CN106750125B - A kind of fluorochemical urethane and the preparation method and application thereof - Google Patents

A kind of fluorochemical urethane and the preparation method and application thereof Download PDF

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CN106750125B
CN106750125B CN201611173215.9A CN201611173215A CN106750125B CN 106750125 B CN106750125 B CN 106750125B CN 201611173215 A CN201611173215 A CN 201611173215A CN 106750125 B CN106750125 B CN 106750125B
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fluorine
added
fluorochemical urethane
reaction
added dropwise
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CN106750125A (en
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李战雄
王蕾
王海朋
童德进
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Suzhou University
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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyethers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a kind of fluorochemical urethanes and the preparation method and application thereof.Polyaddition reaction is carried out in the presence of fluorine-containing solubilizer by the dihydric alcohol of copolyether containing fluoroalkyl and diisocyanate, with tin catalyst catalysis, passes through chain extender chain extension, a kind of fluorochemical urethane is made；Fluoroalkyl pendant type polyether block construction makes fluorochemical urethane have high fluorine content, therefore surface can be low；It is configured to working solution after emulsifying polyurethane, 139.5o is higher than to water contact angle for fabric post-treatment, there is excellent waterproofing function.

Description

A kind of fluorochemical urethane and the preparation method and application thereof
Technical field
The present invention relates to a kind of polyurethane, and in particular to one kind is with pendant perfluoroalkyl group copolyether dihydric alcohol and diisocyanate The fluorochemical urethane and the preparation method and application thereof that ester addition polymerization obtains belongs to polyurethane high molecule and textile finishing aid neck Domain.
Background technique
Surface free energy (the γ of polymeric solidc) related with the element of its surface composition.The introducing of fluorine atom makes surface It freely can significantly reduce, and fluorine atom substitution is more, then the effect for reducing surface free energy is more obvious.If fluorine atom is introduced To fabric fibre surface, when so that fabric surface fluorine atom reaching a certain concentration, the critical surface tension of fiber will be significantly Decline, and when critical surface tension is reduced to water and oil cannot be sprawled voluntarily, water repellent will be generated in fabric surface refuse Oily effect.Fluorine-contained finishing agent confirms principle and development and application accordingly.The fabric waterproofing agent overwhelming majority used at present is side chain Fluothane fundamental mode polyacrylate, can be on polymer molecule backbone because passing through free radical polymerization by fluorine-containing alkyl acrylate Easily introduce side group fluoroalkyl.
Although polyurethane material has high temperature performance more superior than polyacrylate and mechanical property, in polyurethane Fluoroalkyl is introduced in side group to be but not easy to.It is well known that the raw material of synthesis of polyurethane is that polymer-type dihydric alcohol is (or polynary Alcohol) and diisocyanate.Since the monomer of synthetic polymer type dihydric alcohol lacks fluoroalkylation product, therefore, it is difficult to obtain side group Type fluoropolymer dihydric alcohol；Realize that the thinking of polyurethane fluoroalkylation is asked there is also many by diisocyanate fluoroalkylation Topic, such as diisocyanate since molecular weight is small, is difficult to introduce many fluothane on polyurethane macromolecular fluoroalkylation Base.
Summary of the invention
The purpose of the present invention is to provide a kind of fluorochemical urethanes and preparation method thereof, have excellent low-surface-energy, refuse Aqueous energy.
The chemical structural formula of fluorochemical urethane disclosed by the invention are as follows:
Wherein, w is 2 ~ 7；M is 3 ~ 100；N is 1 ~ 100；X is 1 ~ 50；Y is 1 ~ 20；
R is-(CH2)6Or-Ph (CH3)-；R ' is-(CH2)4-。
The invention also discloses a kind of preparation methods of fluorochemical urethane, under the effect of fluorine-containing solubilizer, by containing fluoroalkyl Polyether Glycols and diisocyanate addition polymerization, obtain fluorochemical urethane through chain extending reaction.Include the following steps, ketone is molten The dihydric alcohol of copolyether containing fluoroalkyl, dibutyl tin dilaurate is added after agent, the mixing of fluorine-containing solubilizer；Then at 40~65 DEG C Diisocyanate is added dropwise, reacts 1~12 hour；Then 1,4-butanediol is added, the reaction was continued 1~12 hour, obtains fluorine-containing poly- Urethane.
In above-mentioned technical proposal, the ketones solvent is any one in acetone, butanone or cyclohexanone；The fluorine-containing increasing Solvent is any one in benzotrifluoride and 1,3- bis- (trifluoromethyl) benzene；The diisocyanate is toluene di-isocyanate(TDI) (TDI) any one and in hexamethylene diisocyanate (HDI).
