CN110205818A - A kind of fluorine-free ecological waterproofing agent and preparation method thereof of highly crosslinkable energy - Google Patents
A kind of fluorine-free ecological waterproofing agent and preparation method thereof of highly crosslinkable energy Download PDFInfo
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- CN110205818A CN110205818A CN201910621400.7A CN201910621400A CN110205818A CN 110205818 A CN110205818 A CN 110205818A CN 201910621400 A CN201910621400 A CN 201910621400A CN 110205818 A CN110205818 A CN 110205818A
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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
- C08F220/16—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
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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
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
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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
- C08F220/16—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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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Abstract
The present invention discloses a kind of fluorine-free ecological waterproofing agent of highly crosslinkable energy, by weight percentage, including 10-90% component A, 1-50% component B, 1-10% component C and 10-90% component D；The total amount of component A, B, C and D are 100%；The component A is monomer a), b), c) and d) reacts obtained copolymer；Component B is water-miscible organic solvent；Component C is surfactant；Component D is water.The present invention has CH by introducing2=CH (CH2)nSiX3The comonomer b) of structure, pass through the hydrolysis-condensation reaction of siloxy, waterproofing agent and textile substrates surface is set to form the film of strong cross-linking, greatly improve the adhesive force of waterproofing agent and substrate surface, to provide the waterproof ability of waterproofing agent, the shelf stability of washable duration and waterproofing agent is washed.
Description
Technical field
The present invention relates to a kind of fluorine-free ecological waterproofing agents and preparation method thereof of highly crosslinkable energy, belong to textile fabric auxiliary agent neck
Domain.
Background technique
As production and improvement of living standard, people are higher and higher to the Functional Requirement of fabric, waterproof fabric is exactly
One such, in order to give textile water proof performance, fluorinated acrylate polymer is widely used in textile substrates table
Face.Acrylate containing fluorine polymer has unique C-F backbone, and the surface tension of textile substrates can be made far below water
Surface tension, to play outstanding waterproof performance.But it is found in use, acrylate containing fluorine polymer can generate pair
Human body and the harmful substance of ecological environment, and the price of acrylate containing fluorine polymer is relatively expensive, therefore it is limited in use.
And without fluoro water proofing agent due to its innocuousness to environment, cost performance is high, good water-proof effect, increasingly by people
Like.The type without fluoro water proofing agent has alkane long-chain class at present；Acrylate polymer；Organopolysiloxane and polyurethane
Class.No fluoro water proofing agent is that washable duration is poor compared to the disadvantage of fluorinated acrylate, and influence factor is waterproofing agent and base
The crosslinking ability on material surface.
Such as Chinese patent free-floride water-proofing composition (CN106661303A), include at least component (A) and (B) and optionally
At least one of component (C) to (E): polyacrylate (M1) CH that (A) is obtained in the polymerization reaction of following monomer2=
CR3COO-R1With (M2) CH2=CR3COO-R2Optionally (M3) CH2=CR3-X-R4；(B) isocyanates (D) of wax (C) sealing end
Organopolysiloxane；(E) melamine resin；Wherein R1It is the group containing 1-8 carbon atom；R2It is containing 9-40 carbon atom
Group；R3It is H, CH3Or C2H5；X=COO, CONHR4It is glycidyl or CH2(CH2)n-OR5, wherein n is within the scope of 1-10
Integer and R5It is H or the group containing 1-6 carbon atom；And wherein the composition is based on water and/or organic solvent simultaneously
It and is floride-free.The composition includes acrylate copolymer, paraffin and dispersing agent, since the difficult emulsibility of paraffin makes waterproofing agent
Waterproofness, washability and stability are restricted.
Patent document WO2014/160906 is related to a kind of no fluoro water proofing agent, the poly- ammonia comprising isocyanates and aliphatic ester
The polyurethane of ester compounds, isocyanates and aliphatic ester has outstanding washability, but since the stability of isocyanates is poor
The stability and waterproof effect for causing waterproofing agent are restricted.
Patent document EP1899391 is related to a kind of waterproofing agent, includes (methyl) acrylate, hydroxyl (methyl) acryloyl
Amine, this copolymer have outstanding stability, but since the limitation of acrylate polymer causes the waterproof of waterproofing agent to imitate
Fruit and patience are restricted.
