CN105924573A - Perfluoroalkyl polyene ester waterproof agent, preparation method and application - Google Patents

Perfluoroalkyl polyene ester waterproof agent, preparation method and application Download PDF

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CN105924573A
CN105924573A CN201610414212.3A CN201610414212A CN105924573A CN 105924573 A CN105924573 A CN 105924573A CN 201610414212 A CN201610414212 A CN 201610414212A CN 105924573 A CN105924573 A CN 105924573A
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perfluoroalkyl
acid ester
emulsion
sulfur
heterochain
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CN105924573B (en
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李战雄
袁艳华
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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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
    • 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)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a perfluoroalkyl polyene ester waterproof agent, preparation method and application. The effective component of the waterproof agent is sulfur-containing long-heterochain perfluoroalkyl polyene ester copolymer, the sulfur-containing long-heterochain perfluoroalkyl polyene ester copolymer, butyl acrylate, methyl methacrylate and hydroxyethyl methacrylate make up a mixed monomer, and the perfluoroalkyl polyene ester waterproof agent is obtained by initiating polymerization of emulsion through initiator under the action of nonionic surfactant and anion surfactant. The finishing agent is applied to cotton fabric finishing and waterproof excellently. Moreover, the long-heterochain perfluoroalkyl group contains carbon and sulfur contained keys and is easily degradable, toxicity accumulation is avoided, and the perfluoroalkyl polyene ester waterproof agent isn't a fluorine-containing chemical. Meanwhile, the waterproof agent is made by traditional emulsion copolymerization, is moderate in reaction, low in equipment requirements, convenient in process, easy to control and suitable for industrial production.

Description

A kind of perfluoroalkyl polyolefin acid ester waterproofing agent, preparation method and application
Technical field
The present invention relates to a kind of perfluoroalkyl polyolefin acid ester waterproofing agent, preparation method and applications, be specifically related to one and contain Sulfur long heterochain perfluoroalkyl polyolefin acid ester emulsion and preparation method thereof, and it is applied to fabric waterproof Final finishing, belong to fine chemistry Product and weaving auxiliary chemicals field.
Background technology
People find during studying the waterproof oil-proof finishing of fabric, with containing fluoroalkyle compound to fabric Carry out processing and can give the waterproof new energy that fabric is excellent.Through the research and development of decades, fluorine-containing textile finishing agent commodity Changing and occupy the biggest market, the development of these fluorine-containing textile finishing agents is greatly enriched the research field of organic fluorine material, And become one of them important branch, obtain the very big concern of domestic and international researcher.
Nineteen fifty, Du Pont company of the U.S. takes the lead in using using politef (PTFE) emulsion as fabric finishing agent, And applied for patent.Nineteen fifty-three, Minnesota Mining and Manufacturing Company succeeds in developing with perfluorocarboxylic acid chromium complex CF3(CF2) nCO2CrOH is main The fabric finishing agent of body, the effective ingredient of this kind of waterproof oil-repellent agent of little molecule-type can be also the quaternary ammonium compound of perfluor amide, as CF3(CF2)6CONH (CH2) 3N+(CH3)2C2H5Br-.But, owing to washing fastness is poor, they are quickly preferably contained by performance Fluoroacrylate polymer is replaced, as 3M Developed in 1956 with " Scotchgard FC2208 " as representative The effective ingredient of FC series fabric finishing agent is fluorine-containing olefine acid ester polymer.
Fluorine-containing olefin(e) acid esters polymer can provide waterproof functional oil of refusing to have benefited from the fluoroalkyl on its side chain, these fluoroalkyls Protect with zigzag chain conformation and shield main polymer chain so that polymeric film has low-surface-energy, thus provides excellent preventing Water refuses functional oil.Wherein, perfluoro capryl polyacrylate is proved to be to provide the fabric of the most superior waterproof oil repellency whole Reason agent, thus obtain extensively application.But, more and more study confirmation, carbon chain lengths is complete equal to or more than 8 carbon atoms Fluoroalkyl in most of environmental conditions are tested all without hydrolysis, photodissociation or biodegradation, these long carbon chain perfluor alkyl occur The root that be proven with persistent environments inertia and bioaccumulation toxicity, environment can be worked the mischief.European Union member countries are at present Through completely forbidding perfluorinated octyl sulfuryl amine derivant (PFOS) the class finish materials producing and using containing Long carbon chain fluoroalkyl And derived product.
