CN105567047A - Anti-freezing coating and preparation method thereof - Google Patents
Anti-freezing coating and preparation method thereof Download PDFInfo
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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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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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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Abstract
The invention discloses an anti-freezing coating which is prepared from, by weight, 110-120 parts of material A and 12-15 parts of material B. The material A is formed by mixing a main solution and an auxiliary solution. The material B is formed by mixing calcined kaolin powder, calcium carbonate powder and borax. The good anti-freezing performance of the coating can still be kept after repeated freezing and deicing processes.
Description
Technical field
The present invention relates to paint field, particularly a kind of freezing coating and preparation method thereof.
Background technology
At present, in cold climates, need, at the surface-coated such as equipment, road freezing coating, to occur to prevent freezing phenomena.Conventional freezing coating adopts the coating with super hydrophobic surface, and this coating has larger water contact angle, can prevent water droplet from freezing in coating surface aggegation.But, under some severe weather (as sleet etc.), even if also certain icing phenomenon can be produced at super hydrophobic surface, at this moment need manually to carry out deicing process or wait for nature deicing (temperature is melted after raising).Applicant finds through large quantity research, and for super hydrophobic surface, freezing repeatedly, after ice detachment, ice obviously strengthens at the sticking power of super hydrophobic surface, freezing time is obviously accelerated.This may be because icing, ice detachment repeatedly causes destruction to the micro nano structure of coatingsurface, water droplet is more easily gathered in the gap destroyed and formed, causes rapidly under cryogenic freezing.In addition applicant also finds, freezing repeatedly-ice detachment can reduce the low-temperature impact resistance of coating, makes its condition in cold very easily be subject to hail, ice rain etc. and impacts and damage inefficacy.
Summary of the invention
The object of this invention is to provide a kind of freezing coating and preparation method thereof, freezing repeatedly, still can keep good freezing performance after ice detachment.
To achieve these goals, a kind of freezing coating provided by the invention, is made up of the component of following weight part:
110 ~ 120 parts, A material;
12 ~ 15 parts, B material;
Described A material is prepared by following methods:
2-hydroxypropyl acrylate, ethylene glycol dimethacrylate and initiator are mixed, is dissolved in ethanol and stirs, make main solution;
Promoting agent and emulsifying agent are dissolved in ethanol, stir, obtain auxiliary solution;
Be added dropwise to gradually by main solution in auxiliary solution, temperature of reaction is 85 ~ 87 DEG C, and time for adding is 45 ~ 50min, when the color transition of reaction soln is white, stops dripping, reaction soln is left standstill 20-24 hour at 60 ~ 65 DEG C, obtain A material;
Described B material is prepared by following methods:
Get kaolin starting material to calcine, calcining temperature is warming up to 710 DEG C gradually from 650 DEG C, temperature rise rate is 5 DEG C/min, then at 710 DEG C, 1.5 hours are calcined again, be incubated 1 hour, discharging after naturally cooling, finally makes the kaolin starting material after calcining the calcined kaolin powder that mean particle size is below 300nm;
Get calcium carbonate, grind to form the Paris white of mean particle size 1-20 μm;
Calcined kaolin powder, Paris white and the borax mass ratio according to 3:2:1 is mixed, obtains B material.
Preferably, described initiator is dibenzoyl peroxide.
Preferably, in described main solution, the concentration of each component is: 2-hydroxypropyl acrylate 0.62 ~ 0.64mol/L, ethylene glycol dimethacrylate 7.1 ~ 7.4mmol/L, dibenzoyl peroxide 3.6 ~ 3.8mmol/L.
Preferably, in described main solution, the concentration of each component is: 2-hydroxypropyl acrylate 0.62mol/L, ethylene glycol dimethacrylate 7.1mmol/L, dibenzoyl peroxide 3.6mmol/L.
Preferably, described promoting agent is Sodium dodecylbenzene sulfonate, and described emulsifying agent is OP-15 emulsifying agent.
Preferably, the concentration of described Sodium dodecylbenzene sulfonate is 5.4 ~ 6.3mmol/L, and the concentration of described OP-15 emulsifying agent is 5.4 ~ 5.8mmol/L.