Summary of the invention
In view of the above existing problems in the prior art, the present invention provides a kind of highly crosslinkable can fluorine-free ecological waterproofing agent,
Improve the waterproof ability, the washable duration of washing and waterproofing agent shelf stability of waterproofing agent.
To achieve the goals above, a kind of fluorine-free ecological waterproofing agent for highly crosslinkable energy that the present invention uses, by weight hundred
Divide than meter, including 10-90% component A, 1-50% component B, 1-10% component C and 10-90% component D；Component A, B, C and D's
Total amount is 100%；
The component A is monomer a), b), c) and d) reacts obtained copolymer；
Wherein monomer a) has general formula R1COOC(R2)=CH2, R1For the alkyl comprising 1-24 carbon atom；R2For H, CH3
Or CH2CH3；
Monomer b) has general formula CH2=CH (CH2)nSiX3The substance of structure, the wherein integer in n=0-4, X be-CL ,-
OCH3、-OCH2CH3、-OCH2-OCH3Or-OCOCH3；
Monomer c) has the polymerizable monomer of reactive group；
Monomer d) is vinyl chloride or vinylidene chloride；
Component B is water-miscible organic solvent；
Component C is surfactant；
Component D is water.
The monomer a), which is used, has carbon atom number for the saturations or undersaturated straight chain shape or branched-chain alkyl of 1-24
(methyl) alkyl acrylate or (methyl) acrylate base ester.
The monomer b) using vinyl trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane,
One of vinyl three (methoxy ethoxy) silane, three tert-butoxy silane of vinyl or vinyltriacetoxy silane
Or several mixing.
The monomer c) using without containing F atom and at least one be capable of acrylate reactions reactive group or
C=C key.
The component B is using in tripropylene glycol, dipropylene glycol, 1,2- propylene glycol, hexylene glycol, propylene glycol, ethylene glycol, acetone
One or more of mixing.
The surfactant uses anionic surfactant, cationic surfactant, nonionic surfactant
Or one of amphoteric surfactant or a variety of mixing.
The nonionic surfactant uses polyethyleneglycol moon esters of silicon acis, polyethylene glycol mono stearate, dehydration mountain
The mixing of one or more of pears sugar alcohol monolaurate, dehydrating sorbitol monooleate；
The cationic surfactant uses octadecyl ammonium acetate, dodecyl trimethyl ammonium chloride, cetyl
The mixing of one or more of trimethyl ammonium chloride, octadecyltrimethylammonium chloride；
The anionic surfactant uses one of aliphatic alcohol sulfate, alkylsulfonate, alkylbenzene sulfonate
Or several mixing.
In addition, first existing the present invention also provides a kind of preparation method of the fluorine-free ecological waterproofing agent of highly crosslinkable energy
Component B, component C are added in component D, stirs evenly, adds monomer a), the monomer b) and monomer c) in component A, is warming up to
It is stirred evenly after 40-70 DEG C, mixing and emulsifying is uniform, in the lotion after monomer d) to be then added to homogeneous, in polymerization initiator
In the presence of protective gas, it is uniform to be warming up to 40-90 DEG C of reactive polymeric.
The polymerization initiator is using water-soluble or oil-soluble radical polymerization initiator.
Finally, the application the present invention provides a kind of fluorine-free ecological waterproofing agent in fabric waterproof processing, the nothing
Individually or after compound with other surfaces inorganic agent, coated, dipping sprays, any in pad dyeing or roller coating the agent of fluorine ecological waterproof
Mode, for carrying out water-proofing treatment in natural fiber, synthetic fibers or rayon.
Compared with prior art, the present invention has CH by introducing2=CH (CH2)nSiX3The comonomer b) of structure leads to
The hydrolysis-condensation reaction for crossing siloxy makes waterproofing agent and textile substrates surface form the film of strong cross-linking, greatly improves anti-
The adhesive force of aqua and substrate surface washes the storage of washable duration and waterproofing agent to provide the waterproof ability of waterproofing agent
Stability.
Specific embodiment
In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention is carried out below further detailed
It describes in detail bright.However, it should be understood that the specific embodiments described herein are merely illustrative of the present invention, it is not limited to this hair
Bright range.
