CN109943213A - A kind of preparation method of the environmentally friendly super-hydrophobic coat of high mechanical endurance - Google Patents
A kind of preparation method of the environmentally friendly super-hydrophobic coat of high mechanical endurance Download PDFInfo
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- CN109943213A CN109943213A CN201910205616.5A CN201910205616A CN109943213A CN 109943213 A CN109943213 A CN 109943213A CN 201910205616 A CN201910205616 A CN 201910205616A CN 109943213 A CN109943213 A CN 109943213A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a kind of preparation methods of high mechanical endurance environmental protection super-hydrophobic coat, belong to the preparation technical field of coating.The preparation method is the following steps are included: first to filter the waste cooking oils after purifying as raw material; synthesis waste cooking oils fat amide is reacted by aminolysis; again using waste cooking oils fat amide and toluene di-isocyanate(TDI) as raw material; base polyurethane prepolymer for use as is prepared using one-step method; then base polyurethane prepolymer for use as is blocked by double ended type ammonia alkyl silicone oil; modified polyurethane is obtained; finally organic silicon modified polyurethane is mixed with the silicon-carbide particle that hydrophobic treatment is crossed; it is sprayed on ground after magnetic agitation; after dry solidification to get.The coating being prepared by the method for the invention is low in cost and environmentally friendly, has good thermally conductive, wear-resisting and self-cleaning performance, can solve dust pollution question related with air cooler for mining fin, guarantees the heat exchange efficiency of air cooler in use.
Description
Technical field
The present invention relates to the preparation technical fields of coating, and in particular to a kind of preparation method of environmental protection super-hydrophobic coat.
Background technique
Due to exploiting for a long time, shallow buried coal seam is exhausted, and most of coal mine has to exploit buried coal seam.With mining depth
The increase of degree, country rock temperature also rise with it, and the risk of heat evil in mining is caused to be continuously increased.For high-temperature mine, one
As in the case of only not can solve Climatic regionalization problem by mine ventilation.In order to guarantee the normal work of employee, in most cases must
Corresponding cooling system must be built.Along with the innovation of technology, air cooler falling temperature technique has been widely used in coal mining industry,
As one of the main means for reducing mine high-temperature.Air cooler for mining be typically located at down-hole mining working face or working face into
In air way road, and underground air is contaminated than more serious, and coal dust is more, high temperature and humidity, and narrow space.The severe work of mine
Environment makes the very easy dust accumulation of fin surface, seriously affects the heat transfer effect of air cooler.
Super hydrophobic surface causes academia and work because it is in automatically cleaning, anti-freeze and anticorrosion field potential application
The great interest of industry.Most of modern coatings can provide hydrophobic/superhydrophobic surfaces by synthesis.Manufacture hydrophobic coating has
Two essential requirements: one is low-surface-energy material, the other is micro-nano layered structure.Super-hydrophobic coat is due to low
Adhesion strength between surface energy component and substrate is poor, and micro nano structure is very fragile, when surface to impact, the machinery such as friction
Effect is easy to damage and lose ultra-hydrophobicity, and the super-hydrophobic coat of high-mechanical property is not difficult to play in practical applications
Effect.
Currently, the prior art mainly has in relation to the preparation of super hydrophobic coating/layer:
CN108505319A discloses a kind of environment-friendly type super hydrophobic material and its preparation method and application, mainly using receiving
Rice material modifies the whole three-dimensional structure of base material, so that the roughness of base material entirety three-dimensional structure is improved,
Prepare the excellent super hydrophobic material of hydrophobic performance, main approaches are as follows: ferric trichloride, urea, dodecyl sodium sulfate is molten
Solution obtains mixed liquor in deionized water, is then added to mixed liquor and base material in the autoclave of teflon lining and carries out
Hydro-thermal reaction, cooled to room temperature obtain environment-friendly type super hydrophobic material with deionized water rinsing, drying；
CN109207023A discloses a kind of controllable method for preparing of aeronautical material surface environmental protection hydrophobic coating, the preparation
Method is bonded the following steps are included: by being sprayed on processed aeronautical material substrate after epoxy resin acetone solution
Layer, is then added curing agent with mechanical stirring for zinc stearate powder and epoxy resin after mixing, adds suitable third
Ketone is sprayed on adhesive layer after mixing, gained coating sample is dried at room temperature, then by it in acetic acid solution
Middle etching modifies after cleaning-drying in stearic ethanol solution, is drying to obtain hydrophobic coating；
CN107880770A discloses a kind of preparation method of environment protection multifunctional super-hydrophobic coat, and preparation method mainly wraps
It includes the preparation of nano-titanium dioxide powder, the preparation for the nano-titanium dioxide powder that octadecylisocyanate is modified, silicone resin and changes
Property nano-titanium dioxide powder mixed coating preparation, by resulting hydrophobic coating be coated in substrate on to get super-hydrophobic painting
Layer.
