CN105970628B - A kind of compound water-repellent breathable fabric finishing agent of water-based hollow fluorine silicon and preparation method - Google Patents
A kind of compound water-repellent breathable fabric finishing agent of water-based hollow fluorine silicon and preparation method Download PDFInfo
- Publication number
- CN105970628B CN105970628B CN201610365004.9A CN201610365004A CN105970628B CN 105970628 B CN105970628 B CN 105970628B CN 201610365004 A CN201610365004 A CN 201610365004A CN 105970628 B CN105970628 B CN 105970628B
- Authority
- CN
- China
- Prior art keywords
- water
- emulsion
- preparation
- monomer
- finishing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/11—Oleophobic properties
-
- 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
Landscapes
- 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
It is hollow type fluorine-contaninig polyacrylate siloxanes composite polymeric high polymer shell the invention discloses a kind of compound water-repellent breathable fabric finishing agent of water-based hollow fluorine silicon and preparation method, its active principle, the preparation method of the fabric finishing agent is broadly divided into three phases：（1）The preparation of emulsification system；（2）The preparation of core-shell emulsion：It is that raw material is made under initiator, buffer, emulsifying agent, defoamer effect through Core-shell Emulsion Polymerization method with fluorochemical monomer, acrylate monomer, unsaturated carboxylic acid monomer, organic silicon monomer, other functional monomers etc.；（3）Hollow processing.The present invention is introduced organic silicon monomer in a manner of radical polymerization, it is crosslinked synergy with fluorochemical monomer, enhance water resistance, resistance to washability and the pliability of fabric while holding C F long-chain polymer emulsions good water repellency.In addition, its unique hollow structure not only increases permeability, also improve light scattering property, reduce cost.
Description
Technical field
The present invention relates to a kind of fabric finishing agent, especially a kind of water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon
And preparation method.
Background technology
With the development of science and technology, the level of consumption of people and consumption idea change therewith.Specific to selection of fabric side
Face, simple warming wearability of dispeling cold can not meet people's life and production requirement, water repellent, refuse it is oily, ventilative, resistance to
Wash, be antistatic, be weather-proof, be fire-retardant, lightweight, be thinned etc. multifunction have become fabric post-treatment industry study hotspot.Knit
Thing finishing agent is that one kind makes fabric while original wearability is kept, and it is a variety of to increase its pliability height, water repellent, ventilative etc.
The finishing agent of property.
For many years, researcher arranges to the functionalization of fabric water and oil repellant and has carried out substantial amounts of exploratory development, early stage
It it is solid paraffin finishing agent period, its water and oil repellant effect is poor；Organic silicone finishing agent period is followed by, its water repellent effect is more excellent
It is different but to refuse oily effect poor；Fluorine-contained finishing agent period is currently in, its water and oil repellant excellent effect.Nineteen fifty, E.I.Du Pont Company is most
First to file patent, by tetrachloro-ethylene emulsion applications in the final finishing of fabric.
Fluorine-containing fabric fluorine finishing agent is a kind of very important finishing agent in after-finishing of textile products.The finishing agent is unique with it
Water repellent, to refuse oily, antifouling, water-fastness, weatherability, gas permeability superior and enjoy the favor of piece market, with its function
Variation, application are also constantly expanding, and have turned into the main flow of textile industry and the processing of other industry water and oil repellant at present
Product.At present, in the world production have fluorine-containing textile finishing agent commercial product company include Dupont (Du Pont) company,
3M companies, Hao Site (Hoechst) company of Germany, Daikin (Daikin) company etc..
At present, substantial amounts of work, patent and document etc. have been done by the synthesis in fluorine-containing textile finishing agent and application aspect, foreign countries
Report more, and some has realized industrialized production.The production of fluorine-containing water-refusing oil-refusing finishing agent product is at present mainly by the U.S.
E.I.Du Pont Company and several families such as 3M companies, German Hoechst companies, French Atochem companies, Japan AGC and great Jin
Company is monopolized.The fluorine industry in China is concentrated mainly in the production of the traditional products such as polytetrafluoroethylene (PTFE) and Kynoar, is contained
Fluorine water-refusing oil-refusing finishing agent not yet realizes the production of industrially scalable, the fluorine-containing textile finishing agent master that the current country uses at home
External import is relied on, compounding then is diluted to the high concentration product emulsion of foreign countries and forms the product of oneself.
In the preparation process of fluorine-containing fabric water repellent finishing agent, fluorochemical monomer is the portion that price is the most expensive in whole system
Point, and the major reason place that fluorine-containing fabric water repellent finishing agent holds at high price.Most allusion quotation in fluorine-containing fabric water repellent finishing agent
Type surely belongs to fluorine-containing polyacrylic acid fabric finishing agent.Fluorine-containing polyacrylic acid fabric finishing agent because F electronegativity of element therein is maximum,
F atom radius is small, thus in fluorine molecule lone pair electrons repulsive force it is quite big, and fluorine is without available d tracks, therefore can not
D-p pi bonds are formed, C-F Chemical bond energies are larger, and polarizability is low, and its fabric exhibits after arranging goes out good surface-active and hated
Water-based energy.Simple fluorochemical monomer is because its is expensive and the degree of polymerization is relatively low in the polymerization, while the fabric after arrangement is soft
Soft comfort level and washable weather resistance also need further to improve, and introduce high hydrophobicity, the organic silicon monomer of high bond energy just makes
Above-mentioned deficiency is improved.Si-O bond energys are larger (450kJ/mol) in siloxane molecule structure, much larger than C-C bond energys (345kJ/
Mol) and C-O bond energys (351kJ/mol), while its molecular structure feature makes it have good resistant of high or low temperature, weatherability, ventilative
Property, surface softness and excellent mechanical property, receive the extensive concern of scientific research personnel.
The fluorinated acrylate market price is expensive, and is difficult to combine with most of base materials because its surface energy is extremely low,
In order to be combined with fabric tightness, typically entered using fluorinated acrylate and other non-fluorochemical monomers or functional monomer
Row copolymerization, so as to establish firm combine with fabric in textile finishing.Obtained copolymer gathers in heat treatment process
The fluoro-containing group of compound can migrate to fabric face, fabric is had excellent surface property.Fluorine-containing polyisocyanate polyaddition at present
The most frequently used synthetic method of thing is emulsion polymerization, and for this method using water as solvent, environmental pollution is small, reacts obtained polymer phase
And particle diameter big to molecular weight is small.