When using the carbon chain lengths short carbon chain fluoroalkyl less than 8 as side base, the fluoropolymer obtained then can drop naturally Solve.In recent years the synthesis having emerged in large numbers many short fluorocarbon chain compounds both at home and abroad is reported with applied research, and research finds, due to fluorine film table The short carbon chain perfluoroalkyl rigidity in face is little, nodeless mesh, it is impossible to form stable liquid crystal structure arrangement, the short carbon chain halothane constructed Base protecting film fluorocarbon chain Duan Yi after contact liq redirects, topples over, and easily makes basal body structure expose so that the shielding of fluorine film is lost , i.e. there is so-called short carbon chain perfluoroalkyl " surface reconstruction ", thus cause side base end trifluoromethyl (-CF in effect3) layer suffers Destroy and even cave in, thus do not reach effective liquid repellent function.
Summary of the invention
The present invention is directed to long carbon chain perfluor alkyl difficult degradation and have cumulative toxicity, short carbon chain fluoroalkyl crystallinity difference and refuse The contradiction of liquid poor effect, it is provided that a kind of sulfur-bearing long heterochain perfluoroalkyl olefine acid ester polymer waterproofing agent, it is thus achieved that polymer contain Perfluoroalkyl long heterochain side base, is prone to degraded, there is not cumulative toxicity because side base contains thia key, is not belonging to disable fluorine-containing Chemicals.Meanwhile, long heterochain perfluoroalkyl has again crystallinity and rigidity so that fluoropolymer surface conformational stability, thus There is superior liquid repellent function.This finishing agent is applied to Cotton Fabric and can obtain the most excellent waterproof effect.
To achieve the above object of the invention, the technical solution adopted in the present invention is to provide a kind of perfluoroalkyl polyolefin acid ester and prevents Water preparation, its effective ingredient is sulfur-bearing long heterochain perfluoroalkyl olefin(e) acid ester, butyl acrylate, methyl methacrylate and methyl-prop The copolymer of olefin(e) acid hydroxyl ethyl ester, the structural formula of copolymer is:
,
In formula, R=CH3 Or H；X=3～15；Y=10～30；Z=8～25；W=1～5.
Technical solution of the present invention also includes the preparation method of perfluoroalkyl polyolefin acid ester waterproofing agent as above, including list The preparation of body pre-emulsion and polyreaction, specifically comprise the following steps that
1, monomer pre-emulsion preparation
The most by weight, by 10～80 parts of sulfur-bearing long heterochain perfluoroalkyl olefin(e) acid esters, 10～20 parts of butyl acrylate, 1～10 part Methyl methacrylate and 0.5～5 part of hydroxyethyl methylacrylate mixing, obtain monomer mixture；
B. 0.1～1.5 portion of nonionic surfactant and 0.1～1.5 part of cationic surfactant are joined 50～250 In part deionized water, after stirring and dissolving, add monomer mixture, under high shear agitation conditions, prepare monomer pre-emulsion；Described Nonionic surfactant is fatty alcohol-polyoxyethylene ether AEO-9, appointing in fatty alcohol-polyoxyethylene ether AEO-6 or Span-80 Meaning one；Described cationic surfactant is octadecyl trimethyl ammonium chloride (1831), Cetyltrimethylammonium bromide In any one；
2, polyreaction
The most by weight, 0.1～2.0 part of initiator is dissolved in 10～30 parts of deionized waters, obtains initiator solution；Institute Stating initiator is any one in Ammonium persulfate., potassium peroxydisulfate or sodium peroxydisulfate；
B. monomer pre-emulsion prepared by step 1 is joined in reactor, be heated to 50～95 DEG C, drip initiator solution, drip Adding the time is 0.5～5 hour, adds rear insulation reaction 1～24 hours.
C. reactant liquor is cooled to room temperature, regulates pH to 6～7 with strong aqua ammonia, obtains a kind of perfluoroalkyl polyolefin acid ester waterproof Agent.
In technical solution of the present invention, the reaction temperature in polymerization procedure b is 70～85 DEG C, and the insulation reaction time is 1～6 hour.
The application of perfluoroalkyl polyolefin acid ester waterproofing agent of the present invention, uses it for the water-proof finish of textile.
Specifically comprising the following steps that of water-proof finish
A. open dilute: described fluoropolymer emulsion is diluted with deionized water, obtains textile finishing working solution；
B. dipping: bafta is immersed in working solution, dip time 30 minutes～2 hours, two leachings two roll, pick-up rate 90%～ 105%；
