oxirane and complete fluorine-substituted alkyl glycidyl ether and quaternary cyclic ethers or five-membered ring ether
One of them is copolymerized, the advantageous effect with aspects several in this way：(1) it can be shunk by changing complete fluorine-substituted alkyl
Three's material rate of one of glycerin ether and subsituted oxirane and quaternary cyclic ethers or five-membered ring ether, synthesize it is expected not
With the fluorine-containing copolyether glycol of side chain of fluorine content, expensive fluorine raw material is made full use of to greatest extent；(2) due to a variety of knots
Structure group can be substituted on propylene oxide, can carry out the original that next step is reacted according to the fluorine-containing copolyether glycol of side chain in this way
Expect structure, select have with next step participate in the same or similar substituent group of reaction raw materials solubility parameters propylene oxide monomer into
Row copolymerization, in this way when synthesized side chain fluorochemical polyether glycol is reacted with next step raw material, so that it may organic easily to solve
Serious split-phase, immiscible problem in fluorine compounds processing；(3) the fluorine-containing copolyether glycol of such side chain it is industrially general,
Easy to dissolve in cheap non-toxic or low-toxic solvent, this can largely reduce processing cost, reduce processing environment
Pollution.In short, the fluorine-containing copolyether glycol of side chain provided by the invention is extremely convenient in follow-up various uses, also in suitable journey
The use space of such polyetherdiol has been expanded on degree.
Specific implementation mode
The essentiality content of the present invention is specifically introduced with reference to embodiment, but the protection model of the present invention is not limited with this
It encloses.The routine test operation that the test operation not being described in detail in experiment is well known to the skilled person.
Embodiment 1
By 0.05 mole of 2- (27 fluorine tridecyl) ethyl ether and 2- methylphenylglycidyl ethers
0.95 mole is dissolved in together with 100mL dichloromethane, the dichloromethane solution of formation.
Then, into 1000mL kettles, after air in pure nitrogen gas displacement kettle, -10 DEG C is cooled to, 5 moles of oxa- is added
Cyclobutane, 50mL dichloromethane, 0.15 mole of 98% concentrated sulfuric acid and 0.18 mole of ethylene glycol cool to -10 DEG C and stir 20 minutes
Afterwards and this temperature is maintained, 0.05 mole of 2- (27 fluorine tridecyl) ethyl ether is added dropwise and 2- aminomethyl phenyls shrink
The dichloromethane solution that 0.95 mole of glycerin ether, control drip off in 2 hours.- 10 DEG C are maintained, is reacted 10 hours.It is added
20ml deionized waters terminate reaction, steam solvent, are neutralized to neutrality with sodium carbonate liquor.100mL deionized waters washing 20 is added
Minute, stratification.Oil phase is washed with distilled water once again, stratification.Oil phase removes remaining molten through Rotary Evaporators
Agent obtains the fluorine-containing thick polyetherdiol of side chain.It is dried in vacuo at 120 DEG C, under 5mm mercurypressures again, it is colourless viscous to obtain product
Thick liquid, yield 73.5% are measured through gpc analysis instrument,Fluorinated volume
6.8%, side chain fluorochemical polyether glycol number is CFJM-1.
Embodiment 2
0.5 mole of 0.1 mole of 2- (17 fluoro-octane base) ethyl ether and benzyl glycidyl ether is molten together
In with 200mL ether, the diethyl ether solution of formation.
