Halogen-free flame-retardant master batch as well as preparation method and application thereof
By using activated and modified aluminum diethylphosphite, melamine resin microcapsules to encapsulate ammonium polyphosphate, and the synergistic use of organically modified montmorillonite and melamine polyphosphate, the processing difficulties and environmental issues of halogen-free flame retardant masterbatch were solved, achieving a balance between high-efficiency flame retardant performance and good processing performance.
Patent Information
- Application Number
- CN202512016368.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-30
- Publication Date
- 2026-02-13
AI Technical Summary
Existing halogen-free flame retardant masterbatches suffer from problems such as difficulty in high-filling processing, insufficient carbon layer density, coarse particle size leading to easy agglomeration, difficulty in achieving UL-94V-0 rating for thin-walled products, and poor versatility. Furthermore, traditional flame retardants release toxic substances during combustion, making it difficult to meet environmental protection requirements.
A halogen-free flame retardant system was formed by combining activated and modified aluminum diethyl phosphite, melamine resin microcapsules encapsulating ammonium polyphosphate, organically modified montmorillonite, and melamine polyphosphate. Flame retardant masterbatch was prepared by twin-screw extruder to ensure uniform dispersion and good flowability.
It achieves high-efficiency flame retardancy with low additive dosage, the product reaches UL-94V-0 level, the heat release rate is reduced by 40%, the dripping inhibition effect is significant, it meets environmental protection regulations, and the processing performance is excellent.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of flame-retardant modified polyolefin masterbatch materials, and in particular to a halogen-free flame-retardant masterbatch and its preparation method. Background Technology
[0002] With the increasing demand for lightweight, low-cost, and high-performance polymer materials in the electronics, automotive, and construction industries, polymer materials are often flammable and prone to dripping. While traditional bromine / chlorine-based flame retardants are highly efficient, they release toxic hydrogen halides and dioxins during combustion, and are subject to restrictions under regulations such as RoHS and REACH.
[0003] Existing halogen-free technologies mainly rely on hydroxides, ammonium polyphosphate (APP), phosphorus-nitrogen expansion systems, or aluminum diethylphosphite (ADP). However, hydroxides require high filler content (≥50%), making processing difficult; APP has poor adaptability to processing temperatures; expansion systems require large addition amounts (15-25%), resulting in insufficient carbon layer density; and ADP has coarse particle size, is prone to agglomeration, and makes it difficult for thin-walled products to achieve UL-94V-0. Furthermore, existing masterbatch carriers are mostly designed for single resins, lacking versatility, and the insufficient aspect ratio of twin-screw extruders leads to uneven dispersion of high-filled halogen-free systems. Therefore, there is an urgent need for a low-addition, halogen-free, and easily scalable flame-retardant masterbatch. Summary of the Invention
[0004] To address the technical problems existing in current flame retardant masterbatches, this invention provides a halogen-free flame retardant masterbatch, its preparation method, and its application.
[0005] The halogen-free flame retardant masterbatch provided by this invention is achieved through the following technical solution: A halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 20-40 parts of carrier resin, 50-75 parts of halogen-free flame retardant system, 2-6 parts of coupling-dispersion composite additive, 0.3-1.0 parts of antioxidant, 0.2-0.8 parts of lubricant, and 0.1-0.5 parts of nucleating agent; wherein the carrier resin is selected from at least one of PET, PP, and PE; wherein the halogen-free flame retardant system comprises the following raw materials in parts by weight: 30-50 parts of activated modified aluminum diethyl phosphite (ADP), 10-20 parts of melamine resin microcapsule-encapsulated ammonium polyphosphate (APP), 5-15 parts of melamine polyphosphate (MPP), and 3-8 parts of organically modified montmorillonite (OMMT).
[0006] Preferably, the activated and modified aluminum diethylphosphite is prepared by pre-activation treatment with 0.3-1.0 wt% aminosilane; the aminosilane is at least one selected from γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropyltriethoxysilane.
[0007] Preferably, the method for preparing the activated and modified aluminum diethylphosphite is as follows: The median particle size D... 50 ≤3μm diethylaluminum hypophosphite is added to a high-speed mixer and heated to 80±5℃. An aminosilane / anhydrous ethanol mixture is added dropwise at 0.3-1.0wt% of the mass of the diethylaluminum hypophosphite, wherein the mass ratio of aminosilane to anhydrous ethanol in the aminosilane / anhydrous ethanol mixture is 1:1. The speed is adjusted to 1000-1200rpm and stirred for 5-8min. Then, the temperature is raised to 110-120℃ and stirred for 10-15min to allow the ethanol to completely evaporate, thus obtaining activated and modified diethylaluminum hypophosphite.