Emulsion polymerization refers to that using water as medium monomer forms emulsion in the presence of assistant for emulsifying agent, by mechanical agitation and entered
And it polymerize.The solvent-free pollution of this method, temperature is easily controllable, can obtain heavy polymer, polymerization speed is fast, cost
Relatively low and product emulsion is more suitable for the deep processing of fabric.Common emulsion polymerization has following several：
(1) conventional emulsion polymerization
Conventional emulsion polymerization refers to fluoroacrylate monomer and functional monomer, non-fluorochemical monomer etc. in initiator and breast
In the presence of agent, free radical emulsion copolymerization occurs, synthesizes fluorinated acrylate polymer emulsion.It using aqueous phase is continuous that it, which is,
Phase, oil phase are the polymerization of dispersed phase.Linemann etc. uses emulsion polymerization, in emulsifying agent Cetyltrimethylammonium bromide and
In the presence of initiator water-soluble azo class solid wako V-50, poly- (methyl) acrylic acid tetrahydrochysene perfluoro decyl is obtained.
Shimokawa etc. is successfully entered perfluoroalkyl methacrylate and acrylic acid, acrylate by the method for conventional emulsion polymerization
Row copolymerization, obtain the fluoro-acrylate copolymer emulsion of excellent effect.
(2) mini-emulsion polymerization
Mini-emulsion polymerization refers to that in the presence of high shear force monomer forming properties in aqueous phase are stable, good dispersion
Fine droplet, monomer that drop includes, initiator, emulsifying agent, assistant for emulsifying agent etc., reacts new what is carried out in units of drop
Type polymerisation.Fine droplet is typically in the range of between 50-500nm, using microemulsified technique so that the problem of fluorochemical monomer indissoluble
It is eased.The reaction system of mini-emulsion polymerization and the difference of conventional emulsion polymerization are assistant for emulsifying agent, its existing conventional emulsions
The advantages that the advantages of polymerization such as polymerization speed are fast, molecular weight is high, the application of emulsion polymerization has been expanded again, can apply to high hydrophobicity
Monomer and multicomponent system, obtain various polymer.The fine emulsion polymerization such as Chen Yanjun, in emulsifier sodium lauryl sulfate and
In the presence of assistant for emulsifying agent hexadecanol, using ultrasonic emulsification, trifluoroethyl methacrylate and butyl acrylate are obtained
Copolymer miniemulsion.
(3) micro-emulsion polymerization
Micro-emulsion polymerization component includes water, emulsifying agent, assistant for emulsifying agent, and it is a kind of water-oil dispersed system of appearance transparent,
Its thermodynamic stability is also fine.Microemulsion is in fully decentralized state, monomer particulate be typically in the range of 10nm-100nm it
Between, there is excellent storage stability, anti-shear stability and thermodynamic stability.If the valid density reacted in system is not
Become, emulsion particle diameter is reduced to original 1/10 in system, and that emulsion particle quantity adds 1000 times, and this effectively improves surface and changed
The efficiency of property.Thomas etc. reports successfully to be synthesized except perfluoroalkyl methacrylate and acrylic acid using micro-emulsion polymerization
The copolymer of butyl ester.
(4) emulsifier-free emulsion polymerization
Conventional emulsion polymerization needs to add polymerization system of the emulsifying agent to be stablized, but the addition of emulsifying agent may
Properties of product are influenceed, while are also had a negative impact to environment.Emulsifier-free emulsion polymerization is being not added with emulsifying agent or is adding micro breast
Emulsion polymerization is carried out in the case of agent, obtained latex particle surface is clean, scattered single.But soap-free emulsion is not due to having
There is emulsifying agent, emulsion does not reach higher stability.Generally, add emulsifiable comonomer, add low molecular homopolymer
The stability of emulsifier-free emulsion polymerization system can be improved as emulsifying agent or the methods of adding certain organic additive.Kang Kai etc.
Methyl methacrylate, ethyl acrylate, acrylic acid ternary system are polymerize using emulsifier-free emulsion polymerization method, polymerize institute
Obtain emulsion-stabilizing.
(5) nuclear-shell emulsion polymerization
Core-shell hybrid emulsion polymerization refers to microphase, the composition structure that polymer is determined by MOLECULE DESIGN, from not
Congenerous monomer carries out emulsion copolymerization as the stratum nucleare or shell of polymer, synthesizes the emulsion particle with core shell structure.Nucleocapsid
The feed postition of shell monomers is smoothed out very big influence to reaction in emulsion polymerization.Main technique has pre-swollen
Method, semi-continuous process, batch process.Shell monomer is added in emulsion system and carries out pre-emulsification and at a certain temperature by pre-swollen method
It is swelled, subsequent initiated polymerization.Semi-continuous process is that shell monomers have been slowly dropped into seed breast existing for initiator
In liquid.Batch process is by monomer, seed emulsion, water, the emulsifying agent added while added in reactor, is then triggered with initiator
Polymerization.At present, semi-continuous emulsion polymerizing is the industrial method generally used.
Hollow type polymer emulsion assigns that its density is low, stability is good, surface gas because of the distinctive hollow structure of its component
The features such as body permeability is good, surface light scattering property is good.Hollow structure polymer is increasingly becoming the focus of polymer arts research.
The main preparation methods of hollow structure polymer include：Acid/base swelling method, semicontinuous acid/base facture, dynamic swelling method etc..
At present, acid/base swelling method is the most frequently used method.
Soda acid swelling method, carboxylic seed emulsion is prepared first, then in the stratum nucleare microparticle surfaces with carboxylic group
Shell polymerization and expanding reaction are carried out, under more than or equal to shell glass transition temperature, with alkali and stratum nucleare particulate institute band
Carboxyl, water caused by neutralization are penetrated into core, and after emulsion particle is by being swelled solvent swell, alkali lye can easily enter core-shell structure copolymer
Reacted inside emulsion particle with carboxyl, the reaction of alkali lye and carboxyl adds the degree of ionization of particle, adds electric charge
Between repulsive interaction, making strand, particle volume expands to migrating outside particle, obtains containing water and polycarboxylate electricity
The polymer particles of matter are solved, Procedure of Polymerized Micro-Particles with Hollow is obtained after being cooled to room temperature.
In general, the cost of fabric finishing agent needs further to be reduced at present, needs to be sought milder to be more easily controlled
Polymeric reaction condition, the properties of fabric finishing agent need further to be improved.