Above-mentioned super-hydrophobic coat in the prior art all has super-hydrophobicity, however, its mechanical endurance can be unable to satisfy
It is required that with the exhaustion of fossil resource, in addition the raising of people's environmental consciousness, is made using more sustainable and environmentally friendly raw material
Bio-based polymers are made to receive more and more attention.In summary, it is necessary to research and develop a kind of with high mechanical endurance
Environmentally friendly super-hydrophobic coat.
Summary of the invention
In order to solve this technical problem underlying of bad mechanical property, this hair existing for above-mentioned super-hydrophobic coat in the prior art
A kind of preparation method of the bright environmentally friendly super-hydrophobic coat for proposing high mechanical endurance, the coating being prepared by this method its
Mechanical endurance can be excellent.
In order to solve the above-mentioned technical problem, the invention adopts the following technical scheme:
It is a kind of environmental protection super-hydrophobic coat preparation method, successively the following steps are included:
A prepares waste cooking oils fat amide,
To filter the waste cooking oils after purifying as raw material, synthesis waste cooking oils fat acyl is reacted by aminolysis
Amine；
B prepares base polyurethane prepolymer for use as,
At room temperature, waste cooking oils fat amide is dissolved in acetone, obtains the waste cooking oils of 50wt%
Waste cooking oils fat amide solution is added in toluene di-isocyanate(TDI) by fatty acid amide solution, uses two fourth of tin dilaurate
Ji Xi is stirred at a certain temperature as catalyst, and reaching dumpable viscosity can be obtained base polyurethane prepolymer for use as；
C prepares modified polyurethane,
Base polyurethane prepolymer for use as is blocked by double ended type ammonia alkyl silicone oil, modified polyurethane is made；
D prepares environmentally friendly super-hydrophobic coat,
Silicon-carbide particle is obtained into hydrophobic silicon carbide powder by hydrophobic treatment, then by the modified polyurethane with it is described
Hydrophobic silicon carbide powder mixing, sprayed on ground after magnetic agitation, after dry solidification to obtain the final product；
In step d, hydrophobic treatment step are as follows: silicon-carbide particle is dispersed in ethanol solution by being ultrasonically treated, then
Double ended type ammonia alkyl silicone oil is added, magnetic agitation, obtains modified Nano carborundum solution, by centrifuge washing at a certain temperature
To get hydrophobic silicon carbide powder after drying；
The mass ratio of the hydrophobic silicon carbide powder and the modified polyurethane is 2~10:1.
As a preferred solution of the present invention, in step a, the preparation step of waste cooking oils fat amide are as follows: first
Sodium methoxide and diethanol amine are placed in a reaction flask, heater switch and magnetic stirring apparatus, the heating stirring 20 at 80 DEG C are opened
Minute, the waste cooking oils after purification is then added dropwise in 60 minutes, after the waste cooking oils after purification are added completely into,
Reaction temperature is risen to 120 DEG C and continues to be stirred to react 3 hours at such a temperature to get, the sodium methoxide, diethanol amine and useless
The molar ratio for abandoning edible oil is 1:45:15.
As another preferred embodiment of the invention, in step b, waste cooking oils fat amide and toluene di-isocyanate(TDI)
Molar ratio 1:1.2, stir 2h at 70 DEG C and reach dumpable viscosity.
