CN105924573B - A kind of perfluoroalkyl polyolefin acid ester waterproofing agent, preparation method and application - Google Patents
A kind of perfluoroalkyl polyolefin acid ester waterproofing agent, preparation method and application Download PDFInfo
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- CN105924573B CN105924573B CN201610414212.3A CN201610414212A CN105924573B CN 105924573 B CN105924573 B CN 105924573B CN 201610414212 A CN201610414212 A CN 201610414212A CN 105924573 B CN105924573 B CN 105924573B
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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
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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
- 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
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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
- 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
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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
- D06M15/21—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
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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
- C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
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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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of perfluoroalkyl polyolefin acid ester waterproofing agent, preparation method and application.Waterproofing agent active ingredient is the long heterochain perfluoroalkyl olefin(e) acid ester copolymer of sulfur-bearing, mix monomer is constituted with the long heterochain perfluoroalkyl olefin(e) acid ester of sulfur-bearing, butyl acrylate, methyl methacrylate and hydroxyethyl methacrylate, under nonionic surface active agent and anionic surfactant emulsification, emulsion polymerization is triggered to obtain with initiator.The finishing agent is applied into Cotton Fabric can provide very excellent water-proof function.Because the long heterochain perfluoroalkyl of sulfur-bearing has crystallinity, therefore without surface reconstruction phenomenon during olefin(e) acid ester copolymer contact liq, water-proof function is excellent.Moreover, the long carbon containing thia key of heterochain perfluoroalkyl, be easy to degraded, in the absence of cumulative toxicity, be not belonging to disable fluorine-containing chemical.Meanwhile, the waterproofing agent that the present invention is provided is made by traditional emulsion copolymerization, and reaction condition is gentle, and equipment requirement is low, and technique is easy, it is easy to control, and is adapted to industrialized production.
Description
Technical field
The present invention relates to a kind of perfluoroalkyl polyolefin acid ester waterproofing agent, preparation method and applications, and in particular to Yi Zhonghan
Long heterochain perfluoroalkyl polyolefin acid ester emulsion of sulphur and preparation method thereof, and applied to fabric waterproof Final finishing, belong to fine chemistry
Product and weaving auxiliary chemicals field.
Background technology
People have found during studying the waterproof oil-proof finishing of fabric, with containing fluoroalkyle compound to fabric
Progress processing can assign the excellent waterproof of fabric new energy.By the research and development of decades, fluorine-containing textile finishing agent commodity
Change and occupy very big market, the development of these fluorine-containing textile finishing agents is greatly enriched the research field of organic fluorine material,
And as one of them important branch, obtained the very big concern of domestic and international researcher.
Nineteen fifty, Du Pont companies of the U.S. take the lead in using as fabric finishing agent using polytetrafluoroethylene (PTFE) (PTFE) emulsion,
And applied for patent.Nineteen fifty-three, Minnesota Mining and Manufacturing Company is succeeded in developing with perfluorocarboxylic acid chromium complex CF3(CF2) nCO2Based on CrOH
The fabric finishing agent of body, the active ingredient of this micromolecular type waterproof oil-repellent agent can also be the quaternary ammonium compound of perfluor acid amides, such as
CF3(CF2)6CONH (CH2) 3N+(CH3)2C2H5Br-.However, because washing fastness is poor, they are preferably contained by performance quickly
Fluoroacrylate polymer is replaced, if 3M Developeies in 1956 are with " Scotchgard FC2208 " are representative
The active ingredient of FC series fabric finishing agents is fluorine-containing olefine acid ester polymer.
Fluorine-containing olefin(e) acid esters polymer, which can provide waterproof, to be refused oily function and has benefited from fluoroalkyl on its side chain, these fluoroalkyls
Protected with sawtooth chain conformation and shield main polymer chain so that polymer film has low-surface-energy, so as to provide excellent anti-
Water refuses oily function.Wherein, perfluoro capryl polyacrylate be proved to be to provide very superior waterproof oil repellency fabric it is whole
Agent is managed, thus obtains extensive use.But, increasing research is confirmed, carbon chain lengths are equal to or more than the complete of 8 carbon atoms
Fluoroalkyl is in the test of most of environmental conditions all without appearance hydrolysis, photodissociation or biodegradation, these long carbon chain perfluor alkyl
The root that be proven with persistent environments inertia and bioaccumulation toxicity, can cause harm to environment.Current European Union member countries are
Through completely forbidding production and the perfluorinated octyl sulfuryl amine derivative using the fluoroalkyl containing Long carbon chain（PFOS）Class finish materials
And derived product.
