CN109400802B - Hydrophobic and oleophobic modifier and preparation method thereof, and preparation method of modified powder - Google Patents
Hydrophobic and oleophobic modifier and preparation method thereof, and preparation method of modified powder Download PDFInfo
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- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/72—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with metaphosphoric acids or their salts; with polyphosphoric acids or their salts; with perphosphoric acids or their salts
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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- C08J2433/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/24—Homopolymers or copolymers of amides or imides
Abstract
The invention provides a hydrophobic and oleophobic modifier, which is formed by the following components: 30-70 parts by weight of perfluoroalkyl ethyl acrylate; 0-30 parts by weight of an acrylate active monomer; 10-40 parts by weight of acrylamide compounds; 1-3 parts of a chain transfer agent. Compared with the prior art, the perfluoroalkyl ethyl acrylate is used as a main monomer unit, has better hydrophobic and oleophobic properties, can further improve the hydrophobic and oleophobic properties of the modifier after the perfluoroalkyl ethyl acrylate is grafted with the acrylamide compound, can also enhance the flexibility of a perfluoro group, and can be used for modifying nano powder with the diameter of 100 nanometers and more; the hydrophobic and oleophobic modifier provided by the invention has the advantages of easily available raw materials, no toxicity, no harm and no environmental pollution.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a hydrophobic and oleophobic modifier, a preparation method of the hydrophobic and oleophobic modifier and a preparation method of modified powder.
Background
The hydrophobic and oleophobic modifier is widely used in daily life, and after being treated by the hydrophobic and oleophobic modifier, such as cloth, clothing material, umbrella and the like, the hydrophobic and oleophobic modifier can enhance the water resistance and oil resistance, and even achieve the effect of no-washing; in addition, electronic products are also often subjected to hydrophobic and oleophobic treatment, for example, after mobile phone and tablet personal computer protective films are subjected to hydrophobic and oleophobic treatment, the screen can be kept neat and bright, and the electronic products have good aesthetic property; in addition, the hydrophobic and oleophobic modifier can be used in some micro-nano particles.
For hydrophobic and oleophobic treatment of contact surfaces such as fabrics and protective films, research is more and the treatment is more convenient, and the treatment is generally carried out by changing the microstructure of the contact surfaces and introducing a substance with larger electronegativity, namely a fluorocarbon bond. However, for powder, the powder has inhomogeneous structure and shape, complex surface components and high microscopic etching difficulty, so that the effect cannot be achieved by using the common commercially available oleophobic and oleophobic modifier, and therefore, a special modifier for powder is needed.
In the prior art, people also have made a lot of researches on the surface modification of powder, for example, chinese patent publication No. CN103951279 discloses a one-pot method for preparing silica nanoparticle sol with two particle sizes, a micro-nano composite two-stage rough structure required for water and oil repellency is obtained by one-step spin coating, and after the hydrophobic and oil repellency silica-based light-transmitting coating film is modified by fluorocarbon surfactant, the process steps are greatly simplified, and the structural proportion of the thickness and the size of the coating film is easy to adjust. Although the method simplifies the process, the preparation of the solution and the preparation of the micro-nano composite two-stage rough structure are complicated, and the method is not suitable for large-scale industrialization.
Chinese patent publication No. CN106893391A discloses a method for hydrophobic and oleophobic modification of nanopowder, which comprises mixing nanopowder with organic solvent, ultrasonically dispersing to obtain suspension, adding dropwise a fluorinating agent into the suspension for immersion treatment, and spray drying to obtain modified fluorinated nanopowder. Since the modifier for the powder is a single molecule, it has a certain oil-repellent effect, but the performance of the modifier is far from the requirement, and the fluorinating agent required in the method is expensive, which makes the practical application difficult.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a hydrophobic and oleophobic modifier with good hydrophobic and oleophobic modification effect, simple operation steps and low cost, a preparation method thereof, and a preparation method of modified powder.
The invention provides a hydrophobic and oleophobic modifier, which is formed by the following components:
preferably, the number of carbon atoms of the alkyl group in the perfluoroalkylethyl acrylate is 6 to 12.
Preferably, the perfluoroalkylethyl acrylate is selected from one or more of perfluorohexylethyl acrylate, perfluorooctylethyl acrylate, perfluorodecylethyl acrylate and perfluorododecylethyl acrylate.