A kind of fluorine-free ecological waterproofing agent of highly crosslinkable energy, (% appeared below is using weight by weight percentage
Measure percentages), including 10-90% component A, preferably 20-80%, more preferable 25-60%, wherein component A be monomer a),
B), c) and d) obtained copolymer is reacted；
Wherein, monomer a) has general formula R1COOC(R2)=CH2, R1For the alkyl comprising 1-24 carbon atom；R2For H, CH3
Or CH2CH3；
As monomer a), from waterproof effect, it is preferable to use the saturation or unsaturation that are 1-24 with carbon atom number
Straight-chain or branched-chain alkyl (methyl) alkyl acrylate or (methyl) acrylate base ester, such as (methyl) third
Olefin(e) acid isobornyl thiocyanoacetate, (methyl) acrylic acid tetradecyl ester, (methyl) 2-EHA, (methyl) isodecyl acrylate,
(methyl) dodecyl acrylate, (methyl) cyclohexyl acrylate, ten five-ester of (methyl) acrylic acid, (methyl) Process Conditions of Cetane Acrylate,
(methyl) octadecyl acrylate etc., preferably (methyl) Process Conditions of Cetane Acrylate and (methyl) octadecyl acrylate；
In addition, monomer a) not fluorine-containing acrylate accounts for about 10-80%, preferably 25-80% in component A, it is further excellent
Select 40-80%；
Comonomer b) is with general formula CH2=CH (CH2)nSiX3The substance of structure, the wherein integer in n=0-4, X
For-CL ,-OCH3、-OCH2CH3、-OCH2-OCH3Or-OCOCH3Deng；
Monomer b) is formed the film of strong cross-linking with substrate surface, can be improved anti-by siloxy group hydrolysis-condensation reaction
The waterproof effect of aqua and washable duration are, it is preferable to use vinyl trichlorosilane, vinyltrimethoxysilane, vinyl three
Ethoxysilane, vinyl three (methoxy ethoxy) silane, three tert-butoxy silane of vinyl, vinyl triacetoxy silicon
Alkane, it is preferred to use vinyltrimethoxysilane and vinyltriethoxysilane；
Comonomer b) accounts for about 1-20%, preferably 1-15% in component A, further preferably about 1-10%.
Cross-linking monomer c) is the polymerizable monomer with reactive group, polymerizable monomer refer to without containing F atom and
It can include ethoxy with the reactive group of acrylate reactions or C=C key, the reactive group of polymerizable monomer at least one
Base, halogen atom, hydroxyl, amide groups, amino, imino group, sealing end or the isocyanates not blocked etc.；
Include, but are not limited to have (methyl) acrylic acid -3- chlorine-2-hydroxyl propyl ester, (methyl) propylene as polymerizable monomer
Acid -2- hydroxyl ethyl ester, (methyl) acrylamide, N- methylol (methyl) acrylamide, diacetone (methyl) acrylate, N, N- bis-
Methyl (methyl) acrylamide, poly- (ethylene glycol/propylene glycol) single (methyl) acrylate, (methyl) glycidyl ether,
Wherein preferred N- methylol (methyl) acrylamide and (methyl) glycidyl ether；
As sealing end or the isocyanates that does not block, isocyanates include but is not limited to hexamethylene diisocyanate,
The aliphatic polyisocyantes such as lysine diisocyanate or isophorone diisocyanate, toluene di-isocyanate(TDI) etc. are alicyclic
Polyisocyanates；End-capping reagent can be oximes, ketoxime class, phenols, lactams, including but not limited to diacetylmonoxime, phenol, and 3,5-
Dimethyl pyrazole, caprolactam etc.；
Cross-linking monomer c) accounts for about 1-15%, preferably from about 1-10% in component A, further preferably about 1-5%；
Comonomer d) is vinyl chloride or vinylidene chloride；By the way that comonomer d) is added, it is possible to provide waterproofing agent is to basis
Adhesive force, so that washable duration is improved, from production technology, preferably vinylidene chloride；
Comonomer d) accounts for about 1-30%, preferably from about 3-20% in component A, further preferably about 3-15%.
Other than component A, the present invention is preferably added to water-miscible organic solvent component B, and aqueous solution organic solvent is added can be with
Mitigate degree of difficulty when component A copolymerization significantly, while stability of finished product during using and storing can be improved, but group
Divide B to be not easy very few, otherwise will affect stability and shelf stability of the lotion in reaction, but be also not easy excessively, it otherwise can shadow
The waterproof effect of lotion in use is rung, component B accounts for the 1-50% of entire invention weight, preferably 5-30%, more preferable 5-
15%.
