CN117777460A - Preparation method of POSS modified polyaspartic acid ester and polyurea coating - Google Patents
Preparation method of POSS modified polyaspartic acid ester and polyurea coating Download PDFInfo
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- CN117777460A CN117777460A CN202311835393.3A CN202311835393A CN117777460A CN 117777460 A CN117777460 A CN 117777460A CN 202311835393 A CN202311835393 A CN 202311835393A CN 117777460 A CN117777460 A CN 117777460A
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- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
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- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
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- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical group O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 20
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- Paints Or Removers (AREA)
Abstract
The application relates to the technical field of coatings, and particularly discloses a preparation method of POSS modified polyaspartic acid ester and a polyurea coating. The preparation method of the POSS modified polyaspartic acid ester comprises the following steps: s1, adding amino cage type polysilsesquioxane into polyaspartic acid ester, stirring, adding a base catalyst, and reacting for 5-16 hours, wherein the mass ratio of the amino cage type polysilsesquioxane to the polyaspartic acid ester to the base catalyst is 1:2-3:0.01-0.01; s2, adding an extraction liquid into the product obtained in the step S1, wherein the extraction liquid comprises ethyl acetate and water, extracting, and taking an upper layer solution for rotary evaporation. The method has simple steps and is easier for mass production, and the prepared POSS modified polyaspartic acid ester can be uniformly dispersed in a polyaspartic acid ester system, so that the coating has higher heat resistance and corrosion resistance, and is endowed with certain hydrophobicity and flame retardance.
Description
Technical Field
The application relates to the technical field of coatings, in particular to a preparation method of POSS modified polyaspartic acid ester and a polyurea coating.
Background
The polyaspartic acid ester resin is prepared by a Michael addition method of aliphatic or alicyclic diamine or polyamine and maleate or fumarate. The secondary amino group reactivity of the polyaspartic acid ester is lower than the hydroxyl group reactivity of the common polyurethane resin, the reaction speed is faster and slower, the longer trial period can be realized, the polyaspartic acid ester is not required to be baked, heated and cured, the molecular weight of the polyaspartic acid ester is small, the viscosity is low, and the polyaspartic acid ester can be constructed without adding a solvent, so that the polyaspartic acid ester is commonly used for being combined with isocyanate to prepare the environment-friendly coating. The coating construction mode can be spraying, compared with the prior polyurea system, no special and expensive construction equipment is needed, and the coating can be widely applied to the fields of corrosion protection of outdoor steel structures, petrochemical facility coating needing antistatic, heat insulation and corrosion protection, industrial coating of power equipment, protection of wind power towers and fan blades, concrete surface decoration protection, tunnel repair and the like.
In the prior art, the application number is that Chinese patent document discloses a polyurea type polyaspartic acid ester waterproof coating, which consists of a component A and a component B; the preparation raw materials of the component A comprise 90-110 parts of polyaspartic acid ester and 0-1 part of auxiliary agent according to parts by weight; the preparation raw materials of the component B comprise 70-90 parts of polyisocyanate and 15-25 parts of solvent according to parts by weight.
The polyurea type polyaspartic acid ester can have higher wear resistance, strength and cohesiveness, can be constructed in various modes, and forms a smooth coating on the surface of pouring and the like, but the problems that the polyaspartic acid ester has small molecular weight and high ester bond content in molecules, the contact angle between the prepared polyaspartic acid ester polyurea coating and water after reacting with isocyanate is lower, and the hydrophobicity and the water resistance are poor, and meanwhile, the corrosion resistance is deficient still exist.
Disclosure of Invention
In order to improve the hydrophobicity of the polyaspartic acid ester polyurea coating, the application provides a preparation method of POSS modified polyaspartic acid ester and the polyurea coating.
