Flame-retardant multifunctional carrier-free masterbatch based on ionic liquid and preparation method and application thereof
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- GUANGXI XINJING TECH
- Filing Date
- 2026-01-30
- Publication Date
- 2026-05-29
AI Technical Summary
Traditional flame retardants suffer from problems such as large addition amounts, poor compatibility with the matrix, and deterioration of the mechanical properties of materials. Furthermore, traditional flame retardant masterbatches have dilution effects and powder agglomeration problems, making it difficult to achieve efficient flame retardant and smoke suppression effects.
Flame-retardant multifunctional carrier-free masterbatch was prepared by using ionic liquid functionalized layered bimetallic hydroxide and ionic liquid-coated expanded graphite, combined with gas-phase flame retardants and processing aids, through room temperature dry roll pressing granulation process, achieving multifunctional integration of flame retardancy, smoke suppression, and enhanced mechanical properties.
It achieves a combination of high flame retardant efficiency (UL94 V-0 rating), low smoke, anti-dripping and good mechanical properties, reduces the amount to be added, broadens the application range, and avoids the dilution and compatibility problems of traditional methods.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of flame retardant technology for polymer materials, specifically to a flame retardant multifunctional carrier-free masterbatch based on ionic liquids, its preparation method, and its application in plastic modification. Background Technology
[0002] With the increasingly widespread application of plastic products in construction, transportation, and electronics, the requirements for the flame retardant properties of plastic products in these fields are also becoming more stringent. Traditional flame retardants, such as halogenated flame retardants, while highly efficient, release toxic gases and soot during combustion, and their use has been restricted by regulations such as the EU RoHS. Halogen-free flame retardants, such as phosphorus-nitrogen-based and metal hydroxides, have become the mainstream choice, but they generally suffer from problems such as high addition amounts, poor compatibility with the matrix, and deterioration of the material's mechanical properties.
[0003] Masterbatch technology is one of the effective ways to solve the above problems. Traditional flame retardant masterbatches usually blend high-concentration flame retardants with carrier resins and granulate them. However, the carrier resin will dilute the concentration of flame retardants and may have compatibility problems with the modified resin matrix. In addition, most flame retardants are solid powders, which are prone to agglomeration under masterbatch processing and high filling, affecting the performance of the final composite material.
[0004] Ionic liquids, as a novel type of functional liquid material, possess advantages such as high thermal stability, low volatility, and strong designability. In recent years, research has discovered that certain ionic liquids containing phosphorus, nitrogen, and boron exhibit flame-retardant properties and can also serve as excellent surface modifiers.
[0005] Currently, there are no reports on the development of integrated flame retardant masterbatches that simultaneously utilize ionic liquids as flame retardant active components, filler modifiers, and masterbatch processing aids. Summary of the Invention
[0006] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a flame-retardant multifunctional carrier-free masterbatch based on ionic liquids, its preparation method, and its applications. This masterbatch utilizes the multiple functions of ionic liquids to achieve integrated flame retardancy, smoke suppression, and enhanced mechanical properties, while exhibiting good compatibility with plastic matrices, requiring only a small amount, and demonstrating excellent overall performance.
[0007] To achieve the above objectives, the present invention adopts the following technical solution: The present invention provides a flame-retardant multifunctional carrier-free masterbatch based on ionic liquid, which is composed of the following components in parts by weight: 20-50 parts of ionic liquid functionalized layered bimetallic hydroxide, 20-50 parts of ionic liquid-coated expanded graphite, 20-40 parts of gas phase flame retardant, 2-5 parts of antioxidant, and 2-5 parts of processing aid.
