Preparation method of super-hydrophobic flame-retardant coating with excellent performance

文档序号:1083184 发布日期:2020-10-20 浏览:12次 中文

阅读说明:本技术 一种具有优异性能的超疏水阻燃涂层的制备方法 (Preparation method of super-hydrophobic flame-retardant coating with excellent performance ) 是由 李宗晟 于 2020-06-24 设计创作,主要内容包括:本发明公开了一种具有优异性能的超疏水阻燃涂层的制备方法,制备步骤如下:取<Image he="24" wi="34" file="DEST_PATH_IMAGE002.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>分散于无水乙醇和氨水混合液中,超声搅拌后加热,将十八烷基三甲氧基硅烷加入至混合液中,得到溶液A;取双酚A型环氧树脂将其溶于无水乙醇中,采用超声搅拌,得到溶液B;将溶液A与溶液B混合均匀后迅速加入TEOS,并加入阻燃剂中间体继续搅拌,得到悬浮液C;将悬浮液C喷涂到基底上固化,即得到超疏水阻燃涂层;本发明的利用微纳米结构与环氧树脂相结合,成功制备出一种具有良好机械稳定性以及化学稳定性的阻燃超疏水涂层,该涂层制备成本较低,制备工艺简单,易于实现大规模工业化应用。(The invention discloses a preparation method of a super-hydrophobic flame-retardant coating with excellent performance, which comprises the following steps: get Dispersing in a mixed solution of absolute ethyl alcohol and ammonia water, heating after ultrasonic stirring, and adding octadecyltrimethoxysilane into the mixed solution to obtain a solution A; dissolving bisphenol A epoxy resin in absolute ethyl alcohol, and performing ultrasonic stirring to obtain a solution B; uniformly mixing the solution A and the solution B, quickly adding TEOS, adding a flame retardant intermediate, and continuously stirring to obtain a suspension C; spraying the suspension C on a substrate for curing to obtain the super-hydrophobicA flame retardant coating; the flame-retardant super-hydrophobic coating with good mechanical stability and chemical stability is successfully prepared by combining the micro-nano structure with the epoxy resin, and the coating is low in preparation cost, simple in preparation process and easy to realize large-scale industrial application.)

1. A preparation method of a super-hydrophobic flame-retardant coating with excellent performance is characterized by comprising the following steps: the method comprises the following specific steps:

the method comprises the following steps: get

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step two: adding octadecyltrimethoxysilane into the mixed solution, and stirring to obtain a solution A;

step three: dissolving bisphenol A epoxy resin in absolute ethyl alcohol, and ultrasonically stirring to obtain a solution B;

step four: mixing the solution A and the solution B, stirring and then quickly adding TEOS; adding the flame retardant intermediate, and continuously stirring to obtain a suspension C;

step five: and uniformly spraying the obtained suspension C on a substrate by using a spray gun, and curing to obtain the super-hydrophobic flame-retardant coating.

2. The method for preparing a super-hydrophobic flame retardant coating with excellent performance as claimed in claim 1, wherein: in the first step, the solution is dispersed in absolute ethyl alcohol and ammonia waterThe specification of (A) is two or more; dispersed in absolute ethyl alcohol

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3. The method for preparing a super-hydrophobic flame retardant coating with excellent performance as claimed in claim 1, wherein: in the first step, the ratio of absolute ethyl alcohol to ammonia water is 25: 1;the proportion of the anhydrous ethanol to the ammonia water is as follows: of two sizes per 0.2g

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4. The method for preparing a super-hydrophobic flame retardant coating with excellent performance as claimed in claim 1, wherein: in the second step, the ratio of the octadecyl trimethoxy silane to the absolute ethyl alcohol is as follows: 1 g of octadecyltrimethoxysilane, 10mL of anhydrous ethanol was added in volume.

5. The method for preparing a super-hydrophobic flame retardant coating with excellent performance as claimed in claim 1, wherein: in the third step, the proportion of the bisphenol A type epoxy resin to the absolute ethyl alcohol is as follows: 1 g of bisphenol A epoxy resin, 10mL of absolute ethanol in volume is added.

6. The method for preparing a super-hydrophobic flame retardant coating with excellent performance as claimed in claim 1, wherein: in the fourth step, the flame retardant intermediate is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

7. The method for preparing a super-hydrophobic flame retardant coating with excellent performance as claimed in claim 1, wherein: in the fourth step, the proportion of the solution A, the solution B, TEOS and the flame retardant intermediate is as follows: after mixing 1 part of solution A and 1 part of solution B, 0.6 mL TEOS and 0.5g flame retardant intermediate were added.

