CN106832194A - A kind of textile water repellent finish liquid based on fluorochemical urethane and preparation method and application - Google Patents
A kind of textile water repellent finish liquid based on fluorochemical urethane and preparation method and application Download PDFInfo
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- CN106832194A CN106832194A CN201710114768.5A CN201710114768A CN106832194A CN 106832194 A CN106832194 A CN 106832194A CN 201710114768 A CN201710114768 A CN 201710114768A CN 106832194 A CN106832194 A CN 106832194A
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- fluorine
- water repellent
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- repellent finish
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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
- C08G18/28—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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- 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
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- 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
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- 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
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- 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 Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of textile water repellent finish liquid based on fluorochemical urethane and preparation method and application；Nonionic surfactant and cationic surfactant are added in deionized water, and polyurethane solutions containing fluoroalkyl are slowly added dropwise, and continue high-speed stirred, obtain uniform dressing liquid；Polyurethane containing fluoroalkyl carries out polyaddition reaction by the dihydroxylic alcohols of copolyether containing fluoroalkyl and diisocyanate in the presence of fluorine-containing solubilizer；Fluoroalkyl pendant type polyether block construction makes fluorochemical urethane have Oil repellent high, therefore surface can be low；Dressing liquid is configured to after emulsifying polyurethane, for fabric post-treatment to water contact angle higher than 139.5o, with excellent waterproofing function.
Description
Technical field
The present invention relates to a kind of polyurethane dressing liquid, and in particular to a kind of textile water repellent finish based on fluorochemical urethane
Liquid and preparation method and application, belongs to polyurethane high molecule and textile finishing auxiliary agent field.
Background technology
The surface free energy of polymeric solid（γc）Element with its surface composition is relevant.The introducing of fluorine atom makes surface
Free energy is significantly reduced, 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 so that when fabric face fluorine atom reaches finite concentration, the critical surface tension of fiber will be significantly
Decline, and when critical surface tension is reduced to water and can not voluntarily be sprawled with oil, in fabric face water repellent will be produced to refuse
Oily effect.Fluorine-contained finishing agent confirms principle and development and application accordingly.The fabric waterproofing agent overwhelming majority for being used at present is side chain
Fluothane fundamental mode polyacrylate, because by can be on polymer molecule backbone by radical polymerization containing fluoroalkyl
Easily introduce side base fluoroalkyl.
Although polyurethane material is with the high temperature performance more superior than polyacrylate and mechanical property, in polyurethane
Fluoroalkyl is introduced in side base to be but not easy to.It is well known that the raw material of synthesis of polyurethane is polymer-type dihydroxylic alcohols（Or it is polynary
Alcohol）And diisocyanate.Because the monomer of synthetic polymer type dihydroxylic alcohols lacks fluoroalkylation product, therefore, it is difficult to obtain side base
Type fluoropolymer dihydroxylic alcohols；Realize that the thinking of polyurethane fluoroalkylation there is also many asking by diisocyanate fluoroalkylation
Topic, such as diisocyanate are small due to molecular weight, even if fluoroalkylation is also difficult to introduce many fluothane on polyurethane macromolecular
Base.
The content of the invention
It is an object of the invention to provide a kind of textile water repellent finish liquid based on fluorochemical urethane and preparation method thereof,
With excellent low-surface-energy, water repellency.
The invention discloses a kind of preparation method of the textile water repellent finish liquid based on fluorochemical urethane, including following step
Suddenly, nonionic surfactant and cationic surfactant are added in deionized water, the poly- ammonia containing fluoroalkyl is then added dropwise
Ester solution, stirring obtains the textile water repellent finish liquid based on fluorochemical urethane；The chemical structural formula of the fluorochemical urethane
For：
Wherein, w is 2 ~ 7；M is 3 ~ 100；N is 1 ~ 100；X is 1 ~ 50；Y is 1 ~ 20；
R is-(CH2)6- or-Ph (CH3)-；R ' is-(CH2)4-。
In above-mentioned technical proposal, under the effect of fluorine-containing solubilizer, added with diisocyanate by fluorine-containing alkyl, polyether dihydroxylic alcohols
Into polymerization, fluorochemical urethane is obtained through chain extending reaction.Comprise the following steps, added after ketones solvent, fluorine-containing solubilizer are mixed
The dihydroxylic alcohols of copolyether containing fluoroalkyl, dibutyl tin laurate；Then in being added dropwise diisocyanate at 40~65 DEG C, reaction 1~
12 hours；BDO is subsequently adding, continues to react 1~12 hour, obtain fluorochemical urethane.
