Environment-friendly flame-retardant cellulose material and preparation method thereof

Abstract

The invention provides a green and environment-friendly flame-retardant cellulose material and a preparation method thereof. The green and environment-friendly flame-retardant cellulose material is prepared from the following components in parts by weight: 20 to 40 parts of bio-based cellulose, 60 to 90 parts of phosphate, 30 to 90 parts of urea, 5 to 10 parts of amino silicon oil microemulsion and 90 to 150 parts of melamine. The flame-retardant cellulose material prepared by the invention has excellent flame retardance, realizes waste utilization and environment-friendly production at the same time, adopts cellulose with a wide source, is low in cost, and meets the requirements of sustainable development; the flame retardant property of the cellulose is remarkably improved through synergistic modification. High-temperature and high-pressure conditions are provided through the hydrothermal reaction kettle, uniform combination of phosphate and cellulose molecules is promoted, the modification efficiency is improved, and excessive damage of high temperature to the cellulose molecular structure is avoided. Meanwhile, through the auxiliary effect of urea, the temperature required by the phosphorylation reaction is reduced, and the integrity of cellulose molecules is protected; the reaction activity of hydroxyl is improved, and the modification uniformity is promoted; the compatibility of the material and thermoplastic resin is improved.

Description

Technical Field

[0001] The invention relates to the technical field of flame-retardant cellulose, and in particular to a green and environment-friendly flame-retardant cellulose material and a preparation method thereof. Background Art

[0002] With the rapid development of social economy, energy and ecological environment problems are becoming increasingly severe. Especially in the context of the rapid growth of the new energy vehicle industry, the safety of its power batteries has attracted much attention. The risk of thermal runaway of lithium battery packs makes flame retardancy a key requirement. Traditional flame retardant materials are based on petrochemical products, and have problems such as resource shortages, high costs and environmental pollution. Cellulose is a natural polymer material with a wide range of sources and biodegradability. Its unique physical and chemical properties make it an ideal choice for the development of green and environmentally friendly flame retardant materials. However, the flame retardancy of natural cellulose is insufficient and needs to be improved through reasonable chemical modification.

[0003] The present invention aims to solve the deficiencies of existing flame retardant materials in terms of performance, cost and environmental protection, develop a green and environmentally friendly flame retardant cellulose material, and provide an efficient preparation method thereof. Summary of the invention

[0004] The purpose of the present invention is to solve the defects of the above-mentioned prior art and provide a green and environmentally friendly flame retardant cellulose material and a preparation method thereof. Bio-based cellulose is used as raw material and is synergistically modified by amino silicone oil microemulsion, phosphate and melamine to prepare a flame retardant cellulose material with superior performance, low cost and green environmental protection.

[0005] According to one object of the present invention, the present invention provides a green and environmentally friendly flame retardant cellulose material, comprising the following components in parts by weight:

[0006] 20-40 parts of bio-based cellulose, 60-90 parts of phosphate, 30-90 parts of urea, 5-10 parts of amino silicone oil microemulsion and 90-150 parts of melamine.

[0007] Further, the following components are included in parts by weight:

[0008] 30 parts of bio-based cellulose, 75 parts of phosphate, 45 parts of urea, 10 parts of amino silicone oil microemulsion and 120 parts of melamine.

[0009] According to another object of the present invention, the present invention provides a method for preparing the above-mentioned green and environmentally friendly flame-retardant cellulose material, comprising the following steps:

[0010] S1. Cellulose pretreatment: adding bio-based cellulose to a diluted amino silicone oil microemulsion solution and subjecting it to ultrasonic vibration treatment to form a modified cellulose raw material;

[0011] S2, mixing treatment: mixing the modified cellulose with the phosphate / urea solution, and stirring thoroughly to dissolve;

[0012] S3, hydrothermal reaction: placing the above mixed solution in a hydrothermal reactor, and reacting under certain temperature and pressure conditions;

[0013] S4, post-treatment: mixing the hydrothermal reaction product with the melamine solution and further heating the reaction;

[0014] S5. Finished product processing: filtering, washing, and drying to obtain the final product.

