CN109265583A - The fluorine-containing amphiphobic material of polyethylene contains its coating and preparation method thereof - Google Patents
The fluorine-containing amphiphobic material of polyethylene contains its coating and preparation method thereof Download PDFInfo
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- CN109265583A CN109265583A CN201710585938.8A CN201710585938A CN109265583A CN 109265583 A CN109265583 A CN 109265583A CN 201710585938 A CN201710585938 A CN 201710585938A CN 109265583 A CN109265583 A CN 109265583A
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
Abstract
The present invention provides a kind of fluorine-containing amphiphobic material of polyethylene, contain its coating and preparation method thereof.Amphiphobic material has following structure general formula I:
Description
Technical field
The present invention relates to amphiphobic material preparation fields, in particular to a kind of fluorine-containing amphiphobic material of polyethylene, contain it
Coating and preparation method thereof.
Background technique
The Nature imparts the conduct that lotus leaf goes out mud without dye, and the feather of aquatic bird body surface will not be spontaneously wet out by water, this
A little biological phenomenas cause the common concern of people in recent years, but the surface of lotus leaf without Ester and is not non-ordinary light
Sliding.In fact, lotus leaf surface, plumage are observed under the microscope, it is a kind of poroid group similar to sponge or Bird's Nest
Structure is knitted, is filled in crack through air, it is therefore prevented that water or dirt are adsorbed in solid.This kind of materials are known as super by scientific and technical personnel
Hydrophobic surface material.Currently, we, which define super hydrophobic material surface-stable contact angle, is greater than 150 °, it is in rolling contact angle and is less than
10°.Novel super hydrophobic material using very extensive, comprising: for can be to prevent accumulated snow on exterior aerial；It can for ocean-going ship
To reach antifouling, corrosion-resistant effect；Conveying for petroleum pipeline.
Currently, having been look for preparation amphiphobic material, both hydrophobic or oleophobic skin-material, in the world to such material in the world
Material has done more research, provides not only a possibility that forming new super hydrophobic material, and propose and prepare this kind of function
The methods of material, such as: polyurethane-coated waterproof coating；Polyacrylic plasma polymerization in the presence of polytetrafluoroethylene (PTFE)；It is molten
Porous gel film etc. of the polypropylene through vacuum high-temperature is decomposed in agent.Due to super-hydrophobic coating at present in the application, generally all
Expensive hydrophobic material (material that abutment angle is 90 degree or more) is needed, and preparation process is cumbersome, some fillers (such as help
Agent) there are free formaldehyde, toluene etc., it is unfavorable for environmental protection and human health, therefore makes to be applied clinically and popularized work very slow.
In short, preparing double thin skin-materials at present mainly has two major classes technology path: 1, being manufactured in body structure surface bionical micro-
Structure is seen, for example, class butterfly's wing surface microstructure or class lotus leaf surface microstructure etc., but the technology path is more multiple
It is miscellaneous；2, ultra low surface energy materials are coated in body structure surface, for example, fluorine resin or containing silicone resin etc., but the technology path at
This is higher.
Summary of the invention
The main purpose of the present invention is to provide a kind of fluorine-containing amphiphobic material of polyethylene, contain its coating and its preparation side
Method, to solve the problems, such as amphiphobic material production complexity and higher cost in the prior art.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of fluorine-containing amphiphobic material of polyethylene, double
Thin material has following structure general formula I:
General structure I
Wherein, it is 2~4 that m, which is 20~300, n,.
Further, above-mentioned m is 100~200, preferably n=4.
According to another aspect of the present invention, a kind of coating, including amphiphobic material are provided, which is any of the above-described
The amphiphobic material of kind.
Further, above-mentioned coating further includes solvent, and solvent is perfluor ether compound, preferably perfluor octyl ether.
According to another aspect of the invention, a kind of preparation method of fluorine-containing amphiphobic material of polyethylene, the preparation side are provided
Method includes:
Step S1 mixes the compound A with general structure II with polyvinyl alcohol oligomer, initiator, forms reaction
System；Step S2 is kneaded reaction system at 150~165 DEG C, obtains having the polyethylene of general structure I fluorine-containing double
Dredge material, wherein general structure II are as follows:
N is 2~4；
General structure I:
M is 20~200.
Further, the molecular weight of above-mentioned polyvinyl alcohol oligomer is 4000~5000.
Further, above-mentioned initiator includes the cumyl peroxide and benzoyl peroxide that the mass ratio of the material is 1:1.
Further, the amount ratio of above compound A and polyvinyl alcohol oligomer is 50~200ml:45~100g；It is preferred that
The weight ratio of polyvinyl alcohol oligomer and initiator is 45~100:0.2~1.2.
Further, above-mentioned steps S1 includes: that polyvinyl alcohol oligomer and initiator are successively added into compound A, is obtained
To composition；And stirred composition 10~30 minutes with 50~150 revs/min of revolving speed, obtain reaction system.
Further, above-mentioned steps S2 includes: and reaction system exists under nitrogen atmosphere or inert gas atmosphere protection
It is kneaded 60~180 minutes at 150~165 DEG C, obtains the product system containing the fluorine-containing amphiphobic material of polyethylene, it is preferably close in mixing
The twin-screw revolving speed of mill is 60~120 revs/min；Product system is separated by solid-liquid separation, is obtained with poly- second existing for solid phase
The fluorine-containing amphiphobic material of alkene.
