Low-temperature type waterproof and oil-proof agent and preparation method thereof
阅读说明：本技术 一种低温型防水防油剂及其制备方法 (Low-temperature type waterproof and oil-proof agent and preparation method thereof ) 是由 王梅玲 周青烽 何浩鹏 陈秀莹 于 2019-10-10 设计创作，主要内容包括：本发明公开了一种低温型防水防油剂及其制备方法。本发明的低温型防水防油剂由含氟单体和多种功能单体共聚得到,其制备方法包括以下步骤：1)将单体、表面活性剂、链转移剂、助溶剂和水混合,进行预乳化；2)将步骤1)的物料转入反应釜,再加入引发剂,70～90℃反应6～10h。本发明的低温型防水防油剂安全环保、价格低廉,在低温下便可以对织物进行防水防油处理,处理过的织物防水防油性能优异,且可以耐多次洗涤。(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.)
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
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.
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
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.