CN106480737B - A kind of preparation method and applications of end-sealed type fluorine-containing aqueous polyurethane finishing agent - Google Patents

A kind of preparation method and applications of end-sealed type fluorine-containing aqueous polyurethane finishing agent Download PDF

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CN106480737B
CN106480737B CN201611075003.7A CN201611075003A CN106480737B CN 106480737 B CN106480737 B CN 106480737B CN 201611075003 A CN201611075003 A CN 201611075003A CN 106480737 B CN106480737 B CN 106480737B
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reaction
finishing agent
diisocyanate
aqueous polyurethane
sealed type
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CN106480737A (en
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冉巍巍
李荣龙
杨双兰
陈荣平
王连军
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Hunan Institute of Engineering
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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
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • 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
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • 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
    • 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
    • D06M2200/01—Stain or soil resistance
    • 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
    • D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
    • 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
    • D06M2200/50—Modified hand or grip properties; Softening compositions

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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)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention discloses a kind of preparation method and applications of end-sealed type fluorine-containing aqueous polyurethane finishing agent, is related to Textile Engineering field.The end-sealed type fluorine-containing aqueous polyurethane finishing agent is by fluorine-containing triol R1, polyether triol R2With diisocyanate R3It first passes through step-reaction polymerization and generates performed polymer P1f, using end-capping reagent RyIt is obtained after sealing end.After gained end-sealed type fluorine-containing aqueous polyurethane finishing agent of the invention is used for finish fabric, pliability is good, comfortable feel, has good hydrophily, is not easy fold, breathes freely and soil repellency can be excellent, have good industrial applications foreground.

Description

A kind of preparation method and applications of end-sealed type fluorine-containing aqueous polyurethane finishing agent
Technical field
The invention belongs to Textile Engineering fields, and in particular to a kind of preparation side of end-sealed type fluorine-containing aqueous polyurethane finishing agent Method and its application.
Background technology
Aqueous polyurethane has many advantages, such as non-ignitable, nontoxic, pollution-free, energy saving and easy to process using water as medium； Polyurethane has excellent filming performance and water resistance, has been widely used in the finishing functions of textile；However it is aqueous poly- Hydrophilic segment included in urethane has higher surface free energy, has seriously affected the water and oil repellant of fabric after arranging Can, the method for making up this disadvantage is exactly that the fluorine-containing groups of low-surface-energy are introduced in polyurethane structural.Fluoropolymer, which has, to be permitted Mostly excellent inside and surface property such as has good weatherability and water and oil repellant, low frictional properties, corrosion resistance and low table The performances such as face energy, fluorine element are introduced into the main chain and side chain of polyurethane to reduce the surface tension of polyether polyols.Cotton color Woven fabric is first to dye cotton warp, weft yarn respectively, is then weaved through warping, cotton dyed fabric texture comfortable ventilating, flower pattern Pattern is beautiful, has three-dimensional sense, and due to using ingrain, dyestuff penetration is strong, therefore general color fastness is preferable, but fabric is contaminating The effect of various mechanical frictions and dyeization auxiliary agent is subjected in whole process, the color-woven fabric of not post-treated processing, feel It is very poor, while in order to meet the needs of people are to different-style fabric, cotton dyed fabric enterprise is all in the function of carrying out various fabrics It arranges, reaches the maximum added value of pursuit.The present invention first designs a series of fluorinated isocyanates of synthesis, fluorinated ethylene alcohol and fluorination Polyethers is used in combination end-capping reagent appropriate to carry out polyurethane end group then by a series of fluorochemical urethanes of combinatorial compound appropriate Sealing end, when use, are unsealed under catalyst appropriate and temperature appropriate, are added other auxiliary agents and are carried out work(to cotton dyed fabric It can arrange, the fabric finally obtained refuses dirty, crease-resistant, ventilative and soft comfortable feel with hydrophilic.
Invention content
It is an object of the invention to synthesize a kind of preparation method of end-sealed type fluorine-containing aqueous polyurethane finishing agent and answered In being arranged with cotton dyed fabric, fabric obtains after its arrangement hydrophilic refuses dirty, crease-resistant and ventilative a variety of specific functions such as smooth.
