CN106554695A - A kind of super hydrophobic material and preparation method thereof - Google Patents
A kind of super hydrophobic material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of super hydrophobic material, it includes substrate and coating, wherein, the coating is made up of the component of following parts by weight：100 parts of organic solvent, 0.01～5 part of antioxidant, 0.01～5 part of light stabilizer, 0.20～80 part of coating additive.Present invention also offers the preparation technology of the super hydrophobic material.The durable super-hydrophobic coat of the present invention, mastoid process is formed using the synergism of the Microphase Structure of the combination and thermoplastic elastomer (TPE) of micro nano structure, the dispersion of this mastoid process even structure can be made, this micro nano structure can be repaired again in use automatically, so that micro nano structure is kept well, effectively overcome because of mastoid process structural damage and the decline of caused hydrophobic performance.Preparation method of the present invention, process is simple, workable, production efficiency are high, low cost, realize the durability of super-hydrophobic coat, have expanded the purposes and application of super-hydrophobic coat.
Description
Technical field
The present invention relates to a kind of super hydrophobic material and preparation method thereof.
Background technology
" lotus leaf effect " in nature is enlightened, the super hydrophobic surface with micro nano structure has many unique surfaces
Performance, such as automatically cleaning, hydrophobic, low-friction coefficient, deicing properties etc..Super-hydrophobic coating material can be widely applied to aircraft, vapour
Car vehicle window, heavy construction, transmission of electricity electric wire, blade of wind-driven generator, clothing etc., with wide market prospect and space.
Shown by the research to the hydrophobic substance surface texture such as Folium Nelumbinis, feather：Super-hydrophobic coat is by the micro-nano on surface
Rice material provides coarse structure and low-surface-energy chemical substance composition.In the last thirty years, preparation side of the scholar to super-hydrophobic coat
Method and application have carried out substantial amounts of research, are prepared for the hydrophobic material of various excellent performances.However, due to mechanical friction, weather
The reason such as aging, particularly ice-melt, freeze dynamic melt expansion in cyclic process, shrink the damaged and fortune that causes mastoid process structure
Dynamic, surface roughness declines, and causes hydrophobic performance to reduce, it is difficult to realize permanently effective hydrophobic performance.
For the research of super-hydrophobic durability, patent CN 201010294025 reports a kind of using with photocatalysis work
Property nanoparticle, the material such as low surface energy polymeric and cross-linking agent through dry solidification, prepare the super-hydrophobic from clear of durability
Clean coating material.The technology energy effectively solving is reduced in the hydrophobic performance that surface aggregation causes because of impurity, but still unresolved micro-
The mastoid process structure received destruction problem in use.Patent CN201380062223 discloses a kind of by Covalent bonding together
Granule and resin, realize to the hydrophobically modified of granule so that the reservation of three surface topographies of hydrophobic granule, reach durability
Target.But the technical method complex process, intractability are big.
The content of the invention
It is an object of the invention to provide a kind of new super hydrophobic material.Present invention also offers the system of the super hydrophobic material
Preparation Method.
The invention provides a kind of super hydrophobic material, it includes substrate and coating, wherein, the coating is by following weight
The component of number：
100 parts of organic solvent, 0.01～5 part of antioxidant, 0.01～5 part of light stabilizer, 0.20～80 part of coating additive.
It is further preferred that the weight proportion of described component is：100 parts of organic solvent, 0.1～3 part of antioxidant, light are steady
Determine 0.1～3 part of agent, 6.05～58 parts of coating additive.
Wherein, described organic solvent is selected from one or more in hexamethylene, toluene, dehydrated alcohol, dimethylbenzene；
Described antioxidant is selected from one or more in antioxidant 1330, antioxidant 1010, irgasfos 168, antioxidant 245；
The one kind or two of described light stabilizer in light stabilizer 119, light stabilizer 234, light stabilizer 770, light stabilizer 622
More than kind.
Wherein, described coating additive is made up of the component of following heavy reason numbers：
0.1～40 part of nano-particle, 0.1～40 part of thermoplastic elastomer (TPE), 0.01～5 part of compatilizer.
It is further preferred that described coating additive is made up of the component of following parts by weight：Nano-particle 5～25
Part, 1～30 part of thermoplastic elastomer (TPE), 0.05～3 part of compatilizer.
