Oily environment-friendly macromolecular flame-retardant coating and preparation method thereof

Abstract

The invention provides an oily environment-friendly macromolecular flame-retardant coating and a preparation method thereof, and belongs to the technical field of coating compositions. The oily environment-friendly macromolecular flame-retardant coating is prepared from the following raw materials in parts by weight: 10-20 parts of SBS, 5-15 parts of terpene resin, 2-10 parts of terpene-phenolic resin, 5-15 parts of petroleum resin, 1-10 parts of tert-butyl phenolic vulcanized resin, 10-50 parts of a flame retardant, 1-7 parts of titanium dioxide, 1-5 parts of micaceous iron oxide gray, 0.1-1 part of a defoaming agent, 0.1-1.5 parts of an anti-aging agent, 25-70 parts of an environment-friendly solvent and 0-1 part of perfume. According to the oily environment-friendly polymer coating provided by the invention, the fire resistance is improved, and the coating has excellent corrosion resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of coating compositions, and in particular relates to an oily environmentally friendly polymer flame retardant coating and a preparation method thereof. Background Art

[0002] Flame retardant coating is an important functional material that combines decoration and protection. It is widely used in many industries and effectively meets the needs of fire safety. In recent years, with the rapid development of science and technology and the increasing diversification of industry needs, the development of multifunctional integrated environmentally friendly flame retardant coatings has become a hot topic pursued by many scientific researchers.

[0003] At present, although water-based paints are environmentally friendly, they have problems such as uneven dispersion of flame retardants and poor water resistance. In addition, some flame-retardant paints cannot meet other properties, such as corrosion resistance, while meeting flame-retardant properties. Moreover, most oil-based flame-retardant paints on the market still contain a lot of volatile harmful substances, making it difficult to meet higher environmental protection requirements.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide an oily environmentally friendly polymer coating that improves fire resistance and has excellent corrosion resistance.

[0006] In order to solve the above technical problems, the technical solution adopted by the present invention is: an oily environmentally friendly polymer flame retardant coating, which is made of the following raw materials in parts by weight: 10-20 parts of SBS, 5-15 parts of terpene resin, 2-10 parts of terpene phenol resin, 5-15 parts of petroleum resin, 1-10 parts of tert-butyl phenolic vulcanized resin, 10-50 parts of flame retardant, 1-7 parts of titanium dioxide, 1-5 parts of mica iron oxide ash, 0.1-1 parts of defoaming agent, 0.1-1.5 parts of antioxidant, 25-70 parts of environmentally friendly solvent, and 0-1 part of fragrance.

[0007] Optionally, the flame retardant is two or more of DEEP flame retardant, antimony trioxide, zinc borate and decabromodiphenylethane.

[0008] Optionally, the flame retardant is a composition of DEEP flame retardant, antimony trioxide, zinc borate and decabromodiphenylethane, and the mass ratio is (1-15): (0.5-2): (1-10): (1-12).

[0009] Optionally, the defoaming agent is a silicone defoaming agent.

[0010] Optionally, the antioxidant is 2,6-di-tert-butyl-p-cresol (BHT) or pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0011] Optionally, the environmentally friendly solvent is a composition of n-butyl acetate and propylene glycol methyl ether acetate, and the mass ratio of the two is 6:(3-5).

[0012] Optionally, the weight portion of the fragrance is 0.01-0.5 portion, and the fragrance is limonene, linalool or menthol.

[0013] The present invention also provides a preparation method of an oily environmentally friendly polymer flame retardant coating, comprising the following steps: S1: Heat the environmentally friendly solvent to above 65°C, under low-speed stirring, add SBS and terpene resin, keep warm until completely dissolved; raise the temperature to above 85°C, add terpene phenolic resin, keep warm and stir for 40-45 min; evacuate, raise the temperature to above 88°C, add tert-butyl phenol formaldehyde sulfide resin, keep warm and stir for 50-60 min; then cool down to below 70°C, add petroleum resin, keep warm and stir for 25-30 min to obtain a matrix; S2: Cool the matrix to below 45°C, under high-speed stirring, add the flame retardant in batches, stir evenly, then add titanium dioxide and mica iron oxide, stir for 15-20 min; after vacuum degassing treatment, add an antifoaming agent, an antioxidant and a fragrance, stir for 10-15 min, and stand still to obtain a product.