Further, the heat released in reaction process is taken away using reflux condensation mode mode in mixing process, preferably existed
It is kneaded under conditions of setting desiccant, further preferred desiccant includes the KOH and CaCl that mass ratio is 1:12。
It applies the technical scheme of the present invention, the big fluorine atom of the fluorine resin amount with above structure general formula I is introduced in
In polyvinyl alcohol units segment, therefore its not soluble in water is also insoluble in organic matter.And the above-mentioned amphiphobic material of the application uses entirely
Fluorine acyl fluorides and polyvinyl alcohol, which carry out mixing polymerization, can be obtained, and preparation method is simple, while raw material is conventional raw material, is fabricated to
This is lower.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As the application background technique is analyzed, amphiphobic material makes complicated and higher cost in the prior art, to understand
The certainly problem this application provides the fluorine-containing amphiphobic material of polyethylene, contains its coating and preparation method thereof.
In a kind of typical embodiment of the application, a kind of fluorine-containing amphiphobic material of polyethylene, the amphiphobic material are provided
Have following structure general formula I:
Wherein, it is 2~4 that m, which is 20~300, n,.It is preferred that m is 100~200, preferably n=4.
The big fluorine atom of fluorine resin amount with above structure general formula I is introduced in polyvinyl alcohol units segment, because
This its not soluble in water be also insoluble in organic matter.And the above-mentioned amphiphobic material of the application is close using perfluoroacyl fluoride and polyvinyl alcohol progress
Refining polymerization can be obtained, and preparation method is simple, while raw material is conventional raw material, and cost of manufacture is lower.
In another typical embodiment of the application, a kind of coating, including amphiphobic material are provided, the amphiphobic material
For any of the above-described kind of amphiphobic material.Since the amphiphobic material of the application has good hydrophobic oleophobic performance, using containing
The coating of its coating production also has good hydrophobic oleophobic performance.
When preparing coating into coating, as coating solvent can conventional amphiphobic material from the prior art solvent
In selected, preferably above-mentioned solvent be perfluor ether compound to realize good dissolubility.Further applied to reduce
The cost of material, preferred solvent are perfluor octyl ether.
In the application in another typical embodiment, a kind of preparation side of fluorine-containing amphiphobic material of polyethylene is provided
Method, the preparation method include: step S1, and the compound A with general structure II is mixed with polyvinyl alcohol oligomer, initiator
It closes, forms reaction system；Step S2 is kneaded reaction system at 150~165 DEG C, obtains having gathering for general structure I
The fluorine-containing amphiphobic material of ethylene, wherein
General structure II are as follows:
N is 2~4；
General structure I:
M is 20~300, preferably 100~200.
Above-mentioned preparation method is reacted by perfluoroacyl fluoride and alcoholic extract hydroxyl group, prepares fluorine resin, and the technology path is not only
Operating procedure is simple, and synthesis material is from a wealth of sources, therefore cost is relatively low.Utilize the alcoholic extract hydroxyl group and perfluor penta in polyvinyl alcohol
Alcoholysis reaction occurs for acyl fluorides, since hydroxy radical content drastically reduces in fluorine resin while a large amount of fluorine atom is introduced into after alcoholysis
Into polyvinyl alcohol units segment, so that fluorine resin is not soluble in water to be also insoluble in organic matter.In addition, in order to further enhance chain
Segment length, initiator are also added in reaction system, are kneaded further polymerization by 150~165 DEG C and hot Banbury, finally
Obtain amphiphobic material.
In order to control going on smoothly for accounting and polymerization reaction of the fluorine atom in the fluorine-containing amphiphobic material of polyethylene, preferably
The molecular weight of above-mentioned polyvinyl alcohol oligomer is 4000~5000.
The application is promotion chain length using the main purpose of initiator, therefore can be using routine in the prior art
Radical initiator, preferably above-mentioned initiator include the cumyl peroxide and benzoyl peroxide that the mass ratio of the material is 1:1,
To improve polymerization efficiency.
Further, in order to further fluorine-containing to improve polyethylene by the accounting of control fluorine atom and the length of segment
Double thin performances of amphiphobic material, the preferably amount ratio of above compound A and polyvinyl alcohol oligomer be 50~200ml:45~
100g；It is preferred that the weight ratio of polyvinyl alcohol oligomer and initiator is 45~100:0.2~1.2.
In a preferred embodiment of the present application, above-mentioned steps S1 includes: successively to add polyvinyl alcohol into compound A
Oligomer and initiator, obtain composition；And stirred composition 10~30 minutes with 50~150 revs/min of revolving speed, it obtains
Reaction system.Polyvinyl alcohol oligomer, compound A and initiator are realized into adequately mixing through the above way, in favor of under
One-step polymerization reaction is gone on smoothly.