During using short carbon chain fluoroalkyl of the carbon chain lengths less than 8 as side base, obtained fluoropolymer can then drop naturally
Solution.The synthesis and application study for having emerged in large numbers many short fluorocarbon chain compounds in recent years both at home and abroad report that research is found, due to fluorine film table
The short carbon chain perfluoroalkyl in face is rigidly small, nodeless mesh, it is impossible to form stable liquid crystal structure arrangement, the short carbon chain fluothane constructed
Base protecting film fluorocarbon chain Duan Yi after contact liq is redirected, toppled over, and easily exposes basal body structure so that fluorine film shielding is lost
Effect, that is, occur so-called short carbon chain perfluoroalkyl " surface reconstruction ", so as to cause side base end trifluoromethyl（-CF3）Layer by
Destruction is even caved in, thus does not reach effective liquid repellent function.
The content of the invention
The present invention has cumulative toxicity, short carbon chain fluoroalkyl crystallinity poor and refused for the difficult degradation of long carbon chain perfluor alkyl
The not good contradiction of liquid effect contains there is provided a kind of long heterochain perfluoroalkyl olefine acid ester polymer waterproofing agent of sulfur-bearing, the polymer of acquisition
The long heterochain side base of perfluoroalkyl, because side base contains thia key and is easy to degraded, in the absence of cumulative toxicity, is not belonging to disabling fluorine-containing
Chemicals.Meanwhile, long heterochain perfluoroalkyl has crystallinity and rigidity again so that fluoropolymer surface conformational stability, thus
With superior liquid repellent function.This finishing agent is applied into Cotton Fabric can obtain very 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 prevented
Aqua, its active ingredient is the long heterochain perfluoroalkyl olefin(e) acid ester of sulfur-bearing, 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 described above, including list
Body pre-emulsion is prepared and polymerisation, is comprised the following steps that：
1st, monomer pre-emulsion is prepared
A. by weight, by the long heterochain perfluoroalkyl olefin(e) acid ester of 10~80 parts of sulfur-bearings, 10~20 parts of butyl acrylates, 1~
10 parts of methyl methacrylates and 0.5~5 part of hydroxyethyl methacrylate mixing, obtain monomer mixture；
B. 0.1~1.5 portion of nonionic surfactant and 0.1~1.5 part of cationic surfactant are added to 50~
In 250 parts of deionized waters, after stirring and dissolving, add and monomer pre-emulsion is made under monomer mixture, high shear agitation conditions；Institute
Nonionic surfactant is stated in AEO AEO-9, AEO AEO-6 or Span-80
Any one；The cationic surfactant is OTAC（1831）, octadecyl trimethyl bromination
Any one in ammonium；
2nd, polymerisation
A. by weight, 0.1~2.0 part of initiator is dissolved in 10~30 parts of deionized waters, obtains initiator molten
Liquid；The initiator is any one in ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate；
B. monomer pre-emulsion prepared by step 1 is added in reactor, is heated to 50~95 DEG C, initiator is added dropwise molten
Liquid, time for adding is 0.5~5 hour, adds rear insulation reaction 1~24 hour.
C. reaction solution is cooled to room temperature, adjusts pH to 6~7 with concentrated ammonia liquor, obtains a kind of perfluoroalkyl polyolefin acid ester waterproof
Agent.
In technical solution of the present invention, 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.
Water-proof finish is comprised the following steps that：
A. open dilute：Described fluoropolymer emulsion is diluted with deionized water, textile finishing working solution is obtained；
B. impregnate：Bafta is immersed in working solution, dip time 30 minutes~2 hours, two leachings two are rolled, pick-up rate