The technical scheme is that：
A kind of preparation method of end-sealed type fluorine-containing aqueous polyurethane finishing agent, the end-sealed type fluorine-containing aqueous polyurethane finishing agent With PfU is indicated, passes through R1、R2、R3Gradually polymerization obtains fluorochemical urethane performed polymer P1f, P1fUsing end-capping reagent RyIt is blocked It is obtained after reaction, PfThe synthesis path of U such as (a) is shown,
Wherein, R1For fluorine-containing triol, structural formula is such as shown in (I)：
Wherein, RxIndicate alkyl, optimizing alkyl or alkenyl, more preferably (CH2)a+2,-CH=C (CH2)bCH2Or-CH=C (CH3)(CH2)bCH2, the integer that a is 0~16, the integer that b is 0~15, the integer that m is 1~10；
R2For polyether-tribasic alcohol, structural formula is such as shown in (II)：
Wherein, p, q are 1~18 integer,
R3Can be aliphatic diisocyanate and aromatic diisocyanate for diisocyanate；
PfU has the advantages that storage, transport and using very easily, passes through for example fluorine-containing triol R of parameter of change each component1 Middle m, polyether-tribasic alcohol R2Middle p, q and different diisocyanate R3, the multifunction finishing agent of different performance can be obtained.
Further, RxIt is preferred that CH=CH, CH2CH2, CH=CHCH2、CH2CH2CH2CH2, CH=C (CH3)CH2Or CH= CHCH2CH2。
Further, R3For aliphatic diisocyanate, mainly there are hexamethylene diisocyanate (HDI), two isocyanide of isophorone Acid esters (IPDI), dicyclohexyl methyl hydride -4,4'- diisocyanate (H12MDI), 2,2,4- trimethyls hexamethylene diisocyanate (TMDI), methylcyclohexane diisocyanate (HTDI)；Aromatic diisocyanate, mainly have toluene di-isocyanate(TDI) (TDI), Methyl diphenylene diisocyanate (MDI), naphthalene diisocyanate (NDI), the secondary methyl diisocyanate of durol (TMXDI), benzene dimethylene diisocyanate (XDI) etc. considers, more from cost of material and to whether fabric generates yellowing Preferably hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), two isocyanides of dicyclohexyl methyl hydride -4,4'- Acid esters (H12MDI), toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI) and naphthalene diisocyanate (NDI).
Further, end-capping reagent RyPreferably NaHSO3Or KHSO3。
Further, fluorine-containing triol R1Synthesis path indicated with reaction process (b), specifically comprise the following steps：
(1) it selects sodium dithionite to make initiator, causes perfluoroalkyl iodides, that is, compound 5 and addition reaction occurs for ethylene The Addition on ethylene object i.e. compound 4 of perfluoroiodoalkyl is obtained, reaction temperature is 40~60 DEG C, preferably 1~3 hour time, temperature mistake Low then reaction speed is slower, and the excessively high then easy generation by-product sulphite of temperature, addition reaction only needs the company two of catalytic amount A small amount of acid absorbent, such as NaHCO can be added in sodium sulfite3、CaO、NaHPO4, NaOH etc..Reaction carries out in water, Ke Yijia Enter a small amount of acetonitrile and methanol as cosolvent.To reacting without significant impact whether the addition of above-mentioned acid absorbent and cosolvent. In addition, the pressure of ethylene, to reacting also without significant impact, in the range of 0.5~2.5MPa, reaction can be carried out smoothly, Conversion ratio can reach 100% in general 3 hours；
(2) alkene, that is, compound 3 of the elimination reaction generation containing fluoroalkyl, reaction knot occur under alkaline condition for compound 4 There is the solid of white to generate after beam in reaction bulb, be KI, be dissolved in water, mixed liquor layering detaches organic layer, and water layer directly carries out Distillation；Experiment finds that water layer is extracted with dichloromethane, is then combined with organic phase distillation, has azeotropic mixture generation, therefore reacting Post-processing in do not extract directly distillation and compound 3；
(3) in no underwater operation, catalyst, compound 3 and HSiCl are made with Karstedt ' s3Addition reaction occurs to generate 2, Karstedt ' s catalyst reaction activity of silane compound, that is, compound is big, and has regioselectivity to the addition of double bond；