In a first aspect, the present application provides a preparation method of a POSS modified polyaspartic acid ester, which adopts the following technical scheme:
a preparation method of POSS modified polyaspartic acid ester comprises the following steps:
s1, adding amino cage type polysilsesquioxane into polyaspartic acid ester, stirring, adding a base catalyst, and reacting at 120-150 ℃ for 5-16 hours, wherein the mass ratio of the amino cage type polysilsesquioxane to the polyaspartic acid ester to the base catalyst is 1 (2-3) (0.01-0.01);
s2, adding an extraction liquid into the product obtained in the step S1, extracting the extraction liquid comprising ethyl acetate and water, and taking an upper layer solution for rotary evaporation to obtain POSS modified polyaspartic acid ester.
By adopting the technical scheme, the cage Polysilsesquioxane (POSS) is an inorganic-organic nano hybrid material with a three-dimensional space structure, si atoms are taken as vertexes, alternating Si-O-Si bonds form a cage-shaped structure, and organic functional groups are connected to the positions of the vertexes, so that the cage-shaped Polysilsesquioxane (POSS) has the advantages of inorganic-organic materials, and the cage-shaped polysilsesquioxane has excellent characteristics in mechanical property, thermal stability, chemical resistance, ultralow dielectric constant and biocompatibility; performing an ester ammonolysis reaction on the polyaspartic acid ester and the cage-type polysilsesquioxane with amino groups on the surface to form O=C-N bond, so that the amination cage-type polysilsesquioxane and the polyaspartic acid ester are chemically bonded, and the amination cage-type polysilsesquioxane is chemically grafted to the crown structure of the polyaspartic acid ester, so that the POSS modified polyaspartic acid ester has better heat resistance, corrosion resistance and hydrophobicity and flame retardance compared with a coating prepared from conventional polyaspartic acid ester; in addition, the preparation method of the POSS modified polyaspartic acid ester adopts chemical bonds to synthesize amide bonds, and the amino cage type polysilsesquioxane and the polyaspartic acid ester are firmly combined together, so that the amino cage type polysilsesquioxane has better dispersibility in the polyaspartic acid ester, and the performance of the amino cage type polysilsesquioxane is better exerted.
The coating formed by the material has a labyrinth effect and certain water repellency, the corrosion resistance of the coating is greatly improved, meanwhile, the application of the aminated cage-type polysilsesquioxane in the flame-retardant field is that the aminated cage-type polysilsesquioxane can form a compact silicon oxide film layer at high temperature due to the stable structure of Si-O-Si, and small molecules can be effectively prevented from escaping and dripping after the polymer is cracked, and oxygen and heat are prevented from being transferred into the polymer, so that the flame-retardant property of the coating is improved.
Optionally, the aminated cage polysilsesquioxane is an aminopropyl heptyl-cage polysilsesquioxane.
By adopting the technical scheme, amino groups are contained in the aminopropyl heptyl-cage type polysilsesquioxane, and the aminopropyl heptyl-cage type polysilsesquioxane and the polyaspartic acid ester are subjected to an ester ammonolysis reaction, so that the dispersibility of the aminated cage type polysilsesquioxane in the polyaspartic acid ester is improved, and the weather resistance, flame retardance and hydrophobicity of the polyaspartic acid ester type polyurea coating are improved.
Optionally, the polyaspartic acid ester is selected from any one of polyaspartic acid ester F420, polyaspartic acid ester F520, polyaspartic acid ester F220 and polyaspartic acid ester F330.
By adopting the technical scheme, the polyaspartic acid of the type can be subjected to ester ammonolysis reaction with the aminated cage-type polysilsesquioxane, so that a coating with excellent leveling property, glossiness, weather resistance and water resistance is formed.
Optionally, the stirring speed is 2000-3000r/min, and the stirring time is 2-3h.
By adopting the technical scheme, the stirring speed and the stirring time can ensure that the amination cage-type polysilsesquioxane and the polyaspartic acid ester are fully mixed and react.
Optionally, the alkali catalyst is ammonia water or sodium hydroxide solution with the concentration of 0.2-1 mol/l.
By adopting the technical scheme, ammonia water or sodium hydroxide solution is used as a base catalyst, so that the amination cage type polysilsesquioxane and the polyaspartic acid ester can undergo an ester ammonolysis reaction, the amination cage type polysilsesquioxane is grafted on the polyaspartic acid ester, and the dispersibility of the amination cage type polysilsesquioxane in the polyaspartic acid ester type polyurea coating is improved, so that the weather resistance, flame retardance and hydrophobicity of the polyurea coating are improved.