Wherein, the particle diameter of the nano-particle is 5～500nm.
Two or more mixing of the described nano-particle selected from different-grain diameter in nano silicon；Wherein, the grain of granule
Footpath ratio is 4:1～1:4；" the particle diameter ratio of granule " refers to the ratio of the particle diameter of variable grain in nano-particle.
Described thermoplastic elastomer (TPE) is styrene series thermoplastic elastomer；Described compatilizer is selected from two isobutyl of azo
One or more in nitrile, benzoyl peroxide, cumyl peroxide.
Described styrene series thermoplastic elastomer is selected from polystyrene-polybutadiene-polystyrene block copolymer, gathers
Styrene-hydrogenated butadiene polymer-polystyrene block copolymer, polystyrene-hydrogenated polyisoprene-polystyrene block are common
One or more in polymers.
Described substrate is metal material, alloy material, plastics, rubber or inorganic ceramic material.
Present invention also offers a kind of method for preparing described super hydrophobic material, comprises the steps：
1) nano silicon, compatilizer, thermoplastic elastomer (TPE), light stabilizer and antioxidant are dissolved in into organic solvent
In, form solution；
2) by step 1) obtained by solution in the ultrasound wave of 50-200w power, ultrasonic 30-60min, temperature control exist
25-50℃；
3) by step 2) obtained by solution room temperature condition using 10 μm of -250 μm of coating machines aluminum alloy surface coat；
4) by step 3) obtained by coating, 3-8h, Ran Hou are processed in the environment of temperature 20-35 DEG C, humidity 40-80%
Solidify 2-8h in 60-140 DEG C of vacuum drying oven, obtain final product super hydrophobic material.
The present invention durable super-hydrophobic coat, using combination and the Microphase Structure of thermoplastic elastomer (TPE) of micro nano structure
Synergism forms mastoid process, can make the dispersion of this mastoid process even structure, and this micro nano structure can obtain again in use
To reparation automatically so that micro nano structure is kept well, is effectively overcome caused because of mastoid process structural damage
Hydrophobic performance declines.With reference to compatilizer in ultrasound, the chemical reaction of cure stage, matrix, thermoplastic elastomer (TPE) and two are increased
The chemical bond interface binding power of silicon oxide, can effectively suppress destruction of the micro nano structure in freeze-thaw cycle.So as to realize surpassing
The durability of hydrophobic coating, has expanded the purposes and application of super-hydrophobic coat.And preparation method of the present invention, technique letter
Single, workable, production efficiency is high, low cost.
Obviously, the above of the invention, according to the ordinary technical knowledge and customary means of this area, without departing from
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification of other various ways can also be made, is replaced or is changed.
The specific embodiment of form, remakes further specifically to the above of the present invention by the following examples
It is bright.But this scope for being interpreted as above-mentioned theme of the invention should not be only limitted to Examples below.It is all based on the above of the present invention
The technology realized belongs to the scope of the present invention.
Description of the drawings
Fig. 1 carries out the surface topography map before freezing and thawing test for 2 gained super-hydrophobic coat of embodiment.
Fig. 2 is surface topography map of the 2 gained super-hydrophobic coat of embodiment Jing after 50 freeze-thaw cycle.
Specific embodiment
Raw material, equipment used in the specific embodiment of the invention is known product, is obtained by buying commercially available prod.
Wherein：
Dehydrated alcohol, AR：Aladdin reagent；Hexamethylene, AR：Aladdin reagent；Toluene, AR：Aladdin reagent；Azo two
Isopropyl cyanide (AIBN), AR, Aladdin reagent；Benzoyl peroxide (BPO), AR, Aladdin reagent；Cumyl peroxide
(DCP), AR, Aladdin reagent；
Nano silicon, particle diameter 15nm, 30nm, 50nm, 100nm, 200nm, 300nm, Degussa；
Thermoplastic elastomer (TPE), SBS (polystyrene-polybutadiene-polystyrene block copolymer), SEBS (polystyrene-
Hydrogenated butadiene polymer-polystyrene block copolymer), (wherein, hard section styrene-content is for sinopec Ba Ling petrochemical industry branch company
32% (wt), soft section butadiene or hydrogenated butadiene content are 68% (wt))；
Antioxidant 1330, antioxidant 1010, irgasfos 168, Ciba Specialty Chemicals of Switzerland；
Light stabilizer 119, light stabilizer 234, light stabilizer 770, Ciba Specialty Chemicals of Switzerland.
