CN109988264A - A kind of no fluoro water proofing agent and its preparation method and application - Google Patents
A kind of no fluoro water proofing agent and its preparation method and application Download PDFInfo
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- CN109988264A CN109988264A CN201711472849.9A CN201711472849A CN109988264A CN 109988264 A CN109988264 A CN 109988264A CN 201711472849 A CN201711472849 A CN 201711472849A CN 109988264 A CN109988264 A CN 109988264A
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- proofing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—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
-
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (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
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (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
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Abstract
The invention discloses a kind of no fluoro water proofing agents and its preparation method and application.The no fluoro water proofing agent includes the component of following mass percent: floride-free copolymer 1 0-20%, surfactant 1-5%, cosolvent 2-10%, paraffin 5-15%, remaining is water.The comonomer of the no fluo-copolymer includes: acrylate monomer a, carbon-carbon double bonds blocked isocyanate monomer b, vinyl silicane coupling agent monomer c and other function monomer d.The no fluoro water proofing agent not only has excellent waterproof effect, and can assign fabric good feel, improves the washing fastness of fabric.
Description
Technical field
The present invention relates to textile auxiliary fields, and in particular to a kind of no fluoro water proofing agent used for textiles and preparation method thereof and answers
With.
Background technique
The waterproof performance of textile is usually to arrange and obtain through waterproofing agent.The water repellent finish of textile is to pass through physics
Or chemical method, fabric surface energy is reduced, to achieve the purpose that fabric surface is not easy to be soaked by hydrone.Chemical method frequently with
Water repellent finishing agent, wherein the water repellent effect with fluorocarbons is best.But fluorine carbon water repellent finishing agent monomer perfluoro caprylic acid (PFOA)
It is potential carcinogen with perfluorooctane sulfonyl compound (PFOS), toxic fluorine can be discharged during arrangement and after arranging
Compound, harmful to human and environment.On June 27th, 2008, European Union formally implement limitation and use perfluorooctane sulfonyl compound
(PFOS) instruction.The instruction will affect the outlet of China's textile, leather, papermaking, packaging, printing and dyeing assistant, cosmetics etc..Cause
This, finds the substitute of fluorine-contained finishing agent, and is the research hotspot of water repellent finish using new finishing technique, using no fluoro water proofing agent
It is development trend.
Chinese patent CN102333915B discloses a kind of waterproofing agent, comprising based on acrylate copolymer, paraffin and
Dispersing agent.Paraffin of the patent using fusing point lower than 80 degree makes the waterproofness and washing resistance performance of waterproofing agent as key component
Limited to.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of no fluoro water proofing agent and preparation method thereof, institutes
Stating no fluoro water proofing agent not only has excellent waterproof effect, and can assign fabric good feel, improves the washability of fabric
Energy.
In order to achieve the above objectives, The technical solution adopted by the invention is as follows:
On the one hand, the present invention provides a kind of no fluoro water proofing agent, the component comprising following mass percent: without fluo-copolymer
10-20%, surfactant 1-5%, cosolvent 2-10%, paraffin 5-15%, remaining is water；The copolymerization of the no fluo-copolymer
Monomer include: acrylate monomer a, carbon-carbon double bonds blocked isocyanate monomer b, vinyl silicane coupling agent monomer c and
Other function monomer d.
Further, the carbon-carbon double bonds blocked isocyanate monomer b is by end-capping reagent and isocyanic acid with α ethylene linkage
Ester reacts to obtain.
Further, the end-capping reagent with α ethylene linkage is the terminal hydroxy group acrylate with α ethylene linkage.
Further, the terminal hydroxy group acrylate with α ethylene linkage be selected from hydroxy-ethyl acrylate, hydroxypropyl acrylate,
One of hydroxyethyl methacrylate, hydroxy propyl methacrylate, hy-droxybutyl, methacrylate or extremely
Few two kinds of combination.
Further, the isocyanates is selected from monoisocyanates, diisocyanate or polyisocyanates.
Specifically, the isocyanates is different selected from isocyanatoethyl, acrylic acid isocyano group ethyl ester, toluene two
Cyanate, diphenyl methane -4,4- diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate, two methylene of benzene
Group diisocyanate, naphthalene -1,5- diisocyanate, cyclohexyl diisocyanate ester, dicyclohexyl methyl hydride diisocyanate, tetramethyl
One of base benzene dimethylene diisocyanate, isophorone diisocyanate or at least two combination.