Further, in step c, double ended type ammonia alkyl silicone oil is added dropwise in base polyurethane prepolymer for use as, using acetone
Regulation system viscosity continues to be stirred to react 3 hours at 55 DEG C to get modified polyurethane；The base polyurethane prepolymer for use as and double
The molar ratio of end type ammonia alkyl silicone oil is 1:2.
Further, in the hydrophobic treatment step, silicon-carbide particle is dispersed in ethanol solution by ultrasonic treatment
In, continue 30min, double ended type ammonia alkyl silicone oil, the magnetic agitation 4h at 70 DEG C is then added.
Further, the double ended type ammonia alkyl silicone oil is by three second of hydroxyl dimethyl silicone polymer and 3- aminopropyl
Oxysilane synthesis.
Further, in step d, the partial size of the silicon-carbide particle is 30~100nm, and grain shape is ball-type.
Further, the mass ratio of the silicon-carbide particle, ethanol solution and double ended type ammonia alkyl silicone oil is followed successively by 2:3:
10, drying temperature is 130 DEG C.
Further, the ground is glass, copper, aluminium or iron.
Reaction mechanism of the invention is described briefly below, is below the reaction equation of modified polyurethane:
Compared with prior art, present invention offers following advantageous effects:
In terms of the selection of raw material, using waste cooking oils as raw material, waste was not only handled but also had reduced its dirt to environment
Dye, it is cheap and environmentally friendly；
In terms of preparation method, base polyurethane prepolymer for use as is blocked using double ended type ammonia alkyl silicone oil, improves poly- ammonia
The crosslinking ability of ester, and then enhance the binding ability of coating and ground；Using excellent physical properties silicon-carbide particle as
Filler improves the mechanical endurance of coating, in order to avoid agglomeration carries out hydrophobic treatment to silicon-carbide particle, by dredging
Nanometer silicon carbide after water process has good dispersibility, can be evenly distributed in modified polyurethane, build coarse
Micro-nano surface, further increase the hydrophobic performance of coating, using volatile acetone as solvent, coating forms rear base
This noresidue；The environmentally friendly super-hydrophobic coat that the present invention is prepared has good mechanical performance, passes through after sand paper wear test
DSA100 contact angle analyzer carries out contact angle test, measures the coating to the contact angle of water droplet at 150 ° or more.
It should be strongly noted that the application significantly improves coating by carrying out hydrophobic treatment to silicon-carbide particle
Hydrophobic performance, concrete outcome is referring to comparative example 1.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawing:
Fig. 1 is the preparation technology flow chart of the environmentally friendly super-hydrophobic coat of the present invention；
Fig. 2 is the infrared spectrum of waste cooking oils fat amide；
Fig. 3 is the infrared spectrum of base polyurethane prepolymer for use as；
Fig. 4 is the infrared spectrum of modified polyurethane；
Fig. 5 is the stereoscan photograph for the super-hydrophobic coat that embodiment 1 is prepared；
Fig. 6 is its contact angle of the embodiment of the present invention and the relational graph for wearing number.
Specific embodiment
It is of the invention in order to make the invention proposes a kind of preparation method of the environmentally friendly super-hydrophobic coat of high mechanical endurance
Advantage, technical solution are clearer, clear, elaborate combined with specific embodiments below to the present invention.
Raw material selected by the present invention can be bought by commercial channel and be obtained.
The preparation method of the environmentally friendly super-hydrophobic coat of the high mechanical endurance of the present invention, as shown in Figure 1, after using purification first
Waste cooking oils base polyurethane prepolymer for use as is prepared, then base polyurethane prepolymer for use as is sealed using double ended type ammonia alkyl silicone oil
End obtains modified polyurethane, finally mixes modified polyurethane with the silicon-carbide particle that hydrophobic treatment is crossed, and spraying obtains high machinery
The environmentally friendly super-hydrophobic coat of durability.