In the application another kind preferred embodiment, above-mentioned steps S2 includes: in nitrogen atmosphere or inert gas gas
Under atmosphere protection, reaction system is kneaded 60~180 minutes at 150~165 DEG C, is obtained containing the fluorine-containing amphiphobic material of polyethylene
Product system, the twin-screw revolving speed of mixer is 60~120 revs/min preferably in mixing；Product system is separated by solid-liquid separation,
It obtains with the fluorine-containing amphiphobic material of polyethylene existing for solid phase.Above-mentioned nitrogen atmosphere or inert gas atmosphere, which form initiator, to be protected
Shield, ensure that reaction is gone on smoothly, accelerates polymerization efficiency；It further, is 60~120 by controlling the revolving speed of twin-screw
Rev/min, so that mixing and polymerization match.
Heat can be released in mixing process, it is excellent in order to guarantee that the stabilization of reaction temperature is taken away in time and then guaranteed to heat
It is selected in mixing process and the heat released in reaction process is taken away using reflux condensation mode mode.It certainly can also be using other condensations
Mode, for example reaction vessel is placed in cooling device to the control for realizing temperature.It is preferred that under conditions of desiccant is set into
Row is kneaded, and further preferred desiccant includes the KOH and CaCl that mass ratio is 1:12。
Below with reference to embodiment and comparative example, the beneficial effect of the application is further illustrated.
Embodiment 1
The first step, on 250mL three-necked flask, configure blender and with 60g (desiccant mass ratio be 1:1 KOH with
CaCl2) drying tube reflux condensing tube.50ml perfluor valeryl fluorine is placed in into three-necked flask, then to adding in perfluor valeryl fluorine
Adding 45g polyvinyl alcohol oligomer (molecular weight is about 4500) and 0.2g radical initiator, (the mass ratio of the material is the peroxidating of 1:1
Diisopropylbenzene (DIPB) and benzoyl peroxide), composition is formed, mechanical agitator stirs the composition 10 with 50 revs/min of revolving speed
Minute obtains mixture；Mixture is added in hot Banbury and is kneaded 60 minutes, obtains fluorine-containing containing polyethylene by second step
The product system of amphiphobic material is passed through nitrogen protection in mixing process, and mixer twin-screw revolving speed is 60 revs/min, is kneaded temperature
Degree is 150 DEG C；Third step, solid-liquid is layered after product system is cooled to room temperature, then, solid is one hour dry at 60 DEG C
It is added in perfluor octyl ether afterwards to get the hydrophobic coating for being 4500 or so to average molecular weight, the hydrophobic coating is total by nuclear-magnetism
Vibration verifying is really with the structure of general structure I.Finally, hydrophobic coating is sprayed on using on the clean glass plate of alcohol washes,
After natural air drying 24 hours, connecing for water droplet and olive oil droplet is tested using German Kruss DSA20 standard type contact angle measurement
Feeler, every kind of drop test 20 be then averaged the result shows that, it is 9 ° that the contact angle of water droplet, which is 163 °, is in rolling contact angle,
It is 8 ° that the contact angle of olive oil droplet, which is 160 °, is in rolling contact angle.
Embodiment 2
The first step, on 250mL three-necked flask, configure blender and with 60g (desiccant mass ratio be 1:1 KOH with
CaCl2) drying tube reflux condensing tube.200ml perfluor valeryl fluorine is placed in into three-necked flask, then to adding in perfluor valeryl fluorine
Adding 100g polyvinyl alcohol oligomer (molecular weight is about 4500) and 1.2g radical initiator, (the mass ratio of the material is the peroxide of 1:1
Change diisopropylbenzene (DIPB) and benzoyl peroxide), composition is formed, mechanical agitator stirs the composition with 150 revs/min of revolving speed
Obtain mixture within 30 minutes；Mixture is added in hot Banbury and is kneaded 180 minutes, obtains containing polyethylene by second step
The product system of fluorine-containing amphiphobic material is passed through nitrogen protection in mixing process, and mixer twin-screw revolving speed is 120 revs/min, mixes
Refining temperature is 165 DEG C；Third step, solid-liquid is layered after product system is cooled to room temperature, then, by solid dry one at 60 DEG C
It is added in perfluor octyl ether after hour to get the hydrophobic coating for being 10000 or so to average molecular weight, which passes through core
Magnetic resonance verifying is really with the structure of general structure I.Finally, hydrophobic coating is sprayed on the clean glass plate of alcohol washes,
After natural air drying 24 hours, connecing for water droplet and olive oil droplet is tested using German Kruss DSA20 standard type contact angle measurement
Feeler, every kind of drop test 20 be then averaged the result shows that, it is 8 ° that the contact angle of water droplet, which is 162 °, is in rolling contact angle,
It is 9 ° that the contact angle of olive oil droplet, which is 161 °, is in rolling contact angle.
