Polymer green water-based paint for alpine region and preparation process thereof

Abstract

The application discloses a kind of polymer green water-based paint for high-cold region and preparation process, it is related to water-based paint technical field.A kind of polymer green water-based paint for high-cold region includes the following raw materials by mass fraction: high molecular film forming agent 45-60 parts, filler 20-30 parts, environmental protection anti-freezing agent 5-8 parts, environmental protection film forming aid 2-5 parts, dispersing agent 0.5-1.5 parts, defoaming agent 0.3-0.8 parts, weather-resistant aid 0.8-1.5 parts, deionized water 15-25 parts.The weather-resistant aid of the application is absorbed by specific molecular structure and is converted into heat energy, thereby effectively delaying the aging and discoloration of coating, weather-resistant aid and film forming system synergistic effect, significantly improve the cohesion and toughness of coating film, so that it can better withstand the temperature change of high-cold region, significantly prolong the service life of coating in high-cold strong ultraviolet environment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of water-based paint, in particular to a high-molecular green water-based paint for high-cold regions and a preparation process thereof. BACKGROUND

[0002] In high-cold regions, traditional paints often fail to meet the performance requirements in special environments. On the one hand, due to extremely low temperatures in high-cold regions, the molecular chain activity of film-forming substances in ordinary paints is greatly reduced at low temperatures, which hinders the film-forming process and makes it difficult to guarantee the continuity and compactness of the film layer, thereby affecting the protective and decorative effects of the paint. On the other hand, the temperature difference changes dramatically, and the paint film layer bears a large thermal expansion and contraction stress, which is prone to cracking, peeling and other phenomena, shortening the service life of the paint. In addition, high-cold regions usually have long sunshine time and high ultraviolet intensity, and ordinary paints lack sufficient ultraviolet resistance, which can easily cause film aging, discoloration and other problems. At the same time, in order to cope with low-temperature environments, traditional paints often add organic solvent-type antifreeze agents, which not only have high volatile organic compound (VOC) emissions and pollute the environment, but also have safety hazards such as flammability, which is contrary to the current trend of green and environmentally friendly paints.

[0003] Therefore, it is particularly important to develop a high-molecular green water-based paint designed specifically for high-cold regions. This paint should have excellent low-temperature film-forming properties to ensure that a uniform, continuous and dense film layer can still be formed at extremely low temperatures; it should have good temperature difference resistance to withstand dramatic temperature changes and reduce film cracking and peeling; it should also enhance its ultraviolet resistance to extend the service life of the paint. In addition, the paint should use environmentally friendly antifreeze agents to reduce VOC emissions, meet the development concept of green paint, and meet the dual requirements of performance and environmental friendliness in high-cold regions. SUMMARY

[0004] The purpose of the present application is to solve the problems of film-forming difficulty, poor temperature difference resistance and insufficient ultraviolet resistance of traditional paints in low-temperature environments in the prior art, and to provide a high-molecular green water-based paint for high-cold regions and a preparation process thereof. The paint can form a uniform, continuous and dense film layer at extremely low temperatures, effectively resist dramatic temperature changes and strong ultraviolet radiation, and use environmentally friendly raw materials to meet the dual requirements of performance and environmental friendliness in high-cold regions.

[0005] To achieve the above-mentioned purpose, the technical solution adopted by the present application is:

[0006] A kind of high polymer green water-based paint for high-cold region, by mass fraction includes the following raw materials: high polymer film forming agent 45-60 parts, filler 20-30 parts, environmental protection anti-freezing agent 5-8 parts, environmental protection film forming aid 2-5 parts, dispersing agent 0.5-1.5 parts, defoaming agent 0.3-0.8 parts, weathering aid 0.8-1.5 parts, deionized water 15-25 parts;

[0007] The weathering aid is a compound represented by formula 1:

[0008] Formula 1: ;

[0009] R1 in the chemical formula 1 is a substituent group, and R1 is selected from any one of methyl, hydroxyl, carboxyl, amino and methoxy.

