Heat-insulating coating for architectural glass and method for preparing the same

Abstract

The application relates to the technical field of high polymer coating and discloses heat-insulating coating for building glass and a preparation method thereof.The heat-insulating coating for building glass comprises the following raw materials: methyl methacrylate, ethyl methacrylate, propyl acrylate, alkenyl titanium dioxide, acetone, sodium dodecyl benzene sulfonate, an initiator, a film-forming aid, a defoaming agent and multifunctional cross-linking additive.Through the participation of the multifunctional cross-linking additive in the preparation process of the heat-insulating coating for building glass, the selective property of the alkenyl titanium dioxide to the sunlight spectrum is utilized to shield infrared light and block ultraviolet light, so that the heat-insulating effect of the coating is realized; the prepared coating has excellent mechanical strength, corrosion resistance, adhesion, waterproof and antifouling properties and heat-insulating effect and has a long service life.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer coating, in particular to a heat insulation coating for building glass and a preparation method thereof. BACKGROUND

[0002] With the acceleration of urbanization, glass has become an indispensable building material. Due to its transparent and smooth surface, it is widely used in the fields of curtain walls and windows of commercial buildings, significantly improving the aesthetics of buildings. However, ordinary glass has poor heat insulation performance. When the external temperature is high, the glass absorbs a large amount of heat energy, which easily leads to an increase in the temperature inside the building. When the external temperature is low, the glass radiates a large amount of heat energy to the outside, which leads to a decrease in the temperature inside the building, affecting people's living and working experience.

[0003] In order to improve the heat insulation performance of building glass, heat insulation coatings for building glass have emerged. The coatings are applied to the glass, and a protective film is formed after curing, giving the glass heat insulation effect. However, the mechanical properties of traditional heat insulation coatings for building glass are poor, and the water resistance, corrosion resistance and adhesion are poor, resulting in a short service life and difficulty in meeting the use requirements in various environments. In order to improve the performance of building glass coatings, people often modify them during use. For example, the patent with publication number CN105086537B discloses a transparent super-hydrophobic self-cleaning coating. The silica nanoparticles with active hydrophobic groups are synthesized by one-step direct hydrolysis method, and then the coating is prepared, obtaining a high transparent self-cleaning coating. The coating has good self-cleaning function, good water and stain resistance, corrosion resistance and excellent adhesion, and can be widely used in building glass curtain walls with good service life. For example, the patent with publication number CN101851461B discloses a two-component water-based polyurethane glass transparent heat insulation coating. The coating has low VOC, high transparency, high hardness, strong adhesion, good water resistance, excellent infrared reflectivity and weather resistance, and can bring people an excellent living experience when applied to building glass. SUMMARY

[0004] The present application aims to provide a heat insulation coating for building glass and a preparation method thereof, which solves the following technical problems: (1) the adhesion and mechanical strength of ordinary heat insulation coatings for building glass are poor, and the service life is short; (2) the water resistance and corrosion resistance of ordinary heat insulation coatings for building glass are poor.

[0005] The object of the present application can be achieved by the following technical solutions:

[0006] The application discloses a heat insulation coating for building glass, which comprises the following raw materials in parts by weight: 20-25 parts of methyl methacrylate, 15-20 parts of ethyl methacrylate, 12-15 parts of propyl acrylate, 6-10 parts of alkenyl titanium dioxide, 50-100 parts of acetone, 2-5 parts of sodium dodecyl benzene sulfonate, 3-5 parts of an initiator, 2-3 parts of a film forming aid, and 3-5 parts of an antifoaming agent; and further comprises 10-12 parts of a multifunctional cross-linking additive.

[0007] Further, the preparation method of the alkenyl titanium dioxide is as follows:

[0008] The nano titanium dioxide is placed in anhydrous ethanol, ultrasonically dispersed for 10-15 min, silane coupling agent KH570 is added, an oxalic acid solution with a concentration of 1-2 mol / L is used to adjust the pH to 4-5, the temperature is raised to 65-70 DEG C, and the reaction is carried out for 2-3 h; after filtration, washing and drying, the alkenyl titanium dioxide is obtained.