Embodiment 3
The first step, on 250mL three-necked flask, configure blender and with 60g (desiccant mass ratio be 1:1 KOH with
CaCl2) drying tube reflux condensing tube.75ml perfluor valeryl fluorine is placed in into three-necked flask, then to adding in perfluor valeryl fluorine
Adding 50g polyvinyl alcohol oligomer (molecular weight is about 4500) and 0.3g radical initiator, (the mass ratio of the material is the peroxidating of 1:1
Diisopropylbenzene (DIPB) and benzoyl peroxide), composition is formed, mechanical agitator stirs the composition 15 with 60 revs/min of revolving speed
Minute obtains mixture；Mixture is added in hot Banbury and is kneaded 70 minutes, obtains fluorine-containing containing polyethylene by second step
The product system of amphiphobic material is passed through nitrogen protection in mixing process, and mixer twin-screw revolving speed is 70 revs/min, is kneaded temperature
Degree is 163 DEG C；Third step, solid-liquid is layered after product system is cooled to room temperature, then, solid is one hour dry at 60 DEG C
It is added in perfluor octyl ether afterwards to get the hydrophobic coating for being 4500 or so to average molecular weight, the hydrophobic coating is total by nuclear-magnetism
Vibration verifying is really with the structure of general structure I.Finally, hydrophobic coating is sprayed on the clean glass plate of alcohol washes, it is natural
After air-drying 24 hours, the contact angle of water droplet and olive oil droplet is tested using German Kruss DSA20 standard type contact angle measurement,
Every kind of drop test 20 be then averaged the result shows that, it is 9 ° that the contact angle of water droplet, which is 165 °, is in rolling contact angle, olive oil
It is 8 ° that the contact angle of drop, which is 163 °, is in rolling contact angle.
Embodiment 4:
The first step, on 250mL three-necked flask, configure blender and with 60g (desiccant mass ratio be 1:1 KOH with
CaCl2) drying tube reflux condensing tube.90ml perfluor valeryl fluorine is placed in into three-necked flask, then to adding in perfluor valeryl fluorine
Adding 55g polyvinyl alcohol oligomer (molecular weight is about 4500) and 0.4g radical initiator, (the mass ratio of the material is the peroxidating of 1:1
Diisopropylbenzene (DIPB) and benzoyl peroxide), composition is formed, mechanical agitator stirs the composition 18 with 140 revs/min of revolving speed
Minute obtains mixture；Mixture is added in hot Banbury and is kneaded 170 minutes, obtains containing containing polyethylene by second step
The product system of fluorine amphiphobic material is passed through nitrogen protection in mixing process, and mixer twin-screw revolving speed is 60 revs/min, is kneaded
Temperature is 150 DEG C；Third step, solid-liquid is layered after product system is cooled to room temperature, and then, by solid, drying one is small at 60 DEG C
When after be added in perfluor octyl ether, that is, obtain average molecular weight be 5500 or so hydrophobic coating, the hydrophobic coating pass through nuclear-magnetism
Resonance verifying is really with the structure of general structure I.Finally, hydrophobic coating is sprayed on the clean glass plate of alcohol washes, from
After so air-drying 24 hours, using the contact of German Kruss DSA20 standard type contact angle measurement test water droplet and olive oil droplet
Angle, every kind of drop test 20 be then averaged the result shows that, it is 7 ° that the contact angle of water droplet, which is 159 °, is in rolling contact angle, olive
It is 6 ° that the contact angle of olive oil droplet, which is 162 °, is in rolling contact angle.
Embodiment 5:
The first step, on 250mL three-necked flask, configure blender and with 60g (desiccant mass ratio be 1:1 KOH with
CaCl2) drying tube reflux condensing tube.120ml perfluor valeryl fluorine is placed in into three-necked flask, then to adding in perfluor valeryl fluorine
Adding 60g polyvinyl alcohol oligomer (molecular weight is about 4500) and 0.5g radical initiator, (the mass ratio of the material is the peroxidating of 1:1
Diisopropylbenzene (DIPB) and benzoyl peroxide), composition is formed, mechanical agitator stirs the composition 20 with 70 revs/min of revolving speed
Minute obtains mixture；Mixture is added in hot Banbury and is kneaded 80 minutes, obtains fluorine-containing containing polyethylene by second step
The product system of amphiphobic material is passed through nitrogen protection in mixing process, and mixer twin-screw revolving speed is 80 revs/min, is kneaded temperature
Degree is 155 DEG C；Third step, solid-liquid is layered after product system is cooled to room temperature, then, solid is one hour dry at 60 DEG C
It is added in perfluor octyl ether afterwards to get the hydrophobic coating for being 6000 or so to average molecular weight, the hydrophobic coating is total by nuclear-magnetism
Vibration verifying is really with the structure of general structure I.Finally, hydrophobic coating is sprayed on the clean glass plate of alcohol washes, it is natural
After air-drying 24 hours, the contact angle of water droplet and olive oil droplet is tested using German Kruss DSA20 standard type contact angle measurement,
Every kind of drop test 20 be then averaged the result shows that, it is 9 ° that the contact angle of water droplet, which is 160 °, is in rolling contact angle, olive oil
It is 7 ° that the contact angle of drop, which is 159 °, is in rolling contact angle.