[0008] Preferably, the method for preparing the ionic liquid functionalized modified layered bimetallic hydroxide includes the following steps: (1) Calcining the layered bimetallic hydroxide at 350-450℃ for 2-4 hours yields the calcined product; (2) The roasted product is pulverized to an average particle size of less than 10 μm to obtain ultrafine powder; (3) The ultrafine powder, ionic liquid and water are added together to the hydrothermal reactor for hydrothermal reaction. The weight ratio of ultrafine powder to ionic liquid and water is 100:1-20:100-400. After the reaction is completed, the solid and liquid are separated and the solid part is taken. (4) The solid part is dried until the moisture content is less than 0.5 wt%, then crushed to obtain ionic liquid functionalized layered bimetallic hydroxide.
[0009] Preferably, in step (2), the temperature of the hydrothermal reaction is 100-200℃ and the reaction time is 6-12 hours.
[0010] In the ionic liquid functionalized layered bimetallic hydroxide described above, the layered bimetallic hydroxide is reconstructed after calcination, and the ionic liquid is successfully inserted between its layers. The introduction of the ionic liquid not only improves the dispersibility of the layered bimetallic hydroxide in the polymer matrix, but its own phosphorus, nitrogen, and phosphorus elements also synergize with the metal catalytic effect of the layered bimetallic hydroxide, promoting the formation of a dense char layer during combustion and significantly improving the flame retardant and smoke-suppressing effects.
[0011] Preferably, the ionic liquid-coated expanded graphite is prepared using the following steps: Expanded graphite and ionic liquid are mixed together at a weight ratio of 100:1-20, added to a stirrer, protected by nitrogen or inert gas, heated to 50-150℃, reacted for 1-4 hours, and rotated at 200-800 rpm. After the reaction is completed, expanded graphite coated with ionic liquid is obtained. Wherein, the particle size of the expanded graphite is equal to or less than 50 micrometers; In the expanded graphite coated with ionic liquid, the ionic liquid exists in the lamellar structure of expanded graphite through physical adsorption and partial intercalation. This effectively solves the problem of structural damage to expanded graphite during processing. At the same time, the ionic liquid can promote the expansion of expanded graphite when heated, forming a denser and more stable expanded carbon layer, which plays a role in heat insulation, oxygen isolation and smoke suppression.
[0012] Preferably, the ionic liquid is one or more of 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate, and tetrabutylphosphine tris(2,4,6-trioxo-1,3,5-triazine-1-yl)borate.
[0013] Preferably, the gas phase flame retardant is one or more of phosphorus-based gas phase flame retardants and nitrogen-based gas phase flame retardants.
[0014] The phosphorus-based gas-phase flame retardants include, but are not limited to, resorcinol bis(diphenyl phosphate); the nitrogen-based gas-phase flame retardants include, but are not limited to, melamine cyanurate, melamine phosphate, and dicyandiamide.
[0015] The gas-phase flame retardant and the ionic liquid-functionalized filler produce a good synergistic flame retardant effect. For example, the gas phase effect "treats the symptoms" (suppresses the flame), while the condensed phase effect "treats the root cause" (protects the substrate), forming a three-dimensional protective system.
[0016] Preferably, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a 1:1 ratio.
[0017] And / or, the processing aid is at least one of ethylene-vinyl acetate copolymer, polyethylene wax, and silicone masterbatch.
[0018] The second aspect of this invention provides a method for preparing the above-described flame-retardant multifunctional carrier-free masterbatch based on ionic liquids, comprising the following steps: S1. Weigh each component according to the proportion; S2. Add the ionic liquid functionalized layered bimetallic hydroxide, ionic liquid coated expanded graphite, gas phase flame retardant, antioxidant and processing aid into a pulverizer and mix at 500-1500 rpm for 1-10 minutes to obtain a premix. S3. Granulation is carried out using a dry roller pressing process to obtain 1.0-3.0 mm particles, thus obtaining flame-retardant multifunctional carrier-free masterbatch.
[0019] The preparation method of this invention employs a room-temperature dry roller pressing granulation process. Since the entire granulation process is carried out at room temperature, the thermal decomposition problem of traditional phosphorus-nitrogen flame retardants during high-temperature granulation is avoided.