In above-mentioned technical proposal, the ketones solvent is any one in acetone, butanone or cyclohexanone；The fluorine-containing increasing
Solvent is benzotrifluoride and 1,3- bis-（Trifluoromethyl）Any one in benzene；The diisocyanate is toluene di-isocyanate(TDI)
（TDI）And hexamethylene diisocyanate（HDI）In any one.
In above-mentioned technical proposal, ketones solvent, fluorine-containing solubilizer, the dihydroxylic alcohols of copolyether containing fluoroalkyl, the fourth of tin dilaurate two
Ji Xi, diisocyanate, the mass ratio of 1,4- butanediols are（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 dihydroxylic alcohols of copolyether containing fluoroalkyl is by fluorine-containing oxetanes and fluorine-containing epoxy monomer
Polymerization is obtained.Alkyl chloride varsol and initiator are added in the reactor；Then in addition boron trifluoride second at 0~10 DEG C
Ether；Then fluorine-containing oxetanes and fluorine-containing epoxy monomer is added dropwise, ring-opening polymerization is carried out, copolyether containing fluoroalkyl two is obtained
First alcohol；The initiator is any one in ethylene glycol, 1,4- butanediols, 1,6-HD.
In above-mentioned technical proposal, mixing allyl acetate, sodium acid carbonate, sodium dithionite, organic solvent, water, so
After at -20~5 DEG C, perfluoroalkyl iodides are added dropwise, carry out synthetic reaction, alkali lye is then added dropwise, carry out cyclization, prepare fluorine-containing
Epoxy monomer；Mixing acetic acid alkene butyl ester, sodium acid carbonate, sodium dithionite, organic solvent and water, then in -20~5 DEG C
Under, perfluoroalkyl iodides are added dropwise, synthetic reaction is carried out, it is subsequently adding alkali lye and carries out cyclization 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 alkali lye is
Any one in the NaOH aqueous solution, the KOH aqueous solution；The alkyl chloride varsol is dichloromethane, dichloroethanes, three chloromethanes
Any one in alkane, carbon tetrachloride.
In technical solution of the present invention, the preparation of fluorochemical urethane is using the dihydroxylic alcohols of copolyether containing fluoroalkyl and two isocyanic acids
Ester carries out polyaddition reaction, and with tin catalyst catalysis, by BDO chain extension, reaction equation is as follows：
In above-mentioned technical proposal, the nonionic surfactant is AEO-6；The cationic surfactant is octadecyl
Trimethylammonium bromide or OTAC；Solvent is ketones solvent/contain in the polyurethane solutions containing fluoroalkyl
Fluorine solubilizer mixed liquor；The fluorine-containing solubilizer is benzotrifluoride and 1,3- bis-（Trifluoromethyl）Any one in benzene；It is added dropwise
Time containing fluoroalkyl polyurethane solutions is 10~20 minutes.
It is nonionic surfactant, cationic surfactant, deionized water, poly- containing fluoroalkyl in above-mentioned technical proposal
The mass ratio of urethane solution is（1.5~2）∶（1.5~2）∶（100~120）∶（25~32）；The fluoroalkyl polyurethane solutions
Mass concentration be 60~75%.
Prepared the invention also discloses according to the preparation method of the above-mentioned textile water repellent finish liquid based on fluorochemical urethane
The textile water repellent finish liquid based on fluorochemical urethane and its application in textile water repellent finish.
The present invention further discloses a kind of method of textile water repellent finish, comprise the following steps, adjustment is based on fluorine-containing
The solid content of the textile water repellent finish liquid of polyurethane is 40g/L；Then by textile according to infiltrating, pad, preliminary drying, bakee
Technique carries out water repellent finish.
The present invention obtains polyurethane prepolymer by the dihydroxylic alcohols of copolyether containing fluoroalkyl and diisocyanate polyaddition reaction,
There is chain extending reaction in the residual isocyanate base that prepolymer contains, fluorochemical urethane is obtained, in breast with chain extender BDO
Change obtains dressing liquid.The structure of the outmost surface layer that fluoropolymer is covered on base material provides predominantly that fluoro-containing group is most
Outer layer is constituted；The fluorine-containing alkyl polymer of side base can provide more superior low-surface-energy due to side chain fluoroalkyl in surface enrichment.