Further, shown in the structure such as formula (I) of the vinyl silicane coupling agent monomer c: CH2=CH (CH2)nSiX3
(I), wherein n=1~5, X are selected from chlorine, methoxyl group, ethyoxyl, methoxy ethoxy, acetoxyl group or tert-butoxy.
Further, the vinyl silicane coupling agent monomer c is selected from vinyl trichlorosilane, vinyl trimethoxy silicon
Alkane, vinyltriethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, three tert-butoxy silane of vinyl, ethylene
One of base triacetoxysilane or at least two combination.
Further, the other function monomer d is selected from hydroxy-ethyl acrylate, hydroxyethyl methacrylate, acrylic acid contracting
Water glyceride, glycidyl methacrylate, 3- chlorine-2-hydroxyl propyl methacrylate, vinyl chloride, dihydroxypropyl second
The polycaprolactone of ester, one of the polycaprolactone of hydroxyethyl methacrylate or at least two combination.
Further, mass percent shared by the Component units based on monomer a is 30-70% in the no fluo-copolymer,
Mass percent shared by Component units based on monomer b is 10-50%, mass percent shared by the Component units based on monomer c
For 1-50%, mass percent shared by the Component units based on monomer d is 1-30%.
On the other hand, the present invention also provides the preparation methods of above-mentioned no fluoro water proofing agent, comprising the following steps: causes in polymerization
By the monomer a, the monomer b, the monomer c and the monomer d and surfactant, cosolvent, stone in the presence of agent
Wax is add to deionized water mixing, and no fluoro water proofing agent is obtained after emulsification.
Further, the present invention also provides the textiles being process using above-mentioned no fluoro water proofing agent.
Invention is detailed
1, without fluoro water proofing agent
(1) without fluo-copolymer
In the no fluoro water proofing agent, the mass percent of no fluo-copolymer is 10-20%, preferably 15-20%.
(i) acrylate monomer a
The acrylate monomer a is floride-free acrylic ester compound.
Preferably, the acrylic monomers a is acrylate or methacrylate comprising 1 to 22 carbon atom.
Specifically, the non-limiting example of the acrylate monomer a includes: (methyl) methyl acrylate, (methyl) third
Olefin(e) acid ethyl ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) propylene
The just own ester of acid, (methyl) 2-ethyl hexyl acrylate, (methyl) decyl acrylate, (methyl) dodecyl acrylate, (methyl) acrylic acid ten
Octaester, (methyl) Behenyl acrylate, (methyl) stearyl acrylate base ester, 3- ethoxycarbonyl propyl acrylate, methoxyl group fourth
Base acrylate, 2- g. ethyl butyl acrylate, 1,3- dimethylbutyl acrylate, 2- methyl amyl acrylate, etc..
In the no fluo-copolymer, mass percent shared by the Component units based on monomer a is 30-70%, preferably
30-60%, more preferably 35-50%.
(ii) carbon-carbon double bonds blocked isocyanate monomer b
It is described containing double carbon-carbon bond blocked isocyanate monomer b by with α ethylene linkage end-capping reagent and isocyanates react
It arrives.
The end-capping reagent with α ethylene linkage is the terminal hydroxy group acrylate with α ethylene linkage.
Specifically, the non-limiting example of the terminal hydroxy group acrylate with α ethylene linkage include: hydroxy-ethyl acrylate,
Hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate, hy-droxybutyl, methacrylate,
Etc..
The isocyanates is selected from monoisocyanates, diisocyanate or polyisocyanates.
The polyisocyanates be band there are three or three or more isocyanate groups substance.
Specifically, the non-limiting example of the isocyanates includes: isocyanatoethyl (IEMA), propylene
Sour isocyano group ethyl ester, toluene di-isocyanate(TDI) (TDI), diphenyl methane -4,4- diisocyanate (MDI), hexa-methylene two are different
Cyanate (HDI), hexamethylene diisocyanate (HDI), benzene dimethylene diisocyanate (XDI), naphthalene -1,5- diisocyanate
(NDI), cyclohexyl diisocyanate ester (HTDI), dicyclohexyl methyl hydride diisocyanate (HMDI), tetramethylxylene
Diisocyanate (TMXDI), isophorone diisocyanate (IPDI), etc..