[0009] In the scheme, the nano titanium dioxide is modified by KH570 to obtain the alkenyl titanium dioxide, which is involved in the free radical polymerization process of the coating mixed solution, so that it can be uniformly dispersed, the mechanical properties and the hydrophobic ability of the coating are enhanced, the reflection performance of the coating is improved by using the ideal selectivity of the alkenyl titanium dioxide to the sunlight spectrum and the high refractive index, the surface temperature of the coating is reduced by radiation heat exchange, and the coating has excellent heat insulation effect.

[0010] Further, the initiator is any one of azobisisobutyronitrile and azobisisoheptyl nitrile; the film forming aid is any one of adipic dihydrazide and malonic dihydrazide; and the antifoaming agent is any one of dimethyl silicone oil and polyethylene oxide alcohol.

[0011] Further, the preparation method of the multifunctional cross-linking additive comprises the following steps:

[0012] S1: polyether amine and methyl-5-norbornene-2,3-dicarboxylic anhydride are placed in toluene, a catalyst is added after sufficient stirring, the temperature is raised to 60-70 DEG C, the reaction is carried out for 5-8 h, the product is collected after vacuum distillation, and the modified polyether amine is obtained;

[0013] S2: the modified polyether amine is placed in N, N-dimethyl formamide, 1 H, 1 H, 2H, 2H-tridecafluoro-1-n-octanol and p-toluenesulfonic acid are added, the temperature is raised to carry out the reaction, the temperature is lowered to room temperature, and the product is collected, so that the multifunctional cross-linking additive is obtained.

[0014] In the scheme, under the action of the catalyst, the amino groups at both ends of the polyether amine undergo ring-opening reaction with the anhydride groups in the structure of methyl-5-norbornene-2,3-dicarboxylic anhydride, to obtain modified polyether amine with double bonds and carboxyl groups at both ends, and then under the action of p-toluenesulfonic acid, the carboxyl groups at both ends of the modified polyether amine undergo esterification reaction with the hydroxyl groups in the structure of 1H,1H,2H,2H-tridecafluoro-1-n-octanol, to obtain a multifunctional crosslinking additive. The multifunctional crosslinking additive is involved in the free radical polymerization process of the coating mixture, the double bonds at both ends of the structure can undergo crosslinking reaction with the matrix to form a crosslinked structure, thereby improving the mechanical properties of the coating, the multiple ether bonds in the structure can enhance the adhesion between the coating and the glass, thereby reducing the risk of coating peeling, the norbornene groups in the structure have a chair structure, which can enhance the mechanical strength of the coating, and the structure also contains a large number of carbon-fluorine bonds, which can produce a synergistic effect with titanium dioxide in the coating matrix, thereby improving the waterproof and antifouling properties and corrosion resistance of the coating, and prolonging the service life of the coating.

[0015] Further, in step S1, the weight average molecular weight of the polyether amine is 2000-5000.

[0016] Further, in step S1, the catalyst is ferric chloride.

[0017] Further, in step S2, the reaction temperature is 110-120 DEG C, and the time is 6-8 h.

[0018] A preparation method of a heat insulation coating for building glass, comprising the following steps:

[0019] Step one, methyl methacrylate, ethyl methacrylate, propyl acrylate, alkenyl titanium dioxide and multifunctional crosslinking additive are added to acetone and mixed thoroughly, sodium dodecylbenzenesulfonate is added and stirred thoroughly to form a mixture;

[0020] Step two, an initiator is added to the mixture, the temperature is raised to 50-55 DEG C and reacted for 5-8 h, then the temperature is lowered to room temperature, film-forming aids and defoaming agents are added, stirred for 2-3 h, and then discharged to obtain a heat insulation coating for building glass.