[0008] By adopting the above technical solution, the compatibility between activated and modified aluminum diethyl phosphite and the carrier resin can be improved, so that the activated and modified aluminum diethyl phosphite can be evenly distributed inside the carrier resin.
[0009] Preferably, the polyphosphate in the melamine resin microcapsule-encapsulated ammonium polyphosphate has a degree of polymerization n≥1000 and is of type II crystallization. The melamine resin microcapsule encapsulation is 2-5 wt%, which can improve the processing temperature adaptability of the flame retardant masterbatch. Furthermore, the melamine resin microcapsule-encapsulated ammonium polyphosphate synergistically constructs a phosphorus-nitrogen expansion system with melamine polyphosphate, enhancing the flame retardant effect.
[0010] Preferably, the preparation method of the organically modified montmorillonite is as follows: Step 1: Mix 4-6 parts of sodium montmorillonite, 40-50 parts of ethanol and 40-60 parts of deionized water at room temperature to obtain suspension A; Simultaneously, dissolve 2.5-3.0 parts of hexadecyltributylphosphine bromide in 15-30 parts of acetone and 20-30 parts of deionized water to obtain solution B; Step 2: Add solution B to suspension A, heat to 65-75℃, and mechanically stir for 6-10 hours to obtain suspension C; Step 3: Filter the suspension C obtained in Step 2, wash the filter cake with ethanol and deionized water at least 3 times alternately until the bromide ion content in the filtrate is 0, dry for 20-24 hours, grind and sieve to obtain quaternary phosphate intercalated modified montmorillonite. Step 4: Mix 4-6 parts of the quaternary phosphate salt intercalated modified montmorillonite prepared in Step 3, 40-50 parts of ethanol and 40-60 parts of deionized water at room temperature to obtain suspension D. Simultaneously, 4-6 parts of hexadecyltrimethoxysilane, 35-45 parts of ethanol and 4-8 parts of deionized water are mixed evenly, and the pH of the system is adjusted to 4-5 with glacial acetic acid. The mixture is stirred and mixed evenly at room temperature to obtain solution E. Step 5: Add solution E to suspension D, heat to 48-52℃, and mechanically stir for 20-24 hours to obtain suspension F; Step 6: Filter the suspension F obtained in Step 5, wash the filter cake with ethanol and deionized water alternately at least 3 times until the bromide ion content in the filtrate is 0, dry for 20-24 hours, grind and sieve to obtain organic modified montmorillonite OMMT.
[0011] The resulting organically modified montmorillonite has an interlayer spacing d001 ≥ 3.0 nm, which plays a nano-layer barrier role. When used in conjunction with melamine polyphosphate, melamine resin microcapsule-encapsulated ammonium polyphosphate, and activated modified diethyl aluminum hypophosphite, it effectively improves the overall flame retardancy. Furthermore, the prepared flame retardant masterbatch has good flowability.
[0012] Preferably, when the carrier resin is PET, the intrinsic viscosity IV of PET is 0.70-0.85 dL / g.
[0013] Preferably, when the carrier resin is copolymer polypropylene, the melt flow rate (MFR) of the copolymer polypropylene at 230°C / 2.16 kg is 5-15 g / 10 min.
[0014] Preferably, the carrier resin is linear low-density polyethylene (LLDPE) with a density of 0.918-0.93 g / cm³.
[0015] Preferably, the coupling-dispersing composite agent is composed of γ-glycidoxypropyltrimethoxysilane and bis-stearamide; the mass ratio of γ-glycidoxypropyltrimethoxysilane to bis-stearamide is 1:(1-3).
[0016] By adopting the above technical solution, the interfacial compatibility between the halogen-free flame retardant system and the carrier resin is improved, which in turn facilitates the uniform distribution of melamine polyphosphate, melamine resin microcapsule-encapsulated ammonium polyphosphate, activated and modified aluminum diethylphosphite, and organically modified montmorillonite inside the carrier resin, thus endowing it with excellent flame retardant properties.