In some embodiments, described to be selected from hydroxyethyl methacrylate second containing double carbon-carbon bond blocked isocyanate monomer b
Ester blocks isocyanatoethyl, hydroxy-ethyl acrylate blocks isocyanatoethyl, hydroxypropyl acrylate
Block acrylic acid isocyano group acetate monomer, hydroxyethyl methacrylate blocks hexamethylene diisocyanate, hydroxyethyl methacrylate
Propyl ester blocks toluene di-isocyanate(TDI), hydroxy propyl methacrylate blocks tetramethylxylylene diisocyanate, acrylic acid
It is different that hydroxyl ethyl ester blocks tetramethylxylylene diisocyanate, hydroxy propyl methacrylate sealing end tetramethylxylene two
Cyanate ester monomer, hydroxypropyl acrylate block the combination of one of six dimethylene diisocyanates or at least two.
In the no fluo-copolymer, mass percent shared by the Component units based on monomer b is 10-50%, preferably
15-50%, more preferably 15-30%.
(iii) vinyl silicane coupling agent monomer c
Shown in the structure such as formula (I) of the vinyl silicane coupling agent monomer c: CH2=CH (CH2)nSiX3(I), wherein n
=1~5, X are selected from chlorine, methoxyl group, ethyoxyl, methoxy ethoxy, acetoxyl group or tert-butoxy.
Specifically, the non-limiting example of the vinyl silicane coupling agent monomer c includes: vinyl trichlorosilane, second
Alkenyl trimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, the tertiary fourth of vinyl three
Oxysilane, vinyltriacetoxy silane, etc..
In some embodiments, the vinyl silicane coupling agent monomer c is selected from vinyl trichlorosilane, vinyl three
Methoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, three tert-butoxy silicon of vinyl
One of alkane, vinyltriacetoxy silane or at least two combination.
In the no fluo-copolymer, mass percent shared by the Component units based on monomer c is 1-50%, preferably
10-30%, more preferably 15-30%.
(iiii) other function monomer d
The other function monomer d is the bridging property fluorine-free monomer other than demonomerization a, monomer b, monomer c.
Specifically, the non-limiting example of the other function monomer d includes: hydroxy-ethyl acrylate, hydroxyethyl methacrylate
Ethyl ester, glycidyl acrylate, glycidyl methacrylate, 3- chlorine-2-hydroxyl propyl methacrylate, chloroethene
Alkene, the polycaprolactone of Hydroxyethyl Acrylate, polycaprolactone of hydroxyethyl methacrylate, etc..
In some embodiments, the other function monomer d be selected from hydroxy-ethyl acrylate, hydroxyethyl methacrylate,
Glycidyl acrylate, glycidyl methacrylate, 3- chlorine-2-hydroxyl propyl methacrylate, in vinyl chloride
Two or three.
In the no fluo-copolymer, mass percent shared by the Component units based on monomer d is 1-30%.
From the perspective of rub resistance, it is preferred that mass ratio shared by the Component units based on monomer d is 1-20%, more
Preferably 10-20%.
(2) surfactant
As surfactant, hydrocarbon-surfactant can be enumerated, can enumerate respectively nonionic surfactant, sun from
Sub- property surfactant or amphoteric surfactant.
As surfactant, from the perspective of dispersion stabilization, preferably and with nonionic surfactant with
Cationic surfactant or amphoteric surfactant, or anionic surfactant is used alone, more preferably it is used in combination
Nonionic surfactant and cationic surfactant.
The nonionic surfactant and sun indicated with nonionic surfactant/cationic surfactant from
The ratio of sub- property surfactant is preferably 97:3-4:60 by quality ratio.
In the specific combination of nonionic surfactant and cationic surfactant, can be quality account for it is floride-free anti-
The 1-5% of aqueous emulsion quality can reduce the adverse effect to the water repellency of article.