Water soluble organic solvent includes, but are not limited to tripropylene glycol, dipropylene glycol, 1,2-PD, hexylene glycol, and the third two
Alcohol, ethylene glycol, acetone and other substances, preferably tripropylene glycol or dipropylene glycol.
It needs that component C Surface activating agent is added in polymerization process of the present invention, wherein surfactant accounts for entire initiator weight
1-10%, preferably 1-7%, more preferable 1-5%.
As surfactant, one in various anion, cation, nonionic or amphoteric surfactant can be used
Kind or several mixing.
Nonionic surfactant includes polyethyleneglycol moon esters of silicon acis, polyethylene glycol mono stearate, Sorbitan
Alcohol monolaurate, dehydrating sorbitol monooleate etc.；Cationic surfactant includes octadecyl ammonium acetate, dodecane
Base trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride etc.；Anionic surfactant packet
Include aliphatic alcohol sulfate such as lauryl sodium sulfate；Alkylsulfonate such as dodecyl sodium sulfate；Alkylbenzene sulfonate such as nonyl
Phenol ether sulfate etc.；
Decentralized medium of the invention is water, and wherein component D water accounts for 10-90%, preferably 20-80%, more preferable 40-75%.
The present invention can pass through dispersion copolymerization method, emulsion polymerization, the production such as suspension polymerization.
Surfactant wherein is added preferably in dispersion water and water-miscible organic solvent stirs evenly, adds monomer
A)-c) it is warming up to 40-70 DEG C and stirs evenly, with mixer for well-distribution or high-pressure emulsification agent by monomer, surfactant and aqueous Jie
Matter mixing and emulsifying is uniform, in the lotion after monomer d) to be then added to homogeneous, in the presence of polymerization initiator and protective gas
Under, it is uniform to be warming up to 40-90 DEG C of reactive polymeric.
Thermal polymerization, Photoepolymerizationinitiater initiater, radiation polymerization initiator, free radical can be enumerated as polymerization initiator
Polymerization initiator etc..Preferred aqueous solutions of the present invention or oil-soluble radical polymerization initiator.
Common radical polymerization initiator includes azo-initiator, peroxide initiator, redox system initiation
Agent etc., the preferred azo-initiator of the present invention, particularly preferred water-soluble azo class initiator, particularly preferred two NSC 18620 salt of azo
Hydrochlorate.Polymerization initiator accounts for the 0.1-10% of component A weight, preferably from about 0.5-7%.
In addition, in monomer polymerization can also use molecular weight regulator, as n-dodecyl mercaptan, n octylmercaptan,
Mercaptoethanol etc., preferably n-dodecyl mercaptan.
Embodiment 1
A kind of preparation method of the fluorine-free ecological waterproofing agent of highly crosslinkable energy, comprising the following steps:
1) 37.8g water, 11.5g tripropylene glycol, 1.3g sorbitan monostearate (sapn are added in glass beaker
60), 0.7g isomerous tridecanol polyoxyethylene ether 8,1.5g hexadecyltrimethylammonium chloride are warming up to 60 DEG C, and stirring and dissolving is uniform
10 minutes, continuously add 25.7g octadecyl acrylate, 2.6g vinyltriethoxysilane, 1.3gN- hydroxymethyl acrylamide,
0.3g lauryl mercaptan, constant temperature stir evenly 30 minutes in 60 DEG C；
2) by above-mentioned mixed liquor at 60 DEG C, processing 30min is carried out at 40MPa using high-pressure emulsification machine, is obtained uniformly
Lotion.By lotion glass flask is added, nitrogen displacement is carried out to gas, is cooled to 25 DEG C, is added different with 0.3g azo two
Butyl ether hydrochloride (is dissolved) with 10g water, is stirred evenly, and 7g vinylidene chloride is added dropwise, is to slowly warm up to 50 DEG C, polymerize at 50 DEG C
Reaction 8 hours, obtains fine homogeneous lotion.