Optionally, the mass ratio of ethyl acetate to water in the extract is 1:20-200.
In a second aspect, the present application provides a polyurea coating, which adopts the following technical scheme:
a polyurea coating comprising the steps of: the material comprises the following raw materials in parts by weight: 8-12 parts of POSS modified polyaspartic acid ester, 75.6-84.4 parts of polyaspartic acid ester, 0.8-1.2 parts of defoamer, 0.8-1.2 parts of flatting agent and 6-10 parts of butyl ester solution.
By adopting the technical scheme, the POSS modified polyaspartic acid ester improves the dispersibility of the amino cage type polysilsesquioxane and the polyaspartic acid ester, and the amino cage type polysilsesquioxane has the advantages of good heat resistance, weather resistance and the like, and after being firmly combined with the polyaspartic acid ester, the POSS modified polyaspartic acid ester improves the weather resistance of the polyurea coating, and the coating has certain flame retardance and hydrophobicity.
Optionally, the polyurea coating further comprises 1-3 parts by weight of modified graphene oxide.
By adopting the technical scheme, the graphene oxide has a layered structure, and can be added into the coating layer by layer to form a more complex diffusion erosion prevention path, and the physical isolation effect of the graphene oxide is more obvious, so that the modified coating has better performance, and the corrosion resistance of the substrate can be improved when the modified coating is coated on the substrate such as metal; the graphene oxide can optimize the structure of the resin in a chemical bond forming mode, the arrangement uniformity among molecules is improved, the structural defects of the paint are reduced, a compact protective film is formed, the permeation resistance, adhesive force and impact resistance of the paint are further enhanced, the air tightness of the coating can be improved by the graphene oxide with a lamellar structure, the passing path of oxygen in the coating is increased, the thermal oxygen outside the material can be better isolated, and the temperature resistance of the film layer is better.
Optionally, the modified graphene oxide is pretreated by:
adding trisilyl-cage polysilsesquioxane into N-methylpyrrolidone, stirring for dissolving, adding nano silicon dioxide, performing ultrasonic dispersion for 20-30min, adding graphene oxide, dipping for 10-20min under negative pressure, filtering, drying, wherein the mass ratio of the graphene oxide to the trisilyl-cage polysilsesquioxane to the nano silicon dioxide is 1:0.2-0.4:0.05-0.1.
By adopting the technical scheme, the trisilyl phenyl-cage polysilsesquioxane is widely used in the fields of high temperature resistance and flame retardance by virtue of the rigidity and the super-excellent thermal stability of an aromatic hydrocarbon structure, contains active-Si-OH, can be dispersed in most organic solvents, is dissolved by NMP, and can form hydrogen bonds with hydroxyl groups on graphene oxide along with the infiltration of the solvent into graphene oxide under negative pressure; the nano silicon dioxide is added into the dissolved trisilyl-cage polysilsesquioxane, the trisilyl-cage polysilsesquioxane molecule contains a silicon bond and a silicon hydroxyl structure which are highly similar to those of silicon dioxide, and the nano silicon dioxide and the silicon bond and the hydroxyl on the surface of the nano silicon dioxide form chemical bond interaction, so that the nano silicon dioxide can be uniformly dispersed in the trisilyl-cage polysilsesquioxane, and is tightly wrapped by the trisilyl-cage polysilsesquioxane, the wear resistance and the corrosion resistance of the graphene oxide are improved, and the compactness and the corrosion resistance of a coating film are improved.
In a third aspect, the present application provides a POSS modified corrosion-resistant asparagus polyurea coating, which adopts the following technical scheme:
the POSS modified anticorrosion asparagus polyurea coating comprises a primer layer and a finish layer which are sequentially arranged from bottom to top, wherein the finish layer is formed by mixing and spraying a polyurea coating and an isocyanate curing agent according to the mass ratio of 100:96-100.
