CN110670359A - Low-temperature type waterproof and oil-proof agent and preparation method thereof - Google Patents
Low-temperature type waterproof and oil-proof agent and preparation method thereof Download PDFInfo
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- CN110670359A CN110670359A CN201910957751.5A CN201910957751A CN110670359A CN 110670359 A CN110670359 A CN 110670359A CN 201910957751 A CN201910957751 A CN 201910957751A CN 110670359 A CN110670359 A CN 110670359A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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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
- D06M2200/11—Oleophobic properties
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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
Abstract
The invention discloses a low-temperature water-proof and oil-proof agent and a preparation method thereof. The low-temperature water-proof and oil-proof agent is obtained by copolymerizing a fluorine-containing monomer and a plurality of functional monomers, and the preparation method comprises the following steps: 1) mixing a monomer, a surfactant, a chain transfer agent, a cosolvent and water, and pre-emulsifying; 2) transferring the material obtained in the step 1) into a reaction kettle, adding an initiator, and reacting at 70-90 ℃ for 6-10 h. The low-temperature type waterproof and oilproof agent disclosed by the invention is safe and environment-friendly, is low in price, can be used for performing waterproof and oilproof treatment on the fabric at low temperature, and the treated fabric has excellent waterproof and oilproof performances and can resist repeated washing.
Description
Technical Field
The invention relates to a low-temperature water-proof and oil-proof agent and a preparation method thereof.
Background
In recent years, with the increasing performance requirements of people on certain high value-added fabrics, the functional finishing of the fabrics such as water resistance, oil resistance, stain resistance, flame retardance, radiation resistance and the like becomes a hot point for research. The water-proof and oil-proof finishing is to apply a finishing agent on the fabric to change the surface performance of the fabric, so that the fabric is not wetted by water and common oil stains, and the water-proof and oil-proof performance of the fabric is improved.
The fluorine-containing waterproof and oilproof agent is a widely applied waterproof and oilproof finishing agent, can endow fabric with waterproof and oilproof performances, but has the following general defects:
1) the existing fluorine-containing waterproof and oil-proof agent has poor washing resistance, the washing resistance times can only reach about 5 times, and the waterproof effect is obviously reduced after washing;
2) the existing fluorine-containing water and oil resistant agent usually needs to add a cross-linking agent (comprising two ways: one is adding cross-linking agent in fluorine-containing water-proof and oil-proof agent during after-finishing, and the other is introducing cross-linking monomer in the process of synthesizing fluorine-containing water-proof and oil-proof agent copolymer) can obtain better washing resistance effect, but the washing resistance frequency is not more than 10 times;
3) the existing fluorine-containing waterproof and oil-proof agent needs to carry out waterproof and oil-proof finishing on the fabric in a high-temperature baking mode (above 150 ℃), and the fabrics such as wool, silk, polypropylene fiber and the like are not suitable for high-temperature baking, so that the problems of yellowing of the fabrics, scorching of the fabrics and the like easily occur.
Therefore, it is necessary to develop a water-and oil-repellent agent having excellent water-and oil-repellency and excellent washing resistance.
Disclosure of Invention
The invention aims to provide a low-temperature water-proof and oil-proof agent and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the low-temperature water-proof and oil-proof agent is prepared from the following raw materials in parts by mass:
a monomer a: 35-65 parts of a solvent;
a monomer b: 5-30 parts of a solvent;
a monomer c: 1-20 parts;
a monomer d: 1-20 parts;
a monomer e: 1-20 parts;
surfactant (b): 1-10 parts;
initiator: 0.05-1 part;
chain transfer agent: 0.05-1 part;
cosolvent: 10-50 parts;
water: 100-400 parts;
the monomer a is C1～C6Polyfluoroalkyl acrylates, C1～C6At least one polyfluoroalkyl methacrylate;
the monomer b is C16～C28Alkyl acrylate, C16～C28At least one of alkyl methacrylate;
the monomer c is closed isocyanate containing double bonds and has a structural formula
In the formula, R1is-COOCH2CH2-，R2is-CH3or-H, R3、R4、R5、R6And R7Are independently-OH, -H, -CH3-F, -Cl or Br;
the monomer d is at least one of acrylic ester with an alkyl group, methacrylic ester with an alkyl group, benzyl acrylate, benzyl methacrylate, styrene, methyl styrene and p-chlorostyrene;
the monomer e is 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate, methacryloyl morpholine, acryloyl morpholine, chlorinated methacryloxyethyl trimethylamine, chlorinated acryloxyethyl trimethylamine, chlorinated methacryloxypropyl trimethylamine, chlorinated acryloxypropyl trimethylamine, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, N-hydroxyethyl methacrylate, N-, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, polyoxyalkylene glycol monomethacrylate, polyoxyalkylene glycol monoacrylate, methacrylic acid, acrylic acid, 2-methacryloyloxyethyl acrylic acid, 2-acryloxyethyl acrylic acid, 2-methacryloyloxyhexahydrophthalic acid, 2-acryloxyhexahydrophthalic acid, 2-methacryloyloxyethyl acid phosphate, 2-acryloxyethyl acid phosphate, allyl methacrylate, allyl acrylate, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl- (2-vinyloxazoline), At least one of polycaprolactone of hydroxyethyl methacrylate, polycaprolactone of hydroxyethyl acrylate, 2- (2-methyl-1-oxy-2-propenyl) oxyethyl 3-oxybutyrate ester, polycaprolactone of hydroxyethyl methacrylate, polycaprolactone of hydroxyethyl acrylate and hydroxyethyl methacrylate.