The non-limiting example of nonionic surfactant includes: that mono laurate Isosorbide Dinitrate, monostearate are de-
Water sorbitol ester, single palm fibre put sour Isosorbide Dinitrate, single sorbitan oleate, sesquialter stearic acid Isosorbide Dinitrate, three
Stearic acid Isosorbide Dinitrate, mono laurate Sorbitan ethoxylate, single palm fibre put sour Sorbitan ethoxylate,
Monostearate Sorbitan ethoxylate, single oleic acid Sorbitan ethoxylate, the dehydration of three stearic acid polyoxyethylenes
Sorbitol ester, etc..
As other nonionic surface active agent, the saturation and/or unsaturated lipid of straight-chain and/or branched can be
Epoxides addition product, straight-chain and/or the branched of fat race base are saturated and/or the polyalkylene glycol of unsaturated fatty acid
The epoxidation of ester, polyoxyethylene (POE)/polyoxypropylene (POP) copolymer (random copolymer or block copolymer), acetylenediol
Object addition product etc..Wherein, the structure of preferred epoxide addition part and polyalkylene glycol moiety be polyoxyethylene (POE) or
Polyoxypropylene (POP) or POE/POP copolymer (random copolymer or block copolymer).
Cationic surfactant is quaternary ammonium salt, and non-limiting example includes: dodecyl trimethyl ammonium acetate, 14
Alkyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyltrimethylammonium chloride, behenyl chlorine
Change ammonium, (dodecyl methyl section base) trimethyl ammonium chloride, two (dodecyl) alkyl dimethyl ammonium chlorides, two (octadecyl) diformazans
Ammonium chloride, benzododecinium ammonium chloride, antipyrineazopyrogallol, benzyl octadecyldimethyl
Ammonium chloride, etc..
The non-limiting example of amphoteric surfactant includes: alkyl betaine, alkylsulfobetaines, fatty acid amide
Propyl betaine, 2- alkyl-N- carboxymethyl-N- hydroxyethyl imidazole glycine betaine, alkyl (or dialkyl group) diethylidene triamido
Acetic acid, alkyl amide oxide, etc..
The dosage of the surfactant accounts for the 1-5% entirely without fluoro water proofing agent quality, preferably 2-5%.
(3) cosolvent
The preferably water-soluble organic solvent of the cosolvent, such as ketone, alcohols, ethers.
Specifically, the non-limiting example of the cosolvent include: acetone, methyl ethyl ketone, ethyl alcohol, propyl alcohol, isopropanol,
N-butanol, isobutanol, 3-Methoxy-3-methyl-1-butanol, 2- tert-butoxy ethyl alcohol, ethylene glycol, propylene glycol, dipropylene glycol, three
Propylene glycol, four propylene glycol, glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether (EGMBE), propylene glycol monoethyl ether, propylene glycol two
Butyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol-800, etc..
The dosage of the cosolvent accounts for the 2-10% entirely without fluoro water proofing agent quality, preferably 6-8%.
(4) paraffin
The preferred melting range of paraffin is particularly preferred between 35-105 DEG C of paraffin, more preferably 45-85 DEG C of paraffin
For 55-65 DEG C of paraffin.
The dosage of the paraffin accounts for the 5-15% entirely without fluoro water proofing agent quality, preferably 10-15%.
2, without the preparation of fluoro water proofing agent
The preparation method of the no fluoro water proofing agent includes:
By the monomer a, the monomer b, the monomer c and the monomer d, Yi Jibiao in the presence of polymerization initiator
Face activating agent, cosolvent, paraffin are add to deionized water mixing, and no fluoro water proofing agent is obtained after emulsification.
The initiator is oil-soluble polymerization initiator or water-soluble polymerization initiator.
In some embodiments, the initiator is selected from 2,2- azodiisobutyronitrile, benzoyl peroxide amine, two tertiary fourths
Base peroxide, ammonium persulfate, potassium peroxydisulfate or azobisisobutryamide chloride.
Average molecular weight of the present invention containing fluorine free polymer is between 10000-250000.It is obtained by emulsion polymerization
Water-proof and oil-proof composition of the average molecular weight containing fluorine free polymer within the scope of 10000-250000 all show it is very excellent
Different waterproof and oilproof performance.
In order to obtain the excellent polymer being dispersed in water in terms of storage stability, it is generally desirable to by using can
The emulsifier (for example, high-pressure homogenizer and ultrasonic homogenizer) for applying Strong shear energy, emulsifies monomer fine in water, with
It is polymerize afterwards using water-soluble polymerization initiator.