[0010] Further, the high polymer film forming agent is selected from a compound of benzene propylene emulsion and acrylic emulsion, and the mass ratio of the two is 1:0.8-1.2.

[0011] Further, the filler is selected from at least one of titanium dioxide, talcum powder and heavy calcium carbonate.

[0012] Further, the environmental protection anti-freezing agent is selected from at least one of ethylene glycol or propylene glycol.

[0013] Further, the environmental protection film forming aid is selected from at least one of dodecanol ester or benzyl alcohol.

[0014] Further, the dispersing agent is selected from at least one of polyacrylammonium or dodecyl benzene sulfonic acid ammonium.

[0015] Further, the defoaming agent is at least one of BYK BKY052 and BYK BKY054.

[0016] Further, the weathering aid is any one of the compounds represented by the following structure:

[0017] ;

[0018] ;

[0019] .

[0020] A preparation process of a high polymer green water-based paint for high-cold region, comprising the following steps:

[0021] 1) Add about 60% deionized water in a reaction kettle, add the environmentally friendly antifreeze, dispersant and half of the amount of defoaming agent in turn, stir at room temperature at 200-400 r / min for 10 minutes until completely dissolved, then add the high molecular film forming agent, control the temperature at 25-30℃, stir and mix at 200-400 r / min for 15 minutes, obtain a premix;

[0022] 2) Add the filler to the premix, adjust the speed to 1500-2000 r / min, stir at 25-30℃ for 25-35 min, obtain slurry A;

[0023] 3) Add the environmentally friendly film forming aid and weather resistant aid to the slurry A, heat to 40-45℃, stir at 600-800 r / min for 20-25 min, obtain slurry B;

[0024] 4) Add the remaining defoaming agent and the remaining deionized water to the slurry B, stir at low speed of 200-300 r / min for 5-10 min, stand for 10-20 min to remove bubbles, obtain a uniform coating liquid;

[0025] 5) Use a grinding machine to grind the coating liquid, grind to a fineness of ≤50 μm, filter, package, obtain a high-molecular green water-based paint for high-cold regions.

[0026] Further, the grinding medium of the grinding machine in step 5) is zirconium beads, the diameter of the zirconium beads is 0.8-1.2 mm, and the slurry temperature is controlled to ≤40℃ during the grinding process.

[0027] The application of a high-molecular green water-based paint for high-cold regions in the protection and decoration of concrete substrates, metal substrates or wood substrates in high-cold regions.

[0028] The high-molecular green water-based paint for high-cold regions is a new type of ink, which is suitable for high-cold regions.

[0029] The weather-resistant additive of the present application is characterized by its multiple protective functions for coating materials through a specific chemical structure. Firstly, in terms of anti-ultraviolet, the benzene ring structure in the molecule acts as a conjugated system, which can effectively absorb high-energy ultraviolet light and convert it into harmless heat energy, thereby reducing the damage of ultraviolet light to the film-forming polymer chain. In addition, the amino group in the molecule can further form p-π conjugation with the benzene ring through its lone pair of electrons, enhancing the ultraviolet absorption range and efficiency of the whole molecule, effectively delaying the aging and discoloration of the coating caused by photooxidation. Secondly, in terms of improving the temperature difference resistance of the coating, the polar groups in the molecule can form strong hydrogen bond interactions with the film-forming agent molecular chain. This intermolecular force helps to enhance the cohesion and toughness of the coating, so that the coating can better buffer the internal stress generated by thermal expansion and cold contraction when it experiences severe temperature changes in high-cold regions, reducing the generation of cracks. At the same time, these groups can also form firm chemical or ionic bonding with the surface of substrates such as concrete and metal, significantly improving the adhesion and preventing peeling. Furthermore, its stable free radical function cannot be ignored. When the coating generates free radicals due to external factors, the active groups in the molecular structure can act as free radical traps to interrupt the chain oxidation reaction, thereby improving the overall durability of the coating.