Preferably, the low-temperature water-proof and oil-proof agent is prepared from the following raw materials in parts by mass:
a monomer a: 50-65 parts;
a monomer b: 9-20 parts of a solvent;
a monomer c: 5-10 parts;
a monomer d: 4-15 parts;
a monomer e: 3-10 parts;
surfactant (b): 5-10 parts;
initiator: 0.5-1 part;
chain transfer agent: 0.05-0.2 part;
cosolvent: 30-50 parts of a solvent;
water: 200-300 parts;
the monomer a is at least one of perfluorohexylethyl methacrylate, perfluorohexylethyl acrylate, perfluorobutylethyl methacrylate and perfluorobutylethyl acrylate;
the monomer b is at least one of behenyl methacrylate, behenyl acrylate, stearyl acrylate and stearyl methacrylate;
the monomer c is at least one of 3-bromophenol-sealed isocyano ethyl methacrylate, 3-bromophenol-sealed isocyano ethyl acrylate, 3-bromo-5-fluorophenol-sealed isocyano ethyl methacrylate, 3-bromo-5-fluorophenol-sealed isocyano ethyl acrylate, 4-propylphenol-sealed isocyano ethyl methacrylate, 4-propylphenol-sealed isocyano ethyl acrylate, p-tert-butylphenol-sealed isocyano ethyl methacrylate, p-isopropylphenol-sealed isocyano ethyl methacrylate and p-isopropylphenol-sealed isocyano ethyl acrylate;
the monomer d is at least one of cyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyl acrylate, benzyl methacrylate, styrene, methyl styrene and p-chlorostyrene;
the monomer e is at least one of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, polycaprolactone of hydroxyethyl acrylate and hydroxyethyl methacrylate.
Preferably, the surfactant is at least one of a hydrocarbon surfactant and a fluorine surfactant.
Further preferably, the surfactant is at least one of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60, tween 80, fatty alcohol polyoxyethylene ether, dodecyl trimethyl ammonium acetate, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, docosyl trimethyl ammonium chloride, benzyl dodecyl dimethyl ammonium chloride, benzyl tetradecyl dimethyl ammonium chloride, benzyl octadecyl dimethyl ammonium chloride, alkyl betaine and thiobetaine.
Preferably, the initiator is at least one of 2,2' -azobis (2-methylpropionitrile), 2' -azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, ammonium persulfate, potassium persulfate, and 2,2' -azobisisobutylamidine hydrochloride.
Preferably, the chain transfer agent is n-dodecyl mercaptan.
Preferably, the cosolvent is a water-soluble organic solvent.
More preferably, the cosolvent is at least one of water-soluble ketones, water-soluble alcohols, and water-soluble ethers.
Still more preferably, the cosolvent is at least one of acetone, methyl ethyl ketone, ethanol, propanol, isopropanol, n-butanol, isobutanol, 3-methoxy-3-methyl-1-butanol, 2-tert-butoxyethanol, ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, and polyethylene glycol.
The preparation method of the low-temperature water-proof and oil-proof agent comprises the following steps:
1) mixing a monomer a, a monomer b, a monomer c, a monomer d, a monomer e, a surfactant, a chain transfer agent, a cosolvent and water, and pre-emulsifying;
2) transferring the material obtained in the step 1) into a reaction kettle, adding an initiator, and carrying out polymerization reaction to obtain the low-temperature waterproof and oil-proof agent.
