Environment-friendly biomass-based water-based flame retardant and preparation method thereof

Abstract

The invention discloses an environment-friendly biomass-based water-based flame retardant and a preparation method thereof, and belongs to the technical field of high value-added utilization of biomass resources. The environment-friendly bio-based water-based flame retardant is prepared from the following raw materials: orange peel tannin, catechin, sodium carboxymethyl cellulose, sodium dodecyl benzene sulfonate, an oxidizing agent, a reducing agent, an acid catalyst, a base catalyst and deionized water. Through the polymerization reaction of catechin and orange peel tannin, a stable carbonized layer can be formed at high temperature, the solid-phase flame-retardant effect is enhanced, the adhesion and stability of the flame retardant can be further improved through compounding with sodium carboxymethyl cellulose and sodium dodecyl benzene sulfonate, and it is ensured that the flame retardant is evenly coated on the surface of a material. The orange peel tannin and catechin are natural plant extracts, are prepared from renewable biomass raw materials, and are environment-friendly.

Description

Technical Field

[0001] The invention belongs to the technical field of high value-added utilization of biomass resources, and in particular relates to an environmentally friendly biomass-based water-based flame retardant and a preparation method thereof. Background Art

[0002] Flame retardants are a class of substances that can prevent materials from being ignited or inhibit the spread of flames. They are widely used in the flame retardant polymer material industry. Traditional flame retardants mainly include brominated flame retardants, chlorinated flame retardants and phosphated flame retardants. These flame retardants can effectively slow down or prevent the combustion of materials to a certain extent, but they also have some disadvantages: 1. Environmental pollution: Brominated and chlorinated flame retardants may have a negative impact on the environment. These chemicals may be released into the atmosphere or released into the soil and water when waste materials are processed, causing potential harm to the ecosystem.

[0003] 2. Bioaccumulation: Some brominated and chlorinated flame retardants are bioaccumulative, which means they gradually accumulate in the food chain. This may pose a potential toxicity risk to top predators in the food chain.

[0004] 3. Difficulty in degradation: Some brominated and chlorinated flame retardants may be difficult to degrade, especially in the natural environment. This may cause them to persist in the environment for a long time, further increasing their potential hazards.

[0005] Bio-based flame retardants refer to functional additives made from biomass that can make flammable materials flame retardant, prevent materials from being ignited and inhibit the spread of flames. This flame retardant developed based on bio-based materials with the characteristics of high efficiency, environmental protection, greenness, low smoke and low toxicity has become an effective way for scientists to solve the frequent fires in the application process of polymer materials. In addition, bio-based materials are biodegradable in the environment and are expected to solve the excessive carbon emissions, unsustainability and resource shortages caused by non-renewable substances such as petroleum-based compounds. Therefore, the research on the development of "green flame retardants" based on bio-based materials has great market value. Summary of the invention

[0006] The purpose of the present invention is to provide an environmentally friendly biomass-based water-based flame retardant and a preparation method thereof, in particular, a bio-based water-based flame retardant produced with orange peel tannin as a raw material, and discloses a method of increasing the number of phenolic hydroxyl groups of orange peel tannin through a polymerization reaction of catechins and orange peel tannin, forming a stable carbonized layer at high temperature, enhancing the solid phase flame retardant effect, and further compounding with sodium carboxymethyl cellulose and sodium dodecylbenzene sulfonate to further improve the adhesion and stability of the flame retardant, ensuring that the flame retardant is evenly coated on the surface of the material. The process is simple, water is used as a solvent, the reaction process is relatively green and environmentally friendly, and has the potential for large-scale production.