8. The method for preparing a super-hydrophobic flame retardant coating with excellent performance as claimed in claim 7, wherein: 1 part of solution A is 0.4g of 50nm

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9. The method for preparing a super-hydrophobic flame retardant coating with excellent performance as claimed in claim 1, wherein: in the fifth step, after spraying, the coating is cured at 60 ℃ for 1 hour.

10. The coating produced by the production method according to any one of claims 1 to 9, characterized in that: the super-hydrophobic flame-retardant coating with excellent performance is prepared by any one of the preparation methods.

Technical Field

The invention relates to the field of preparation of super-hydrophobic coatings, in particular to a preparation method of a super-hydrophobic flame-retardant coating with excellent performance.

Background

The super-hydrophobic surface is a material surface with a static contact angle of a water drop larger than 150 degrees and a rolling angle smaller than 10 degrees; inspired by the self-cleaning effect of lotus leaves in nature, the coating surface can form an air cushion physical barrier layer by using a unique micro-nano coarse structure and low surface energy property; the discovery is widely applied to the fields of self-cleaning, corrosion prevention, icing prevention, drag reduction and other engineering; however, with the rapid development of industrialization, a coating with a single property has not been able to meet the actual needs of people.

How to make the different properties compatible on the coating in practical applications; in the aspect of flame retardance, the preparation of the flame retardant at the present stage is usually dependent on polar groups such as phosphorus element, and the hydrophobicity requires that the polar groups on the surface of the coating are reduced as much as possible; meanwhile, the physical abrasion or the complex use environments such as strong acid and high temperature generally affect the performance of the coating, and even the coating directly loses lyophobicity seriously; in addition, most of the current research on the super-hydrophobic coating focuses on the laboratory stage, and large-scale industrial application is difficult to realize.

Disclosure of Invention

In order to overcome the problems, the invention provides a preparation method of a super-hydrophobic flame-retardant coating with excellent performance, a micro-nano structure is combined with epoxy resin to successfully prepare the flame-retardant super-hydrophobic coating with good mechanical stability and chemical stability, so that different performances are compatible on the coating, and more importantly, the coating has the advantages of low preparation cost, simple preparation process and easy realization of large-scale industrial application.

In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a super-hydrophobic flame-retardant coating with excellent performance is characterized by comprising the following steps: the method comprises the following specific steps:

the method comprises the following steps: getDispersing in the mixed solution of absolute ethyl alcohol and ammonia water, ultrasonically stirring, and heating;

step two: adding octadecyltrimethoxysilane into the mixed solution, and stirring to obtain a solution A;

step three: dissolving bisphenol A epoxy resin in absolute ethyl alcohol, and performing ultrasonic stirring to fully dissolve the bisphenol A epoxy resin to obtain a solution B;

step four: mixing the solution A and the solution B, stirring uniformly, and then quickly adding TEOS; adding the flame retardant intermediate, and continuously stirring to obtain a suspension C;

step five: and uniformly spraying the obtained suspension C on a substrate by using a spray gun, and curing to obtain the super-hydrophobic flame-retardant coating.

Further, in the first step, the solution is dispersed in absolute ethyl alcohol and ammonia waterThe specification of (A) is two or more; dispersed in absolute ethyl alcoholAnd dispersed in aqueous ammoniaThe particle diameter ratio of (a) to (b) is preferably 1: 100.

Further, in the first step, the ratio of the absolute ethyl alcohol to the ammonia water is 25: 1.

Further, in the first step,

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the proportion of the anhydrous ethanol to the ammonia water is as follows: of two sizes per 0.2g

Figure 6516DEST_PATH_IMAGE001

Dispersed in 25 mL of absolute ethanol and 1 mL of ammonia water, respectively.

Further, in the second step, the ratio of the octadecyl trimethoxy silane to the absolute ethyl alcohol is as follows: 1 g of octadecyltrimethoxysilane, 10mL of anhydrous ethanol was added in volume.

Further, in the third step, the ratio of the bisphenol a epoxy resin to the absolute ethyl alcohol is as follows: 1 g of bisphenol A epoxy resin, 10mL of absolute ethanol in volume is added.

Further, in the fourth step, the flame retardant intermediate is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Further, in the fourth step, the ratio of the solution a, the solution B, TEOS and the flame retardant intermediate is: after mixing 1 part of solution A and 1 part of solution B, 0.6 ml of TEOS and 0.5g of a flame retardant intermediate were added.