The content of the invention
In order to solve deficiency of the prior art, it is an object of the invention to provide one kind enhancing surface gas permeability,
Improve light scattering property, reduce cost, polymeric reaction condition it is gentle it is easily controllable, in original single fluorine-containing polyisocyanate polyaddition
Collaboration enhances the water of strong fabric water and oil repellant, pliability, resistance to washability, weatherability and the degree of polymerization on the basis of thing finishing agent
The compound water-repellent breathable fabric finishing agent of the hollow fluorine silicon of property and preparation method.
To achieve the above object, the present invention uses following technical scheme：
A kind of water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon, its active principle is the fluorine-containing polyacrylic acid of hollow type
Ester-siloxanes composite polymeric high polymer shell, shown in the high polymer shell structure such as formula (I)：
* represents polymerisation site in the formula (I)；RSHigh polymer shell construction unit is represented, m, n, x, y and z represent 1
Integer between~100, including end value 1 and 100；
RfFluorochemical monomer is represented, shown in its structural formula such as formula (II)：
R in the formula (II)1For H, Me or Et；a1Integer between=0~5, including end value 0 and 5；B1=3~6 it
Between integer, including end value 3 and 6；
RSiOrganic silicon monomer is represented, shown in its structural formula such as formula (III)：
R in the formula (III)1For H, Me or Et；R2For one in halogen, Me, Et, OMe, OEt, MeOH, EtOH ,-OH
Kind；a2Integer between=0~5, including end value 0 and 5；
RUOther functional monomers are represented, are α-methacrylic acid hydroxyl ethyl ester, α-methacrylic acid hydroxypropyl acrylate, metering system
It is a kind of or more in acid glycidyl ester, NMA, benzyl methacrylate, isobornyl methacrylate
Kind；The concrete function of other functional monomers is chain extender, end-capping reagent or expanding dose.
The Rf、RSi、RUPolymerization site be at C=C.
It includes the component of following parts by weight：
Emulsification system：
Initiation system：
0.01~0.03 part of initiator
15.0~20.0 parts of distilled water
Buffer system：
0.005~0.02 part of buffer
15.0~20.0 parts of distilled water
Core pre-emulsion：
Shell pre-emulsion：
Remaining component：
0.035~0.09 part of other functional monomers.
The defoamer is dimethyl silicone polymer, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy third
One or more in alcohol amidogen ether, polypropylene glycerol aether.
The unsaturated carboxylic acid monomer is α-methacrylic acid, acrylic acid, β-butenoic acid, allyl acetic acid, trans -2- first
One or more in base -2- butenoic acids.
The initiator is the one or more in persulfate, azodiisobutyronitrile, AMBN.
The buffer is the one or more in sodium acid carbonate, ammonium hydrogen carbonate, saleratus.
A kind of preparation method of the water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon, it comprises the following steps：
A. the preparation of emulsification system：The each component of emulsification system is weighed by each component parts by weight, by Sorbitan alcohol ester
Fat acid esters (Span80), APES (OP-10), lauryl sodium sulfate (SDS), AEO
(AES) 10~40min is stirred in magnetic agitation reactor it is prepared into emulsified body with distilled water by matching at a temperature of 5~95 DEG C
It is standby, mixing speed=800~2500rpm；
B. the preparation of system is triggered：The each component of initiation system is weighed by each component parts by weight, by initiator and distilled water
Mixing, it is standby to be prepared into initiation system；
C. the preparation of buffer system：The each component of buffer system is weighed by each component parts by weight, by buffer and distilled water
Mixing, it is standby to be prepared into buffer system；
D. the preparation of core pre-emulsion：The each component of core pre-emulsion is weighed by each component parts by weight, by methyl methacrylate
(MMA), butyl acrylate (BA), organic silicon monomer, unsaturated carboxylic acid monomer, defoamer are placed in magnetic agitation reactor by proportioning
In, add emulsification system 20%~40% is used as emulsifying agent, in N210~40min of stirring under protective condition, mixing speed=
800~2500rpm, it is standby to be prepared into core pre-emulsion；
E. the preparation of shell pre-emulsion：The each component of shell pre-emulsion is weighed by each component parts by weight, by methyl methacrylate
(MMA), butyl acrylate (BA), fluorochemical monomer, organic silicon monomer, other functional monomers, defoamer are placed in magnetic force by proportioning
In stirred reactor, add emulsification system 20%~40% is used as emulsifying agent, in N210~40min is stirred under protective condition,
Mixing speed=800~2500rpm, it is standby to be prepared into shell pre-emulsion；
F. core pre-emulsion and 60%~80% initiation system are added dropwise to containing remaining emulsification system dropwise simultaneously, delayed
Rush system, agitator, thermometer, condenser pipe, N2Among the isothermal reactor of gatherer, return stirring at a temperature of 50~80 DEG C
Nuclear phase polymerisation is carried out, it is dominant to the obvious blue-fluorescence light of emulsion appearance, by other functional monomers in remaining component
Isothermal reactor is added dropwise with shell pre-emulsion and remaining initiation system, carries out shell polymerisation, reaction time 2-3h；
G. hollow processing：Isothermal reactor temperature is increased to 80~90 DEG C, adds hollow sweller, makes reaction system pH
Reach 12~13, quick 10~40min of stirring reaction, mixing speed=800~2500rpm, question response terminates to be cooled to rapidly
Room temperature, obtain water-based hollow fluorine silicon complex emulsions.
The cavitation sweller is one kind or more in LiOH, NaOH, KOH aqueous solution that concentration is 0.15~6mol/L
Kind.
The present invention uses above technical scheme, has following beneficial effect：
(1) by methyl methacrylate, butyl acrylate, fluorochemical monomer, organic silicon monomer and other functional monomers profit
Multipolymer is prepared with core-shell type radical polymerization mode, its each monomer is formed cooperative effect, so as to original single
Fluorinated acrylate polymer finishing agent on the basis of collaboration enhance strong fabric water and oil repellant, pliability, resistance to washability, resistance to
Time property and the degree of polymerization；
(2) polymeric reaction condition is gentle easily controllable and reduces the use of fluorochemical monomer and silicon-containing monomer on the original basis
Amount；
(3) hollow structure is incorporated into the preparation of high polymer textile finishing agent emulsion using hollow alkali swell process, protected
While holding original height water repellency, enhance the water vapour permeability of finish fabric, reached enhancing surface gas permeability,
Improve light scattering property, reduce cost and other effects；
(4) the compound synergy of fluorine silicon and special hollow structure under equal conditions effectively reduce the use of fluorochemical monomer
Amount, reduces finishing agent processing cost, improves economic benefit, saved fluorine resource, reduce fluorine element in environmental transport and transfer
Harm.