By adopting the technical scheme, the coating containing the POSS modified polyaspartic acid ester is used, and the aminated POSS is introduced, so that the corrosion resistance and weather resistance of the coating are improved, and certain flame retardance and hydrophobicity are endowed to the coating.
In summary, the present application has the following beneficial effects:
1. as the amination cage type polysilsesquioxane is adopted to carry out ester ammonolysis reaction liquid on the polyaspartic acid ester, the amination cage type polysilsesquioxane is chemically grafted on the crown structure of the polyaspartic acid ester, so that the dispersibility and the compatibility of the amination cage type polysilsesquioxane and the polyaspartic acid ester type polyurea coating are improved, the weather resistance, the corrosion resistance and the flame retardance of the coating are further enhanced, and the hydrophobicity and the water resistance of the coating are improved.
2. In the application, aminopropyl heptyl-cage polysilsesquioxane is preferably adopted to carry out chemical grafting reaction on polyaspartic acid ester, so that the heat resistance of the polyurea coating can be improved.
3. In the application, modified graphene oxide is preferably added into the polyurea coating, and is modified by trisilyl phenyl-cage polysilsesquioxane and nano silicon dioxide, so that the dispersibility of the graphene oxide in the polyurea coating is increased, the compactness of the coating is enhanced, the corrosion resistance and weather resistance of the coating are further improved, and the impact resistance is improved.
Detailed Description
The following examples illustrate the present application in further detail.
Preparation examples 1 to 4 of modified graphene oxide
In the preparation example, trisilanolphenyl-cage polysilsesquioxane is selected from the company of Fosman technology (Beijing), the product number is 9502013, nano silicon dioxide is selected from the company of New Material, jing Rui Guangzhou, the particle size is 10nm, graphene oxide is selected from Xianfeng nanometer, and the product number is 100602.
Preparation example 1: adding 9g of trisilyl-cage polysilsesquioxane into N-methylpyrrolidone, stirring and dissolving to prepare a solution with the concentration of 0.9g/10mL, adding nano silicon dioxide, performing ultrasonic dispersion for 20min at the power of 500W, adding graphene oxide, soaking for 20min under the pressure of-0.03 MPa, filtering, and drying, wherein the mass ratio of the graphene oxide, the trisilyl-cage polysilsesquioxane to the nano silicon dioxide is 1:0.4:0.1.
Preparation example 2: adding 6g of trisilyl-cage polysilsesquioxane into N-methylpyrrolidone, stirring and dissolving to prepare a solution with the concentration of 0.6g/10mL, adding nano silicon dioxide, performing ultrasonic dispersion for 10min at the power of 500W, adding graphene oxide, soaking for 10min under the pressure of-0.05 MPa, filtering, and drying, wherein the mass ratio of the graphene oxide, the trisilyl-cage polysilsesquioxane to the nano silicon dioxide is 1:0.2:0.05.
Preparation example 3: the difference from preparation 1 is that trisilanolphenyl-cage polysilsesquioxane is replaced with an equal amount of deionized water.
Preparation example 4: the difference from preparation example 1 is that no nanosilica was added.
Examples
In the examples, the aminopropyl heptyl-cage polysilsesquioxane is selected from the group consisting of Sian Ji Yue organism, ethyl acetate is selected from Shandong Taixi chemical Co., ltd, the polyaspartate is selected from the group consisting of Shenzhen Feiyang Jun research New Material Co., ltd, model F520, and the defoamer is selected from the group consisting of Yingzhang Industy, germany, modelAirex900, the leveling agent is selected from the group consisting of Pycnochemical Co., ltd. In Germany, model BYK-300,
example 1: a preparation method of POSS modified polyaspartic acid ester comprises the following steps:
s1, adding amino cage type polysilsesquioxane into polyaspartic acid ester, stirring for 3 hours at a stirring speed of 2000r/min, adding a base catalyst, and reacting for 16 hours at 120 ℃, wherein the mass ratio of the amino cage type polysilsesquioxane to the polyaspartic acid ester to the base catalyst is 1:3:0.01, the amino cage type polysilsesquioxane is aminopropyl heptyl-cage type polysilsesquioxane, the particle size is 3nm, and the base catalyst is sodium hydroxide solution with the concentration of 1 mol/L;
s2, adding an extraction liquid into the product obtained in the step S1, extracting the extraction liquid to obtain an upper layer solution, and performing rotary evaporation to obtain POSS modified polyaspartic acid ester, wherein the mass ratio of the ethyl acetate to the water is 1:20, and the temperature during rotary evaporation is 80 ℃ for 20min.