Preferably, the method for preparing the low-temperature water and oil repellent agent comprises the following steps:
1) adding a monomer a, a monomer b, a monomer c, a monomer d, a monomer e, a surfactant, a chain transfer agent, a cosolvent and water into a high-speed dispersion machine, heating to 50-70 ℃, and pre-emulsifying;
2) transferring the materials in the high-speed dispersion machine into a reaction kettle, adding an initiator, heating to 70-90 ℃, and reacting at constant temperature for 6-10 hours to obtain the low-temperature waterproof and oil-proof agent.
A water-and oil-repellent composition comprising the low-temperature water-and oil-repellent agent.
Preferably, the water and oil proofing composition further comprises at least one of a penetrant, a defoamer, a water absorbent, an antistatic agent, a crease-resist agent, a hand feeling modifier, a film forming aid, a curing agent, a thermal curing catalyst, a crosslinking catalyst, a fiber stabilizer and inorganic particles.
The invention has the beneficial effects that: the low-temperature type waterproof and oilproof agent disclosed by the invention is safe and environment-friendly, is low in price, can be used for performing waterproof and oilproof treatment on the fabric at low temperature, and the treated fabric has excellent waterproof and oilproof performances and can resist repeated washing.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a low-temperature type water and oil resistant agent comprises the following raw materials in percentage by weight:
TABLE 1 composition of raw materials of low-temperature type water-and oil-repellent agent
The preparation method of the low-temperature water-proof and oil-proof agent comprises the following steps:
1) adding a monomer a, a monomer b, a monomer c, a monomer d, a monomer e, a surfactant, a chain transfer agent, a cosolvent and water into a high-speed dispersion machine, heating to 60 ℃, and pre-emulsifying;
2) and transferring the materials in the high-speed dispersion machine into a reaction kettle, adding an initiator, heating to 90 ℃, and reacting at constant temperature for 8 hours to obtain the low-temperature waterproof and oil-proof agent.
Example 2:
a low-temperature type water and oil resistant agent comprises the following raw materials in percentage by weight:
TABLE 2 composition of raw materials of low-temperature type water and oil repellent agent
The preparation method of the low-temperature water-proof and oil-proof agent comprises the following steps:
1) adding a monomer a, a monomer b, a monomer c, a monomer d, a monomer e, a surfactant, a chain transfer agent, a cosolvent and water into a high-speed dispersion machine, heating to 60 ℃, and pre-emulsifying;
2) and transferring the materials in the high-speed dispersion machine into a reaction kettle, adding an initiator, heating to 87 ℃, and reacting at constant temperature for 8 hours to obtain the low-temperature waterproof and oil-proof agent.
Example 3:
a low-temperature type water and oil resistant agent comprises the following raw materials in percentage by weight:
TABLE 3 composition of raw materials of low-temperature type water and oil repellent agent
The preparation method of the low-temperature water-proof and oil-proof agent comprises the following steps:
1) adding a monomer a, a monomer b, a monomer c, a monomer d, a monomer e, a surfactant, a chain transfer agent, a cosolvent and water into a high-speed dispersion machine, heating to 60 ℃, and pre-emulsifying;
2) and transferring the materials in the high-speed dispersion machine into a reaction kettle, adding an initiator, heating to 87 ℃, and reacting at constant temperature for 8 hours to obtain the low-temperature waterproof and oil-proof agent.
Example 4:
a low-temperature type water and oil resistant agent comprises the following raw materials in percentage by weight:
TABLE 4 composition of raw materials of low-temperature type water and oil repellent agent
The preparation method of the low-temperature water-proof and oil-proof agent comprises the following steps:
1) adding a monomer a, a monomer b, a monomer c, a monomer d, a monomer e, a surfactant, a chain transfer agent, a cosolvent and water into a high-speed dispersion machine, heating to 60 ℃, and pre-emulsifying;
2) and transferring the materials in the high-speed dispersion machine into a reaction kettle, adding an initiator, heating to 87 ℃, and reacting at constant temperature for 8 hours to obtain the low-temperature waterproof and oil-proof agent.