In summary, the compound water-repellent breathable fabric finishing agent of water-based hollow fluorine silicon of the invention and preparation method design are closed
Reason, has good economic and social benefits.
Brief description of the drawings
The present invention is described in further details below in conjunction with the drawings and specific embodiments：
Fig. 1 is the contact angle test result image for the product that the present invention obtains.
Embodiment
As shown in figure 1, the invention discloses a kind of water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon, its effective group
It is divided into hollow type fluorine-contaninig polyacrylate-siloxanes composite polymeric high polymer shell, the high polymer shell structure such as formula (I) institute
Show：
* represents polymerisation site in the formula (I)；RSHigh polymer shell construction unit is represented, m, n, x, y and z represent 1
Integer between~100, including end value 1 and 100；
RfFluorochemical monomer is represented, shown in its structural formula such as formula (II)：
R in the formula (II)1For H, Me or Et；a1Integer between=0~5, including end value 0 and 5；B1=3~6 it
Between integer, including end value 3 and 6；
RSiOrganic silicon monomer is represented, shown in its structural formula such as formula (III)：
R in the formula (III)1For H, Me or Et；R2For one in halogen, Me, Et, OMe, OEt, MeOH, EtOH ,-OH
Kind；a2Integer between=0~5, including end value 0 and 5；
RUOther functional monomers are represented, are α-methacrylic acid hydroxyl ethyl ester, α-methacrylic acid hydroxypropyl acrylate, metering system
It is a kind of or more in acid glycidyl ester, NMA, benzyl methacrylate, isobornyl methacrylate
Kind；The concrete function of other functional monomers is chain extender, end-capping reagent or expanding dose.
The Rf、RSi、RUPolymerization site be at C=C.
It includes the component of following parts by weight：
Emulsification system：
Initiation system：
0.01~0.03 part of initiator
15.0~20.0 parts of distilled water
Buffer system：
0.005~0.02 part of buffer
15.0~20.0 parts of distilled water
Core pre-emulsion：
Shell pre-emulsion：
Remaining component：
0.035~0.09 part of other functional monomers.
The defoamer is dimethyl silicone polymer, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy third
One or more in alcohol amidogen ether, polypropylene glycerol aether.
The unsaturated carboxylic acid monomer is α-methacrylic acid, acrylic acid, β-butenoic acid, allyl acetic acid, trans -2- first
One or more in base -2- butenoic acids.
The initiator is the one or more in persulfate, azodiisobutyronitrile, AMBN.
The buffer is the one or more in sodium acid carbonate, ammonium hydrogen carbonate, saleratus.
A kind of preparation method of the water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon, it comprises the following steps：
A. the preparation of emulsification system：The each component of emulsification system is weighed by each component parts by weight, by Sorbitan alcohol ester
Fat acid esters (Span80), APES (OP-10), lauryl sodium sulfate (SDS), AEO
(AES) 10~40min is stirred in magnetic agitation reactor it is prepared into emulsified body with distilled water by matching at a temperature of 5~95 DEG C
It is standby, mixing speed=800~2500rpm；
B. the preparation of system is triggered：The each component of initiation system is weighed by each component parts by weight, by initiator and distilled water
Mixing, it is standby to be prepared into initiation system；
C. the preparation of buffer system：The each component of buffer system is weighed by each component parts by weight, by buffer and distilled water
Mixing, it is standby to be prepared into buffer system；
D. the preparation of core pre-emulsion：The each component of core pre-emulsion is weighed by each component parts by weight, by methyl methacrylate
(MMA), butyl acrylate (BA), organic silicon monomer, unsaturated carboxylic acid monomer, defoamer are placed in magnetic agitation reactor by proportioning
In, add emulsification system 20%~40% is used as emulsifying agent, in N210~40min of stirring under protective condition, mixing speed=
800~2500rpm, it is standby to be prepared into core pre-emulsion；
E. the preparation of shell pre-emulsion：The each component of shell pre-emulsion is weighed by each component parts by weight, by methyl methacrylate
(MMA), butyl acrylate (BA), fluorochemical monomer, organic silicon monomer, other functional monomers, defoamer are placed in magnetic force by proportioning
In stirred reactor, add emulsification system 20%~40% is used as emulsifying agent, in N210~40min is stirred under protective condition,
Mixing speed=800~2500rpm, it is standby to be prepared into shell pre-emulsion；
F. core pre-emulsion and 60%~80% initiation system are added dropwise to containing remaining emulsification system dropwise simultaneously, delayed
Rush system, agitator, thermometer, condenser pipe, N2Among the isothermal reactor of gatherer, return stirring at a temperature of 50~80 DEG C
Nuclear phase polymerisation is carried out, it is dominant to the obvious blue-fluorescence light of emulsion appearance, by other functional monomers in remaining component
Isothermal reactor is added dropwise with shell pre-emulsion and remaining initiation system, carries out shell polymerisation, reaction time 2-3h；
G. hollow processing：Isothermal reactor temperature is increased to 80~90 DEG C, adds hollow sweller, makes reaction system pH
Reach 12~13, quick 10~40min of stirring reaction, mixing speed=800~2500rpm, question response terminates to be cooled to rapidly
Room temperature, obtain water-based hollow fluorine silicon complex emulsions.
The cavitation sweller is one kind or more in LiOH, NaOH, KOH aqueous solution that concentration is 0.15~6mol/L
Kind.
Embodiment 1
A kind of water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon, its active principle is the fluorine-containing polyacrylic acid of hollow type
Ester-siloxanes composite polymeric high polymer shell, shown in the high polymer shell structure such as formula (I)：
* represents polymerisation site in the formula (I)；RSRepresent high polymer shell construction unit, m=1, n=100, x=
50th, y=50, z=50；
RfFluorochemical monomer is represented, shown in its structural formula such as formula (II)：
R in the formula (II)1For H；a1=0；B1=4；
RSiOrganic silicon monomer is represented, shown in its structural formula such as formula (III)：
R in the formula (III)1For Et；R2For halogen；a2=0；
RUOther functional monomers are represented, are α-methacrylic acid hydroxyl ethyl ester；The specific work(of other functional monomers
Can be chain extender, end-capping reagent or expanding dose.