(4) alkyl R is introduced by grignard reactionx, halogenated hydrocarbons is generated into alkyl halogenation in anhydrous ether and magnesium metal effect Magnesium, that is, alkyl Grignard Reagent, when Grignard Reagent processed, most importantly avoid side reaction, concentration and institute of the halogenated hydrocarbons in ether The grignard reagent concentration of formation, for whether side reaction occurring having a great impact.The concentration of both certain substances is smaller, into The chance of row side reaction is smaller, but excessive ether and excessive liquor capacity, and not only economic effect is bad, and operation is not also square Just.Therefore, be there are one concentration appropriate, this is also related with the activity of halogenated hydrocarbons.For not very active halogenated hydrocarbons, such as 1- Bromobutane, bromobenzene etc., they are preferably 1 with the molar ratio of ether：4~6, more preferably 1：5；Compare active halogenated hydrocarbons, than Such as bromoethane, iodomethane etc., they should preferably 1 with the molar ratio of ether：7~9, more preferably 1：8；And as very active halogenated Hydrocarbon such as allyl bromide, bromoallylene etc., they should preferably 1 with the molar ratio of ether：9~12, more preferably 1：10；
Wherein, RxIndicate alkyl, optimizing alkyl or alkenyl, more preferably (CH2)a+2,-CH=C (CH2)bCH2Or-CH=C (CH3)(CH2)bCH2, the integer that a is 0~16, the integer that b is 0~15；Further preferably CH=CH, CH2CH2, CH= CHCH2、CH2CH2CH2CH2, CH=C (CH3)CH2Or CH=CHCH2CH2；The integer that m is 1~10；X indicates halogen atom, preferably Cl、Br、I；
Grignard Reagent alkyl magnesium halide obtained occurs coupling reaction with compound 2 and obtains compound 1, i.e. organic-magnesium Object is nucleopilic reagent, therefore the Grignard Reagent with cloud density compared with macoradical, such as bromination allyl magnesium, with larger Activity.So during grignard reaction, centainly it is noted that the concentration of Grignard Reagent should not be excessive, and will under stiring slowly It is added dropwise, to avoid coupling.In addition, reaction temperature will also influence the reactivity of Grignard Reagent：Temperature is excessively high, allyl Grignard examination Agent is also easy to happen coupling.Therefore, in Grignard Reagent processed, controlling reaction temperature is at 0~5 DEG C.When preparing Grignard Reagent, need The iodine grain that catalytic amount is added carrys out initiation reaction, and purpose may be to generate the magnesium iodide with catalytic action or be only Corrosion magnesium chips surface and promote to react；
(5) compound 1 is in monoborane (BH3) and THF exist and alkaline condition under with H2O2Anti- raw oxidation to get to containing Fluorine triol R1；Monoborane (BH3) be easy to generate alkyl borane with alkene addition, due to the electrophilicity of boron atom, hydroboration Reaction has very high regioselectivity for terminal olefin reaction.Alkyl borane can change many functional groups, and most important Be by alkaline H2O2And it is oxidized to corresponding alcohol.
It is worth noting that each compound is distinguished with following number.
Application of the end-sealed type fluorine-containing aqueous polyurethane finishing agent that above-mentioned preparation method obtains in cotton dyed fabric arrangement, Cotton dyed fabric is dipped in containing finishing agent PfU, it in the dressing liquid of catalyst and cationic softener, soaks, roll alternating, then 70 ~100 DEG C dry 3~5 minutes, and 130~170 DEG C bake 3~5 minutes.
Further, the preferred NaHCO of catalyst3。
Further, quaternary, fatty acid ester type, polyethylene, organic siliconresin type can be selected in cationic softener Deng wherein quaternary ammonium softener application is most, and type is also very much, considers preferred quaternary softening agent from cost and actual effect CMA-100 (production of TaiWan, China Ju Yi Chemical Co., Ltd.s), many yarn-dyed fabric factories select the product at present.
Further, it soaks, roll alternately preferably twice, i.e., two leachings two are rolled (pick-up is up to 90-100%).
Performance characterization
Hydrophily is tested：
It is dripped a drop water to the fabric surface sprawled of level from from from fabric 2cm height with standard dropper (25 drops/mL), and Start timing, when droplet reflectance is gradually reduced to a completely non-reflective watermark, the stop recording time.
Hand valuation
Using digital palpation for examination of trauma and grading.Hand valuation is carried out to the cloth specimen arranged by 5 professionals, is graded by 1~5,5 Grade is best, and feel is most soft smooth, and former cloth hand feel evaluation is 1 grade, is worst, results are averaged.
Huge dirt evaluation
Huge dirt performance is according to The Hydrocarbon Resistance Test Method (AATCC Test Method 118-2002) test.Normal fluid and its corresponding grade are as shown in table 1.