3, fabric post-processes
It is of the invention to can be applied to various fiber surface substrates without fluoro water proofing agent, including various cotton fibers, nylon, terylene,
Nonwoven surface.
It can use conventional method known in the art and carry out fabric post-processing.
In some embodiments, the post-processing approach of fabric is as follows:
Spending preparation ionized water without fluoro water proofing agent and be diluted to concentration 30g/L, is soaked in dilution 15 points for cotton
Clock is rolled once, liquid carrying rate 100% with padding machine, and after an immersing and rolling technique, cotton is dried 5 minutes at 170 DEG C respectively.
The beneficial effects of the present invention are:
(1) fluorine free polymer in the present invention has used double bond containing blocked isocyanate monomer, can be with no fluoropropene
Acid esters polymerize to form the copolymer containing blocked isocyanate groups, can be cross-linked to form stable chemistry with generating on fabric
Key is conducive to the washing fastness for improving fabric；
(2) fluorine free polymer in the present invention has used vinyl silicane coupling agent, can be with floride-free acrylic ester polymerization shape
At silicon oxygen bond and silicon-carbon bonds are contained, the hardness of fabric can be reduced, keeps fabric more soft；
(3) no fluoro water proofing agent provided by the invention, environmentally friendly, industrial prospect is good.
Specific embodiment
As described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited to following preferred implementation side
Formula.It should be pointed out that for those skilled in the art on the basis of the inventive concept, several deformations for making and
It improves, belongs to protection scope of the present invention, in order to further describe the present invention, illustrate combined with specific embodiments below.
Embodiment 1
Methyl methacrylate 5g is taken, hydroxyethyl methacrylate blocks hexamethylene diisocyanate monomer 2g, ethylene
Base trichlorosilane 2g, glycidyl methacrylate 1g, paraffin 10g, mono laurate Isosorbide Dinitrate 1g, dipropylene glycol
5g, acetic acid 0.1g, cetyl trimethylammonium bromide 1g are added in deionized water 40g, and high speed emulsification 30 minutes obtains pre-
Lotion.It adjusts pre-emulsion temperature and 0.5g glycidyl acrylate is added to 62 DEG C, while being passed through nitrogen 30 minutes.It is added
0.1g azobisisobutryamide chloride, 0.5g vinyl chloride, insulation reaction 8 hours.System temperature is finally down to room temperature, through 300
Mesh filter-cloth filtering is to get no fluoro water proofing agent.
Embodiment 2
Octadecyl methacrylate 5g is taken, hydroxy propyl methacrylate blocks toluene diisocyanate monomer 2g, vinyl
Triethoxysilane 2g, glycidyl methacrylate 1g, paraffin 10g, mono laurate Isosorbide Dinitrate 1g, dipropylene glycol
5g, gram acetic acid 0.1g, cetyl trimethylammonium bromide 1g are added in deionized water 40g, and high speed emulsification 30 minutes obtains
Pre-emulsion.It adjusts pre-emulsion temperature and 0.5g glycidyl acrylate is added to 62 DEG C, while being passed through nitrogen 30 minutes.It is added
0.1g azobisisobutryamide chloride, 0.5g vinyl chloride, insulation reaction 8 hours.System temperature is finally down to room temperature, through 300
Mesh filter-cloth filtering is to get no fluoro water proofing agent.
Embodiment 3
Butyl methacrylate 5g is taken, hydroxy propyl methacrylate blocks tetramethylxylylene diisocyanate monomer
2g, vinyl three ('beta '-methoxy ethyoxyl) silane 2g, glycidyl methacrylate 1g, paraffin 10g, mono laurate dehydration
Sorbitol ester 1g, dipropylene glycol 5g, acetic acid 0.1g, cetyl trimethylammonium bromide 1g are added in deionized water 40g, high
Speed emulsification 30 minutes, obtains pre-emulsion.Pre-emulsion temperature is adjusted to 62 DEG C, 0.5g glycidyl acrylate is added, is led to simultaneously
Enter nitrogen 30 minutes.Addition 0.1g azobisisobutryamide chloride, 0.5g vinyl chloride, insulation reaction 8 hours.Finally by system temperature
Degree is down to room temperature, through 300 mesh filter-cloth filterings to get no fluoro water proofing agent.
