Flame-retardant full-biodegradable composition and preparation method thereof
By introducing a compound of arginine-phytic acid flame retardant and plant microcrystalline cellulose onto biodegradable layered organic silica nanosheets, the problems of flammability of biodegradable materials and the non-renewable and non-degradable nature of traditional flame retardants are solved, thus achieving high-efficiency flame retardancy and sustainability of the material.
Patent Information
- Application Number
- CN202511286520.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-10
- Publication Date
- 2025-11-07
AI Technical Summary
Fully biodegradable materials are flammable and exhibit severe dripping during combustion. Traditional flame retardants are neither renewable nor degradable, limiting their application in the automotive, electronics, and construction industries.
A biodegradable layered organic silica nanosheet loaded with arginine-phytic acid was used as the main flame retardant, and compounded with plant microcrystalline cellulose. The flame retardant performance was improved by utilizing the dehydration, pyrolysis and carbonization of the nanosheet during the heating process, while the interfacial effect of the plant microcrystalline cellulose was used to enhance the charring ability.
It improves the flame retardant properties of fully biodegradable materials, broadens their application areas, and realizes the renewable and degradable characteristics of flame retardants.
Smart Images
Figure CN120904651A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of full biodegradable flame retardant, in particular to a full biodegradable flame-retardant composition and a preparation method thereof. BACKGROUND
[0002] Full biodegradable materials are renewable, degradable, have good mechanical properties, processing properties and biocompatibility, and are green polymer materials that can replace petroleum-based polymers, and have a wide range of applications. However, full biodegradable materials are flammable and have serious melt dripping phenomenon during combustion, which greatly limits their application in the automotive industry, electronics and electrical appliances, and construction industry.
[0003] Traditional organic or inorganic flame retardants have their respective shortcomings. Inorganic flame retardants have good environmental protection and low cost, but generally have a high addition amount, poor compatibility with resin matrix, and can adversely affect the mechanical properties of the resin matrix. Organic flame retardants have a low addition amount and good flame retardant effect, but can migrate in the resin matrix due to environmental factors such as temperature and humidity, affecting the flame retardant effect and causing environmental pollution. Moreover, most of the current flame retardants are not renewable and degradable, which is contrary to the advantages of biobased polymer materials, such as being renewable and degradable. SUMMARY
[0004] To solve the problem of the contradiction between flame retardation and full degradation mentioned in the background, the purpose of the present application is to develop a full biodegradable flame-retardant composition that can improve the flame retardation of materials while maintaining the advantages of being renewable and degradable, and expanding the application field. In order to achieve the above purpose, the technical scheme adopted by the present application is as follows: A full biodegradable flame-retardant composition, comprising the following components by weight fraction: biobased resin 40-60 parts; plant microcrystalline cellulose 5-10 parts; biobased flame retardant 5-15 parts; compatibility agent 2-5 parts; toughening agent 5-10 parts; antioxidant 0.1-0.5 parts.
[0005] As a preferred scheme, the biobased flame retardant is degradable layered organosilica nanosheet loaded with arginine-phytic acid, and the preparation method comprises the following steps: Step (one): 5-10 g of arginine-phytic acid is weighed and added to a flask, then silane coupling agent ethanol solution is added in sequence, and the reaction is heated and stirred in a 50-80℃ oil bath for 0.5-1.5 h. After the reaction is completed, the product is obtained by washing with ethanol for 3-5 times to obtain solution A; Step (two): add the degradable layered organosilica nanosheet to solution A, stir and heat to 50-80℃, and fully react for 10-20h. After the reaction is completed, product B is obtained; Step (three): centrifuge, filter, dry, and grind product B to obtain the degradable layered organosilica nanosheet loaded arginine-phytic acid bio-based flame retardant.
[0006] As a preferred solution, the preparation method of arginine-phytic acid in step (one) comprises the following steps: (1) weigh 5-10g of arginine and add it to 100-200mL of deionized water, and disperse in an ultrasonic for 10-30min to obtain an arginine solution; (2) weigh 5-10g of 70% phytic acid solution and 100-200mL of deionized water, and disperse in an ultrasonic for 10-30min to obtain a phytic acid solution; (3) add the arginine solution prepared in step (1) to the phytic acid solution in step (2), then place the reactants on a magnetic stirrer and react for 0.5-1.5h. After the reaction is completed, the liquid reactant is slowly poured into 300-500mL of ethanol, and then washed, dried, and ground to obtain arginine-phytic acid with a yield of 85.5%.
[0007] As a preferred solution, the coupling agent in step (one) is at least one of silane coupling agents KH-550, KH-560, and KH-570.