[0015] Beneficial effects:

[0016] The flame-retardant cellulose material prepared by the present invention has excellent flame-retardant properties, realizes waste utilization and environmentally friendly production at the same time, adopts cellulose from a wide range of sources, has low cost, and meets the needs of sustainable development; synergistic modification significantly improves the flame-retardant properties of cellulose, and meets the needs of high-safety applications; the process is simple and easy to promote industrialization; the product is non-toxic and harmless after combustion, and is green and environmentally friendly.

[0017] The present invention provides high temperature and high pressure conditions through a hydrothermal reactor to promote the uniform combination of phosphate and cellulose molecules, improve the modification efficiency, and avoid excessive damage to the cellulose molecular structure by high temperature. At the same time, through the auxiliary effect of urea, the temperature required for the phosphorylation reaction is reduced to protect the integrity of the cellulose molecules; the reaction activity of the hydroxyl group is increased to promote the uniformity of the modification; and the compatibility of the material with the thermoplastic resin is improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a flow chart of green and environmentally friendly flame-retardant cellulose modification according to an embodiment of the present invention. DETAILED DESCRIPTION

[0019] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention is described clearly and completely below. Obviously, the described embodiments are 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.

[0020] Example 1

[0021] A green and environment-friendly flame-retardant cellulose material is prepared according to the following weight ratio: 30 parts of bio-based cellulose, 75 parts of phosphate, 45 parts of urea, 10 parts of amino silicone oil microemulsion and 120 parts of melamine.

[0022] like Figure 1 As shown, the preparation method thereof comprises the following steps:

[0023] Cellulose pretreatment:

[0024] After 10 parts of amino silicone oil microemulsion was diluted 20 times, 30 parts of bio-based cellulose were added, the solution was placed in an ultrasonic instrument for 20 minutes, and then filtered and dried to obtain a modified cellulose raw material.

[0025] Mixed Processing:

[0026] The modified cellulose is added into the mixed solution of phosphate and urea, and stirred until it is completely dissolved to form a uniform mixed solution.

[0027] Hydrothermal reaction:

[0028] The mixed solution was transferred into a hydrothermal reactor and heated at 100°C for 90 minutes. After the reaction was completed, it was cooled and taken out for later use.

[0029] Post-processing:

[0030] A melamine solution (mass ratio of melamine to distilled water: 1:5) was added to the hydrothermal reaction product, and the mixture was stirred and reacted at 90° C. for 90 minutes to form a solid product.

[0031] Finished product processing:

[0032] The product is filtered, washed and dried to obtain a green and environment-friendly flame-retardant cellulose material.

[0033] Example 2

[0034] A green and environment-friendly flame-retardant cellulose material is prepared according to the following weight ratio: 20 parts of bio-based cellulose, 60 parts of phosphate, 30 parts of urea, 5 parts of amino silicone oil microemulsion and 90 parts of melamine.

[0035] The preparation method thereof comprises the following steps:

[0036] Cellulose pretreatment:

[0037] After 5 parts of amino silicone oil microemulsion were diluted 20 times, 20 parts of bio-based cellulose were added, the solution was placed in an ultrasonic instrument for 30 minutes, and then filtered and dried to obtain a modified cellulose raw material.

[0038] Mixed Processing:

[0039] The modified cellulose is added into the mixed solution of phosphate and urea, and stirred until it is completely dissolved to form a uniform mixed solution.

[0040] Hydrothermal reaction:

[0041] The mixed solution was transferred into a hydrothermal reactor and heated at 110°C for 90 minutes. After the reaction was completed, it was cooled and taken out for later use.

[0042] Post-processing:

[0043] A melamine solution (mass ratio of melamine to distilled water: 1:5) was added to the hydrothermal reaction product, and the mixture was stirred and reacted at 90° C. for 60 minutes to form a solid product.

[0044] Finished product processing:

[0045] The product is filtered, washed and dried to obtain a green and environment-friendly flame-retardant cellulose material.

[0046] Example 3

[0047] A green and environment-friendly flame-retardant cellulose material is prepared according to the following weight ratio: 40 parts of bio-based cellulose, 90 parts of phosphate, 90 parts of urea, 10 parts of amino silicone oil microemulsion and 150 parts of melamine.