[0020] The third aspect of this invention provides the application of the above-described ionic liquid-based flame-retardant multifunctional carrier-free masterbatch in flame-retardant plastics.
[0021] Preferably, the amount of the flame-retardant multifunctional carrier-free masterbatch based on ionic liquid added to the flame-retardant plastic is 10-20 wt%.
[0022] The main components of flame-retardant plastics also include a matrix resin, which is preferably at least one of polyethylene, polypropylene, polyamide, polyester, polycarbonate, and ABS resin.
[0023] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention innovatively utilizes ionic liquid to achieve the three-in-one functional integration of "flame retardant active component - surface modifier - processing aid", which can be processed and molded without the addition of carrier resin, thereby simplifying the masterbatch formula and preparation process, avoiding the problem of dilution of flame retardant concentration caused by adding carrier resin, and also reducing the probability of compatibility problems between it and the base resin of plastic.
[0024] (2) The present invention functionalizes layered bimetallic hydroxides and expanded graphite by using ionic liquids, which significantly improves their dispersibility and interfacial compatibility in polymer matrices, thereby effectively improving flame retardant efficiency while reducing the amount added.
[0025] (3) The various flame-retardant components used in this invention produce a significant synergistic flame-retardant effect, so that the final flame-retardant plastic has comprehensive properties such as high flame retardancy (UL94 V-0 grade), low smoke, anti-dripping and good mechanical retention.
[0026] (4) The preparation method used in this invention has the advantages of low temperature and mild conditions, and is suitable for processing heat-sensitive flame retardants, thus broadening the application range of flame retardant masterbatches. Detailed Implementation
[0027] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.
[0028] Example 1
[0029] A flame-retardant multifunctional carrier-free masterbatch based on ionic liquid is composed of the following components in parts by weight: 40 parts of magnesium aluminum hydrotalcite functionalized with 1-butyl-3-methylimidazolium hexafluorophosphate, 29 parts of expanded graphite coated with tetrabutylphosphine tris(2,4,6-trioxo-1,3,5-triazine-1-yl)borate, 25 parts of melamine cyanurate, 1.5 parts of antioxidant 1010, 1.5 parts of antioxidant 168, and 3 parts of ethylene-vinyl acetate copolymer.
[0030] Example 2
[0031] A flame-retardant multifunctional carrier-free masterbatch based on ionic liquid is composed of the following components in parts by weight: 22 parts of magnesium aluminum hydrotalcite functionalized with 1-butyl-3-methylimidazolium hexafluorophosphate, 40 parts of expanded graphite coated with tetrabutylphosphine tris(2,4,6-trioxo-1,3,5-triazine-1-yl)borate, 30 parts of resorcinol bis(diphenyl phosphate), 2 parts of antioxidant 1010, 2 parts of antioxidant 168, and 4 parts of polyethylene wax.
[0032] Comparative Example 1 A flame-retardant multifunctional carrier-free masterbatch is composed of the following components in parts by weight: 40 parts magnesium aluminum hydrotalcite, 29 parts expanded graphite coated with tetrabutylphosphine tris(2,4,6-trioxo-1,3,5-triazine-1-yl)borate, 25 parts melamine cyanurate, 1.5 parts antioxidant 1010, 1.5 parts antioxidant 168, and 3 parts ethylene-vinyl acetate copolymer.
[0033] Comparative Example 2 A flame-retardant multifunctional carrier-free masterbatch is composed of the following components in parts by weight: 40 parts of 1-butyl-3-methylimidazolium hexafluorophosphate functionalized modified magnesium aluminum hydrotalcite, 29 parts of expanded graphite, 25 parts of melamine cyanurate, 1.5 parts of antioxidant 1010, 1.5 parts of antioxidant 168, and 3 parts of ethylene-vinyl acetate copolymer.