In above-mentioned technical proposal, ketones solvent, fluorine-containing solubilizer, the dihydric alcohol of copolyether containing fluoroalkyl, two fourth of tin dilaurate Ji Xi, diisocyanate, 1,4- butanediol mass ratio be (10~50): (10~30): (10~50): (0.2~1): (5~ 30): (0.4~3).
In above-mentioned technical proposal, the time that diisocyanate is added dropwise is 15 minutes~1 hour.
In above-mentioned technical proposal, the dihydric alcohol of copolyether containing fluoroalkyl is by fluorine-containing oxetanes and fluorine-containing epoxy monomer Polymerization obtains.Alkyl chloride hydrocarbon solvent and initiator are added in the reactor；Then boron trifluoride second is added at 0~10 DEG C Ether；Then fluorine-containing oxetanes and fluorine-containing epoxy monomer is added dropwise, carries out ring-opening polymerization, obtains copolyether containing fluoroalkyl two First alcohol；The initiator is ethylene glycol, 1,4- butanediol, any one in 1,6-HD.
In above-mentioned technical proposal, allyl acetate, sodium bicarbonate, sodium dithionite, organic solvent, water are mixed, so Afterwards at -20~5 DEG C, perfluoroalkyl iodides are added dropwise, carry out synthetic reaction, lye is then added dropwise, carries out cyclization, prepares fluorine-containing Epoxy monomer；Acetic acid alkene butyl ester, sodium bicarbonate, sodium dithionite, organic solvent and water are mixed, then in -20~5 DEG C Under, perfluoroalkyl iodides are added dropwise, carry out synthetic reaction, lye progress cyclization is then added and obtains fluorine-containing oxetanes.
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 organic solvent is N,N-dimethylformamide；The lye is Any one in NaOH aqueous solution, KOH aqueous solution；The alkyl chloride hydrocarbon solvent is methylene chloride, dichloroethanes, three chloromethanes Any one in alkane, carbon tetrachloride.
The adjustable product solid content of the present invention, specifically comprises the following steps:
(1) by weight, 10 ~ 50 after mixing by 10 ~ 50 parts of ketones solvents and 10 ~ 30 parts of fluorine-containing solubilizer, are added Part dihydric alcohol of copolyether containing fluoroalkyl and 0.2 ~ 1.0 part of dibutyl tin dilaurate (DBTL), are uniformly mixed；
(2) after being warming up to 40 ~ 65 DEG C, 5 ~ 30 parts of diisocyanate is added dropwise at a slow speed, add within 15 minutes ~ 1 hour；
(3) heat preservation is reacted 1 ~ 12 hour in 40 ~ 65 DEG C, 0.4 ~ 3 part of 1,4-butanediol is added, the reaction was continued 1 ~ 12 hour；
(4) vacuum distillation removes most of solvent, the mixing formed with ketones solvent/fluorine-containing solubilizer (volume ratio 1:1) It is about 60 ~ 75% that solvent, which is diluted to mass concentration, and cooling, discharge to obtain fluorochemical urethane solution；The vacuum distillation condition is temperature 50 ~ 80 DEG C of degree, vacuum degree are 10 ~ 20mmHg.
In technical solution of the present invention, the preparation of fluorochemical urethane is using the dihydric alcohol of copolyether containing fluoroalkyl and diisocyanate Ester carries out polyaddition reaction, with tin catalyst catalysis, passes through 1,4-butanediol chain extension, reaction equation is as follows:
The present invention obtains polyurethane prepolymer by the dihydric alcohol of copolyether containing fluoroalkyl and diisocyanate polyaddition reaction, Chain extending reaction occurs for the residual isocyanate base and chain extender 1,4-butanediol that prepolymer contains, and fluorochemical urethane is made.It is fluorine-containing The structure that polymer covers outmost surface layer on base material provides the outermost layer composition of predominantly fluoro-containing group；Side group is fluorine-containing Alkyl polymer in surface enrichment can provide more superior low-surface-energy due to side chain fluoroalkyl.Therefore, the invention also discloses Application of the above-mentioned fluorochemical urethane in textile water repellent finish.