[0021] The beneficial effects of the present application are as follows:

[0022] The multifunctional cross-linking additive is prepared and participates in the preparation process of the heat insulation coating for building glass, the infrared light is shielded and the ultraviolet light is blocked by using the selectivity of the alkenyl titanium dioxide to the sunlight spectrum, so that the heat insulation effect of the coating is realized, the tensile strength of the prepared coating after curing is as high as 18.2 MPa, the salt spray resistance is as high as 1900 h, the adhesion grade is 1, the water contact angle is as high as 153°, the thermal conductivity is as low as 0.0211, the coating has excellent mechanical strength, corrosion resistance, adhesion, waterproof and antifouling properties and heat insulation effect, and has a long service life.

[0023] Of course, implementing any product of the present application does not necessarily require all the advantages described above to be achieved at the same time. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed for the description of the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0025] Figure 1 The infrared spectrum of the modified polyether amine and the multifunctional cross-linking additive in the embodiments of the present application. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present application will be described clearly and completely in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only some embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0027] The preparation methods of the multifunctional cross-linking additive and the alkenyl titanium dioxide in the following embodiments and comparative examples of the present application are as follows:

[0028] I. Preparation of multifunctional cross-linking additive

[0029] S1: 3g of polyether amine with a weight average molecular weight of 2000 and 2g of methyl-5-norbornene-2,3-dicarboxylic anhydride were placed in 80ml of toluene, 0.05g of ferric chloride was added after sufficient stirring, the temperature was raised to 60℃ and reacted for 5h, and the product was collected after distillation under reduced pressure to obtain modified polyether amine;

[0030] S2: Place 3.5g of modified polyetheramine in 100ml of N,N-dimethylformamide, add 2g of 1H,1H,2H,2H-tridecylfluoro-1-n-octanol and 0.1g of p-toluenesulfonic acid, heat to 110℃ and react for 6h, then cool to room temperature and collect the product to obtain the multifunctional crosslinking additive.

[0031] Modified polyetheramine, multifunctional crosslinking additive, and potassium bromide were separately mixed and ground, then prepared into tablets, and infrared spectra were measured using a Fourier transform infrared spectrometer; Figure 1 It can be seen that in the infrared spectrum of modified polyetheramine, 1692 cm⁻¹ -1 The absorption peak is at 3402 cm⁻¹, representing the carbon-oxygen double bond in the carboxyl group. -1 The absorption peak for the nitrogen-hydrogen bond in imine is 3042 cm⁻¹. -1 The absorption peak for the carbon-hydrogen bond in the alkenyl group; in the infrared spectrum of the multifunctional crosslinking additive, 1723 cm⁻¹ is the peak value. -1 The absorption peak at 1234 cm⁻¹ represents the carbon-oxygen double bond in the ester group. -1 The absorption peak at 1692 cm⁻¹ represents the carbon-fluorine bond. Compared to the infrared spectrum of modified polyetheramine, this peak is significantly lower. -1 The absorption peak of the carbon-oxygen double bond in the carboxyl group disappears at 1723 cm⁻¹. -1 The presence of carbon-oxygen double bonds in the ester group indicates that the carboxyl group in the modified polyether ammonium structure reacted with 1H,1H,2H,2H-tetrafluoro-1-n-octanol.

[0032] II. Preparation of Alkenylated Titanium Dioxide

[0033] 2g of nano-titanium dioxide was placed in 60ml of anhydrous ethanol and ultrasonically dispersed for 10min. 1.5g of silane coupling agent KH570 was added, and the pH was adjusted to 4 with 1mol / L oxalic acid solution. The temperature was raised to 65℃ and reacted for 2h. After filtration, washing and drying, alkenylated titanium dioxide was obtained.