The advantage of the invention is that：
1st, using the synthesis of polyurethane of copolyether glycol containing fluoroalkyl, there is fluorochemical urethane the present invention pendant type fluoroalkyl to construct,
Product Oil repellent is high, it is possible to provide excellent low-surface-energy, excellent for textile finishing water repellency；The polyurethane for obtaining is used to knit
Thing Final finishing is higher than 139.5o to water contact angle, with excellent waterproofing function；
2nd, the present invention improves the compatibility of the dihydroxylic alcohols of copolyether containing fluoroalkyl and diisocyanate, solution by adding fluorine-containing solubilizer
Due to fluorochemical polyether oleophobic, the difficult problem with diisocyanate addition reaction is improved poly- containing fluoroalkyl prior art of having determined
The polyaddition reaction of ether dihydroxylic alcohols and diisocyanate, be smoothed out addition reaction, is uniformly dispersed, good fluidity
Polyurethane；
3rd, fluorochemical urethane disclosed by the invention, fluoroalkyl is contained in its product macromolecular side base, and Oil repellent is high, therefore with excellent
Good low-surface-energy；And synthesize fluorochemical urethane raw material to be easy to get, reaction condition is gentle, technique is easy, easy industrialized production.
Brief description of the drawings
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 with reference to embodiment and accompanying drawing.
Embodiment 1
（1）Fluorine-containing alkyl epoxy monomer synthesis
A. nine fluorine oxetanes synthesis
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, 26.6g sodium acid carbonates（NaHCO3）, 55.0g sodium dithionites, 220g DMFs, 210g water, dropwise addition
55.4g perfluoro butyl iodine alkane, -15 DEG C of reaction 3h, is slowly increased to room temperature, insulation reaction 2h.After reaction terminates, with 150g toluene point
3 extractions.Combining extraction liquid, washes 3 times, and the fluorine butyl -3- iodine butyl acetate solutions of 4- nine are obtained, and adds it to 1000mL
In there-necked flask, the sodium hydroxide solution that 305g mass concentrations are 20% is added dropwise, is incubated and reacts 3h in 15 DEG C.Reaction divides after terminating
Layer.Organic layer is washed 3 times, dry, vacuum distillation, obtains 3-（The fluorine amyl group of 1H, 1H- nine）Oxetanes 33.8g, yield is
75.9%。
B. nine fluorine expoxy propane synthesis
In the 1000mL there-necked flasks protected equipped with thermometer, ice-water bath and magnetic stirring apparatus, 14.2g acetic acid pi-allyls are added
Ester, 26.6g sodium acid carbonates, 55.0g sodium dithionites, 220g DMFs, 210g water is added dropwise 55.4g perfluors
Butyl iodide alkane, -20 °C of reaction 4h, is slowly increased to room temperature, insulation reaction 4h.After reaction terminates, with 3 extractions of 180g benzotrifluorides point
Take.Combining extraction liquid, washes 4 times, and the fluorine butyl -2- iodine propyl-acetic acid ester liquid of 3- nine is obtained, and is added directly into 1000mL tri-
In mouth flask, the sodium hydroxide solution that 533g mass concentrations are 10% is added dropwise, is incubated and reacts 1h in 12 DEG C.Reaction is layered after terminating.
Organic layer is washed 3 times, and dry, vacuum distillation removes solvent, obtains 1H, the fluorine amyl group expoxy propane 33.9g of 1H- nine, and yield is
80.3%。
（2）Fluorine-containing alkyl, polyether synthesis
A. mix monomer
By the 3- of 27.8g（The fluorine amyl group of 1H, 1H- nine）The fluorine amyl group expoxy propane of the 1H of oxetanes and 26.4g, 1H- nine mixes
Uniformly, mix monomer is obtained.
B. copolymerization
In the there-necked flask equipped with thermometer, agitator and constant pressure funnel, add under nitrogen protection, add 50g bis-
Chloromethanes and 0.32g1,4- butanediol, ice-water bath are cooled to 2 DEG C, are slowly added into 0.11gBF3.Et2O, temperature about rises 3 DEG C, instead
After answering 30 minutes, the above-mentioned mix monomer for preparing is added dropwise, adds within 35 minutes.After adding, 30 DEG C are warming up to, continue to react 24h.
Stop reaction.
C. post-process
Above-mentioned ring opening copolymer reaction solution adds 10g2.5%NaHCO3The aqueous solution, terminating reaction, stirring reaction uses 120g after 1 hour
Dichloromethane is extracted 3 times, merges organic layer, adds drier anhydrous magnesium sulfate to dry 1 hour, after being filtered to remove drier, filter
Liquid boils off solvent and obtains product 49.3g, yield 91.2%.