[0014] Optionally, the stirring speed in the low-speed stirring state is 100-600 rpm.

[0015] Optionally, adding the flame retardant in batches includes adding the flame retardant in three batches, and the mass ratio of the addition amounts in the three batches is 2:3:1.

[0016] Optionally, the rotation speed in the high-speed stirring state is 1200-1500 rpm.

[0017] Optionally, the process parameters of the vacuum degassing treatment include a pressure of -0.05~-0.08 MPa and a time of 30~40 min.

[0018] Generally, a flame retardant coating is mainly composed of a binder, a flame retardant and other additives, and its performance is affected by various factors. As a film-forming substance, the binder needs to be well compatible with the flame retardant to ensure the uniformity and stability of the coating. There are synergistic or antagonistic effects between different types of flame retardants. For example, the phosphorus-nitrogen based flame retardants have good synergistic effects and can improve the flame retardancy efficiency, while some fillers may compete with the flame retardant for reaction sites and reduce the flame retardant performance. Although the addition of additives can improve the processing performance and service performance of the coating, it may also affect the flame retardant effect. Therefore, the development of a flame retardant coating needs to comprehensively consider the compatibility between various components.

[0019] Currently, users pay relatively high attention to the environmental protection performance of coatings. Waterborne coatings have advantages such as environmental protection and safety, and their main components include water, emulsion, pigments and fillers, and additives, etc. What volatilizes after the construction of waterborne coatings is water and a small amount of additives, which causes less pollution to the atmospheric environment and meets the requirements of modern environmental protection. Waterborne coatings also have advantages such as good air permeability, fast drying, and fast recoating. Although waterborne coatings have many advantages, there are also some obvious deficiencies. First of all, their physical and chemical properties are relatively weaker than solvent-based coatings, such as corrosion resistance, weather resistance, stain resistance, etc., resulting in a generally shorter service life. Secondly, waterborne coatings have relatively high requirements for the construction environment. Generally, construction needs to be carried out in an environment above 5°C, and the construction environment should be kept dry and ventilated.

[0020] Compared with waterborne coatings, solvent-based coatings have high film quality and strong adaptability to the construction environment, and can be constructed within a relatively wide range of temperatures and humidities. However, solvent-based coatings also have some deficiencies. For example, solvent-based coatings perform poorly in terms of environmental protection, and their environmental protection performance is still insufficient. In order to improve the practical performance of solvent-based coatings and achieve better effects in terms of component formulation and dispersion uniformity, researchers usually make concessions in terms of environmental protection performance during the R & D process. Therefore, although the environmental protection performance of the coatings meets the standards, the amount of compliance is slightly lower than the standard requirements, and more organic substances will be volatilized during the construction process compared to coatings with better environmental protection performance, resulting in greater potential hazards. Another example is that the air permeability of solvent-based coatings is relatively poor. If not prepared properly, it is easy to form bubbles inside the coating film, affecting the durability and stability of the coating film.

[0021] Therefore, in view of the advantages and disadvantages of waterborne coatings and solvent-based coatings, the present invention is committed to providing an oil-based environmentally friendly polymer flame-retardant coating to improve the deficiencies of traditional oil-based coatings and enhance their practical properties such as environmental protection and corrosion resistance.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows: Based on the above technical solutions, the present invention provides an oil-based environmentally friendly polymer flame-retardant coating, expecting the coating to be comprehensively improved in terms of fire resistance, corrosion resistance and other aspects.

[0023] The present invention uses SBS, terpene resin, terpene phenolic resin, petroleum resin, and tert-butylphenol formaldehyde sulfide resin as the matrix resin system. The functions of each resin complement each other to improve the basic properties of the coating. Among them: SBS acts as an elastomeric substrate, providing flexibility and adhesion, and can melt to form a protective layer during combustion to delay heat transfer; terpene resin can increase the viscosity of the coating and improve the leveling property during construction; terpene phenolic resin is a polarity regulator. When this coating is used for the protection of metal substrates, it can enhance the bonding force with the metal substrate and improve the corrosion resistance; petroleum resin can lower the glass transition temperature of the system and improve the low-temperature toughness; tert-butylphenol formaldehyde sulfide resin provides crosslinking nodes to fix the resin segments through sulfur bonds. When combustion occurs, SBS melts to wrap the flame retardant and delays thermal decomposition; terpene phenolic resin forms carbon and dehydrates at high temperature to generate an aromatized carbon layer, forming an interpenetrating network with the expanded carbon layer of the DEEP flame retardant; tert-butylphenol formaldehyde sulfide resin undergoes sulfur bond crosslinking at high temperature to form a three-dimensional network, inhibiting the resin flow at high temperature and preventing the carbon layer from cracking. Therefore, the matrix resin system of the present invention can not only enhance the flame retardancy but also improve the heat resistance and corrosion resistance of the coating.