[0007] The specific technical solutions are as follows: An environmentally friendly biomass-based water-based flame retardant and a preparation method thereof. The raw materials of the environmentally friendly biomass-based water-based flame retardant are, by weight, 8 to 10 parts of orange peel tannin, 4.2 to 5.3 parts of catechins, 0.8 to 1.2 parts of sodium carboxymethyl cellulose, 0.3 to 0.5 parts of sodium dodecylbenzene sulfonate, 0.4 to 0.6 parts of oxidant, 0.1 to 0.3 parts of reducing agent, 0.08 to 0.12 parts of acid catalyst, 0.08 to 0.12 parts of alkaline catalyst and 180 to 210 parts of deionized water. The preparation method of the environmentally friendly biomass-based water-based flame retardant comprises the following steps: S1 raw material premix: a. In a multifunctional reactor, deionized water, orange peel tannin and catechin are added according to weight, the stirring rate is 1300-1500 r / min, and the mixture is mixed and stirred at 50-60° C. for 180-240 minutes; b. After step a, add sodium carboxymethyl cellulose by weight, stir at a rate of 1000 to 1200 r / min, mix and stir at 60 to 70° C. for 20 to 30 minutes, and perform ultrasonic treatment for 30 to 60 minutes to ensure full dispersion and avoid agglomeration; c. After step b, sodium dodecylbenzene sulfonate is added in parts by weight, and heating and stirring are continued during the addition process, the temperature is maintained at 60 to 70° C., and the stirring rate is 1300 to 1500 r / min for 30 to 60 minutes to obtain a raw material premix; S2 oxidation modification: after step S1, add oxidant by weight into the multifunctional reactor, stir at a rate of 1000-1200 r / min, and react at 50-60°C for 130-160 minutes; S3 reduction modification: in a multifunctional reactor, add a reducing agent by weight, stir at a rate of 1000-1200 r / min, and react at 50-60°C for 50-80 minutes; S4 Acid Catalysis: In a multifunctional reactor, add an acid catalyst by weight, adjust the pH value of the reaction system to 4.0-5.0, and continue stirring for 30-60 minutes; S5 base catalysis: In a multifunctional reactor, add base catalyst by weight, adjust the pH value of the reaction system to 6.0-7.0, continue stirring for 30-60 minutes, cool at 5-10°C for 50-80 minutes, and obtain an environmentally friendly bio-based water-based flame retardant.

[0008] In some embodiments, the oxidant may be a combination of one or more of hydrogen peroxide, potassium permanganate and sodium chlorate.

[0009] In some embodiments, the reducing agent may be a combination of one or more of sodium thiosulfate, carbon disulfide and hydrosulfuric acid.

[0010] In some embodiments, the acid catalyst may be a combination of one or more of sulfuric acid, phosphoric acid and hydrochloric acid.

[0011] In some embodiments, the base catalyst may be a combination of one or more of sodium hydroxide, potassium hydroxide and ammonia water.

[0012] In some embodiments, when sodium carboxymethyl cellulose is added in step S1, it needs to be added in 3 to 5 times, and the time interval between two additions is 10 to 20 minutes.

[0013] In some embodiments, when the acid catalyst is added in step S4 and the base catalyst is added in step S5, the adding speed needs to be controlled to be 10-15 g per minute.

[0014] The present invention has the following advantages: 1. Environmentally friendly: Orange peel tannins and catechins are both natural plant extracts, reducing dependence on petroleum-based chemicals; the base solvent of the flame retardant is water, avoiding the use of organic solvents, and having little impact on the environment during production and use; 2. Low bioaccumulation: The components of biomass-based water-based flame retardants are more easily degraded in the natural environment and have a low degree of accumulation in organisms; 3. Fast degradation rate: The main raw materials in the present invention are biodegradable materials, which degrade quickly in the environment, reducing potential harm to soil, water sources and organisms. DETAILED DESCRIPTION

[0015] The following will combine the technical process steps, specific implementation conditions and materials in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Example

[0016] In a multifunctional reactor, deionized water, orange peel tannins and catechins were added by weight, the stirring rate was 1300 r / min, and the mixture was mixed and stirred at 50°C for 180 minutes; sodium carboxymethyl cellulose was added by weight in 3 times, the time interval between two additions was 12 minutes, the stirring rate was 1000 r / min, the mixture was mixed and stirred at 60°C for 25 minutes, and ultrasonic treatment was performed for 40 minutes to ensure sufficient dispersion and avoid agglomeration; sodium dodecylbenzene sulfonate was added by weight, and heating and stirring were continued during the addition process, the temperature was maintained at 60°C, the stirring rate was 1300 r / min, and the mixture was continued for 40 minutes to obtain a raw material premix solution for standby use.

[0017] Table 1 Ratio of raw materials for preparing raw material premix solution in Example 1 Deionized water 185 copies Orange peel tannin 8 servings Catechins 4.5 servings Sodium Carboxymethyl Cellulose 0.8 parts Sodium dodecylbenzenesulfonate 0.35 Example

[0018] In a multifunctional reactor, deionized water, orange peel tannins and catechins were added according to weight portions, the stirring rate was 1300 r / min, and the mixture was mixed and stirred at 50°C for 180 minutes; sodium carboxymethyl cellulose was added according to weight portions in 3 times, the time interval between two additions was 12 minutes, the stirring rate was 1200 r / min, the mixture was mixed and stirred at 70°C for 30 minutes, and ultrasonic treatment was performed for 50 minutes to ensure sufficient dispersion and avoid agglomeration; sodium dodecylbenzene sulfonate was added according to weight portions, and heating and stirring were continued during the addition process, the temperature was maintained at 70°C, the stirring rate was 1300 r / min, and the mixture was stirred for 50 minutes to obtain a raw material premix solution for standby use.