The Rf、RSi、RUPolymerization site be at C=C.
It includes the component of following parts by weight：
Emulsification system：
Initiation system：
0.02 part of persulfate
17.5 parts of distilled water
Buffer system：
0.02 part of sodium acid carbonate
15.0 parts of distilled water
Core pre-emulsion：
Shell pre-emulsion：
Remaining component：
0.035 part of α-methacrylic acid hydroxyl ethyl ester.
A kind of preparation method of the water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon, it comprises the following steps：
A. the preparation of emulsification system：The each component of emulsification system is weighed by each component parts by weight, by Sorbitan alcohol ester
Fat acid esters (Span80), APES (OP-10), lauryl sodium sulfate (SDS), AEO
(AES) with distilled water 25min is stirred in magnetic agitation reactor to be prepared into emulsification system standby by matching at a temperature of 50 DEG C,
Mixing speed=800rpm；
B. the preparation of system is triggered：The each component of initiation system is weighed by each component parts by weight, by persulfate and distillation
Water mixes, and it is standby to be prepared into initiation system；
C. the preparation of buffer system：The each component of buffer system is weighed by each component parts by weight, by sodium acid carbonate and distillation
Water mixes, and it is standby to be prepared into buffer system；
D. the preparation of core pre-emulsion：The each component of core pre-emulsion is weighed by each component parts by weight, by methyl methacrylate
(MMA), butyl acrylate (BA), organic silicon monomer, α-methacrylic acid, dimethyl silicone polymer are placed in magnetic agitation by proportioning
In reactor, add emulsification system 20% is used as emulsifying agent, in N2Stir 25min under protective condition, mixing speed=
2500rpm, it is standby to be prepared into core pre-emulsion；
E. the preparation of shell pre-emulsion：The each component of shell pre-emulsion is weighed by each component parts by weight, by methyl methacrylate
(MMA), butyl acrylate (BA), fluorochemical monomer, organic silicon monomer, α-methacrylic acid hydroxyl ethyl ester, dimethyl silicone polymer are pressed
Proportioning is placed in magnetic agitation reactor, and add emulsification system 40% is used as emulsifying agent, in N2Stirred under protective condition
25min, mixing speed=800rpm, it is standby to be prepared into shell pre-emulsion；
F. core pre-emulsion and 60% initiation system are added dropwise to containing remaining emulsification system, buffer body dropwise simultaneously
System, agitator, thermometer, condenser pipe, N2Among the isothermal reactor of gatherer, return stirring carries out nuclear phase at a temperature of 65 DEG C
Polymerisation, it is dominant to the obvious blue-fluorescence light of emulsion appearance, by the α-methacrylic acid hydroxyl ethyl ester and shell in remaining component
Isothermal reactor is added dropwise with remaining initiation system in pre-emulsion, carries out shell polymerisation, reaction time 2h；
G. hollow processing：Isothermal reactor temperature is increased to 90 DEG C, 0.15mol/L LiOH is added, makes reaction system
PH reaches 12, quick stirring reaction 10min, mixing speed=800rpm, and question response terminates to be cooled to room temperature rapidly, obtained water-based
Hollow fluorine silicon complex emulsions.
Fabric is arranged：Two leachings two roll (pick-up 75%) by 80 DEG C of preliminary drying 3min, 150 DEG C of baking 5min, take
Go out 3 dischargings of washing.
Embodiment 2
A kind of water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon, its active principle is the fluorine-containing polyacrylic acid of hollow type
Ester-siloxanes composite polymeric high polymer shell, shown in the high polymer shell structure such as formula (I)：
* represents polymerisation site in the formula (I)；RSRepresent high polymer shell construction unit, m=50, n=50, x=
1st, y=100, z=1；
RfFluorochemical monomer is represented, shown in its structural formula such as formula (II)：
R in the formula (II)1For Me；a1=3；B1=3；
RSiOrganic silicon monomer is represented, shown in its structural formula such as formula (III)：
R in the formula (III)1For Me；R2For Me；a2=5；
RUOther functional monomers are represented, are α-methacrylic acid hydroxypropyl acrylate；The specific work(of other functional monomers
Can be chain extender, end-capping reagent or expanding dose.
The Rf、RSi、RUPolymerization site be at C=C.
It includes the component of following parts by weight：
Emulsification system：
Initiation system：
0.01 part of azodiisobutyronitrile
20.0 parts of distilled water
Buffer system：
0.005 part of ammonium hydrogen carbonate
20.0 parts of distilled water
Core pre-emulsion：
Shell pre-emulsion：
Remaining component：
0.09 part of α-methacrylic acid hydroxypropyl acrylate.
A kind of preparation method of the water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon, it comprises the following steps：
A. the preparation of emulsification system：The each component of emulsification system is weighed by each component parts by weight, by Sorbitan alcohol ester
Fat acid esters (Span80), APES (OP-10), lauryl sodium sulfate (SDS), AEO
(AES) with distilled water 10min is stirred in magnetic agitation reactor to be prepared into emulsification system standby by matching at a temperature of 5 DEG C,
Mixing speed=2500rpm；
B. the preparation of system is triggered：The each component of initiation system is weighed by each component parts by weight, by azodiisobutyronitrile and
Distilled water mixes, and it is standby to be prepared into initiation system；
C. the preparation of buffer system：The each component of buffer system is weighed by each component parts by weight, by ammonium hydrogen carbonate and distillation
Water mixes, and it is standby to be prepared into buffer system；
D. the preparation of core pre-emulsion：The each component of core pre-emulsion is weighed by each component parts by weight, by methyl methacrylate
(MMA), butyl acrylate (BA), organic silicon monomer, acrylic acid, polyoxyethylene polyoxypropylene pentaerythrite ether are placed in magnetic by proportioning
In power stirred reactor, add emulsification system 30% is used as emulsifying agent, in N210min, mixing speed are stirred under protective condition
=800rpm, it is standby to be prepared into core pre-emulsion；
E. the preparation of shell pre-emulsion：The each component of shell pre-emulsion is weighed by each component parts by weight, by methyl methacrylate
(MMA), butyl acrylate (BA), fluorochemical monomer, organic silicon monomer, α-methacrylic acid hydroxypropyl acrylate, polyoxyethylene polyoxypropylene
Pentaerythrite ether is placed in magnetic agitation reactor by proportioning, and add emulsification system 20% is used as emulsifying agent, in N2Ceiling
10min is stirred under part, mixing speed=2500rpm, it is standby to be prepared into shell pre-emulsion；
F. core pre-emulsion and 80% initiation system are added dropwise to containing remaining emulsification system, buffer body dropwise simultaneously
System, agitator, thermometer, condenser pipe, N2Among the isothermal reactor of gatherer, return stirring carries out nuclear phase at a temperature of 50 DEG C
Polymerisation, it is dominant to the obvious blue-fluorescence light of emulsion appearance, by the α-methacrylic acid hydroxypropyl acrylate and shell in remaining component
Isothermal reactor is added dropwise with remaining initiation system in pre-emulsion, carries out shell polymerisation, reaction time 3h；
G. hollow processing：Isothermal reactor temperature is increased to 80 DEG C, adds 6mol/L NaOH, reaches reaction system pH
To 13, quick stirring reaction 40min, mixing speed=2500rpm, question response terminates to be cooled to room temperature rapidly, obtain it is water-based in
Empty fluorine silicon complex emulsions.