[0034] The preparation method of 1-butyl-3-methylimidazolium hexafluorophosphate functionalized modified magnesium aluminum hydrotalcite in Examples 1, 2 and Comparative Example 2 above includes the following steps: (1) Take 100g of magnesium aluminum hydrotalcite (Mg / Al molar ratio 2:1) and calcine it in a muffle furnace at 400℃ for 3 hours to obtain the calcined product; (2) Use a ball mill to grind the average particle size of the calcined product to less than 5μm to obtain ultrafine powder; (3) Add the ultrafine powder, 10g of 1-butyl-3-methylimidazolium hexafluorophosphate and 200g of deionized water into a hydrothermal reactor, seal it, raise the temperature to 150℃, and react for 10 hours. After the reaction is completed, separate the solid and liquid and take the solid part; (4) Dry the solid part in a forced-air drying oven at 90℃ until the water content is less than 0.5wt% to obtain 1-butyl-3-methylimidazolium hexafluorophosphate functionalized modified magnesium aluminum hydrotalcite.
[0035] In Examples 1, 2, and Comparative Example 1 above, the preparation method of tetrabutylphosphine tris(2,4,6-trioxo-1,3,5-triazine-1-yl)borate coated expanded graphite includes the following steps: Take 50g of expanded graphite (400 mesh) and 5g of tetrabutylphosphine tris(2,4,6-trioxo-1,3,5-triazine-1-yl)borate, add them to a high-speed stirrer, under nitrogen protection, heat to 100℃, react for 2 hours, and stir at 500 rpm; after the reaction is completed, cool to room temperature to obtain expanded graphite coated with tetrabutylphosphine tris(2,4,6-trioxo-1,3,5-triazine-1-yl)borate.
[0036] The preparation methods of the flame retardant masterbatches in Examples 1-2 and Comparative Examples 1-2 above include the following steps: S1. Weigh each component according to the formula; S2. Add each component to a pulverizer and mix at 1000 rpm for 3 minutes to obtain a premix; S3. Granulate using a dry roller pressing granulation process to separate 1.5-2.5 mm particles to obtain a flame-retardant multifunctional carrier-free masterbatch.
[0037] Application Example 1 The flame-retardant multifunctional carrier-free masterbatch prepared in Example 1 was mixed with polyamide 6 (PA6) resin at a weight ratio of 1:5, granulated by a twin-screw extruder at 230-250°C, and then injection molded to prepare flame-retardant PA6 test strips.
[0038] Application Example 2 The flame-retardant multifunctional carrier-free masterbatch prepared in Example 2 was mixed with polypropylene (PP) resin at a weight ratio of 1:5, and then molded at 190-210℃ using an injection molding machine to prepare flame-retardant PP test strips.
[0039] Application Comparative Example 1 The flame-retardant multifunctional carrier-free masterbatch prepared in Comparative Example 1 was mixed with polyamide 6 (PA6) resin at a weight ratio of 1:5, granulated at 230-250℃ using a twin-screw extruder, and then injection molded to prepare flame-retardant PA6 test strips.
[0040] Application Comparative Example 2 The flame-retardant multifunctional carrier-free masterbatch prepared in Comparative Example 2 was mixed with polyamide 6 (PA6) resin at a weight ratio of 1:5, granulated at 230-250℃ using a twin-screw extruder, and then injection molded to prepare flame-retardant PA6 test strips.
[0041] Performance tests were conducted using test samples from Application Examples 1-2 and Comparative Examples 1-2. The test results are shown in Table 1.
[0042] Table 1 Performance test results of flame-retardant plastic composite materials
[0043]
[0044] As shown in Table 1, the flame-retardant multifunctional carrier-free masterbatch prepared in this invention achieves the highest flame-retardant rating of UL94 V-0 when applied to PP and PA6 resins. Furthermore, the PP plastic prepared with this masterbatch exhibits higher flame-retardant rating and limiting oxygen index, and significantly reduced smoke density compared to the comparative example, while maintaining good mechanical properties and processing flowability. Application Example 1, compared to Comparative Example 1, demonstrates the importance of ionic liquid functionalization modification of magnesium aluminum hydrotalcite; Application Example 1, compared to Comparative Example 2, demonstrates the importance of ionic liquid coating of expanded graphite.