[0019] Table 2 Ratio of raw materials for preparing raw material premix solution in Example 2 Deionized water 205 copies Orange peel tannin 9 servings Catechins 5.2 servings Sodium Carboxymethyl Cellulose 1.2 servings Sodium dodecylbenzenesulfonate 0.5 serving Example

[0020] In a multifunctional reactor, add an oxidant and the raw material premix obtained in Example 1 according to the mass fraction, stir at a rate of 1000 r / min, and react at 50°C for 130 minutes; add a reducing agent according to the mass fraction, stir continuously, stir at a rate of 1000 r / min, and react at 50°C for 50 minutes; add an acid catalyst according to the mass fraction, add it to the multifunctional reactor at a rate of 10 g per minute, adjust the pH value to 4.0, and stir continuously for 50 minutes. Add a base catalyst according to the mass fraction, add it to the multifunctional reactor at a rate of 10 g per minute, adjust the pH value to 7.0, stir continuously for 50 minutes, and cool at 5°C for 60 minutes to obtain an environmentally friendly bio-based water-based flame retardant.

[0021] Table 3 Raw material ratios for preparing environmentally friendly bio-based water-based flame retardants in Example 3 Raw material premix 200 copies Hydrogen Peroxide 0.4 parts Sodium Thiosulfate 0.1 part sulfuric acid 0.08 Sodium hydroxide 0.08 Example

[0022] In a multifunctional reactor, add an oxidant and the raw material premix obtained in Example 2 according to the mass fraction, stir at a rate of 1200 r / min, and react at 55°C for 140 minutes; add a reducing agent according to the mass fraction, stir continuously, stir at a rate of 1200 r / min, and react at 60°C for 60 minutes; add an acid catalyst according to the mass fraction, add it to the multifunctional reactor at a rate of 10 g per minute, adjust the pH value to 4.0, and stir continuously for 50 minutes. Add a base catalyst according to the mass fraction, add it to the multifunctional reactor at a rate of 10 g per minute, adjust the pH value to 6.0, stir continuously for 50 minutes, and cool at 5°C for 60 minutes to obtain an environmentally friendly bio-based water-based flame retardant.

[0023] Table 4 Raw material ratios for preparing environmentally friendly bio-based water-based flame retardants in Example 4 Raw material premix 200 copies potassium permanganate 0.5 serving Carbon disulfide 0.2 parts Phosphoric acid 0.1 part Potassium hydroxide 0.08 According to the national standard GB / 17835-2008 "Water-based Fire Extinguishing Agents" test, take a certain amount of samples, conduct a high temperature test in an environment of (60±2)℃ for 7 days, and finally place them in an environment of (20±5)℃ for 24 hours or more before filling the fire extinguisher.

[0024] Class A fire extinguishing test and Class B fire extinguishing test were carried out respectively. No visible flame appeared after the flame was extinguished. The fire was extinguished successfully and met the national standards. Example

[0025] In a multifunctional reactor, add an oxidant and the raw material premix obtained in Example 2 according to the mass fraction, stir at a rate of 1200 r / min, and react at 60°C for 160 minutes; add a reducing agent according to the mass fraction, stir continuously, stir at a rate of 1200 r / min, and react at 60°C for 60 minutes; add an acid catalyst according to the mass fraction, add it to the multifunctional reactor at a rate of 10 g per minute, adjust the pH value to 5.0, and stir continuously for 50 minutes. Add a base catalyst according to the mass fraction, add it to the multifunctional reactor at a rate of 10 g per minute, adjust the pH value to 7.0, stir continuously for 50 minutes, and cool at 5°C for 60 minutes to obtain an environmentally friendly bio-based water-based flame retardant.

[0026] Table 5 Raw material ratios for preparing environmentally friendly bio-based water-based flame retardants in Example 5 Raw material premix 200 copies Sodium chlorate 0.6 parts Hydrogen Sulfate 0.3 parts hydrochloric acid 0.12 parts Potassium hydroxide 0.1 part According to the national standard GB / 17835-2008 "Water-based Fire Extinguishing Agents" test, take a certain amount of samples, conduct a high temperature test in an environment of (60±2)℃ for 7 days, and finally place them in an environment of (20±5)℃ for 24 hours or more before filling the fire extinguisher.

[0027] Class A fire extinguishing test and Class B fire extinguishing test were carried out respectively. No visible flame appeared after the flame was extinguished. The fire was extinguished successfully and met the national standards.

[0028] Comparative Example 1 No catechin was added to the raw material premix, and the other steps were the same as those in Example 4.

[0029] According to the national standard GB / 17835-2008 "Water-based Fire Extinguishing Agents" test, take a certain amount of samples, conduct a high temperature test in an environment of (60±2)℃ for 7 days, and finally place them in an environment of (20±5)℃ for 24 hours or more before filling the fire extinguisher.

