CN109162097A - One kind having core-shell structure high-efficient, no-freon waterproofing agent and preparation method thereof - Google Patents
One kind having core-shell structure high-efficient, no-freon waterproofing agent and preparation method thereof Download PDFInfo
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- CN109162097A CN109162097A CN201810883592.4A CN201810883592A CN109162097A CN 109162097 A CN109162097 A CN 109162097A CN 201810883592 A CN201810883592 A CN 201810883592A CN 109162097 A CN109162097 A CN 109162097A
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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
-
- 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
-
- 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
- D06M15/273—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having epoxy groups
-
- 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
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
- D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
-
- 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
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (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
- D06M2200/12—Hydrophobic properties
Abstract
By selecting the long-chain alkyl groups acrylic monomer with crystal property to substitute fluorine-containing material, its feature of environmental protection is improved；By selecting the special emulsifier and special synthesis technology with reactable group, synthesizes and improved the waterproof performance without fluoro water proofing agent without fluoro water proofing agent with core-shell structure.It should be pointed out that preferred embodiment described above, is not construed as limiting the scope of the invention, also within protection scope of the present invention for the improvement, change and retouching made without departing from the inventive concept of the premise.
Description
Technical field
The invention belongs to technical field of fine, and in particular to one kind have core-shell structure high-efficient, no-freon waterproofing agent and its
Preparation method.
Background technique
In textile auxiliary field, the waterproof performance of fabric is arranged by anti-aqueous dispersions to be obtained.Its essence is in fabric table
A layered low-surface energy substance is adsorbed in face, achievees the purpose that water and oil repellant with this, therefore, surface can be lower, and waterproof effect is generally got over
Good, waterproofing agent is mainly the most extensive with the dispersion liquid of fluorine-containing material at present, studies also the most active.Predominantly there is perfluoro alkane
The polymer of base or perfluoro alkenyl or acrylic or isobutene acidic group.In recent years, because people's environmental consciousness enhances,
It is also more and more clear for the limitation regulation of fluorine-containing water repellent gradually in the use for reducing fluorine-containing water repellent.U.S.EPA adds
Many productions and use for organizing all to have standardized perfluoroalkyl Long carbon chain compound in the world such as environmental organization of putting on airs and European Union, connection
State's environment administration is closed also PFOS (perfluorooctane sulfonate) and PFOA (perfluoro caprylic acid) have been included in " about persistence organic pollutant
Convention of Stockholm ".Therefore, exploitation high-performance environment protection type is whole as fluoro containing polymers waterproof without fluoro water proofing agent fabric finishing agent
The substitute of agent, the update to fluorine-containing water-proof aagent are managed, the protection to environment all has great importance.
The critical surface tension of fluorine-containing water repellent most ideally can reach 6mN/m, with minimum surface energy, but together
When, reach fluorochemical monomer, more fluorine-containing material, suitable cross-linked structure that the perfect condition needs special long-chain；And conduct
Hydrocarbon, the attainable minimum critical surface tension of long chain alkane are 20mN/m, can be realized by the crystal face that crystallization is formed
The minimum surface energy.As the liquid to be prevented of fabric, such as milk surface tension is 43mN/m, and grape wine surface tension is
45mN/m, water surface tension 72.8mN/m, the surface tension of these liquid is all more than long chain alkane critical surface tension, reason
By the upper wetting and pollution that can prevent these liquid completely to fabric.
The common waterproofing agent containing chain alkyl leads to its waterproof performance because of the missing or imperfect of crystal plane structure
It has certain loss, when critical surface tension is close to liquid such as water, milk, results in wetting of these liquid to fabric.Cause
This has the special particle of core-shell structure by synthesizing, while using can response type non-ionic surface in order to solve this problem
Activating agent sufficiently improves long chain alkane in the crystalline perfection energy on surface, sufficiently improves the waterproof performance without fluoro water proofing agent.Together
When, this without fluoro water proofing agent to environment not enough at pressure, it is environmentally protective.