90%~105%；
C. preliminary drying：90~105 DEG C of preliminary drying temperature, preliminary drying time 2~5 minutes；
D. bake：150~175 DEG C of baking temperature, bakes the time 1~5 minute, obtains waterproof cotton fabric.
The long heterochain perfluoroalkyl olefin(e) acid ester of sulfur-bearing of the present invention is 1H, 1H, 2H, 2H-7- thia perfluor undecyls
Any one in acrylate or 1H, 1H, 2H, 2H-7- thia perfluor undecyl methacrylate, or both with any
Monomer of the weight than mixing.The structural formula of monomer is：
,
In formula, R=H or CH3 。
The preparation method of the long heterochain perfluoroalkyl olefin(e) acid ester of sulfur-bearing, step is as follows：
1st, telomerisation
By weight, successively by 30~60 part of nine fluorine butyl tetrafluoro halogenation sulphur, 0.1~1 part of organic peroxide, 0.1~
0.8 part of calcium carbonate and 10~50 parts of fluorine-containing aromatic hydrocarbon solvents are added in reactor；The organic peroxide is peroxidating two
Any one in benzoyl, or tert-butyl peroxide；
The nine fluorine butyl tetrafluoro halogenation sulphur is nine fluorine butyl tetrafluoro sulfur chlorides, nine fluorine butyl tetrafluoro sulfur bromides or nine fluorine fourths
Any one in base tetrafluoro iodine bisulfide；
Nitrogen atmosphere, temperature be 50~100 DEG C, stir speed (S.S.) be under conditions of 30~110 revs/min, to reactor
In be passed through tetrafluoroethene 2~3 hours, tetrafluoroethene is passed through speed for 5~15 parts/hour, and pressure is 0.4~0.8MPa；Stop
Only it is passed through after tetrafluoroethene, continues to react 1~10 hour；
Stop after reaction, cool down, reactant mixture vacuum distillation is removed fluorine-containing aromatic hydrocarbon solvent, obtains product by discharging
Thia perfluor nonyl halogen；
2nd, single Electron Transfer Reactions
By weight, by 40~80 portions of thia perfluor nonyl halogen, 0.5~1.0 part of noble metal catalyst and 10~210 parts of ethers
Class solvent is added in reactor；The noble metal catalyst is four（Triphenylphosphine）Palladium or three（Triphenylphosphine）In palladium bichloride
Any one；
Nitrogen atmosphere, temperature be 30~90 DEG C, stir speed (S.S.) be under conditions of 30~110 revs/min, into reactor
3~15 parts of ethene is passed through, is reacted 1~3 hour；
Stop after reaction, cool down, reactant mixture vacuum distillation is removed ether solvent, obtains product thia complete by discharging
Fluorine nonyl ethylidene halogen；
3rd, esterification
By weight, 10~30 portions of olefin(e) acid salt and 5~50 parts of dry solvent N, N- dimethyl formyls are put into the reactor
Under amine, stirring condition, 59~70 portions of thia perfluor nonyl ethylidene halogen are added dropwise within the time of 30 minutes~2 hours, drip
Bi Hou, the insulation reaction 1~24 hour under conditions of temperature is 30~100 DEG C；
Stop after reaction, be filtered to remove the accessory substance halogen of generation；10~50 parts of esters solvents are added in filtrate, to go
After ion water washing, add 0.6~2.0 part of desiccant dryness and handle 0.5~12 hour；Drier is removed by filtration again, depressurizes
Esters solvent is distilled off, the long heterochain perfluoroalkyl olefin(e) acid ester of faint yellow product sulfur-bearing is obtained.
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 tetrahydrofuran, 1,4- dioxane or glycol dinitrate
Any one in ether.During described olefin(e) acid salt is acrylic acid silver, methacrylic acid silver, PAA or Sodium methacrylate
Any one.Described esters solvent is any one in ethyl acetate or methyl acetate.Described drier is anhydrous sulphur
Any one in sour magnesium, anhydrous sodium sulfate or anhydrous calcium chloride.