[0008] As a preferred solution, the preparation method of the degradable layered organosilica nanosheet in step (two) comprises the following steps: (1) weigh 0.5-1.5g of sodium hydroxide solution and add it to 50-100mL of pure water, then slowly add 1-5mL of tetraethyl orthosilicate and 1-5mL of ethyl acetate while stirring, fully react for 3-5h, then slowly add 0.1-0.5mL of 3-aminopropyltriethoxysilane, add 0.1-0.5g of cetyltrimethylammonium bromide and 0.01-0.05mL of NaOH solution, fully stir for 1-5h, then add tetraethyl orthosilicate and tripropyl ethoxysilane ethanol solution, and then centrifuge at a speed of 10000-13000r / min for 5-10min to collect the product, and then wash and extract using hydrochloric acid ethanol at a temperature of 50-80℃ to obtain the degradable sandwich organosilica nanosheet; (2) add the sandwich degradable layered organosilica nanosheet prepared in step (1) to a sodium borohydride solution with a concentration of 50-100mg / mL, fully react for 30-60min at room temperature, and then wash, filter, and dry to obtain the degradable layered organosilica nanosheet.
[0009] As a preferred solution, the bio-based resin is at least two of PLA, PBS, PBAT and PCL.
[0010] As a preferred solution, the plant microcrystalline cellulose is at least one of rice straw microcrystalline cellulose, cotton microcrystalline cellulose, bamboo microcrystalline cellulose and wheat straw microcrystalline cellulose.
[0011] As a preferred solution, the compatilizer is at least one of POE-g-MAH, EAA-g-MAH and EVA-g-MAH; the toughening agent is at least one of POE, EVA and EAA; and the weight ratio of the antioxidants 168 and 1076 is 1: (1-3).
[0012] As a preferred solution, a preparation method of the full-biodegradable composition with flame retardation according to claim 1 comprises the following steps: Step one, mixing and discharging the bio-based resin, plant microcrystalline cellulose, bio-based flame retardant, compatilizer, toughening agent and antioxidant to obtain a full-biodegradable composition with flame retardation mixture; Step two, melt-extruding the full-biodegradable composition with flame retardation mixture through a double-screw extruder to obtain a full-biodegradable composition with flame retardation modifier.
[0013] Compared with the prior art, the present application has the following beneficial effects: 1. Introducing a flame retardant into a bio-based resin is the most common method for preparing a flame-retardant degradable material. Traditional flame-retardant systems include halogen-based, phosphorus-based, nitrogen-based and silicon-based flame retardants. These flame-retardant systems have the disadvantages of producing toxic and harmful gases, low flame-retardant efficiency and large addition amount. Moreover, traditional flame retardants are mostly chemical raw materials prepared through complex reactions, and chemical raw materials are mostly non-renewable, which cannot truly realize sustainable development of renewable and degradable. The bio-based flame retardant prepared in the present application is derived from nature and has the advantages of being renewable and degradable.
[0014] 2. The present application uses arginine-phytic acid as the main flame retardant by preparing degradable layered organosilica nanosheets loaded with arginine-phytic acid. Arginine-phytic acid is used as an acid source, and its dehydration, pyrolysis and carbonization during heating improve the flame-retardant performance of the system. Meanwhile, plant microcrystalline cellulose is compounded as a carbon source, and the strong interfacial interaction between the nanosized structure of the plant microcrystalline cellulose and the bio-based resin improves the carbonization capacity and protects the matrix, effectively improving the flame-retardant performance of the full-degradable material.
[0015] 3. The application develops a full-biodegradable composition with flame retardation, solves the problem of poor flame retardation of traditional degradable materials, and widens the application field. BRIEF DESCRIPTION OF DRAWINGS
[0016] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without any creative labor.
[0017] Figure 1 SEM image of the degradable layered organosilica nanosheet prepared in Example 1 of the present application.
[0018] Figure 2 SEM image of the combustion carbon layer of the full-biodegradable composition with flame retardation prepared in Example 1 of the present application. DETAILED DESCRIPTION
[0019] The present application will be further described in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present application and not used to limit the scope of the present application. In addition, it should be understood that those skilled in the art can make various modifications or changes to the present application after reading the content taught by the present application, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
[0020] The present application also provides Examples 1-5 and Comparative Examples 1-3 as follows: Table 1: List of components and proportions of Examples 1-5 and Comparative Examples 1-3 The specific preparation method is as follows: The preparation method of the bio-based flame retardant includes the following steps: Step (one): 5-10g of arginine-phytic acid is weighed and added to a flask, then silane coupling agent ethanol solution is added in sequence, and the reaction is heated and stirred magnetically in an oil bath at 50-80℃ for 0.5-1.5h. After the reaction is completed, the product is obtained by washing with ethanol for 3-5 times to obtain solution A; Step (two): biodegradable layered organosilica nanosheets are added to solution A, heated to 50-80℃ while stirring, and fully reacted for 10-20h. After the reaction is completed, product B is obtained. Step (three): product B is centrifuged, filtered, dried, and ground to obtain biodegradable layered organosilica nanosheet loaded arginine-phytic acid bio-based flame retardant.