Summary of the invention
It is an object of that present invention to provide one kind to have core-shell structure high-efficient, no-freon waterproofing agent and preparation method thereof, can assign and knit
The excellent waterproof performance of object substrate, at the same it is environmentally protective, pressure is not constituted to environment.With overcome the deficiencies in the prior art.
Technical scheme is as follows: one kind having core-shell structure high-efficient, no-freon waterproofing agent, which is characterized in that the tool
Have core-shell structure high-efficient, no-freon waterproofing agent includes following components by mass percentage: (R) acrylate long chain alkane monomer 15%-
34%, functional free radical polymerizable monomer 1%-20%, surfactant 1%-5%, hydrophilic solvent 4%-10%, pH tune
Save auxiliary agent 0.01%-3%, surplus is water；Functional free radical polymerizable monomer is (methyl) vinyl cycloalkane, (methyl) third
Olefin(e) acid ester cycloalkane, (methyl) vinyl halide alkane, copolymerizable crosslinkable monomers；
The synthesis mode with core-shell structure high-efficient, no-freon waterproofing agent be by (R) acrylate long chain alkane monomer,
Functional monomer is caused under the emulsification of emulsifier by free radical, is synthesized in a manner of seeded emulsion polymerization.
Above-mentioned to have core-shell structure high-efficient, no-freon waterproofing agent, the alkyl of (R) the acrylate long chain alkane monomer is straight
Chain, carbon atom number are 8-30, R H, Cl, Br, F or CH3。
It is above-mentioned that there is core-shell structure high-efficient, no-freon waterproofing agent, (methyl) vinyl cycloalkane, (methyl) acrylate
The cycloalkane of cycloalkane includes monocycle, polycyclic and bridged ring, can be saturated alkane, or unsaturated alkane；Monocycle is big
Small preferred five-membered ring and hexatomic ring, polycyclic preferably bicyclic or tricyclic；Preferably be selected from phenyl, cyclohexyl, cyclopenta, bicyclopentyl,
One of isobornyl is a variety of.
Above-mentioned to have core-shell structure high-efficient, no-freon waterproofing agent, the halogen of (methyl) the vinyl halide alkane is I, Br, Cl
Or F.
Above-mentioned to have core-shell structure high-efficient, no-freon waterproofing agent, the copolymerizable crosslinkable monomers have hydroxyl, carboxyl, ammonia
Base, chloromethyl, methoxyl group, ethyoxyl, azido, double bond, three key isoreactivity groups it is one or more.
Above-mentioned to have core-shell structure high-efficient, no-freon waterproofing agent, emulsifier includes cationic emulsifier, nonionic emulsifier.
Above-mentioned to have core-shell structure high-efficient, no-freon waterproofing agent, the cationic emulsifier is fat-based ammonium salt, wherein fat
Base is mainly straight chain and long-chain saturation and unsaturated alkane containing branch, and carbon atom number is in 4-22；
Surfactant is the polyoxyethylene for having different chain length, polyoxypropylene and the nonionic table for having active group
Face activating agent；Repetitive unit CH2CH2O、CH2CH(CH3) O is respectively 0-100, preferably 5-50.
Above-mentioned have a core-shell structure high-efficient, no-freon waterproofing agent, the active group end of the surfactant include double bond,
One of three keys, epoxy group, isocyanate group of hydroxyl, chloromethyl, amino, carboxyl, azido or sealing end are a variety of.
The above-mentioned preparation method with core-shell structure high-efficient, no-freon waterproofing agent: it is added in the reactor by emulsifying
Total amount 80-100% (R) acrylate long chain alkane monomer, total amount 0%-50% part functionalities free radical polymerizable monomer, always
It measures 50%-90% surfactant, hydrophilic solvent, pH and adjusts auxiliary agent, the mixture lotion of total amount 80%-90% water and total
Measure 10%-90% initiator, control temperature at 50-70 DEG C, reaction 0.5-5 hour after, adjusting temperature of reactor to 30-50 DEG C,
By remaining 0%-20% (R) acrylate long chain alkane monomer, residue 50%-100% functionality free radical polymerizable monomer, remain
Remaining 10%-50% surfactant, residue 10%-20% water and residue 10%-90% initiator are added, and continue to be stirred to react
Stop reaction after 0.5-6 hours, obtain after filter-cloth filtering having core-shell structure without fluoro water proofing agent product.