The preparation of 1 super hydrophobic material of the present invention of embodiment
By 100g hexamethylene, 2.5g nano silicons (15nm), 2.5g nano silicons (50nm), 1g thermoplastic elastomehcs
Gonosome SBS, 0.05g compatilizer AIBN, 0.1g antioxidant 1010s, 0.1g light stabilizers 770 are mixed to form solution, in the super of 50W
In sound wave, ultrasound 30min, obtains coating solution.
Coated in aluminum alloy surface using 10 μm of coating instrument, 3h is processed under 20 DEG C, 40% environment of humidity, at 80 DEG C
Solidify 2h in vacuum drying oven, obtain final product super hydrophobic material of the present invention.
The preparation of 2 super hydrophobic material of the present invention of embodiment
By 2g dehydrated alcohol, 98g hexamethylene, 5g nano silicons (15nm), 20g nano silicons (50nm), 30g
Thermoplastic elastomer SBS, 3g compatilizer DCP, 0.6g antioxidant 1330,0.6g light stabilizers 234 are mixed to form solution,
In the ultrasound wave of 200W, ultrasound 60min, obtains coating solution.
Coated in aluminum alloy surface using 250 μm of coating instrument, 8h is processed under 35 DEG C, 80% environment of humidity, at 140 DEG C
Vacuum drying oven in solidify 8h, obtain final product super hydrophobic material of the present invention.
The preparation of 3 super hydrophobic material of the present invention of embodiment
By 50g hexamethylene, 50 parts of toluene, 10g nano silicons (100nm), 15g nano silicons (300nm),
15g thermoplastic elastomer SBSs, 1.5g compatilizer BPO, 0.3g irgasfos 168s, 0.3g light stabilizers 770 are mixed to form solution,
In the ultrasound wave of 100W, ultrasound 45min, obtains coating solution.
Coated in aluminum alloy surface using 100 μm of coating instrument, 6h is processed under 30 DEG C, 60% environment of humidity, at 120 DEG C
Vacuum drying oven in solidify 6h, obtain final product super hydrophobic material of the present invention.
The preparation of 4 super hydrophobic material of the present invention of embodiment
48g by hexamethylene, 48 parts of toluene, 4g dehydrated alcohol, 10g nano silicons (100nm), 12.5g nano-silicas
SiClx (200nm), 10g thermoplastic elastomer SBSs, 5g thermoplastic elastomer (TPE) SEBS, 0.1g compatilizer BPO, 0.1g compatilizers
AIBN, 0.1g irgasfos 168,0.1g antioxidant 1330,0.1g light stabilizers 770,0.3g light stabilizers 234 are mixed to form molten
Liquid, in the ultrasound wave of 100W, ultrasound 45min, obtains coating solution.
Coated in aluminum alloy surface using 100 μm of coating instrument, 6h is processed under 30 DEG C, 60% environment of humidity, at 120 DEG C
Vacuum drying oven in solidify 4h, obtain final product super hydrophobic material of the present invention.
The preparation of 5 super hydrophobic material of the present invention of embodiment
By 2g dehydrated alcohol, 98g toluene, 5g nano silicons (50nm), 20g nano silicons (100nm), 10g
Thermoplastic elastomer SBS, 0.1g compatilizer AIBN, 0.1g compatilizer DCP, 0.5g antioxidant 1330,0.5g antioxidant 1010s,
0.5g irgasfos 168s, 0.1g light stabilizers 234,0.1g light stabilizers 770,0.1g light stabilizers 119 are mixed to form solution,
In the ultrasound wave of 150W, ultrasound 40min, obtains coating solution.
Coated in aluminum alloy surface using 70 μm of coating instrument, 5h is processed under 25 DEG C, 70% environment of humidity, at 110 DEG C
Vacuum drying oven in solidify 7h, obtain final product super hydrophobic material of the present invention.