Table 1 is used to refuse the normal fluid and its corresponding grade of oil test
aVol%In n-hexadecane
Sample is lain in smooth plane, phase selection should be tested with reagent step by step from low to high, at specimen surface interval Certain distance drips 2 droplet test solutions simultaneously, often drips diameter about 5mm, Wet Out of the observation drop in 30s.If not soaked in 30s Cloth cover, then sample cloth experiment is continued until can't pass by the grade, take finally by rank.The correct mark of fabric wetting As if fabric deepens at oil droplet, oil droplet disappears, the imbibition of oil droplet outer ring or oil droplet flash of light disappear.
Fabric crease-resistant performance test method
Wrinkle resistance test method selection AATCC 66-1998, instrument are：Fabric elasticity test instrument, the U.S. P500570.It is balanced 24 ± 4 hours under conditions of relative humidity 65 ± 2%, 21 ± 1 DEG C of temperature before sample test.
The beneficial effects of the present invention are：
(1) fluorine-containing groups of low-surface-energy are introduced into polyurethane structural by the present invention, overcome polyurethane as weaving Product functional finishing agent has the shortcomings that high surfaces free energy；
(2) waterborne blocked polyurethane deblocking temperature is low, uses NaHSO3Or KHSO3Make end-capping reagent, uses NaHCO3It urges Agent, these are all common industrial chemicals in textile dyeing and finishing industry, operation and easy to use, non-toxic, no nuisance residual, Product of the present invention is easy to store and transport simultaneously；
(3) present invention gained end-sealed type fluorine-containing aqueous polyurethane finishing agent is for after finish fabric, pliability to be good, feel Comfortably, there is good hydrophily, be not easy fold, breathe freely and soil repellency can be excellent.
Specific implementation mode
The present invention is described in further details with reference to specific embodiment, but the present invention is not limited thereto.
PfU is specific as follows to cotton dyed fabric textile finishing：
Experiment test fabric：100% Cotton Colored Woven Fabric, specification：Cloth weight 118g/m2, density (warp：133/10cm, Latitude：117/10cm), through enzyme desizing, desizing before arranging：Pure cotton yarn-dyed fabric is used into HT333 medium temperature starch at 60 DEG C Enzyme 2g/L desizing 30min, draining are washed 2 times, and water inlet is warming up to 80 DEG C of processing 15min, and draining, into washing 2 times, drying is whole after Reason.
Finishing technique：Fabric functional is organized on the vertical letter Monforts forming machines of MATEX 6000STANDARD and carries out, and will knit Object is immersed in containing finishing agent PfU, catalyst (NaHCO3) and the dressing liquid of cationic softener CMA-100 in, two leachings two are rolled and (are rolled Remaining rate 90-100%), it is dried at 80 DEG C 3 minutes, 160 DEG C bake 3 minutes.
Formula is as follows：
PfU (%owb)：Concentration changes to 5.0 from 2.0, amplitude of variation 0.5；NaHCO3：5g/l；CMA-100：2g/l.
Embodiment 1
By perfluorooctane iodide (520g, 1.16mmol), Na2S2O4(20.9g, 0.12mol), Na2HPO4(21.5g), Acetonitrile (900mL) and water (300mL) are added in 2L autoclaves, and are passed through ethylene gas, and pressure is made to reach 40atm.In 40-45 Sustained response finds that ethylene pressure significantly decreases after 3 hours at DEG C.19F NMR tracking reactions find that raw material is reacted complete Entirely, stop reaction, excessive ethylene gas is discharged, detach lower organic layer, washing, saturated common salt is washed, then through anhydrous slufuric acid Sodium dry, organic solvent is removed under vacuum, obtain compound perfluorooctane ethyl iodide be white solid (525g, yield 95%, mp56-57℃)。1H NMR (300MHz, CDCl3)δ：2.3-3.1 (m, 2H), 3.1-3.5 (m, 2H).
19F NMR (282MHz, CDCl3)：- 81.38 (t, J=9.9Hz, 3F), -113.73--113.66 (m, 2F), - 121.96--121.91 (m, 6F), -122.26 (s, 2F), -123.15 (s, 2F), -126.63 (s, 2F).