[0024] The present invention uses DEEP, antimony trioxide, zinc borate, and decabromodiphenylethane as flame retardants to significantly improve the flame retardant effect and reduce the smoke toxicity. Among them: DEEP is diethyl ethylphosphonate, which releases phosphoryl radicals at high temperature, captures the free radicals generated during combustion, interrupts the combustion chain reaction, and at the same time forms a charred layer on the material surface to play a role in heat insulation and oxygen isolation; antimony trioxide, on the one hand, synergizes with decabromodiphenylethane to generate SbBr3 with a large relative density, covering the polymer surface to play a covering effect and delaying the combustion chain reaction. At the same time, SbBr3 interrupts the combustion chain reaction through the gas-phase free radical capture mechanism; on the other hand, SbBr3 catalyzes the dehydration and carbonization of the DEEP flame retardant to form an expanded carbon layer to isolate oxygen and heat. Zinc borate decomposes at high temperature to generate ZnO and B2O3. ZnO can react with HBr generated by the reaction of decabromodiphenylethane to generate solid ZnBr2, reducing the HBr concentration in the smoke, significantly reducing the acidic toxicity, and the B2O3 generated by the decomposition of zinc borate can react with antimony oxide at high temperature to generate a stable glassy substance SbBO3, inhibiting the volatilization of antimony, reducing toxicity, and improving the environmental friendliness of use. Thus, the flame retardants of the present invention cooperate through multiple mechanisms. At the same time, the synergism between antimony trioxide and zinc borate significantly reduces the smoke toxicity and maintains high-efficiency flame retardancy. The flame retardant grade of the coating reaches V-0 level.

[0025] The present invention selects titanium dioxide and micaceous iron oxide gray as functional fillers. Among them, titanium dioxide can enhance the ultraviolet shielding and delay the photoaging; micaceous iron oxide gray has a lamellar structure, which can extend the diffusion path of the corrosive medium, improve the corrosion resistance, and can also increase the density of the carbon layer at high temperature and enhance the flame retardancy.

[0026] In addition, the present invention also selects suitable defoamers, anti-aging agents, and fragrances as additives. The defoamer can inhibit the formation of bubbles during high-speed dispersion, improve the coating quality, and reduce pinhole defects; the anti-aging agent can synergistically enhance the anti-aging performance with titanium dioxide and improve the service durability; the fragrance can be selected to mask odors and improve the user experience.

[0027] In the present invention, n-butyl acetate and propylene glycol methyl ether acetate are used as solvents. Both have good environmental friendliness and low volatility. When used in combination, their dissolving power is balanced, which can better dissolve the above matrix resin system, optimize the curing time, and enhance the construction performance.

[0028] According to the characteristics and effects of each component, the present invention continuously optimizes the preparation steps and parameters, and finally obtains a preparation method with better effects. In the present invention, SBS and terpene resin have similar polarities and form a homogeneous solution at 65°C, providing a stable dispersion medium for subsequent high-polarity resins. At the same time, the tackifying effect of terpene resin inhibits the entanglement of SBS chains and avoids mechanical degradation of molecular chains during the subsequent high-temperature stage; terpene phenolic resin has a moderate polarity and binds to the styrene segment of SBS through non-covalent bonds. The phenolic hydroxyl groups are adsorbed on the surface of the sulfurized resin, reducing the risk of phase separation. Keeping the temperature at 85°C for 40 - 45 minutes promotes partial pre-crosslinking of terpene phenolic resin and enhances the high-temperature viscosity stability of the system; under vacuum at 88°C, it promotes the formation of a hydrogen bond network between tert-butyl phenolic sulfurized resin and terpene phenolic resin to avoid premature crosslinking; adding petroleum resin during cooling dilutes the polarity of the system, reduces the glass transition temperature, and improves the low-temperature toughness. Moreover, the branched-chain structure of petroleum resin interferes with the ordered arrangement of the styrene segment of SBS and prevents the coating from becoming brittle. Adding the flame retardant in batches below 45°C improves the dispersion uniformity of the flame retardant; adding titanium dioxide and mica iron oxide ash enhances the anti-aging and corrosion resistance of the coating, and at the same time, high-speed stirring is used to disperse them evenly to prevent precipitation; vacuum degassing treatment removes dissolved oxygen, and subsequent defoamers eliminate new bubbles generated during high-speed dispersion. The combination of these two methods significantly improves the pinhole defects of the coating. It can be seen that the preparation method of the present invention strictly controls the step parameters and finally achieves a significant improvement in flame retardancy and corrosion resistance.