[0034] Example 1

[0035] Preparation of heat-insulating coatings for architectural glass

[0036] Step 1: Add 20 parts methyl methacrylate, 15 parts ethyl methacrylate, 12 parts propyl acrylate, 6 parts alkenylated titanium dioxide and 10 parts multifunctional crosslinking additive to 50 parts acetone and mix thoroughly. Add 2 parts sodium dodecylbenzenesulfonate and stir thoroughly to form a mixture.

[0037] Step 2: Add 3 parts of azobisisobutyronitrile to the mixture, heat to 50℃ and react for 5 hours. After cooling to room temperature, add 2 parts of adipic acid dihydrazide and 3 parts of dimethyl silicone oil. Stir for 2 hours and then discharge to obtain a heat-insulating coating for building glass.

[0038] Example 2

[0039] Preparation of heat insulation coating for building glass

[0040] Step one, 22 parts of methyl methacrylate, 18 parts of ethyl methacrylate, 14 parts of propyl acrylate, 8 parts of alkenyl titanium dioxide and 11 parts of multifunctional crosslinking additive are added into 80 parts of acetone for mixing, 3 parts of sodium dodecyl benzene sulfonate is added for stirring, and then a mixed solution is formed;

[0041] Step two, 4 parts of azobisdimethyl isobutyronitrile is added into the mixed solution, the temperature is raised to 52℃ for 6h, then the temperature is lowered to room temperature, 2.5 parts of malonic acid dihydrazide and 4 parts of polyethylene glycol are added, stirring for 2.5h, then the material is discharged, and the heat insulation coating for building glass is obtained.

[0042] Example 3

[0043] Preparation of heat insulation coating for building glass

[0044] Step one, 25 parts of methyl methacrylate, 20 parts of ethyl methacrylate, 15 parts of propyl acrylate, 10 parts of alkenyl titanium dioxide and 12 parts of multifunctional crosslinking additive are added into 100 parts of acetone for mixing, 5 parts of sodium dodecyl benzene sulfonate is added for stirring, and then a mixed solution is formed;

[0045] Step two, 5 parts of azobisdimethyl isobutyronitrile is added into the mixed solution, the temperature is raised to 55℃ for 8h, then the temperature is lowered to room temperature, 3 parts of adipic acid dihydrazide and 5 parts of dimethyl silicone oil are added, stirring for 3h, then the material is discharged, and the heat insulation coating for building glass is obtained.

[0046] Comparative example 1

[0047] Preparation of heat insulation coating for building glass

[0048] Step one, 22 parts of methyl methacrylate, 18 parts of ethyl methacrylate, 14 parts of propyl acrylate, 8 parts of alkenyl titanium dioxide are added into 80 parts of acetone for mixing, 3 parts of sodium dodecyl benzene sulfonate is added for stirring, and then a mixed solution is formed;

[0049] Step two, 4 parts of azobisdimethyl isobutyronitrile is added into the mixed solution, the temperature is raised to 52℃ for 6h, then the temperature is lowered to room temperature, 2.5 parts of malonic acid dihydrazide and 4 parts of polyethylene glycol are added, stirring for 2.5h, then the material is discharged, and the heat insulation coating for building glass is obtained.

[0050] Comparative example 2

[0051] Preparation of heat insulation coating for building glass

[0052] Step one, 22 parts of methyl methacrylate, 18 parts of ethyl methacrylate, 14 parts of propyl acrylate, 11 parts of multifunctional crosslinking additive are added into 80 parts of acetone for mixing, 3 parts of sodium dodecyl benzene sulfonate is added for stirring, and then a mixed solution is formed;

[0053] Step two, 4 parts of azobisisobutyronitrile was added to the mixed solution, heated to 52℃ for 6h, after cooling to room temperature, 2.5 parts of malonic acid dihydrazide, 4 parts of polyethylene glycol alkyl, stirred for 2.5h, then discharged, to obtain the heat insulation coating for building glass.