Further, in the fourth step, 0.4g of 50nm solution A is taken as 1 part、0.4 g 5 μmDispersing in 50 mL of mixed solution of anhydrous ethanol and 2 mL of ammonia water, ultrasonically stirring for 30 min, heating at 60 ℃, dropwise adding 1 mL of octadecyl trimethoxy silane into the mixed solution, and stirring at 60 ℃ for 4 hours to obtain the product; and 1 part of solution B is obtained by taking 1 g of bisphenol A epoxy resin, dissolving the bisphenol A epoxy resin in 10mL of absolute ethyl alcohol, and carrying out ultrasonic stirring for 30 min to fully dissolve the bisphenol A epoxy resin.

Further, in step five, after spraying, curing was carried out at 60 ℃ for 1 hour.

The super-hydrophobic flame-retardant coating with excellent performance is prepared by the preparation method of the super-hydrophobic flame-retardant coating with excellent performance in the first to fifth steps, and the prepared coating is within the protection scope of the application. In a specific embodiment, the superhydrophobic flame retardant coating of the present application was tested for mechanical stability, coating chemical stability, and flame retardant properties of the coating, respectively. In the mechanical stability test, two physical destructive means (sandpaper abrasion and tape stripping) were selected to test the mechanical stability of the multifunctional coating on the glass substrate; in the chemical stability test of the coating, a strong corrosive environment, an extreme temperature environment, ultraviolet irradiation and thermal fluid impact are selected for testing; among the tests of flame retardancy of the coating, the smoke density test and the limiting oxygen index and contact angle test were selected.

As a better technical solution, the stepsIn one section

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Are two or more, including but not limited to 50nm

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、5μm(ii) a In the step one

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The proportion of the alcohol to the absolute ethyl alcohol and the proportion of the ammonia water to the absolute ethyl alcohol are respectively as follows:

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0.8 g, 50 mL of absolute ethyl alcohol and 2 mL of ammonia water; in the step one

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The proportion of the anhydrous ethanol to the ammonia water is as follows: 0.4g 50nm、0.4 g 5μm50 mL of absolute ethyl alcohol and 2 mL of ammonia water.

As a better technical scheme, in the first step, heating is carried out at 60 ℃ after ultrasonic stirring is carried out for 30 min; in the second step, the octadecyl trimethoxy silane is dropwise added into the mixed solution A, and the stirring time is 4 hours at 60 ℃; in the third step, ultrasonic stirring is carried out for 30 min.

As a better technical solution, the suspension C in the fourth step is prepared by: taking 0.4g of 50nm、0.4 g 5 μm

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Dispersing in 50 mL of mixed solution of anhydrous ethanol and 2 mL of ammonia water, ultrasonically stirring for 30 min, heating at 60 ℃, dropwise adding 1 mL of octadecyl trimethoxy silane into the mixed solution, and stirring at 60 ℃ for 4 hours to obtain solution A. Dissolving 1 g of bisphenol A epoxy resin in 10mL of absolute ethyl alcohol, and ultrasonically stirring for 30 min to fully dissolve the bisphenol A epoxy resin to obtain a solution B. Mixing the solution A and the solution B, stirring uniformly at 60 ℃, quickly adding 0.6 mL TEOS, adding 0.5g9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and continuously stirring for two hours to obtain a suspension C.

As a better technical proposal, the obtained suspension C is evenly sprayed on a substrate by a spray gun and cured for 1 hour at 60 ℃, thus obtaining the multifunctional coating with excellent performance.

Compared with the prior art, the preparation method of the super-hydrophobic flame-retardant coating with excellent performance successfully prepares the flame-retardant super-hydrophobic coating with good mechanical stability and chemical stability by combining the micro-nano structure with the epoxy resin, and more importantly, the coating has the advantages of low preparation cost, simple preparation process and easy realization of large-scale industrial application.

The parts not involved in the scheme are the same as or can be realized by the prior art.

Drawings

Fig. 1 is a test chart of mechanical stability and chemical stability of a preparation method of a super-hydrophobic flame retardant coating with excellent performance according to the present invention.

FIG. 2 is a coating flame retardant property test chart of a preparation method of a super-hydrophobic flame retardant coating with excellent performance according to the invention.

Detailed Description

The super-hydrophobic flame-retardant coating disclosed by the invention is used for testing the mechanical stability, the chemical stability and the flame-retardant property of the coating. In the mechanical stability test, two physical destructive means (sandpaper abrasion and tape stripping) were selected to test the mechanical stability of the multifunctional coating on the glass substrate; in the chemical stability test of the coating, a strong corrosive environment, an extreme temperature environment, ultraviolet irradiation and thermal fluid impact are selected for testing; among the tests of flame retardancy of the coating, the smoke density test and the limiting oxygen index and contact angle test were selected.