The beneficial effects of the present invention are:
The present invention relates to the high-efficient, no-freon waterproofing agents with core-shell structure, mainly contain polymer and surfactant, institute
The homopolymer or copolymer that polymeric component is one or more kinds of components are stated, the polymer contains (a) (R) acrylate long-chain
Arrcostab；(b) (methyl) vinyl cycloalkane, (methyl) vinyl halide alkane, (methyl) acrylate cycloalkanes hydrocarbon polymer, with
And the crosslinkable monomers that can be copolymerized with it；The surfactant, which contains (a) cationic surfactant (b), has reactive base
The nonionic surfactant of group.Surfactant component (b) is the polyoxyethylene containing different chain length, polyoxypropylene and band
The nonionic surfactant of active group.
The present invention relates to the special particles that the high-efficient, no-freon waterproofing agent with core-shell structure has core-shell structure, pass through spy
Different synthesis technology and step obtains the particle with core-shell structure, sufficiently improves long chain alkane in the crystalline perfection on surface
Can, sufficiently improve the waterproof performance without fluoro water proofing agent.
Using not fluorine-containing chain alkyl can polycondensation monomer synthesis with core-shell structure without fluoro water proofing agent, in cyclic group
Under the collaboration of the specific monomers such as halogenated alkane, by can response type nonionic surfactant and cationic surfactant into
Row seeded emulsion polymerization, what is obtained has stronger waterproof performance without fluoro water proofing agent.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
In invention is further explained, it should not be understood as limiting the scope of the invention, the people that is skilled in technique in the field
Member can make some nonessential modifications and adaptations according to the content of aforementioned present invention, still fall within protection scope of the present invention.
High-efficient, no-freon waterproofing agent with core-shell structure of the invention include polymer, surfactant, hydrophilic solvent,
PH adjusting agent and water.
One, polymer
Polymer includes: (a) (R) acrylate long chain alkane (b) functional monomer.
(a) (R) acrylate long chain alkane monomer is expressed as follows:
CH2=C (- R)-(C=O)-X-CnH2n
Wherein, R H, Cl, Br, F or CH3；
X is chemical single bond or-O- ,-NH- ,-NR1-、-NH-SO2-、-NR1-SO2One or more；R1For H or
Person is the alkyl of 8-30 carbon atom；
N is the integer of 8-30；
Because the long chain alkane of only low critical surface tension has crystal plane after crystallisation, could reduce to greatest extent critical
Surface tension provides preferable waterproof performance.It is therefore preferable that long alkyl chain alkyl carbon number is the monomer of 8-30.Wherein (R) propylene
Acid esters long chain alkane Exemplary monomers include but unlimited (methyl) dodecylacrylate, (methyl) acrylic acid tetradecane base ester,
(methyl) aliphatic acrylate, (methyl) octadecyl acrylate, (CI) octadecyl acrylate, (F) acrylic acid
Stearyl, (Br) octadecyl acrylate, (methyl) acrylic acid eicosane base ester, (methyl) behenyl base
Ester.
(b) functional monomer is expressed as follows:
The functional monomer includes (methyl) ethylene basic ring (halogen) alkane, (methyl) acrylate cycloalkane, can hand over
The monomer of connection.
(methyl) ethylene basic ring (halogen) alkane, (methyl) acrylate cycloalkane, wherein cycloalkane include monocycle, it is more
Ring and bridged ring can be saturated alkane, or unsaturated alkane.The preferred five-membered ring of cyclic annular size and hexatomic ring are more
Ring is preferably bicyclic, tricyclic.The example of cyclic hydrocarbon radical includes but unlimited phenyl, cyclohexyl, cyclopenta, bicyclopentyl, isobornyl.
(methyl) ethylene basic ring (halogen) alkane, halogen is I, Br, Cl or F in alkyl halide hydrocarbon therein.