A preparation method for above-mentioned freezing coating, comprising:
Preparation A material:
2-hydroxypropyl acrylate, ethylene glycol dimethacrylate and initiator are mixed, is dissolved in ethanol and stirs, make main solution;
Promoting agent and emulsifying agent are dissolved in ethanol, stir, obtain auxiliary solution;
Be added dropwise to gradually by main solution in auxiliary solution, temperature of reaction is 85 ~ 87 DEG C, and time for adding is 45 ~ 50min, when the color transition of reaction soln is white, stops dripping, reaction soln is left standstill 20-24 hour at 60 ~ 65 DEG C, obtain A material;
Preparation B material:
Get kaolin starting material to calcine, calcining temperature is warming up to 710 DEG C gradually from 650 DEG C, temperature rise rate is 5 DEG C/min, then at 710 DEG C, 1.5 hours are calcined again, be incubated 1 hour, discharging after naturally cooling, finally makes the kaolin starting material after calcining the calcined kaolin powder that mean particle size is below 300nm;
Get calcium carbonate, grind to form the Paris white of mean particle size 1-20 μm;
Calcined kaolin powder, Paris white and the borax mass ratio according to 3:2:1 is mixed, obtains B material; And
Mixing: A material is expected to mix with B.
Preferably, described mixing is carried out under ultrasound condition.
Preferably, described ultrasound condition is: ultrasonic frequency 15KHz ~ 30KHz, and ultrasonic time is 2 ~ 5 hours.
A kind of freezing coating provided by the invention and preparation method thereof, by the considered critical to raw material and preparation process thereof, each component is functionally worked in coordination with each other, improve material repeatedly freeze-except the freezing performance under ice condition and low-temperature impact-resistant toughness.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of freezing coating provided by the present invention.
Embodiment
In order to make those skilled in the art person understand the present invention program better, below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment one
A kind of freezing coating that the present embodiment provides, is made up of the component of following weight part:
A expects 110 parts
B expects 15 parts
This coating preparation flow please refer to Fig. 1.
Wherein, A material is prepared by the following method:
2-hydroxypropyl acrylate (HPA), ethylene glycol dimethacrylate (EGD) and initiator dibenzoyl peroxide (BPO) are mixed, is dissolved in etoh solvent and stirs, make main solution; 2-hydroxypropyl acrylate concentration is 0.63mol/L, ethylene glycol dimethacrylate concentration is 7.2mmol/L, dibenzoyl peroxide concentration is 3.7mmol/L.
Sodium dodecylbenzene sulfonate and OP-15 emulsifying agent are dissolved in ethanol, stir, obtain auxiliary solution; The concentration of Sodium dodecylbenzene sulfonate is 5.4mmol/L, and the concentration of described OP-15 emulsifying agent is 5.8mmol/L.
Be added dropwise to gradually by main solution in auxiliary solution, temperature of reaction is 85 ~ 87 DEG C, and time for adding is 45 ~ 50min, when the color transition of reaction soln is white, stops dripping, reaction soln is left standstill 20 hours at 60 ~ 65 DEG C, obtain A material.
B material is prepared by the following method:
Get kaolin starting material to calcine, calcining temperature is warming up to 710 DEG C gradually from 650 DEG C, temperature rise rate is 5 DEG C/min, then at 710 DEG C, 1.5 hours are calcined again, be incubated 1 hour, discharging after naturally cooling, finally makes the kaolin starting material after calcining the calcined kaolin powder that mean particle size is below 300nm;
Get calcium carbonate, grind to form the Paris white that mean particle size is 10 μm;
Calcined kaolin powder, Paris white and the borax mass ratio according to 3:2:1 is mixed, obtains B material.
Mixing: A material and B material are mixed under ultrasound condition, carry out ultrasonic disperse process, ultrasonic frequency 15KHz, ultrasonic time is 5 hours.Freezing coating is obtained after discharging.