The long heterochain perfluoroalkyl olefin(e) acid ester of sulfur-bearing in the present invention is anti-by telomerization, single Electron Transfer Reactions and three steps of esterification
It should prepare, product can be used for synthesis low-surface-energy and environment-friendly fluoropolymer.Perfluoroalkyl halogenation sulphur 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 using nine fluorine butyl tetrafluoro sulfur chloride therein or nine fluorine butyl tetrafluoro sulfur bromides as end-capping reagent, and tetrafluoroethene is adjusted
After poly- reaction, the thia perfluoroalkyl halide oligomer of different polymerization degree is obtained, rectifying obtains thia perfluor nonyl halogen（Also known as sulphur
Miscellaneous halo Perfluorononane）；It is occurred into single Electron Transfer Reactions with ethene again, thia perfluor nonyl ethylidene halogen is obtained, thus
Synthesize a kind of heteroatomic long long heterochain perfluoroalkyl olefin(e) acid ester of heterochain sulfur-bearing of sulfur-bearing.Sulfur heteroatom long-chain in fluorine-containing olefin(e) acid ester
Keep functional fluoropolymer base rigidity and it is crystalline simultaneously, the long carbon containing thia key of heterochain, it is easy to degrade, thus without accumulation
Toxicity, overcomes the contradiction of long chain fluorine-containing function base rigidity and 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：Using nine fluorine butyl tetrafluoro halogenation sulphur as end-capping reagent, 5- thias are obtained by tetrafluoroethene telomerization complete
Fluorine nonyl -1- halogen（Also known as 5- thias -1- chlorine Perfluorononanes）；Passed through again by 5- thia perfluor nonyl -1- halogen with ethylene gas
1H, 1H, 2H, 2H-7- thia perfluor undecyl -1- halogen is made in single electron addition reaction；And further occur ester with olefin(e) acid salt
Change reaction and obtain the long heterochain perfluoroalkyl olefin(e) acid ester of target product sulfur-bearing.Reaction equation is as follows：
,
In formula, R=H or CH3；X=Cl, Br or I.
The present invention mechanism be：With the long heterochain perfluoroalkyl olefin(e) acid ester of sulfur-bearing, butyl acrylate, methyl methacrylate and
Hydroxyethyl methacrylate is mix monomer, in nonionic surface active agent and cationic surface active agent emulsification
Under, the cation type emulsion being had good stability by radical copolymerization, emulsion is configured to working solution applied to bafta
Arrange, obtain very 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, technical scheme its advantage that the present invention is provided is：
1st, in the fabric waterproof finishing agent that the present invention is provided, functional fluoropolymer monomer is the long heterochain perfluoroalkyl olefin(e) acid of sulfur-bearing
Ester, the long heterochain perfluoroalkyl for playing waterproof action contains thia key, it is easy to degrades, in the absence of cumulative toxicity, is not belonging to disabling and contains
Fluorine chemical, belongs to Green Textile Base auxiliary agent.
2nd, in perfluoroalkyl olefin(e) acid ester copolymer disclosed by the invention, the long heterochain perfluoroalkyl of side base has crystallinity, because
This makes fluoropolymer surface conformational stability, with excellent liquid repellent function.
3rd, fabric finishing agent disclosed by the invention is cation type emulsion, is easy to when padding fabric negatively charged with surface
The fabric and fiber of lotus attract and adsorbed, and by cross-linking monomer chain link when baking with fiber surface activity radical reaction and carry
For durable waterproof function.
4th, the present invention prepares fabric waterproofing agent using emulsion polymerization, and reaction condition is gentle, and equipment requirement is low, reaction process letter
Just, it is adapted to industrialized production and popularization and application.
Brief description of the drawings
Fig. 1 is perfluoroalkyl polyolefin acid ester infrared spectrogram prepared by the technical scheme of the embodiment of the present invention one.
Fig. 2~5 are perfluoroalkyl polyolefin acid ester emulsion finishing of cotton textiles prepared by various embodiments of the present invention technical scheme
Contact angle test chart.
Embodiment
Technical solution of the present invention is further described with reference to the accompanying drawings and examples.
Embodiment one
1st, 1H, 1H, 2H, 2H-7- thias-perfluor undecyl methacrylate are synthesized
A. by the fluorine butyl tetrafluoro sulfur bromides of 46.9g nine, 0.40g di-t-butyl peroxides, 0.4g calcium carbonate and 48g1,3- bis-
（Trifluoromethyl）Benzene solvent is added in reactor, sealing, after vacuumizing, is filled with the air in nitrogen displacement reactor, then take out
Vacuum, displacement.Replace 4 times altogether.It is warming up to after 45 DEG C, tetrafluoroethene is passed through reactor insulation, stirring reaction, control stirring
Speed is 55 revs/min, and the speed that is passed through of tetrafluoroethene is 12g/ hours, and pressure is 0.48MPa, stops being passed through four after 2 hours
PVF, continues to react 2 hours.After cooling, reactant mixture vacuum distillation is removed into 1,3- bis-（Trifluoromethyl）Benzene, decompression is steamed
Condition is evaporated for temperature 50 C, and vacuum is 16mmHg.Obtain product thia perfluor nonyl bromine.