Embodiment 1:
Step 1: the preparation of waste cooking oils fat amide, first by sodium methoxide (0.007mol) and diethanol amine
(0.32mol) is placed in three neck round bottom, opens heater switch and magnetic stirring apparatus, heating stirring 20 is divided at 80 DEG C
Clock, the waste cooking oils (0.1mol) after purification is then added dropwise in 60 minutes.Waste cooking oils after purification are complete
After addition, reaction temperature is risen to 120 DEG C and continues to be stirred to react at such a temperature obtains within 3 hours waste cooking oils fat acyl
Amine；
Step 2: the preparation of base polyurethane prepolymer for use as, is raw material by waste cooking oils fat amide and toluene di-isocyanate(TDI),
Base polyurethane prepolymer for use as is prepared using one-step method.At room temperature, waste cooking oils fat amide is dissolved in acetone, is obtained
The waste cooking oils fat amide solution of 50wt%.Waste cooking oils fat amide solution is added to toluene di-isocyanate(TDI)
In, holding NCO/OH ratio is 1.2:1, uses dibutyl tin dilaurate as catalyst, and 2h is stirred at 70 DEG C and reaches and can incline
Base polyurethane prepolymer for use as can be obtained in viscosity；
Step 3: the preparation of modified polyurethane, double ended type ammonia alkyl silicone oil is added dropwise in base polyurethane prepolymer for use as, protect
The molar ratio for holding double ended type ammonia alkyl silicone oil and base polyurethane prepolymer for use as is 2:1, using acetone regulation system viscosity, at 55 DEG C after
It is continuous to be stirred to react 3 hours, obtain organic silicon modified polyurethane.
Fig. 2 is the infrared spectrum of waste cooking oils fat amide, wherein 3358cm-1Place be OH stretching vibration peak, 2852
And 2920cm-1The absorption band that place observes is due to CH respectively2And CH3The symmetrical and asymmetric stretching of group, 1357cm-1With
1456cm-1Place is CH2Flexural vibrations peak, 1614cm-1Place is the C=O stretching vibration peak in amide group, in 1207cm-1Place is
The presence of C-N stretching vibration peak ,-N-C=O and-OH prove the synthesis of waste cooking oils fat amide.
Fig. 3 is the infrared spectrum of base polyurethane prepolymer for use as, wherein 3340cm-1For N-H stretching vibration peak, 1725cm-1For amino
The stretching vibration peak of formic acid esters C=O, 1600cm-1For the stretching vibration peak of phenyl ring skeleton, 1230cm-1For C-O stretching vibration peak.
Fig. 4 is the infrared spectrum of modified polyurethane, 1075cm-1Absorption peak becomes strong, be because Si-O-Si stretching vibration peak with
C-O-C stretching vibration overlap of peaks as a result, illustrating that Si-O-Si is successfully introduced into polyurethane backbone.
Step 4: the preparation of environmentally friendly super-hydrophobic coat, passes through ultrasonic treatment point for the silicon-carbide particle that partial size is 30 nanometers
It is dispersed in ethanol solution, continues 30min, double ended type ammonia alkyl silicone oil is then added, magnetic agitation 4h, is modified at 70 DEG C
Nanometer silicon carbide solution obtains dewatering nano silicon carbide powder after centrifuge washing is dry.By organic silicon modified polyurethane with
The mass ratio of hydrophobic silicon carbide powder mixing, modified polyurethane and hydrophobic silicon carbide powder is 4:1, is sprayed after magnetic agitation
Onto ground, the environmentally friendly super-hydrophobic coat of corresponding high mechanical endurance is can be obtained in dry solidification.
DSA100 contact angle analyzer is used to measure the super-hydrophobic coat to the contact angle of water droplet as 163 °.
Fig. 5 is the stereoscan photograph of the super-hydrophobic coat of preparation, and Cong Tuzhong is it can be found that spherical carbide silicon particle is uniform
In matrix, coarse micro-nano surface is formd.
By sand paper wear test evaluate super-hydrophobic coat wear-resisting property, by weight be 200g counterweight be placed in be coated with it is super
On the sample of hydrophobic coating, super-hydrophobic coat is contacted with sand paper, and sample is moved 20 centimetres, altogether 10 times in the same direction.Its
The relationship of contact angle and abrasion number illustrates system of the present invention as shown in fig. 6, the contact angle of each group drop is all larger than 150 ° in Fig. 6
Standby super-hydrophobic coat has good mechanical endurance energy.