The present invention has the advantages that
1, the present invention uses the synthesis of polyurethane of copolyether glycol containing fluoroalkyl, and fluorochemical urethane has pendant type fluoroalkyl structure It makes, product fluorine content is high, it is possible to provide excellent low-surface-energy, it is excellent for textile finishing water repellency；Obtained polyurethane is used 139.5o is higher than to water contact angle in fabric post-treatment, there is excellent waterproofing function；
2, the present invention improves the compatible of the dihydric alcohol of copolyether containing fluoroalkyl and diisocyanate by the way that fluorine-containing solubilizer is added Property, solves the prior art due to fluorochemical polyether oleophobic, and the problem with diisocyanate addition reaction difficulty is improved containing fluothane The polyaddition reaction of base polyether Glycols and diisocyanate, goes on smoothly addition reaction, is uniformly dispersed, mobility Good polyurethane；
3, fluorochemical urethane disclosed by the invention contains fluoroalkyl in product macromolecular side group, and fluorine content is high, therefore has There is excellent low-surface-energy；And it synthesizes fluorochemical urethane raw material to be easy to get, reaction condition is mild, simple process, is easy industrialization Production.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of fluorochemical urethane film prepared by embodiment 1；
Fig. 2 be embodiment 1 prepare fluorochemical urethane finishing of cotton textiles after to water contact angle test chart；
Fig. 3 be embodiment 2 prepare fluorochemical urethane finishing of cotton textiles after to water contact angle test chart；
Fig. 4 be embodiment 3 prepare fluorochemical urethane finishing of cotton textiles after to water contact angle test chart；
Fig. 5 be embodiment 4 prepare fluorochemical urethane finishing of cotton textiles after to water contact angle test chart.
Specific embodiment
Technical solution of the present invention is further described below with reference to embodiment and attached drawing.
Embodiment 1
(1) fluorine-containing alkyl epoxy monomer synthesis
A. nine fluorine oxetanes synthesize
In the 1000mL three-necked flask equipped with thermometer, ice-water bath and magnetic stirring apparatus protection, 16.5g acetic acid alkene is added Butyl ester, 26.6g sodium bicarbonate (NaHCO3), 55.0g sodium dithionite, 220g n,N-Dimethylformamide, 210g water, 55.4g perfluoro butyl iodine alkane is added dropwise, -15 DEG C of reaction 3h are slowly increased to room temperature, insulation reaction 2h.After reaction, with 150g first 3 extractions of benzene point.Combining extraction liquid is washed 3 times, and 4- nona-fluoro butyl group -3- iodine butyl acetate solution is made, adds it to In 1000mL three-necked flask, the sodium hydroxide solution that 305g mass concentration is 20% is added dropwise, keeps the temperature in 15 DEG C of reaction 3h.Reaction knot It is layered after beam.Organic layer is washed 3 times, and dry, vacuum distillation obtains 3-(1H, nine fluorine amyl group of 1H-) oxetanes 33.8g, yield It is 75.9%.
B. nine fluorine propylene oxide synthesize
In the 1000mL three-necked flask equipped with thermometer, ice-water bath and magnetic stirring apparatus protection, 14.2g acetic acid alkene is added 55.4g is added dropwise in propyl diester, 26.6g sodium bicarbonate, 55.0g sodium dithionite, 220g n,N-Dimethylformamide, 210g water Perfluoro butyl iodine alkane, -20 °C of reaction 4h, is slowly increased to room temperature, insulation reaction 4h.After reaction, with 180g benzotrifluoride point 3 Secondary extraction.Combining extraction liquid is washed 4 times, and 3- nona-fluoro butyl group -2- iodine propyl-acetic acid ester liquid is made, is added directly into In 1000mL three-necked flask, the sodium hydroxide solution that 533g mass concentration is 10% is added dropwise, keeps the temperature in 12 DEG C of reaction 1h.Reaction knot It is layered after beam.Organic layer is washed 3 times, and dry, vacuum distillation removes solvent, obtains 1H, nine fluorine amyl group propylene oxide 33.9g of 1H-, is received Rate is 80.3%.
(2) fluorine-containing alkyl, polyether synthesis
A. mix monomer
By the 3-(1H of 27.8g, nine fluorine amyl group of 1H-) 1H of oxetanes and 26.4g, nine fluorine amyl group propylene oxide of 1H- It is uniformly mixed, obtains mix monomer.
B. it is copolymerized
It in the three-necked flask equipped with thermometer, blender and constant pressure funnel, is added, is added under nitrogen protection 50g methylene chloride and 0.32g1,4- butanediol, ice-water bath are cooled to 2 DEG C, are slowly added into 0.11gBF3.Et2O, temperature about rise 3 DEG C, after reaction 30 minutes, above-mentioned prepared mix monomer is added dropwise, adds within 35 minutes.After adding, 30 DEG C are warming up to, is continued anti- It should for 24 hours.Stop reaction.