B. by 65.4g thia perfluor nonyls bromine, 0.50g tri-（Triphenylphosphine）Palladium bichloride is added to instead with 70g tetrahydrofurans
Answer in kettle, seal, after vacuumizing, be filled with the air in nitrogen displacement reactor, then vacuumize, replace.Replace 5 times altogether.Heating
To after 40 DEG C, ethene is passed through reactor, is incubated, stirring reaction, it is 50 revs/min to control stir speed (S.S.), is reacted 2 hours, altogether
Absorb ethene 6.2g.Stop after reaction, cool down, solvent is distilled off in reactant mixture by discharging, and vacuum distillation condition is temperature
55 DEG C, vacuum is 10mmHg.Obtain product thia perfluor nonyl ethylidene bromine.
C. input 20.3g methacrylic acids silver and 18.1g dry solvent DMF in the reactor, stir
Mix, be heated to after 40 DEG C, 65.3g thia perfluor nonyl ethylidene bromines are added dropwise, time for adding is 0.6 hour, is incubated after adding
Reaction 5 hours.Stop reaction, be filtered to remove in silver bromide, filtrate and add after 48g ethyl acetate, washed 4 times with deionized water,
Washing uses deionized water 10ml every time.After the completion of washing, 1.5g anhydrous sodium sulfate dryings are added 2 hours.Cross and filter out drier,
Vacuum distillation removes solvent, and vacuum distillation condition is 40 DEG C of temperature, and vacuum is 10mmHg.Thick pale yellow slurry is obtained,
For 1H, 1H, 2H, 2H-7- thias-perfluor undecyl acrylate.
2nd, monomer pre-emulsion is prepared
A. 1H, 1H, 2H, 2H-7- thias-perfluor undecyl methacrylate are sequentially added in beaker in tall form
30.5g, 17.8g butyl acrylate, 8.2g methyl methacrylates and the mixing of 2.5g hydroxyethyl methacrylates, obtain uniform flow
The good monomer mixture of dynamic property.
B. by AEO-9 and 0.8g parts of cationic surfactant octadecyl trimethyls of 0.8g nonionic surfactants
Ammonium bromide is added in 105 parts of deionized waters, stirring and dissolving, is then added under above-mentioned monomer mixture, 8000 revs/min of rotating speeds
High shear agitation 15 minutes, obtains monomer pre-emulsion.
3rd, polymerisation
A. 0.6g ammonium persulfates are dissolved in 15g deionized waters, obtain initiator solution, it is standby.
B. the above-mentioned monomer pre-emulsion prepared is added in reactor, is heated to 72 DEG C, is added dropwise has prepared at a slow speed
Initiator solution, time for adding be 45 minutes, add rear insulation reaction 3 hours.
C. reaction solution is cooled to room temperature, adjusts pH to 6~7 with concentrated ammonia liquor, obtains spreading unchecked the fluoropolymer emulsion of light.
4th, water-proof finish
A. open dilute：Above-mentioned fluoropolymer emulsion is diluted with 2830g deionized waters, it is 2% to obtain active constituent content
Textile finishing working solution.
B. impregnate：Bafta is immersed in working solution, dip time 0.5 hour, two leachings two are rolled（Pick-up rate 100%）.
C. preliminary drying：102 DEG C of preliminary drying temperature, preliminary drying time 2 minutes.
D. bake：165 DEG C of baking temperature, bakes the time 2 minutes, obtains waterproof cotton fabric.
5th, test
With reference to GB4745-84《Textile fabric surface moisture-resistant assay method》, water drenching test is carried out on water drenching instrument, after arrangement
The scoring of bafta water proofing property is 90, and fabric face reaches 2 grades without the adhesion globule, oil repellency.Using OCA40Micro types surface
Contact angle instrument is detected to the bafta after arrangement, measures fabric face contact angle for 142.8o, its result is referring to accompanying drawing 2.
Embodiment two
1st, 1H, 1H, 2H, 2H-7- thias-perfluor undecyl methacrylate are synthesized according to embodiment one
2nd, monomer pre-emulsion is prepared
A. 1H, 1H, 2H, 2H-7- thias-perfluor undecyl methacrylate are sequentially added in beaker in tall form
28.8g, 18.1g butyl acrylate, 9.1g methyl methacrylates and the mixing of 2.6g hydroxyethyl methacrylates, obtain uniform flow
The good monomer mixture of dynamic property.