The preparation of 6 super hydrophobic material of the present invention of embodiment
By 10g dehydrated alcohol, 90g hexamethylene, 10g nano silicons (100nm), 5g nano silicons (30nm),
10g thermoplastic elastomer (TPE) SEBS, 0.2g compatilizer DCP, 0.5g irgasfos 168s, 0.3g light stabilizers 119 are mixed to form solution,
In the ultrasound wave of 50W, ultrasound 50min, obtains coating solution.
Coated in aluminum alloy surface using 10 μm of coating instrument, 7h is processed under 20 DEG C, 80% environment of humidity, at 130 DEG C
Vacuum drying oven in solidify 5h, obtain final product super hydrophobic material of the present invention.
Beneficial effects of the present invention are illustrated by tests below example.
Test example 1, performance test
Coating prepared by embodiment 1-6 is compared with following comparative examples：
Comparative example 1
By 2g dehydrated alcohol, 98g hexamethylene, 10g nano silicon 15nm, 5g nano silicon 50nm, 0.3g phases
Hold agent AIBN, 0.3g antioxidant 1330,0.3g light stabilizers 234 are mixed to form solution, the ultrasound in the ultrasound wave of 100W
40min, obtains coating solution, is coated in aluminum alloy surface using 70 μm of coating instrument, processes under 25 DEG C, 60% environment of humidity
6h, solidifies 4h in 120 DEG C of vacuum drying oven, obtains final product contrast coating B-1.
Pad thermoplastic elastic is not contained in comparative example 1 in coating additive.
Comparative example 2
By 2g dehydrated alcohol, 98g toluene, 10g thermoplastic elastomer SBSs, 0.3g compatilizer BPO, 0.3g antioxidant 1010s,
0.3g light stabilizers 770, are mixed to form solution, and in the ultrasound wave of 100W, ultrasound 40min, obtains coating solution, using 70 μm
Coating instrument is coated in aluminum alloy surface, processes 7h, solidify 3h in 110 DEG C of vacuum drying oven under 25 DEG C, 60% environment of humidity,
Obtain final product contrast coating B-2.
In comparative example 2, coating additive does not contain nano-particle.
Comparative example 3
By 2g dehydrated alcohol, 98g toluene, 10g nano silicon 15nm, 5g nano silicons (50nm), 10g thermoplastics
Property elastomer SBS, 0.3g irgasfos 168s, 0.3g light stabilizers 119 be mixed to form solution, the ultrasound in the ultrasound wave of 80W
50min, obtains coating solution, is coated in aluminum alloy surface using 80 μm of coating instrument, processes under 20 DEG C, 60% environment of humidity
4h, solidifies 6h in 130 DEG C of vacuum drying oven, obtains final product contrast coating B-3.
Compatilizer is not contained in comparative example 3.
Contrast as follows by freezing and thawing test and comparative example 1-3：
Freezing and thawing test：Distilled water is freezed in -20 DEG C of refrigerators the formation subcooled water of 3h；By subcooled water from being inclined to
30 ° of coating top is slowly toppled over, and makes coating surface freeze completely；The coating of icing is freezed into 8h in -20 DEG C of refrigerator；Will
The coating of freezing is in thaw at RT 16h, and 8h is dried in 60 DEG C of vacuum drying oven, takes out and places 16h in room temperature.It is 1 above
Secondary freeze-thaw cycle, is so repeated test.
The coating contact angle of Jing freeze-thaw cycle is tested using contact angle tester, test result is shown in Table 1.
The numerical value in freeze-thaw cycle cycle is bigger, represents that coating keeps the ability of ultra-hydrophobicity stronger, it is, representing super
The service life of hydrophobic coating extends.
The durability of table 1, super-hydrophobic coat compares
By embodiment 1-6 and the comparison of comparative example 1-3, when thermoplastic elastomer (TPE) is used alone, without ultra-hydrophobicity, receive
When rice silicon dioxide is used alone, there are ultra-hydrophobicity, but coating without durability.It is primarily due to：Stable micro-nano cannot be formed
Rice structure, coating do not possess durability.By the micro phase separation structure synergism of nano silicon and thermoplastic elastomer (TPE)
Micro-nano mastoid process structure is formed, in use the selfreparing of mastoid process structure, initial configuration is maintained, so as to greatly improve
The durability of hydrophobic coating.