Embodiment 2
A kind of preparation method of the fluorine-free ecological waterproofing agent of highly crosslinkable energy, comprising the following steps:
1) 37.8g water, 11.5g tripropylene glycol, 1.3g sorbitan monostearate (sapn are added on glass beaker
60), 0.7g isomerous tridecanol polyoxyethylene ether 8,1.5g hexadecyltrimethylammonium chloride are warming up to 60 DEG C, and stirring and dissolving is uniform
10 minutes, continuously add 23g octadecyl acrylate, 5.3g vinyltriethoxysilane, 1.3gN- hydroxymethyl acrylamide,
0.3g lauryl mercaptan, constant temperature stir evenly 30 minutes in 60 DEG C；
2) by above-mentioned mixed liquor at 60 DEG C, processing 30min is carried out at 40MPa using high-pressure emulsification machine, is obtained uniformly
Lotion.By lotion glass flask is added, nitrogen displacement is carried out to gas, is cooled to 25 DEG C, is added different with 0.3g azo two
Butyl ether hydrochloride (is dissolved) with 10g water, is stirred evenly, and 7g vinylidene chloride is added dropwise, is to slowly warm up to 50 DEG C, polymerize at 50 DEG C
Reaction 8 hours, obtains fine homogeneous lotion.
Embodiment 3
A kind of preparation method of the fluorine-free ecological waterproofing agent of highly crosslinkable energy, comprising the following steps:
1) 37.8g water, 11.5g tripropylene glycol, 1.3g sorbitan monostearate (sapn are added on glass beaker
60), 0.7g isomerous tridecanol polyoxyethylene ether 8,1.5g hexadecyltrimethylammonium chloride are warming up to 60 DEG C, and stirring and dissolving is uniform
10 minutes, continuously add 15g octadecyl acrylate, 8g methacrylic acid -2- ethylhexyl, 5.3g vinyl triethoxyl silicon
Alkane, 1.3gN- hydroxymethyl acrylamide, 0.3g lauryl mercaptan, constant temperature stir evenly 30 minutes in 60 DEG C；
2) by above-mentioned mixed liquor at 60 DEG C, processing 30min is carried out at 40MPa using high-pressure emulsification machine, is obtained uniformly
Lotion.By lotion glass flask is added, nitrogen displacement is carried out to gas, is cooled to 25 DEG C, is added different with 0.3g azo two
Butyl ether hydrochloride (is dissolved) with 10g water, is stirred evenly, and 7g vinylidene chloride is added dropwise, is to slowly warm up to 50 DEG C, polymerize at 50 DEG C
Reaction 8 hours, obtains fine homogeneous lotion.
Embodiment 4
A kind of preparation method of the fluorine-free ecological waterproofing agent of highly crosslinkable energy, comprising the following steps:
1) 37.8g water, 11.5g tripropylene glycol, 1.3g sorbitan monostearate (sapn are added on glass beaker
60), 0.7g isomerous tridecanol polyoxyethylene ether 8,1.5g hexadecyltrimethylammonium chloride are warming up to 60 DEG C, and stirring and dissolving is uniform
10 minutes, continuously add 12g octadecyl acrylate, 11g Isobutyl methacrylate, 5.3g vinyltriethoxysilane,
1.3gN- hydroxymethyl acrylamide, 0.3g lauryl mercaptan, constant temperature stir evenly 30 minutes in 60 DEG C；
2) by above-mentioned mixed liquor at 60 DEG C, processing 30min is carried out at 40MPa using high-pressure emulsification machine, is obtained uniformly
Lotion.By lotion glass flask is added, nitrogen displacement is carried out to gas, is cooled to 25 DEG C, is added different with 0.3g azo two
Butyl ether hydrochloride (is dissolved) with 10g water, is stirred evenly, and 7g vinylidene chloride is added dropwise, is to slowly warm up to 50 DEG C, polymerize at 50 DEG C
Reaction 8 hours, obtains fine homogeneous lotion.
Comparative example A
A kind of preparation method of waterproofing agent, comprising the following steps:
1) 37.8g water, 11.5g tripropylene glycol, 1.3g sorbitan monostearate (sapn are added on glass beaker
60), 0.7g isomerous tridecanol polyoxyethylene ether 8,1.5g hexadecyltrimethylammonium chloride are warming up to 60 DEG C, and stirring and dissolving is uniform
10 minutes, continuously add 28.3 octadecyl acrylates, 1.3gN- hydroxymethyl acrylamide, 0.3g lauryl mercaptan, constant temperature in
60 DEG C stir evenly 30 minutes；
2) by above-mentioned mixed liquor at 60 DEG C, processing 30min is carried out at 40MPa using high-pressure emulsification machine, is obtained uniformly
Lotion.By lotion glass flask is added, nitrogen displacement is carried out to gas, is cooled to 25 DEG C, is added different with 0.3g azo two
Butyl ether hydrochloride (is dissolved) with 10g water, is stirred evenly, and 7g vinylidene chloride is added dropwise, is to slowly warm up to 50 DEG C, polymerize at 50 DEG C
Reaction 8 hours, obtains fine homogeneous lotion.