[0030] When conducting Class A fire extinguishing test and Class B fire extinguishing test respectively, visible flames appeared after the flames were extinguished, indicating fire extinguishing failure, which does not meet national standards.

[0031] Comparative Example 2 No sodium carboxymethyl cellulose was added to the raw material premix, and the other steps were the same as those in Example 4.

[0032] According to the national standard GB / 17835-2008 "Water-based Fire Extinguishing Agents" test, take a certain amount of samples, conduct a high temperature test in an environment of (60±2)℃ for 7 days, and finally place them in an environment of (20±5)℃ for 24 hours or more before filling the fire extinguisher.

[0033] When conducting Class A fire extinguishing test and Class B fire extinguishing test respectively, visible flames appeared after the flames were extinguished, indicating fire extinguishing failure, which does not meet national standards.

[0034] Technical personnel should note that although the present invention has been described according to the above specific implementation methods, the inventive concept of the present invention is not limited to this invention, and any modification using the inventive concept will be included in the scope of protection of this patent.

Claims

1. An environmentally friendly biomass-based water-based flame retardant and a preparation method thereof, characterized in that: The raw materials of the environmentally friendly bio-based water-based flame retardant are: 8-10 parts of orange peel tannin, 4.2-5.3 parts of catechins, 0.8-1.2 parts of sodium carboxymethyl cellulose, 0.3-0.5 parts of sodium dodecylbenzene sulfonate, 0.4-0.6 parts of oxidant, 0.1-0.3 parts of reducing agent, 0.08-0.12 parts of acid catalyst, 0.08-0.12 parts of base catalyst and 180-210 parts of deionized water. The preparation method of the environmentally friendly bio-based water-based flame retardant comprises the following steps: S1 raw material premixing: a. In a multifunctional reactor, add deionized water, orange peel tannin and catechin according to weight, stir at a rate of 1300-1500 r / min, and mix and stir at 50-60° C. for 180-240 minutes; b. After step a, add sodium carboxymethyl cellulose by weight, stir at a rate of 1000 to 1200 r / min, mix and stir at 60 to 70° C. for 20 to 30 minutes, and perform ultrasonic treatment for 30 to 60 minutes to ensure full dispersion and avoid agglomeration; c. After step b, sodium dodecylbenzene sulfonate is added in parts by weight, and heating and stirring are continued during the addition process, the temperature is maintained at 60 to 70° C., and the stirring rate is 1300 to 1500 r / min for 30 to 60 minutes to obtain a raw material premix; S2 oxidation modification: after step S1, add oxidant by weight into the multifunctional reactor, stir at a rate of 1000-1200 r / min, and react at 50-60°C for 130-160 minutes; S3 reduction modification: in a multifunctional reactor, add a reducing agent by weight, stir at a rate of 1000-1200 r / min, and react at 50-60°C for 50-80 minutes; S4 Acid Catalysis: In a multifunctional reactor, add an acid catalyst by weight, adjust the pH value of the reaction system to 4.0-5.0, and continue stirring for 30-60 minutes; S5 base catalysis: In a multifunctional reactor, add base catalyst by weight, adjust the pH value of the reaction system to 6.0-7.0, continue stirring for 30-60 minutes, cool at 5-10°C for 50-80 minutes, and obtain an environmentally friendly bio-based water-based flame retardant.

2. An environmentally friendly biomass-based water-based flame retardant and a preparation method thereof according to claim 1, characterized in that: The oxidant may be a combination of one or more of hydrogen peroxide, potassium permanganate and sodium chlorate.

3. The environmentally friendly biomass-based water-based flame retardant and the preparation method thereof according to claim 1, characterized in that: The reducing agent may be a combination of one or more of sodium thiosulfate, carbon disulfide and hydrosulfuric acid.

4. The environmentally friendly biomass-based water-based flame retardant and the preparation method thereof according to claim 1, characterized in that: The acid catalyst may be a combination of one or more of sulfuric acid, phosphoric acid and hydrochloric acid.

5. The environmentally friendly biomass-based water-based flame retardant and the preparation method thereof according to claim 1, characterized in that: The alkaline catalyst may be a combination of one or more of sodium hydroxide, potassium hydroxide and ammonia water.

6. The environmentally friendly biomass-based water-based flame retardant and the preparation method thereof according to claim 1, characterized in that: When sodium carboxymethyl cellulose is added in step S1, it needs to be added in 3 to 5 times, with the time interval between two additions being 10 to 20 minutes.

7. The environmentally friendly biomass-based water-based flame retardant and the preparation method thereof according to claim 1, characterized in that: When the acid catalyst is added in step S4 and the base catalyst is added in step S5, the adding speed needs to be controlled to be 10-15 g per minute.