（3）Polyurethane synthesizes
Equipped with magnetic stirring apparatus, thermometer, reflux condenser and N2In the 500ml there-necked flasks of protection device, 35g fourths are added
Ketone, 15g benzotrifluorides add the 38g dihydroxylic alcohols of copolyether containing fluoroalkyl, and stirring and dissolving is subsequently adding the fourth of 0.5g tin dilaurates two
Ji Xi（DBTL）, after being warming up to 55 DEG C, 14.9g hexamethylene diisocyanates are added dropwise（HDI）, 30min adds.Add after 55
DEG C reaction 6 hours, reaction fluid viscosity increase after, add 1.1g BDOs, continue react 3 hours after, vacuum distillation is removed
Most of solvent is removed, butanone/benzotrifluoride is added while hot（Volume ratio 1:1）Mixed solvent, be by product dilution to weight
82.5g, mass concentration is about 65%, and cooling discharging must contain fluoroalkyl polyurethane solutions.After product film forming, test infrared spectrum is shown in
Accompanying drawing 1, FT-IR（KBr compressing tablets）: 1717.6cm-1Belong to the key of acid amides I and ester group（C=O）, 1538.3cm-1Belong to acid amides
II key（N-H deformation vibrations）, 1127.6 cm-1Belong to C-F characteristic absorption peaks.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）Arrange application
A. emulsification treatment
By AEO-6 and 1.8g part of cationic surfactant octadecyl three of 1.8g nonionic surfactants in beaker in tall form
Methyl bromide ammonium is added in 110 parts of deionized waters, stirring and dissolving.8000 revs/min of rotating speed high shear agitations, are slowly added dropwise
The 31.2g of polyurethane solutions containing fluoroalkyl, is added for 15 minutes, and high-speed stirred is continued 15 minutes after adding, and obtains uniform emulsion.
B. textile finishing
The fluorochemical urethane that will be obtained is diluted to 40g/L, is applied to Cotton Fabric, and technological process is：Infiltration（30min, bath raio
1:20）→ bis- leachings two are rolled（Pick-up 100%, room temperature）→ preliminary drying（90℃×3min）→ bake（160℃×3min）.
（5）Contact angle is tested
Finishing of cotton textiles tests the contact angle to water, and referring to accompanying drawing 2, contact angle is 139.5 ° to test result.
Embodiment 2
（1）Fluorine-containing alkyl epoxy monomer synthesis
A. nine fluorine oxetanes synthesis
In the 1000mL there-necked flasks protected equipped with thermometer, ice-water bath and magnetic stirring apparatus, 16.8g acetic acid alkene butyl is added
Ester, 27.2g sodium acid carbonates（NaHCO3）, 55.6g sodium dithionites, 225g DMFs, 200g water, dropwise addition
55.8g perfluoro butyl iodine alkane, -13 DEG C of reaction 3h, is slowly increased to room temperature, insulation reaction 4h.After reaction terminates, with 160g toluene point
3 extractions.Combining extraction liquid, washes 3 times, and the fluorine butyl -3- iodine butyl acetate solutions of 4- nine are obtained, and adds it to 1000mL
In there-necked flask, the sodium hydroxide solution that 312g mass concentrations are 15% is added dropwise, is incubated and reacts 4h in 12 DEG C.Reaction divides after terminating
Layer.Organic layer is washed 3 times, dry, vacuum distillation, obtains 3-（The fluorine amyl group of 1H, 1H- nine）Oxetanes 35.2g, yield is
77.4%。
B. nine fluorine expoxy propane synthesis
In the 1000mL there-necked flasks protected equipped with thermometer, ice-water bath and magnetic stirring apparatus, 14.3g acetic acid pi-allyls are added
Ester, 26.8g sodium acid carbonates, 54.8g sodium dithionites, 218g DMFs, 206g water is added dropwise 55.9g perfluors
Butyl iodide alkane, -19 DEG C of reaction 4h, is slowly increased to room temperature, insulation reaction 4h.After reaction terminates, with 3 extractions of 185g benzotrifluorides point
Take.Combining extraction liquid, washes 4 times, and the fluorine butyl -2- iodine propyl-acetic acid ester liquid of 3- nine is obtained, and is added directly into 1000mL tri-
In mouth flask, the sodium hydroxide solution that 425g mass concentrations are 15% is added dropwise, is incubated and reacts 2h in 12 DEG C.Reaction is layered after terminating.
Organic layer is washed 3 times, and dry, vacuum distillation removes solvent, obtains 1H, the fluorine amyl group expoxy propane 34.2g of 1H- nine, and yield is
81.5%。
（2）Fluorine-containing alkyl, polyether synthesis
A. mix monomer
By the 3- of 21.3g（The fluorine amyl group of 1H, 1H- nine）The fluorine amyl group expoxy propane of the 1H of oxetanes and 32.6g, 1H- nine mixes
Uniformly, mix monomer is obtained.
B. copolymerization
In the there-necked flask equipped with thermometer, agitator and constant pressure funnel, add under nitrogen protection, add 62g bis-
Chloromethanes and 0.40g1,4- butanediol, ice-water bath are cooled to 2 DEG C, are slowly added into 0.15gBF3.Et2O, temperature about rises 3 DEG C, instead
After answering 50 minutes, the above-mentioned mix monomer for preparing is added dropwise, adds within 35 minutes.After adding, 30 DEG C are warming up to, continue to react 36h.