Example 2: a preparation method of POSS modified polyaspartic acid ester comprises the following steps:
s1, adding amino cage type polysilsesquioxane into polyaspartic acid ester, stirring for 2 hours at a stirring speed of 3000r/min, adding a base catalyst, and reacting for 5 hours at 150 ℃, wherein the mass ratio of the amino cage type polysilsesquioxane to the polyaspartic acid ester to the base catalyst is 1:3:0.1, the amino cage type polysilsesquioxane is aminopropyl heptyl-cage type polysilsesquioxane, the particle size is 1nm, and the base catalyst is sodium hydroxide solution with the concentration of 0.2 mol/L;
s2, adding an extraction liquid into the product obtained in the step S1, extracting the extraction liquid to obtain an upper layer solution, and performing rotary evaporation to obtain POSS modified polyaspartic acid ester, wherein the mass ratio of the ethyl acetate to the water is 1:200, and the temperature during rotary evaporation is 60 ℃ for 50min.
Example 3: a preparation method of POSS modified polyaspartic acid ester comprises the following steps:
s1, adding amino cage type polysilsesquioxane into polyaspartic acid ester, stirring for 2.5 hours at a stirring speed of 2500r/min, adding a base catalyst, and reacting at 140 ℃ for 8 hours, wherein the mass ratio of the amino cage type polysilsesquioxane to the polyaspartic acid ester to the base catalyst is 1:2:0.01, the amino cage type polysilsesquioxane is aminopropyl heptyl-cage type polysilsesquioxane, the particle size is 1nm, and the base catalyst is sodium hydroxide solution with the concentration of 0.6 mol/L;
s2, adding an extraction liquid into the product obtained in the step S1, extracting the extraction liquid to obtain an upper layer solution, and performing rotary evaporation to obtain POSS modified polyaspartic acid ester, wherein the mass ratio of the ethyl acetate to the water is 1:120, and the temperature during rotary evaporation is 70 ℃ for 40min.
Example 4: a preparation method of POSS modified polyaspartic acid ester comprises the following steps:
s1, adding amino cage type polysilsesquioxane into polyaspartic acid ester, stirring for 3 hours at a stirring speed of 2500r/min, adding a base catalyst, and reacting for 12 hours at 130 ℃, wherein the mass ratio of the amino cage type polysilsesquioxane to the polyaspartic acid ester to the base catalyst is 1:2:0.1, the amino cage type polysilsesquioxane is aminopropyl heptyl-cage type polysilsesquioxane, the particle size is 1nm, and the base catalyst is sodium hydroxide solution with the concentration of 0.8 mol/L;
s2, adding an extraction liquid into the product obtained in the step S1, extracting the extraction liquid to obtain an upper layer solution, and performing rotary evaporation to obtain POSS modified polyaspartic acid ester, wherein the mass ratio of the ethyl acetate to the water is 1:160, and the temperature during rotary evaporation is 80 ℃ for 50min.
Example 5: the polyurea coating comprises the following raw materials in parts by weight: 10kg of POSS modified polyaspartic acid ester prepared in example 1, 80kg of polyaspartic acid ester F520, 1kg of defoamer, 1kg of flatting agent and 8kg of butyl ester solution, and the preparation method of the polyurea coating comprises the following steps: and uniformly mixing the POSS modified polyaspartic acid ester, the polyaspartic acid ester F520, the defoamer, the flatting agent and the butyl ester solution to obtain the polyurea coating.
Example 6: a polyurea coating differs from example 5 in that POSS modified polyaspartic acid esters were made from example 2.