(methyl) ethylene basic ring (halogen) the alkane specific example include but unlimited styrene, methyl styrene, to methyl
Styrene, vinyl cyclohexane, vinyl cyclopentane, vinylidene chloride, vinylacetate.(methyl) the acrylate cycloalkane
Polymer specific example include (methyl) cyclohexyl acrylate, (methyl) acrylic acid ring pentyl ester, (methyl) dicyclopentanyl acrylate,
(methyl) isobornyl acrylate.
The crosslinkable monomer, wherein the group containing polymerizable reactive group and other cross-linking reaction.It can
The example of polymerization includes that the example of double bond and reactive group includes but unlimited double bond, three keys, epoxy group, hydroxyl, chloromethyl, first
The isocyanate group of oxygroup, ethyoxyl, amino, carboxyl, azido, sealing end.The crosslinkable monomers specific example includes N- hydroxyl
Methacrylamide, (methyl) acrylic acid hydroxyl first (second) ester, chloro- 2 hydroxypropyl acrylate of (methyl) acrylic acid 3-, butadiene, chlorobutadiene,
Glycidyl methacrylate.
The each component ratio of copolymer: (a) being weight 20%-100%；It (b) is weight 0%-80%；It is preferred that (a) attaches most importance to
Measure 25%-80%；It (b) is weight 25%-20%.
Two, surfactant
Surfactant includes: (a) cationic surfactant (b) nonionic surfactant.
(a) cationic surfactant:
The polar hydrophilic base of cationic surfactant predominantly main primary ammonium salt, secondary ammonium salt, tertiary amine salt, quaternary ammonium salt；Sun
The nonpolar lipophilic group of ionic surface active agent is mainly straight chain and long-chain saturation and unsaturated alkane containing branch, carbon
Atom number is in 4-22, preferably 10-20.
(b) nonionic surfactant:
The polar hydrophilic base of nonionic surfactant is mainly polyoxyethylene, and polyoxypropylene class or the two all have；It is non-
The nonpolar lipophilic group of ionic surface active agent is mainly straight chain or long-chain saturation or unsaturated alkane containing branch, carbon
Atom number is in 4-22, preferably 10-20.And this patent improves the key of waterproof effect and is, controls polyoxyethylene, polyoxy third
The length of the repetitive unit of alkene, range include 1-100, preferably (CH2CH2) or (CH O2CH(CH3) O) number is in 5-50.Together
When, non-ionic surface active Group Terminal contains reactive group, such as double bond, three keys, epoxy group, hydroxyl, chloromethyl, ammonia
Base, carboxyl, azido, sealing end the groups such as isocyanates.It can be copolymerized with polymer or cross-linking reaction, improve latex
The stability of grain, prevents its structure when contacting anion from destroying.
The component ratio of surfactant: the weight fraction (a) relative to polymer is weight 0.1%-10%；(b) it is
Weight 0.1%-20%；It is preferred that (a) is weight fraction 0.5%-5%；It (b) is weight fraction 0.5%-10%.
Three, hydrophilic solvent
Common decentralized medium is aqueous medium and hydrophilic solvent, and hydrophilic solvent includes: dipropylene glycol, 3 the third two
One or more of alcohol, four glycerine, dipropylene glycol methyl ether, tripropylene glycol methyl ether, tripropylene glycol ether.
Four, pH adjusting agent
It includes acid or alkali that pH, which adjusts auxiliary agent, and waterproofing agent pH value is between 4-7.
Five, polymerization technique
To realize that synthesis has the high-efficient, no-freon waterproofing agent of core-shell structure, the total amount Jing Guo emulsifying is added in reactor
80-100% (R) acrylate long chain alkane monomer, total amount 0%-50% part functionalities free radical polymerizable monomer, total amount
50%-90% surfactant, hydrophilic solvent, pH adjust auxiliary agent, total amount 80%-90% water, total amount 50%-100% chain and turn
The mixture lotion and total amount 10%-90% initiator of agent are moved, temperature is controlled at 50-70 DEG C, after reaction 0.5-5 hours, adjusts
Temperature of reactor is saved to 30-50 DEG C, by remaining 0%-20% (R) acrylate long chain alkane monomer, 50%-100% function
Property free radical polymerizable monomer, 10%-50% surfactant, 0%-50% chain-transferring agent, 10%-20% water and 10%-
90% initiator is added, and continues to stop reaction after being stirred to react 0.5-6 hours, obtains the nothing with core-shell structure after filter-cloth filtering
Fluoro water proofing agent product.