C. it post-processes
10g2.5%NaHCO is added in above-mentioned ring opening copolymer reaction solution3Aqueous solution terminates reaction, after being stirred to react 1 hour, uses 120g methylene chloride extracts 3 times, merges organic layer, and drier anhydrous magnesium sulfate drying 1 hour is added, is filtered to remove desiccant Afterwards, filtrate boils off solvent and obtains product 49.3g, yield 91.2%.
(3) polyurethane synthesizes
Magnetic stirring apparatus, thermometer, reflux condenser and N are being housed2In the 500ml three-necked flask of protective device, it is added 38g copolyether containing fluoroalkyl dihydric alcohol is added in 35g butanone, 15g benzotrifluoride, then 0.5g tin dilaurate is added in stirring and dissolving Dibutyl tin (DBTL) after being warming up to 55 DEG C, is added dropwise 14.9g hexamethylene diisocyanate (HDI), 30min is added.After adding It is reacted 6 hours in 55 DEG C, after reacting fluid viscosity increase, 1.1g 1,4-butanediol is added, after the reaction was continued 3 hours, decompression is steamed Most of solvent is removed in distillation, and butanone/benzotrifluoride (volume ratio 1:1) mixed solvent is added while hot, is by product dilution to weight 82.5g, mass concentration are about 65%, and cooling discharging must contain fluoroalkyl polyurethane solutions.After product film forming, test infrared spectroscopy is shown in Attached drawing 1, FT-IR(KBr tabletting): 1717.6cm-1Belong to I key of amide and ester group (C=O), 1538.3cm-1Belong to amide II key (N-H deformation vibration), 1127.6 cm-1Belong to C-F characteristic absorption peak.Gained polyurethane structural formula is as follows:
Wherein, m is 3~10；N is 2~10；X is 3 ~ 30；Y is 3 ~ 20；
(4) application is arranged
A. emulsification treatment
By AEO-6 and 1.8g parts of cationic surfactant octadecanes of 1.8g nonionic surfactant in beaker in tall form Base trimethylammonium bromide is added in 110 parts of deionized waters, stirring and dissolving.8000 revs/min of revolving speed high shear agitations, slowly The 31.2g of polyurethane solutions containing fluoroalkyl is added dropwise, adds within 15 minutes, continues high-speed stirred 15 minutes after adding, obtain uniform cream Liquid.
B. textile finishing
Obtained fluorochemical urethane is diluted to 40g/L, is applied to Cotton Fabric, process flow are as follows: infiltration (30min, Bath raio 1:20) → second dipping and rolling (pick-up 100%, room temperature) → preliminary drying (90 DEG C × 3min) → bake (160 DEG C × 3min).
(5) contact angle test
Finishing of cotton textiles tests the contact angle to water, and for test result referring to attached drawing 2, contact angle is 139.5 °.
Embodiment 2
(1) fluorine-containing alkyl epoxy monomer synthesis
A. nine fluorine oxetanes synthesize
In the 1000mL three-necked flask equipped with thermometer, ice-water bath and magnetic stirring apparatus protection, 16.8g acetic acid alkene is added Butyl ester, 27.2g sodium bicarbonate (NaHCO3), 55.6g sodium dithionite, 225g n,N-Dimethylformamide, 200g water, 55.8g perfluoro butyl iodine alkane is added dropwise, -13 DEG C of reaction 3h are slowly increased to room temperature, insulation reaction 4h.After reaction, with 160g first 3 extractions of benzene point.Combining extraction liquid is washed 3 times, and 4- nona-fluoro butyl group -3- iodine butyl acetate solution is made, adds it to In 1000mL three-necked flask, the sodium hydroxide solution that 312g mass concentration is 15% is added dropwise, keeps the temperature in 12 DEG C of reaction 4h.Reaction knot It is layered after beam.Organic layer is washed 3 times, and dry, vacuum distillation obtains 3-(1H, nine fluorine amyl group of 1H-) oxetanes 35.2g, yield It is 77.4%.
B. nine fluorine propylene oxide synthesize
In the 1000mL three-necked flask equipped with thermometer, ice-water bath and magnetic stirring apparatus protection, 14.3g acetic acid alkene is added 55.9g is added dropwise in propyl diester, 26.8g sodium bicarbonate, 54.8g sodium dithionite, 218g n,N-Dimethylformamide, 206g water Perfluoro butyl iodine alkane, -19 DEG C of reaction 4h, is slowly increased to room temperature, insulation reaction 4h.After reaction, with 185g benzotrifluoride point 3 Secondary extraction.Combining extraction liquid is washed 4 times, and 3- nona-fluoro butyl group -2- iodine propyl-acetic acid ester liquid is made, is added directly into In 1000mL three-necked flask, the sodium hydroxide solution that 425g mass concentration is 15% is added dropwise, keeps the temperature in 12 DEG C of reaction 2h.Reaction knot It is layered after beam.Organic layer is washed 3 times, and dry, vacuum distillation removes solvent, obtains 1H, nine fluorine amyl group propylene oxide 34.2g of 1H-, is received Rate is 81.5%.