Example 7: a polyurea coating differs from example 5 in that POSS modified polyaspartic acid ester was prepared from example 3.
Example 8: a polyurea coating differs from example 5 in that POSS modified polyaspartic acid ester was prepared from example 4.
Example 9: a polyurea coating was distinguished from example 5 in that the starting material of the polyurea coating also included 3kg of modified graphene oxide, which was prepared from preparation example 1.
Example 10: a polyurea coating is distinguished from example 5 in that the starting material of the polyurea coating further comprises 1kg of modified graphene oxide, which is prepared from preparation example 2.
Example 11: a polyurea coating was distinguished from example 5 in that the starting material of the polyurea coating also included 3kg of modified graphene oxide, which was prepared from preparation example 3.
Example 12: a polyurea coating was distinguished from example 5 in that the starting material of the polyurea coating also included 3kg of modified graphene oxide, which was prepared from preparation example 4.
Application example 13: a polyurea coating differs from example 5 in that the starting material of the polyurea coating further comprises 3kg of graphene oxide selected from the group consisting of Nanfeng nanometers, having a product number of 100602.
Comparative example
Comparative example 1: a polyurea coating differs from example 5 in that an equivalent amount of polyaspartate F520 was used instead of the POSS modified polyaspartate made in example 1.
Application example
Application example 1: the POSS modified anticorrosion asparagus polyurea coating comprises a primer layer and a top coat layer which are sequentially arranged from bottom to top, wherein the primer layer is prepared by brushing epoxy paint, the epoxy paint is zinc-rich primer, the model is Earthwter P5160, the thickness of the primer layer is 30 mu m, the top coat is prepared by uniformly mixing the polyurea coating prepared in the example 5 with an isocyanate curing agent according to the mass ratio of 100:96 and then spraying the mixture on the primer layer, the isocyanate curing agent is selected from HDI trimer, the HDI trimer is selected from Shenzhen flying and grinding, the model is HT100, and the thickness of the top coat layer is 80 mu m.
Application example 2: the POSS modified anticorrosion asparagus polyurea coating is different from application example 1 in that the finish paint layer is prepared by uniformly mixing the polyurea coating prepared in example 6 with an isocyanate curing agent according to the mass ratio of 100:96 and then spraying the mixture on a primer layer, wherein the isocyanate curing agent is selected from HDI trimer, the HDI trimer is selected from Shenzhen fly courser grinding, the model is HT100, and the thickness of the finish paint layer is 80 mu m.
Application example 3: the POSS modified anticorrosion asparagus polyurea coating is different from application example 1 in that the finish paint layer is prepared by uniformly mixing the polyurea coating prepared in example 7 with an isocyanate curing agent according to the mass ratio of 100:96 and then spraying the mixture on a primer layer, wherein the isocyanate curing agent is selected from HDI trimer, the HDI trimer is selected from Shenzhen fly courser grinding, the model is HT100, and the thickness of the finish paint layer is 80 mu m.
Application example 4: the POSS modified anticorrosion asparagus polyurea coating is different from application example 1 in that the finish paint layer is prepared by uniformly mixing the polyurea coating prepared in example 8 with an isocyanate curing agent according to the mass ratio of 100:96 and then spraying the mixture on a primer layer, wherein the isocyanate curing agent is selected from HDI trimer, the HDI trimer is selected from Shenzhen fly courser grinding, the model is HT100, and the thickness of the finish paint layer is 80 mu m.
Application example 5: the POSS modified anticorrosion asparagus polyurea coating is different from application example 1 in that the finish paint layer is prepared by uniformly mixing the polyurea coating prepared in example 9 with an isocyanate curing agent according to the mass ratio of 100:96 and then spraying the mixture on a primer layer, wherein the isocyanate curing agent is selected from HDI trimer, the HDI trimer is selected from Shenzhen fly courser grinding, the model is HT100, and the thickness of the finish paint layer is 80 mu m.