In the kettle of the 1000mL equipped with blender, after air in pure nitrogen gas displacement kettle, -5 DEG C is cooled to, is added
0.072 mole and 0.12 mole 1.8 moles of oxetanes, perchloric acid butanediol is added as solvent in 100mL ether.It is added dropwise
It is above-mentioned by 2- (17 fluoro-octane base) 0.1 mole of ethyl ethers and the dissolving of 0.5 mole of benzyl glycidyl ether and 200mL
The diethyl ether solution of the formed ternary of ether, control are added dropwise and are completed in 3 hours.It is kept for -5 DEG C, reacted 8 hours, 30mL is added and goes
Ionized water terminates reaction, steams solvent, is neutralized to neutrality with sodium bicarbonate solution.200mL deionized waters stirring washing 20 is added
Minute, stratification, oil phase is washed with distilled water once again, stratification.Oil phase removes solvent through Rotary Evaporators, obtains
The fluorine-containing thick polyetherdiol of side chain.It is dried in vacuo at 120 DEG C, under 5mm mercurypressures again, obtains product colorless viscous shape liquid
Body, yield 82% are measured through gpc analysis instrument,Fluorinated volume 16.6%, the side
Chain fluorochemical polyether glycol number is CFJM-2.
Embodiment 3
0.3 mole of 0.15 mole of 1- (nona-fluoro butyl group) methyl glycidyl ether and benzyl glycidyl ether are dissolved in use together
250mL acetone forms three acetone soln.
In the kettle of the 1000mL equipped with blender, after air in pure nitrogen gas displacement kettle, -0 DEG C of addition 100mL is cooled to
0.0225 mole and 0.027 mole 0.45 mole of tetrahydrofuran, perchloric acid butanediol is added as solvent in acetone.It is added dropwise above-mentioned
250mL acetone institute is dissolved in by 0.3 mole of 0.15 mole of 1- (nona-fluoro butyl group) methyl glycidyl ether and benzyl glycidyl ether
The acetone soln of formation, control are added dropwise and are completed in 3 hours.It is kept for 0 DEG C, reacted 10 hours, 50ml deionized waters are added and terminate
Reaction, steams solvent, is neutralized to neutrality with carbonic acid amine aqueous solution.200mL deionized waters are added to wash 20 minutes, stratification,
Oil phase is washed with distilled water once again, stratification.Oil phase is dried in vacuo at 120 DEG C, under 5mm mercurypressures again, is obtained
Product colorless viscous shape liquid, yield 89% are measured through gpc analysis instrument, Contain
Fluorine amount 24.7%, side chain fluorochemical polyether glycol number is CFJM-3.
Embodiment 4
0.2 mole of 0.1 mole of 2- (15 fluorine heptyl) ethyl ether and butyl glycidyl ether are dissolved in together
With 200mL tetrahydrofurans, the tetrahydrofuran solution of formation.
In the kettle of the 1000mL equipped with blender, after air in pure nitrogen gas displacement kettle, 5 DEG C of addition oxa- rings are cooled to
0.024 mole and 0.072 mole 0.9 mole of butane, trifluoroacetic acid 1,2- propylene glycol.It is added dropwise above-mentioned by 2- (15 fluorine heptyl)
0.2 mole of 0.1 mole of ethyl ether and butyl glycidyl ether be dissolved in together be formed by with 200mL tetrahydrofurans it is molten
Liquid, control are added dropwise and are completed in 2 hours.It is kept for 5 DEG C, reacted 6 hours, 30ml deionized waters are added and terminate reaction, steam solvent,
It is neutralized to neutrality with sodium carbonate liquor.200mL deionized waters stirring washing 20 minutes is added, stratification, oil phase is again with steaming
Distilled water washed once, stratification.Oil phase is dried in vacuo at 120 DEG C, under 5mm mercurypressures again, obtains product colorless viscous
Shape liquid, yield 72% are measured through gpc analysis instrument,Fluorinated volume 38.8%,
Side chain fluorochemical polyether glycol number is CFJM-4.
Embodiment 5
1 mole of 0.25 mole of 2- (17 fluorine octyl) ethyl ether and butyl glycidyl ether are dissolved in use together
150mL tetrahydrofurans, the tetrahydrofuran solution of formation.