[0021] The preparation method of arginine-phytic acid in step (1) of the above scheme comprises the following steps: (1) Take 5-10 g of arginine and add it to 100-200 mL of deionized water, and place it in an ultrasonic device for 10-30 min to obtain an arginine solution; (2) Take 5-10 g of 70% phytic acid solution and add it to 100-200 mL of deionized water, and place it in an ultrasonic device for 10-30 min to obtain a phytic acid solution; (3) Add the arginine solution prepared in step (1) to the phytic acid solution prepared in step (2), then place the reactants on a magnetic stirrer for 0.5-1.5 h, and after the reaction is completed, obtain a liquid reactant, slowly pour the liquid reactant into 300-500 mL of ethanol, and after washing, drying, and grinding, obtain arginine-phytic acid, with a yield of 85.5% The preparation method of the degradable layered organosilica nanosheet in step (2) of the above scheme comprises the following steps: (1) Take 0.5-1.5 g of sodium hydroxide solution and add it to 50-100 mL of pure water, while stirring, slowly add 1-5 mL of tetraethyl orthosilicate and 1-5 mL of ethyl acetate, stir for 3-5 h for complete reaction, then slowly add 0.1-0.5 mL of 3-aminopropyl triethoxysilane, add 0.1-0.5 g of cetyltrimethylammonium bromide and 0.01-0.05 mL of NaOH solution, stir for 1-5 h, then add tetraethyl orthosilicate and tripropyl ethoxysilane ethanol solution, and then centrifuge at a speed of 10,000-13,000 r / min for 5-10 min to collect the product, and then wash, extract, and wash the product using hydrochloric acid ethanol at a temperature of 50-80°C to obtain the degradable sandwiched organosilica nanosheet; (2) Add the sandwiched degradable organosilica nanosheet prepared in step (1) to a sodium borohydride solution with a concentration of 50-100 mg / mL, stir at room temperature for 30-60 min for complete reaction, and then wash, filter, and dry to obtain the degradable layered organosilica nanosheet.
[0022] A preparation method of a flame-retardant full-biodegradable composition comprises the following steps: Step one, mix and discharge the bio-based resin, plant microcrystalline cellulose, bio-based flame retardant, compatibilizer, toughening agent, and antioxidant to obtain a flame-retardant full-biodegradable composition mixture; Step two, melt-extrude the flame-retardant full-biodegradable composition mixture through a twin-screw extruder to obtain a modified flame-retardant full-biodegradable composition.
[0023] The specific performance detection and result evaluation are as follows: The samples obtained in the above Examples 1-5 and Comparative Examples 1-3 were subjected to vertical burning rating test according to GB / T 2408-2021 "Determination of the flammability of plastics - Horizontal and vertical method", limiting oxygen index test according to "Determination of the flammability of plastics - Part 2: Room temperature test by the oxygen index method", and 180d biodegradation rate according to ISO 14855-1-2012; the test results are shown in Table 2.
[0024] Table 2 Test results of Examples 1-5 and Comparative Examples 1-3 Test item Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Flame retardant rating V-0 V-1 V-1 V-0 V-0 None V-2 None Oxygen index (%) 33.5 28.2 27.1 36.3 32.8 19.1 25.3 18.9 180Biodegradability (%) 91.3 91.3 90.8 90.9 91.2 91.8 92.1 92.3 As can be seen from the results in Table 2, in Examples 1-5 and Comparative Examples 1-3, whether it is an example or a comparative example, the addition of the flame retardant can effectively improve the flame retardant performance of the degradable material. Comparative Example 1 does not add a bio-based flame retardant, and the material basically does not have flame retardant performance; Comparative Example 2 simply adds a bio-based flame retardant without adding plant microcrystalline cellulose, and its flame retardant effect is obviously not as good as that of the examples, indicating that the bio-based flame retardant and the plant microcrystalline cellulose have good flame retardant synergistic effect. As can be seen, the use of bio-based flame retardant and plant microcrystalline cellulose can effectively improve the flame retardant performance of the degradable material, and the flame retardant is green and degradable. The prepared degradable layered organosilica nanosheet loaded arginine-phytic acid as the main flame retardant, utilizes the interlayer structure of the degradable layered organosilica nanosheet to load arginine-phytic acid, uses arginine-phytic acid as an acid source, utilizes its dehydration, pyrolysis and carbonization during the heating process to improve the flame retardant performance of the system, and at the same time, the plant microcrystalline cellulose is compounded as a carbon source, which utilizes the strong interfacial action between the nanoscale structure of the plant microcrystalline cellulose and the bio-based resin to improve the charring capacity and thus protect the matrix, effectively improving the flame retardant performance of the fully degradable material.