[0054] Comparative example 3

[0055] Preparation of heat insulation coating for building glass

[0056] Step one, 22 parts of methyl methacrylate, 18 parts of ethyl methacrylate, 14 parts of propyl acrylate, 8 parts of alkenyl titanium dioxide and 11 parts of modified polyether amine were added to 80 parts of acetone and mixed thoroughly, 3 parts of sodium dodecyl benzene sulfonate was added and stirred thoroughly to form a mixed solution;

[0057] Step two, 4 parts of azobisisobutyronitrile was added to the mixed solution, heated to 52℃ for 6h, after cooling to room temperature, 2.5 parts of malonic acid dihydrazide, 4 parts of polyethylene glycol alkyl, stirred for 2.5h, then discharged, to obtain the heat insulation coating for building glass.

[0058] Comparative example 4

[0059] Preparation of heat insulation coating for building glass

[0060] Step one, 22 parts of methyl methacrylate, 18 parts of ethyl methacrylate, 14 parts of propyl acrylate, 8 parts of alkenyl titanium dioxide and 11 parts of modified polyether amine were added to 80 parts of acetone and mixed thoroughly, 3 parts of sodium dodecyl benzene sulfonate was added and stirred thoroughly to form a mixed solution;

[0061] Step two, 4 parts of azobisisobutyronitrile was added to the mixed solution, heated to 52℃ for 6h, after cooling to room temperature, 2.5 parts of malonic acid dihydrazide, 4 parts of polyethylene glycol alkyl, stirred for 2.5h, then discharged, to obtain the heat insulation coating for building glass.

[0062] Comparative example 5

[0063] Preparation of heat insulation coating for building glass

[0064] Step one, 22 parts of methyl methacrylate, 18 parts of ethyl methacrylate, 14 parts of propyl acrylate, 8 parts of alkenyl titanium dioxide and 11 parts of polyether amine were added to 80 parts of acetone and mixed thoroughly, 3 parts of sodium dodecyl benzene sulfonate was added and stirred thoroughly to form a mixed solution;

[0065] Step two, 4 parts of azobisisobutyronitrile was added to the mixed solution, heated to 52℃ for 6h, after cooling to room temperature, 2.5 parts of malonic acid dihydrazide, 4 parts of polyethylene glycol alkyl, stirred for 2.5h, then discharged, to obtain the heat insulation coating for building glass.

[0066] Performance test

[0067] The heat insulation coating prepared by example 1 to example 3 and comparative example 1 to comparative example 5 was coated on a composite specification steel plate, and after curing at 80℃ for 1 h, a sample meeting the specification was prepared. The tensile strength of the sample was tested according to the standard GB / T1040-2006 to determine its mechanical properties; the salt spray resistance of the sample was tested according to the standard GB / T1771-2007; the adhesion grade of the sample was tested according to the standard GB / T1727-2021; the water contact angle of the sample was tested using an SZ-CAMA1 contact angle measuring instrument; and the thermal conductivity of the sample was determined using a TC3000 type thermal conductivity instrument. The smaller the thermal conductivity, the stronger the heat insulation ability of the sample. The specific test results are shown in the following table:

[0068]

[0069] As can be seen from the above table, the samples prepared by example 1 to example 3 all have excellent mechanical strength, corrosion resistance, adhesion, water and stain resistance, and heat insulation ability. The sample prepared by comparative example 1 does not contain a multifunctional cross-linking additive, but contains alkenyl titanium dioxide, so it has good heat insulation effect, general mechanical properties and water and stain resistance, which are inferior to the examples, and poor adhesion. The sample prepared by comparative example 2 does not contain alkenyl titanium dioxide, and has good mechanical strength, corrosion resistance, adhesion, water and stain resistance, but is inferior to the examples and has poor heat insulation performance. The sample prepared by comparative example 3 does not contain alkenyl titanium dioxide or a multifunctional cross-linking additive, and has poor mechanical properties, corrosion resistance, adhesion, water and stain resistance, and heat insulation performance. The sample prepared by comparative example 4 directly contains modified polyether amine, and has good mechanical properties and heat insulation performance, and has certain water and stain resistance. The sample prepared by comparative example 5 directly contains polyether amine, and does not form a cross-linked structure in the matrix, so it has poor mechanical properties, general corrosion resistance, and poor adhesion. Since it contains alkenyl titanium dioxide, it has certain water and stain resistance and excellent heat insulation performance.