B. by AEO-6 and 0.8g parts of cationic surfactant octadecyl trimethyls of 0.8g nonionic surfactants
Ammonium bromide is added in 110 parts of deionized waters, stirring and dissolving, is then added under above-mentioned monomer mixture, 8000 revs/min of rotating speeds
High shear agitation 15 minutes, obtains monomer pre-emulsion.
3rd, polymerisation
A. 0.7g ammonium persulfates are dissolved in 20g deionized waters, obtain initiator solution, it is standby.
B. the above-mentioned monomer pre-emulsion prepared is added in reactor, is heated to 78 DEG C, is added dropwise has prepared at a slow speed
Initiator solution, time for adding be 45 minutes, add rear insulation reaction 6 hours.
C. reaction solution is cooled to room temperature, adjusts pH to 6 ~ 7 with concentrated ammonia liquor, obtains spreading unchecked the fluoropolymer emulsion of light.
4th, water-proof finish
A. open dilute：Above-mentioned fluoropolymer emulsion is diluted with 2750g deionized waters, it is 2% to obtain active constituent content
Textile finishing working solution.
B. impregnate：Bafta is immersed in working solution, dip time 1 hour, two leachings two are rolled（Pick-up rate 95%）.
C. preliminary drying：95 DEG C of preliminary drying temperature, preliminary drying time 3 minutes.
D. bake：168 DEG C of baking temperature, bakes the time 2 minutes, obtains waterproof cotton fabric.
5th, test
With reference to GB4745-84《Textile fabric surface moisture-resistant assay method》, water drenching test is carried out on water drenching instrument, after arrangement
The scoring of bafta water proofing property is 90, and fabric face reaches 2 grades without the adhesion globule, oil repellency.Using OCA40Micro types surface
Contact angle instrument is detected to the bafta after arrangement, measures fabric face contact angle for 139.4o, its result is referring to accompanying drawing 3.
Embodiment three
1st, 1H, 1H, 2H, 2H-7- thias-perfluor undecyl acrylate are synthesized
A. by the fluorine butyl tetrafluoro sulfur bromides of 45.8g nine, 0.5g dibenzoyl peroxides, 0.4g calcium carbonate and 55g fluoroforms
Benzene solvent is added in reactor, sealing, after vacuumizing, is filled with the air in nitrogen displacement reactor, then is vacuumized, and is replaced.
Replace 4 times altogether.It is warming up to after 45 DEG C, tetrafluoroethene is passed through reactor insulation, stirring reaction, it is 60 to control stir speed (S.S.)
Rev/min, the speed that is passed through of tetrafluoroethene is 13g/ hours, and pressure is 0.50MPa, stops being passed through tetrafluoroethene after 2 hours, after
Continuous reaction 3 hours.After cooling, reactant mixture vacuum distillation is removed into benzotrifluoride, vacuum distillation condition is temperature 50 C, very
Reciprocal of duty cycle is 20mmHg.Obtain product thia perfluor nonyl bromine.
B. by 60.2g thia perfluor nonyls bromine, 0.60g tri-（Triphenylphosphine）Palladium bichloride is added to instead with 80g tetrahydrofurans
Answer in kettle, seal, after vacuumizing, be filled with the air in nitrogen displacement reactor, then vacuumize, replace.Replace 5 times altogether.Heating
To after 40 DEG C, ethene is passed through reactor, is incubated, stirring reaction, it is 60 revs/min to control stir speed (S.S.), is reacted 3 hours, altogether
Absorb ethene 5.8g.Stop after reaction, cool down, solvent is distilled off in reactant mixture by discharging, and vacuum distillation condition is temperature
40 DEG C, vacuum is 16mmHg.Obtain product thia perfluor nonyl ethylidene bromine.
C. input 18.6g acrylic acid silver and 20g dry solvent DMF in the reactor, stir, heating
To after 40 DEG C, 55.6g thia perfluor nonyl ethylidene bromines are added dropwise, time for adding is 1 hour, adds rear insulation reaction 3 hours.