Embodiment 2:
Step 1: the preparation of waste cooking oils fat amide, first by sodium methoxide (0.007mol) and diethanol amine
(0.32mol) is placed in three neck round bottom, opens heater switch and magnetic stirring apparatus, heating stirring 20 is divided at 80 DEG C
Clock, the waste cooking oils (0.1mol) after purification is then added dropwise in 60 minutes.Waste cooking oils after purification are complete
After addition, reaction temperature is risen to 120 DEG C and continues to be stirred to react at such a temperature obtains within 3 hours waste cooking oils fat acyl
Amine；
Step 2: the preparation of base polyurethane prepolymer for use as, is raw material by waste cooking oils fat amide and toluene di-isocyanate(TDI),
Base polyurethane prepolymer for use as is prepared using one-step method.At room temperature, waste cooking oils fat amide is dissolved in acetone, is obtained
The waste cooking oils fat amide solution of 50wt%.Waste cooking oils fat amide solution is added to toluene di-isocyanate(TDI)
In, holding NCO/OH ratio is 1.2:1, uses dibutyl tin dilaurate as catalyst, and 2h is stirred at 70 DEG C and reaches and can incline
Base polyurethane prepolymer for use as can be obtained in viscosity；
Step 3: the preparation of modified polyurethane, double ended type ammonia alkyl silicone oil is added dropwise in base polyurethane prepolymer for use as, protect
The molar ratio for holding double ended type ammonia alkyl silicone oil and base polyurethane prepolymer for use as is 2:1, using acetone regulation system viscosity, at 55 DEG C after
It is continuous to be stirred to react 3 hours, obtain organic silicon modified polyurethane.
Step 4: the preparation of environmentally friendly super-hydrophobic coat, passes through ultrasonic treatment point for the silicon-carbide particle that partial size is 30 nanometers
It is dispersed in ethanol solution, continues 30min, double ended type ammonia alkyl silicone oil is then added, magnetic agitation 4h, is modified at 70 DEG C
Nanometer silicon carbide solution obtains dewatering nano silicon carbide powder after centrifuge washing is dry.By organic silicon modified polyurethane with
The mass ratio of hydrophobic silicon carbide powder mixing, modified polyurethane and hydrophobic silicon carbide powder is 10:1, is sprayed after magnetic agitation
It is coated on ground, corresponding environmentally friendly super-hydrophobic coat can be obtained in dry solidification.
DSA100 contact angle analyzer is used to measure the super-hydrophobic coat to the contact angle of water droplet as 150 °.
Embodiment 3:
Step 1: the preparation of waste cooking oils fat amide, first by sodium methoxide (0.007mol) and diethanol amine
(0.32mol) is placed in three neck round bottom, opens heater switch and magnetic stirring apparatus, heating stirring 20 is divided at 80 DEG C
Clock, the waste cooking oils (0.1mol) after purification is then added dropwise in 60 minutes.Waste cooking oils after purification are complete
After addition, reaction temperature is risen to 120 DEG C and continues to be stirred to react at such a temperature obtains within 3 hours waste cooking oils fat acyl
Amine；
Step 2: the preparation of base polyurethane prepolymer for use as, is raw material by waste cooking oils fat amide and toluene di-isocyanate(TDI),
Base polyurethane prepolymer for use as is prepared using one-step method.At room temperature, waste cooking oils fat amide is dissolved in acetone, is obtained
The waste cooking oils fat amide solution of 50wt%.Waste cooking oils fat amide solution is added to toluene di-isocyanate(TDI)
In, holding NCO/OH ratio is 1.2:1, uses dibutyl tin dilaurate as catalyst, and 2h is stirred at 70 DEG C and reaches and can incline
Base polyurethane prepolymer for use as can be obtained in viscosity；
Step 3: the preparation of modified polyurethane, double ended type ammonia alkyl silicone oil is added dropwise in base polyurethane prepolymer for use as, protect
The molar ratio for holding double ended type ammonia alkyl silicone oil and base polyurethane prepolymer for use as is 2:1, using acetone regulation system viscosity, at 55 DEG C after
It is continuous to be stirred to react 3 hours, obtain organic silicon modified polyurethane.