In the kettle of the 1000mL equipped with blender, after air in pure nitrogen gas displacement kettle, 2 DEG C of addition tetrahydrochysene furans are cooled to
It mutters 0.25 mole and 0.25 mole 1.9 moles, boron trifluoride ether 1,2- propylene glycol.It is added dropwise above-mentioned by 2- (17 fluorine octyl) second
1 mole of 0.25 mole of base glycidol ether and butyl glycidyl ether are dissolved in is formed by solution with 150mL tetrahydrofurans, controls
Dropwise addition is completed in 3 hours.It is kept for 2 DEG C, reacted 5 hours, 50ml deionized waters are added and terminate reaction, steams solvent, uses carbonic acid
Hydrogen sodium solution is neutralized to neutrality.250mL deionized waters stirring washing 20 minutes is added, stratification, oil phase uses distilled water again
It washed once, stratification.Obtain the fluorine-containing thick polyetherdiol of side chain.The oil phase vacuum at 120 DEG C, under 5mm mercurypressures again
It is dry, product colorless viscous shape liquid is obtained, yield 79% is measured through gpc analysis instrument, Fluorinated volume 17.5%, side chain fluorochemical polyether glycol number is CFJM-5.
Embodiment 6
0.5 mole of 0.1 mole of 1- (ten trifluoro heptane bases) methyl glycidyl ether and 1,2- 7-oxa-bicyclo[4.1.0s is molten together
In with 200mL1,4- dioxane, Isosorbide-5-Nitrae-dioxane solution of formation.
In the kettle of the 1000mL equipped with blender, after air in pure nitrogen gas displacement kettle, 10 DEG C is cooled to, Isosorbide-5-Nitrae-is added
Dioxane 100mL makees solvent, and 0.09 mole and 0.165 mole 2.4 moles of oxetanes, boron trifluoride ether second two is added
Alcohol.It is added dropwise above-mentioned by the 0.5 mole of dissolving of 0.1 mole of 1- (ten trifluoro heptane bases) methyl glycidyl ether and 1,2- 7-oxa-bicyclo[4.1.0s
With 200mL1,4- dioxane is formed by Isosorbide-5-Nitrae-dioxane solution, and control is added dropwise and is completed in 5 hours.Kept for 10 DEG C, instead
It answers 15 hours, 60ml deionized waters is added and terminate reaction, steam solvent, are neutralized to neutrality with sodium bicarbonate solution.200mL is added
Deionized water stirring washing 20 minutes, stratification, oil phase is washed with distilled water once again, and stratification obtains side chain and contains
The thick polyetherdiol of fluorine.Oil phase is dried in vacuo at 120 DEG C, under 5mm mercurypressures again, obtains product colorless viscous shape liquid,
Yield is 79%, is measured through gpc analysis instrument,Fluorinated volume 13.7%, the side chain contain
Perfluoroalkyl polyether glycol number is CFJM-6.
Comparative example 7 is synthesized according to granted patent ZL201310738875.7 embodiments
150mL dichloromethane is added in the autoclave pressure of the 500mL equipped with stirring as solvent, is replaced in kettle with pure nitrogen gas
Air 20 minutes.Then according to tetrahydrofuran:2- (seven fluorine n-propyls) methyl glycidyl ether:2- (11 fluorine n-pentyl) methyl
Glycidol ether:2- (15 fluorine n-heptyl) methyl glycidyl ether:Boron trifluoride etherate:Mole of 1,4- butanediols
Than being 0.35:0.15:0.2:0.3:0.07:0.07 ratio gets out various reactants.Weigh respectively 0.35 mole of tetrahydrofuran,
0.15 mole of 2- (seven fluorine n-propyls) methyl glycidyl ether, 0.2 mole of 2- (11 fluorine n-pentyl) methyl glycidyl ether and
0.3 mole of 2- (15 fluorine n-heptyl) methyl glycidyl ether.It is spare that latter three one is reinstated into the dissolving of 70mL dichloromethane.It is controlling
When temperature is 5 DEG C in reaction kettle processed, boron trifluoride etherate and 1,4-butanediol are added into kettle, and be added at one time
0.35 mole of tetrahydrofuran stirs 20 minutes.Then the dichloromethane solution of three kinds of fluorine-containing methyl glycidyl ethers is added dropwise, three
It is added dropwise to complete in hour.Reflux temperature is warming up to react 24 hours.20ml deionized waters are added and terminate reaction.Reduce reaction system
Temperature to environment temperature.100mL deionized waters are added to stir 20 minutes, stratification, oil phase is washed with distilled water one again
It is secondary, stratification.Oil phase removes impurity under 120 DEG C, 2mm mercury column pressure again, obtains side chain and contains different perfluor substitution alkyl
Polyetherdiol.Yield 78%, gpc analysis instrument measure,Fluorinated volume 43.2%.