Embodiment two
A kind of freezing coating that the present embodiment provides, is made up of the component of following weight part:
A expects 120 parts
B expects 12 parts
This coating preparation flow please refer to Fig. 1.
Wherein, A material is prepared by the following method:
2-hydroxypropyl acrylate (HPA), ethylene glycol dimethacrylate (EGD) and initiator dibenzoyl peroxide (BPO) are mixed, is dissolved in etoh solvent and stirs, make main solution; 2-hydroxypropyl acrylate concentration is 0.64mol/L, ethylene glycol dimethacrylate concentration is 7.4mmol/L, dibenzoyl peroxide concentration is 3.8mmol/L.
Sodium dodecylbenzene sulfonate and OP-15 emulsifying agent are dissolved in ethanol, stir, obtain auxiliary solution; The concentration of Sodium dodecylbenzene sulfonate is 6.3mmol/L, and the concentration of described OP-15 emulsifying agent is 5.4mmol/L.
Be added dropwise to gradually by main solution in auxiliary solution, temperature of reaction is 85 ~ 87 DEG C, and time for adding is 45 ~ 50min, when the color transition of reaction soln is white, stops dripping, reaction soln is left standstill 24 hours at 60 ~ 65 DEG C, obtain A material.
B material is prepared by the following method:
Get kaolin starting material to calcine, calcining temperature is warming up to 710 DEG C gradually from 650 DEG C, temperature rise rate is 5 DEG C/min, then at 710 DEG C, 1.5 hours are calcined again, be incubated 1 hour, discharging after naturally cooling, finally makes the kaolin starting material after calcining the calcined kaolin powder that mean particle size is below 300nm;
Get calcium carbonate, grind to form the Paris white that mean particle size is 20 μm;
Calcined kaolin powder, Paris white and the borax mass ratio according to 3:2:1 is mixed, obtains B material.
Mixing: A material and B material are mixed under ultrasound condition, carry out ultrasonic disperse process, ultrasonic frequency 30KHz, ultrasonic time is 2 hours.Freezing coating is obtained after discharging.
Embodiment three
A kind of freezing coating that the present embodiment provides, is made up of the component of following weight part:
A expects 115 parts
B expects 15 parts
This coating preparation flow please refer to Fig. 1.
Wherein, A material is prepared by the following method:
2-hydroxypropyl acrylate (HPA), ethylene glycol dimethacrylate (EGD) and initiator dibenzoyl peroxide (BPO) are mixed, is dissolved in etoh solvent and stirs, make main solution; 2-hydroxypropyl acrylate concentration is 0.62mol/L, ethylene glycol dimethacrylate concentration is 7.1mmol/L, dibenzoyl peroxide concentration is 3.6mmol/L.
Sodium dodecylbenzene sulfonate and OP-15 emulsifying agent are dissolved in ethanol, stir, obtain auxiliary solution; The concentration of Sodium dodecylbenzene sulfonate is 6.3mmol/L, and the concentration of described OP-15 emulsifying agent is 5.6mmol/L.
Be added dropwise to gradually by main solution in auxiliary solution, temperature of reaction is 85 ~ 87 DEG C, and time for adding is 45 ~ 50min, when the color transition of reaction soln is white, stops dripping, reaction soln is left standstill 22 hours at 60 ~ 65 DEG C, obtain A material.
B material is prepared by the following method:
Get kaolin starting material to calcine, calcining temperature is warming up to 710 DEG C gradually from 650 DEG C, temperature rise rate is 5 DEG C/min, then at 710 DEG C, 1.5 hours are calcined again, be incubated 1 hour, discharging after naturally cooling, finally makes the kaolin starting material after calcining the calcined kaolin powder that mean particle size is below 300nm;
Get calcium carbonate, grind to form the Paris white that mean particle size is 10 μm;
Calcined kaolin powder, Paris white and the borax mass ratio according to 3:2:1 is mixed, obtains B material.
Mixing: A material and B material are mixed under ultrasound condition, carry out ultrasonic disperse process, ultrasonic frequency 20KHz, ultrasonic time is 3 hours.Freezing coating is obtained after discharging.