Stop reaction.
C. post-process
Above-mentioned ring opening copolymer reaction solution adds 10g2.5%NaHCO3The aqueous solution, terminating reaction, stirring reaction uses 120g after 1 hour
Dichloromethane is extracted 3 times, merges organic layer, adds drier anhydrous magnesium sulfate to dry 1 hour, after being filtered to remove drier, filter
Liquid boils off solvent and obtains product 48.1g, yield 89.2%.
（3）Polyurethane synthesizes
Equipped with magnetic stirring apparatus, thermometer, reflux condenser and N2In the 500ml there-necked flasks of protection device, 32g fourths are added
Ketone, 18g benzotrifluorides add the 40.1g dihydroxylic alcohols of copolyether containing fluoroalkyl, and stirring and dissolving is subsequently adding 0.5g tin dilaurates two
Butyl tin（DBTL）, after being warming up to 60 DEG C, 15.6g hexamethylene diisocyanates are added dropwise（HDI）, 30min adds.Add after
55 DEG C are reacted 6 hours, after reaction fluid viscosity increases, add 1.5g BDOs, after continuing to react 3 hours, vacuum distillation
Most of solvent is removed, butanone/benzotrifluoride is added while hot（Volume ratio 1:1）Mixed solvent, be by product dilution to weight
80g, mass concentration is 69.5%, and 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）Arrange application
A. emulsification treatment
By AEO-6 and 1.8g part of cationic surfactant octadecyl three of 2.0g nonionic surfactants in beaker in tall form
Ammonio methacrylate is added in 108 parts of deionized waters, stirring and dissolving.8000 revs/min of rotating speed high shear agitations, are slowly added dropwise
The 30.1g of polyurethane solutions containing fluoroalkyl, is added for 15 minutes, and high-speed stirred is continued 15 minutes after adding, and obtains uniform emulsion.
B. textile finishing
The fluorochemical urethane that will be obtained is diluted to 40g/L, is applied to Cotton Fabric, and technological process is：Infiltration（30min, bath raio
1:20）→ bis- leachings two are rolled（Pick-up 100%, room temperature）→ preliminary drying（90℃×3min）→ bake（160℃×3min）.
（5）Contact angle is tested
Finishing of cotton textiles tests the contact angle to water, and referring to accompanying drawing 3, contact angle is 141.7 ° to test result.
Embodiment 3
（1）Fluorine-containing alkyl epoxy monomer synthesis
A. ten trifluoro oxetanes synthesis
In the 1000mL there-necked flasks protected equipped with thermometer, ice-water bath and magnetic stirring apparatus, 16.8g acetic acid alkene butyl is added
Ester, 27.9g sodium acid carbonates, 54.8g sodium dithionites, 235g DMFs, 230g water is added dropwise 72.6g perfluors
Hexyl iodide alkane, -14 DEG C of reaction 5h, is slowly increased to room temperature, insulation reaction 6h.After reaction terminates, with 3 extractions of 188g benzotrifluorides point
Take.Combining extraction liquid, washes 3 times, and the trifluoro hexyl -3- iodine butyl acetate solutions of 4- ten are obtained, and is added directly into
In 1000mL there-necked flasks, the sodium hydroxide solution that 511g mass concentrations are 10% is added dropwise, is incubated and reacts 6h in 15 DEG C.Reaction knot
It is layered after beam.Organic layer is washed 3 times, dry, vacuum distillation, obtains 3-（The trifluoro heptyl of 1H, 1H- ten）Oxetanes 39.4g, receives
Rate is 65.8%.
B. ten trifluoro-epoxy propanes synthesis
In the 1000mL there-necked flasks protected equipped with thermometer, ice-water bath and magnetic stirring apparatus, 14.7g acetic acid pi-allyls are added
Ester, 27.1g sodium acid carbonates, 55.4g sodium dithionites, 226g DMFs, 215g water is added dropwise 73.9g perfluors
Hexyl iodide alkane, -16 DEG C of reaction 4h, is slowly increased to room temperature, insulation reaction 6h.After reaction terminates, divided 3 times with the benzotrifluoride of 190g
Extraction.Combining extraction liquid, washes 3 times, and the trifluoro hexyl -2- iodine propyl-acetic acid ester solutions of 3- ten are obtained, and is added directly into
In 1000mL there-necked flasks, the sodium hydroxide solution that 522g mass concentrations are 10% is added dropwise, is incubated and reacts 4h in 20 DEG C.Reaction knot
It is layered after beam.Organic layer is washed 3 times, dry, vacuum distillation, obtains 1H, the trifluoro heptyl expoxy propane 41.3g of 1H- ten, and yield is
70.9%。
（2）Fluorine-containing alkyl, polyether synthesis
A. ring opening copolymer
By the 3- of 25.2g（The trifluoro heptyl of 1H, 1H- ten）The trifluoro heptyl expoxy propane of the 1H of oxetanes and 48.1g, 1H- ten
It is well mixed, obtain mix monomer.