Side chain fluorochemical polyether glycol number is CFJM-7.
8 effect example of embodiment
Different solvents dissolution experiment, specific experiment side are carried out to the fluorine-containing copolyether glycol of side chain of embodiment 1-7 synthesis
Method is：Take the single-necked flask of eight 50mL, be added in eight flasks respectively 40mL ether, 40mL dibutyl ethers, 40mL acetone,
40mL butanone, 40mL cyclohexanone, 40mL dichloromethane, 40mL ethyl acetate, 40mL butyl acetates and 40mL tetrahydrofurans, then
It is added in each solvent bottle in the fluorine-containing copolyether glycol of side chain for weighing 10 grams of above example, magneton is added and stirs 30 points
Clock was placed 24 hours using ultrasonic disperse 10 minutes, observed the dissolving situation in each sample flask.Experimental result such as table 1.
Dissolving result table of the 1 each embodiment sample of table in common solvent
The present invention is using subsituted oxirane and complete fluorine-substituted alkyl glycidyl ether and quaternary cyclic ethers or five-membered ring ether
One of them is copolymerized, the advantageous effect with aspects several in this way：(1) it can be shunk by changing complete fluorine-substituted alkyl
Three's material rate of one of glycerin ether and subsituted oxirane and quaternary cyclic ethers or five-membered ring ether, synthesize it is expected not
With the fluorine-containing copolyether glycol of side chain of fluorine content, expensive fluorine raw material is made full use of to greatest extent；(2) due to a variety of knots
Structure group can be substituted on propylene oxide, can carry out the original that next step is reacted according to the fluorine-containing copolyether glycol of side chain in this way
Expect structure, select have with next step participate in the same or similar substituent group of reaction raw materials solubility parameters propylene oxide monomer into
Row copolymerization, in this way when synthesized side chain fluorochemical polyether glycol is reacted with next step raw material, so that it may organic easily to solve
Serious split-phase, immiscible problem in fluorine compounds processing；(3) the fluorine-containing copolyether glycol of such side chain it is industrially general,
Easy to dissolve in cheap non-toxic or low-toxic solvent, this can largely reduce processing cost, reduce processing environment
Pollution.In short, the fluorine-containing copolyether glycol of side chain provided by the invention is extremely convenient in follow-up various uses, also in suitable journey
The use space of such polyetherdiol has been expanded on degree.
The effect of above-described embodiment is specifically to introduce the essentiality content of the present invention, but those skilled in the art should know
Protection scope of the present invention should not be confined to the specific embodiment by road.
Claims (9)
1. the side chain that a kind of subsituted oxirane, perfluoroalkyl glycidol ether and oxetanes or tetrahydrofuran copolymerization obtain
Fluorine-containing copolyether glycol, which is characterized in that there is the molecular structure as shown in structural formula I：
Wherein：
P is any number in 1 or 2；N is any number in 1 or 2；M is any one natural number in 4~13；Q is in 0 or 3 the two
Any number；X, y and z are any one natural number in 1~100；
y：(x+z) it is 5~1：In 1 range；x：Z is 20~1：In 1 range；
R is any one in hydrogen, saturated alkyl, saturation alkoxy, phenoxy group, benzyloxy.