Claims (10)
1. a kind of super hydrophobic material, it is characterised in that：It includes substrate and coating, wherein, the coating is by following weight portion
Several component compositions：
100 parts of organic solvent, 0.01～5 part of antioxidant, 0.01～5 part of light stabilizer, 0.20～80 part of coating additive.
2. super hydrophobic material according to claim 1, it is characterised in that：The weight proportion of described component is：It is organic molten
100 parts of agent, 0.1～3 part of antioxidant, 0.1～3 part of light stabilizer, 6.05～58 parts of coating additive.
3. super hydrophobic material according to claim 2, it is characterised in that：Described organic solvent selected from hexamethylene, toluene,
One or more in dehydrated alcohol, dimethylbenzene；Described antioxidant is selected from antioxidant 1330, antioxidant 1010, antioxygen
One or more in agent 168, antioxidant 245；Described light stabilizer selected from light stabilizer 119, light stabilizer 234,
One or more in light stabilizer 770, light stabilizer 622.
4. super hydrophobic material according to claim 1 and 2, it is characterised in that：Described coating additive is by following weight
The component composition of number：
0.1～40 part of nano-particle, 0.1～40 part of thermoplastic elastomer (TPE), 0.01～5 part of compatilizer.
5. super hydrophobic material according to claim 4, it is characterised in that：Described coating additive is by following parts by weight
Component composition：5～25 parts of nano-particle, 1～30 part of thermoplastic elastomer (TPE), 0.05～3 part of compatilizer.
6. super hydrophobic material according to claim 5, it is characterised in that：The particle diameter of the nano-particle is 5～500nm.
7. the super hydrophobic material according to claim 4-6 any one, it is characterised in that：Described nano-particle is selected from
Two kinds of different-grain diameter and mixed above in nano silicon, the particle diameter ratio of granule is 4:1～1:4；Described thermoplastic elastomehc
Gonosome is styrene series thermoplastic elastomer；Described compatilizer is selected from azodiisobutyronitrile, benzoyl peroxide, peroxidating two
One or more in isopropylbenzene.
8. super hydrophobic material according to claim 7, it is characterised in that：Described styrene series thermoplastic elastomer is selected from
Polystyrene-polybutadiene-polystyrene block copolymer, polystyrene-hydrogenated butadiene polymer-polystyrene block copolymerization
One or more in thing, polystyrene-hydrogenated polyisoprene-polystyrene block copolymer.
9. super hydrophobic material according to claim 1, it is characterised in that：Described substrate be metal material, alloy material,
Plastics, rubber or inorganic ceramic material.
10. a kind of method for preparing the super hydrophobic material described in claim 7-9 any one, comprises the steps：
1) nano silicon, compatilizer, thermoplastic elastomer (TPE), light stabilizer and antioxidant are dissolved in organic solvent, shape
Into solution；
2) by step 1) obtained by solution in the ultrasound wave of 50-200w power, ultrasonic 30-60min, temperature control is in 25-50
℃；
3) by step 2) obtained by solution room temperature condition using 10 μm of -250 μm of coating machines aluminum alloy surface coat；
4) by step 3) obtained by coating, 3-8h is processed in the environment of temperature 20-35 DEG C, humidity 40-80%, then in 60-
Solidify 2-8h in 140 DEG C of vacuum drying oven, obtain final product super hydrophobic material.
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| CN109346709A (en) * | 2018-11-21 | 2019-02-15 | 湖北彩砼新材料有限公司 | The anode material for lithium-ion batteries and preparation method thereof of super hydrophobic material cladding |
| CN109354963A (en) * | 2018-11-12 | 2019-02-19 | 黄艳芬 | A kind of corrosion-resistant super hydrophobic coating and its preparation method and application |
| WO2020250748A1 (en) * | 2019-06-14 | 2020-12-17 | 日本ゼオン株式会社 | Resin solution for printing |
| CN113652125A (en) * | 2021-09-08 | 2021-11-16 | 东北石油大学 | Micro-nano structure repair type super-hydrophobic coating and preparation method thereof |
| CN117866486A (en) * | 2023-12-20 | 2024-04-12 | 南京航空航天大学 | Preparation method, material and application of flexible polymer-based superhydrophobic coating material for tritium protection |
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