[0029] In summary, through the synergistic cooperation of each component, the coating obtained by the present invention has excellent fire resistance and corrosion resistance, and meets the relevant environmental protection standards. It is suitable for flame retardant protection on the surfaces of equipment, factories, warehouses and other places. Detailed Embodiments

[0030] To better understand the present invention, the following further clearly elaborates the content of the present invention in combination with embodiments. However, the protected content of the present invention is not limited to the following embodiments. In the following description, a large number of specific details are given to provide a more thorough understanding of the present invention. However, it is obvious to those skilled in the art that the present invention can be implemented without one or more of these details.

[0031] In all the examples shown and discussed here, any specific values should be construed as merely exemplary and not as a limitation. Thus, other examples of the exemplary embodiments may have different values.

[0032] Unless otherwise specified, all raw materials are commercially available products, and unless otherwise specified, they do not contain other unspecified components except for inevitable impurities.

[0033] Example 1: An oil-based environmentally friendly polymer flame retardant coating is made from the following raw materials in parts by weight: 15 parts of SBS, 10 parts of terpene resin, 6 parts of terpene phenol resin, 10 parts of petroleum resin, 6 parts of tert-butyl phenolic aldehyde sulfide resin, 30 parts of flame retardant, 4 parts of titanium dioxide, 3 parts of mica iron oxide gray, 0.5 part of defoamer, 0.8 part of antioxidant, and 50 parts of environmentally friendly solvent.

[0034] Among them, the flame retardant is a composition of DEEP flame retardant, antimony trioxide, zinc borate, and decabromodiphenylethane, and the mass ratio is 8:1.3:6:6. The defoamer is polydimethylsiloxane. The antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. The environmentally friendly solvent is a composition of n-butyl acetate and propylene glycol methyl ether acetate, and the mass ratio of the two is 6:4.

[0035] A preparation method of an oil-based environmentally friendly polymer flame retardant coating includes the following steps: S1: Heat the environmentally friendly solvent to 65°C, add SBS and terpene resin under low-speed stirring, keep warm until completely dissolved; raise the temperature to 85°C, add terpene phenol resin, and keep warm and stir for 40 min; evacuate, raise the temperature to 88°C, add tert-butyl phenolic aldehyde sulfide resin, and keep warm and stir for 55 min; then cool down to 70°C, add petroleum resin, and keep warm and stir for 28 min to obtain the matrix. S2: Cool the matrix to 45°C, add the flame retardant in batches under high-speed stirring, stir evenly, then add titanium dioxide and mica iron oxide gray, and stir for 18 min; after vacuum defoaming treatment, add the defoamer and antioxidant, stir for 12 min, and let it stand to obtain the product.

[0036] Among them, the stirring speed in the low-speed stirring state is 300 rpm. Adding the flame retardant in batches includes adding the flame retardant in three batches, and the mass ratio of the three batches of addition amounts is 2:3:1. The rotation speed in the high-speed stirring state is 1300 rpm. The process parameters of the vacuum defoaming treatment include a pressure of -0.08 MPa and a time of 30 min.

[0037] Example 2: An oil-based environmentally friendly polymer flame retardant coating is made from the following raw materials in parts by weight: 10 parts of SBS, 5 parts of terpene resin, 2 parts of terpene phenol resin, 5 parts of petroleum resin, 1 part of tert-butyl phenolic sulfide resin, 10 parts of flame retardant, 1 part of titanium dioxide, 1 part of mica iron oxide gray, 0.1 part of defoamer, 0.1 part of antioxidant, and 25 parts of environmentally friendly solvent.