Example 5:
a low-temperature type water and oil resistant agent comprises the following raw materials in percentage by weight:
TABLE 5 composition of raw materials of low-temperature type water and oil repellent agent
The preparation method of the low-temperature water-proof and oil-proof agent comprises the following steps:
1) adding a monomer a, a monomer b, a monomer c, a monomer d, a monomer e, a surfactant, a chain transfer agent, a cosolvent and water into a high-speed dispersion machine, heating to 60 ℃, and pre-emulsifying;
2) and transferring the materials in the high-speed dispersion machine into a reaction kettle, adding an initiator, heating to 87 ℃, and reacting at constant temperature for 8 hours to obtain the low-temperature waterproof and oil-proof agent.
Example 6:
a low-temperature type water and oil resistant agent comprises the following raw materials in percentage by weight:
TABLE 6 composition of raw materials of low-temperature type water and oil repellent agent
The preparation method of the low-temperature water-proof and oil-proof agent comprises the following steps:
1) adding a monomer a, a monomer b, a monomer c, a monomer d, a monomer e, a surfactant, a chain transfer agent, a cosolvent and water into a high-speed dispersion machine, heating to 60 ℃, and pre-emulsifying;
2) and transferring the materials in the high-speed dispersion machine into a reaction kettle, adding an initiator, heating to 87 ℃, and reacting at constant temperature for 8 hours to obtain the low-temperature waterproof and oil-proof agent.
Example 7:
a low-temperature type water and oil resistant agent comprises the following raw materials in percentage by weight:
TABLE 7 composition of raw materials of low-temperature type water and oil repellent agent
The preparation method of the low-temperature water-proof and oil-proof agent comprises the following steps:
1) adding a monomer a, a monomer b, a monomer c, a monomer d, a monomer e, a surfactant, a chain transfer agent, a cosolvent and water into a high-speed dispersion machine, heating to 60 ℃, and pre-emulsifying;
2) and transferring the materials in the high-speed dispersion machine into a reaction kettle, adding an initiator, heating to 87 ℃, and reacting at constant temperature for 8 hours to obtain the low-temperature waterproof and oil-proof agent.
Example 8:
a low-temperature type water and oil resistant agent comprises the following raw materials in percentage by weight:
TABLE 8 composition of raw materials of low-temperature type water and oil repellent
The preparation method of the low-temperature water-proof and oil-proof agent comprises the following steps:
1) adding a monomer a, a monomer b, a monomer c, a monomer d, a monomer e, a surfactant, a chain transfer agent, a cosolvent and water into a high-speed dispersion machine, heating to 60 ℃, and pre-emulsifying;
2) and transferring the materials in the high-speed dispersion machine into a reaction kettle, adding an initiator, heating to 87 ℃, and reacting at constant temperature for 8 hours to obtain the low-temperature waterproof and oil-proof agent.
Example 9:
a low-temperature type water and oil resistant agent comprises the following raw materials in percentage by weight:
TABLE 9 composition of raw materials of low-temperature type water and oil repellent
The preparation method of the low-temperature water-proof and oil-proof agent comprises the following steps:
1) adding a monomer a, a monomer b, a monomer c, a monomer d, a monomer e, a surfactant, a chain transfer agent, a cosolvent and water into a high-speed dispersion machine, heating to 60 ℃, and pre-emulsifying;
2) and transferring the materials in the high-speed dispersion machine into a reaction kettle, adding an initiator, heating to 87 ℃, and reacting at constant temperature for 8 hours to obtain the low-temperature waterproof and oil-proof agent.
Example 10:
a low-temperature type water and oil resistant agent comprises the following raw materials in percentage by weight:
TABLE 10 composition of raw materials of low-temperature type water and oil repellent agent
The preparation method of the low-temperature water-proof and oil-proof agent comprises the following steps:
1) adding a monomer a, a monomer b, a monomer c, a monomer d, a monomer e, a surfactant, a chain transfer agent, a cosolvent and water into a high-speed dispersion machine, heating to 60 ℃, and pre-emulsifying;
2) and transferring the materials in the high-speed dispersion machine into a reaction kettle, adding an initiator, heating to 89 ℃, and reacting at constant temperature for 8 hours to obtain the low-temperature waterproof and oil-proof agent.
Comparative example 1:
a common water-and oil-repellent agent comprises the following raw materials in percentage by weight:
TABLE 11 raw material composition table of a common water and oil repellent agent
The preparation method of the common waterproof and oil-proof agent comprises the following steps:
1) adding a monomer a, a monomer b, a monomer d, a monomer e, a surfactant, a chain transfer agent, a cosolvent and water into a high-speed dispersion machine, heating to 60 ℃, and pre-emulsifying;
2) and transferring the materials in the high-speed dispersion machine into a reaction kettle, adding an initiator, heating to 90 ℃, and reacting at constant temperature for 8 hours to obtain the common waterproof and oil-proof agent.