Fabric is arranged：Two leachings two roll (pick-up 75%) by 80 DEG C of preliminary drying 3min, 150 DEG C of baking 5min, take
Go out 3 dischargings of washing.
Embodiment 3
A kind of water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon, its active principle is the fluorine-containing polyacrylic acid of hollow type
Ester-siloxanes composite polymeric high polymer shell, shown in the high polymer shell structure such as formula (I)：
* represents polymerisation site in the formula (I)；RSRepresent high polymer shell construction unit, m=100, n=1, x=
100th, y=1, z=100；
RfFluorochemical monomer is represented, shown in its structural formula such as formula (II)：
R in the formula (II)1For Et；a1=5；B1=6；
RSiOrganic silicon monomer is represented, shown in its structural formula such as formula (III)：
R in the formula (III)1For H；R2For Et；a2=3；
RUOther functional monomers are represented, are GMA；Other functional monomers it is specific
Function is chain extender, end-capping reagent or expanding dose.
The Rf、RSi、RUPolymerization site be at C=C.
It includes the component of following parts by weight：
Emulsification system：
Initiation system：
0.03 part of AMBN
15.0 parts of distilled water
Buffer system：
0.01 part of saleratus
17.0 parts of distilled water
Core pre-emulsion：
Shell pre-emulsion：
Remaining component：
0.063 part of GMA.
A kind of preparation method of the water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon, it comprises the following steps：
A. the preparation of emulsification system：The each component of emulsification system is weighed by each component parts by weight, by Sorbitan alcohol ester
Fat acid esters (Span80), APES (OP-10), lauryl sodium sulfate (SDS), AEO
(AES) with distilled water 40min is stirred in magnetic agitation reactor to be prepared into emulsification system standby by matching at a temperature of 95 DEG C,
Mixing speed=1600rpm；
B. the preparation of system is triggered：The each component of initiation system is weighed by each component parts by weight, by AMBN and
Distilled water mixes, and it is standby to be prepared into initiation system；
C. the preparation of buffer system：The each component of buffer system is weighed by each component parts by weight, by saleratus and distillation
Water mixes, and it is standby to be prepared into buffer system；
D. the preparation of core pre-emulsion：The each component of core pre-emulsion is weighed by each component parts by weight, by methyl methacrylate
(MMA), butyl acrylate (BA), organic silicon monomer, β-butenoic acid, polyoxyethylene polyoxy propyl alcohol amidogen ether are placed in magnetic force by proportioning and stirred
Mix in reactor, add emulsification system 40% is used as emulsifying agent, in N2Stir 40min under protective condition, mixing speed=
1600rpm, it is standby to be prepared into core pre-emulsion；
E. the preparation of shell pre-emulsion：The each component of shell pre-emulsion is weighed by each component parts by weight, by methyl methacrylate
(MMA), butyl acrylate (BA), fluorochemical monomer, organic silicon monomer, GMA, polyoxyethylene polyoxy third
Alcohol amidogen ether is placed in magnetic agitation reactor by proportioning, and add emulsification system 30% is used as emulsifying agent, in N2Under protective condition
40min is stirred, mixing speed=1600rpm, it is standby to be prepared into shell pre-emulsion；
F. core pre-emulsion and 70% initiation system are added dropwise to containing remaining emulsification system, buffer body dropwise simultaneously
System, agitator, thermometer, condenser pipe, N2Among the isothermal reactor of gatherer, return stirring carries out nuclear phase at a temperature of 80 DEG C
Polymerisation, it is dominant to there is obvious blue-fluorescence light to emulsion, by the GMA in remaining component and
Isothermal reactor is added dropwise with remaining initiation system in shell pre-emulsion, carries out shell polymerisation, reaction time 2.5h；
G. hollow processing：Isothermal reactor temperature is increased to 85 DEG C, adds 3.1mol/L KOH, makes reaction system pH
Reach 12, quick stirring reaction 25min, mixing speed=1600rpm, question response terminates to be cooled to room temperature rapidly, obtain water-based
Hollow fluorine silicon complex emulsions.
Fabric is arranged：Two leachings two roll (pick-up 75%) by 80 DEG C of preliminary drying 3min, 150 DEG C of baking 5min, take
Go out 3 dischargings of washing.
Embodiment 4
R in the formula (III)2For OMe；
RUOther functional monomers are represented, are NMA；
α-methacrylic acid hydroxyl ethyl ester in embodiment 1 is replaced with into NMA；
α-methacrylic acid in embodiment 1 is replaced with into allyl acetic acid；
Dimethyl silicone polymer in embodiment 1 is replaced with into polypropylene glycerol aether；
Remaining is the same as embodiment 1.
Embodiment 5
R in the formula (III)2For OEt；
RUOther functional monomers are represented, are benzyl methacrylate；
α-methacrylic acid hydroxyl ethyl ester in embodiment 1 is replaced with into benzyl methacrylate；
α-methacrylic acid in embodiment 1 is replaced with into trans -2- methyl-2-butenoic acids；
Remaining is the same as embodiment 1.