[0038] Among them, the flame retardant is two or more of DEEP flame retardant, antimony trioxide, zinc borate, and decabromodiphenylethane. The flame retardant is a composition of DEEP flame retardant, antimony trioxide, zinc borate, and decabromodiphenylethane, and the mass ratio is 1:0.5:1:1. The defoamer is silicone defoamer AFE-1410. The antioxidant is 2,6-di-tert-butyl-p-cresol (BHT). The environmentally friendly solvent is a composition of n-butyl acetate and propylene glycol methyl ether acetate, and the mass ratio of the two is 6:3.

[0039] A preparation method of an oil-based environmentally friendly polymer flame retardant coating includes the following steps: S1: Heat the environmentally friendly solvent to 65°C, under low-speed stirring, add SBS and terpene resin, keep warm until completely dissolved; raise the temperature to 85°C, add terpene phenol resin, keep warm and stir for 42 min; evacuate, raise the temperature to 88°C, add tert-butyl phenolic sulfide resin, keep warm and stir for 50 min; then cool down to 70°C, add petroleum resin, keep warm and stir for 25 min to obtain a matrix. S2: Cool the matrix to 45°C, under high-speed stirring, add the flame retardant in batches, stir evenly, then add titanium dioxide and mica iron oxide gray, stir for 15 min; after vacuum degassing treatment, add the defoamer and antioxidant, stir for 10 min, and let stand to obtain the product.

[0040] Among them, the stirring speed in the low-speed stirring state is 100 rpm. Adding the flame retardant in batches includes adding the flame retardant in three batches, and the mass ratio of the three batches of addition amounts is 2:3:1. The rotation speed in the high-speed stirring state is 1200 rpm. The process parameters of the vacuum degassing treatment include a pressure of -0.07 MPa and a time of 35 min.

[0041] Example 3: An oil-based environmentally friendly polymer flame retardant coating is made from the following raw materials in parts by weight: 20 parts of SBS, 15 parts of terpene resin, 10 parts of terpene phenol resin, 15 parts of petroleum resin, 10 parts of tert-butyl phenolic sulfide resin, 50 parts of flame retardant, 7 parts of titanium dioxide, 5 parts of mica iron oxide gray, 1 part of defoamer, 1.5 parts of antioxidant, and 70 parts of environmentally friendly solvent.

[0042] Among them, the flame retardant is a composition of DEEP flame retardant, antimony trioxide, zinc borate and decabromodiphenylethane, and the mass ratio is 15:2:10:12. The defoamer is silicone defoamer SGR1830. The antioxidant is pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. The environmental protection solvent is a composition of n-butyl acetate and propylene glycol methyl ether acetate, and the mass ratio of the two is 6:5.

[0043] A preparation method of an oil-based environmentally friendly polymer flame retardant coating includes the following steps: S1: Heat the environmental protection solvent to above 68°C, add SBS and terpene resin under low-speed stirring, keep warm until completely dissolved; raise the temperature to 87°C, add terpene phenolic resin, and keep warm and stir for 45 min; evacuate, raise the temperature to 90°C, add tert-butylphenol formaldehyde sulfide resin, and keep warm and stir for 60 min; then cool down to 68°C, add petroleum resin, and keep warm and stir for 30 min to obtain a matrix. S2: Cool the matrix to 43°C, add the flame retardant in batches under high-speed stirring, stir evenly, then add titanium dioxide and mica iron oxide gray, and stir for 20 min; after vacuum defoaming treatment, add the defoamer and antioxidant, stir for 15 min, and let stand to obtain the product.

[0044] Among them, the stirring speed in the low-speed stirring state is 600 rpm. Adding the flame retardant in batches includes adding the flame retardant in three batches, and the mass ratio of the three batches of addition amounts is 2:3:1. The rotation speed in the high-speed stirring state is 1500 rpm. The process parameters of the vacuum defoaming treatment include a pressure of -0.05 MPa and a time of 40 min.

[0045] Example 4: An oil-based environmentally friendly polymer flame retardant coating is made from the following raw materials in parts by weight: 12 parts of SBS, 8 parts of terpene resin, 4 parts of terpene phenolic resin, 7 parts of petroleum resin, 3 parts of tert-butylphenol formaldehyde sulfide resin, 20 parts of flame retardant, 3 parts of titanium dioxide, 2 parts of mica iron oxide gray, 0.3 part of defoamer, 0.5 part of antioxidant, 35 parts of environmental protection solvent, and 0.01 part of fragrance.