Embodiment 6:
The first step, on 250mL three-necked flask, configure blender and with 60g (desiccant mass ratio be 1:1 KOH with
CaCl2) drying tube reflux condensing tube.140ml perfluor valeryl fluorine is placed in into three-necked flask, then to adding in perfluor valeryl fluorine
Adding 80g polyvinyl alcohol oligomer (molecular weight is about 4500) and 0.7g radical initiator, (the mass ratio of the material is the peroxidating of 1:1
Diisopropylbenzene (DIPB) and benzoyl peroxide), composition is formed, mechanical agitator stirs the composition 26 with 130 revs/min of revolving speed
Minute obtains mixture；Mixture is added in hot Banbury and is kneaded 100 minutes, obtains containing containing polyethylene by second step
The product system of fluorine amphiphobic material is passed through nitrogen protection in mixing process, and mixer twin-screw revolving speed is 100 revs/min, is kneaded
Temperature is 153 DEG C；Third step, solid-liquid is layered after the mixture after mixing is cooled to room temperature, and then, solid is done at 60 DEG C
It is added in perfluor octyl ether after dry one hour to get the hydrophobic coating for being 8000 or so to average molecular weight, hydrophobic coating warp
Nuclear magnetic resonance verifying is crossed really with the structure of general structure I.Finally, hydrophobic coating is sprayed on the clean glass plate of alcohol washes
On, after natural air drying 24 hours, water droplet and olive oil droplet are tested using German Kruss DSA20 standard type contact angle measurement
Contact angle, every kind of drop test 20 be then averaged the result shows that, the contact angle of water droplet, which is 166 °, is in rolling contact angle is
6 °, it is 8 ° that the contact angle of olive oil droplet, which is 161 °, is in rolling contact angle.
Embodiment 7:
The first step, on 250mL three-necked flask, configure blender and with 60g (desiccant mass ratio be 1:1 KOH with
CaCl2) drying tube reflux condensing tube.160ml perfluor valeryl fluorine is placed in into three-necked flask, then to adding in perfluor valeryl fluorine
Adding 90g polyvinyl alcohol oligomer (molecular weight is about 4500) and 0.8g radical initiator, (the mass ratio of the material is the peroxidating of 1:1
Diisopropylbenzene (DIPB) and benzoyl peroxide), composition is formed, mechanical agitator stirs the composition 24 with 110 revs/min of revolving speed
Minute obtains mixture；Mixture is added in hot Banbury and is kneaded 135 minutes, obtains containing containing polyethylene by second step
The product system of fluorine amphiphobic material is passed through nitrogen protection in mixing process, and mixer twin-screw revolving speed is 95 revs/min, is kneaded
Temperature is 158 DEG C；Third step, solid-liquid is layered after product system is cooled to room temperature, and then, by solid, drying one is small at 60 DEG C
When after be added in perfluor octyl ether to get to average molecular weight be 9000 or so hydrophobic coating, the hydrophobic coating pass through nuclear-magnetism
Resonance verifying is really with the structure of general structure I.Finally, hydrophobic coating is sprayed on the clean glass plate of alcohol washes, from
After so air-drying 24 hours, using the contact of German Kruss DSA20 standard type contact angle measurement test water droplet and olive oil droplet
Angle, every kind of drop test 20 be then averaged the result shows that, it is 8 ° that the contact angle of water droplet, which is 157 °, is in rolling contact angle, olive
It is 8 ° that the contact angle of olive oil droplet, which is 158 °, is in rolling contact angle.
Embodiment 8
The first step, on 250mL three-necked flask, configure blender and with 60g (desiccant mass ratio be 1:1 KOH with
CaCl2) drying tube reflux condensing tube.180ml perfluor valeryl fluorine is placed in into three-necked flask, then to adding in perfluor valeryl fluorine
Adding 70g polyvinyl alcohol oligomer (molecular weight is about 4500) and 0.9g radical initiator, (the mass ratio of the material is the peroxidating of 1:1
Diisopropylbenzene (DIPB) and benzoyl peroxide), composition is formed, mechanical agitator stirs the composition 16 with 60 revs/min of revolving speed
Minute obtains mixture；Mixture is added in hot Banbury and is kneaded 85 minutes, obtains fluorine-containing containing polyethylene by second step
The product system of amphiphobic material is passed through nitrogen protection in mixing process, and mixer twin-screw revolving speed is 72 revs/min, is kneaded temperature
Degree is 162 DEG C；Third step, solid-liquid is layered after product system is cooled to room temperature, then, solid is one hour dry at 60 DEG C
It is added in perfluor octyl ether afterwards to get the hydrophobic coating for being 7000 or so to average molecular weight, the hydrophobic coating is total by nuclear-magnetism
Vibration verifying is really with the structure of general structure I.Finally, hydrophobic coating is sprayed on the clean glass plate of alcohol washes, it is natural
After air-drying 24 hours, the contact angle of water droplet and olive oil droplet is tested using German Kruss DSA20 standard type contact angle measurement,
Every kind of drop test 20 be then averaged the result shows that, it is 7 ° that the contact angle of water droplet, which is 159 °, is in rolling contact angle, olive oil
It is 7 ° that the contact angle of drop, which is 163 °, is in rolling contact angle.