Comparative example B
A kind of preparation method of waterproofing agent, comprising the following steps:
1) 37.8g water, 11.5g tripropylene glycol, 1.3g sorbitan monostearate (sapn are added on glass beaker
60), 0.7g isomerous tridecanol polyoxyethylene ether 8,1.5g hexadecyltrimethylammonium chloride are warming up to 60 DEG C, and stirring and dissolving is uniform
10 minutes, continuously add 20.3g octadecyl acrylate, 8g methacrylic acid -2- ethylhexyl, 1.3gN- methylol acryloyl
Amine, 0.3g lauryl mercaptan, constant temperature stir evenly 30 minutes in 60 DEG C；
2) by above-mentioned mixed liquor at 60 DEG C, processing 30min is carried out at 40MPa using high-pressure emulsification machine, is obtained uniformly
Lotion.By lotion glass flask is added, nitrogen displacement is carried out to gas, is cooled to 25 DEG C, is added different with 0.3g azo two
Butyl ether hydrochloride (is dissolved) with 10g water, is stirred evenly, and 7g vinylidene chloride is added dropwise, is to slowly warm up to 50 DEG C, polymerize at 50 DEG C
Reaction 8 hours, obtains fine homogeneous lotion.
Test method
1) fabric treating
The present invention is made polymer and can be used in compounding together with other surfaces inorganic agent.In water by Inventive polymers
Its solid content constituent concentration is diluted to about 0.1-10 weight % or so, is applicable to various fabrics such as natural fiber, synthesis is fine
Dimension, the fabrics such as staple fibre.Application method can be impregnated, spraying, pad dyeing using coating, roller coating or their combination method.
Specific method: by will wish to get solid component concentration be set as 0.1-10 weight % as pad dyeing bathe use,
Pad dyeing is carried out to processed material in pad dyeing bath, next, removing superfluous liquid with squeezing roller, is dried.It is processed
Material it is dry usually about 80~120 DEG C at a temperature of carry out drying in about 1 minute~1 hour or so, then about 150~180
It is carried out under conditions of about 1 minute at about 1~3 minute, particularly preferred 170 DEG C at about 1~3 minute, preferably 150~170 DEG C at DEG C
Curing terminates water-proofing treatment.
2) waterproof effect is tested
Measurement waterproof effect (according to JIS L1092) carries out anti-water drenching test.Anti- shower water is indicated with waterproofness NO.
(as shown in following table 1.Suffix "+" after being attached to numerical value indicates that performance is slightly better than the performance that the numerical value indicates.
The anti-shower water of table 1
| Waterproofness NO. | State |
| 100 | Surface not wet or water droplet attachment |
| 90 | Surface does not soak, but has small water droplet to adhere to |
| 80 | Surface has independent small drops wet |
| 70 | Half moistened surface, and have the independent small wet of infiltration cloth |
| 50 | Whole surface is wet |
| 0 | It is wet before and after whole surface |
3) the washing resistance test of waterproofness
According to JIS L-0217-103 method, 25 minutes (5 minutes * HL, continuous 5 times) are washed with 40 DEG C of cleaning solution, dehydration 3
Minute rinses 2 minutes, decolourizes 3 minutes, rinses 2 minutes, decolourizes 3 minutes, progress roller drying, the waterproof effect after evaluating,
Program is repeated 4 times in this way, the effect after test washing 10 times, 15 times, 20 times.
The anti-water quality evaluation of the various embodiments described above and comparative example is as shown in table 1 below.