C. preliminary drying: preliminary drying temperature 90～105 DEG C, preliminary drying time 2～5 minutes；
D. bake: baking temperature 150～175 DEG C, bake time 1～5 minutes, obtain waterproof cotton fabric.
Sulfur-bearing of the present invention long heterochain perfluoroalkyl olefin(e) acid ester is 1H, 1H, 2H, 2H-7-thia perfluor undecyl Acrylate or 1H, any one in 1H, 2H, 2H-7-thia perfluor undecyl methacrylate, or both are with arbitrarily The monomer of weight ratio mixing.The structural formula of monomer is:
,
In formula, R=H or CH3 。
The preparation method of sulfur-bearing long heterochain perfluoroalkyl olefin(e) acid ester, step is as follows:
1, telomerisation
By weight, successively by 30～60 part of nine fluorine butyl tetrafluoro halogenation sulfur, 0.1～1 part of organic peroxide, 0.1～0.8 part Calcium carbonate and 10～50 parts of fluorine-containing aromatic hydrocarbon solvents join in reactor；Described organic peroxide is diphenyl peroxide first Any one in acyl, or tert-butyl peroxide；
Described nine fluorine butyl tetrafluoro halogenation sulfur are nine fluorine butyl tetrafluoro Disulfur dichlorides, nine fluorine butyl tetrafluoro sulfur bromide or nine fluorine butyl four Any one in fluorine iodine bisulfide；
Nitrogen atmosphere, temperature be 50～100 DEG C, under conditions of stir speed (S.S.) is 30～110 revs/min, logical in reactor Entering tetrafluoroethene 2～3 hours, the speed that is passed through of tetrafluoroethene is 5～15 parts/hour, and pressure is 0.4～0.8MPa；Stop logical After entering tetrafluoroethene, continue reaction 1～10 hour；
After stopped reaction, cooling, discharging, reactant mixture decompression is distilled off fluorine-containing aromatic hydrocarbon solvent, obtains product thia Perfluor nonyl halogen；
2, single Electron Transfer Reactions
By weight, by molten to 40～80 portions of thia perfluor nonyl halogen, 0.5～1.0 part of noble metal catalyst and 10～210 parts of ethers Agent joins in reactor；Described noble metal catalyst is any in tetrakis triphenylphosphine palladium or three (triphenylphosphine) Palladous chloride. A kind of；
It is 30～90 DEG C in nitrogen atmosphere, temperature, under conditions of stir speed (S.S.) is 30～110 revs/min, is passed through in reactor Ethylene 3～15 parts, react 1～3 hour；
After stopped reaction, cooling, discharging, reactant mixture decompression is distilled off ether solvent, obtains product thia perfluor nonyl Base ethylidene halogen；
3, esterification
By weight, put into 10～30 portions of olefin(e) acid salt and 5～50 parts of dry solvent DMFs in the reactor, stir Under the conditions of mixing, within the time of 30 minutes～2 hours, drip 59～70 portions of thia perfluor nonyl ethylidene halogen, after dropping, Insulation reaction 1～24 hours under conditions of temperature is 30～100 DEG C；
After stopped reaction, it is filtered to remove the by-product halogen of generation；10～50 parts of esters solvents are added, with deionization in filtrate After water washing, add 0.6～2.0 part of desiccant dryness and process 0.5～12 hour；Desiccant, decompression distillation are removed by filtration again Remove esters solvent, obtain faint yellow product sulfur-bearing long heterochain perfluoroalkyl olefin(e) acid ester.
Fluorine-containing aromatic hydrocarbon solvent described in technical solution of the present invention is benzotrifluoride or two (trifluoromethyl) benzene, or both press The mixed solvent mixed according to any mass ratio.Described ether solvent is oxolane, 1,4-dioxane or glycol dinitrate Any one in ether.Described olefin(e) acid salt is in acrylic acid silver, methacrylic acid silver, sodium acrylate or Sodium methacrylate. Any one.Described esters solvent is any one in ethyl acetate or methyl acetate.Described desiccant is anhydrous sulfur Any one in acid magnesium, anhydrous sodium sulfate or anhydrous calcium chloride.
Sulfur-bearing long heterochain perfluoroalkyl olefin(e) acid ester in the present invention by telomerizing, single Electron Transfer Reactions and esterification three step anti- Should prepare, product can be used for synthesizing low-surface-energy and eco-friendly fluoropolymer.Perfluoroalkyl halogenation sulfur has been disclosed Report ([1] Paul R. S. and John T. W. Preparation and utility of organic pentafluorosulfanyl-containing compounds. Chemical Reviews. 2015,115: 1230- 1190), the present invention is with nine fluorine butyl tetrafluoro Disulfur dichlorides therein or nine fluorine butyl tetrafluoro sulfur bromides as end-capping reagent, and tetrafluoroethene is adjusted After poly-reaction, obtaining the thia perfluoroalkyl halide oligomer of different polymerization degree, rectification obtains thia perfluor nonyl halogen and (is also called sulfur Miscellaneous halo Perfluorononane)；Again by itself and ethylene generation single Electron Transfer Reactions, obtain thia perfluor nonyl ethylidene halogen, thus A kind of heteroatomic long heterochain sulfur-bearing of sulfur-bearing long heterochain perfluoroalkyl olefin(e) acid ester of synthesis.Sulfur heteroatom long-chain in fluorine-containing olefin(e) acid ester Keep functional fluoropolymer base rigidity and crystalline while, long heterochain carbon containing thia key, it is easy to degraded, the most not there is accumulation Toxicity, overcomes long chain fluorine-containing function base rigidity and the contradiction of the unfriendly property of environment.Meanwhile, long fluorine chain maintains rigidity and crystallization Property, superior liquid repellent performance can be obtained.