[0046] Among them, the flame retardant is a composition of DEEP flame retardant, antimony trioxide, zinc borate and decabromodiphenylethane, and the mass ratio is 3:0.9:3:4. The defoamer is polydimethylsiloxane. The antioxidant is pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. The environmental protection solvent is a composition of n-butyl acetate and propylene glycol methyl ether acetate, and the mass ratio of the two is 6:4. The fragrance is menthol.

[0047] A preparation method of an oil-based environmentally friendly polymer flame retardant coating includes the following steps: S1: Heat the environmental protection solvent to 65°C, add SBS and terpene resin under low-speed stirring, keep warm until completely dissolved; heat up to 85°C, add terpene phenolic resin, keep warm and stir for 40 min; evacuate, heat up to 88°C, add tert-butyl phenolic aldehyde sulfide resin, keep warm and stir for 55 min; then cool down to 70°C, add petroleum resin, keep warm and stir for 28 min to obtain the matrix. S2: Cool the matrix to 45°C, add the flame retardant in batches under high-speed stirring, stir evenly, then add titanium dioxide and mica iron oxide grey, stir for 18 min; after vacuum degassing treatment, add defoamer, antioxidant and fragrance, stir for 12 min, and let it stand to obtain the product.

[0048] Among them, the stirring speed in the low-speed stirring state is 300 rpm. Adding the flame retardant in batches includes adding the flame retardant in three batches, and the mass ratio of the addition amounts in the three batches is 2:3:1. The rotation speed in the high-speed stirring state is 1300 rpm. The process parameters of the vacuum degassing treatment include a pressure of -0.08 MPa and a time of 30 min.

[0049] Example 5: An oil-based environmentally friendly polymer flame retardant coating is made from the following raw materials in parts by weight: 18 parts of SBS, 12 parts of terpene resin, 8 parts of terpene phenolic resin, 12 parts of petroleum resin, 8 parts of tert-butyl phenolic aldehyde sulfide resin, 40 parts of flame retardant, 6 parts of titanium dioxide, 4 parts of mica iron oxide grey, 0.8 part of defoamer, 1.2 parts of antioxidant, 60 parts of environmental protection solvent, and 0.1 part of fragrance.

[0050] Among them, the flame retardant is a composition of DEEP flame retardant, antimony trioxide, zinc borate and decabromodiphenyl ethane, and the mass ratio is 10:1.5:8:10. The defoamer is polydimethylsiloxane. The antioxidant is 2,6-di-tert-butyl-p-cresol (BHT). The environmental protection solvent is a composition of n-butyl acetate and propylene glycol methyl ether acetate, and the mass ratio of the two is 6:3. The fragrance is menthol.

[0051] The preparation method of the oil-based environmentally friendly polymer flame retardant coating in this example refers to Example 4.

[0052] Example 6: An oil-based environmentally friendly polymer flame retardant coating is made from the following raw materials in parts by weight: 14 parts of SBS, 6 parts of terpene resin, 3 parts of terpene phenolic resin, 6 parts of petroleum resin, 4 parts of tert-butyl phenolic aldehyde sulfide resin, 15 parts of flame retardant, 3 parts of titanium dioxide, 3 parts of mica iron oxide grey, 0.5 part of defoamer, 0.3 part of antioxidant, 30 parts of environmental protection solvent, and 0.8 part of fragrance.

[0053] Among them, the flame retardant is a composition of DEEP flame retardant, antimony trioxide, zinc borate and decabromodiphenylethane, and the mass ratio is 5:1:3:3. The defoaming agent is polydimethylsiloxane. The antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. The environmentally friendly solvent is a composition of n-butyl acetate and propylene glycol methyl ether acetate, and the mass ratio of the two is 6:5. The fragrance is linalool.

[0054] For the preparation method of an oily environmentally friendly polymer flame retardant coating in this example, refer to Example 4.

[0055] Example 7: An oily environmentally friendly polymer flame retardant coating is made from the following raw materials in parts by weight: 17 parts of SBS, 14 parts of terpene resin, 9 parts of terpene phenol resin, 13 parts of petroleum resin, 9 parts of tert-butyl phenol formaldehyde sulfide resin, 45 parts of flame retardant, 6 parts of titanium dioxide, 4 parts of mica iron oxide gray, 0.9 part of defoaming agent, 1.3 parts of antioxidant, 63 parts of environmentally friendly solvent, and 1 part of fragrance.