[0017] Preferably, the antioxidant is a mixture of hindered phenolic antioxidant and phosphite antioxidant in a mass ratio of 1:(0.5-2), which can prevent resin degradation during processing.
[0018] Preferably, the lubricant is a polyethylene wax with a molecular weight of 2000-5000 g / mol, which can improve processing fluidity.
[0019] Preferably, the nucleating agent is sodium benzoate and / or sorbitol acetal nucleating agent, which can improve the crystallization performance of the carrier resin in the flame retardant masterbatch.
[0020] More preferably, the halogen-free flame retardant system comprises the following raw materials in parts by weight: 35-45 parts of activated modified aluminum diethylphosphite, 12-18 parts of melamine resin microcapsule-coated ammonium polyphosphate, 8-12 parts of melamine polyphosphate, and 4-6 parts of organically modified montmorillonite.
[0021] The halogen-free flame retardant masterbatch prepared in this invention has a limiting oxygen index ≥31%, a vertical burning rating of UL-94V-0, and a melt flow rate (MFR) ≥6g / 10min at 230℃ / 2.16kg.
[0022] The present invention provides a method for preparing halogen-free flame retardant masterbatch, which is achieved through the following technical solution: A method for preparing a halogen-free flame retardant masterbatch includes the following steps: S1, accurately measured activated modified aluminum diethyl phosphite, melamine resin microcapsules coated with ammonium polyphosphate, melamine polyphosphate, and organic modified montmorillonite are mixed evenly to prepare a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is vacuum dried at 110-120℃ for 3-4 hours. S2, add carrier resin, coupling-dispersion composite additive, antioxidant, lubricant and nucleating agent into a high-speed mixer, and premix for 5-10 minutes at 80-100℃ and 800-1200rpm to obtain resin premix; S3: The halogen-free flame-retardant composition dried in step S1 is fed into a twin-screw extruder via side feeding. Simultaneously, the resin premix from S2 is fed into the twin-screw extruder via main feeding. The screw length-to-diameter ratio (L / D) is 40-48, the screw speed is 200-400 rpm, and the vacuum degree is ≤-0.08 MPa. When the carrier resin is PET, the extrusion temperature is set as follows: Zone 1 220-240℃, Zone 2 230-250℃, Zone 3 240-260℃, Zones 4-7 250-285℃, and the die head 270-290℃. When the carrier resin is PP, the extrusion temperature is set as follows: Zone 1 160-165℃, Zone 2 180-185℃, Zone 3 200-290℃, Zone 4-7 250-285℃, and the die head 270-290℃. The extrusion temperature is set as follows: Zone 1: 140-150℃, Zone 2: 160-170℃, Zone 3: 175-180℃, Zones 4-7: 185-200℃, Die head: 200-210℃. When the carrier resin is PE, the extrusion temperature is set as follows: Zone 1: 160-185℃, Zone 2: 170-175℃, Zone 3: 185-190℃, Zones 4-7: 200-230℃, Die head: 230-240℃. The melt is water-cooled, stretched, pelletized, and dried to obtain flame-retardant masterbatch with a particle size of 2-4mm and a moisture content of ≤0.05wt%.
[0023] Preferably, the melt is water-cooled, stretched, and pelletized, and then dried in a fluidized bed at 90-110℃ for 1-2 hours to obtain flame-retardant masterbatch with a particle size of 2-4 mm and a moisture content of ≤0.05 wt%.
[0024] Preferably, when the carrier resin is PET, the PET resin needs to be pre-crystallized at 130±5℃ for 100-125 min before use, and then vacuum dried at 140-150℃ for 4-6 h.
[0025] Preferably, when the carrier resin is PP and / or PE, it needs to be dried at 80-90℃ for 2-3 hours before use.
[0026] The application of the halogen-free flame retardant masterbatch prepared in this invention involves mixing the halogen-free flame retardant masterbatch with a matrix resin at a mass ratio of 1:(4-9), and then obtaining flame retardant products through injection molding or extrusion molding; the matrix resin is at least one of PET, PP, and PE, and the matrix resin is the same as or compatible with the carrier resin in the halogen-free flame retardant masterbatch.
[0027] In summary, the present invention has the following advantages: 1. High flame retardant efficiency: The quaternary synergy of ADP / APP / MPP / OMMT, with the combined action of the gas phase and condensed phase, requires only 8-12wt% masterbatch addition to enable PET / PP / PE products to reach UL-94V-0 level (1.6mm) with a limiting oxygen index ≥30%.