Embodiment 9
The first step, on 250mL three-necked flask, configure blender and with 60g (desiccant mass ratio be 1:1 KOH with
CaCl2) drying tube reflux condensing tube.60ml perfluor valeryl fluorine is placed in into three-necked flask, then to adding in perfluor valeryl fluorine
Adding 58g polyvinyl alcohol oligomer (molecular weight is about 4500) and 1.1g radical initiator, (the mass ratio of the material is the peroxidating of 1:1
Diisopropylbenzene (DIPB) and benzoyl peroxide), composition is formed, mechanical agitator stirs the composition 22 with 125 revs/min of revolving speed
Minute obtains mixture；Mixture is added in hot Banbury and is kneaded 105 minutes, obtains containing containing polyethylene by second step
The product system of fluorine amphiphobic material is passed through nitrogen protection in mixing process, and mixer twin-screw revolving speed is 105 revs/min, is kneaded
Temperature is 159 DEG C；Third step, solid-liquid is layered after product system is cooled to room temperature, and then, by solid, drying one is small at 60 DEG C
When after be added in perfluor octyl ether to get to average molecular weight be 5500 or so hydrophobic coating, the hydrophobic coating pass through nuclear-magnetism
Resonance verifying is really with the structure of general structure I.Finally, hydrophobic coating is sprayed on the clean glass plate of alcohol washes, from
After so air-drying 24 hours, using the contact of German Kruss DSA20 standard type contact angle measurement test water droplet and olive oil droplet
Angle, every kind of drop test 20 be then averaged the result shows that, it is 8 ° that the contact angle of water droplet, which is 162 °, is in rolling contact angle, olive
It is 7 ° that the contact angle of olive oil droplet, which is 164 °, is in rolling contact angle.
Embodiment 10
The first step, on 250mL three-necked flask, configure blender and with 60g (desiccant mass ratio be 1:1 KOH with
CaCl2) drying tube reflux condensing tube.220ml perfluor valeryl fluorine is placed in into three-necked flask, then to adding in perfluor valeryl fluorine
Adding 80g polyvinyl alcohol oligomer (molecular weight is about 4500) and 0.7g radical initiator, (the mass ratio of the material is the peroxidating of 1:1
Diisopropylbenzene (DIPB) and benzoyl peroxide), composition is formed, mechanical agitator stirs the composition 26 with 130 revs/min of revolving speed
Minute obtains mixture；Mixture is added in hot Banbury and is kneaded 100 minutes, obtains containing containing polyethylene by second step
The product system of fluorine amphiphobic material is passed through nitrogen protection in mixing process, and mixer twin-screw revolving speed is 100 revs/min, is kneaded
Temperature is 153 DEG C；Third step, solid-liquid is layered after the mixture after mixing is cooled to room temperature, and then, solid is done at 60 DEG C
It is added in perfluor octyl ether after dry one hour to get the hydrophobic coating for being 8000 or so to average molecular weight, hydrophobic coating warp
Nuclear magnetic resonance verifying is crossed really with the structure of general structure I.Finally, hydrophobic coating is sprayed on the clean glass plate of alcohol washes
On, after natural air drying 24 hours, water droplet and olive oil droplet are tested using German Kruss DSA20 standard type contact angle measurement
Contact angle, every kind of drop test 20 be then averaged the result shows that, the contact angle of water droplet, which is 157 °, is in rolling contact angle is
10 °, it is 11 ° that the contact angle of olive oil droplet, which is 154 °, is in rolling contact angle.
Embodiment 11
The first step, on 250mL three-necked flask, configure blender and with 60g (desiccant mass ratio be 1:1 KOH with
CaCl2) drying tube reflux condensing tube.140ml perfluor valeryl fluorine is placed in into three-necked flask, then to adding in perfluor valeryl fluorine
Adding 80g polyvinyl alcohol oligomer (molecular weight is about 4500) and 0.7g radical initiator, (the mass ratio of the material is the peroxidating of 1:1
Diisopropylbenzene (DIPB) and benzoyl peroxide), composition is formed, mechanical agitator stirs the composition 8 with 40 revs/min of revolving speed and divides
Clock obtains mixture；Mixture is added in hot Banbury and is kneaded 100 minutes, obtains fluorine-containing containing polyethylene by second step
The product system of amphiphobic material is passed through nitrogen protection in mixing process, and mixer twin-screw revolving speed is 100 revs/min, is kneaded temperature
Degree is 153 DEG C；Third step, solid-liquid is layered after the mixture after mixing is cooled to room temperature, then, solid is dry at 60 DEG C
It is added in perfluor octyl ether after one hour to get the hydrophobic coating for being 8000 or so to average molecular weight, which passes through
Nuclear magnetic resonance verifying is really with the structure of general structure I.Finally, hydrophobic coating is sprayed on the clean glass plate of alcohol washes
On, after natural air drying 24 hours, water droplet and olive oil droplet are tested using German Kruss DSA20 standard type contact angle measurement
Contact angle, every kind of drop test 20 be then averaged the result shows that, the contact angle of water droplet, which is 162 °, is in rolling contact angle is
9 °, it is 12 ° that the contact angle of olive oil droplet, which is 157 °, is in rolling contact angle.