[0025] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.
Claims
1. A flame retardant, fully biodegradable composition, characterized in that, Comprise the following components by weight parts: Bio-based resin 40~60 parts; Plant microcrystalline cellulose 5~10 parts; Bio-based flame retardant 5~15 parts; Compatibilizer 2~5 parts; Toughening agent 5~10 parts; Antioxidant 0.1~0.5 parts; The bio-based flame retardant is degradable layered organic silicon dioxide nanosheet loaded arginine-phytic acid, and its preparation method comprises the following steps: Step (one): weigh 5~10g arginine-phytic acid into a flask, then add silane coupling agent ethanol solution in turn, place in 50~80℃ oil bath pot magnetic stirring heating reaction 0.5~1.5h, after reaction, ethanol washing 3~5 times to obtain product, obtain solution A; Step (two): add degradable layered organic silicon dioxide nanosheet to solution A, stir and heat to 50~80℃, fully react, reaction time is 10~20h, after reaction is completed, product B is obtained; Step (three): product B is centrifuged, filtered, dried and ground to obtain degradable layered organic silicon dioxide nanosheet loaded arginine-phytic acid bio-based flame retardant; The preparation method of arginine-phytic acid in step (one) comprises the following steps: (1) weigh 5~10g arginine into 100~200mL deionized water, disperse in ultrasonic for 10~30min to obtain arginine solution; (2) weigh 5~10g 70% phytic acid solution and 100~200mL deionized water, disperse in ultrasonic for 10~30min to obtain phytic acid solution; (3) add the arginine solution prepared in step (1) to the phytic acid solution in step (2), then place the reactants on magnetic stirring for 0.5~1.5h, after reaction, the liquid reactant is obtained, the liquid reactant is slowly poured into 300~500mL ethanol, washed, dried and ground to obtain arginine-phytic acid, the yield is 85.5%; The coupling agent in step (one) is at least one of silane coupling agents KH-550, KH-560 and KH-570; The preparation method of degradable layered organic silicon dioxide nanosheet in step (two) comprises the following steps: (1) weigh 0.5~1.5g sodium hydroxide solution into 50~100mL pure water, slowly add 1~5mL tetraethyl orthosilicate and 1~5mL ethyl acetate while stirring, fully react after stirring for 3~5h, slowly add 0.1~0.5mL 3-aminopropyl triethoxysilane, add 0.1~0.5g cetyltrimethylammonium bromide and 0.01~0.05mL NaOH solution, fully stir for 1~5h, then add tetraethyl orthosilicate and tripropyl ethoxysilane ethanol solution, then centrifuge at 10000~13000r / min for 5~10min to collect the product, wash and extract with hydrochloric acid ethanol at 50~80℃ to obtain degradable layered organic silicon dioxide nanosheet; (2) The sandwich degradable layered organosilica nanosheet prepared in step (1) is added to a sodium borohydride solution with a concentration of 50-100 mg / mL, and after stirring at room temperature for 30-60 min for sufficient reaction, the degradable layered organosilica nanosheet is obtained by washing, filtering and drying; The bio-based resin is at least two of PLA, PBS, PBAT and PCL; The plant microcrystalline cellulose is at least one of rice straw microcrystalline cellulose, cotton microcrystalline cellulose, bamboo microcrystalline cellulose and wheat straw microcrystalline cellulose; The compatilizer is at least one of POE-g-MAH, EAA-g-MAH and EVA-g-MAH; the toughening agent is at least one of POE, EVA and EAA; and the weight ratio of the antioxidants 168 and 1076 is 1: (1-3).
2. A process for the preparation of a flame retardant, wholly biodegradable composition as claimed in claim 1, characterized in that, The method comprises the following steps: Step one, mixing bio-based resin, plant microcrystalline cellulose, bio-based flame retardant, compatilizer, toughening agent and antioxidant, and discharging to obtain a flame-retardant full-biodegradable composition mixture; Step two, melting and extruding the flame-retardant full-biodegradable composition mixture through a twin-screw extruder to obtain a flame-retardant full-biodegradable composition modified material.