Embodiment 4
Dodecyl acrylate 5g is taken, hydroxy propyl methacrylate blocks tetramethylxylylene diisocyanate monomer
2g, glycidyl methacrylate 1g, paraffin 10g, mono laurate Isosorbide Dinitrate 1g, dipropylene glycol 5g, acetic acid 0.1g,
Cetyl trimethylammonium bromide 1g is added in deionized water 40g, and high speed emulsification 30 minutes obtains pre-emulsion.Adjust pre- cream
0.5g hydroxyethyl methacrylate, ('beta '-methoxy ethyoxyl) silane of 2g vinyl three and 2g methyl is added to 62 DEG C in liquid temperature
Hydroxypropyl acrylate blocks tetramethylxylylene diisocyanate monomer, while being passed through nitrogen 30 minutes.It is even that 0.1g is added
Two isobutyl of nitrogen narrows hydrochloride, 0.5g vinyl chloride, and insulation reaction 8 hours.System temperature is finally down to room temperature, through 300 mesh filter clothes
Filtering is to get no fluoro water proofing agent.
Embodiment 5
Lauryl methacrylate 5g is taken, hydroxy-ethyl acrylate blocks tetramethylxylylene diisocyanate monomer
2g, glycidyl methacrylate 1g, paraffin 10g, mono laurate Isosorbide Dinitrate 1g, dipropylene glycol 5g, acetic acid 0.1g,
Cetyl trimethylammonium bromide 1g is added in deionized water 40g, and high speed emulsification 30 minutes obtains pre-emulsion.Adjust pre- cream
0.5g hydroxyethyl methacrylate, ('beta '-methoxy ethyoxyl) silane of 2g vinyl three and 2g methyl is added to 62 DEG C in liquid temperature
Hydroxypropyl acrylate blocks tetramethylxylylene diisocyanate monomer, while being passed through nitrogen 30 minutes.It is even that 0.1g is added
Two isobutyl of nitrogen narrows hydrochloride, 0.5g vinyl chloride, and insulation reaction 8 hours.System temperature is finally down to room temperature, through 300 mesh filter clothes
Filtering is to get no fluoro water proofing agent.
Embodiment 6
Behenyl acrylate 5g is taken, hydroxypropyl acrylate blocks the chloro- 2- of isocyanatoethyl monomer 2g, 3-
Hydroxy propyl methacrylate 1g, paraffin 10g, mono laurate Isosorbide Dinitrate 1g, dipropylene glycol 5g, acetic acid 0.1g, ten
Six alkyl trimethyl ammonium bromide 1g, are added in deionized water 40g, and high speed emulsification 30 minutes obtains pre-emulsion.Adjust pre-emulsion
Vinyl three ('beta '-methoxy ethyoxyl) silane 2g is added to 62 DEG C in temperature, and hydroxy propyl methacrylate blocks durol two
Methylene diisocyanate monomer 2g, while being passed through nitrogen 30 minutes.0.1g azobisisobutryamide chloride, 0.5g chloroethene is added
Alkene, insulation reaction 8 hours.System temperature is finally down to room temperature, through 300 mesh filter-cloth filterings to get no fluoro water proofing agent.
Embodiment 7
20 diester 5g of methacrylic acid is taken, hydroxypropyl acrylate blocks the chloro- 2- of acrylic acid isocyano group acetate monomer 2g, 3-
Hydroxy propyl methacrylate 1g, vinyl three tert-butoxy silane 2g, paraffin 10g, mono laurate Isosorbide Dinitrate 1g,
Dipropylene glycol 5g, acetic acid 0.1g, cetyl trimethylammonium bromide 1g are added in deionized water 40g, 30 points of high speed emulsification
Clock obtains pre-emulsion.Pre-emulsion temperature is adjusted to 62 DEG C, while being passed through nitrogen 30 minutes.Two isobutyl of 0.1g azo is added and narrows salt
Hydrochlorate, 0.5g vinyl chloride, insulation reaction 8 hours.System temperature is finally down to room temperature, through 300 mesh filter-cloth filterings to get free-floride
Waterproofing agent.