(2) fluorine-containing alkyl, polyether synthesis
A. mix monomer
By the 3-(1H of 21.3g, nine fluorine amyl group of 1H-) 1H of oxetanes and 32.6g, nine fluorine amyl group propylene oxide of 1H- It is uniformly mixed, obtains mix monomer.
B. it is copolymerized
It in the three-necked flask equipped with thermometer, blender and constant pressure funnel, is added, is added under nitrogen protection 62g methylene chloride and 0.40g1,4- butanediol, ice-water bath are cooled to 2 DEG C, are slowly added into 0.15gBF3.Et2O, temperature about rise 3 DEG C, after reaction 50 minutes, above-mentioned prepared mix monomer is added dropwise, adds within 35 minutes.After adding, 30 DEG C are warming up to, is continued anti- Answer 36h.Stop reaction.
C. it post-processes
10g2.5%NaHCO is added in above-mentioned ring opening copolymer reaction solution3Aqueous solution terminates reaction, after being stirred to react 1 hour, uses 120g methylene chloride extracts 3 times, merges organic layer, and drier anhydrous magnesium sulfate drying 1 hour is added, is filtered to remove desiccant Afterwards, filtrate boils off solvent and obtains product 48.1g, yield 89.2%.
(3) polyurethane synthesizes
Magnetic stirring apparatus, thermometer, reflux condenser and N are being housed2In the 500ml three-necked flask of protective device, it is added 40.1g copolyether containing fluoroalkyl dihydric alcohol is added in 32g butanone, 18g benzotrifluoride, then bis- laurel of 0.5g is added in stirring and dissolving Sour dibutyl tin (DBTL) after being warming up to 60 DEG C, is added dropwise 15.6g hexamethylene diisocyanate (HDI), 30min is added.It adds It is reacted 6 hours in 55 DEG C afterwards, after reacting fluid viscosity increase, 1.5g 1,4-butanediol is added, after the reaction was continued 3 hours, decompression Most of solvent is distilled off, butanone/benzotrifluoride (volume ratio 1:1) mixed solvent is added while hot, by product dilution to weight For 80g, mass concentration 69.5%, cooling discharging must contain fluoroalkyl polyurethane solutions.
Wherein, polyurethane structural formula is as follows:
Wherein, m is 3~8；N is 5~20；X is 3 ~ 30；Y is 3 ~ 20；
(4) application is arranged
A. emulsification treatment
By AEO-6 and 1.8g parts of cationic surfactant octadecanes of 2.0g nonionic surfactant in beaker in tall form Base trimethyl ammonium chloride is added in 108 parts of deionized waters, stirring and dissolving.8000 revs/min of revolving speed high shear agitations, slowly The 30.1g of polyurethane solutions containing fluoroalkyl is added dropwise, adds within 15 minutes, continues high-speed stirred 15 minutes after adding, obtain uniform cream Liquid.
B. textile finishing
Obtained fluorochemical urethane is diluted to 40g/L, is applied to Cotton Fabric, process flow are as follows: infiltration (30min, Bath raio 1:20) → second dipping and rolling (pick-up 100%, room temperature) → preliminary drying (90 DEG C × 3min) → bake (160 DEG C × 3min).
(5) contact angle test
Finishing of cotton textiles tests the contact angle to water, and for test result referring to attached drawing 3, contact angle is 141.7 °.
Embodiment 3
(1) fluorine-containing alkyl epoxy monomer synthesis
A. ten trifluoro oxetanes synthesize
In the 1000mL three-necked flask equipped with thermometer, ice-water bath and magnetic stirring apparatus protection, 16.8g acetic acid alkene is added 72.6g is added dropwise in butyl ester, 27.9g sodium bicarbonate, 54.8g sodium dithionite, 235g n,N-Dimethylformamide, 230g water Perfluoro-hexyl iodide alkane, -14 DEG C of reaction 5h, is slowly increased to room temperature, insulation reaction 6h.After reaction, with 188g benzotrifluoride point 3 Secondary extraction.Combining extraction liquid is washed 3 times, and ten trifluoro hexyl -3- iodine butyl acetate solution of 4- is made, is added directly into In 1000mL three-necked flask, the sodium hydroxide solution that 511g mass concentration is 10% is added dropwise, keeps the temperature in 15 DEG C of reaction 6h.Reaction knot It is layered after beam.Organic layer is washed 3 times, and dry, vacuum distillation obtains 3-(1H, ten trifluoro heptyl of 1H-) oxetanes 39.4g, is received Rate is 65.8%.