Its reaction mechanism is: with nine fluorine butyl tetrafluoro halogenation sulfur as end-capping reagent, tetrafluoroethene telomerize that to obtain 5-thia complete Fluorine nonyl-1-halogen (is also called 5-thia-1-chlorine Perfluorononane)；Passed through with ethylene gas by 5-thia perfluor nonyl-1-halogen again Single electron additive reaction prepares 1H, 1H, 2H, 2H-7-thia perfluor undecyl-1-halogen；And further with olefin(e) acid salt generation ester Change reaction and obtain target product sulfur-bearing long heterochain perfluoroalkyl olefin(e) acid ester.Reaction equation is as follows:
,
In formula, R=H or CH3；X=Cl, Br or I.
The mechanism of the present invention is: with sulfur-bearing long heterochain perfluoroalkyl olefin(e) acid ester, butyl acrylate, methyl methacrylate and Hydroxyethyl methylacrylate is mix monomer, at nonionic surfactant and cationic surface active agent emulsification Under, the cation type emulsion having good stability is obtained by radical copolymerization, emulsion is configured to working solution and is applied to bafta Arrange, it is thus achieved that the most excellent waterproof effect.Copolyreaction formula is as follows:
In formula, R=CH3 Or H；X=3～15；Y=10～30；Z=8～25；W=1～5.
Compared with prior art, the present invention provide technical scheme its have the beneficial effects that:
1, in the fabric waterproof finishing agent that the present invention provides, functional fluoropolymer monomer is sulfur-bearing long heterochain perfluoroalkyl olefin(e) acid ester, rises The long heterochain perfluoroalkyl of waterproof action contains thia key, it is easy to degraded, there is not cumulative toxicity, is not belonging to disabling containing fluorine chemistry Product, belong to Green Textile Base auxiliary agent.
2, in perfluoroalkyl olefin(e) acid ester copolymer disclosed by the invention, base long heterochain perfluoroalkyl in side has crystallinity, because of This makes fluoropolymer surface conformational stability, has the liquid repellent function of excellence.
3, fabric finishing agent disclosed by the invention is cation type emulsion, is easy to electronegative with surface when padding fabric The fabric of lotus and fiber attract and absorption, and by cross-linking monomer chain link when baking with fiber surface activity radical reaction and carry For durable waterproof function.
4, the present invention uses emulsion polymerization to prepare fabric waterproofing agent, and reaction condition is gentle, and equipment requirements is low, reaction process letter Just, it is suitable for industrialized production and popularization and application.
Accompanying drawing explanation
Fig. 1 is perfluoroalkyl polyolefin acid ester infrared spectrogram prepared by the embodiment of the present invention one technical scheme.
Fig. 2～5 is perfluoroalkyl polyolefin acid ester emulsion finishing of cotton textiles prepared by various embodiments of the present invention technical scheme Contact angle test figure.
Detailed description of the invention
With embodiment, technical solution of the present invention is further described below in conjunction with the accompanying drawings.
Embodiment one
1, synthesis 1H, 1H, 2H, 2H-7-thia-perfluor undecyl methacrylate
A. by 46.9g nine fluorine butyl tetrafluoro sulfur bromide, 0.40g di-t-butyl peroxide, 0.4g calcium carbonate and 48g1,3-bis-(three Methyl fluoride) benzene solvent joins in reactor, seals, and after evacuation, it is filled with the air in nitrogen replacement reaction kettle, then takes out true Sky, displacement.Displacement 4 times altogether.After being warming up to 45 DEG C, tetrafluoroethene is passed through the insulation of this reactor, stirring reaction, controls stirring speed Rate is 55 revs/min, and the speed that is passed through of tetrafluoroethene is 12g/ hour, and pressure is 0.48MPa, stops being passed through tetrafluoro after 2 hours Ethylene, continues reaction 2 hours.After cooling, reactant mixture decompression being distilled off 1,3-bis-(trifluoromethyl) benzene, decompression is distilled Condition is temperature 50 C, and vacuum is 16mmHg.Obtain product thia perfluor nonyl bromine.
B. 65.4g thia perfluor nonyl bromine, 0.50g tri-(triphenylphosphine) Palladous chloride. are joined instead with 70g oxolane Answer in still, seal, after evacuation, be filled with the air in nitrogen replacement reaction kettle, then evacuation, displacement.Displacement 5 times altogether.Heat up After 40 DEG C, ethylene being passed through reactor, insulation, stirring reaction, controlling stir speed (S.S.) is 50 revs/min, reacts 2 hours, altogether Absorb ethylene 6.2g.After stopped reaction, cooling, discharging, reactant mixture is distilled off solvent, decompression distillation condition is temperature 55 DEG C, vacuum is 10mmHg.Obtain product thia perfluor nonyl ethylidene bromine.