The anti-water quality evaluation of each embodiment of table 1 and comparative example
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of fluorine-free ecological waterproofing agent of highly crosslinkable energy, which is characterized in that by weight percentage, including 10-90% group
Divide A, 1-50% component B, 1-10% component C and 10-90% component D；The total amount of component A, B, C and D are 100%；
The component A is monomer a), b), c) and d) reacts obtained copolymer；
Wherein monomer a) has general formula R1COOC(R2)=CH2, R1For the alkyl comprising 1-24 carbon atom；R2For H, CH3Or
CH2CH3；
Monomer b) has general formula CH2=CH (CH2)nSiX3The substance of structure, wherein the integer in n=0-4, X are-CL ,-OCH3、-
OCH2CH3、-OCH2-OCH3Or-OCOCH3；
Monomer c) has the polymerizable monomer of reactive group；
Monomer d) is vinyl chloride or vinylidene chloride；
Component B is water-miscible organic solvent；
Component C is surfactant；
Component D is water.
2. a kind of fluorine-free ecological waterproofing agent of highly crosslinkable energy according to claim 1, which is characterized in that the monomer
A) using has carbon atom number for the saturations or undersaturated straight chain shape of 1-24 or (methyl) acrylic acid alkyl of branched-chain alkyl
Ester or (methyl) acrylate base ester.
3. a kind of fluorine-free ecological waterproofing agent of highly crosslinkable energy according to claim 1, which is characterized in that the monomer
B) vinyl trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, (the methoxyl group second of vinyl three are used
Oxygroup) one or more of silane, three tert-butoxy silane of vinyl or vinyltriacetoxy silane mixing.
4. a kind of fluorine-free ecological waterproofing agent of highly crosslinkable energy according to claim 1, which is characterized in that the monomer
C) it is capable of the reactive group or C=C key of acrylate reactions using without containing F atom and at least one.
5. a kind of fluorine-free ecological waterproofing agent of highly crosslinkable energy according to claim 1, which is characterized in that the component B
Using the mixed of one or more of tripropylene glycol, dipropylene glycol, 1,2- propylene glycol, hexylene glycol, propylene glycol, ethylene glycol, acetone
It closes.
6. a kind of fluorine-free ecological waterproofing agent of highly crosslinkable energy according to claim 1, which is characterized in that the surface is living
Property agent using in anionic surfactant, cationic surfactant, nonionic surfactant or amphoteric surfactant
One or more mixing.
7. a kind of fluorine-free ecological waterproofing agent of highly crosslinkable energy according to claim 6, which is characterized in that the nonionic
Surfactant uses polyethyleneglycol moon esters of silicon acis, polyethylene glycol mono stearate, sorbitan monolaurate, mistake
The mixing of one or more of water sorbitol monooleate；
The cationic surfactant uses octadecyl ammonium acetate, dodecyl trimethyl ammonium chloride, cetyl front three
The mixing of one or more of ammonium chloride, octadecyltrimethylammonium chloride；
The anionic surfactant uses one of aliphatic alcohol sulfate, alkylsulfonate, alkylbenzene sulfonate or several
The mixing of kind.
8. a kind of preparation method of the fluorine-free ecological waterproofing agent of any one of claim 1-7 highly crosslinkable energy, feature exist
In, component B, component C are first added in component D, stirs evenly, adds monomer a), the monomer b) and monomer c) in component A,
It is stirred evenly after being warming up to 40-70 DEG C, mixing and emulsifying is uniform, in the lotion after monomer d) to be then added to homogeneous, is polymerizeing
In the presence of initiator and protective gas, it is uniform to be warming up to 40-90 DEG C of reactive polymeric.
9. the preparation method of the fluorine-free ecological waterproofing agent of highly crosslinkable energy according to claim 8, which is characterized in that described poly-
Initiator is closed using water-soluble or oil-soluble radical polymerization initiator.
10. a kind of application of any one of claim 1-9 fluorine-free ecological waterproofing agent in fabric waterproof processing, feature exist
In, the fluorine-free ecological waterproofing agent individually or after compound with other surfaces inorganic agent, coated, dipping is sprayed, pad dyeing or roller coating
In either formula, for carrying out water-proofing treatment in natural fiber, synthetic fibers or rayon.
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| CN111335041A (en) * | 2020-03-13 | 2020-06-26 | 东莞市百思兰鞋材科技有限公司 | Fluoride-free waterproof agent and preparation method thereof |
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| CN114687210A (en) * | 2021-12-22 | 2022-07-01 | 浙江科峰新材料有限公司 | Environment-friendly washable waterproof and oil-proof agent and preparation method thereof |
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