Antioxidant flame-retardant water-based plastic oil and preparation method thereof

Abstract

The present application relates to the technical field of water-based plastic oil, and discloses an antioxidant and flame-retardant water-based plastic oil and a preparation method thereof, which comprises the following components in the adding proportion: water-based polyurethane resin 35%, styrene-acrylic acid copolymer 15%, acrylic resin 10%, golden sand powder 12%, melamine phosphate salt 8%, antioxidant 1024 40.4%, polyether modified silicone surfactant 1.5%, water-based polypropylene wax 4% and deionized water 14.1%. The preparation method comprises the following steps: adding 50% deionized water into a reaction kettle, then adding pH regulator, surfactant, defoaming agent and part of film-forming aid in sequence, adding polyurethane resin and acrylic resin into the mixed solution and heating, then adding golden sand powder and flame retardant, after the high-speed dispersion machine mixes and cools the solution, adding antioxidant 1024, polypropylene wax emulsion and the rest of film-forming aid and deionized water in sequence, adjusting the viscosity and filtering to obtain the product. The present application effectively avoids the problems of poor antioxidant and flame-retardant performance of traditional water-based plastic oil.

Description

Technical Field

[0001] This invention relates to the field of water-based plasticizers, and more particularly to an antioxidant and flame-retardant water-based plasticizer and its preparation method. Background Technology

[0002] Water-based plastic substitute oil is an environmentally friendly coating that uses water as a solvent. It is mainly used to replace traditional plastic packaging materials and achieves the functional substitution of plastics by improving the waterproof, moisture-proof, and wear-resistant properties of paper-based materials.

[0003] Existing flame retardants in water-based plasticizers (such as halogenated and phosphorus-based ones) have a large polarity difference from the water-based system, which can easily lead to precipitation or uneven dispersion, resulting in a short-lived flame retardant effect and thus reducing flame retardancy. At the same time, water-based plasticizers use water as the dispersion medium, and the chemical bonds of their polymer chains (such as acrylate copolymers) are susceptible to free radical attack, which accelerates the oxidation chain reaction and reduces their antioxidant properties. Therefore, we provide an antioxidant flame retardant water-based plasticizer and its preparation method. Summary of the Invention

[0004] To address the problems of poor antioxidant and flame-retardant properties of traditional water-based plasticizers in the aforementioned background technology, this invention provides an antioxidant and flame-retardant water-based plasticizer and its preparation method.

[0005] This invention is achieved using the following technical solution: an antioxidant and flame-retardant water-based plasticizer, comprising the following components in the specified proportions: The composition includes 35% waterborne polyurethane resin, 15% styrene-acrylic copolymer, 10% acrylic resin, 12% gold powder, 8% melamine phosphate salt, 0.4% antioxidant 1024, 1.5% polyether modified silicone surfactant, 4% waterborne polypropylene wax, and 14.1% deionized water.

[0006] The preparation method of the antioxidant and flame-retardant water-based plasticizer includes the following steps: Add 50% deionized water to the reactor and stir at 300 rpm. Then, add pH adjuster, surfactant, defoamer, and some film-forming aids in sequence and mix. Slowly add polyurethane resin and acrylic resin to the mixture and heat to 30°C while increasing the stirring speed to 800 rpm. Then, add gold powder and flame retardant and treat with a high-speed disperser at 1200 rpm for 30 minutes until the fineness is ≤20μm. After the mixture cools down to 25°C, add antioxidant 1024, polypropylene wax emulsion, the remaining film-forming aids, and deionized water in sequence. Adjust the viscosity to 25-35s and filter through a 300-mesh filter to obtain the final product.

[0007] As a further improvement to the above solution, the method for preparing the waterborne polyurethane resin is as follows: S1. Mix polyol with excess diisocyanate and react at 60-80℃ for 2h to generate a prepolymer with terminal -NCO groups; S2. Add a hydrophilic chain extender and stir to mix, introducing hydrophilic groups; S3. Water and prepolymer are subjected to high-speed shearing in an emulsifier to form a stable emulsion.

[0008] As a further improvement to the above scheme, the preparation method of the styrene-acrylic acid copolymer is as follows: S1. Styrene and acrylic monomers are added to water at a temperature of 70-80℃ and stirred for 3 hours. S2. Nitrogen gas is introduced into the mixture to remove oxygen; S3. Add the initiator and continue mixing and stirring for 30 minutes.

[0009] As a further improvement to the above scheme, the particle size of the gold powder is controlled at 5-15μm.