2. copolyether glycol according to claim 1, it is characterised in that：Its number-average molecular weight is 1000~10000g/
mol。
3. the preparation method of copolyether glycol described in claims 1 or 2, which is characterized in that by perfluoroalkyl glycidol ether, take
Copolyreaction is carried out for propylene oxide and oxetanes or tetrahydrofuran to be prepared, reaction equation is expressed from the next：
Wherein：
P is any number in 1 or 2；N is any number in 1 or 2；M is any one natural number in 4~13；Q is in 0 or 3 the two
Any number；X, y and z are any one natural number in 1~100；
y：(x+z) it is 5~1：In 1 range；x：Z is 20~1：In 1 range；
R is any one in hydrogen, saturated alkyl, saturation alkoxy, phenoxy group, benzyloxy.
4. preparation method according to claim 3, which is characterized in that the perfluoroalkyl glycidol ether is selected from following knot
Any one in structure compound：
Wherein, n is any number in 1 or 2；M is any one natural number in 4~13.
5. preparation method according to claim 3, which is characterized in that include the following steps：
(1) raw material preparation：Subsituted oxirane and perfluoroalkyl glycidol ether, the sum of molal quantity of the two and oxetanes
Or the ratio between molal quantity of one of tetrahydrofuran is 1：In 5~1 ranges, wherein subsituted oxirane and perfluoroalkyl shrink sweet
Oily ether molar ratio is 20~1：1, the amount of the released cationic substance of cationic initiator accounts for the 2% of the amount of total monomer total material
~7%, glycol initiator accounts for the 2.5%~7% of the amount of total monomer substance；By subsituted oxirane and perfluoroalkyl glycidol
Ether is dissolved into solvent, and solute concentration is 1~20 mol/L in solution；
(2) solvent, oxetanes or tetrahydrofuran are added in reaction kettle of the anhydrous and oxygen-free equipped with blender, cation causes
Substituted epoxy third in above-mentioned steps (1) is slowly added dropwise simultaneously into kettle at a temperature of -10 DEG C~15 DEG C in agent and glycol initiator
Alkane and perfluoroalkyl glycidol ethereal solution, then at -10 DEG C~15 DEG C, polymerisation is added 3~10 after 5~15 hours
The deionized water of the amount of times glycol starter substance terminates reaction；
(3) it after terminating reaction, steams and recycles the organic solvent in reaction kettle, 1.5~2.5 of mixture after distilling then are added
The distilled water of times volume, in alkali compounds and pH value is to 7, agitator treating, stratification separate water phase, and oil phase is used again
Distilled water washed once, stratification, after oil phase dehydration and drying, through removing solvent up to the fluorine-containing copolyether glycol of side chain.
6. preparation method according to claim 5, it is characterised in that：Subsituted oxirane in step (2) and perfluor alkane
Base glycidol ethereal solution should be added dropwise to complete in 1~6 hour.
7. preparation method according to claim 5, it is characterised in that：Step (1) dissolves subsituted oxirane and perfluor alkane
The solvent of base glycidol ether is selected from dichloromethane, Isosorbide-5-Nitrae-dioxane, ether, tetrahydrofuran, acetone, butanone, dibutyl ethers
In it is one or more.
8. preparation method according to claim 5, it is characterised in that：The cationic initiator is selected from mass fraction 20%
Oleum, perchloric acid, trifluoroacetic acid, trifluoromethane sulfonic acid, boron trifluoride ether, trichloroacetic acid, phosphoric acid, tri-chlorination
One kind in aluminium, titanium tetrachloride, butter of tin, zinc chloride, Antimony pentachloride；Step (3) described alkali compounds be selected from sodium carbonate,
Sodium bicarbonate, ammonium carbonate, ammonium hydrogen carbonate or sodium hydroxide.