Comparative example one
A kind of freezing coating that the present embodiment provides, is made up of the component of following weight part:
A expects 100 parts
B expects 20 parts
This coating preparation flow please refer to Fig. 1.
Wherein, A material is prepared by the following method:
2-hydroxypropyl acrylate (HPA), ethylene glycol dimethacrylate (EGD) and initiator dibenzoyl peroxide (BPO) are mixed, is dissolved in etoh solvent and stirs, make main solution; 2-hydroxypropyl acrylate concentration is 0.58mol/L, ethylene glycol dimethacrylate concentration is 7.8mmol/L, dibenzoyl peroxide concentration is 3.2mmol/L.
Sodium dodecylbenzene sulfonate and OP-15 emulsifying agent are dissolved in ethanol, stir, obtain auxiliary solution; The concentration of Sodium dodecylbenzene sulfonate is 6.8mmol/L, and the concentration of described OP-15 emulsifying agent is 5.0mmol/L.
Be added dropwise to gradually by main solution in auxiliary solution, temperature of reaction is 70-80 DEG C, and time for adding is 45 ~ 50min, when the color transition of reaction soln is white, stops dripping, reaction soln is left standstill 16 hours at 70-80 DEG C, obtain A material.
B material is prepared by the following method:
Get kaolin starting material to calcine, calcining temperature is warming up to 700 DEG C gradually from 630 DEG C, temperature rise rate is 5 DEG C/min, then at 700 DEG C, 3 hours are calcined again, be incubated 2 hours, discharging after naturally cooling, finally makes the kaolin starting material after calcining the calcined kaolin powder that mean particle size is below 200nm;
Get calcium carbonate, grind to form the Paris white that mean particle size is 30 μm;
Calcined kaolin powder, Paris white and the borax mass ratio according to 2:2:1 is mixed, obtains B material.
Mixing: A material and B material are mixed under ultrasound condition, carry out ultrasonic disperse process, ultrasonic frequency 15KHz, ultrasonic time is 5 hours.Freezing coating is obtained after discharging.
Comparative example two
A kind of freezing coating that the present embodiment provides, is made up of the component of following weight part:
A expects 130 parts
B expects 10 parts
This coating preparation flow please refer to Fig. 1.
Wherein, A material is prepared by the following method:
2-hydroxypropyl acrylate (HPA), ethylene glycol dimethacrylate (EGD) and initiator dibenzoyl peroxide (BPO) are mixed, is dissolved in etoh solvent and stirs, make main solution; 2-hydroxypropyl acrylate concentration is 0.67mol/L, ethylene glycol dimethacrylate concentration is 6.5mmol/L, dibenzoyl peroxide concentration is 4.2mmol/L.
Sodium dodecylbenzene sulfonate and OP-15 emulsifying agent are dissolved in ethanol, stir, obtain auxiliary solution; The concentration of Sodium dodecylbenzene sulfonate is 5.0mmol/L, and the concentration of described OP-15 emulsifying agent is 6.3mmol/L.
Be added dropwise to gradually by main solution in auxiliary solution, temperature of reaction is 60-70 DEG C, and time for adding is 70 ~ 85min, when the color transition of reaction soln is white, stops dripping, reaction soln is left standstill 20 hours at 45 ~ 60 DEG C, obtain A material.
B material is prepared by the following method:
Get kaolin starting material to calcine, calcining temperature is warming up to 720 DEG C gradually from 670 DEG C, temperature rise rate is 5 DEG C/min, then at 720 DEG C, 1 hour is calcined again, be incubated 2 hours, discharging after naturally cooling, finally makes the kaolin starting material after calcining the calcined kaolin powder that mean particle size is below 400nm;
Get calcium carbonate, grind to form the Paris white that mean particle size is 30 μm;
Calcined kaolin powder, Paris white and the borax mass ratio according to 2:3:1 is mixed, obtains B material.
Mixing: A material and B material are mixed under ultrasound condition, carry out ultrasonic disperse process, ultrasonic frequency 15KHzKHz, ultrasonic time is 5 hours.Freezing coating is obtained after discharging.