[0010] As a further improvement to the above scheme, the antioxidant 1024 is an acylhydrazine antioxidant to prevent the polymer from undergoing thermo-oxidative degradation.

[0011] As a further improvement to the above scheme, the pH adjuster is ammonia water, and the pH value needs to be adjusted to 8.5.

[0012] As a further improvement to the above scheme, the amount of both the surfactant and the defoamer is 0.2%.

[0013] As a further improvement to the above scheme, the film-forming aid is ethylene glycol butyl ether and the dosage is 2%.

[0014] As a further improvement to the above scheme, the high-speed shearing speed is 4000 rpm.

[0015] As a further improvement to the above scheme, the common molar ratio of styrene and acrylic monomers is 1:1.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: The melamine phosphate salt in this invention is a halogen-free flame retardant. It improves the flame retardancy level through the phosphorus-nitrogen synergistic effect. Furthermore, the two-step pre-dispersion method avoids direct contact between the phosphate and the resin, which could lead to gelation and thus ensure the stability of the flame retardant performance of the material.

[0017] The styrene-acrylic copolymer in this invention can enhance the hardness of the coating and reduce costs, while also resisting the erosion of ultraviolet rays, oxygen and chemicals.

[0018] This invention avoids the decomposition of active ingredients caused by high temperatures by adding an antioxidant at the end of the paint mixing stage.

[0019] The ingredients of this invention do not contain flammable solvents such as isobutanol and comply with EU REACH regulations.

[0020] The waste disposal of this invention can be achieved through biodegradation, with a COD value 60% lower than that of traditional solvent-based products, making it green and environmentally friendly. Detailed Implementation

[0021] The present invention will now be further described in conjunction with specific embodiments. It should be noted that, without conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments. Example 1

[0022] This embodiment of an antioxidant and flame-retardant water-based plasticizer includes the following components in the following proportions: The composition includes 35% waterborne polyurethane resin, 15% styrene-acrylic copolymer, 10% acrylic resin, 12% gold powder, 8% melamine phosphate salt, 0.4% antioxidant 1024, 1.5% polyether modified silicone surfactant, 4% waterborne polypropylene wax, and 14.1% deionized water.

[0023] The preparation method of antioxidant and flame-retardant water-based plasticizer includes the following steps: Add 50% deionized water to the reactor and stir at 300 rpm. Then, add pH adjuster, surfactant, defoamer, and some film-forming aids sequentially and mix. The pH adjuster is ammonia water, and the pH value needs to be adjusted to 8.5. The amount of surfactant and defoamer is 0.2% each. The film-forming aid is ethylene glycol butyl ether, and the amount is 2%. Slowly add polyurethane resin and acrylic resin to the mixture and heat to 30°C. Polyurethane resin provides flexibility and adhesion, while acrylic resin improves gloss and weather resistance. To improve the properties of the mixture, increase the stirring speed to 800 rpm, then add gold powder and flame retardant. The particle size of the gold powder is controlled at 5-15 μm. It is then processed for 30 minutes using a high-speed disperser at 1200 rpm until the fineness is ≤20 μm. After the mixture cools down to 25℃, antioxidant 1024, polypropylene wax emulsion, the remaining film-forming aids, and deionized water are added in sequence. Antioxidant 1024 is an acylhydrazine antioxidant to prevent the thermo-oxidative degradation of the polymer. The viscosity is adjusted to 25-35s, and the mixture is then filtered through a 300-mesh filter to obtain the final product.

[0024] The preparation method of waterborne polyurethane resin is as follows: S1. Mix polyol with excess diisocyanate and react at 60-80℃ for 2h to generate a prepolymer with terminal -NCO groups; S2. Add a hydrophilic chain extender and stir to mix, introducing hydrophilic groups; S3. Water and prepolymer are subjected to high-speed shearing in an emulsifier to form a stable emulsion at a speed of 4000 rpm.

[0025] The preparation method of styrene-acrylic acid copolymer is as follows: S1. Styrene and acrylic monomers are added to water at a temperature of 70-80℃ and stirred for 3 hours. The common molar ratio of styrene to acrylic monomers is 1:1. S2. Nitrogen gas is introduced into the mixture to remove oxygen; S3. Add the initiator and continue mixing and stirring for 30 minutes. Example 2:

[0026] This embodiment of an antioxidant and flame-retardant water-based plasticizer includes the following components in the following proportions: The composition includes 35% waterborne polyurethane resin, 15% styrene-acrylic copolymer, 10% acrylic resin, 12% gold powder, 8% melamine phosphate salt, 0.4% antioxidant 1024, 1.5% polyether modified silicone surfactant, 4% waterborne polypropylene wax, and 14.1% deionized water.