9. preparation method according to claim 5, it is characterised in that：The glycol initiator is selected from ethylene glycol, 1,2- third
One kind in glycol, 1,3- propylene glycol, 1,4- butanediols.
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| CN201710155902.6A CN106832246B (en) | 2017-03-16 | 2017-03-16 | A kind of fluorine-containing copolyether glycol of readily soluble side chain by perfluoroalkyl glycidol ether and the copolymerization of polynary cyclic ethers |
| PCT/CN2018/078672 WO2018166413A1 (en) | 2017-03-16 | 2018-03-12 | Easily soluble fluorine-containing side chain copolyether glycol copolymerised from perfluoroalkyl glycidyl ether and polycyclic ether |
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| CN109337063A (en) * | 2018-10-13 | 2019-02-15 | 郑州博物馆 | A kind of end hydroxy polyether synthetic method for historical relic bonding agent |
| CN110041818A (en) * | 2019-04-23 | 2019-07-23 | 南京信息工程大学 | A kind of corrosion resistant super-hydrophobic, oleophobic automatic cleaning coating of solvent resistant and preparation method thereof |
| CN110003433A (en) * | 2019-04-23 | 2019-07-12 | 南京信息工程大学 | A kind of one pack system ambient self-crosslinking fluorochemical urethane coating material and preparation method thereof |
| CN111116890A (en) * | 2019-12-12 | 2020-05-08 | 西南科技大学 | Polypentafluoropropyl glycidyl ether, use thereof and preparation method thereof |
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| CN101824130A (en) * | 2009-12-31 | 2010-09-08 | 广东银洋树脂有限公司 | Preparation method of soft segment lateral chain fluorine-containing waterborne polyurethane |
| CN103772692A (en) * | 2013-12-27 | 2014-05-07 | 南京信息工程大学 | Copolymerized glycol of perfluoroalkyl glycidyl ethers and cyclic ether and preparation method of copolymerized glycol |
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| CA2447132C (en) * | 2001-05-14 | 2008-10-07 | Omnova Solutions Inc. | Polymeric surfactants derived from cyclic monomers having pendant fluorinated carbon groups |
| CN100392001C (en) * | 2006-05-18 | 2008-06-04 | 中国科学技术大学 | Preparation process of polyether diatomic alcohol containing fluorine |
| JP5722913B2 (en) * | 2009-12-17 | 2015-05-27 | インヴィスタ テクノロジーズ エスアエルエル | Consistent production of copolyether glycols |
| US20140323772A1 (en) * | 2013-04-25 | 2014-10-30 | Invista North America S.A R.L. | Polyether glycol manufacturing process |
| CN103709388B (en) * | 2013-12-27 | 2015-09-23 | 南京信息工程大学 | Copolymer glycols of a kind of perfluor substituted epoxy ethane and cyclic ethers and preparation method thereof |
| CN106832246B (en) * | 2017-03-16 | 2018-09-04 | 南京信息工程大学 | A kind of fluorine-containing copolyether glycol of readily soluble side chain by perfluoroalkyl glycidol ether and the copolymerization of polynary cyclic ethers |
| CN107022072B (en) * | 2017-03-16 | 2019-04-19 | 孔庆刚 | A kind of readily soluble side chain fluorochemical polyether glycol by perfluor substituted epoxy ethane and the copolymerization of polynary cyclic ethers |
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| CN101824130A (en) * | 2009-12-31 | 2010-09-08 | 广东银洋树脂有限公司 | Preparation method of soft segment lateral chain fluorine-containing waterborne polyurethane |
| CN103772692A (en) * | 2013-12-27 | 2014-05-07 | 南京信息工程大学 | Copolymerized glycol of perfluoroalkyl glycidyl ethers and cyclic ether and preparation method of copolymerized glycol |
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