Embodiment 8
Octadecyl acrylate 5g is taken, hydroxypropyl acrylate blocks the six chloro- 2- hydroxyls of dimethylene diisocyanate monomer 2g, 3-
Base propyl methacrylate 1g, vinyl three tert-butoxy silane 2g, paraffin 10g, mono laurate Isosorbide Dinitrate 1g, gram
Dipropylene glycol 5g, acetic acid 0.1g, cetyl trimethylammonium bromide 1g are added in deionized water 40g, 30 points of high speed emulsification
Clock obtains pre-emulsion.2g vinyltrimethoxysilane is added, stirring adjusts pre-emulsion temperature to 62 DEG C, while being passed through nitrogen
30 minutes, addition 0.1g azobisisobutryamide chloride, 0.5g vinyl chloride, insulation reaction 8 hours.Finally system temperature is down to
Room temperature, through 300 mesh filter-cloth filterings to get no fluoro water proofing agent.
9 performance of embodiment and application
1, without the performance test of fluoro water proofing agent
Molecular weight, average grain diameter, mechanical stability and storage-stable are carried out without fluoro water proofing agent by what Examples 1 to 8 obtained
Property test, test result is as shown in table 1.
Mechanical stability: mechanical stability be in l0mL centrifuge tube be added without fluoro water proofing agent, in centrifuge with
3000r/min is centrifuged 30 minutes, and without fluoro water proofing agent, whether there is or not the wild effects such as floating, layering and precipitating for observation.
Storage stability: aqueous liquid dispersion is saved 1 month at 40 DEG C, observes the generation of sedimentation.
Ο: absolutely not generation condensation product
△: seldom condensation product is generated
×: generate many condensation products
The performance test results of the table 1 without fluoro water proofing agent
From the test data of table 1 can be seen that no fluoro water proofing agent prepared by the present invention with good mechanical stability and
Storage stability.
2, fabric treating and performance
Fabric finishing process: spending what Examples 1 to 8 obtained ionized water without fluoro water proofing agent and be diluted to concentration 30g/L, will
Cotton is soaked in dilution 15 minutes, is rolled once with padding machine, liquid carrying rate 100%, after an immersing and rolling technique, by cotton in
It is dried 5 minutes at 170 DEG C, obtains the cotton that floride-free waterproofing agent treatment is crossed.
The cotton that above-mentioned floride-free waterproofing agent treatment is crossed is subjected to following performance detection, test result is as shown in table 4.
(1) waterproofing tests method
Open flow water drenching test is carried out according to AATCC-22.It indicates to prevent with waterproofing grade shower resistance.Suffix after being attached to data
"+" means that performance is slightly better than the grade performance of numerical representation method, and suffix "-" means that performance is slightly inferior to the rank character of numerical representation method
Energy.Evaluation criteria is shown in Table 2.
2 waterproofing grade explanation of table
| Waterproofing grade | Evaluation criteria |
| 1 grade | It is all soaked by leaching surface |
| 2 grades | There is a dewetting by leaching surface |
| 3 grades | Only had discontinuous small area wetting by leaching surface |
| 4 grades | It is not soaked by leaching surface, but surface speckles with droplet |
| 5 grades | It is not soaked by leaching surface, surface does not speckle with droplet |
(2) washfastness test method
It is washed l0 minutes at 40 DEG C with 2g/L detergent, 1:30 bath raio in washing machine, then releases cleaning solution, used
40 DEG C of clear water wash 5 minutes, dehydration.If desired washing repeatedly, then repeats above operation.Last naturally dry is dried at 80 DEG C
30 minutes.Then its waterproof and oilproof performance is tested.Test result is as shown in table 4.
(3) hand valuation
To treated, cotton is evaluated, and evaluates feel according to organ sensation rating method, evaluation criterion is as shown in table 3.