Application example 6: the POSS modified anticorrosion asparagus polyurea coating is different from application example 1 in that the finish paint layer is prepared by uniformly mixing the polyurea coating prepared in example 10 with an isocyanate curing agent according to the mass ratio of 100:96 and then spraying the mixture on a primer layer, wherein the isocyanate curing agent is selected from HDI trimer, the HDI trimer is selected from Shenzhen fly courser grinding, the model is HT100, and the thickness of the finish paint layer is 80 mu m.
Application example 7: the POSS modified anticorrosion asparagus polyurea coating is different from application example 1 in that the finish paint layer is prepared by uniformly mixing the polyurea coating prepared in example 11 with an isocyanate curing agent according to the mass ratio of 100:96 and then spraying the mixture on a primer layer, wherein the isocyanate curing agent is selected from HDI trimer, the HDI trimer is selected from Shenzhen fly courser grinding, the model is HT100, and the thickness of the finish paint layer is 80 mu m.
Application example 8: the POSS modified anticorrosion asparagus polyurea coating is different from application example 1 in that the finish paint layer is prepared by uniformly mixing the polyurea coating prepared in example 12 with an isocyanate curing agent according to a mass ratio of 100:96 and then spraying the mixture on a primer layer, wherein the isocyanate curing agent is selected from HDI trimer, the HDI trimer is selected from Shenzhen fly courser grinding, the model is HT100, and the thickness of the finish paint layer is 80 mu m.
Application example 9: the POSS modified anticorrosion asparagus polyurea coating is prepared by uniformly mixing the polyurea coating prepared in example 13 with an isocyanate curing agent according to the mass ratio of 100:96, and then spraying the mixture on a primer layer, wherein the isocyanate curing agent is selected from HDI trimer, the HDI trimer is selected from Shenzhen fly courser, the model is HT100, and the thickness of the finish layer is 80 mu m.
Application example 10: the POSS modified anticorrosion asparagus polyurea coating is different from application example 1 in that the finish paint layer is prepared by uniformly mixing the polyurea coating prepared in comparative example 1 with an isocyanate curing agent according to the mass ratio of 100:96 and then spraying the mixture on a primer layer, wherein the isocyanate curing agent is selected from HDI trimer, the HDI trimer is selected from Shenzhen fly courser grinding, the model is HT100, and the thickness of the finish paint layer is 80 mu m.
Performance test
The POSS modified anticorrosion asparaurea coating was prepared according to the method in the application example, and the properties of the coating were examined with reference to the following method, and the examination results are recorded in table 1.
1. Salt spray resistance: the detection is carried out by referring to GB/T1771-2007 determination of neutral salt spray resistance of paint and varnish.
2. Aging resistance: detection is carried out by referring to GB/T16777-2008 building waterproof paint test method
3. Surface contact angle: the test was performed with reference to the 16 th coating contact angle test in GB/T13448-2019 method for color coated Steel sheet and Steel strip test.
4. Flame retardancy: the detection is carried out with reference to GB/T12441-2018 decorative fireproof paint and GB/T8624-2012 building materials and product combustion performance classification.
5. Heat resistance: the detection was carried out with reference to GB/T1735-2009 determination of heat resistance of paints and varnishes.
6. Impact resistance: GB/T1732-1993 "impact resistance assay of paint film".
7. Abrasion resistance (750 g/1000 r): the measurement was carried out according to GB/T1768-2996 method for measuring abrasion resistance of colored paint and varnish by rotating rubber grinding wheel.
TABLE 1
The polyurea coatings prepared in examples 5-8 were used in examples 1-4, respectively, and the polyurea coatings in examples 5-8 contained POSS modified polyaspartic acid esters prepared in examples 1-4, respectively, in combination with the data in examples 1-9 and Table 1, the data in Table 1 shows that the topcoat layers prepared in examples 1-4 have a large contact angle with water, good hydrophobic effect, and flame retardancy reaching class A, and impact resistance reaching 50kg cm -1 The salt spray resistance and the aging resistance are excellent.
Application example 5 and application example 6 also modified graphene oxide was added to the polyurea coating forming the topcoat layer, as compared to application example 1, and it is shown in table 1 that the coatings prepared in application example 5 and application example 6 still have excellent weather resistance, flame retardancy and hydrophobicity, and impact resistance is increased and abrasion resistance is further improved.