In the there-necked flask equipped with thermometer, agitator and constant pressure funnel, add under nitrogen protection, add
60g dichloromethane and 0.52g1,4- butanediol, ice-water bath are cooled to 2 DEG C, are slowly added into 0.8gBF3.Et2O, temperature about rises 5
DEG C, after reacting 50 minutes, the above-mentioned mix monomer for preparing is added dropwise, add within 1 hour.After adding, 28 DEG C are warming up to, continue to react
24h.Stop reaction.
B. post-process
Above-mentioned ring-opening polymerization liquid adds 16g2.5%Na2CO3The aqueous solution, terminating reaction, stirring reaction uses 186g after 2 hours
Dichloromethane is extracted 3 times, merges organic layer, adds drier anhydrous sodium sulfate drying 1 hour, after being filtered to remove drier, filter
Liquid boils off solvent and obtains product 65.2g, yield 88.0%.
（3）Polyurethane synthesizes
Equipped with magnetic stirring apparatus, thermometer, reflux condenser and N2In the 500ml there-necked flasks of protection device, 37g third is added
Ketone, 18g benzotrifluorides add the 32g dihydroxylic alcohols of copolyether containing fluoroalkyl, and stirring and dissolving is subsequently adding the fourth of 0.5g tin dilaurates two
Ji Xi（DBTL）, after being warming up to 55 DEG C, 11.2g toluene di-isocyanate(TDI)s are added dropwise（TDI）, 35min adds.Add anti-after 55 DEG C
Answer 5 hours, after reaction fluid viscosity increases, add 1.1g BDOs, after continuing to react 3 hours, 65 DEG C, 20mmHg bars
Vacuum distillation removes most of solvent under part, and acetone/benzotrifluoride is added while hot（Volume ratio 1:1）Mixed solvent is dilute by product
It is 67.5g to release 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）Arrange application
A. emulsification treatment
By AEO-6 and 1.8g part of cationic surfactant octadecyl three of 1.9g nonionic surfactants in beaker in tall form
Ammonio methacrylate is added in 100 parts of deionized waters, stirring and dissolving.8000 revs/min of rotating speed high shear agitations, are slowly added dropwise
The 26.5g of polyurethane solutions containing fluoroalkyl, is added for 15 minutes, and high-speed stirred is continued 15 minutes after adding, and obtains uniform emulsion.
B. textile finishing
The fluorochemical urethane that will be obtained is diluted to 40g/L, is applied to Cotton Fabric, and technological process is：Infiltration（30min, bath raio
1:20）→ bis- leachings two are rolled（Pick-up 100%, room temperature）→ preliminary drying（90℃×3min）→ bake（160℃×3min）.
（5）Contact angle is tested
Finishing of cotton textiles tests the contact angle to water, and referring to accompanying drawing 4, contact angle is 143.8o to test result.
Embodiment 4
（1）Fluorine-containing alkyl epoxy monomer synthesis
A. ten trifluoro oxetanes synthesis
In the 1000mL there-necked flasks protected equipped with thermometer, ice-water bath and magnetic stirring apparatus, 16.9g acetic acid alkene butyl is added
Ester, 28.1g sodium acid carbonates, 55.3g sodium dithionites, 241g DMFs, 225g water is added dropwise 73.2g perfluors
Hexyl iodide alkane, -13 DEG C of reaction 6h, is slowly increased to room temperature, insulation reaction 3h.After reaction terminates, with 3 extractions of 180g benzotrifluorides point
Take.Combining extraction liquid, washes 3 times, and the trifluoro hexyl -3- iodine butyl acetate solutions of 4- ten are obtained, and is added directly into
In 1000mL there-necked flasks, the sodium hydroxide solution that 510g mass concentrations are 10% is added dropwise, is incubated and reacts 6h in 15 DEG C.Reaction knot
It is layered after beam.Organic layer is washed 3 times, dry, vacuum distillation, obtains 3-（The trifluoro heptyl of 1H, 1H- ten）Oxetanes 35.1g, receives
Rate is 53.5%.