3 feel testing standard of table
The performance test results of fabric after the floride-free waterproofing agent treatment of table 4
| Number | Waterproof performance before washing | Wash 10 waterproof performances | Wash 20 waterproof performances | Feel grade |
| Embodiment 1 | 5 | 5- | 4 | 4 |
| Embodiment 2 | 5 | 5- | 4 | 4 |
| Embodiment 3 | 5 | 5 | 4 | 4 |
| Embodiment 4 | 5 | 5- | 4 | 3 |
| Embodiment 5 | 5 | 4 | 4 | 4 |
| Embodiment 6 | 5 | 5- | 3 | 3 |
| Embodiment 7 | 4+ | 4 | 3 | 4 |
| Embodiment 8 | 5 | 5- | 4 | 3 |
It can be seen that the cotton after floride-free waterproofing agent treatment prepared by the present invention, waterproofness from the test data of table 4
Grade is optimal up to 5 grades, and has excellent washable effect, and for waterproofing grade still 4 or more, feel is good after washing 20 times.
Claims (10)
1. a kind of no fluoro water proofing agent, which is characterized in that the component comprising following mass percent: floride-free copolymer 1 0-20%, table
Face activating agent 1-5%, cosolvent 2-10%, paraffin 5-15%, remaining is water；The comonomer of the no fluo-copolymer includes:
Acrylate monomer a, carbon-carbon double bonds blocked isocyanate monomer b, vinyl silicane coupling agent monomer c and other function list
Body d.
2. a kind of no fluoro water proofing agent according to claim 1, which is characterized in that described containing double carbon-carbon bond end-sealed type isocyanic acids
Ester monomer b by with α ethylene linkage end-capping reagent and isocyanates react to obtain.
3. a kind of no fluoro water proofing agent according to claim 2, which is characterized in that the end-capping reagent with α ethylene linkage is tool
There is the terminal hydroxy group acrylate of α ethylene linkage.
4. a kind of no fluoro water proofing agent according to claim 3, which is characterized in that the terminal hydroxy group propylene with α ethylene linkage
Acid esters is selected from hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate, acrylic acid hydroxyl
One of butyl ester, methacrylate or at least two combination.
5. a kind of no fluoro water proofing agent according to claim 2, which is characterized in that the isocyanates is selected from methacrylic acid
Isocyano group ethyl ester, acrylic acid isocyano group ethyl ester, toluene di-isocyanate(TDI), diphenyl methane -4,4- diisocyanate, hexa-methylene
Diisocyanate, hexamethylene diisocyanate, benzene dimethylene diisocyanate, naphthalene -1,5- diisocyanate, cyclohexyl two are different
Cyanate ester, dicyclohexyl methyl hydride diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate
One of or at least two combination.
6. a kind of no fluoro water proofing agent according to claim 1, which is characterized in that the vinyl silicane coupling agent monomer c
Structure such as formula (I) shown in: CH2=CH (CH2)nSiX3(I), wherein n=1~5, X are selected from chlorine, methoxyl group, ethyoxyl, methoxy
Base oxethyl, acetoxyl group or tert-butoxy.
7. a kind of no fluoro water proofing agent according to claim 6, which is characterized in that the vinyl silicane coupling agent monomer c
Selected from vinyl trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, (the 'beta '-methoxy second of vinyl three
Oxygroup) silane, three tert-butoxy silane of vinyl, one of vinyltriacetoxy silane or at least two group
It closes.
8. a kind of no fluoro water proofing agent according to claim 1, which is characterized in that the other function monomer d is selected from propylene
Sour hydroxyl ethyl ester, hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 3- chlorine-2-hydroxyl third
Methyl acrylate, vinyl chloride, the polycaprolactone of Hydroxyethyl Acrylate, hydroxyethyl methacrylate polycaprolactone in
One kind or at least two combination.
9. a kind of no fluoro water proofing agent according to claim 1, which is characterized in that in the no fluo-copolymer, be based on monomer a
Component units shared by mass percent be 30-70%, mass percent shared by the Component units based on monomer b is 10-50%,
Mass percent shared by Component units based on monomer c is 1-50%, and mass percent shared by the Component units based on monomer d is
1-30%.
10. a kind of textile, which is characterized in that be process using no fluoro water proofing agent of any of claims 1-9.
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| CN110205818A (en) * | 2019-07-10 | 2019-09-06 | 广东湛丰精细化工有限公司 | A kind of fluorine-free ecological waterproofing agent and preparation method thereof of highly crosslinkable energy |
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| CN114773535A (en) * | 2022-04-02 | 2022-07-22 | 浙江大学衢州研究院 | Fluorine-free carbamate waterproof emulsion and preparation and application thereof |
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