Test example 1
Testing example 1 ~ 3 and comparative example 1,2 freezing coating repeatedly freezing-ice detachment after freezing ability.
Concrete grammar is:
1.1 sample preparations: by paint on substrate, obtain coating sample after drying.
1.2 water contact angles are measured: the water contact angle measuring sample coatings;
1.3 in coatingsurface watering, and inserts in refrigeration chamber, places 2 hours, take out after freezing at-10 DEG C.
1.4 surface is frozen after coating sample insert in whizzer centrifugal, until surperficial ice sheet under centrifugal force peel off after take out.
1.5 repeating step 1.3-1.4, realize, to the simulation of icing-deicing repeatedly, again carrying out water contact angle test after repeating 20 times to sample coatings.
By the test result record of twice water contact angle in front and back in Table 1
Table 1 water contact angle is tested
As seen from the results in Table 1, after freezing repeatedly-ice detachment, the invention provides freezing coating and still there is larger water contact angle, there is excellent freezing effect.
Test example 2
Testing example 1 ~ 3 and comparative example 1,2 freezing coating repeatedly freezing-ice detachment after low-temperature impact-resistant toughness.
Concrete grammar is:
1.1 sample preparations: by paint on substrate, obtain coating sample after drying.
1.2 low-temperature impact resistance tests: the shock-resistance measuring sample coatings at-10 DEG C, whether impact condition is: 1kg weight, 50cm Height Impact, observe surface and ftracture after impacting;
1.3 in coatingsurface watering, and inserts in refrigeration chamber, places 2 hours, take out after freezing at-10 DEG C.
1.4 surface is frozen after coating sample insert in whizzer centrifugal, until surperficial ice sheet under centrifugal force peel off after take out.
1.5 repeating step 1.3-1.4, realize the simulation to icing-deicing repeatedly, again carry out low-temperature impact resistance test to sample coatings after repeating 20 times, test condition is identical with 1.2.
By the test result record of twice low-temperature impact resistance in front and back in table 2.
Table 2 low-temperature impact resistance is tested
| Coatingsurface state | Coatingsurface state | |
| Embodiment one | Do not ftracture | Do not ftracture |
| Embodiment two | Do not ftracture | Do not ftracture |
| Embodiment three | Do not ftracture | Do not ftracture |
| Comparative example one | Do not ftracture | Cracking |
| Comparative example two | Do not ftracture | Cracking |
As seen from the results in Table 2, freezing coating provided by the invention is repeatedly freezing, after deicing process, is still having good low-temperature impact resistance.
Above freezing coating provided by the present invention and preparation method thereof is described in detail.Apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands core concept of the present invention for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (9)
1. a freezing coating, is characterized in that, is made up of the component of following weight part:
110 ~ 120 parts, A material;
12 ~ 15 parts, B material;
Described A material is prepared by following methods:
2-hydroxypropyl acrylate, ethylene glycol dimethacrylate and initiator are mixed, is dissolved in ethanol and stirs, make main solution;
Promoting agent and emulsifying agent are dissolved in ethanol, stir, obtain auxiliary solution;
Be added dropwise to gradually by main solution in auxiliary solution, temperature of reaction is 85 ~ 87 DEG C, and time for adding is 45 ~ 50min, when the color transition of reaction soln is white, stops dripping, reaction soln is left standstill 20-24 hour at 60 ~ 65 DEG C, obtain A material;
Described B material is prepared by following methods:
Get kaolin starting material to calcine, calcining temperature is warming up to 710 DEG C gradually from 650 DEG C, temperature rise rate is 5 DEG C/min, then at 710 DEG C, 1.5 hours are calcined again, be incubated 1 hour, discharging after naturally cooling, finally makes the kaolin starting material after calcining the calcined kaolin powder that mean particle size is below 300nm;
Get calcium carbonate, grind to form the Paris white of mean particle size 1-20 μm;
Calcined kaolin powder, Paris white and the borax mass ratio according to 3:2:1 is mixed, obtains B material.
2. freezing coating according to claim 1, is characterized in that, described initiator is dibenzoyl peroxide.