[0030] The present application aims at the three technical problems of coatings in high-cold regions. Through the synergistic effect of each component, an efficient solution is realized. The synergistic mechanism of the film-forming system: the high molecular film-forming agent serves as the matrix, providing the film-forming framework of the coating, optimizing the flexibility of the molecular chain to ensure that the chain segment activity is not excessively inhibited at low temperatures. The environmentally friendly film-forming aid reduces the glass transition temperature of the film-forming agent, promoting the fusion of the high molecular chain at low temperatures to form a continuous film layer. At the same time, the environmentally friendly anti-freezing agent lowers the freezing point of the system, preventing the water-based medium from freezing, and maintaining the slurry fluidity in cooperation with the film-forming aid, so that the film-forming process can still proceed smoothly at low temperatures. The three work together to overcome the core problem of low-temperature film-forming. The synergistic mechanism of the weather-resistant system: the weather-resistant aid is the key innovation of the present application, and its specific chemical structure improves the weather resistance through multiple ways. First, the benzene ring conjugated system efficiently absorbs ultraviolet rays and converts them into heat energy, reducing photoaging; the p-π conjugation of amino and benzene ring extends the absorption range, enhancing the anti-ultraviolet efficiency. Second, the polar groups form hydrogen bonds with the film-forming agent molecules, enhancing the cohesion and toughness of the coating, buffering the thermal expansion and contraction stress, and reducing cracking. In addition, these groups form chemical bonds with concrete, metal and other substrates, improving adhesion and preventing peeling. The filler provides physical support, and titanium dioxide itself has ultraviolet scattering effect, forming a double protective barrier with the weather-resistant aid, significantly extending the service life of the coating. The synergistic mechanism of the auxiliary system: the dispersant ensures uniform dispersion of the filler and weather-resistant aid, avoiding agglomeration and ensuring the density of the coating; the defoaming agent eliminates bubbles during preparation to prevent film defects. Deionized water, as an environmentally friendly solvent, is compatible with all components and achieves micro-uniformity through the grinding process. The entire system is integrated in an orderly manner in the preparation process: first, disperse the filler and weather-resistant aid, then introduce the film-forming component, and finally defoam and grind to ensure maximum synergistic effect.

[0031] Compared with the prior art, the present application has the following advantages:

[0032] 1. The temperature difference resistance performance is significantly enhanced: by introducing the weather-resistant aid and the film-forming system, the cohesion and toughness of the coating film are significantly improved, enabling it to better withstand the drastic temperature changes in high-cold regions, reducing cracks and peeling caused by thermal expansion and contraction.

[0033] 2. The anti-ultraviolet ability is significantly optimized: the weather-resistant aid of the present application efficiently absorbs ultraviolet rays and converts them into heat energy through a specific molecular structure, while expanding the ultraviolet absorption range, effectively delaying the aging and discoloration of the coating, and significantly extending the service life of the coating in high-cold strong ultraviolet environments.

[0034] 3. The low-temperature film-forming performance is significantly improved: the present application significantly improves the film-forming ability of the coating in low-temperature environments through the synergistic effect of the environmentally friendly film-forming aid and the environmentally friendly anti-freezing agent, ensuring that the film layer is uniform, continuous and dense, solving the problem of difficult film-forming of traditional coatings in high-cold regions. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 NMR chart of weathering aid 1 according to the present application. DETAILED DESCRIPTION

[0036] The technical solutions of the present application will be described clearly and completely below in combination with the drawings in the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but 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 fall within the scope of protection of the present application.

[0037] Synthesis Example 1:

[0038] Synthesis of weathering aid 1:

[0039] ;

[0040] Under a nitrogen atmosphere, 10.00 g of raw material 1, 10.15 g of raw material 2 were dissolved in 150 ml of a toluene solution, 10.43 g of sodium tert-butoxide, 3.14 g of tetrakis(triphenylphosphine)palladium were added, and stirred uniformly, and heated to 120°C, and refluxed for 12 h. After the reaction was completed, the temperature was slightly lowered, and filtered using diatomite, and the filtrate was cooled to room temperature, and washed with water three times, and the organic phase was retained, and then the aqueous phase was extracted with ethyl acetate. The combined organic phase was dried with anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. After rotary evaporation, column chromatography was performed using a mixture of petroleum ether and ethyl acetate as the eluent, and rotary evaporation was performed, and 11.58 g of raw material 3 was obtained.