Embodiment 12
The first step, on 250mL three-necked flask, configure blender and with 60g (desiccant mass ratio be 1:1 KOH with
CaCl2) drying tube reflux condensing tube.140ml perfluor valeryl fluorine is placed in into three-necked flask, then to adding in perfluor valeryl fluorine
Adding 80g polyvinyl alcohol oligomer (molecular weight is about 4500) and 0.7g radical initiator, (the mass ratio of the material is the peroxidating of 1:1
Diisopropylbenzene (DIPB) and benzoyl peroxide), composition is formed, mechanical agitator stirs the composition 26 with 130 revs/min of revolving speed
Minute obtains mixture；Mixture is added in hot Banbury and is kneaded 45 minutes, obtains fluorine-containing containing polyethylene by second step
The product system of amphiphobic material is passed through nitrogen protection in mixing process, and mixer twin-screw revolving speed is 100 revs/min, is kneaded temperature
Degree is 153 DEG C；Third step, solid-liquid is layered after the mixture after mixing is cooled to room temperature, then, solid is dry at 60 DEG C
It is added in perfluor octyl ether after one hour to get the hydrophobic coating for being 8000 or so to average molecular weight, which passes through
Nuclear magnetic resonance verifying is really with the structure of general structure I.Finally, hydrophobic coating is sprayed on the clean glass plate of alcohol washes
On, after natural air drying 24 hours, water droplet and olive oil droplet are tested using German Kruss DSA20 standard type contact angle measurement
Contact angle, every kind of drop test 20 be then averaged the result shows that, the contact angle of water droplet, which is 160 °, is in rolling contact angle is
8 °, it is 10 ° that the contact angle of olive oil droplet, which is 154 °, is in rolling contact angle.
Embodiment 13
The perfluor valeryl fluorine of embodiment 6 is replaced with into perfluoro-propionyl fluoride, obtained hydrophobic coating is verified by nuclear magnetic resonance
Really with the structure of general structure I.Hydrophobic coating is sprayed on the clean glass plate of alcohol washes, and natural air drying 24 hours
Afterwards, using the contact angle of German Kruss DSA20 standard type contact angle measurement test water droplet and olive oil droplet, every kind of drop is surveyed
Examination 20 be then averaged the result shows that, it is 6 ° that the contact angle of water droplet, which is 164 °, is in rolling contact angle, the contact angle of olive oil droplet
For 160 °, to be in rolling contact angle be 8 °.
Embodiment 14
The polyvinyl alcohol oligomer of embodiment 6 is replaced with into the polyvinyl alcohol oligomer that molecular weight is 5000 or so, is obtained
Hydrophobic coating by nuclear magnetic resonance verify really with general structure I structure.It is clean that hydrophobic coating is sprayed on alcohol washes
Glass plate on, after natural air drying 24 hours, water droplet and olive are tested using German Kruss DSA20 standard type contact angle measurement
The contact angle of olive oil droplet, every kind of drop test 20 be then averaged the result shows that, the contact angle of water droplet is 164 °, rolls and connects
Feeler is 7 °, and it is 9 ° that the contact angle of olive oil droplet, which is 160 °, is in rolling contact angle.
Comparative example 1
The melting temperature of embodiment 6 is revised as 145 DEG C.Hydrophobic coating is sprayed on the clean glass plate of alcohol washes,
After natural air drying 24 hours, connecing for water droplet and olive oil droplet is tested using German Kruss DSA20 standard type contact angle measurement
Feeler, every kind of drop test 20 be then averaged the result shows that, it is 14 ° that the contact angle of water droplet, which is 131 °, is in rolling contact angle,
It is 17 ° that the contact angle of olive oil droplet, which is 137 °, is in rolling contact angle.
Comparative example 2
The melting temperature of embodiment 6 is revised as 170 DEG C.Hydrophobic coating is sprayed on the clean glass plate of alcohol washes,
After natural air drying 24 hours, connecing for water droplet and olive oil droplet is tested using German Kruss DSA20 standard type contact angle measurement
Feeler, every kind of drop test 20 be then averaged the result shows that, it is 15 ° that the contact angle of water droplet, which is 147 °, is in rolling contact angle,
It is 15 ° that the contact angle of olive oil droplet, which is 139 °, is in rolling contact angle.
It can be seen that the hydrophobic and oleophobic for the hydrophobic material that each embodiment of the application obtains according to embodiment data above-mentioned
Effect is preferable, and can be seen that melting temperature for finally formed hydrophobic coating according to the comparison of embodiment and comparative example
Hydrophobic and oleophobic effects have and significantly affect.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
The big fluorine atom of fluorine resin amount with above structure general formula I is introduced in polyvinyl alcohol units segment, because
This its not soluble in water be also insoluble in organic matter.And the above-mentioned amphiphobic material of the application is close using perfluoroacyl fluoride and polyvinyl alcohol progress
Refining polymerization can be obtained, and preparation method is simple, while raw material is conventional raw material, and cost of manufacture is lower.
Above-mentioned preparation method is reacted by perfluoroacyl fluoride and alcoholic extract hydroxyl group, prepares fluorine resin, and the technology path is not only
Operating procedure is simple, and synthesis material is from a wealth of sources, therefore cost is relatively low.Utilize the alcoholic extract hydroxyl group and perfluor penta in polyvinyl alcohol
Alcoholysis reaction occurs for acyl fluorides, since hydroxy radical content drastically reduces in fluorine resin while a large amount of fluorine atom is introduced into after alcoholysis
Into polyvinyl alcohol units segment, so that fluorine resin is not soluble in water to be also insoluble in organic matter.In addition, in order to further enhance chain
Segment length, initiator are also added in reaction system, are kneaded further polymerization by 150~165 DEG C and hot Banbury, finally
Obtain amphiphobic material.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (11)
1. a kind of fluorine-containing amphiphobic material of polyethylene, which is characterized in that the amphiphobic material has following structure general formula I:
Wherein, it is 2~4 that m, which is 20~300, n,.
2. amphiphobic material according to claim 1, which is characterized in that the m is 100~200, preferably n=4.