It includes peroxidating that the synthesis, which has seeded emulsion polymerization initiator in the high-efficient, no-freon waterproofing agent of core-shell structure,
Benzoyl, lauroyl peroxide, sodium peroxide, potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile, azo diisobutyl narrow salt
The oil soluble materials such as two carbonic ester of one or more or diisopropyl peroxide of the water-soluble substances such as hydrochlorate.Lotion is poly-
Chain-transferring agent used in conjunction includes straight chain (branch) alkyl hydrosulfide, mercaptopropionic acid, alkyl sulfide alcohol ester.
Wherein, each component ratio in no fluoro water proofing agent: polymerized monomer preferred weight score is 15%-34%；Surface-active
Agent weight fraction is 1%-5%；The preferred 4%-10% of hydrophilic solvent weight；PH adjusting agent weight fraction is 0.01%-3%；
Initiator weight fraction 0.01%-5%, wherein it is preferred that 0.1%-3%；The weight fraction of its Chain transfer agent is 0.001%-
1%, wherein it is preferred that 0.01%-0.1%, surplus are water.
The present invention will not cause stress environment due to using (R) long-chain aliphatic acrylate；Second, this experiment is closed
At the high-efficient, no-freon waterproofing agent with core-shell structure can effectively keep the crystal plane of long chain alkane, improve anti-without fluoro water proofing agent
Water effect.
Of the invention is diluted to 0.1%-15% without fluoro water proofing agent, by coating, impregnates, pad dyeing, roller coating, spraying etc. is single
Or dilution is applied on textile by hybrid mode.Through detecting, quality of textile products is accounted for without fluoro water proofing agent substance on textile
Than in 0.01%-10%.Drying bakes in processing, because weaving breed difference carries out the processing of different durations, temperature, guarantees polymerization
It is full cross-linked between object and textile, to reach optimal waterproof effect and washable effect.Usually between 100 DEG C -180 DEG C
It is 1-90 minutes dry.
Water repellency: spray test.
In order to verify the waterproof effect of the textile after water-proofing treatment of the present invention, can be examined by standard method
It examines, to compare.The standard method is to investigate water repellent effect using AATCC 22, and here is method brief introduction.
22 test method of AATCC:
Three pieces of samples for intercepting 18cm × 18cm, are compressed, and be installed on the firm banking being at an angle of 45 degrees to the horizontal plane with clamper
On, with 250mL, 27 ± 1 DEG C of distilled water rapidly and smoothly in hopper, by the spray head with sample centre distance,
In 25 to 30 seconds, averagely continuously sprayed towards sample center.Spray finishes, and picks up ring-like folder bottom edge, fabric face to
Under, beat the opposite side of hand against a hard object, rotate 180 °, then beat it is primary, immediately will wet or speckle patterns and
Grading card compares, and evaluates the front of sample, determines the series of every piece of sample.
Rating scale text are as follows:
Suffix "+" after being attached to numerical value or "-" indicate to be slightly better than or slightly poorer to the numerical value performance.
100 surfaces do not soak or water droplet attachment；
90 surfaces do not soak, but have small water droplet to adhere to；
There is independent small water droplet wetting on 80 surfaces；
70 half moistened surfaces, and have the independent small wetting of infiltration cloth；
The wetting of 50 whole surfaces；
Wetting before and after 0 whole surface.
Mechanical stability and shelf-stability test:
Mechanical stability is that waterproofing agent is added in 10mL centrifuge tube, is centrifuged 30 minutes in centrifuge with 3000r/min,
Observing waterproofing agent, whether there is or not the wild effects such as floating, layering and precipitating.