Put into 20.3g methacrylic acid silver the most in the reactor and 18.1g is dried solvent DMF, stir Mixing, after being heated to 40 DEG C, drip 65.3g thia perfluor nonyl ethylidene bromine, time for adding is 0.6 hour, is incubated after adding React 5 hours.Stopped reaction, is filtered to remove Silver monobromide, adds after 48g ethyl acetate in filtrate, with deionized water wash 4 times, Washing uses deionized water 10ml every time.After having washed, add 1.5g anhydrous sodium sulfate and be dried 2 hours.Cross and filter desiccant, Decompression is distilled off solvent, and decompression distillation condition is temperature 40 DEG C, and vacuum is 10mmHg.Obtain thick pale yellow slurry, For 1H, 1H, 2H, 2H-7-thia-perfluor undecyl acrylate.
2, monomer pre-emulsion preparation
A. in beaker in tall form, it is sequentially added into 1H, 1H, 2H, 2H-7-thia-perfluor undecyl methacrylate 30.5g, 17.8g butyl acrylate, 8.2g methyl methacrylate and the mixing of 2.5g hydroxyethyl methylacrylate, obtain uniform flow good Good monomer mixture.
B. by 0.8g nonionic surfactant AEO-9 and 0.8g part cationic surfactant octadecyl trimethyl Ammonium bromide joins in 105 parts of deionized waters, stirring and dissolving, is subsequently adding above-mentioned monomer mixture, under 8000 revs/min of rotating speeds High shear agitation 15 minutes, obtains monomer pre-emulsion.
3, polyreaction
A. 0.6g Ammonium persulfate. is dissolved in 15g deionized water, obtains initiator solution, standby.
B. the above-mentioned monomer pre-emulsion prepared is added in reactor, be heated to 72 DEG C, drip at a slow speed and prepared Initiator solution, time for adding is 45 minutes, adds rear insulation reaction 3 hours.
C. reactant liquor is cooled to room temperature, regulates pH to 6～7 with strong aqua ammonia, obtains spreading unchecked the fluoropolymer emulsion of light.
4, water-proof finish
A. opening dilute: diluted with 2830g deionized water by above-mentioned fluoropolymer emulsion, obtaining active constituent content is 2% knit Thing housekeeping liquid.
B. dipping: be immersed in working solution by bafta, dip time 0.5 hour, (pick-up rate 100%) is rolled in two leachings two.
C. preliminary drying: preliminary drying temperature 102 DEG C, preliminary drying time 2 minutes.
D. bake: baking temperature 165 DEG C, bake the time 2 minutes, obtain waterproof cotton fabric.
5, test
With reference to GB4745-84 " textile fabric surface moisture-resisting assay method ", carrying out trickle test on trickle instrument, after arrangement, cotton is knitted The scoring of thing water proofing property is 90, and fabric face is without the adhesion globule, and oil repellency reaches 2 grades.Use the contact of OCA40Micro type surface Bafta after arranging is detected by angle instrument, and recording fabric face contact angle is 142.8, and its result sees accompanying drawing 2.
Embodiment two
1,1H, 1H, 2H, 2H-7-thia-perfluor undecyl methacrylate are synthesized according to embodiment one
2, monomer pre-emulsion preparation
A. in beaker in tall form, it is sequentially added into 1H, 1H, 2H, 2H-7-thia-perfluor undecyl methacrylate 28.8g, 18.1g butyl acrylate, 9.1g methyl methacrylate and the mixing of 2.6g hydroxyethyl methylacrylate, obtain uniform flow good Good monomer mixture.
B. by 0.8g nonionic surfactant AEO-6 and 0.8g part cationic surfactant octadecyl trimethyl Ammonium bromide joins in 110 parts of deionized waters, stirring and dissolving, is subsequently adding above-mentioned monomer mixture, under 8000 revs/min of rotating speeds High shear agitation 15 minutes, obtains monomer pre-emulsion.
3, polyreaction
A. 0.7g Ammonium persulfate. is dissolved in 20g deionized water, obtains initiator solution, standby.
B. the above-mentioned monomer pre-emulsion prepared is added in reactor, be heated to 78 DEG C, drip at a slow speed and prepared Initiator solution, time for adding is 45 minutes, adds rear insulation reaction 6 hours.
C. reactant liquor is cooled to room temperature, regulates pH to 6 ~ 7 with strong aqua ammonia, obtains spreading unchecked the fluoropolymer emulsion of light.
4, water-proof finish
A. opening dilute: diluted with 2750g deionized water by above-mentioned fluoropolymer emulsion, obtaining active constituent content is 2% knit Thing housekeeping liquid.