[0056] Among them, the flame retardant is a composition of DEEP flame retardant, antimony trioxide, zinc borate and decabromodiphenylethane, and the mass ratio is 13:1.6:9:11. The defoaming agent is dimethyl siloxane. The antioxidant is 2,6-di-tert-butyl-p-cresol (BHT). The environmentally friendly solvent is a composition of n-butyl acetate and propylene glycol methyl ether acetate, and the mass ratio of the two is 6:4. The fragrance is menthol.

[0057] For the preparation method of an oily environmentally friendly polymer flame retardant coating in this example, refer to Example 4.

[0058] Example 8: An oily environmentally friendly polymer flame retardant coating in this example is different from Example 1 in that: the flame retardant is a composition of DEEP flame retardant, antimony trioxide, zinc borate and decabromodiphenylethane, and the mass ratio is 2:1.2:5:8.

[0059] The following are comparative implementation schemes.

[0060] Comparative Example 1: An oily environmentally friendly polymer flame retardant coating is different from Example 1 in that: SEBS is used to replace SBS, and the other components and parts by weight remain unchanged.

[0061] Comparative Example 2: An oily environmentally friendly polymer flame retardant coating is different from Example 1 in that: the terpene phenol resin is omitted, and the other raw materials and parts by weight remain unchanged.

[0062] Comparative Example 3: An oily environmentally friendly polymer flame retardant coating is different from Example 1 in that: dimethyl methylphosphonate is used to replace the DEEP flame retardant (diethyl ethylphosphonate), and the other components and contents remain unchanged.

[0063] Comparative Example 4: An oil-based environmentally friendly polymer flame retardant coating, which is different from Example 1 in that magnesium hydroxide is used to replace the DEEP flame retardant, and the other components and their contents remain unchanged.

[0064] Comparative Example 5: An oil-based environmentally friendly polymer flame retardant coating, which is different from Example 1 in that the flame retardant is a composition of DEEP flame retardant, antimony trioxide, zinc borate and decabromodiphenyl ethane, and the mass ratio is 8:4:0.5:6.

[0065] Comparative Example 6: An oil-based environmentally friendly polymer flame retardant coating, which is different from Example 1 in that the flame retardant is a composition of DEEP flame retardant, antimony trioxide, zinc borate and decabromodiphenyl ethane, and the mass ratio is 0.5:1.3:6:15.

[0066] The preparation of the flame retardant coatings in the above Comparative Examples 1-6 was carried out with reference to Example 1.

[0067] Comparative Example 7: An oil-based environmentally friendly polymer flame retardant coating, which is different from Example 1 in that the vacuum degassing treatment is omitted.

[0068] Next, the coatings prepared in Examples 1-3 and Comparative Examples 1-7 were subjected to performance evaluation.

[0069] Specimens were made in accordance with GB 14907-2018 "Fire Retardant Coatings for Steel Structures", and were respectively subjected to freeze-thaw cycle resistance, acid resistance, alkali resistance and salt spray corrosion resistance tests. The appearance defects of the coating and the attenuation amount of the heat insulation efficiency were recorded and expressed in %.

[0070] Specimens were made in accordance with GB 14907-2018 "Fire Retardant Coatings for Steel Structures", and were respectively subjected to fire resistance tests. A 36b hot-rolled I-beam (section modulus is 126m -1 ') specified in GB / T706-2016 was used as the test substrate, and the heating condition was to heat up to 500 °C at a rate of 10 °C / min, and the coating thickness was 2 mm. The fire resistance time was recorded, accurate to 0.01 h.

[0071] The VOC content was tested according to the method specified in GB / T23985-2009 "Determination of Volatile Organic Compound (VOC) Content in Paints and Varnishes - Difference Method".

[0072] The test results are shown in Table 1 and Table 2.

[0073] Table 1 Test Results of the Coatings in Examples 1-3 The above results show that the coating surface of the coating obtained by the present invention is flat and smooth, without pinholes, sags, orange peel, shrinkage holes, cracks, and exposed substrate defects. The coatings in the freeze-thaw cycle resistance, acid resistance, alkali resistance, and salt spray corrosion resistance tests have no appearance defects, and the attenuation of the heat insulation efficiency is less than 35%. The fire resistance performance is ≥2h, and the volatile organic compounds meet the standard requirements, meeting the high environmental protection requirements and having outstanding comprehensive performance.