B. ten trifluoro-epoxy propanes synthesize
In the 1000mL three-necked flask equipped with thermometer, ice-water bath and magnetic stirring apparatus protection, 14.7g acetic acid alkene is added 73.9g is added dropwise in propyl diester, 27.1g sodium bicarbonate, 55.4g sodium dithionite, 226g n,N-Dimethylformamide, 215g water Perfluoro-hexyl iodide alkane, -16 DEG C of reaction 4h, is slowly increased to room temperature, insulation reaction 6h.After reaction, with the benzotrifluoride of 190g Divide 3 extractions.Combining extraction liquid is washed 3 times, and ten trifluoro hexyl -2- iodine propyl-acetic acid ester solution of 3- is made, is directly added into Into 1000mL three-necked flask, the sodium hydroxide solution that 522g mass concentration is 10% is added dropwise, keeps the temperature in 20 DEG C of reaction 4h.Reaction After be layered.Organic layer is washed 3 times, and dry, vacuum distillation obtains 1H, ten trifluoro heptyl propylene oxide 41.3g of 1H-, yield is 70.9%。
(2) fluorine-containing alkyl, polyether synthesis
A. ring opening copolymer
By the 3-(1H of 25.2g, ten trifluoro heptyl of 1H-) 1H of oxetanes and 48.1g, ten trifluoro heptyl epoxy of 1H- Propane is uniformly mixed, and obtains mix monomer.
It in the three-necked flask equipped with thermometer, blender and constant pressure funnel, is added, is added under nitrogen protection 60g methylene chloride and 0.52g1,4- butanediol, ice-water bath are cooled to 2 DEG C, are slowly added into 0.8gBF3.Et2O, temperature about rise 5 DEG C, after reaction 50 minutes, above-mentioned prepared mix monomer is added dropwise, adds within 1 hour.After adding, 28 DEG C are warming up to, the reaction was continued 24h.Stop reaction.
B. it post-processes
16g2.5%Na is added in above-mentioned ring-opening polymerization liquid2CO3Aqueous solution terminates reaction, after being stirred to react 2 hours, uses 186g methylene chloride extracts 3 times, merges organic layer, and desiccant anhydrous sodium sulfate drying 1 hour is added, is filtered to remove desiccant Afterwards, filtrate boils off solvent and obtains product 65.2g, yield 88.0%.
(3) polyurethane synthesizes
Magnetic stirring apparatus, thermometer, reflux condenser and N are being housed2In the 500ml three-necked flask of protective device, it is added 32g copolyether containing fluoroalkyl dihydric alcohol is added in 37g acetone, 18g benzotrifluoride, then 0.5g tin dilaurate is added in stirring and dissolving Dibutyl tin (DBTL) after being warming up to 55 DEG C, is added dropwise 11.2g toluene di-isocyanate(TDI) (TDI), 35min is added.In 55 after adding DEG C reaction 5 hours, react fluid viscosity increase after, be added 1.1g 1,4-butanediol, after the reaction was continued 3 hours, 65 DEG C, Vacuum distillation removes most of solvent under the conditions of 20mmHg, and acetone/benzotrifluoride (volume ratio 1:1) mixed solvent is added while hot, It is 67.5g by product dilution to weight, mass concentration is about 66%, and cooling discharging must contain fluoroalkyl polyurethane solutions.
Wherein, polyurethane structural formula is as follows:
Wherein, m is 3~10；N is 3~20；X is 5 ~ 30；Y is 5 ~ 20；
(4) application is arranged
A. emulsification treatment
By AEO-6 and 1.8g parts of cationic surfactant octadecanes of 1.9g nonionic surfactant in beaker in tall form Base trimethyl ammonium chloride is added in 100 parts of deionized waters, stirring and dissolving.8000 revs/min of revolving speed high shear agitations, slowly The 26.5g of polyurethane solutions containing fluoroalkyl is added dropwise, adds within 15 minutes, continues high-speed stirred 15 minutes after adding, obtain uniform cream Liquid.
B. textile finishing
Obtained fluorochemical urethane is diluted to 40g/L, is applied to Cotton Fabric, process flow are as follows: infiltration (30min, Bath raio 1:20) → second dipping and rolling (pick-up 100%, room temperature) → preliminary drying (90 DEG C × 3min) → bake (160 DEG C × 3min).