Step 4: the preparation of environmentally friendly super-hydrophobic coat, passes through ultrasonic treatment point for the silicon-carbide particle that partial size is 30 nanometers
It is dispersed in ethanol solution, continues 30min, double ended type ammonia alkyl silicone oil is then added, magnetic agitation 4h, is modified at 70 DEG C
Nanometer silicon carbide solution obtains dewatering nano silicon carbide powder after centrifuge washing is dry.By organic silicon modified polyurethane with
The mass ratio of hydrophobic silicon carbide powder mixing, modified polyurethane and hydrophobic silicon carbide powder is 8:1, is sprayed after magnetic agitation
Onto ground, corresponding environmentally friendly super-hydrophobic coat is can be obtained in dry solidification.
DSA100 contact angle analyzer is used to measure the super-hydrophobic coat to the contact angle of water droplet as 155 °.
Embodiment 4:
Step 1: the preparation of waste cooking oils fat amide, first by sodium methoxide (0.007mol) and diethanol amine
(0.32mol) is placed in three neck round bottom, opens heater switch and magnetic stirring apparatus, heating stirring 20 is divided at 80 DEG C
Clock, the waste cooking oils (0.1mol) after purification is then added dropwise in 60 minutes.Waste cooking oils after purification are complete
After addition, reaction temperature is risen to 120 DEG C and continues to be stirred to react at such a temperature obtains within 3 hours waste cooking oils fat acyl
Amine；
Step 2: the preparation of base polyurethane prepolymer for use as, is raw material by waste cooking oils fat amide and toluene di-isocyanate(TDI),
Base polyurethane prepolymer for use as is prepared using one-step method.At room temperature, waste cooking oils fat amide is dissolved in acetone, is obtained
The waste cooking oils fat amide solution of 50wt%.Waste cooking oils fat amide solution is added to toluene di-isocyanate(TDI)
In, holding NCO/OH ratio is 1.2:1, uses dibutyl tin dilaurate as catalyst, and 2h is stirred at 70 DEG C and reaches and can incline
Base polyurethane prepolymer for use as can be obtained in viscosity；
Step 3: the preparation of modified polyurethane, double ended type ammonia alkyl silicone oil is added dropwise in base polyurethane prepolymer for use as, protect
The molar ratio for holding double ended type ammonia alkyl silicone oil and base polyurethane prepolymer for use as is 2:1, using acetone regulation system viscosity, at 55 DEG C after
It is continuous to be stirred to react 3 hours, obtain organic silicon modified polyurethane.
Step 4: the preparation of environmentally friendly super-hydrophobic coat, passes through ultrasonic treatment point for the silicon-carbide particle that partial size is 30 nanometers
It is dispersed in ethanol solution, continues 30min, double ended type ammonia alkyl silicone oil is then added, magnetic agitation 4h, is modified at 70 DEG C
Nanometer silicon carbide solution obtains dewatering nano silicon carbide powder after centrifuge washing is dry.By organic silicon modified polyurethane with
The mass ratio of hydrophobic silicon carbide powder mixing, modified polyurethane and hydrophobic silicon carbide powder is 6:1, is sprayed after magnetic agitation
Onto ground, corresponding environmentally friendly super-hydrophobic coat is can be obtained in dry solidification.
DSA100 contact angle analyzer is used to measure the super-hydrophobic coat to the contact angle of water droplet as 159 °.