B. dipping: be immersed in working solution by bafta, dip time 1 hour, (pick-up rate 95%) is rolled in two leachings two.
C. preliminary drying: preliminary drying temperature 95 DEG C, preliminary drying time 3 minutes.
D. bake: baking temperature 168 DEG C, bake the time 2 minutes, obtain waterproof cotton fabric.
5, test
With reference to GB4745-84 " textile fabric surface moisture-resisting assay method ", carrying out trickle test on trickle instrument, after arrangement, cotton is knitted The scoring of thing water proofing property is 90, and fabric face is without the adhesion globule, and oil repellency reaches 2 grades.Use the contact of OCA40Micro type surface Bafta after arranging is detected by angle instrument, and recording fabric face contact angle is 139.4, and its result sees accompanying drawing 3.
Embodiment three
1, synthesis 1H, 1H, 2H, 2H-7-thia-perfluor undecyl acrylate
A. by 45.8g nine fluorine butyl tetrafluoro sulfur bromide, 0.5g dibenzoyl peroxide, 0.4g calcium carbonate and 55g benzotrifluoride are molten Agent joins in reactor, seals, after evacuation, is filled with the air in nitrogen replacement reaction kettle, then evacuation, displacement.Put altogether Change 4 times.After being warming up to 45 DEG C, tetrafluoroethene being passed through the insulation of this reactor, stirring reaction, controlling stir speed (S.S.) is 60 revs/min Clock, the speed that is passed through of tetrafluoroethene is 13g/ hour, and pressure is 0.50MPa, stops being passed through tetrafluoroethene after 2 hours, continues anti- Answer 3 hours.After cooling, reactant mixture decompression being distilled off benzotrifluoride, decompression distillation condition is temperature 50 C, vacuum For 20mmHg.Obtain product thia perfluor nonyl bromine.
B. 60.2g thia perfluor nonyl bromine, 0.60g tri-(triphenylphosphine) Palladous chloride. are joined instead with 80g oxolane Answer in still, seal, after evacuation, be filled with the air in nitrogen replacement reaction kettle, then evacuation, displacement.Displacement 5 times altogether.Heat up After 40 DEG C, ethylene being passed through reactor, insulation, stirring reaction, controlling stir speed (S.S.) is 60 revs/min, reacts 3 hours, altogether Absorb ethylene 5.8g.After stopped reaction, cooling, discharging, reactant mixture is distilled off solvent, decompression distillation condition is temperature 40 DEG C, vacuum is 16mmHg.Obtain product thia perfluor nonyl ethylidene bromine.
Put into 18.6g acrylic acid silver the most in the reactor and 20g is dried solvent DMF, stirring, heating After 40 DEG C, dripping 55.6g thia perfluor nonyl ethylidene bromine, time for adding is 1 hour, adds rear insulation reaction 3 hours. Stopped reaction, is filtered to remove the by-product Silver monobromide of generation, after adding 48g methyl acetate in filtrate, with deionized water wash 4 Secondary, washing uses deionized water 10ml every time.After having washed, add 1.5g anhydrous sodium sulfate and be dried 4 hours.Cross filter dry Agent, decompression is distilled off solvent, and decompression distillation condition is temperature 40 DEG C, and vacuum is 20mmHg.Obtain faint yellow thickness pulpous state Thing, is sulfur-bearing long heterochain perfluoroalkyl olefin(e) acid ester products 1H, 1H, 2H, 2H-7-thia-perfluor undecyl acrylate.
2, monomer pre-emulsion preparation
A. in beaker in tall form, it is sequentially added into 1H, 1H, 2H, 2H-7-thia-perfluor undecyl acrylate 28.6g, 17.6g Butyl acrylate, 8.5g methyl methacrylate and the mixing of 2.7g hydroxyethyl methylacrylate, obtain uniform flow good Monomer mixture.
B. by 0.9g nonionic surfactant AEO-9 and 0.8g part cationic surfactant octadecyl trimethyl Ammonium chloride joins in 110 parts of deionized waters, stirring and dissolving, is subsequently adding above-mentioned monomer mixture, under 8000 revs/min of rotating speeds High shear agitation 15 minutes, obtains monomer pre-emulsion.
3, polyreaction
A. 0.7g Ammonium persulfate. is dissolved in 20g deionized water, obtains initiator solution, standby.
B. the above-mentioned monomer pre-emulsion prepared is added in reactor, be heated to 75 DEG C, drip at a slow speed and prepared Initiator solution, time for adding is 30 minutes, adds rear insulation reaction 4 hours.
C. reactant liquor is cooled to room temperature, regulates pH to 6 ~ 7 with strong aqua ammonia, obtains spreading unchecked the fluoropolymer emulsion of light.
4, water-proof finish
A. opening dilute: diluted with 2800g deionized water by above-mentioned fluoropolymer emulsion, obtaining active constituent content is 2% knit Thing housekeeping liquid.