B. ten trifluoro-epoxy propanes synthesis
In the 1000mL there-necked flasks protected equipped with thermometer, ice-water bath and magnetic stirring apparatus, 14.5g acetic acid pi-allyls are added
Ester, 27.0g sodium acid carbonates, 55.1g sodium dithionites, 219g DMFs, 220g water is added dropwise 73.4g perfluors
Hexyl iodide alkane, -15 DEG C of reaction 4h, is slowly increased to room temperature, insulation reaction 6h.After reaction terminates, divided 3 times with the benzotrifluoride of 185g
Extraction.Combining extraction liquid, washes 3 times, and the trifluoro hexyl -2- iodine propyl-acetic acid ester solutions of 3- ten are obtained, and is added directly into
In 1000mL there-necked flasks, the sodium hydroxide solution that 520g mass concentrations are 10% is added dropwise, is incubated and reacts 6h in 20 DEG C.Reaction knot
It is layered after beam.Organic layer is washed 4 times, dry, vacuum distillation, obtains 1H, the trifluoro heptyl expoxy propane 39.8g of 1H- ten, and yield is
68.4%。
（2）Fluorine-containing alkyl, polyether synthesis
A. ring opening copolymer
By the 3- of 36.4g（The trifluoro heptyl of 1H, 1H- ten）The trifluoro heptyl expoxy propane of the 1H of oxetanes and 28.9g, 1H- ten
It is well mixed, obtain mix monomer.
In the there-necked flask equipped with thermometer, agitator and constant pressure funnel, add under nitrogen protection, add
55g dichloromethane and 0.45g1,4- butanediol, ice-water bath are cooled to 2 DEG C, are slowly added into 0.6gBF3.Et2O, temperature about rises 4
DEG C, after reacting 45 minutes, the above-mentioned mix monomer for preparing is added dropwise, add within 1 hour.After adding, 25 DEG C are warming up to, continue to react
24h.Stop reaction.
B. post-process
Above-mentioned ring-opening polymerization liquid adds 12g2.5%Na2CO3The aqueous solution, terminating reaction, stirring reaction uses 165g after 2 hours
Dichloromethane is extracted 3 times, merges organic layer, adds drier anhydrous sodium sulfate drying 1 hour, after being filtered to remove drier, filter
Liquid boils off solvent and obtains product 51.1g, yield 78.6%.
（3）Polyurethane synthesizes
Equipped with magnetic stirring apparatus, thermometer, reflux condenser and N2In the 500ml there-necked flasks of protection device, 35g third is added
Ketone, 20g benzotrifluorides add the 28g dihydroxylic alcohols of copolyether containing fluoroalkyl, and stirring and dissolving is subsequently adding the fourth of 0.4g tin dilaurates two
Ji Xi（DBTL）, after being warming up to 55 DEG C, 9.5g toluene di-isocyanate(TDI)s are added dropwise（TDI）, 35min adds.Add anti-after 55 DEG C
Answer 5 hours, after reaction fluid viscosity increases, add 1.0g BDOs, after continuing to react 3 hours, vacuum distillation removes big
Partial solvent, adds acetone/benzotrifluoride while hot（Volume ratio 1:1）Mixed solvent, is 56.5g, matter by product dilution to weight
Amount concentration is 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）Arrange application
A. emulsification treatment
By AEO-6 and 1.6g part of cationic surfactant octadecyl three of 1.5g nonionic surfactants in beaker in tall form
Methyl bromide ammonium is added in 100 parts of deionized waters, stirring and dissolving.8000 revs/min of rotating speed high shear agitations, are slowly added dropwise
The 25.3g of polyurethane solutions containing fluoroalkyl, is added for 15 minutes, and high-speed stirred is continued 15 minutes after adding, and obtains uniform emulsion.
B. textile finishing
The fluorochemical urethane that will be obtained is diluted to 40g/L, is applied to Cotton Fabric, and technological process is：Infiltration（30min, bath raio
1:20）→ bis- leachings two are rolled（Pick-up 100%, room temperature）→ preliminary drying（90℃×3min）→ bake（160℃×3min）.
（5）Contact angle is tested
Finishing of cotton textiles tests the contact angle to water, and referring to accompanying drawing 5, contact angle is 144.6o to test result.
Claims (10)
1. a kind of preparation method of the textile water repellent finish liquid based on fluorochemical urethane, it is characterised in that comprise the following steps,
Nonionic surfactant and cationic surfactant are added in deionized water, polyurethane containing fluoroalkyl are then added dropwise molten
Liquid, stirring obtains the textile water repellent finish liquid based on fluorochemical urethane；The chemical structural formula of the fluorochemical urethane is：
Wherein, w is 2 ~ 7；M is 3 ~ 100；N is 1 ~ 100；X is 1 ~ 50；Y is 1 ~ 20；
R is-(CH2)6- or-Ph (CH3)-；R ' is-(CH2)4-。
2. the preparation method of the textile water repellent finish liquid of fluorochemical urethane is based on according to claim 1, it is characterised in that
Comprise the following steps, the dihydroxylic alcohols of copolyether containing fluoroalkyl, the fourth of tin dilaurate two are added after ketones solvent, fluorine-containing solubilizer are mixed
Ji Xi；Then in diisocyanate is added dropwise at 40~65 DEG C, react 1~12 hour；BDO is subsequently adding, continues to react
1~12 hour, obtain polyurethane containing fluoroalkyl.