Stop reaction, be filtered to remove in the accessory substance silver bromide of generation, filtrate and add after 48g methyl acetates, 4 are washed with deionized water
Secondary, washing every time uses deionized water 10ml.After the completion of washing, 1.5g anhydrous sodium sulfate dryings are added 4 hours.Cross and filter out drying
Agent, vacuum distillation removes solvent, and vacuum distillation condition is 40 DEG C of temperature, and vacuum is 20mmHg.Obtain faint yellow sticky pulpous state
Long heterochain perfluoroalkyl olefin(e) acid ester products 1H, 1H, 2H, 2H-7- thia-the perfluor undecyl acrylate of thing, as sulfur-bearing.
2nd, monomer pre-emulsion is prepared
A. 1H, 1H, 2H are sequentially added in beaker in tall form, 2H-7- thias-perfluor undecyl acrylate 28.6g,
17.6g butyl acrylates, 8.5g methyl methacrylates and the mixing of 2.7g hydroxyethyl methacrylates, obtain uniform flow good
Good monomer mixture.
B. by AEO-9 and 0.8g parts of cationic surfactant octadecyl trimethyls of 0.9g nonionic surfactants
Ammonium chloride is added in 110 parts of deionized waters, stirring and dissolving, is then added under above-mentioned monomer mixture, 8000 revs/min of rotating speeds
High shear agitation 15 minutes, obtains monomer pre-emulsion.
3rd, polymerisation
A. 0.7g ammonium persulfates are dissolved in 20g deionized waters, obtain initiator solution, it is standby.
B. the above-mentioned monomer pre-emulsion prepared is added in reactor, is heated to 75 DEG C, is added dropwise has prepared at a slow speed
Initiator solution, time for adding be 30 minutes, add rear insulation reaction 4 hours.
C. reaction solution is cooled to room temperature, adjusts pH to 6 ~ 7 with concentrated ammonia liquor, obtains spreading unchecked the fluoropolymer emulsion of light.
4th, water-proof finish
A. open dilute：Above-mentioned fluoropolymer emulsion is diluted with 2800g deionized waters, it is 2% to obtain active constituent content
Textile finishing working solution.
B. impregnate：Bafta is immersed in working solution, dip time 1 hour, two leachings two are rolled（Pick-up rate 95%）.
C. preliminary drying：95 DEG C of preliminary drying temperature, preliminary drying time 3 minutes.
D. bake：170 DEG C of baking temperature, bakes the time 2 minutes, obtains waterproof cotton fabric.
5th, test
With reference to GB4745-84《Textile fabric surface moisture-resistant assay method》, water drenching test is carried out on water drenching instrument, after arrangement
The scoring of bafta water proofing property is 100, and fabric face reaches 3 grades without the adhesion globule, oil repellency.Using OCA40Micro types surface
Contact angle instrument is detected to the bafta after arrangement, measures fabric face contact angle for 140.3o, its result is referring to accompanying drawing 4.
Example IV
1st, 1H, 1H, 2H, 2H-7- thias-perfluor undecyl acrylate are synthesized according to embodiment three
2nd, monomer pre-emulsion is prepared
A. 1H, 1H, 2H, 2H-7- thias-perfluor undecyl methacrylate are sequentially added in beaker in tall form
26.9g, 16.8g butyl acrylate, 8.2g methyl methacrylates and the mixing of 2.5g hydroxyethyl methacrylates, obtain uniform flow
The good monomer mixture of dynamic property.
B. by AEO-9 and 0.8g parts of cationic surfactant octadecyl trimethyls of 0.7g nonionic surfactants
Ammonium chloride is added in 110 parts of deionized waters, stirring and dissolving, is then added under above-mentioned monomer mixture, 8000 revs/min of rotating speeds
High shear agitation 18 minutes, obtains monomer pre-emulsion.
3rd, polymerisation
A. 0.8g ammonium persulfates are dissolved in 18g deionized waters, obtain initiator solution, it is standby.
B. the above-mentioned monomer pre-emulsion prepared is added in reactor, is heated to 78 DEG C, is added dropwise has prepared at a slow speed
Initiator solution, time for adding be 30 minutes, add rear insulation reaction 3 hours.
C. reaction solution is cooled to room temperature, adjusts pH to 6 ~ 7 with concentrated ammonia liquor, obtains spreading unchecked the fluoropolymer emulsion of light.
4th, water-proof finish
A. open dilute：Above-mentioned fluoropolymer emulsion is diluted with 2820g deionized waters, it is 2% to obtain active constituent content
Textile finishing working solution.