[0048] The preparation method thereof comprises the following steps:

[0049] Cellulose pretreatment:

[0050] After 10 parts of amino silicone oil microemulsion was diluted 20 times, 40 parts of bio-based cellulose were added, and the solution was placed in an ultrasonic instrument for 30 minutes, and then filtered and dried to obtain a modified cellulose raw material.

[0051] Mixed Processing:

[0052] The modified cellulose is added into the mixed solution of phosphate and urea, and stirred until it is completely dissolved to form a uniform mixed solution.

[0053] Hydrothermal reaction:

[0054] The mixed solution was transferred into a hydrothermal reactor and heated at 120°C for 70 minutes. After the reaction was completed, it was cooled and taken out for later use.

[0055] Post-processing:

[0056] A melamine solution (mass ratio of melamine to distilled water: 1:5) was added to the hydrothermal reaction product, and the mixture was stirred and reacted at 90° C. for 90 minutes to form a solid product.

[0057] Finished product processing:

[0058] The product is filtered, washed and dried to obtain a green and environment-friendly flame-retardant cellulose material.

[0059] Example 4

[0060] This embodiment is basically the same as Embodiment 1, except that the phosphate is adjusted to a mixture of phosphorous acid and metaphosphoric acid (mass ratio 1:1), and the remaining steps and conditions are consistent with Embodiment 1, and finally a cellulose material with stable performance and higher flame retardancy is obtained.

[0061] Example 5

[0062] This embodiment is basically the same as Embodiment 1, except that the heating temperature of the hydrothermal reactor is adjusted to 120° C. and the reaction time is reduced to 70 minutes. The obtained product also has excellent flame retardant properties.

[0063] The flame-retardant cellulose material prepared by the present invention has excellent flame-retardant properties, realizes waste utilization and environmentally friendly production at the same time, adopts cellulose from a wide range of sources, has low cost, and meets the needs of sustainable development; synergistic modification significantly improves the flame-retardant properties of cellulose, and meets the needs of high-safety applications; the process is simple and easy to promote industrialization; the product is non-toxic and harmless after combustion, and is green and environmentally friendly.

[0064] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A green and environmentally friendly flame retardant cellulose material, characterized in that: The composition comprises the following components in parts by weight: 20-40 parts of bio-based cellulose, 60-90 parts of phosphate, 30-90 parts of urea, 5-10 parts of amino silicone oil microemulsion and 90-150 parts of melamine.

2. The green and environmentally friendly flame retardant cellulose material according to claim 1, characterized in that: The phosphate is one or a mixture of phosphoric acid, phosphorous acid, hypophosphorous acid or metaphosphoric acid.

3. The green and environmentally friendly flame retardant cellulose material according to claim 1, characterized in that: The dilution ratio of the amino silicone oil microemulsion is 10-20 times.

4. A method for preparing a green and environmentally friendly flame-retardant cellulose material, characterized in that: The steps include: 1) adding bio-based cellulose to a diluted amino silicone oil microemulsion and ultrasonically dispersing the mixture to obtain a modified material A; 2) adding modified material A to the phosphate / urea mixed solution and stirring until dissolved to obtain a mixed solution B; 3) placing the mixed solution B in a hydrothermal reactor for heating and reaction to form a reaction product C; 4) adding melamine solution to the reaction product C, stirring and heating to react; 5) filtering, washing and drying to obtain a flame retardant cellulose material.

5. The preparation method according to claim 4, characterized in that: The ultrasonic dispersion time in step 1) is 20-30 minutes.

6. The preparation method according to claim 4, characterized in that: In step 3), the hydrothermal reaction temperature is 100-120° C. and the reaction time is 70-90 minutes.

7. The preparation method according to claim 4, characterized in that: In step 4), the mass ratio of melamine to distilled water is 1:

5.

8. The preparation method according to claim 4, characterized in that: In step 5), the temperature of the constant temperature magnetic stirrer is set to 90° C. for 60-90 minutes.

9. The green and environmentally friendly flame-retardant cellulose material according to claim 1, characterized in that: The material has excellent flame retardant properties and only produces water vapor, carbon dioxide, nitrogen and ammonia after combustion.

10. The preparation method according to claim 4, characterized in that: The obtained flame retardant cellulose material has multiple flame retardant functional layers.

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