Be added equipped with reflux condensing tube, in the 250mL three-necked flasks of dropping funel and thermometer KOH (7.0g, 0.1mol) with methanol 30mL, magnetic agitation is uniform at room temperature, and compound perfluorooctane ethyl iodide (47.4g, 0.1mol) is dissolved in In 100mL Freon-113 solvents, then this solution is slowly added dropwise in the methanol solution of KOH.Exothermic heat of reaction simultaneously has a large amount of Solid generate.After being added dropwise, it is heated to reflux 3 hours.Reaction mixture is poured into 250mL water, organic layer is detached, is used in combination Anhydrous Na2SO4It dries and distills to obtain compound perfluorooctyl ethylene (28.0g, yield 81%).1H NMR (300MHz, CDCl3)δ：5.8 (m, 3H).19F NMR (282MHz, CDCl3)：- 81.24 (t, J=9.8Hz, 3F), -114.30 (m, 2F), -121.96--121.91 (m, 6F), -123.12 (s, 2F), -124.02 (s, 2F), -126.51 (s, 2F).
Be added equipped with reflux condensing tube, in the 250mL three-necked flasks of dropping funel and thermometer compound 5 (34.6g, 0.1mol) and Karstedt ' s catalyst (0.2mL), under nitrogen protection by HSiCl3(20mL) is added slowly thereto.It is added dropwise After, the reaction was continued at 60 DEG C 4 hours for reaction mixture.Then the compound perfluoro capryl second being evaporated under reduced pressure Base trichlorosilicane is colourless liquid (38.3g, yield 80%, 105-110 DEG C of boiling point/40mmHg).
Under nitrogen protection, magnesium chips (10.0g) and anhydrous ether (150mL) are added to the three-necked flask of 500mL dryings In, several iodine grains are added and are maintained at 0-5 DEG C.The mixed solution of a few drop allyl bromide, bromoallylenes and anhydrous ether is first added dropwise, waits for that reaction causes After be further continued for be added dropwise allyl bromide, bromoallylene (30mL).It reacts highly exothermic, pays attention to controlling temperature at 0-5 DEG C.At 0-5 DEG C after being added dropwise The reaction was continued 2 hours.Then obtained allylic bromination magnesium solution is transferred in dropping funel under nitrogen protection, then slowly dripped It is added to equipped with compound perfluorooctylethyl group trichlorosilicane (24.5g, 0.05mmol) and anhydrous ether (150mL) and has returned In the three-necked flask of stream.State is maintained the reflux for, the reaction was continued 24 hours.After reaction, by the NH of saturation4Cl solution slowly drips It is added in reaction mixture.Organic layer is detached, water layer is extracted with ether.Merge organic layer, is washed with water, saturated salt solution It washes, anhydrous MgSO4It is dry, distillation obtain compound perfluorooctylethyl group three (acrylic) silicon (20.4g, yield 82%, b.p.88-90℃/0.7mmHg)。1H NMR (300MHz, CDCl3)δ：0.82-0.88 (m, 2H), 1.63-1.68 (m, 6H), 2.0-2.18 (m, 2H), 4.90-4.96 (m, 6H), 5.71-5.85 (m, 3H).
19F NMR (282MHz, CDCl3)：- 80.73 (t, J=9.9Hz, 3F), -113.73--113.66 (m, 2F), - 121.96--121.91 (m, 6F), -122.86 (s, 2F), -123.56 (s, 2F), -126.22 (s, 2F).
IR(KBr)：2978,1633,1243,1207,1153,901,812cm-1。
MS m/z (%) 489 (2), 388 (3), 151 (4), 101 (100).
Anal.Calcd for C19H19F17Si：C：38.10 H：3.2, Found：C:38.26 H：3.32%.
Under nitrogen protection, by the anhydrous THF of compound perfluorooctylethyl group three (acrylic) silicon (25g, 15mmol) (90mL) solution is slowly dropped to BF at 10 DEG C3.THF in THF (45mL) solution of (THF of 27mL, 1M) mixed liquor in room After the lower stirring of temperature 3 hours, the NaOH (30mL) of 3M is added, adds H2O2(30%, 4.5mL).Pay attention to maintaining the temperature at 20 DEG C of left sides The right side adds water to after continuing stirring 2 hours in above-mentioned reaction mixture.Use CH2Cl2Extract mixed liquor.Merge organic layer, uses Washing, saturated common salt washing, anhydrous MgSO4It is dry, remove solvent under vacuum.Purified with silica gel column chromatography, with CH2Cl2：CH3OH (15：1) fluorine-containing triol R is obtained as eluent1-1For white solid (6.3g, yield 76%).1H NMR (300MHz, CDCl3)δ： 0.55-0.62 (m, 6H), 0.72-0.80 (m, 2H), 1.52-1.61 (m, 6H), 1.98-2.05 (m, 5H), 3.62 (t, J= 7.0Hz, 6H).19F NMR (282MHz, CDCl3)：- 80.74 (t, J=9.9Hz, 3F), -113.72--113.59 (m, 2F), -121.95--121.90 (m, 6F), -122.79 (s, 2F), -123.50 (s, 2F), -126.20 (s, 2F).IR (KBr)：3338,2930,2875,1239,1210,1145,1065,894,745cm-1.MS m/z (%) 103 (100), 105 (71.57), 81 (48.95), 69 (29.23), 77 (27.46), 51 (18.27), 119 (17.66), 123 (15.80). Anal.Calcd for C19H25F17O3Si：C：34.98 H：3.86 Found：C:34.87 H：3.71%.