B. impregnate：Bafta is immersed in working solution, dip time 1 hour, two leachings two are rolled（Pick-up rate 95%）.
C. preliminary drying：102 DEG C of preliminary drying temperature, preliminary drying time 3 minutes.
D. bake：172 DEG C of baking temperature, bakes the time 2 minutes, obtains waterproof cotton fabric.
5th, test
With reference to GB4745-84《Textile fabric surface moisture-resistant assay method》, water drenching test is carried out on water drenching instrument, after arrangement
The scoring of bafta water proofing property is 90, and fabric face reaches 2 grades without the adhesion globule, oil repellency.Using OCA40Micro types surface
Contact angle instrument is detected to the bafta after arrangement, measures fabric face contact angle for 137.0o, its result is referring to accompanying drawing 5.
Claims (5)
1. a kind of perfluoroalkyl polyolefin acid ester waterproofing agent, it is characterised in that：The active ingredient of the waterproofing agent is the long heterochain of sulfur-bearing
Perfluoroalkyl olefin(e) acid ester, butyl acrylate, the copolymer of methyl methacrylate and hydroxyethyl methacrylate, 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；
Wherein：The long heterochain perfluoroalkyl olefin(e) acid ester of described sulfur-bearing is 1H, 1H, 2H, 2H-7- thia perfluor undecyl acrylic acid
Any one in ester or 1H, 1H, 2H, 2H-7- thia perfluor undecyl methacrylate, or both with any weight ratio
The monomer of mixing.
2. a kind of preparation method of perfluoroalkyl polyolefin acid ester waterproofing agent as claimed in claim 1, it is characterised in that including list
Body pre-emulsion is prepared and polymerisation, is comprised the following steps that：
（1）Monomer pre-emulsion is prepared
A. by weight, by the long heterochain perfluoroalkyl olefin(e) acid ester of 10~80 parts of sulfur-bearings, 10~20 parts of butyl acrylates, 1~10 part
Methyl methacrylate and 0.5~5 part of hydroxyethyl methacrylate mixing, obtain monomer mixture；The long heterochain of described sulfur-bearing
Perfluoroalkyl olefin(e) acid ester is 1H, and 1H, 2H, 2H-7- thias perfluor undecyl acrylate or 1H, 1H, 2H, 2H-7- thia are complete
Any one in fluorine undecyl methacrylate, or both monomer with any weight than mixing；
B. 0.1~1.5 portion of nonionic surfactant and 0.1~1.5 part of cationic surfactant are added to 50~250
In part deionized water, after stirring and dissolving, add and monomer pre-emulsion is made under monomer mixture, high shear agitation conditions；It is described
Nonionic surfactant is times in AEO AEO-9, AEO AEO-6 or Span-80
Meaning is a kind of；The cationic surfactant is OTAC（1831）, Cetyltrimethylammonium bromide
In any one；
（2）Polymerisation
A. by weight, 0.1~2.0 part of initiator is dissolved in 10~30 parts of deionized waters, obtains initiator solution；Institute
State any one of initiator for ammonium persulfate, in potassium peroxydisulfate or sodium peroxydisulfate；
B. by step（1）The monomer pre-emulsion of preparation is added in reactor, is heated to 50~95 DEG C, and initiator solution is added dropwise,
Time for adding is 0.5~5 hour, adds rear insulation reaction 1~24 hour；
C. reaction solution is cooled to room temperature, adjusts pH to 6~7 with concentrated ammonia liquor, obtains a kind of perfluoroalkyl polyolefin acid ester waterproofing agent.
3. a kind of preparation method of perfluoroalkyl polyolefin acid ester waterproofing agent according to claim 2, 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.
4. 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.
5. the application of perfluoroalkyl polyolefin acid ester waterproofing agent according to claim 4, it is characterised in that：The tool of water-proof finish
Body step is as follows：
A. open dilute：Perfluoroalkyl polyolefin acid ester waterproof agent emulsion is diluted with deionized water, textile finishing working solution is obtained；
B. impregnate：Bafta is immersed in working solution, dip time is 30 minutes~2 hours, and two leachings two are rolled, pick-up rate 90%
~105%；
C. preliminary drying：90~105 DEG C of preliminary drying temperature, preliminary drying time 2~5 minutes；
D. bake：150~175 DEG C of baking temperature, bakes the time 1~5 minute, obtains waterproof cotton fabric.
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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