Embodiment 6
R in the formula (III)2For MeOH；
RUOther functional monomers are represented, are isobornyl methacrylate；
α-methacrylic acid hydroxyl ethyl ester in embodiment 1 is replaced with into isobornyl methacrylate；
Remaining is the same as embodiment 1.
Embodiment 7
R in the formula (III)2For EtOH；
Remaining is the same as embodiment 1.
Embodiment 8
R in the formula (III)2For-OH；
Remaining is the same as embodiment 1.
The properties of sample comparison sheet of 1 each embodiment of table
Note：Emulsion solid content is the mass percent that remainder accounts for total amount after drying under prescribed conditions.Control sample is
Chinese certain enterprise production, the proximate composition water-refusing oil-refusing finishing agent applied to domestic textile enterprise.
As can be seen from Table 1 case study on implementation 1 to the emulsion emulsion solid content of case study on implementation 8 not less than 10%, product
Contact angle more than 130 °, washing 5 times after contact angle more than 128 °, illustrate have after cloth is collated
Excellent water repellency and washing stability is preferable, and is superior to the existing close product in market.Permeability can reach 175mm/s
More than, it is superior to the existing close product in market.Increased weight under equal conditions not less than 1.15g/dm2.The surface water droplet residence time
>20min, the properties of product after arrangement are preferable.Pliability reaches 2.5 grades, compared with former cloth material and approximate product, has bright
Aobvious lifting.Prove that the product has good hydrophobic permeable performance, pliability and the property having good stability by indices
Energy.
The all derivative done in the scope of the claims of the present invention, change and modification, all should belong to protection scope of the present invention.
Claims (8)
1. a kind of water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon, it is characterised in that its active principle contains for hollow type
Fluorine polyacrylate-siloxanes composite polymeric high polymer shell, shown in the high polymer shell structure such as formula (I)：
* represents polymerisation site in the formula (I)；RSHigh polymer shell construction unit is represented, m, n, x, y and z represent 1~100
Between integer, including end value 1 and 100；
RfFluorochemical monomer is represented, shown in its structural formula such as formula (II)：
R in the formula (II)1For H, Me or Et；a1Integer between=0~5, including end value 0 and 5；Between b1=3~6
Integer, including end value 3 and 6；
RSiOrganic silicon monomer is represented, shown in its structural formula such as formula (III)：
R in the formula (III)1For H, Me or Et；R2For one kind in halogen, Me, Et, OMe, OEt, MeOH, EtOH ,-OH；a2
Integer between=0~5, including end value 0 and 5；
RUOther functional monomers are represented, are α-methacrylic acid hydroxyl ethyl ester, α-methacrylic acid hydroxypropyl acrylate, methacrylic acid contracting
One or more in water glyceride, NMA, benzyl methacrylate, isobornyl methacrylate；
The Rf、RSi、RUPolymerization site be at C=C.
2. the water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon of one kind according to claim 1, it is characterised in that its
Include the component of following parts by weight：
Emulsification system：
Initiation system：
0.01~0.03 part of initiator
15.0~20.0 parts of distilled water
Buffer system：
0.005~0.02 part of buffer
15.0~20.0 parts of distilled water
Core pre-emulsion：
Shell pre-emulsion：
Remaining component：
0.035~0.09 part of other functional monomers.
3. the water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon of one kind according to claim 2, it is characterised in that institute
Defoamer is stated as dimethyl silicone polymer, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polyoxy
One or more in propylene glycerin ether.
4. the water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon of one kind according to claim 2, it is characterised in that institute
Unsaturated carboxylic acid monomer is stated as α-methacrylic acid, acrylic acid, β-butenoic acid, allyl acetic acid, trans -2- methyl-2-butenes
One or more in acid.
5. the water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon of one kind according to claim 2, it is characterised in that institute
Initiator is stated as the one or more in persulfate, azodiisobutyronitrile, AMBN.
6. the water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon of one kind according to claim 2, it is characterised in that institute
Buffer is stated as the one or more in sodium acid carbonate, ammonium hydrogen carbonate, saleratus.
A kind of 7. preparation side of water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon according to one of claim 2-6
Method, it is characterised in that it comprises the following steps：
A. the preparation of emulsification system：The each component of emulsification system is weighed by each component parts by weight, by sorbitan fatty acid
Ester (Span80), APES (OP-10), lauryl sodium sulfate (SDS), AEO (AES)
With distilled water 10~40min is stirred in magnetic agitation reactor to be prepared into emulsification system standby by matching at a temperature of 5~95 DEG C
With mixing speed=800~2500rpm；
B. the preparation of system is triggered：The each component of initiation system is weighed by each component parts by weight, initiator and distilled water are mixed,
It is standby to be prepared into initiation system；
C. the preparation of buffer system：The each component of buffer system is weighed by each component parts by weight, buffer and distilled water are mixed,
It is standby to be prepared into buffer system；
D. the preparation of core pre-emulsion：The each component of core pre-emulsion is weighed by each component parts by weight, by methyl methacrylate
(MMA), butyl acrylate (BA), organic silicon monomer, unsaturated carboxylic acid monomer, defoamer are placed in magnetic agitation reactor by proportioning
In, add emulsification system 20%~40% is used as emulsifying agent, in N210~40min of stirring under protective condition, mixing speed=
800~2500rpm, it is standby to be prepared into core pre-emulsion；
E. the preparation of shell pre-emulsion：The each component of shell pre-emulsion is weighed by each component parts by weight, by methyl methacrylate
(MMA), butyl acrylate (BA), fluorochemical monomer, organic silicon monomer, other functional monomers, defoamer are placed in magnetic force by proportioning
In stirred reactor, add emulsification system 20%~40% is used as emulsifying agent, in N210~40min is stirred under protective condition,
Mixing speed=800~2500rpm, it is standby to be prepared into shell pre-emulsion；
F. core pre-emulsion and 60%~80% initiation system are added dropwise to containing remaining emulsification system, buffer body dropwise simultaneously
System, agitator, thermometer, condenser pipe, N2Among the isothermal reactor of gatherer, return stirring is carried out at a temperature of 50~80 DEG C
Nuclear phase polymerisation, it is dominant to the obvious blue-fluorescence light of emulsion appearance, by other functional monomers and shell in remaining component
Isothermal reactor is added dropwise with remaining initiation system in pre-emulsion, carries out shell polymerisation, reaction time 2-3h；
G. hollow processing：Isothermal reactor temperature is increased to 80~90 DEG C, adds hollow sweller, reaches reaction system pH
12~13, quick 10~40min of stirring reaction, mixing speed=800~2500rpm, question response terminate to be cooled to room temperature rapidly,
Obtain water-based hollow fluorine silicon complex emulsions.