[0027] The preparation method of antioxidant and flame-retardant water-based plasticizer includes the following steps: Add 50% deionized water to the reactor and stir at 300 rpm. Then, add pH adjuster, surfactant, defoamer, and some film-forming aids sequentially and mix. The pH adjuster is ammonia water, and the pH value needs to be adjusted to 8.5. The amount of surfactant and defoamer is 0.2% each. The film-forming aid is ethylene glycol butyl ether, and the amount is 2%. Slowly add polyurethane resin and acrylic resin to the mixture and heat to 30°C. Polyurethane resin provides flexibility and adhesion, while acrylic resin improves gloss and weather resistance. To improve the properties of the mixture, increase the stirring speed to 800 rpm, then add gold powder and flame retardant. The particle size of the gold powder is controlled at 5-15 μm. It is then processed for 30 minutes using a high-speed disperser at 1200 rpm until the fineness is ≤20 μm. After the mixture cools down to 25℃, antioxidant 1024, polypropylene wax emulsion, the remaining film-forming aids, and deionized water are added in sequence. Antioxidant 1024 is an acylhydrazine antioxidant to prevent the thermo-oxidative degradation of the polymer. The viscosity is adjusted to 25-35s, and the mixture is then filtered through a 300-mesh filter to obtain the final product.

[0028] The preparation method of waterborne polyurethane resin is as follows: S1. Mix polyol with excess diisocyanate and react at 60-80℃ for 2h to generate a prepolymer with terminal -NCO groups; S2. Add a hydrophilic chain extender and stir to mix, introducing hydrophilic groups; S3. Water and prepolymer are subjected to high-speed shearing in an emulsifier to form a stable emulsion at a speed of 4000 rpm.

[0029] The preparation method of styrene-acrylic acid copolymer is as follows: S1. Styrene and acrylic monomers are added to water at a temperature of 70-80℃ and stirred for 3 hours. The common molar ratio of styrene to acrylic monomers is 2:1. S2. Nitrogen gas is introduced into the mixture to remove oxygen; S3. Add the initiator and continue mixing and stirring for 30 minutes.

[0030] Compared with Example 1, the difference is that the common molar ratio of styrene and acrylic monomers is 2:1, while the other components, preparation steps and parameters are the same. Example 3:

[0031] This embodiment of an antioxidant and flame-retardant water-based plasticizer includes the following components in the following proportions: The composition includes 35% waterborne polyurethane resin, 15% styrene-acrylic copolymer, 10% acrylic resin, 12% gold powder, 8% melamine phosphate salt, 0.4% antioxidant 1024, 1.5% polyether modified silicone surfactant, 4% waterborne polypropylene wax, and 14.1% deionized water.

[0032] The preparation method of antioxidant and flame-retardant water-based plasticizer includes the following steps: Add 50% deionized water to the reactor and stir at 300 rpm. Then, add pH adjuster, surfactant, defoamer, and some film-forming aids sequentially and mix. The pH adjuster is ammonia water, and the pH value needs to be adjusted to 8.5. The amount of surfactant and defoamer is 0.2% each. The film-forming aid is ethylene glycol butyl ether, and the amount is 2%. Slowly add polyurethane resin and acrylic resin to the mixture and heat to 30°C. Polyurethane resin provides flexibility and adhesion, while acrylic resin improves gloss and weather resistance. To improve the properties of the mixture, increase the stirring speed to 800 rpm, then add gold powder and flame retardant. The particle size of the gold powder is controlled at 5-15 μm. It is then processed for 30 minutes using a high-speed disperser at 1200 rpm until the fineness is ≤20 μm. After the mixture cools down to 25℃, antioxidant 1024, polypropylene wax emulsion, the remaining film-forming aids, and deionized water are added in sequence. Antioxidant 1024 is an acylhydrazine antioxidant to prevent the thermo-oxidative degradation of the polymer. The viscosity is adjusted to 25-35s, and the mixture is then filtered through a 300-mesh filter to obtain the final product.

[0033] The preparation method of waterborne polyurethane resin is as follows: S1. Mix polyol with excess diisocyanate and react at 60-80℃ for 2h to generate a prepolymer with terminal -NCO groups; S2. Add a hydrophilic chain extender and stir to mix, introducing hydrophilic groups; S3. Water and prepolymer are subjected to high-speed shearing in an emulsifier to form a stable emulsion at a speed of 4000 rpm.