[0041] The CAS of raw material 1 is 101-54-2.

[0042] The CAS of raw material 2 is 74204-00-5.

[0043] ;

[0044] Under a nitrogen atmosphere, 11.58 g of raw material 3, 8.50 g of raw material 4, 21.24 g of potassium phosphate tribasic, 0.05 g of pyridine-2-carboxylic acid, 0.38 g of CuI, and 150 ml of DMSO were mixed, and the reaction mixture was heated at 90°C for 14 h. After cooling, the obtained reaction mixture was extracted with an aqueous ammonia solution and methyl tert-butyl ether, and the organic phase was washed with water five times, and then washed with a saturated NaCl solution twice. Finally, the combined organic phase was dried with anhydrous magnesium sulfate, filtered, and the solvent was removed using a rotary evaporator, and purified using a silica gel column chromatography using a mixture of petroleum ether and ethyl acetate as the eluent, and the solvent was removed using a rotary evaporator, and 12.94 g of weathering aid 1 was obtained.

[0045] The CAS of raw material 4 is 39513-26-3.

[0046] Structure identification:

[0047] Mass spectrum MS-MS +1 of raw material 3: 291;

[0048] Mass spectrum MS-MS +1 of weathering aid 1: 423.

[0049] NMR of weathering aid 1 is seen Figure 1 .

[0050] Synthesis examples 2-5:

[0051] Weathering aids 2-5 were prepared in turn in synthesis examples 2-5, referring to the preparation method of synthesis example 1, replacing raw material 2 therein, and the rest being the same as synthesis example 1. For details, see Table 1.

[0052] Table 1

[0053]

[0054] Example 1:

[0055] Preparation of a high-molecular green water-based paint for high-cold regions:

[0056] a. Raw material mass ratio:

[0057] 50 parts of high-molecular film-forming agent, selected from a compound of benzene propylene emulsion (purchased from Shandong Baoda New Material Co., Ltd., the viscosity of benzene propylene emulsion is 600-5000 mPa·s, BC-01 benzene propylene emulsion) and acrylic emulsion (purchased from Guangdong Huaguoshan Environmental Protection Technology Co., Ltd., solid content (wt%): 43-45, acrylic emulsion Houxian ® 0852) in a mass ratio of 1:0.9;

[0058] 25 parts of filler, selected from titanium white powder, purchased from Jiangsu Bosite Chemical Technology Co., Ltd.;

[0059] 6 parts of environmentally friendly anti-freezing agent, selected from ethylene glycol, purchased from Jiangsu Runfeng Synthetic Technology Co., Ltd.;

[0060] 3 parts of environmentally friendly film-forming aid, selected from dodecanol ester, purchased from Hubei Chengfeng Chemical Co., Ltd.;

[0061] 1 part of dispersing agent, selected from polyacrylamide, purchased from Shanghai Yuan Ye Biological Technology Co., Ltd.;

[0062] 0.6 parts of defoaming agent, selected from BKY052, purchased from Guangzhou Sichuang Chemical Co., Ltd.;

[0063] Weathering aid 1.2 parts, selected from: weathering aid 1 synthesized in synthetic example 1;

[0064] Deionized water 20 parts.

[0065] b. Preparation process:

[0066] 1) Add 12 parts of deionized water in a reaction kettle, add 6 parts of environmentally friendly antifreeze, 1 part of dispersant and 0.3 parts of defoaming agent in turn, stir at room temperature at 300 r / min for 10 minutes until completely dissolved, then add 50 parts of high molecular film forming agent, control the temperature at 27℃, continue to stir and mix at 300 r / min for 15 minutes, get a uniform premix;

[0067] 2) Add 25 parts of filler to the premix, adjust the speed to 1800 r / min, stir at 27℃ for 30 minutes, so that the filler is fully dispersed, get slurry A;