Preferably, the acrylate reactive monomer is selected from hydroxyalkyl methacrylate and/or hydroxyalkyl acrylate; the number of carbon atoms of the alkyl group in the hydroxyalkyl methacrylate and the hydroxyalkyl acrylate is independently 2 to 6.
Preferably, the acrylate reactive monomer is selected from one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.
Preferably, the acrylamide compound is selected from a hydroxyl group-containing acrylamide compound and/or an N, N-dialkylacrylamide compound; the carbon atom number of the alkyl in the N, N-dialkyl acrylamide compound is 1-5.
Preferably, the acrylamide compound is selected from one or more of N-methylolacrylamide, N-hydroxyethyl acrylamide and N, N-diethyl-2-acrylamide.
The invention also provides a preparation method of the hydrophobic and oleophobic modifier, which comprises the following steps:
mixing 30-70 parts by weight of perfluoroalkyl ethyl acrylate, 0-30 parts by weight of acrylate active monomer, 10-40 parts by weight of acrylamide compound and 1-3 parts by weight of chain transfer agent in a first organic solvent, then adding 1-3 parts by weight of initiator, and reacting to obtain the hydrophobic and oleophobic modifier.
Preferably, the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, azobiscyclohexylcarbonitrile and dimethyl azobisisobutyrate;
the organic solvent is selected from one or more of toluene, 1,1, 1-trichloroethane, 1,1, 2-trichloroethane, trichloroethylene, ethyl acetate, trichloromethane and chlorobenzene;
the mixing temperature is 45-75 ℃; the mixing time is 20-60 min;
the initiator is added after being dissolved in a second organic solvent; 1000-3000 parts by weight of the first organic solvent and the second organic solvent;
the reaction time is 5-20 h.
The invention also provides a preparation method of the modified powder, which comprises the following steps:
mixing the hydrophobic and oleophobic modifier and the powder to be modified in an organic solvent, heating for reaction, evaporating and drying to obtain the modified powder.
The invention provides a hydrophobic and oleophobic modifier, which is formed by the following components: 30-70 parts by weight of perfluoroalkyl ethyl acrylate; 0-30 parts by weight of an acrylate active monomer; 10-40 parts by weight of acrylamide compounds; 1-3 parts of a chain transfer agent. Compared with the prior art, the perfluoroalkyl ethyl acrylate is used as a main monomer unit, has better hydrophobic and oleophobic properties, can further improve the hydrophobic and oleophobic properties of the modifier after the perfluoroalkyl ethyl acrylate is grafted with the acrylamide compound, can also enhance the flexibility of a perfluoro group, and can be used for modifying nano powder with the diameter of 100 nanometers and more; the hydrophobic and oleophobic modifier provided by the invention has the advantages of easily available raw materials, no toxicity, no harm and no environmental pollution.
Drawings
FIG. 1 is an infrared spectrum of a hydrophobic and oleophobic modifier obtained in example 1 of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a hydrophobic and oleophobic modifier, which is formed by the following components:
the perfluoroalkyl ethyl acrylate is used as a main monomer unit of the hydrophobic and oleophobic modifier, fluorine is used as an element with the largest natural electronegativity, and the introduction of the perfluoroalkyl ethyl acrylate into the modifier can endow the modified hydrophobic and oleophobic property. However, in general, the introduction of perfluoro will harden the surface of the material, and thus other groups need to be introduced to enhance the flexibility of the perfluoro group. However, the introduction of the excess groups has a large influence on the modifying effect of the modifier. In the perfluoroalkyl ethyl acrylate, the carbon number of the alkyl is preferably 6-12; the perfluoro compound with the carbon number of 6-12 can shield the rest groups. Therefore, the perfluoro branched chain can introduce other active groups into the hydrophobic and oleophobic modifier without influencing the hydrophobic and oleophobic properties of the hydrophobic and oleophobic modifier. More preferably, the perfluoroalkylethyl acrylate is one or more of perfluorohexylethyl acrylate, perfluorooctylethyl acrylate, perfluorodecylethyl acrylate, and perfluorododecylethyl acrylate; in some embodiments provided herein, the perfluoroalkylethyl acrylate is preferably present in an amount of 30 parts by weight; in some embodiments provided herein, the perfluoroalkylethyl acrylate is preferably present in an amount of 50 parts by weight; in some embodiments provided herein, the perfluoroalkylethyl acrylate is preferably present in an amount of 60 parts by weight; in other embodiments provided herein, the perfluoroalkylethyl acrylate is preferably present in an amount of 30 parts by weight.