Comparative example 2:
CTA-562DT, a fluorine-containing water and oil repellent agent, manufactured by Beijing Zhongji chemical industries, Ltd.
Test example:
the water-and oil-repellent agents of examples 1 to 10 and comparative examples 1 to 2 were subjected to performance tests, and the test results are shown in the following table:
TABLE 12 results of Performance test of the water and oil resistant agents of examples 1 to 10 and comparative examples 1 to 2
Note:
the textile finishing process comprises the following steps: diluting the waterproof and oil-proof agent to the concentration of 30g/L, immersing the fabric in the diluted waterproof and oil-proof agent for 15min, rolling the fabric for 1 time by using a padder, and drying the fabric at 80 ℃ for 40min, 100 ℃ for 30min and 120 ℃ for 15min respectively.
Average particle size: the particle size and particle size distribution of the emulsion were tested using a Mastersizer2000 laser particle sizer.
Waterproof grade: the water-and oil-repellent finished fabric was tested with reference to the "AATCC 22 spray test" and the water-and oil-repellent rating indicated the spray-resistance, with the following evaluation criteria: level 1 is the wetting of the surface of the drenched liquid; level 2 is half of the wetted surface; grade 3 is that the drenched surface is only discontinuously wetted by small areas; level 4 is that the surface of the drenched liquid is not wetted, but the surface is stained with water drops; grade 5 is that the surface of the sprayed liquid is not wetted and no water drops are adhered on the surface.
Oil resistance rating: the fabrics finished with the water and oil repellent agent were tested with reference to the "AATCC 118 oil repellency test" for oil repellency rating indicating spray repellency, with the evaluation criteria shown in the following table:
TABLE 13 oil repellency rating Scale
Storage stability the aqueous dispersion (solids content about 30) was stored at 40 ℃ for 1 month and the occurrence of precipitates was observed as evaluated by ○ showing no precipitates at all, △ showing little precipitates, and x showing more precipitates.
Washing times: adding the fabric treated by the waterproof and oil-proof agent into a washing machine, adding a washing solution, washing for 10min at 40 ℃, then discharging the washing solution, washing for 5min by using clear water at 40 ℃, dehydrating, naturally drying or drying for 30min at 80 ℃, finally testing the waterproof and oil-proof performance of the fabric, repeating the above operations if the fabric needs to be washed for multiple times, and counting the reduction of the waterproof and oil-proof performance of the fabric after washing for multiple times.
As can be seen from table 12: the low-temperature water-proof and oil-proof agent can show excellent water-proof effect and oil-proof effect at a lower baking temperature, and the washing times are more than or equal to 10 times.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A low-temperature type water and oil resistant agent is characterized in that: the feed is prepared from the following raw materials in parts by mass:
a monomer a: 35-65 parts of a solvent;
a monomer b: 5-30 parts of a solvent;
a monomer c: 1-20 parts;
a monomer d: 1-20 parts;
a monomer e: 1-20 parts;
surfactant (b): 1-10 parts;
initiator: 0.05-1 part;
chain transfer agent: 0.05-1 part;
cosolvent: 10-50 parts;
water: 100-400 parts;
the monomer a is C1～C6Polyfluoroalkyl acrylates, C1～C6At least one polyfluoroalkyl methacrylate;
the monomer b is C16～C28Alkyl acrylate, C16～C28At least one of alkyl methacrylate;
the monomer c is closed isocyanate containing double bonds and has a structural formula
In the formula, R1is-COOCH2CH2-，R2is-CH3or-H, R3、R4、R5、R6And R7Are independently-OH, -H, -CH3-F, -Cl or Br;
the monomer d is at least one of acrylic ester with an alkyl group, methacrylic ester with an alkyl group, benzyl acrylate, benzyl methacrylate, styrene, methyl styrene and p-chlorostyrene;
the monomer e is 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate, methacryloyl morpholine, acryloyl morpholine, chlorinated methacryloxyethyl trimethylamine, chlorinated acryloxyethyl trimethylamine, chlorinated methacryloxypropyl trimethylamine, chlorinated acryloxypropyl trimethylamine, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, N-hydroxyethyl methacrylate, N-, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, polyoxyalkylene glycol monomethacrylate, polyoxyalkylene glycol monoacrylate, methacrylic acid, acrylic acid, 2-methacryloyloxyethyl acrylic acid, 2-acryloxyethyl acrylic acid, 2-methacryloyloxyhexahydrophthalic acid, 2-acryloxyhexahydrophthalic acid, 2-methacryloyloxyethyl acid phosphate, 2-acryloxyethyl acid phosphate, allyl methacrylate, allyl acrylate, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl- (2-vinyloxazoline), At least one of polycaprolactone of hydroxyethyl methacrylate, polycaprolactone of hydroxyethyl acrylate, 2- (2-methyl-1-oxy-2-propenyl) oxyethyl 3-oxybutyrate ester, polycaprolactone of hydroxyethyl methacrylate, polycaprolactone of hydroxyethyl acrylate and hydroxyethyl methacrylate.