B. dipping: be immersed in working solution by bafta, dip time 1 hour, (pick-up rate 95%) is rolled in two leachings two.
C. preliminary drying: preliminary drying temperature 95 DEG C, preliminary drying time 3 minutes.
D. bake: baking temperature 170 DEG C, bake the time 2 minutes, obtain waterproof cotton fabric.
5, test
With reference to GB4745-84 " textile fabric surface moisture-resisting assay method ", carrying out trickle test on trickle instrument, after arrangement, cotton is knitted The scoring of thing water proofing property is 100, and fabric face is without the adhesion globule, and oil repellency reaches 3 grades.Use the contact of OCA40Micro type surface Bafta after arranging is detected by angle instrument, and recording fabric face contact angle is 140.3, and its result sees accompanying drawing 4.
Embodiment four
1,1H, 1H, 2H, 2H-7-thia-perfluor undecyl acrylate are synthesized according to embodiment three
2, monomer pre-emulsion preparation
A. in beaker in tall form, it is sequentially added into 1H, 1H, 2H, 2H-7-thia-perfluor undecyl methacrylate 26.9g, 16.8g butyl acrylate, 8.2g methyl methacrylate and the mixing of 2.5g hydroxyethyl methylacrylate, obtain uniform flow good Good monomer mixture.
B. by 0.7g nonionic surfactant AEO-9 and 0.8g part cationic surfactant octadecyl trimethyl Ammonium chloride joins in 110 parts of deionized waters, stirring and dissolving, is subsequently adding above-mentioned monomer mixture, under 8000 revs/min of rotating speeds High shear agitation 18 minutes, obtains monomer pre-emulsion.
3, polyreaction
A. 0.8g Ammonium persulfate. is dissolved in 18g deionized water, obtains initiator solution, standby.
B. the above-mentioned monomer pre-emulsion prepared is added in reactor, be heated to 78 DEG C, drip at a slow speed and prepared Initiator solution, time for adding is 30 minutes, adds rear insulation reaction 3 hours.
C. reactant liquor is cooled to room temperature, regulates pH to 6 ~ 7 with strong aqua ammonia, obtains spreading unchecked the fluoropolymer emulsion of light.
4, water-proof finish
A. opening dilute: diluted with 2820g deionized water by above-mentioned fluoropolymer emulsion, obtaining active constituent content is 2% knit Thing housekeeping liquid.
B. dipping: be immersed in working solution by bafta, dip time 1 hour, (pick-up rate 95%) is rolled in two leachings two.
C. preliminary drying: preliminary drying temperature 102 DEG C, preliminary drying time 3 minutes.
D. bake: baking temperature 172 DEG C, bake the time 2 minutes, obtain waterproof cotton fabric.
5, test
With reference to GB4745-84 " textile fabric surface moisture-resisting assay method ", carrying out trickle test on trickle instrument, after arrangement, cotton is knitted The scoring of thing water proofing property is 90, and fabric face is without the adhesion globule, and oil repellency reaches 2 grades.Use the contact of OCA40Micro type surface Bafta after arranging is detected by angle instrument, and recording fabric face contact angle is 137.0, and its result sees accompanying drawing 5.

Claims (6)

1. a perfluoroalkyl polyolefin acid ester waterproofing agent, it is characterised in that: the effective ingredient of described waterproofing agent is the long heterochain of sulfur-bearing Perfluoroalkyl olefin(e) acid ester, butyl acrylate, methyl methacrylate and the copolymer of hydroxyethyl methylacrylate, the knot of copolymer Structure formula is:
,
In formula, R=CH3 Or H；X=3～15；Y=10～30；Z=8～25；W=1～5.
A kind of perfluoroalkyl polyolefin acid ester waterproofing agent the most according to claim 1, it is characterised in that: described sulfur-bearing length is miscellaneous Chain perfluoroalkyl olefin(e) acid ester is 1H, 1H, 2H, 2H-7-thia perfluor undecyl acrylate or 1H, 1H, 2H, 2H-7-thia Any one in perfluor undecyl methacrylate, or both monomers of mixing with any weight ratio.