Shelf-stability is to place waterproofing agent at room temperature 90 days, and whether there is or not floating, layering and precipitatings etc. for observation waterproofing agent
Wild effect.
Embodiment 1
Take 45.00g octadecyl acrylate, 1.00g N hydroxymethyl acrylamide, 2.00g glycidyl acrylate,
18.00g tripropylene glycol, 102.22g deionized water, 1.75g octadecyltrimethylammonium chloride, 1.75g ER-20,1.75g
ER-40,0.088g lauryl mercaptan and 0.02g acetic acid are uniformly mixed, and high speed emulsification 10 minutes obtains pre-emulsion, then in advance
Lotion obtains average grain diameter in the lotion of 100nm after high pressure homogenizer homogeneous.Aforesaid liquid is transferred to 250mL with stirring
The four-hole boiling flask of machine, thermometer, condenser pipe nitrogen gatherer is mixed, is led to nitrogen 30 minutes, is warming up to 60 DEG C, is subsequently added into
0.263g azo diisobutyl narrows hydrochloric acid saline solution, and insulation reaction 4 hours.System temperature is finally down to room temperature, continues to add
Enter 14.00g isobornyl methacrylate, 0.25g octadecyltrimethylammonium chloride, 0.25g ER-20,0.25g ER-40,
0.013g lauryl mercaptan, 0.038g azo diisobutyl narrow hydrochloride, 11.36g deionized water, continue to be stirred to react 6 small
When, through 300 mesh filter-cloth filterings to get with core-shell structure, without fluoro water proofing agent, last average grain diameter is in 110nm or so.Polymerization
The monomer composition of object component and investment is almost the same.
Embodiment 2-6
Embodiment 2-6 has used the type and amount such as table 1 of waterproofing agent synthesis component, meanwhile, embodiment 4-6 consersion unit
Used autoclave, other synthesis modes are same as Example 1, obtain solid component 34% without fluoro water proofing agent lotion.
Comparative example 1
45.00g octadecyl acrylate, 14.00g isobornyl methacrylate, 1.00g N hydroxymethyl acrylamide are taken,
2.00g glycidyl acrylate, 18.00g tripropylene glycol, 113.58g deionized water, 2.00g octadecyl trimethyl chlorination
Ammonium, 1.00g ER-10,1.00g ER-20,2.00gER-40 and 0.02g acetic acid are uniformly mixed, 0.100g lauryl mercaptan,
High speed emulsification 10 minutes, obtains pre-emulsion, then pre-emulsion obtains average grain diameter 100nm's after high pressure homogenizer homogeneous
Lotion.Aforesaid liquid is transferred to 250mL to have in the autoclave of blender, thermometer, condenser pipe nitrogen gatherer,
It logical nitrogen 30 minutes, is subsequently added into 0.300g azo diisobutyl and narrows hydrochloride, be warming up to 60 DEG C, insulation reaction 6 hours.Finally
System temperature is down to room temperature, through 300 mesh filter-cloth filterings to get waterproofing agent, last average grain diameter is in 90nm or so.Polymer group
Divide almost the same with the monomer composition of investment.
Comparative example 2-3
Comparative example 2-3 has used the type and amount such as table 1 of waterproofing agent synthesis component, other synthesis modes and ratio are compared with 1 phase
Together, the floride-free water repellent solution of solid component 34% is obtained.
By selecting the long-chain alkyl groups acrylic monomer with crystal property to substitute fluorine-containing material, its environmental protection is improved
Property；By selecting the special emulsifier and special synthesis technology with reactable group, having synthesized has nucleocapsid knot
Structure improves the waterproof performance without fluoro water proofing agent without fluoro water proofing agent.It should be pointed out that preferred embodiment described above, should not be solved
It is interpreted into and limits the scope of the invention, also exist for the improvement, change and retouching made without departing from the inventive concept of the premise
Within protection scope of the present invention.