3. the preparation method of the textile water repellent finish liquid of fluorochemical urethane is based on according to claim 2, it is characterised in that：
The ketones solvent is any one in acetone, butanone or cyclohexanone；The fluorine-containing solubilizer is benzotrifluoride and 1,3- bis-
（Trifluoromethyl）Any one in benzene；The diisocyanate is toluene di-isocyanate(TDI)（TDI）With the isocyanide of hexa-methylene two
Acid esters（HDI）In any one；Ketones solvent, fluorine-containing solubilizer, the dihydroxylic alcohols of copolyether containing fluoroalkyl, di lauric dibutyl
Tin, diisocyanate, the mass ratio of 1,4- butanediols are（10~50）∶（10~30）∶（10~50）∶（0.2~1）∶（5~30）
∶（0.4~3）；The time that diisocyanate is added dropwise is 15 minutes~1 hour.
4. the preparation method of the textile water repellent finish liquid of fluorochemical urethane is based on according to claim 3, it is characterised in that：
Alkyl chloride varsol and initiator are added in the reactor；Then in adding BFEE at 0~10 DEG C；Then it is added dropwise
Fluorine-containing oxetanes and fluorine-containing epoxy monomer, carry out ring-opening polymerization, obtain the dihydroxylic alcohols of copolyether containing fluoroalkyl；Described
Beginning agent is any one in ethylene glycol, 1,4- butanediols, 1,6-HD；Mix allyl acetate, sodium acid carbonate, connect two
Sodium sulfite, organic solvent, water, then at -20~5 DEG C, are added dropwise perfluoroalkyl iodides, carry out synthetic reaction, and alkali is then added dropwise
Liquid, carries out cyclization, prepares fluorine-containing epoxy monomer；It is mixing acetic acid alkene butyl ester, sodium acid carbonate, sodium dithionite, organic
Solvent and water, then at -20~5 DEG C, are added dropwise perfluoroalkyl iodides, carry out synthetic reaction, are subsequently adding alkali lye and are cyclized
Reaction obtains fluorine-containing oxetanes.
5. the preparation method of the textile water repellent finish liquid of fluorochemical urethane is based on according to claim 4, it is characterised in that：
The perfluoroalkyl iodides are seven fluorine iodopropanes, nine fluorine iodobutanes, ten trifluoro iodohexanes, 15 fluorine iodine heptane, 17 fluorine iodo-octanes
In any one；The organic solvent is N,N-dimethylformamide；The alkali lye is in the NaOH aqueous solution, the KOH aqueous solution
Any one；The alkyl chloride varsol is any one in dichloromethane, dichloroethanes, chloroform, carbon tetrachloride
Kind.
6. the preparation method of the textile water repellent finish liquid of fluorochemical urethane is based on according to claim 1, it is characterised in that：
The nonionic surfactant is AEO-6；The cationic surfactant is Cetyltrimethylammonium bromide or 18
Alkyl trimethyl ammonium chloride；Solvent is ketones solvent/fluorine-containing solubilizer mixed liquor in the polyurethane solutions containing fluoroalkyl；It is described
Fluorine-containing solubilizer is benzotrifluoride and 1,3- bis-（Trifluoromethyl）Any one in benzene；It is added dropwise containing fluoroalkyl polyurethane solutions
Time is 10~20 minutes.
7. the preparation method of the textile water repellent finish liquid of fluorochemical urethane is based on according to claim 1, it is characterised in that：
Nonionic surfactant, cationic surfactant, deionized water, the mass ratio containing fluoroalkyl polyurethane solutions are（1.5~
2）∶（1.5~2）∶（100~120）∶（25~32）；The mass concentration of the fluoroalkyl polyurethane solutions is 60~75%.
8. it is according to claims 1 to 7 any one be based on fluorochemical urethane textile water repellent finish liquid preparation method
The textile water repellent finish liquid based on fluorochemical urethane for preparing.
9. a kind of method of textile water repellent finish, it is characterised in that comprise the following steps, is based on described in adjustment claim 8
The solid content of the textile water repellent finish liquid of fluorochemical urethane is 40g/L；Then by textile according to infiltrating, pad, preliminary drying, baking
The technique of roasting carries out water repellent finish.
10. application of the textile water repellent finish liquid based on fluorochemical urethane in textile water repellent finish described in claim 8.
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