[0074] Table 2 Test results of the coating properties of Comparative Examples 1-7 The above results show that compared with Example 1, the coatings prepared in Comparative Examples 1-7 have varying degrees of decline in corrosion resistance, fire resistance performance, or appearance. This indicates that the coating system of the present invention has better compatibility and can significantly improve the comprehensive performance of the coating.

[0075] It can be seen that the coating of the present invention significantly improves the fire resistance performance by virtue of the scientific ratio and synergistic effect of various raw materials, and at the same time exhibits excellent corrosion resistance, and is safe and environmentally friendly during use. As a fire retardant coating, its protective effect on steel structure parts is particularly significant and has high promotion and application value.

[0076] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Any other modifications or equivalent replacements made by those of ordinary skill in the art to the technical solutions of the present invention should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.

Claims

1. An oily environmentally friendly polymer flame retardant coating, characterized in that: The invention is prepared from the following raw materials in parts by weight: 10-20 parts of SBS, 5-15 parts of terpene resin, 2-10 parts of terpene phenol resin, 5-15 parts of petroleum resin, 1-10 parts of tert-butylphenol vulcanized resin, 10-50 parts of flame retardant, 1-7 parts of titanium dioxide, 1-5 parts of mica iron oxide ash, 0.1-1 parts of defoaming agent, 0.1-1.5 parts of antioxidant, 25-70 parts of environmentally friendly solvent and 0-1 parts of fragrance.

2. The oily environmentally friendly polymer flame retardant coating according to claim 1, characterized in that: The flame retardant is two or more of DEEP flame retardant, antimony trioxide, zinc borate and decabromodiphenylethane.

3. The oily environmentally friendly polymer flame retardant coating according to claim 2, characterized in that: The flame retardant is a composition of DEEP flame retardant, antimony trioxide, zinc borate and decabromodiphenylethane, and the mass ratio is (1-15): (0.5-2): (1-10): (1-12).

4. The oily environmentally friendly polymer flame retardant coating according to claim 1, characterized in that: The defoamer is an organosilicon defoamer.

5. The oily environmentally friendly polymer flame retardant coating according to claim 1, characterized in that: The antioxidant is 2,6-di-tert-butyl-p-cresol (BHT) or pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

6. The oily environmentally friendly polymer flame retardant coating according to claim 1, characterized in that: The environmentally friendly solvent is a composition of n-butyl acetate and propylene glycol methyl ether acetate, and the mass ratio of the two is 6: (3-5).

7. The oily environmentally friendly polymer flame retardant coating according to claim 1, characterized in that: The weight proportion of the fragrance is 0.01-0.5 parts, and the fragrance is limonene, linalool or menthol.

8. A method for preparing an oily environmentally friendly polymer flame retardant coating according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1: Heat the environmentally friendly solvent to above 65°C, add SBS and terpene resin under low-speed stirring, and keep warm until they are completely dissolved; Raise the temperature to above 85°C, add terpene phenol resin, keep warm and stir for 40-45 minutes; evacuate, raise the temperature to above 88°C, add tert-butylphenol aldehyde vulcanized resin, keep warm and stir for 50-60 minutes; then lower the temperature to below 70°C, add petroleum resin, keep warm and stir for 25-30 minutes to obtain a matrix; S2: Cooling the substrate to below 45°C, adding flame retardants in batches under high-speed stirring, stirring evenly, then adding titanium dioxide and mica iron oxide ash, stirring for 15-20 minutes; adding defoaming agent, antioxidant and fragrance after vacuum degassing, stirring for 10-15 minutes, and standing to obtain the product.

9. The method for preparing an oily environmentally friendly polymer flame retardant coating according to claim 8, characterized in that: The adding of the flame retardant in batches includes adding the flame retardant in three batches, and the mass ratio of the addition amounts of the three batches is 2:3:

1.

10. The method for preparing an oily environmentally friendly polymer flame retardant coating according to claim 8, characterized in that: The process parameters of the vacuum degassing treatment include a pressure of -0.05 to -0.08 MPa and a time of 30 to 40 min.

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