Claims (9)
1. one kind has core-shell structure high-efficient, no-freon waterproofing agent, which is characterized in that described that there is core-shell structure high-efficient, no-freon waterproof
Agent includes following components by mass percentage: (R) acrylate long chain alkane monomer 15%-34%, functional free redical are poly-
Monomer 1%-20% is closed, surfactant 1%-5%, hydrophilic solvent 4%-10%, pH adjust auxiliary agent 0.01%-3%, surplus
For water；Functional free radical polymerizable monomer is (methyl) vinyl cycloalkane, (methyl) acrylate cycloalkane, (methyl) second
Alkenyl alkyl halide hydrocarbon, copolymerizable crosslinkable monomers；
The synthesis mode for having the function of core-shell structure high-efficient, no-freon waterproofing agent be by (R) acrylate long chain alkane monomer,
Property monomer is caused under the emulsification of emulsifier by free radical, is synthesized in a manner of seeded emulsion polymerization.
2. having core-shell structure high-efficient, no-freon waterproofing agent according to claim 1, which is characterized in that (R) acrylate
The alkyl of long chain alkane monomer is straight chain, and carbon atom number is 8-30, R H, Cl, Br, F or CH3。
3. having core-shell structure high-efficient, no-freon waterproofing agent according to claim 1, which is characterized in that (methyl) vinyl
Cycloalkane, (methyl) acrylate cycloalkane cycloalkane include monocycle, polycyclic and bridged ring, can be saturated alkane, can also
Think unsaturated alkane；The preferred five-membered ring of monocycle size and hexatomic ring, polycyclic preferably bicyclic or tricyclic；It preferably is selected from phenyl, ring
One of hexyl, cyclopenta, bicyclopentyl, isobornyl are a variety of.
4. having core-shell structure high-efficient, no-freon waterproofing agent according to claim 1, which is characterized in that (methyl) vinyl
The halogen of alkyl halide hydrocarbon is I, Br, Cl or F.
5. having core-shell structure high-efficient, no-freon waterproofing agent according to claim 1, which is characterized in that described copolymerizable hands over
Receipts or other documents in duplicate body have hydroxyl, carboxyl, amino, chloromethyl, methoxyl group, ethyoxyl, azido, double bond, three key isoreactivity groups one
Kind is a variety of.
6. having core-shell structure high-efficient, no-freon waterproofing agent according to claim 1, which is characterized in that emulsifier includes cation
Emulsifier, nonionic emulsifier.
7. having core-shell structure high-efficient, no-freon waterproofing agent according to claim 6, which is characterized in that the cationic emulsifier
For fat-based ammonium salt, wherein fat-based is mainly straight chain and long-chain saturation and unsaturated alkane containing branch, carbon atom
Number is in 4-22；
Surfactant is that the polyoxyethylene for having different chain length, polyoxypropylene and the non-ionic surface with active group are lived
Property agent；Repetitive unit CH2CH2O、CH2CH(CH3) O is respectively 0-100, preferably 5-50.
8. having core-shell structure high-efficient, no-freon waterproofing agent according to claim 5, which is characterized in that the surfactant
Active group end includes the isocyanates of double bond, three keys, epoxy group, hydroxyl, chloromethyl, amino, carboxyl, azido or sealing end
One of base is a variety of.
9. according to claim 1 to 8 any preparation methods with core-shell structure high-efficient, no-freon waterproofing agent, feature exists
In total amount 80-100% (R) acrylate long chain alkane monomer, total amount 0%- Jing Guo emulsifying is added in the reactor
50% part functionalities free radical polymerizable monomer, total amount 50%-90% surfactant, hydrophilic solvent, pH adjust auxiliary agent,
The mixture lotion and total amount 10%-90% initiator of total amount 80%-90% water control temperature at 50-70 DEG C, react 0.5-
After 5 hours, temperature of reactor is adjusted to 30-50 DEG C, by remaining 0%-20% (R) acrylate long chain alkane monomer, residue
50%-100% functionality free radical polymerizable monomer, remaining 10%-50% surfactant, residue 10%-20% water and
Remaining 10%-90% initiator is added, and continues to stop reaction after being stirred to react 0.5-6 hours, obtain after filter-cloth filtering with core
Shell structure without fluoro water proofing agent product.
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