2. The low-temperature type water and oil repellent agent according to claim 1, characterized in that: the feed is prepared from the following raw materials in parts by mass:
a monomer a: 50-65 parts;
a monomer b: 9-20 parts of a solvent;
a monomer c: 5-10 parts;
a monomer d: 4-15 parts;
a monomer e: 3-10 parts;
surfactant (b): 5-10 parts;
initiator: 0.5-1 part;
chain transfer agent: 0.05-0.2 part;
cosolvent: 30-50 parts of a solvent;
water: 200-300 parts;
the monomer a is at least one of perfluorohexylethyl methacrylate, perfluorohexylethyl acrylate, perfluorobutylethyl methacrylate and perfluorobutylethyl acrylate;
the monomer b is at least one of behenyl methacrylate, behenyl acrylate, stearyl acrylate and stearyl methacrylate;
the monomer c is at least one of 3-bromophenol-sealed isocyano ethyl methacrylate, 3-bromophenol-sealed isocyano ethyl acrylate, 3-bromo-5-fluorophenol-sealed isocyano ethyl methacrylate, 3-bromo-5-fluorophenol-sealed isocyano ethyl acrylate, 4-propylphenol-sealed isocyano ethyl methacrylate, 4-propylphenol-sealed isocyano ethyl acrylate, p-tert-butylphenol-sealed isocyano ethyl methacrylate, p-isopropylphenol-sealed isocyano ethyl methacrylate and p-isopropylphenol-sealed isocyano ethyl acrylate;
the monomer d is at least one of cyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyl acrylate, benzyl methacrylate, styrene, methyl styrene and p-chlorostyrene;
the monomer e is at least one of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, polycaprolactone of hydroxyethyl acrylate and hydroxyethyl methacrylate.
3. The low-temperature type water and oil repellent agent according to claim 1 or 2, characterized in that: the surfactant is at least one of hydrocarbon surfactant and fluorine surfactant.
4. The low-temperature type water and oil repellent agent according to claim 1 or 2, characterized in that: the initiator is at least one of 2,2' -azobis (2-methylpropionitrile), 2' -azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, ammonium persulfate, potassium persulfate and 2,2' -azobisisobutylamidine hydrochloride.
5. The low-temperature type water and oil repellent agent according to claim 1 or 2, characterized in that: the chain transfer agent is n-dodecyl mercaptan.
6. The low-temperature type water and oil repellent agent according to claim 1 or 2, characterized in that: the cosolvent is a water-soluble organic solvent.
7. The low-temperature type water and oil repellent agent according to claim 6, characterized in that: the cosolvent is at least one of water-soluble ketones, water-soluble alcohols and water-soluble ethers.
8. A method for preparing a low-temperature water-and oil-repellent agent according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:
1) mixing a monomer a, a monomer b, a monomer c, a monomer d, a monomer e, a surfactant, a chain transfer agent, a cosolvent and water, and pre-emulsifying;
2) transferring the material obtained in the step 1) into a reaction kettle, adding an initiator, and carrying out polymerization reaction to obtain the low-temperature waterproof and oil-proof agent.
9. A water and oil repellent composition characterized by: comprising the low-temperature type water and oil repellent agent according to any one of claims 1 to 7.
10. The water and oil repellent composition according to claim 9, characterized in that: also comprises at least one of penetrant, defoamer, water absorbent, antistatic agent, anti-wrinkling agent, hand feeling modifier, film forming auxiliary agent, curing agent, thermosetting catalyst, crosslinking catalyst, fiber stabilizer and inorganic particles.
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