(5) contact angle test
Finishing of cotton textiles tests the contact angle to water, and test result is referring to attached drawing 4, contact angle 143.8o.
Embodiment 4
(1) fluorine-containing alkyl epoxy monomer synthesis
A. ten trifluoro oxetanes synthesize
In the 1000mL three-necked flask equipped with thermometer, ice-water bath and magnetic stirring apparatus protection, 16.9g acetic acid alkene is added 73.2g is added dropwise in butyl ester, 28.1g sodium bicarbonate, 55.3g sodium dithionite, 241g n,N-Dimethylformamide, 225g water Perfluoro-hexyl iodide alkane, -13 DEG C of reaction 6h, is slowly increased to room temperature, insulation reaction 3h.After reaction, with 180g benzotrifluoride point 3 Secondary extraction.Combining extraction liquid is washed 3 times, and ten trifluoro hexyl -3- iodine butyl acetate solution of 4- is made, is added directly into In 1000mL three-necked flask, the sodium hydroxide solution that 510g mass concentration is 10% is added dropwise, keeps the temperature in 15 DEG C of reaction 6h.Reaction knot It is layered after beam.Organic layer is washed 3 times, and dry, vacuum distillation obtains 3-(1H, ten trifluoro heptyl of 1H-) oxetanes 35.1g, is received Rate is 53.5%.
B. ten trifluoro-epoxy propanes synthesize
In the 1000mL three-necked flask equipped with thermometer, ice-water bath and magnetic stirring apparatus protection, 14.5g acetic acid alkene is added 73.4g is added dropwise in propyl diester, 27.0g sodium bicarbonate, 55.1g sodium dithionite, 219g n,N-Dimethylformamide, 220g water Perfluoro-hexyl iodide alkane, -15 DEG C of reaction 4h, is slowly increased to room temperature, insulation reaction 6h.After reaction, with the benzotrifluoride of 185g Divide 3 extractions.Combining extraction liquid is washed 3 times, and ten trifluoro hexyl -2- iodine propyl-acetic acid ester solution of 3- is made, is directly added into Into 1000mL three-necked flask, the sodium hydroxide solution that 520g mass concentration is 10% is added dropwise, keeps the temperature in 20 DEG C of reaction 6h.Reaction After be layered.Organic layer is washed 4 times, and dry, vacuum distillation obtains 1H, ten trifluoro heptyl propylene oxide 39.8g of 1H-, yield is 68.4%。
(2) fluorine-containing alkyl, polyether synthesis
A. ring opening copolymer
By the 3-(1H of 36.4g, ten trifluoro heptyl of 1H-) 1H of oxetanes and 28.9g, ten trifluoro heptyl epoxy of 1H- Propane is uniformly mixed, and obtains mix monomer.
It in the three-necked flask equipped with thermometer, blender and constant pressure funnel, is added, is added under nitrogen protection 55g methylene chloride and 0.45g1,4- butanediol, ice-water bath are cooled to 2 DEG C, are slowly added into 0.6gBF3.Et2O, temperature about rise 4 DEG C, after reaction 45 minutes, above-mentioned prepared mix monomer is added dropwise, adds within 1 hour.After adding, 25 DEG C are warming up to, the reaction was continued 24h.Stop reaction.
B. it post-processes
12g2.5%Na is added in above-mentioned ring-opening polymerization liquid2CO3Aqueous solution terminates reaction, after being stirred to react 2 hours, uses 165g methylene chloride extracts 3 times, merges organic layer, and desiccant anhydrous sodium sulfate drying 1 hour is added, is filtered to remove desiccant Afterwards, filtrate boils off solvent and obtains product 51.1g, yield 78.6%.
(3) polyurethane synthesizes
Magnetic stirring apparatus, thermometer, reflux condenser and N are being housed2In the 500ml three-necked flask of protective device, it is added 28g copolyether containing fluoroalkyl dihydric alcohol is added in 35g acetone, 20g benzotrifluoride, then 0.4g tin dilaurate is added in stirring and dissolving Dibutyl tin (DBTL) after being warming up to 55 DEG C, is added dropwise 9.5g toluene di-isocyanate(TDI) (TDI), 35min is added.In 55 after adding DEG C reaction 5 hours, react fluid viscosity increase after, be added 1.0g 1,4-butanediol, after the reaction was continued 3 hours, vacuum distillation is removed Most of solvent is removed, acetone/benzotrifluoride (volume ratio 1:1) mixed solvent is added while hot, is by product dilution to weight 56.5g, mass concentration are about 68.1%, and cooling discharging must contain fluoroalkyl polyurethane solutions；
Wherein, polyurethane structural formula is as follows:
Wherein, m is 3~10；N is 2~10；X is 5 ~ 30；Y is 5 ~ 20.