By fluorine triol R1-1(3.92g, 6.0mmol) and R3(1, hexamethylene-diisocyanate) (3.0g, 17.9mmol) is added to In 250mL three-necked flasks, be heated to 120 DEG C under nitrogen protection, insulation reaction 2 hours, by except water polyether-tribasic alcohol R25.55g (m=n=18,2.7mmol) is added in reaction mixture, continue insulated and stirred, using two positive definite amine titrations with Track reacts, until the quantity of isocyanate groups is reduced to 50% or so stopping reaction.Then it is down to room temperature and ethyl acetate is added (3.8g), after stirring evenly, by NaHSO3The aqueous solution (30mL) and absolute ethyl alcohol (70mL) of (1.47g, 14.2mmol) are same When be added in reaction mixture, reacted 1 hour under room temperature, stop reaction, using chemistry titration method test ending ratio be 89%, it is then added between dilute hydrochloric acid adjusting PH to the 3-4 of 0.1mol/L, obtained product PfU1For colourless transparent liquid.19F NMR (282MHz, DMSO-d6)δ：- 80.7 (s, 3F), -113.6 (s, 2F), -121.8 (m, 6F), -122.6 (s, 2F), - 123.4 (s, 2F), -126.0 (s, 2F), ppm.
Cotton yarn-dyed object is arranged according to the method described above, arrangement the results are shown in Table 2.
2 various concentration P of tablefU1Influence to cotton fabric performance after arrangement
*Washing times before test
PfU1It is a kind of polyurethane of end-sealed type, under heat or alkaline condition, it, which can be decomposed, releases free isocyanic acid Ester group, free isocyanates can be reacted with the hydroxyl on cellulose fibre, can also carry out reaction shape with itself Generating polyurethane elastomer, reaction mechanism are as follows：
Embodiment 2
By perflexane iodide (446g, 1mol), Na2S2O4(20.9g, 0.12mol), Na2HPO4(21.5g), acetonitrile (900mL) and water (300mL) are added in 2L autoclaves, and are passed through ethylene gas, and pressure is made to reach 40atm.At 40-45 DEG C Sustained response 3 hours.19F NMR tracking reactions find raw material, and the reaction was complete, stops reaction, excessive ethylene gas is discharged, Lower organic layer, washing, saturated common salt washing are detached, then is dried over anhydrous sodium sulfate, organic solvent is removed under vacuum, obtains white Color solid chemical compound perflexane ethyl iodide (331g, yield 90%, mp52-53 DEG C).
Be added equipped with reflux condensing tube, in the 250mL three-necked flasks of dropping funel and thermometer KOH (14.0g, 0.2mol) with methanol 40mL, magnetic agitation is uniform at room temperature, and compound perflexane ethyl iodide (74.0g, 0.2mol) is dissolved in In 100mL Freon-113 solvents, then this solution is slowly added dropwise in the methanol solution of KOH.Exothermic heat of reaction simultaneously has a large amount of Solid generate.After being added dropwise, it is heated to reflux 3 hours.Reaction mixture is poured into 250mL water, organic layer is detached, is used in combination Anhydrous Na2SO4It dries and distills to obtain compound perfluorohexyl ethylene (51.2g, yield 74%).
Equipped with reflux condensing tube, compound perfluoro hexyl is added in the 250mL three-necked flasks of dropping funel and thermometer Ethylene (34.6g, 0.1mol) and Karstedt ' s catalyst (0.2mL), under nitrogen protection by HSiCl3(20mL) slowly adds Enter wherein.After being added dropwise, the reaction was continued at 60 DEG C 4 hours for reaction mixture.Then the chemical combination being evaporated under reduced pressure Object perfluoro hexyl ethyl trichlorosilicane is colourless liquid (38.3g, yield 80%, 105-110 DEG C of boiling point/40mmHg).