[0068] 3) Add 3 parts of environmentally friendly film forming aid and 1.2 parts of weathering aid to slurry A, heat to 43℃, stir at 700 r / min for 22 minutes, get slurry B;

[0069] 4) Add the remaining 0.3 parts of defoaming agent and the remaining 8 parts of deionized water to slurry B, stir at low speed of 250 r / min for 8 minutes, then stand for 15 minutes to remove bubbles, get a uniform coating liquid;

[0070] 5) Use a grinding machine to grind the coating liquid, the grinding medium is zirconium beads with a diameter of 1mm, control the slurry temperature ≤40℃ during grinding process, after grinding to a fineness ≤50μm, filter and package, get a kind of high polymer green water-based paint for high-cold region.

[0071] Examples 2-5:

[0072] A kind of high polymer green water-based paint for high-cold region is prepared, according to the preparation method of example 1, weathering aid 1 is replaced by weathering aid 2-weathering aid 5 prepared in synthetic example 2-synthetic example 5 in turn, the rest is the same as example 1.

[0073] Comparative example 1:

[0074] A kind of high polymer green water-based paint for high-cold region is prepared, according to the preparation method of example 1, weathering aid 1 is replaced by , CAS: 101-54-2, the rest is the same as example 1.

[0075] Comparative example 2:

[0076] A kind of preparation of high polymer green water-based paint for high-cold region, with reference to the preparation method of example 1, replace weathering aid 1 in it with light stabilizer HS-508 (292), CAS: 82919-37-7, the rest remains the same as example 1.

[0077] Comparative example 3:

[0078] A kind of preparation of high polymer green water-based paint for high-cold region, with reference to the preparation method of example 1, without adding weathering aid 1 in it, the rest remains the same as example 1.

[0079] Comparative example 4:

[0080] A kind of preparation of high polymer green water-based paint for high-cold region, with reference to the preparation method of example 1, without adding environmental protection film forming additive in it, the rest remains the same as example 1.

[0081] Comparative example 5:

[0082] A kind of preparation of high polymer green water-based paint for high-cold region, with reference to the preparation method of example 1, without adding environmental protection anti-freezing agent in it, the rest remains the same as example 1.

[0083] Performance test:

[0084] Test sample: paint is coated on metal substrate plate (size 150mm x 70mm x 5mm) according to standard construction method (spraying), and is cured for 3-5min under 340nm ultraviolet light, and is standby after curing for 24h.

[0085] 1. Adhesion test: refer to GB / T 5210-2006 "color paint and varnish pull-off adhesion test", test the adhesion of coating and substrate (MPa), the results are shown in table 2.

[0086] 2. Temperature difference cycle resistance performance test: refer to GB / T 1865-2009 "color paint and varnish artificial climate aging and artificial radiation exposure filtered xenon arc radiation", cold and hot cycle is carried out on test sample: -30℃ freezing 4h to 25℃ (RH60%) thawing 4h, as a cycle, after 500 cycles, observe whether the film layer appears crack, peeling, discoloration, the results are shown in table 2.

[0087] 3. Weather resistance test: refer to GB / T 1766-2008 "color paint and varnish coating aging rating method", test sample (dry film thickness 100 μm) is put into xenon lamp aging box (irradiance 340nm: 0.71W / m², temperature 65℃, relative humidity 50%);

[0088] After aging for 2000h, the light loss rate (GB / T 11186.2) and discoloration grade (GB / T 11186.3) of the test film layer were tested;

[0089] The light loss rate ≤15% and the discoloration grade ≤1 grade are excellent, the light loss rate >30% and the discoloration grade ≥3 grade are failure, and the results are shown in Table 2.

[0090] Table 2

[0091]

[0092] The data in Table 2 shows the performance comparison of different coating formulations in terms of adhesion, temperature difference cycle resistance and weather resistance. Overall, the coating formulations in the examples perform well in adhesion, temperature difference resistance and weather resistance, and basically remain in the state of no cracking, no peeling and no discoloration, with stable and excellent light loss rate and discoloration grade indicators. However, in the comparative examples, some formulations show performance decline under certain conditions, such as slight discoloration, local peeling or slight cracking, and the light loss rate and discoloration grade increase. This shows that the key components in the formulation (such as weathering aids, film-forming aids and antifreeze agents) have a significant impact on the overall performance of the coating, and reasonable addition and optimization of the above components can effectively improve the comprehensive performance of the coating, making it more suitable for special environmental conditions in high-cold regions.