As shown in FIGS. 1-2, in FIG. 1, FIGS. 1(a-b) are the mechanical property tests of the coating; wherein FIG. 1(a) is a coating peel test; FIG. 1(b) is a coating rub cycle test. FIG. 1(c-f) is a coating chemical stability test; FIG. 1(c) is a corrosion resistance test of the coating; FIG. 1(d) is an extreme temperature resistance test of the coating; FIG. 1(e) is a UV radiation resistance test of the coating; FIG. 1(f) is a coating hot fluid resistance test.

FIG. 2 is a flame retardant performance test of the coatings of the present invention. In which fig. 2 (a) is a smoke density test and fig. 2 (b) is a limiting oxygen index and contact angle test.

The invention relates to a preparation method of a super-hydrophobic flame-retardant coating with excellent performance, which comprises the following preparation steps:

the method comprises the following steps: taking 0.4g of 50nm、0.4 g 5μmDispersing in 50 mL of anhydrous ethanol and 2 mL of ammonia water mixed solution, ultrasonically stirring for 30 min, and heating at 60 ℃;

step two: 1 mL of octadecyltrimethoxysilane was added dropwise to the mixture and stirred at 60 ℃ for 4 hours to give solution A.

Step three: 1 g of bisphenol A epoxy resin is taken and dissolved in 10mL of absolute ethyl alcohol, and the solution is stirred for 30 min by ultrasonic agitation to be fully dissolved, namely solution B.

Step four: and mixing the solution A and the solution B, stirring uniformly at 60 ℃, quickly adding 0.6 mL TEOS, adding 0.5g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and continuously stirring for two hours to obtain a suspension C.

Step five: and uniformly spraying the obtained suspension C on a substrate by using a spray gun, and curing for 1 hour at the temperature of 60 ℃ to obtain the multifunctional coating with excellent performance.

Fig. 1(a-b) is a mechanical stability test of the coating of the present invention. In the present invention, two physical destructive means (sandpaper abrasion and tape stripping) were chosen to test the mechanical stability of the multifunctional coating on the glass substrate. The reason why the mechanical stability test of the coating material was performed is that: the mechanical stability of the coating material is crucial to the indoor and outdoor practical application of multifunctional coatings; generally, superhydrophobic coatings exhibit poor mechanical stability; because the excellent lyophobic performance is highly dependent on a fragile micro-nano structure, the coating is easy to lose the lyophobic performance after suffering a series of physical damages, such as abrasive paper abrasion and adhesive tape stripping; this makes it difficult to realize large-scale industrial applications. Thus, the coatings of the present invention were tested for mechanical stability.

Test environment (1) tape stripping: in the tape peeling test, a piece of tape was stuck to 3cm × 6cm glass having a coating layer and then peeled off; after 50 peeling cycles, the contact angle of water was still 150 ° or more, and the sliding angle was 10 ° or less. As shown in fig. 1(a), the good lyophobicity of the coating is not lost;

test environment (2) sandpaper wear: in the rub resistance test, a coated glass sheet was inverted over a 800 cw model of sandpaper, loaded with a 200 g weight, pulled 10 cm defined as a rubbing cycle, and tested for coating repellency by water drop contact angle. As shown in fig. 1(b), after 40 friction cycles, the super-hydrophobic flame retardant coating of the present invention still has a good lyophobicity with a water contact angle of about 150 °. It is thus clear that the coating according to the invention has good mechanical stability.

The chemical stability of the coating is tested, and the specific environment for testing is as follows: resistance to highly corrosive environments, extreme temperature environments, ultraviolet radiation, and thermal fluid impingement. The reason why the test in a severe environment is performed is that: the mechanical damage only damages the surface of the coating, and when the stability of the coating is tested, the influence of the change of the internal structure of the coating on the performance cannot be measured only by using the mechanical strength, so that the chemical stability of the coating needs to be researched.

The test environment 1 is used for testing the chemical stability of the coating in a strong corrosive environment, wherein the strong corrosive environment is as follows: aqua regia is used for simulating a harsh chemical corrosion environment; aqua regia is high-concentration hydrochloric acid and nitric acid, and the ratio of 3: 1 by volume. The coated glass sheet was immersed in a beaker containing aqua regia for 20 minutes for one cycle period, taken out, rinsed with water and dried, and the contact angle and sliding angle of a water drop were measured.