(4) application is arranged
A. emulsification treatment
By AEO-6 and 1.6g parts of cationic surfactant octadecanes of 1.5g nonionic surfactant in beaker in tall form Base trimethylammonium bromide is added in 100 parts of deionized waters, stirring and dissolving.8000 revs/min of revolving speed high shear agitations, slowly The 25.3g of polyurethane solutions containing fluoroalkyl is added dropwise, adds within 15 minutes, continues high-speed stirred 15 minutes after adding, obtain uniform cream Liquid.
B. textile finishing
Obtained fluorochemical urethane is diluted to 40g/L, is applied to Cotton Fabric, process flow are as follows: infiltration (30min, Bath raio 1:20) → second dipping and rolling (pick-up 100%, room temperature) → preliminary drying (90 DEG C × 3min) → bake (160 DEG C × 3min).
(5) contact angle test
Finishing of cotton textiles tests the contact angle to water, and test result is referring to attached drawing 5, contact angle 144.6o.

Claims (8)

1. a kind of fluorochemical urethane, which is characterized in that the chemical structural formula of the fluorochemical urethane are as follows:
Wherein, w is 2 ~ 7；M is 3 ~ 100；N is 1 ~ 100；X is 1 ~ 50；Y is 1 ~ 20；
R is-(CH2)6Or-Ph (CH3)-；R ' is-(CH2)4-；
The preparation method of the fluorochemical urethane includes the following steps, is added after ketones solvent, fluorine-containing solubilizer are mixed fluorine-containing Alkyl copolyether dihydric alcohol, dibutyl tin dilaurate；Then diisocyanate is added dropwise at 40~65 DEG C, reaction 1~12 is small When；Then 1,4-butanediol is added, the reaction was continued 1~12 hour, obtains fluorochemical urethane；The binary of copolyether containing fluoroalkyl Alcohol is polymerize to obtain by fluorine-containing oxetanes with fluorine-containing epoxy monomer.
2. fluorochemical urethane according to claim 1, it is characterised in that: the ketones solvent is acetone, butanone or cyclohexanone In any one；The fluorine-containing solubilizer is any one in benzotrifluoride and 1,3- bis- (trifluoromethyl) benzene；Described two Isocyanates is any one in toluene di-isocyanate(TDI) (TDI) and hexamethylene diisocyanate (HDI).
3. fluorochemical urethane according to claim 1, it is characterised in that: ketones solvent, fluorine-containing solubilizer are copolymerized containing fluoroalkyl Ether dihydric alcohol, dibutyl tin dilaurate, diisocyanate, 1,4- butanediol mass ratio be (10~50): (10~30): (10~50): (0.2~1): (5~30): (0.4~3).
4. fluorochemical urethane according to claim 1, it is characterised in that: the time that diisocyanate is added dropwise is 15 minutes~1 Hour.
5. fluorochemical urethane according to claim 4, it is characterised in that: alkyl chloride hydrocarbon solvent is added in the reactor and rises Beginning agent；Then boron trifluoride ether is added at 0~10 DEG C；Then fluorine-containing oxetanes and fluorine-containing epoxy monomer is added dropwise, into Row ring-opening polymerization obtains the dihydric alcohol of copolyether containing fluoroalkyl；The initiator be ethylene glycol, 1,4- butanediol, 1,6- oneself Any one in glycol.
6. fluorochemical urethane according to claim 5, it is characterised in that: mixing allyl acetate, sodium bicarbonate, Lian Erya Perfluoroalkyl iodides are added dropwise then at -20~5 DEG C in sodium sulphate, organic solvent, water, carry out synthetic reaction, lye is then added dropwise, Cyclization is carried out, fluorine-containing epoxy monomer is prepared；Mix acetic acid alkene butyl ester, sodium bicarbonate, sodium dithionite, organic solvent And perfluoroalkyl iodides are added dropwise then at -20~5 DEG C in water, carry out synthetic reaction, and lye is then added and carries out cyclization Obtain fluorine-containing oxetanes.
7. fluorochemical urethane according to claim 6, it is characterised in that: the perfluoroalkyl iodides are seven fluorine iodopropanes, nine fluorine Iodobutane, ten trifluoro iodohexanes, 15 fluorine iodine heptane, any one in 17 fluorine iodo-octanes；The organic solvent is N, N- Dimethylformamide；The lye is NaOH aqueous solution, any one in KOH aqueous solution.
8. application of the fluorochemical urethane described in claim 1 in textile water repellent finish.
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