[0034] The preparation method of styrene-acrylic acid copolymer is as follows: S1. Styrene and acrylic monomers are added to water at a temperature of 70-80℃ and stirred for 3 hours. The common molar ratio of styrene to acrylic monomers is 3:1. S2. Nitrogen gas is introduced into the mixture to remove oxygen; S3. Add the initiator and continue mixing and stirring for 30 minutes.

[0035] Compared with Example 1, the difference is that the common molar ratio of styrene to acrylic monomer is 3:1, while the other components, preparation steps and parameters are the same.

[0036] All components of this invention are general standard parts or parts known to those skilled in the art. Their structure and principles can be learned by those skilled in the art through technical manuals or conventional experimental methods. It is obvious to those skilled in the art that this invention is not limited to the details of the above exemplary embodiments, and that it can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects. The scope of this invention is defined by the appended claims rather than the foregoing description, and therefore all variations falling within the meaning and scope of equivalents of the claims are intended to be included within this invention. No markings in the claims should be construed as limiting the scope of the claims.

[0037] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. An antioxidant and flame-retardant water-based plasticizer, characterized in that, The following components are included in the proportions to be added: The composition includes 35% waterborne polyurethane resin, 15% styrene-acrylic copolymer, 10% acrylic resin, 12% gold powder, 8% melamine phosphate salt, 0.4% antioxidant 1024, 1.5% polyether-modified silicone surfactant, 4% waterborne polypropylene wax, and 14.1% deionized water. The preparation method of the antioxidant and flame-retardant water-based plasticizer includes the following steps: Add 50% deionized water to the reactor and stir at 300 rpm. Then, add pH adjuster, surfactant, defoamer, and some film-forming aids in sequence and mix. Slowly add polyurethane resin and acrylic resin to the mixture and heat to 30°C while increasing the stirring speed to 800 rpm. Then, add gold powder and flame retardant and treat with a high-speed disperser at 1200 rpm for 30 minutes until the fineness is ≤20μm. After the mixture cools down to 25°C, add antioxidant 1024, polypropylene wax emulsion, the remaining film-forming aids, and deionized water in sequence. Adjust the viscosity to 25-35s and filter through a 300-mesh filter to obtain the final product.

2. The antioxidant and flame-retardant water-based plasticizer as described in claim 1, characterized in that, The preparation method of the waterborne polyurethane resin is as follows: S1. Mix polyol with excess diisocyanate and react at 60-80℃ for 2h to generate a prepolymer with terminal -NCO groups; S2. Add a hydrophilic chain extender and stir to mix, introducing hydrophilic groups; S3. Water and prepolymer are subjected to high-speed shearing in an emulsifier to form a stable emulsion.

3. The antioxidant and flame-retardant water-based plasticizer as described in claim 2, characterized in that, The preparation method of the styrene-acrylic acid copolymer is as follows: S1. Styrene and acrylic monomers are added to water at a temperature of 70-80℃ and stirred for 3 hours. S2. Nitrogen gas is introduced into the mixture to remove oxygen; S3. Add the initiator and continue mixing and stirring for 30 minutes.

4. The antioxidant and flame-retardant water-based plasticizer as described in claim 3, characterized in that, The particle size of the gold powder is controlled between 5-15 μm.

5. The antioxidant and flame-retardant water-based plasticizer as described in claim 4, characterized in that, The antioxidant 1024 is an acylhydrazine-based antioxidant to prevent the polymer from undergoing thermo-oxidative degradation.

6. The antioxidant and flame-retardant water-based plasticizer as described in claim 5, characterized in that, The pH adjuster is ammonia, and the pH value needs to be adjusted to 8.

5.

7. The antioxidant and flame-retardant water-based plasticizer as described in claim 6, characterized in that, The amount of both the surfactant and the defoamer is 0.2%.

8. The antioxidant and flame-retardant water-based plasticizer as described in claim 7, characterized in that, The film-forming aid is ethylene glycol butyl ether and is used in an amount of 2%.

9. The antioxidant and flame-retardant water-based plasticizer as described in claim 8, characterized in that, The high-speed shearing speed is 4000 rpm.

10. The antioxidant and flame-retardant water-based plasticizer as described in claim 9, characterized in that, The common molar ratio of styrene and acrylic acid monomers is 1:1.