The results are shown in fig. 1(c), after soaking in aqua regia for 60 minutes, the contact angle of water is still around 150 degrees, and the sliding angle is still below 10 degrees, which indicates that the coating of the invention still has excellent lyophobic performance, i.e. the coating can keep good stability under extreme corrosive environment. Fig. 1(c) is additionally described: in the ordinate corresponding to 0-60 minutes, the higher is the contact angle, and the lower is the sliding angle; on the ordinate in fig. 1(c), the left side is the contact angle (in °), and the right side is the sliding angle (in °).

Test environment 2, the present invention tests the chemical stability of the coating in an extreme temperature environment, where extreme temperature: in the aspect of low temperature resistance, the coating is placed in an environment at the temperature of minus 25 ℃ for 6 hours and then taken out, and the coating is to be tested after being recovered to the room temperature; in the aspect of high temperature resistance, the coating is placed in an environment of 250 ℃ for 6h and then taken out, and the coating is recovered to room temperature to be tested.

As shown in fig. 1(d), the contact angle and the sliding angle of the water drop are used to test the performance of the coating, and it can be seen that the contact angle and the sliding angle of the water drop measured at 25 ℃ are not greatly different, so that the coating can be judged to have good performance of resisting extreme temperature.

And 3, testing the chemical stability of the coating in an ultraviolet irradiation environment, wherein the ultraviolet irradiation can possibly cause the coating to lose the performance, so that an ultraviolet irradiation lamp is used as a radiation source to explore the ultraviolet resistance of the coating. The coating was sprayed onto a glass slide substrate and irradiated with 245nm UV light for a long period of 24h with little change in the contact angle of the water droplet and the sliding angle.

The results are shown in fig. 1(e), demonstrating that the coating of the present invention has good uv resistance and can be applied on a large scale in an outdoor environment.

Test environment 4, the present invention tests the chemical stability of the coating in hot fluid resistance, where hot fluid resistance: taking water and ethylene glycol as examples, it can be seen that the contact angle of the water drop gradually decreases but still remains at 155 ° or more with almost no change in the sliding angle as the temperature of water and ethylene glycol increases.

The results are shown in fig. 1(f), indicating that the coating also has good resistance to hot fluids. The conclusion is reached: the coating disclosed by the invention can still keep excellent performance in a severe environment, and can meet the application expectation in the severe environment. Fig. 1(f) is additionally described: the four fold lines are respectively as follows from top to bottom: contact angle of water, contact angle of ethylene glycol, sliding angle of water.

The test results of the present invention in test environments 1-4 show that: the coating formula disclosed by the invention can keep good stability in a severe environment.

FIG. 2 is a flame retardant performance test of the coatings of the present invention. In which fig. 2 (a) is a smoke density test and fig. 2 (b) is a limiting oxygen index and contact angle test. The coating disclosed by the invention has good flame retardant property, the flame retardant property of the coating is explored through smoke density test, limiting oxygen index and contact angle test, and specifically, the flame retardant property of the coating is explored through modifying PU by using the coating and then various numerical values after the PU is combusted.

As shown in FIG. 2 (a), the flame retardant property of the coating is explored through the smoke density, and according to GB/T8323.2-2008, the smoke density of the blank PU and the modified PU is tested on a ZY6166D smoke density experimental device, and it can be seen that compared with the smoke density peak value of the blank PU, the smoke density peak value of the modified PU is reduced by 39.3%. The result shows that the PU is modified by the coating, so that the release of toxic gases such as carbon monoxide, carbon dioxide and the like can be greatly reduced when a fire disaster happens.

As shown in fig. 2 (b), the present invention tests the limiting oxygen index, contact angle, etc. of the material before and after modification. The limit oxygen index of the sample is tested on an FTT0077 oxygen index measuring instrument according to GB/T2406.2-2009, and the result shows that the limit oxygen index of blank PU is about 16.6%, and the blank PU belongs to flammable grade; after modification, the limiting oxygen index of PU is about 27.2 percent, the flame retardant grade is achieved, and the material is changed from a super-hydrophilic state with a contact angle of 0 degrees to a super-hydrophobic state with a contact angle of 163 degrees.

According to the invention, the silicon dioxide with different particle sizes and the carbon-containing chain are combined to prepare the super-hydrophobic coating with excellent performance, and the super-hydrophobic coating has mechanical stability, chemical stability and good flame retardant property; the preparation cost is low, the preparation process is simple, and the preparation method has large-scale industrial value.

The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

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