3. the preparation method of a perfluoroalkyl polyolefin acid ester waterproofing agent as claimed in claim 1, it is characterised in that include list The preparation of body pre-emulsion and polyreaction, specifically comprise the following steps that
(1) monomer pre-emulsion preparation
The most by weight, by 10～80 parts of sulfur-bearing long heterochain perfluoroalkyl olefin(e) acid esters, 10～20 parts of butyl acrylate, 1～10 part Methyl methacrylate and 0.5～5 part of hydroxyethyl methylacrylate mixing, obtain monomer mixture；The long heterochain of described sulfur-bearing Perfluoroalkyl olefin(e) acid ester is 1H, and 1H, 2H, 2H-7-thia perfluor undecyl acrylate or 1H, 1H, 2H, 2H-7-thia is complete Any one in fluorine undecyl methacrylate, or both monomers of mixing with any weight ratio；
B. 0.1～1.5 portion of nonionic surfactant and 0.1～1.5 part of cationic surfactant are joined 50～250 In part deionized water, after stirring and dissolving, add monomer mixture, under high shear agitation conditions, prepare monomer pre-emulsion；Described Nonionic surfactant is fatty alcohol-polyoxyethylene ether AEO-9, appointing in fatty alcohol-polyoxyethylene ether AEO-6 or Span-80 Meaning one；Described cationic surfactant is octadecyl trimethyl ammonium chloride (1831), Cetyltrimethylammonium bromide In any one；
(2) polyreaction
The most by weight, 0.1～2.0 part of initiator is dissolved in 10～30 parts of deionized waters, obtains initiator solution；Institute Stating initiator is any one in Ammonium persulfate., potassium peroxydisulfate or sodium peroxydisulfate；
B. monomer pre-emulsion prepared by step (1) is joined in reactor, is heated to 50～95 DEG C, drip initiator solution, Time for adding is 0.5～5 hour, adds rear insulation reaction 1～24 hours；
C. reactant liquor is cooled to room temperature, regulates pH to 6～7 with strong aqua ammonia, obtains a kind of perfluoroalkyl polyolefin acid ester waterproofing agent.
The preparation method of a kind of perfluoroalkyl polyolefin acid ester waterproofing agent the most according to claim 3, it is characterised in that: polymerization Reaction temperature in reactions steps b is 70～85 DEG C, and the insulation reaction time is 1～6 hour.
5. the application of the perfluoroalkyl polyolefin acid ester waterproofing agent described in claim 1, it is characterised in that: use it for textile Water-proof finish.
The application of perfluoroalkyl polyolefin acid ester waterproofing agent the most according to claim 5, it is characterised in that: the tool of water-proof finish Body step is as follows:
A. open dilute: perfluoroalkyl polyolefin acid ester waterproofing agent emulsion is diluted with deionized water, obtains textile finishing working solution；
B. dipping: being immersed in working solution by bafta, dip time is 30 minutes～2 hours, two soak two rolls, pick-up rate 90% ～105%；
C. preliminary drying: preliminary drying temperature 90～105 DEG C, preliminary drying time 2～5 minutes；
D. bake: baking temperature 150～175 DEG C, bake time 1～5 minutes, obtain waterproof cotton fabric.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107129556A (en) * 2017-04-18 2017-09-05 苏州大学 Convertible smart fabric finishing agent of a kind of close and distant property in surface and preparation method thereof
CN109180857A (en) * 2017-04-18 2019-01-11 南通纺织丝绸产业技术研究院 A kind of close and distant convertible fabric finishing liquor of property in intelligent surface
CN114108321A (en) * 2021-11-30 2022-03-01 苏州联胜化学有限公司 Pure cotton fabric waterproof agent and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102149738A (en) * 2008-09-15 2011-08-10 大金工业株式会社 Water- and oil-repellent composition
CN104594045A (en) * 2015-01-29 2015-05-06 苏州大学 Water and oil repellent finishing agent for fabrics and preparation method of finishing agent
CN105064026A (en) * 2015-08-05 2015-11-18 浙江康德新材料有限公司 Nano latex used as textile finishing agent and phase reversion preparation method thereof
CN105131177A (en) * 2015-08-19 2015-12-09 山东大学 Environment-friendly type perfluoro fabric finishing agent and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102149738A (en) * 2008-09-15 2011-08-10 大金工业株式会社 Water- and oil-repellent composition
CN104594045A (en) * 2015-01-29 2015-05-06 苏州大学 Water and oil repellent finishing agent for fabrics and preparation method of finishing agent
CN105064026A (en) * 2015-08-05 2015-11-18 浙江康德新材料有限公司 Nano latex used as textile finishing agent and phase reversion preparation method thereof
CN105131177A (en) * 2015-08-19 2015-12-09 山东大学 Environment-friendly type perfluoro fabric finishing agent and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107129556A (en) * 2017-04-18 2017-09-05 苏州大学 Convertible smart fabric finishing agent of a kind of close and distant property in surface and preparation method thereof
CN109180857A (en) * 2017-04-18 2019-01-11 南通纺织丝绸产业技术研究院 A kind of close and distant convertible fabric finishing liquor of property in intelligent surface
CN107129556B (en) * 2017-04-18 2019-08-13 苏州大学 Convertible smart fabric finishing agent of a kind of close and distant property in surface and preparation method thereof
CN114108321A (en) * 2021-11-30 2022-03-01 苏州联胜化学有限公司 Pure cotton fabric waterproof agent and preparation method thereof

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