Embodiment 5:
Step 1: prepared by waste cooking oils fat amide, first by sodium methoxide (0.007mol) and diethanol amine
(0.32mol) is placed in three neck round bottom, opens heater switch and magnetic stirring apparatus, heating stirring 20 is divided at 80 DEG C
Clock, the waste cooking oils (0.1mol) after purification is then added dropwise in 60 minutes.Waste cooking oils after purification are complete
After addition, reaction temperature is risen to 120 DEG C and continues to be stirred to react at such a temperature obtains within 3 hours waste cooking oils fat acyl
Amine；
Step 2: prepared by base polyurethane prepolymer for use as, it is raw material by waste cooking oils fat amide and toluene di-isocyanate(TDI), adopts
Base polyurethane prepolymer for use as is prepared with one-step method.At room temperature, waste cooking oils fat amide is dissolved in acetone, is obtained
The waste cooking oils fat amide solution of 50wt%.Waste cooking oils fat amide solution is added to toluene di-isocyanate(TDI)
In, holding NCO/OH ratio is 1.2:1, uses dibutyl tin dilaurate as catalyst, and 2h is stirred at 70 DEG C and reaches and can incline
Base polyurethane prepolymer for use as can be obtained in viscosity；
Step 3: the preparation of modified polyurethane, double ended type ammonia alkyl silicone oil is added dropwise in base polyurethane prepolymer for use as, protect
The molar ratio for holding double ended type ammonia alkyl silicone oil and base polyurethane prepolymer for use as is 2:1, using acetone regulation system viscosity, at 55 DEG C after
It is continuous to be stirred to react 3 hours, obtain organic silicon modified polyurethane.
Step 4: the preparation of environmentally friendly super-hydrophobic coat, passes through ultrasonic treatment point for the silicon-carbide particle that partial size is 30 nanometers
It is dispersed in ethanol solution, continues 30min, double ended type ammonia alkyl silicone oil is then added, magnetic agitation 4h, is modified at 70 DEG C
Nanometer silicon carbide solution obtains dewatering nano silicon carbide powder after centrifuge washing is dry.By organic silicon modified polyurethane with
The mass ratio of hydrophobic silicon carbide powder mixing, modified polyurethane and hydrophobic silicon carbide powder is 2:1, is sprayed after magnetic agitation
Onto ground, corresponding environmentally friendly super-hydrophobic coat is can be obtained in dry solidification.
DSA100 contact angle analyzer is used to measure the super-hydrophobic coat to the contact angle of water droplet as 161 °.
Comparative example 1:
This comparative example compared with Example 1, in step 4, saves the hydrophobic treatment to nano silicon carbide granulate, removes this
Outer method and step is all the same, specific steps are as follows:
Step 1: the preparation of waste cooking oils fat amide, first by sodium methoxide (0.007mol) and diethanol amine
(0.32mol) is placed in three neck round bottom, opens heater switch and magnetic stirring apparatus, heating stirring 20 is divided at 80 DEG C
Clock, the waste cooking oils (0.1mol) after purification is then added dropwise in 60 minutes.Waste cooking oils after purification are complete
After addition, reaction temperature is risen to 120 DEG C and continues to be stirred to react at such a temperature obtains within 3 hours waste cooking oils fat acyl
Amine；
Step 2: the preparation of base polyurethane prepolymer for use as, is raw material by waste cooking oils fat amide and toluene di-isocyanate(TDI),
Base polyurethane prepolymer for use as is prepared using one-step method.At room temperature, waste cooking oils fat amide is dissolved in acetone, is obtained
The waste cooking oils fat amide solution of 50wt%.Waste cooking oils fat amide solution is added to toluene di-isocyanate(TDI)
In, holding NCO/OH ratio is 1.2:1, uses dibutyl tin dilaurate as catalyst, and 2h is stirred at 70 DEG C and reaches and can incline
Base polyurethane prepolymer for use as can be obtained in viscosity；
Step 3: the preparation of modified polyurethane, double ended type ammonia alkyl silicone oil is added dropwise in base polyurethane prepolymer for use as, protect
The molar ratio for holding double ended type ammonia alkyl silicone oil and base polyurethane prepolymer for use as is 2:1, using acetone regulation system viscosity, at 55 DEG C after
It is continuous to be stirred to react 3 hours, obtain organic silicon modified polyurethane.
Step 4: the preparation of coating, organic silicon modified polyurethane is mixed with the silicon-carbide particle that partial size is 30 nanometers, is changed
Property polyurethane and nano silicon carbide granulate mass ratio be 4:1, sprayed to after magnetic agitation on ground, dry solidification
Obtain corresponding coating.
DSA100 contact angle analyzer is used to measure the coating to the contact angle of water droplet as 117 °.