3. freezing coating according to claim 2, it is characterized in that, in described main solution, the concentration of each component is: 2-hydroxypropyl acrylate 0.62 ~ 0.64mol/L, ethylene glycol dimethacrylate 7.1 ~ 7.4mmol/L, dibenzoyl peroxide 3.6 ~ 3.8mmol/L.
4. freezing coating according to claim 3, is characterized in that, in described main solution, the concentration of each component is: 2-hydroxypropyl acrylate 0.62mol/L, ethylene glycol dimethacrylate 7.1mmol/L, dibenzoyl peroxide 3.6mmol/L.
5. freezing coating according to claim 4, is characterized in that, described promoting agent is Sodium dodecylbenzene sulfonate, and described emulsifying agent is OP-15 emulsifying agent.
6. freezing coating according to claim 5, is characterized in that, the concentration of described Sodium dodecylbenzene sulfonate is 5.4 ~ 6.3mmol/L, and the concentration of described OP-15 emulsifying agent is 5.4 ~ 5.8mmol/L.
7. a preparation method for freezing coating described in claim 1, is characterized in that, comprising:
Preparation A material:
2-hydroxypropyl acrylate, ethylene glycol dimethacrylate and initiator are mixed, is dissolved in ethanol and stirs, make main solution;
Promoting agent and emulsifying agent are dissolved in ethanol, stir, obtain auxiliary solution;
Be added dropwise to gradually by main solution in auxiliary solution, temperature of reaction is 85 ~ 87 DEG C, and time for adding is 45 ~ 50min, when the color transition of reaction soln is white, stops dripping, reaction soln is left standstill 20-24 hour at 60 ~ 65 DEG C, obtain A material;
Preparation B material:
Get kaolin starting material to calcine, calcining temperature is warming up to 710 DEG C gradually from 650 DEG C, temperature rise rate is 5 DEG C/min, then at 710 DEG C, 1.5 hours are calcined again, be incubated 1 hour, discharging after naturally cooling, finally makes the kaolin starting material after calcining the calcined kaolin powder that mean particle size is below 300nm;
Get calcium carbonate, grind to form the Paris white of mean particle size 1-20 μm;
Calcined kaolin powder, Paris white and the borax mass ratio according to 3:2:1 is mixed, obtains B material; And
Mixing: A material is expected to mix with B.
8. freezing coating according to claim 7, is characterized in that, described mixing is carried out under ultrasound condition.
9. freezing coating according to claim 8, is characterized in that, described ultrasound condition is: ultrasonic frequency 15KHz ~ 30KHz, and ultrasonic time is 2 ~ 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610075903.5A CN105567047A (en) | 2016-02-03 | 2016-02-03 | Anti-freezing coating and preparation method thereof |
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| CN103881510A (en) * | 2014-03-19 | 2014-06-25 | 湖州百胜涂料有限公司 | Preparation method of superhydrophobic nano thermal-insulation paint |
| CN104046077A (en) * | 2014-05-30 | 2014-09-17 | 青岛辰青信息技术有限公司 | Exterior-wall latex paint |
| KR101480105B1 (en) * | 2014-03-06 | 2015-01-07 | (주) 벽송하이텍 | Aqueous anti-corrosive and high weatherproof silicone acrylic paints using dissolved hydrogen water |
| CN104496540A (en) * | 2014-11-28 | 2015-04-08 | 陶宝进 | Waterproof material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101480105B1 (en) * | 2014-03-06 | 2015-01-07 | (주) 벽송하이텍 | Aqueous anti-corrosive and high weatherproof silicone acrylic paints using dissolved hydrogen water |
| CN103881510A (en) * | 2014-03-19 | 2014-06-25 | 湖州百胜涂料有限公司 | Preparation method of superhydrophobic nano thermal-insulation paint |
| CN104046077A (en) * | 2014-05-30 | 2014-09-17 | 青岛辰青信息技术有限公司 | Exterior-wall latex paint |
| CN104496540A (en) * | 2014-11-28 | 2015-04-08 | 陶宝进 | Waterproof material |
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