The polyurea coating prepared in application example 7 was used in example 11, and the modified graphene oxide added to the polyurea coating prepared in example 11 was prepared in preparation example 3, and the impact resistance, hydrophobicity and weather resistance of the topcoat layer prepared in application example 7 were slightly degraded, compared to application example 1.
The polyurea coating prepared in application example 8 using the polyurea coating prepared in example 12, in which the modified graphene oxide was prepared in preparation example 4, was reduced in impact resistance and abrasion resistance of the topcoat layer prepared in application example 8 as compared to application example 1.
The polyurea coating prepared in application example 9 and using example 13 contains unmodified graphene oxide, and compared with application example 1, the paint-free layer prepared in application example 9 has poor impact resistance and wear resistance due to poor compatibility of graphene oxide in the coating.
In application example 10, a top coat layer was formed using polyaspartate and an isocyanate curing agent, which had a lower contact angle, and a decrease in weather resistance and flame retardancy, as compared with application example 1.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. The preparation method of the POSS modified polyaspartic acid ester is characterized by comprising the following steps of:
s1, adding amino cage type polysilsesquioxane into polyaspartic acid ester, stirring, adding a base catalyst, and reacting at 120-150 ℃ for 5-16 hours, wherein the mass ratio of the amino cage type polysilsesquioxane to the polyaspartic acid ester to the base catalyst is 1 (2-3) (0.01-0.01);
s2, adding an extraction liquid into the product obtained in the step S1, extracting the extraction liquid comprising ethyl acetate and water, and taking an upper layer solution for rotary evaporation to obtain POSS modified polyaspartic acid ester.
2. The method for preparing POSS modified polyaspartic acid ester according to claim 1, characterized in that: the aminated cage-type polysilsesquioxane is aminopropyl heptyl-cage-type polysilsesquioxane.
3. The method for preparing POSS modified polyaspartic acid ester according to claim 1, characterized in that: the polyaspartic acid ester is selected from any one of polyaspartic acid ester F420, polyaspartic acid ester F520, polyaspartic acid ester F220 and polyaspartic acid ester F330.
4. The method for preparing POSS modified polyaspartic acid ester according to claim 1, characterized in that: the stirring speed is 2000-3000r/min, and the stirring time is 2-3h.
5. The method for preparing POSS modified polyaspartic acid ester according to claim 1, characterized in that: the alkali catalyst is ammonia water or sodium hydroxide solution with the concentration of 0.2-1 mol/l.
6. The method for preparing POSS modified polyaspartic acid ester according to claim 1, characterized in that: the mass ratio of ethyl acetate to water in the extract is 1:20-200.
7. The polyurea coating is characterized by comprising the following raw materials in parts by weight: 8-12 parts of POSS modified polyaspartic acid ester prepared by the preparation method of any one of claims 1-6, 75.6-84.4 parts of polyaspartic acid ester, 0.8-1.2 parts of defoamer, 0.8-1.2 parts of flatting agent and 6-10 parts of butyl ester solution.
8. The polyurea coating of claim 7, wherein: the polyurea coating also comprises 1-3 parts by weight of modified graphene oxide.
9. The polyurea coating of claim 8, wherein: the preparation method of the modified graphene oxide comprises the following steps:
adding trisilyl-cage polysilsesquioxane into N-methylpyrrolidone, stirring for dissolving, adding nano silicon dioxide, performing ultrasonic dispersion for 20-30min, adding graphene oxide, dipping for 10-20min under negative pressure, filtering, drying, wherein the mass ratio of the graphene oxide to the trisilyl-cage polysilsesquioxane to the nano silicon dioxide is 1:0.2-0.4:0.05-0.1.
10. A POSS modified anticorrosion asparagus polyurea coating, comprising a primer layer and a top-coat layer which are sequentially arranged from bottom to top, wherein the top-coat layer is formed by mixing and spraying the polyurea coating and the isocyanate curing agent according to the mass ratio of 100:96-100 in any one of claims 7-9.
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