[0093] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and variations can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A polymer green water-based paint for high-cold regions, characterized by, By mass parts, the following raw materials are included: 45-60 parts of a high molecular film forming agent, 20-30 parts of a filler, 5-8 parts of an environmentally friendly anti-freezing agent, 2-5 parts of an environmentally friendly film forming aid, 0.5-1.5 parts of a dispersing agent, 0.3-0.8 parts of an antifoaming agent, 0.8-1.5 parts of a weather-resistant aid, and 15-25 parts of deionized water; The weather-resistant aid is a compound shown in Formula 1: Formula 1: ; R1 in Formula 1 is a substituent, and R1 is selected from any one of a methyl group, a hydroxyl group, a carboxyl group, an amino group, and a methoxyl group.

2. The polymer green water-based paint for high-cold regions according to claim 1, characterized in that, The high molecular film forming agent is selected from a compound of a benzyl lactate emulsion and an acrylic emulsion, and the mass parts ratio of the two is 1:0.8-1.

2.

3. The polymer green water-based paint for high-cold regions according to claim 1, characterized in that, The filler is selected from at least one of titanium white powder, talcum powder, and heavy calcium carbonate.

4. The polymer green water-based paint for high-cold regions according to claim 1, characterized in that, The environmentally friendly anti-freezing agent is selected from at least one of ethylene glycol and propylene glycol.

5. The polymer green water-based paint for high-cold regions according to claim 1, characterized in that, The environmentally friendly film forming aid is selected from at least one of dodecanol ester and benzyl alcohol.

6. The polymer green water-based paint for high-cold regions according to claim 1, characterized in that, The dispersing agent is selected from at least one of polyacrylammonium and dodecyl benzene sulfonic acid ammonium; The antifoaming agent is at least one of BYK BKY052 and BYK BKY054.

7. A preparation process for a polymeric green water-based coating for high-altitude and cold regions as described in any one of claims 1-6, characterized in that, The method comprises the following steps: 1) 60% of deionized water is added to a reaction kettle, and the environmentally friendly anti-freezing agent, the dispersing agent, and half of the amount of the antifoaming agent are sequentially added, stirred at 200-400 r / min at room temperature for 10 minutes until completely dissolved, then the high molecular film forming agent is added, the temperature is controlled at 25-30℃, and stirring is performed at 200-400 r / min for 15 minutes, to obtain a premix; 2) The filler is added to the premix, the stirring speed is adjusted to 1500-2000 r / min, and stirring is performed at 25-30℃ for 25-35 min, to obtain slurry A; 3) The environmentally friendly film forming aid and the weather-resistant aid are added to the slurry A, the temperature is raised to 40-45℃, and stirring is performed at a stirring speed of 600-800 r / min for 20-25 min, to obtain slurry B; 4) The remaining antifoaming agent and the remaining deionized water are added to the slurry B, low-speed stirring is performed at 200-300 r / min for 5-10 minutes, and standing is performed for 10-20 minutes to remove bubbles, to obtain a uniform coating liquid; 5) A grinding machine is used to grind the coating liquid, the grinding is performed to a fineness of ≤50 μm, filtration is performed, and packaging is performed, to obtain a high-molecular green water-based paint for high-cold regions.

8. The preparation process of the polymer green water-based paint for high-cold regions according to claim 7, characterized in that, In the step 5), the grinding medium of the grinding machine is zirconium beads, the diameter of the zirconium beads is 0.8-1.2 mm, and the slurry temperature is controlled to ≤40℃ during the grinding process.

9. Application of the high-molecular green water-based paint for high-cold regions according to any one of claims 1-6 to the protection and decoration of a concrete substrate, a metal substrate, or a wood substrate in a high-cold region.

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