Claims (9)
1. it is a kind of environmental protection super-hydrophobic coat preparation method, which is characterized in that successively the following steps are included:
A prepares waste cooking oils fat amide,
To filter the waste cooking oils after purifying as raw material, synthesis waste cooking oils fat amide is reacted by aminolysis；
B prepares base polyurethane prepolymer for use as,
At room temperature, waste cooking oils fat amide is dissolved in acetone, obtains the waste cooking oils fat of 50wt%
Waste cooking oils fat amide solution is added in toluene di-isocyanate(TDI), uses dibutyl tin dilaurate by amide solution
It as catalyst, stirs at a certain temperature, reaching dumpable viscosity can be obtained base polyurethane prepolymer for use as；
C prepares modified polyurethane,
Base polyurethane prepolymer for use as is blocked by double ended type ammonia alkyl silicone oil, modified polyurethane is made；
D prepares environmentally friendly super-hydrophobic coat,
Silicon-carbide particle is obtained into hydrophobic silicon carbide powder by hydrophobic treatment, then dredges the modified polyurethane and described
Water silicon carbide powder mixing, sprayed on ground after magnetic agitation, after dry solidification to get；
In the step d, hydrophobic treatment step are as follows: silicon-carbide particle is dispersed in ethanol solution by being ultrasonically treated, so
Double ended type ammonia alkyl silicone oil is added afterwards, magnetic agitation, obtains modified Nano carborundum solution, wash by centrifugation at a certain temperature
It washs after drying to get hydrophobic silicon carbide powder；
The mass ratio of the hydrophobic silicon carbide powder and the modified polyurethane is 2~10:1.
2. a kind of preparation method of environmentally friendly super-hydrophobic coat according to claim 1, it is characterised in that: in step a, discard
The preparation step of edible oil fatty acid amide are as follows: sodium methoxide and diethanol amine are placed in a reaction flask first, open heater switch and
Magnetic stirring apparatus, heating stirring 20 minutes at 80 DEG C, the waste cooking oils after purification is then added dropwise in 60 minutes,
After waste cooking oils after purification are added completely into, reaction temperature is risen to 120 DEG C and continues to be stirred to react 3 at such a temperature small
When to get the molar ratio of the sodium methoxide, diethanol amine and waste cooking oils is 1:45:15.
3. a kind of preparation method of environmentally friendly super-hydrophobic coat according to claim 1, it is characterised in that: in step b, discard
The molar ratio 1:1.2 of edible oil fatty acid amide and toluene di-isocyanate(TDI) stirs 2h at 70 DEG C and reaches dumpable viscosity.
4. a kind of preparation method of environmentally friendly super-hydrophobic coat according to claim 2 or 3, it is characterised in that: in step c,
Double ended type ammonia alkyl silicone oil is added dropwise in base polyurethane prepolymer for use as, using acetone regulation system viscosity, is continued at 55 DEG C
3 hours are stirred to react to get modified polyurethane；The molar ratio of the base polyurethane prepolymer for use as and double ended type ammonia alkyl silicone oil is 1:
2。
5. a kind of preparation method of environmentally friendly super-hydrophobic coat according to claim 4, it is characterised in that: the hydrophobic place
It manages in step, silicon-carbide particle is dispersed in ethanol solution by ultrasonic treatment, continues 30min, double ended type ammonia is then added
Alkyl silicone oil, the magnetic agitation 4h at 70 DEG C.
6. a kind of preparation method of environmentally friendly super-hydrophobic coat according to claim 5, it is characterised in that: the double ended type
Ammonia alkyl silicone oil is synthesized by hydroxyl dimethyl silicone polymer and 3-aminopropyltriethoxysilane.
7. a kind of preparation method of environmentally friendly super-hydrophobic coat according to claim 6, it is characterised in that: described in step d
Silicon-carbide particle partial size be 30~100nm, grain shape is ball-type.
8. a kind of preparation method of environmentally friendly super-hydrophobic coat according to claim 7, it is characterised in that: described in step d
The mass ratio of silicon-carbide particle, ethanol solution and double ended type ammonia alkyl silicone oil is followed successively by 2:3:10, and drying temperature is 130 DEG C.
9. a kind of preparation method of environmentally friendly super-hydrophobic coat according to claim 8, it is characterised in that: the ground is
Glass, copper, aluminium or iron.
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