Under nitrogen protection, magnesium chips (10.0g) and anhydrous ether (150mL) are added to the three-necked flask of 500mL dryings In, several iodine grains are added and are maintained at 0-5 DEG C.The mixed solution of a few drop allyl bromide, bromoallylenes and anhydrous ether is first added dropwise, waits for that reaction causes After be further continued for be added dropwise allyl bromide, bromoallylene (30mL).It reacts highly exothermic, pays attention to controlling temperature at 0-5 DEG C.At 0-5 DEG C after being added dropwise The reaction was continued 2 hours.Then obtained allylic bromination magnesium solution is transferred in dropping funel under nitrogen protection, then slowly dripped It is added to equipped with compound perfluoro hexyl ethyl trichlorosilicane (29.0g, 0.1mmol) and anhydrous ether (150mL) and has returned In the three-necked flask of stream.State is maintained the reflux for, the reaction was continued 24 hours.After reaction, by the NH of saturation4Cl solution slowly drips It is added in reaction mixture.Organic layer is detached, water layer is extracted with ether.Merge organic layer, is washed with water, saturated salt solution It washes, anhydrous MgSO4Dry, distillation obtains compound perfluoro hexyl ethyl three (acrylic) silicon (41.3g, yield 83%).
Under nitrogen protection, by the anhydrous THF of compound perfluorooctylethyl group three (acrylic) silicon (50g, 0.1mol) (90mL) solution is slowly dropped to BF at 10 DEG C3.THF in THF (45mL) solution of (THF of 27mL, 1M) mixed liquor in room After the lower stirring of temperature 3 hours, the NaOH (30mL) of 3M is added, adds H2O2(30%, 4.5mL).20 DEG C or so are maintained the temperature at, After continuing stirring 2 hours, add water in above-mentioned reaction mixture.Use CH2Cl2Extract mixed liquor.Merge organic layer, uses water It washes, saturated common salt washing, anhydrous MgSO4It is dry, remove solvent under vacuum.Obtain fluorine-containing triol R1-2For white solid (39.1g, Yield 71%).
By fluorine triol R1-2(11.0g, 20mmol) and R3(isophorone diisocyanate IPDI) (13.2g, 60mmol) adds Enter into 250mL three-necked flasks, be heated to 120 DEG C under nitrogen protection, insulation reaction 2 hours, by except water polyethers ternary Alcohol R237.64g (m=n=12,10mmol) is added in reaction mixture, is continued insulated and stirred, is utilized two positive definite amine titrations Tracking reaction, until the quantity of isocyanate groups is reduced to 50% or so stopping reaction.Then it is down to room temperature and acetic acid second is added Ester (3.8g), after stirring evenly, by NaHSO3The aqueous solution (30mL) and absolute ethyl alcohol (70mL) of (1.47g, 14.2mmol) It is added in reaction mixture, is reacted 1 hour under room temperature simultaneously, stop reaction, ending ratio is tested using the method for chemistry titration It is 89%, is then added between dilute hydrochloric acid adjusting PH to the 3-4 of 0.1mol/L, obtained product PfU2For colourless transparent liquid.
Cotton yarn-dyed object is arranged according to the method described above, arrangement the results are shown in Table 3.Contrast table 2 it is found that arrange after fabric Performance be varied from, pliability, hydrophily and recovering of folds angle are reduced, but change little, the huge dirt of fabric It can decline obvious.
3 various concentration P of tablefU1Influence to cotton fabric performance after arrangement

Claims (10)

1. a kind of preparation method of end-sealed type fluorine-containing aqueous polyurethane finishing agent, which is characterized in that the end-sealed type fluorine-containing aqueous is poly- Urethane finishing agent is with PfU is indicated, passes through R1、R2、R3Gradually polymerization obtains fluorochemical urethane performed polymer P1f, P1fUsing end-capping reagent RyIt is obtained after carrying out end capping reaction, PfThe synthesis path of U is such as（a）It is shown,
（a）
Wherein, R1For fluorine-containing triol, structural formula is such as（I）It is shown：
（I）
Wherein, RxIndicate alkyl, the integer that m is 1 ~ 10；
R2For polyether-tribasic alcohol, structural formula is such as（II）It is shown：
（II）
Wherein, p, q are 1 ~ 18 integer,
R3For diisocyanate, including aliphatic diisocyanate and aromatic diisocyanate.