[0070] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in the present specification and the features of the different embodiments or examples can be combined and combined by those skilled in the art without contradiction.

[0071] The above merely illustrates and explains the concept of the present application. Those skilled in the art can make various modifications or supplements to the specific embodiments described or replace them with similar ways without departing from the scope defined by the concept of the present application, and all of them shall fall within the protection scope of the present application.

Claims

1. A heat-insulating coating for architectural glass, comprising the following raw materials in parts by weight: 20-25 parts methyl methacrylate, 15-20 parts ethyl methacrylate, 12-15 parts propyl acrylate, 6-10 parts alkenylated titanium dioxide, 50-100 parts acetone, 2-5 parts sodium dodecylbenzene sulfonate, 3-5 parts initiator, 2-3 parts film-forming aid, and 3-5 parts defoamer; characterized in that, It also includes 10-12 parts of multifunctional crosslinking additive; The preparation method of the multifunctional crosslinking additive includes the following steps: S1: Polyetheramine and methyl-5-norbornene-2,3-dicarboxylic anhydride are placed in toluene, stirred thoroughly, and then a catalyst is added. The mixture is heated to 60-70℃ and reacted for 5-8 hours. The product is collected by vacuum distillation to obtain modified polyetheramine. S2: The modified polyetheramine was placed in N,N-dimethylformamide, and 1H,1H,2H,2H-tetrafluoro-1-n-octanol and p-toluenesulfonic acid were added. The mixture was heated to react, and the product was collected after cooling to room temperature to obtain a multifunctional crosslinking additive. The film-forming aid is either adipate dihydrazide or malonate dihydrazide.

2. The heat-insulating coating for architectural glass according to claim 1, characterized in that, The preparation method of the alkenylated titanium dioxide is as follows: Nano-titanium dioxide was placed in anhydrous ethanol and ultrasonically dispersed for 10-15 min. Silane coupling agent KH570 was added, and the pH was adjusted to 4-5 using a 1-2 mol / L oxalic acid solution. The temperature was raised to 65-70℃, and the reaction was carried out for 2-3 h. After filtration, washing, and drying, alkenylated titanium dioxide was obtained.

3. The heat-insulating coating for architectural glass according to claim 1, characterized in that, The initiator is any one of azobisisobutyronitrile and azobisisoheptanenitrile; the defoamer is any one of dimethyl silicone oil and polyethylene oxide alcohol.

4. The heat-insulating coating for architectural glass according to claim 1, characterized in that, In step S1, the weight-average molecular weight of the polyetheramine is 2000-5000.

5. The heat-insulating coating for architectural glass according to claim 1, characterized in that, In step S1, the catalyst is ferric chloride.

6. The heat-insulating coating for architectural glass according to claim 1, characterized in that, In step S2, the heating reaction temperature is 110-120℃ and the time is 6-8h.

7. A method for preparing a heat-insulating coating for architectural glass as described in claim 1, characterized in that, Includes the following steps: Step 1: Add methyl methacrylate, ethyl methacrylate, propyl acrylate, alkenylated titanium dioxide and multifunctional crosslinking additive to acetone and mix thoroughly. Add sodium dodecylbenzenesulfonate and stir thoroughly to form a mixture. Step 2: Add an initiator to the mixture, heat to 50-55℃ and react for 5-8 hours. After cooling to room temperature, add film-forming aid and defoamer, stir for 2-3 hours and then discharge to obtain a heat-insulating coating for architectural glass.

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