3. a kind of coating, including amphiphobic material, which is characterized in that the amphiphobic material is double thin materials of any of claims 1 or 2
Material.
4. coating according to claim 3, which is characterized in that the coating further includes solvent, and the solvent is perfluoroether
Class compound, preferably perfluor octyl ether.
5. a kind of preparation method of the fluorine-containing amphiphobic material of polyethylene, which is characterized in that the preparation method includes:
Step S1 mixes the compound A with general structure II with polyvinyl alcohol oligomer, initiator, forms reaction system；
Step S2 is kneaded the reaction system at 150~165 DEG C, obtains the polyethylene with general structure I
Fluorine-containing amphiphobic material, wherein
The general structure II are as follows:
N is 2~4；
The general structure I:
M is 20~200.
6. preparation method according to claim 5, which is characterized in that the molecular weight of the polyvinyl alcohol oligomer is 4000
~5000.
7. preparation method according to claim 5, which is characterized in that the initiator includes that the mass ratio of the material is 1:1
Cumyl peroxide and benzoyl peroxide.
8. preparation method according to claim 5, which is characterized in that the compound A and the polyvinyl alcohol oligomer
Amount ratio be 50~200ml:45~100g；It is preferred that the weight ratio of the polyvinyl alcohol oligomer and the initiator be 45~
100:0.2~1.2.
9. preparation method according to claim 5, which is characterized in that the step S1 includes:
Polyvinyl alcohol oligomer and initiator are successively added into the compound A, obtains composition；And
It is stirred the composition 10~30 minutes with 50~150 revs/min of revolving speed, obtains the reaction system.
10. preparation method according to claim 5, which is characterized in that the step S2 includes:
Under nitrogen atmosphere or inert gas atmosphere protection, the reaction system is kneaded 60~180 at 150~165 DEG C
Minute, the product system containing the fluorine-containing amphiphobic material of the polyethylene is obtained, the twin-screw of mixer turns in the preferably described mixing
Speed is 60~120 revs/min；
The product system is separated by solid-liquid separation, is obtained with the fluorine-containing amphiphobic material of polyethylene existing for solid phase.
11. preparation method according to claim 10, which is characterized in that use reflux condensation mode mode band in mixing process
The heat released in reaction process is walked, preferably carries out the mixing under conditions of desiccant is set, it is further preferably described dry
Drying prescription includes the KOH and CaCl that mass ratio is 1:12。
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1502642A (en) * | 2002-11-25 | 2004-06-09 | 中国科学院化学研究所 | Super-biphobic block polyether type polyurethane copolymer and preparation process and use thereof |
| CN102977291A (en) * | 2012-11-01 | 2013-03-20 | 中科院广州化学有限公司 | Cross-linkable fluorine-containing polymer, and its application in preparation of super-amphiphobic surfaces |
| CN102977292A (en) * | 2012-11-07 | 2013-03-20 | 中科院广州化学有限公司 | Amphiphilic cross-linked fluoropolymer and application thereof in preparation of ultra-amphiphobic surface |
| CN103450727A (en) * | 2013-09-20 | 2013-12-18 | 云南银峰新材料有限公司 | Preparation method of fluoroalkyl chain-containing nano super-amphiphobic coating |
| CN103601826A (en) * | 2013-10-17 | 2014-02-26 | 华南理工大学 | Hydrophilic oleophobic polymer and preparation method thereof, and application thereof in humidity response oil and water separating membrane |
| WO2015013510A1 (en) * | 2013-07-25 | 2015-01-29 | Ecole Polytechnique Federale De Lausanne Epfl | High aspect ratio nanofibril materials |
| CN107033303A (en) * | 2016-10-28 | 2017-08-11 | 佛山科学技术学院 | A kind of preparation method of fluorine-containing microballoon of surface without stabilizer and application |
-
2017
- 2017-07-18 CN CN201710585938.8A patent/CN109265583B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1502642A (en) * | 2002-11-25 | 2004-06-09 | 中国科学院化学研究所 | Super-biphobic block polyether type polyurethane copolymer and preparation process and use thereof |
| CN102977291A (en) * | 2012-11-01 | 2013-03-20 | 中科院广州化学有限公司 | Cross-linkable fluorine-containing polymer, and its application in preparation of super-amphiphobic surfaces |
| CN102977292A (en) * | 2012-11-07 | 2013-03-20 | 中科院广州化学有限公司 | Amphiphilic cross-linked fluoropolymer and application thereof in preparation of ultra-amphiphobic surface |
| WO2015013510A1 (en) * | 2013-07-25 | 2015-01-29 | Ecole Polytechnique Federale De Lausanne Epfl | High aspect ratio nanofibril materials |
| CN103450727A (en) * | 2013-09-20 | 2013-12-18 | 云南银峰新材料有限公司 | Preparation method of fluoroalkyl chain-containing nano super-amphiphobic coating |
| CN103601826A (en) * | 2013-10-17 | 2014-02-26 | 华南理工大学 | Hydrophilic oleophobic polymer and preparation method thereof, and application thereof in humidity response oil and water separating membrane |
| CN107033303A (en) * | 2016-10-28 | 2017-08-11 | 佛山科学技术学院 | A kind of preparation method of fluorine-containing microballoon of surface without stabilizer and application |
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