2. the preparation method of end-sealed type fluorine-containing aqueous polyurethane finishing agent according to claim 1, which is characterized in that RxFor (CH2)a+2Or-CH=C (CH3)(CH2)bCH2, the integer that a is 0 ~ 16, the integer that b is 0 ~ 15.
3. the preparation method of end-sealed type fluorine-containing aqueous polyurethane finishing agent according to claim 1, which is characterized in that RxFor CH=CH、CH2CH2、CH=CHCH2、CH2CH2CH2CH2、CH=C(CH3)CH2Or CH=CHCH2CH2In one kind.
4. the preparation method of end-sealed type fluorine-containing aqueous polyurethane finishing agent according to claim 1, which is characterized in that R3For Hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride -4,4'- diisocyanates in aliphatic diisocyanate One kind in ester, 2,2,4- trimethyls hexamethylene diisocyanate, methylcyclohexane diisocyanate；Or it is aromatic diisocyanate Middle toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, naphthalene diisocyanate, two methine diisocyanate of durol One kind in ester, benzene dimethylene diisocyanate.
5. the preparation method of end-sealed type fluorine-containing aqueous polyurethane finishing agent according to claim 1, which is characterized in that sealing end Agent RyFor NaHSO3Or KHSO3。
6. the preparation method of end-sealed type fluorine-containing aqueous polyurethane finishing agent according to any one of claims 1 to 5, feature It is, fluorine-containing triol R1Synthesis path with reaction process（b）It indicates, specifically comprises the following steps：
(b)
（1）It selects sodium dithionite to make initiator, causes the addition reaction that perfluoroalkyl iodides are compound 5 and ethylene and obtain Addition on ethylene object, that is, compound 4 of perfluoroiodoalkyl, reaction temperature are 40 ~ 60 DEG C, and the reaction time is 1 ~ 3 hour；
（2）Compound 4 occurs elimination reaction and generates alkene, that is, compound 3 containing fluoroalkyl under alkaline condition, after reaction There is the solid of white to generate in reaction bulb, be KI, be dissolved in water, mixed liquor layering detaches organic layer, and water layer is directly steamed It evaporates；
（3）In no underwater operation, catalyst, compound 3 and HSiCl are made with Karstedt ' s3Addition reaction occurs and generates silanization Close object, that is, compound 2；
（4）Alkyl is introduced by grignard reaction, halogenated hydrocarbons is generated into alkyl magnesium halide, that is, hydrocarbon in anhydrous ether and magnesium metal effect Base Grignard Reagent, the molar ratio for controlling halogenated hydrocarbons and ether is 1：9~12；
Grignard Reagent alkyl magnesium halide obtained occurs coupling reaction with compound 2 and obtains compound 1, and Grignard Reagent is stirring Under the conditions of be slowly added dropwise, for controlling reaction temperature at 0 ~ 5 DEG C, catalyst is iodine grain；
（5）Compound 1 monoborane and THF exist and alkaline condition under with H2O2Oxidation reaction occurs to get to fluorine-containing triol R1；
。
7. the end-sealed type fluorine-containing aqueous polyurethane finishing agent that claim 1 to 6 any one of them preparation method obtains is in cotton color Application in woven fabric arrangement, which is characterized in that cotton dyed fabric is dipped in containing finishing agent PfU, catalyst and cationic softener Dressing liquid in, soak, roll alternating, then dried at 70 ~ 100 DEG C 3 ~ 5 minutes, 130 ~ 170 DEG C bake 3 ~ 5 minutes.
8. application of the end-sealed type fluorine-containing aqueous polyurethane finishing agent according to claim 7 in cotton dyed fabric arrangement, It is characterized in that, catalyst NaHCO3。
9. application of the end-sealed type fluorine-containing aqueous polyurethane finishing agent according to claim 7 in cotton dyed fabric arrangement, It is characterized in that, cationic softener is quaternary, fatty acid ester type, polyethylene or organic siliconresin type.
10. application of the end-sealed type fluorine-containing aqueous polyurethane finishing agent according to claim 7 in cotton dyed fabric arrangement, It is characterized in that, soaks, rolls alternately for twice, i.e., two leachings two are rolled.
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