[0045] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the invention without departing from the spirit and scope of the present invention.
Claims
1. A flame-retardant multifunctional carrier-free masterbatch based on ionic liquid, characterized in that, It is composed of the following components in parts by weight: 20-50 parts of ionic liquid functionalized layered bimetallic hydroxide, 20-50 parts of ionic liquid coated expanded graphite, 20-40 parts of vapor phase flame retardant, 2-5 parts of antioxidant, and 2-5 parts of processing aid.
2. The flame-retardant multifunctional carrier-free masterbatch based on ionic liquid according to claim 1, characterized in that, The preparation method of the ionic liquid functionalized modified layered bimetallic hydroxide includes the following steps: (1) Calcining the layered bimetallic hydroxide at 350-450℃ for 2-4 hours yields the calcined product; (2) The roasted product is pulverized to an average particle size of less than 10 μm to obtain ultrafine powder; (3) The ultrafine powder, ionic liquid and water are added together to the hydrothermal reactor for hydrothermal reaction. The weight ratio of ultrafine powder to ionic liquid and water is 100:1-20:100-400. After the reaction is completed, the solid and liquid are separated and the solid part is taken. (4) The solid part is dried until the moisture content is less than 0.5 wt%, then crushed to obtain ionic liquid functionalized layered bimetallic hydroxide.
3. The flame-retardant multifunctional carrier-free masterbatch based on ionic liquid according to claim 2, characterized in that, In step (2), the temperature of the hydrothermal reaction is 100-200℃ and the reaction time is 6-12 hours.
4. The flame-retardant multifunctional carrier-free masterbatch based on ionic liquid according to claim 1, characterized in that, The expanded graphite coated with the ionic liquid was prepared using the following steps: Expanded graphite and ionic liquid are mixed together at a weight ratio of 100:1-20, added to a stirrer, protected by nitrogen or inert gas, heated to 50-150℃, reacted for 1-4 hours, and rotated at 200-800 rpm. After the reaction is completed, expanded graphite coated with ionic liquid is obtained. The expanded graphite has a particle size equal to or less than 50 micrometers.
5. The flame-retardant multifunctional carrier-free masterbatch based on ionic liquid according to any one of claims 1-4, characterized in that, The ionic liquid is one or more of 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate, and tetrabutylphosphine tris(2,4,6-trioxo-1,3,5-triazine-1-yl)borate.
6. The flame-retardant multifunctional carrier-free masterbatch based on ionic liquid according to claim 1, characterized in that, The gas phase flame retardant is one or more of phosphorus-based gas phase flame retardants and nitrogen-based gas phase flame retardants.
7. The flame-retardant multifunctional carrier-free masterbatch based on ionic liquid according to claim 1, characterized in that, The antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 1:
1. And / or, the processing aid is one or more of ethylene-vinyl acetate copolymer, polyethylene wax, and silicone masterbatch.
8. The method for preparing the flame-retardant multifunctional carrier-free masterbatch based on ionic liquids as described in any one of claims 1-7, characterized in that, Includes the following steps: S1. Weigh each component according to the proportion; S2. Add the ionic liquid functionalized layered bimetallic hydroxide, ionic liquid coated expanded graphite, gas phase flame retardant, antioxidant and processing aid into a pulverizer and mix at 500-1500 rpm for 1-10 minutes to obtain a premix. S3. Granulation is carried out using a dry roller pressing process to obtain 1.0-3.0 mm particles, thus obtaining flame-retardant multifunctional carrier-free masterbatch.
9. The application of a flame-retardant multifunctional carrier-free masterbatch based on ionic liquid as described in any one of claims 1-7 in flame-retardant plastics.
10. The application according to claim 9, characterized in that, The amount of the flame-retardant multifunctional carrier-free masterbatch based on ionic liquid added to the flame-retardant plastic is 10-20 wt%.