The acrylate reactive monomer is not particularly limited as long as it is known to those skilled in the art, and in the present invention, hydroxyalkyl methacrylate and/or hydroxyalkyl acrylate are preferable; the carbon atom number of the alkyl in the hydroxyalkyl methacrylate is preferably 2-6, more preferably 2-4, and further preferably 2-3; the carbon atom number of the alkyl in the hydroxyalkyl acrylate is preferably 2-6, more preferably 2-4, and further preferably 2-3; most preferably, the acrylate reactive monomer is one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate; the content of the acrylate active monomer is preferably 5-30 parts by weight, and more preferably 10-30 parts by weight.
According to the invention, an acrylamide compound monomer unit is introduced into the hydrophobic and oleophobic modifier, so that the hydrophobic and oleophobic effects of the perfluoroalkyl ethyl acrylate monomer unit can be further improved; the acrylamide compound is not particularly limited as long as it is known to those skilled in the art, and in the present invention, it is preferably an acrylamide compound containing a hydroxyl group and/or an N, N-dialkylacrylamide compound; the number of carbon atoms in the hydroxyl-containing acrylamide compound is preferably 3-8, more preferably 4-6, and even more preferably 5; the carbon number of the alkyl in the N, N-dialkyl acrylamide compound is preferably 1-5, more preferably 1-4, and still more preferably 1-3; most preferably, the acrylamide compound is one or more of N-methylolacrylamide, N-hydroxyethyl acrylamide and N, N-diethyl-2-acrylamide; the content of the acrylamide compound is preferably 20-40 parts by weight; in some embodiments provided herein, the acrylamide-based compound is preferably present in an amount of 20 parts by weight; in some embodiments provided herein, the acrylamide-based compound is preferably present in an amount of 30 parts by weight; in other embodiments provided by the present invention, the acrylamide-based compound is preferably present in an amount of 40 parts by weight.
The chain transfer agent is a chain transfer agent well known to those skilled in the art, and is not particularly limited, and in the present invention, one or more of dodecyl mercaptan, mercaptoethanol, thioglycolic acid, and isooctyl 3-mercaptopropionate are preferable; the content of the chain transfer agent is preferably 1 to 2 parts by weight.
The perfluoroalkyl ethyl acrylate is used as a main monomer unit, has better hydrophobic and oleophobic properties, can further improve the hydrophobic and oleophobic properties of the modifier after being grafted with the acrylamide compound, can also enhance the flexibility of a perfluoro group, and can be used for modifying micron and partial nanometer powder; the hydrophobic and oleophobic modifier provided by the invention has the advantages of easily available raw materials, no toxicity, no harm and no environmental pollution.
The invention also provides a preparation method of the hydrophobic and oleophobic modifier, which comprises the following steps: mixing 30-70 parts by weight of perfluoroalkyl ethyl acrylate, 0-30 parts by weight of acrylate active monomer, 10-40 parts by weight of acrylamide compound and 1-3 parts by weight of chain transfer agent in a first organic solvent, then adding 1-3 parts by weight of initiator, and reacting to obtain the hydrophobic and oleophobic modifier.
Wherein, the sources of all raw materials are not specially limited and can be sold in the market; the perfluoroalkyl ethyl acrylate, the acrylate active monomer, the acrylamide compound and the like are the same as those mentioned above, and are not described in detail herein.
In the present invention, it is preferable to mix a perfluoroalkylethyl acrylate, an acrylate-based active monomer, an acrylamide-based compound, and a chain transfer agent in a first organic solvent in a protective atmosphere; the protective atmosphere is not particularly limited as long as it is known to those skilled in the art, and nitrogen is preferred in the present invention; the first organic solvent is not particularly limited as long as it is an organic solvent well known to those skilled in the art, and in the present invention, one or more of toluene, 1,1, 1-trichloroethane, 1,1, 2-trichloroethane, trichloroethylene, ethyl acetate, trichloromethane and chlorobenzene are preferred; the mixing method is not particularly limited as long as it is a method known to those skilled in the art, and stirring is preferable in the present invention; the mixing temperature is preferably 45-75 ℃, more preferably 45-70 ℃, further preferably 45-65 ℃, further preferably 45-60 ℃, and most preferably 45-55 ℃; the mixing time is preferably 20-60 min, more preferably 30-50 min, and still more preferably 30-40 min.
Then adding an initiator; the initiator is an initiator well known to those skilled in the art, and is not particularly limited, and in the present invention, an azo-type initiator is preferable, and one or more of azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, azobiscyclohexylcarbonitrile, and dimethyl azobisisobutyrate are more preferable; the initiator is preferably added after being dissolved in the second organic solvent; the second solvent is an organic solvent well known to those skilled in the art, and is not particularly limited, but in the present invention, one or more of toluene, 1,1, 1-trichloroethane, 1,1, 2-trichloroethane, trichloroethylene, ethyl acetate, trichloromethane and chlorobenzene are preferred; the mass ratio of the initiator to the second organic solvent is preferably 1 to (50-200), more preferably 1: (80-150), and more preferably 1: (100-120); the first solvent and the second solvent are preferably 1000-3000 parts by weight in total, and more preferably 1000-2000 parts by weight; the adding mode is preferably dropwise adding, more preferably dropwise adding is completed within 1-3 h, still more preferably dropwise adding is completed within 1.5-2.5 h, and most preferably dropwise adding is completed within 2 h.
Adding an initiator, and reacting; the reaction is preferably carried out under stirring; the reaction time is preferably 5 to 20 hours, more preferably 8 to 15 hours, and further preferably 1 to 12 hours.
After the reaction, preferably pouring the reaction solution into an alcohol solvent, centrifuging, filtering, washing and drying to obtain the hydrophobic and oleophobic modifier; the alcohol solvent is not particularly limited as long as it is well known in the art, and methanol is preferable in the present invention.
The hydrophobic and oleophobic modifier provided by the invention has the advantages of easily available raw materials, no toxicity, no harm, no environmental pollution and simple preparation method, and after the hydrophobic and oleophobic modifier is used for modifying powder, the modified powder has better hydrophobic and oleophobic properties and is not easy to agglomerate.
The invention also provides a preparation method of the modified powder, which comprises the following steps: mixing the hydrophobic and oleophobic modifier and the powder to be modified in an organic solvent, heating for reaction, evaporating and drying to obtain the modified powder.
The powder to be modified is powder with a hydrogen bond-forming receptor on the surface, which is well known to those skilled in the art, and is not particularly limited, and in the invention, the powder is preferably one or more of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, ammonium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium polyphosphate, potassium sulfate, sodium sulfate, calcium carbonate, calcium bicarbonate, calcium sulfate, sodium sulfate, potassium sulfate, ammonium sulfate, talcum powder, mica powder and zeolite powder; the particle size of the powder to be modified is preferably micron-sized or nano-sized; when the particle size is nano-scale, nano-scale powder with the particle size of 100 nm and above is preferred; the mass ratio of the hydrophobic and oleophobic modifier to the powder to be modified is preferably 1: (20 to 100), more preferably 1: (30-80), and more preferably 1: (40-60), most preferably 1: 50; the organic solvent is not particularly limited as long as it is an organic solvent well known to those skilled in the art, and tetrahydrofuran is preferable in the present invention.
Mixing a hydrophobic and oleophobic modifier with powder to be modified in an organic solvent; the mixing method is preferably stirring; the mixing time is preferably 1-6 h, more preferably 2-5 h, and still more preferably 3-4 h.
After mixing, heating for reaction; the temperature of the heating reaction is preferably 45-75 ℃, more preferably 55-75 ℃, further preferably 60-70 ℃ and most preferably 65 ℃; the heating reaction time is preferably 1-5 h, more preferably 2-4 h, and still more preferably 2-3 h.
Heating for reaction, evaporating and drying to obtain modified powder.
In order to further illustrate the present invention, the following will describe a hydrophobic and oleophobic modifier and a preparation method thereof in detail with reference to the examples.
The reagents used in the following examples are all commercially available.
Example 1
The hydrophobic and oleophobic modifier comprises the following raw materials in percentage by mass: 30 parts of perfluorohexyl ethyl acrylate, 30 parts of hydroxyethyl methacrylate, 40 parts of N- (2-hydroxyethyl) acrylamide, 1 part of N-dodecyl mercaptan, 1 part of azodiisobutyronitrile serving as an initiator and 1000 parts of 1,1, 2-trichloroethane.
The preparation method comprises the following steps:
under the protection of nitrogen, dissolving perfluoroacrylate, hydroxyethyl methacrylate, N- (2-hydroxyethyl) acrylamide and N-dodecyl mercaptan in a 1,1, 2-trichloroethane according to the mass ratio in a four-mouth flask with a condenser pipe, an electromagnetic stirrer, a constant pressure funnel and an air inlet, and pre-stirring for 30min at the temperature of 45 ℃;
diluting azodiisobutyronitrile by 100 times by using 1,1, 2-trichloroethane, slowly dripping for 2 hours until the dripping is finished, and then continuously stirring for 10 hours;
and dissolving the reacted liquid in methanol, centrifuging, filtering, washing and drying to obtain the hydrophobic and oleophobic modifier with yield of 78% and purity higher than 90%.
The hydrophobic and oleophobic modifier obtained in example 1 was analyzed by infrared spectroscopy, and the infrared spectrum thereof was as shown in FIG. 1.
Example 2
The hydrophobic and oleophobic modifier comprises the following raw materials in percentage by mass: 50 parts of perfluorooctyl ethyl acrylate, 30 parts of hydroxypropyl methacrylate, 30 parts of N-hydroxyethyl acrylamide, 2 parts of N-dodecyl mercaptan, 2 parts of azo-bis-iso-heptonitrile as an initiator and 1000 parts of toluene.
The preparation method comprises the following steps:
under the protection of nitrogen, dissolving perfluoroacrylate, hydroxypropyl methacrylate, N-hydroxyethyl acrylamide and N-dodecyl mercaptan in toluene according to the mass ratio in a four-mouth flask with a condenser pipe, an electromagnetic stirrer, a constant pressure funnel and an air inlet, and pre-stirring for 30min at 55 ℃;
diluting azodiisoheptanonitrile by 100 times by using a solvent, slowly dropwise adding for 2 hours until the dropwise adding is finished, and then continuously stirring for 10 hours;
and dissolving the reacted liquid in methanol, centrifuging, filtering, washing and drying to obtain the hydrophobic and oleophobic modifier with yield of 82% and purity of over 90%.
Example 3
The hydrophobic and oleophobic modifier comprises the following raw materials in percentage by mass: 60 parts of perfluorodecyl ethyl acrylate, 40 parts of N- (2-hydroxyethyl) acrylamide, 2 parts of N-dodecyl mercaptan, 2 parts of azobisisovaleronitrile and 1000 parts of trichloroethylene.
The preparation method comprises the following steps:
under the protection of nitrogen, dissolving perfluoroacrylate, N- (2-hydroxyethyl) acrylamide and N-dodecyl mercaptan in trichloroethylene according to the mass ratio in a four-mouth flask with a condenser pipe, an electromagnetic stirrer, a constant pressure funnel and an air inlet, and pre-stirring for 30min at 55 ℃;
diluting azodiisovaleronitrile by 100 times by using trichloroethylene, slowly dropwise adding for 2 hours until the dropwise adding is finished, and then continuously stirring for 10 hours;
and dissolving the reacted liquid in methanol, centrifuging, filtering, washing and drying to obtain the hydrophobic and oleophobic modifier with yield of 85% and purity higher than 90%.
Example 4
The hydrophobic and oleophobic modifier comprises the following raw materials in percentage by mass: 70 parts of perfluorododecyl ethyl acrylate, 10 parts of hydroxypropyl acrylate, 20 parts of N, N-diethyl-2-acrylamide, 2 parts of N-dodecyl mercaptan, 2 parts of azobisisovaleronitrile and 1000 parts of ethyl acetate.
The preparation method comprises the following steps:
under the protection of nitrogen, dissolving perfluoroacrylate, N-diethyl-2-acrylamide, hydroxypropyl acrylate and N-dodecyl mercaptan in ethyl acetate according to the mass ratio in a four-mouth flask with a condensing tube, an electromagnetic stirrer, a constant pressure funnel and an air inlet, and pre-stirring for 30min at 55 ℃;
diluting azodicyclohexyl formonitrile by 100 times by using a solvent, slowly dripping for 2 hours until the dripping is finished, and then continuously stirring for 10 hours;
and dissolving the reacted liquid in methanol, centrifuging, filtering, washing and drying to obtain the hydrophobic and oleophobic modifier with yield of 75% and purity higher than 90%.
The hydrophobic and oleophobic modifiers obtained in examples 2 to 4 were analyzed by infrared spectroscopy, and it was confirmed that the obtained products contained characteristic peaks of each monomer.
Test example:
dissolving the hydrophobic and oleophobic modifier obtained in the embodiment 1-4 and ammonium polyphosphate with the powder D90 to be modified being 1 micron in tetrahydrofuran according to the proportion of 1:50, fully stirring and dispersing for 3h, heating to 65 ℃, reacting for 2h, evaporating and drying to obtain modified powder.
Weighing 10g of modified powder, scattering the modified powder into deionized water (aviation kerosene), stirring for 10min, taking out the fire extinguishing agent floating on the water (oil) surface, drying, cooling to room temperature, and weighing to obtain the mass w (g) of the fire extinguishing agent floating on the water (oil) surface. The hydrophobic (oil) ratio of the fire extinguishing agent is calculated as follows:
the hydrophobic (oil) ratio was (w/10). times.100%
The modified powder was subjected to moisture content, hygroscopicity and water repellency tests in accordance with GA 5782005, and the results obtained by the tests are shown in Table 1.
TABLE 1 modified powder Hydrophobicity and oleophobicity test results
| Examples | Example 1 | Example 2 | Example 3 | Example 4 |
| Hydrophobic Rate (%) | 99.5％ | 99.6％ | 99.3％ | 99.0％ |
| Oil repellency (%) | 96.3％ | 95.0％ | 97.2％ | 96.5％ |
| Water content (%) | 0.2％ | 0.15％ | 0.1％ | 0.15％ |
| Moisture absorption (%) | 2.0％ | 2.5％ | 1.9％ | 2.1％ |
| Water repellency | Superior food | Superior food | Superior food | Superior food |
Claims (5)
1. A preparation method of a hydrophobic and oleophobic modifier for micron and nano powder with the diameter of 100 nanometers and above is characterized by comprising the following steps:
mixing 30-70 parts by weight of perfluoroalkyl ethyl acrylate, 0-30 parts by weight of acrylate active monomer, 10-40 parts by weight of acrylamide compound and 1-3 parts by weight of chain transfer agent in a first organic solvent, then adding 1-3 parts by weight of initiator, and reacting to obtain a hydrophobic and oleophobic modifier;
the acrylamide compound is selected from acrylamide compounds containing hydroxyl and/or N, N-dialkyl acrylamide compounds; the carbon atom number of the alkyl in the N, N-dialkyl acrylamide compound is 1-5;
the carbon atom number of alkyl in the perfluoroalkyl ethyl acrylate is 6-12;
the acrylate reactive monomer is selected from hydroxyalkyl methacrylate and/or hydroxyalkyl acrylate; the carbon atoms of the alkyl in the hydroxyalkyl methacrylate and the hydroxyalkyl acrylate are respectively and independently 2-6;
the acrylamide compound is selected from one or more of N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide and N, N-diethyl-2-acrylamide.
2. The method according to claim 1, wherein the perfluoroalkylethyl acrylate is one or more selected from the group consisting of perfluorohexylethyl acrylate, perfluorooctylethyl acrylate, perfluorodecylethyl acrylate and perfluorododecylethyl acrylate.
3. The method according to claim 1, wherein the acrylate-based reactive monomer is one or more selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.
4. The method of claim 1, wherein the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, azobisdicyclohexylcarbonitrile, and dimethyl azobisisobutyrate;
the organic solvent is selected from one or more of toluene, 1,1, 1-trichloroethane, 1,1, 2-trichloroethane, trichloroethylene, ethyl acetate, trichloromethane and chlorobenzene;
the mixing temperature is 45-75 ℃; the mixing time is 20-60 min;
the initiator is added after being dissolved in a second organic solvent; 1000-3000 parts by weight of the first organic solvent and the second organic solvent;
the reaction time is 5-20 h.
5. A method for preparing modified powder is characterized by comprising the following steps:
mixing the hydrophobic and oleophobic modifier prepared by the preparation method of any one of claims 1-4 and powder to be modified in an organic solvent, heating for reaction, evaporating and drying to obtain modified powder; the powder to be modified is a nano powder with the micron diameter and the diameter of 100 nanometers and above.
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| CN110105492A (en) * | 2019-04-30 | 2019-08-09 | 中国科学技术大学 | A kind of hydrophobic oleophobic preparation method of micro/nano level powder modifier and micro/nano level powder |
| CN110038248B (en) * | 2019-05-09 | 2021-05-07 | 中国科学技术大学 | Method for preparing anti-afterburning superfine dry powder extinguishing agent by using polymer sol |
| CN111877016A (en) * | 2020-07-10 | 2020-11-03 | 温州厚德服饰有限公司 | Anti-oil cotton clothes and processing technology thereof |
| CN114196104A (en) * | 2021-12-17 | 2022-03-18 | 江苏尚艾新材料科技有限公司 | Antibacterial oil-stain-resistant polypropylene material and preparation method thereof |
| CN115216042B (en) * | 2022-07-13 | 2023-07-14 | 天津日津科技股份有限公司 | Preparation method of hydrophobic oleophobic PTFE composite membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145912A (en) * | 2013-03-11 | 2013-06-12 | 北京科技大学 | Preparation method of titanium dioxide nano powder-modified fluorine-containing acrylate emulsion |
| CN104558447A (en) * | 2014-12-12 | 2015-04-29 | 杭州吉华高分子材料股份有限公司 | Inorganic nano composite anti-doodling resin and preparation method thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5344903A (en) * | 1993-04-14 | 1994-09-06 | E. I. Du Pont De Nemours And Company | Water- and oil-repellent fluoro(meth)acrylate copolymers |
| EP3598181B1 (en) * | 2008-11-13 | 2021-06-23 | Alcon Inc. | Vinylic monomer and prepolymer comprising same |
| US10494466B2 (en) * | 2013-03-15 | 2019-12-03 | Isp Investments Llc | Polymers polymerized from at least four monomers, and compositions and uses thereof |
| CN103980418B (en) * | 2014-05-23 | 2016-08-31 | 深圳天鼎精细化工制造有限公司 | A kind of cation water-based Organic fluoride acrylate polymer as well as preparation method and application thereof |
| CN104387516B (en) * | 2014-10-22 | 2016-10-26 | 陕西延长石油（集团）有限责任公司 | A kind of preparation method of the fluorine-contaninig polyacrylate core shell emulsion of Oil repellent Gradient distribution |
| CN104562684B (en) * | 2015-02-12 | 2017-03-08 | 王俊 | A kind of water and oil repellent agent and preparation method thereof |
| CN105401429B (en) * | 2015-11-24 | 2017-09-29 | 苏州市职业大学 | A kind of low temperature three-proof finishing agent, preparation method and its application on fabric |
| CN106279518A (en) * | 2016-08-08 | 2017-01-04 | 广州市雷曼兄弟电子科技有限公司 | Fluoropolymer, Waterproof, grease proof treating compound and preparation method thereof and protecting film |
| CN106497254A (en) * | 2016-09-23 | 2017-03-15 | 安徽吉思特智能装备有限公司 | Heat-insulated radial pattern coating of a kind of corrosion resistant fluorine carbon and preparation method thereof |
-
2018
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145912A (en) * | 2013-03-11 | 2013-06-12 | 北京科技大学 | Preparation method of titanium dioxide nano powder-modified fluorine-containing acrylate emulsion |
| CN104558447A (en) * | 2014-12-12 | 2015-04-29 | 杭州吉华高分子材料股份有限公司 | Inorganic nano composite anti-doodling resin and preparation method thereof |
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