8. a kind of preparation method of water-based hollow compound water-repellent breathable fabric finishing agent of fluorine silicon according to claim 7, its
Be characterised by, the cavitation sweller be one kind in LiOH, NaOH, KOH aqueous solution that concentration is 0.15~6mol/L or
It is a variety of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610365004.9A CN105970628B (en) | 2016-05-27 | 2016-05-27 | A kind of compound water-repellent breathable fabric finishing agent of water-based hollow fluorine silicon and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610365004.9A CN105970628B (en) | 2016-05-27 | 2016-05-27 | A kind of compound water-repellent breathable fabric finishing agent of water-based hollow fluorine silicon and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105970628A CN105970628A (en) | 2016-09-28 |
| CN105970628B true CN105970628B (en) | 2017-11-24 |
Family
ID=56956495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610365004.9A Active CN105970628B (en) | 2016-05-27 | 2016-05-27 | A kind of compound water-repellent breathable fabric finishing agent of water-based hollow fluorine silicon and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105970628B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107619451A (en) * | 2017-09-20 | 2018-01-23 | 开翊新材料科技（上海）有限公司 | It is a kind of for the fluorinated copolymers of waterproof and oilproof paper and its preparation method of emulsion |
| CN110066379B (en) * | 2019-04-29 | 2020-09-29 | 四川大学 | Fluorine-containing and silicon-containing polyurethane material with high biological stability and preparation method thereof |
| CN114808455B (en) * | 2022-05-19 | 2023-05-05 | 广州大学 | Environment-friendly fluorine-free fabric waterproof moisture permeable agent, preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396520A (en) * | 2013-08-05 | 2013-11-20 | 陕西科技大学 | Core-shell structure nanometer titanium dioxide/ fluorine-containing polyacrylate soap-free composite emulsion and preparation method thereof |
| CN103435745A (en) * | 2013-08-06 | 2013-12-11 | 浙江大学 | Low-temperature crosslinking fluorine-containing nuclear shell type water-repellent and oil-repellent finishing agent emulsion and preparation method thereof |
| CN103613701A (en) * | 2013-11-21 | 2014-03-05 | 五邑大学 | Fluorosilicon-modified core-shell acrylate soap-free emulsion and preparation method thereof |
| CN105440201A (en) * | 2014-08-13 | 2016-03-30 | 南京理工大学 | Core-shell type short-chain fluorine-containing acrylate emulsion and preparation method thereof |
-
2016
- 2016-05-27 CN CN201610365004.9A patent/CN105970628B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396520A (en) * | 2013-08-05 | 2013-11-20 | 陕西科技大学 | Core-shell structure nanometer titanium dioxide/ fluorine-containing polyacrylate soap-free composite emulsion and preparation method thereof |
| CN103435745A (en) * | 2013-08-06 | 2013-12-11 | 浙江大学 | Low-temperature crosslinking fluorine-containing nuclear shell type water-repellent and oil-repellent finishing agent emulsion and preparation method thereof |
| CN103613701A (en) * | 2013-11-21 | 2014-03-05 | 五邑大学 | Fluorosilicon-modified core-shell acrylate soap-free emulsion and preparation method thereof |
| CN105440201A (en) * | 2014-08-13 | 2016-03-30 | 南京理工大学 | Core-shell type short-chain fluorine-containing acrylate emulsion and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105970628A (en) | 2016-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105111364B (en) | A kind of fluoro-acrylate copolymer finishing agent and preparation method thereof | |
| CN102492087B (en) | Fluorine-containing acrylate copolymer cationic emulsion as well as preparation method and application thereof | |
| CN105970628B (en) | A kind of compound water-repellent breathable fabric finishing agent of water-based hollow fluorine silicon and preparation method | |
| CN104031204B (en) | The preparation method of cationic fluorochemical polyacrylic acid ester soap-free emulsion | |
| CN104532579A (en) | Fluorine-containing water and oil repellent finishing agent and preparation method thereof | |
| CN1646585A (en) | Dispersions containing bicomponent fluoropolymer particles and use thereof | |
| CN105175616B (en) | A kind of Organic fluoride acrylate copolymer emulsion finishing agent, its preparation method and application | |
| CN101550217A (en) | Method for preparing soap-free silicone-acrylic emulsion with core-shell structure | |
| CN106543374A (en) | Fluoro-acrylate copolymer emulsion and preparation method thereof and prepare latex film method | |
| CN102702437A (en) | Styrene-acrylic emulsion as well as preparation method and application thereof | |
| CN101475507B (en) | Fluorinated acrylate, preparation method and preparation of copolymer thereof | |
| CN103570886A (en) | Organic silicon modified fluorinated acrylate polymer and preparation method thereof | |
| CN103396520A (en) | Core-shell structure nanometer titanium dioxide/ fluorine-containing polyacrylate soap-free composite emulsion and preparation method thereof | |
| CN103387645A (en) | Fluorine-containing copolymer grafted modified nano TiO2 compound particle and preparation method thereof | |
| CN109281172A (en) | Hud typed free-floride water-proof aagent and its preparation method and application | |
| CN107056999A (en) | A kind of fluorine-containing porous material preparation method based on the stable High Internal Phase Emulsion of amphipathic fluoride macromolecular block thing | |
| CN109666111A (en) | A kind of Nano-meter SiO_22/ organosilicon-modified acrylate emulsion | |
| CN104428327A (en) | Method for manufacturing fluorine-containing polymer | |
| CN101544723A (en) | Method for preparing fluorinated acrylate copolymer | |
| CN115010932B (en) | Hydrophobic oleophobic fluorine-containing microsphere and preparation method thereof | |
| CN105859950A (en) | Core-shell type fluorine-and-silicon-containing long carbon chain acrylate water and oil repellent agent | |
| CN103073673B (en) | Epoxy-group-containing fluorosilicone modified acrylate emulsion and preparation method thereof | |
| CN108676112A (en) | The preparation method of monodisperse solvent resistant high-carboxyl-content polystyrene microsphere | |
| CN103665242B (en) | A kind of Silica sol/acrylate nano core-shell compound emulsion and preparation method thereof | |
| CN101092289B (en) | A super hydrophobic material with roughened surface |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |