CN109400802A - The preparation method of hydrophobic oleophobic modifying agent and preparation method thereof, modified powder - Google Patents
The preparation method of hydrophobic oleophobic modifying agent and preparation method thereof, modified powder Download PDFInfo
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- CN109400802A CN109400802A CN201811251431.XA CN201811251431A CN109400802A CN 109400802 A CN109400802 A CN 109400802A CN 201811251431 A CN201811251431 A CN 201811251431A CN 109400802 A CN109400802 A CN 109400802A
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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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
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- 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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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
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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
- 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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- D—TEXTILES; PAPER
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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 present invention provides a kind of hydrophobic oleophobic modifying agent, are formed by following components, and the component includes: 30~70 parts by weight of perfluor alkyl ethyl acrylate；0~30 parts by weight of esters of acrylic acid activated monomer；10~40 parts by weight of acrylamides；1~3 parts by weight of chain-transferring agent.Compared with prior art, the present invention is using perfluor alkyl ethyl acrylate as main monomer unit, it is with preferable hydrophobic oleophobic performance, after perfluor alkyl ethyl acrylate and acrylamides grafting, it can further improve the hydrophobic oleophobic performance of modifying agent, the flexibility that full-fluorine group can also be enhanced simultaneously can be used for the modification for the nano-powder that micron and diameter are 100 nanometers or more；And hydrophobic oleophobic modifier raw material provided by the invention is easy to get, nontoxic, does not pollute the environment.
Description
Technical field
The invention belongs to technical field of function materials more particularly to a kind of hydrophobic oleophobic modifying agent and preparation method thereof, change
Property raw powder's production technology.
Background technique
Hydrophobic oleophobic modifying agent uses extensively in daily life, such as face cloth, dress material, umbrella are through hydrophobic oleophobic modifying agent
After processing, its water resistant resistance to oily stain energy, even up to disposable effect can be enhanced；Furthermore, electronic product is also often used
Hydrophobic oleophobic processing can keep the as neat as wax of screen after handling such as mobile phone and tablet computer protective film through hydrophobic oleophobic,
With preferable performance attractive in appearance；In addition, can also use hydrophobic oleophobic modifying agent in some micro-nano particles.
For the processing of the hydrophobic oleophobic of the contact surfaces such as fabric, protective film, research is more, deals with also more square
Just, it is carried out generally by changing contact surface microstructure and introducing the biggish substance carbon-fluorine bond of electronegativity.But it is directed to powder
For body, since powder structure shape is inhomogenous, surface composition is complicated, microcosmic etching difficulty is larger, thus common market is used
On oleophobic oleophobic modifying agent effect is not achieved, it is therefore desirable to it is a kind of to be directed to the special modifying agent of powder.
In existing technology, people also expand numerous studies, such as Publication No. for powder surface modification
The Chinese patent of CN103951279 discloses the Nano particles of silicon dioxide colloidal sol that one kettle way prepares two kinds of partial sizes, passes through a step
Micro-nano composite double-stage coarse structure needed for spin coating obtains hydrophobic oleophobic, after being modified with fluorocarbon surfactant, can be made hydrophobic
Oleophobic titanium dioxide silicon substrate transparent coatings film, enormously simplifies processing step, and can easily be accommodated the structure of thicknesses of layers, size dimension
Ratio.Although such method simplifies technique and does not walk, but the configuration of its solution, micro-nano composite double-stage coarse structure prepare it is equal
It is complex, it is not suitable for extensive industrialization.
The Chinese patent of Publication No. CN106893391A discloses a kind of nanometer powder hydrophobic oleophobic method of modifying, first
Nanometer powder is mixed with organic solvent, suspension is obtained by ultrasonic disperse, fluorization agent is then added dropwise to above-mentioned suspension
Impregnation is carried out in the middle, is finally spray-dried, and modified fluorinated nano powder can be obtained.Due to changing for this kind of powder
Property agent use be unimolecule, though thus have certain oleophobic effects, be also far from the requirment in performance, and
Required fluorization agent somewhat expensive, brings difficulty to actual application in this kind of method.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of hydrophobic oleophobic modified effect it is good, behaviour
Make that step is simple, the preparation method of lower-cost hydrophobic oleophobic modifying agent and preparation method thereof, modified powder.
The present invention provides a kind of hydrophobic oleophobic modifying agent, are formed by following components, and the component includes:
Preferably, the carbon atom number of alkyl is 6~12 in the perfluor alkyl ethyl acrylate.
Preferably, the perfluor alkyl ethyl acrylate is selected from perfluoro hexyl ethyl propylene acid esters, perfluorooctylethyl group
One of acrylate, perfluoro decyl ethyl propylene acid esters and perfluorododecyl ethyl propylene acid esters are a variety of.
Preferably, the esters of acrylic acid activated monomer is selected from hydroxyalkyl methacrylate and/or acrylic acid hydroxy alkyl
Ester；The carbon atom number of alkyl is each independently 2~6 in the hydroxyalkyl methacrylate and acrylic acid hydroxy alkyl ester.
Preferably, the esters of acrylic acid activated monomer is selected from hydroxyethyl methacrylate, hydroxy propyl methacrylate, third
One of olefin(e) acid hydroxyl ethyl ester and hydroxypropyl acrylate are a variety of.
Preferably, the acrylamides are selected from acrylamides and/or N comprising hydroxyl, N- bis-
Alkyl acryl amine compound；The carbon atom number of alkyl is 1~5 in the N, N- dialkylacrylamides class compound.
Preferably, the acrylamides are selected from N hydroxymethyl acrylamide, N- hydroxyethyl acrylamide and N,
One of N- diethyl -2- acrylamide is a variety of.
The present invention also provides a kind of preparation methods of hydrophobic oleophobic modifying agent, comprising:
By the perfluor alkyl ethyl acrylate of 30~70 parts by weight, 0~30 parts by weight esters of acrylic acid activated monomer,
The acrylamides of 10~40 parts by weight mix in the first organic solvent with the chain-transferring agent of 1~3 parts by weight, then
The initiator of 1~3 parts by weight is added, after reaction, obtains hydrophobic oleophobic modifying agent.
Preferably, the initiator is selected from azodiisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, two ring of azo
One of hexyl formonitrile HCN and azo-bis-iso-dimethyl are a variety of；
The organic solvent be selected from toluene, 1,1,1- trichloroethanes, 1,1,2- trichloroethanes, trichloro ethylene, ethyl acetate,
One of chloroform and chlorobenzene are a variety of；
The mixed temperature is 45 DEG C~75 DEG C；The mixed time is 20~60min；
The initiator is added after being dissolved in the second organic solvent；First organic solvent and the second organic solvent totally 1000
~3000 parts by weight；
The time of the reaction is 5~20h.
The present invention also provides a kind of preparation methods of modified powder, comprising:
Above-mentioned hydrophobic oleophobic modifying agent is mixed in organic solvent with powder to be modified, after heating reaction, evaporation,
It is dry, obtain modified powder.
The present invention provides a kind of hydrophobic oleophobic modifying agent, are formed by following components, and the component includes: perfluoroalkyl second
30~70 parts by weight of base acrylate；0~30 parts by weight of esters of acrylic acid activated monomer；10~40 weight of acrylamides
Measure part；1~3 parts by weight of chain-transferring agent.Compared with prior art, the present invention is using perfluor alkyl ethyl acrylate as main
Monomeric unit connects perfluor alkyl ethyl acrylate and acrylamides with preferable hydrophobic oleophobic performance
Branch after, can further improve the hydrophobic oleophobic performance of modifying agent, while can also enhance the flexibility of full-fluorine group, can be used for micron with
And diameter is the modification of 100 nanometers or more of nano-powder；And hydrophobic oleophobic modifier raw material provided by the invention is easy to get,
It is nontoxic, it does not pollute the environment.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of hydrophobic oleophobic modifying agent obtained in the embodiment of the present invention 1.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of hydrophobic oleophobic modifying agent, are formed by following components, and the component includes:
Using perfluor alkyl ethyl acrylate as the main monomer unit of hydrophobic oleophobic modifying agent, fluorine is used as certainly the present invention
The maximum element of right boundary's electronegativity, the introducing in modifying agent will assign modified body hydrophobic oleophobic performance.However, it is general and
Speech, the introducing of perfluor will be such that material surface hardens, thus it is flexible to introduce other group enhancing full-fluorine groups.However, extra base
Group introduce can modified effect to modifying agent by large effect.Alkyl in perfluor alkyl ethyl acrylate in the present invention
Carbon atom number be preferably 6~12；Perfluor object of the carbon atom number in 6~12 sections can mask the effect of remaining group.Cause
And such perfluor branch is used it is hydrophobic thin can not influence its while hydrophobic oleophobic modifying agent introduces other active groups
Oiliness.It is highly preferred that the perfluor alkyl ethyl acrylate is perfluoro hexyl ethyl propylene acid esters, perfluorooctylethyl group propylene
One of acid esters, perfluoro decyl ethyl propylene acid esters and perfluorododecyl ethyl propylene acid esters are a variety of；It is mentioned in the present invention
In some embodiments supplied, the content of the perfluor alkyl ethyl acrylate is preferably 30 parts by weight；Provided by the invention
In some embodiments, the content of the perfluor alkyl ethyl acrylate is preferably 50 parts by weight；More provided by the invention
In embodiment, the content of the perfluor alkyl ethyl acrylate is preferably 60 parts by weight；In other realities provided by the invention
It applies in example, the content of the perfluor alkyl ethyl acrylate is preferably 30 parts by weight.
The esters of acrylic acid activated monomer is esters of acrylic acid activated monomer well known to those skilled in the art, and
It is preferably hydroxyalkyl methacrylate and/or acrylic acid hydroxy alkyl ester in the present invention without special limitation；The metering system
The carbon atom number of alkyl is preferably 2~6 in sour hydroxy alkyl ester, and more preferably 2~4, it is further preferably 2~3；The acrylic acid hydroxyl alkane
The carbon atom number of alkyl is preferably 2~6 in base ester, and more preferably 2~4, it is further preferably 2~3；Most preferably, the acrylic acid
Esters activated monomer is in hydroxyethyl methacrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate and hydroxypropyl acrylate
It is one or more；The content of the esters of acrylic acid activated monomer is preferably 5~30 parts by weight, more preferably 10~30 weight
Part.
The present invention introduces acrylamides monomeric unit in hydrophobic oleophobic modifying agent, can further improve perfluor
The hydrophobic oleophobic effect of alkyl ethyl propylene acid ester monomer unit；The acrylamides are that those skilled in the art are ripe
The acrylamides known, have no special limitation, preferably include the acrylic amide of hydroxyl in the present invention
Close object and/or N, N- dialkylacrylamides class compound；Carbon atom in the acrylamides comprising hydroxyl
Number preferably 3~8, more preferably 4~6, is further preferably 5；The carbon of alkyl in the N, N- dialkylacrylamides class compound
Atomicity is preferably 1~5, and more preferably 1~4, it is further preferably 1~3；Most preferably, the acrylamides are N-
One of hydroxymethyl acrylamide, N- hydroxyethyl acrylamide and N, N- diethyl -2- acrylamide are a variety of；The propylene
The content of amides compound is preferably 20~40 parts by weight；In some embodiments provided by the invention, the acrylamide
The content of class compound is preferably 20 parts by weight；In some embodiments provided by the invention, the acrylamides
Content be preferably 30 parts by weight；In other embodiments provided by the invention, the content of the acrylamides
Preferably 40 parts by weight.
The chain-transferring agent is chain-transferring agent well known to those skilled in the art, has no special limitation, the present invention
In preferably one of lauryl mercaptan, mercaptoethanol, thioacetic acid and 3- isooctyl mercaptopropionate or a variety of；The chain
The content of transfer agent is preferably 1~2 parts by weight.
The present invention uses perfluor alkyl ethyl acrylate as main monomer unit, with preferable hydro-oleophobicity
Can, after perfluor alkyl ethyl acrylate and acrylamides grafting, it can further improve the hydrophobic of modifying agent and dredge
Oiliness energy, while can also enhance the flexibility of full-fluorine group, it can be used for the modification of micron and part nano-powder；And the present invention
The hydrophobic oleophobic modifier raw material of offer is easy to get, nontoxic, does not pollute the environment.
The present invention also provides a kind of preparation methods of above-mentioned hydrophobic oleophobic modifying agent, comprising: by 30~70 parts by weight
Perfluor alkyl ethyl acrylate, the esters of acrylic acid activated monomer of 0~30 parts by weight, 10~40 parts by weight acrylic amide
Compound mixes in the first organic solvent with the chain-transferring agent of 1~3 parts by weight, and the initiator of 1~3 parts by weight is then added,
After reaction, hydrophobic oleophobic modifying agent is obtained.
Wherein, the present invention is not particularly limited the source of all raw materials, is commercially available；The perfluoroalkyl second
Base acrylate, esters of acrylic acid activated monomer and acrylamides and even album and same as above, herein no longer
It repeats.
In the present invention, it is preferred in protective atmosphere, perfluor alkyl ethyl acrylate, esters of acrylic acid activity is single
Body, acrylamides mix in the first organic solvent with chain-transferring agent；The protective atmosphere is those skilled in the art
Protective atmosphere known to member has no special limitation, is preferably nitrogen in the present invention；First organic solvent is ability
Organic solvent known to field technique personnel has no special limitation, is preferably toluene, 1,1,1- tri- chloroethene in the present invention
One of alkane, 1,1,2- trichloroethanes, trichloro ethylene, ethyl acetate, chloroform and chlorobenzene are a variety of；The mixed side
Method is method well known to those skilled in the art, has no special limitation, preferably stirs in the present invention；The mixing
Temperature is preferably 45 DEG C~75 DEG C, more preferably 45 DEG C~70 DEG C, is further preferably 45 DEG C~65 DEG C, is further preferably 45 DEG C~60
DEG C, most preferably 45 DEG C~55 DEG C；The mixed time is preferably 20~60min, more preferably 30~50min, further preferably
For 30~40min.
Then initiator is added；The initiator is initiator well known to those skilled in the art, and it is special to have no
It limits, is preferably azo-initiator, more preferably azodiisobutyronitrile, azobisisoheptonitrile, azo diisoamyl in the present invention
One of nitrile, azo diisopropyl imidazoline hydrochloride and azo-bis-iso-dimethyl are a variety of；The initiator is preferably solved in second
It is added after organic solvent；Second solvent is organic solvent well known to those skilled in the art, has no special limitation,
In the present invention be preferably toluene, 1,1,1- trichloroethanes, 1,1,2- trichloroethanes, trichloro ethylene, ethyl acetate, chloroform with
One of chlorobenzene is a variety of；The mass ratio of the initiator and the second organic solvent is preferably 1: (50~200), more preferably
1:(80~150), be further preferably 1:(100~120)；First solvent and the second solvent preferably totally 1000~3000 weight
Part, more preferably 1000~2000 parts by weight；The mode of the addition is preferably added dropwise, and is more preferably added dropwise in 1~3h,
It is further preferably added dropwise in 1.5~2.5h, is added dropwise in most preferably 2h.
After initiator is added, reaction；The reaction preferably carries out under stirring conditions；The time of the reaction is preferably
5~20h, more preferably 8~15h are further preferably 1)~12h.
After reaction, preferably reaction solution is poured into alcoholic solvent, to obtain hydrophobic oleophobic modified after being centrifuged, be filtered, washed, drying
Agent；The alcoholic solvent that the alcoholic solvent is well known in the art has no special limitation, is preferably methanol in the present invention.
Hydrophobic oleophobic modifier raw material provided by the invention is easy to get, nontoxic, and free from environmental pollution, preparation method is simple,
After it is modified powder, modified powder has preferable hydro-oleophobicity, and not easy to reunite.
The present invention also provides a kind of preparation methods of modified powder, comprising: by above-mentioned hydrophobic oleophobic modifying agent with to
Modified powder mixes in organic solvent, and after heating reaction, evaporation, drying obtain modified powder.
The powder to be modified is that surface well known to those skilled in the art has the powder for the receptor that can form hydrogen bond i.e.
Can, special limitation is had no, is preferably sodium bicarbonate, saleratus, sodium carbonate, potassium carbonate, ammonium dihydrogen phosphate, phosphorus in the present invention
Sour hydrogen ammonium, ammonium polyphosphate, potassium sulfate, sodium sulphate, calcium carbonate, calcium bicarbonate, calcium sulfate, sodium sulphate, potassium sulfate, ammonium sulfate, cunning
One of mountain flour, mica powder and zeolite powder are a variety of；The partial size of the powder to be modified is preferably micron order or nanoscale；
The nanometer grade powder that preferable particle size is 100 nanometers or more when for nanoscale；The hydrophobic oleophobic modifying agent and to be modified
The mass ratio of powder is preferably 1:(20~100), more preferably 1:(30~80), it is further preferably 1:(40~60) and, most preferably
1:50；The organic solvent is organic solvent well known to those skilled in the art, has no special limitation, excellent in the present invention
It is selected as tetrahydrofuran.
Hydrophobic oleophobic modifying agent is mixed in organic solvent with powder to be modified；The mixed method is preferably stirred
It mixes；The mixed time is preferably 1~6h, more preferably 2~5h, is further preferably 3~4h.
After mixing, heating reaction；The temperature of the heating reaction is preferably 45 DEG C~75 DEG C, more preferably 55 DEG C~75
DEG C, it is further preferably 60 DEG C~70 DEG C, most preferably 65 DEG C；The time of the heating reaction is preferably 1~5h, more preferably 2~
4h is further preferably 2~3h.
After heating reaction, evaporate, it is dry, obtain modified powder.
In order to further illustrate the present invention, with reference to embodiments to a kind of hydrophobic oleophobic modifying agent provided by the invention and
Preparation method is described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
Hydrophobic oleophobic modifying agent, raw material is according to mass ratio are as follows: 30 parts of perfluoro hexyl ethyl propylene acid esters, methacrylic acid
30 parts of hydroxyl ethyl ester, 40 parts of acrylamide of N- (2- ethoxy), 1 part of n- dodecyl mereaptan, 1 part of initiator azodiisobutyronitrile, 1,1,
1000 parts of 2- trichloroethanes.
Its preparation method is as follows:
It under nitrogen protection, will be complete in the burning four-hole bottle for having condenser pipe, magnetic stirrer, constant pressure funnel and air inlet
Fluorinated monomer, hydroxyethyl methacrylate, N- (2- ethoxy) acrylamide, n- dodecyl mereaptan are molten according to above-mentioned mass ratio
Solution stirs 30min at 45 DEG C in 1,1,2- trichloroethanes in advance；
Azodiisobutyronitrile is diluted 100 times using 1,1,2- trichloroethanes, 2h is slowly added dropwise to being added dropwise, then after
Continuous stirring 10h；
Liquid after reaction is dissolved in methanol, to obtain hydrophobic oleophobic modified after being centrifuged, be filtered, washed, being dried
Agent, yield 78%, purity are greater than 90%.
Hydrophobic oleophobic modifying agent obtained in embodiment 1 is analyzed using infrared spectroscopy, obtains infrared spectrogram such as
Shown in Fig. 1.
Embodiment 2
Hydrophobic oleophobic modifying agent, raw material is according to mass ratio are as follows: and 50 parts of perfluorooctylethyl group acrylate, methacrylic acid
Hydroxypropyl acrylate, 30 parts of N- hydroxyethyl acrylamide, 2 parts of n- dodecyl mereaptan, 2 parts of initiator azobisisoheptonitrile, 1000 parts of toluene.
Its preparation method is as follows:
It under nitrogen protection, will be complete in the burning four-hole bottle for having condenser pipe, magnetic stirrer, constant pressure funnel and air inlet
Fluorinated monomer, hydroxy propyl methacrylate, N- hydroxyethyl acrylamide, n- dodecyl mereaptan are dissolved according to above-mentioned mass ratio
In toluene, 30min is stirred in advance at 55 DEG C；
Azobisisoheptonitrile is diluted 100 times using solvent, 2h is slowly added dropwise to being added dropwise, then proceedes to stirring 10h；
Liquid after reaction is dissolved in methanol, to obtain hydrophobic oleophobic modified after being centrifuged, be filtered, washed, being dried
Agent, yield 82%, purity are greater than 90%.
Embodiment 3
Hydrophobic oleophobic modifying agent, raw material is according to mass ratio are as follows: 60 parts of perfluoro decyl ethyl propylene acid esters, N- (2- hydroxyl second
Base) 40 parts of acrylamide, 2 parts of n- dodecyl mereaptan, 2 parts of azobisisovaleronitrile, 1000 parts of trichloro ethylene.
Its preparation method is as follows:
It under nitrogen protection, will be complete in the burning four-hole bottle for having condenser pipe, magnetic stirrer, constant pressure funnel and air inlet
Fluorinated monomer, N- (2- ethoxy) acrylamide, n- dodecyl mereaptan are dissolved in trichloro ethylene according to above-mentioned mass ratio,
30min is stirred in advance at 55 DEG C；
Azobisisovaleronitrile is diluted 100 times using trichloro ethylene, 2h is slowly added dropwise to being added dropwise, then proceedes to stir
10h；
Liquid after reaction is dissolved in methanol, to obtain hydrophobic oleophobic modified after being centrifuged, be filtered, washed, being dried
Agent, yield 85%, purity are greater than 90%.
Embodiment 4
Hydrophobic oleophobic modifying agent, raw material is according to mass ratio are as follows: 70 parts of perfluorododecyl ethyl propylene acid esters, acrylic acid
10 parts of hydroxypropyl acrylate, N, N- diethyl -2- 20 parts of acrylamide, 2 parts of n- dodecyl mereaptan, 2 parts of azobisisovaleronitrile, ethyl acetate
1000 parts.
Its preparation method is as follows:
It under nitrogen protection, will be complete in the burning four-hole bottle for having condenser pipe, magnetic stirrer, constant pressure funnel and air inlet
Fluorinated monomer, N, N- diethyl -2- acrylamide, hydroxypropyl acrylate, n- dodecyl mereaptan are dissolved according to above-mentioned mass ratio
In ethyl acetate, 30min is stirred in advance at 55 DEG C；
Azo diisopropyl imidazoline hydrochloride is diluted 100 times using solvent, 2h is slowly added dropwise to being added dropwise, then proceedes to stir
10h；
Liquid after reaction is dissolved in methanol, to obtain hydrophobic oleophobic modified after being centrifuged, be filtered, washed, being dried
Agent, yield 75%, purity are greater than 90%.
Hydrophobic oleophobic modifying agent obtained in embodiment 2~4 is analyzed using infrared spectroscopy, the product confirmed
Characteristic peak containing each monomer.
Test case:
It will obtain hydrophobic oleophobic modifying agent that 1~embodiment of embodiment 4 obtains and powder D90 to be modified be 1 micron poly-
Ammonium phosphate is dissolved in tetrahydrofuran according to 1:50 ratio, and dispersion 3h is sufficiently stirred, is warming up to 65 DEG C, reacts 2h, and evaporation is done
It is dry to obtain modified powder.
10g modified powder is weighed, is sprinkled into deionized water (aviation kerosine), after stirring 10min, water (oil) face will be floated on
Extinguishing chemical pick up, then through drying, be cooled to room temperature after weigh, obtain the extinguishing chemical quality w (g) for floating on water (oil) face.Then go out
Hydrophobic (oil) rate of fiery agent is calculated as follows:
Hydrophobic (oil) rate=(w/10) × 100%
And moisture content, hygroscopicity and repellency are carried out to modified powder according to GA578 2005 and tested, after tested, tied
Fruit is shown in Table 1.
1 modified powder hydrophobic oleophobic test result of table
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Hydrophobic rate (%) | 99.5% | 99.6% | 99.3% | 99.0% |
| Oleophobic rate (%) | 96.3% | 95.0% | 97.2% | 96.5% |
| Moisture content (%) | 0.2% | 0.15% | 0.1% | 0.15% |
| Hygroscopicity (%) | 2.0% | 2.5% | 1.9% | 2.1% |
| Repellency | It is excellent | It is excellent | It is excellent | It is excellent |
Claims (10)
1. a kind of hydrophobic oleophobic modifying agent, which is characterized in that formed by following components, the component includes:
2. hydrophobic oleophobic modifying agent according to claim 1, which is characterized in that in the perfluor alkyl ethyl acrylate
The carbon atom number of alkyl is 6~12.
3. hydrophobic oleophobic modifying agent according to claim 1, which is characterized in that the perfluor alkyl ethyl acrylate choosing
From perfluoro hexyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluoro decyl ethyl propylene acid esters and perfluor dodecane
One of base ethyl propylene acid esters is a variety of.
4. hydrophobic oleophobic modifying agent according to claim 1, which is characterized in that the esters of acrylic acid activated monomer is selected from
Hydroxyalkyl methacrylate and/or acrylic acid hydroxy alkyl ester；The hydroxyalkyl methacrylate and acrylic acid hydroxy alkyl ester
The carbon atom number of middle alkyl is each independently 2~6.
5. hydrophobic oleophobic modifying agent according to claim 1, which is characterized in that the esters of acrylic acid activated monomer is selected from
One of hydroxyethyl methacrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate and hydroxypropyl acrylate are a variety of.
6. hydrophobic oleophobic modifying agent according to claim 1, which is characterized in that the acrylamides are selected from packet
The acrylamides and/or N of hydroxyl, N- dialkylacrylamides class compound；The N, N- dialkyl acrylamides
The carbon atom number of alkyl is 1~5 in aminated compounds.
7. hydrophobic oleophobic modifying agent according to claim 1, which is characterized in that the acrylamides are selected from N-
One of hydroxymethyl acrylamide, N- hydroxyethyl acrylamide and N, N- diethyl -2- acrylamide are a variety of.
8. a kind of preparation method of hydrophobic oleophobic modifying agent characterized by comprising
By the perfluor alkyl ethyl acrylate of 30~70 parts by weight, the esters of acrylic acid activated monomer of 0~30 parts by weight, 10~
The acrylamides of 40 parts by weight mix in the first organic solvent with the chain-transferring agent of 1~3 parts by weight, are then added
The initiator of 1~3 parts by weight after reaction, obtains hydrophobic oleophobic modifying agent.
9. preparation method according to claim 8, which is characterized in that the initiator is selected from azodiisobutyronitrile, azo
One of two different heptonitriles, azobisisovaleronitrile, azo diisopropyl imidazoline hydrochloride and azo-bis-iso-dimethyl are a variety of；
The organic solvent is selected from toluene, 1,1,1- trichloroethanes, 1,1,2- trichloroethanes, trichloro ethylene, ethyl acetate, trichlorine
One of methane and chlorobenzene are a variety of；
The mixed temperature is 45 DEG C~75 DEG C；The mixed time is 20~60min；
The initiator is added after being dissolved in the second organic solvent；First organic solvent and the second organic solvent totally 1000~
3000 parts by weight；
The time of the reaction is 5~20h.
10. a kind of preparation method of modified powder characterized by comprising
It will be prepared by hydrophobic oleophobic modifying agent described in claim 1~7 any one or claim 8~9 any one
Hydrophobic oleophobic modifying agent mixes in organic solvent with powder to be modified, and after heating reaction, evaporation, drying obtain modified powder
Body.
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