[0028] 2. Excellent thermal safety performance: The OMMT nanolayer barrier and ADP catalytic carbonization work synergistically to reduce the peak heat release rate (PHRR) of the product by ≥40% compared with pure resin, effectively suppressing dripping and achieving a smoke density (D4) ≤200, which meets environmental protection requirements.
[0029] 3. Balance between processing and mechanical properties: Coupling-dispersion composite additives improve compatibility, masterbatch MFR≥6g / 10min, good processing fluidity; carrier resin and matrix are "homogeneous", tensile strength retention rate of the product is ≥85%, elongation retention rate is ≥80%.
[0030] 4. Environmental compliance: The formula is halogen-free and complies with regulations such as RoHS, REACH, and IEC61249-2-21, making it suitable for fields with high environmental protection requirements, such as electronics, automobiles, etc. Detailed Implementation
[0031] To further understand the inventiveness and technical advancements of this invention, the preferred embodiments of this invention will be discussed in detail below with reference to examples and comparative examples.
[0032] Example: A halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 20-40 parts of carrier resin, 50-75 parts of halogen-free flame retardant system, 2-6 parts of coupling-dispersion composite additive, 0.3-1.0 parts of antioxidant, 0.2-0.8 parts of lubricant, and 0.1-0.5 parts of nucleating agent.
[0033] The carrier resin is selected from at least one of PET, PP, and PE.
[0034] When the carrier resin is PET, the intrinsic viscosity IV of PET is 0.70-0.85 dL / g. Before use, PET resin needs to be pre-crystallized at 130±5℃ for 100-125 min, and then vacuum dried at 140-150℃ for 4-6 h.
[0035] When the carrier resin is copolymer polypropylene, the melt flow rate (MFR) of copolymer polypropylene at 230℃ / 2.16kg is 5-15g / 10min. It needs to be dried at 80-90℃ for 2-3 hours before use. When the carrier resin is linear low-density polyethylene (LLDPE) with a density of 0.918-0.93 g / cm³, it needs to be dried at 80-90℃ for 2-3 hours before use.
[0036] The coupling-dispersing composite agent is composed of γ-glycidoxypropyltrimethoxysilane and bis-stearamide, with a mass ratio of γ-glycidoxypropyltrimethoxysilane to bis-stearamide of 1:(1-3).
[0037] The antioxidant is a mixture of hindered phenolic antioxidants and phosphite antioxidants in a mass ratio of 1:(0.5-2).
[0038] The lubricant is polyethylene wax with a molecular weight of 2000-5000 g / mol.
[0039] The nucleating agent is sodium benzoate and / or sorbitol acetal nucleating agent.
[0040] The halogen-free flame retardant system comprises the following raw materials in parts by weight: 30-50 parts of activated and modified aluminum diethylphosphite, 10-20 parts of melamine resin microcapsule-coated ammonium polyphosphate, 5-15 parts of melamine polyphosphate, and 3-8 parts of organically modified montmorillonite.
[0041] Preferably, the halogen-free flame retardant system comprises the following raw materials in parts by weight: 35-45 parts of activated modified aluminum diethylphosphite, 12-18 parts of melamine resin microcapsule-coated ammonium polyphosphate, 8-12 parts of melamine polyphosphate, and 4-6 parts of organically modified montmorillonite.
[0042] The activated and modified diethyl aluminum hypophosphite was prepared by pre-activation treatment with 0.3-1.0 wt% aminosilane.
[0043] The aminosilane is at least one of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropyltriethoxysilane.
[0044] The ammonium polyphosphate is encapsulated in melamine resin microcapsules. The degree of polymerization of the ammonium polyphosphate is ≥1000 and it is a type II crystal. The melamine resin microcapsule encapsulation is 2-5 wt%, and the specific choice is Procyfu EPFR-APP231H.
[0045] Organically modified montmorillonite was modified with hexadecyltrimethylammonium bromide, with an interlayer spacing d 001 With a thickness of ≥3.0nm, OMMT exerts a nano-layered barrier effect. When used in conjunction with melamine polyphosphate (MMP), melamine resin microcapsule-encapsulated ammonium polyphosphate (APP), and activated and modified aluminum diethylphosphite (ADP), it effectively improves the overall flame retardancy, and the prepared flame retardant masterbatch has good flowability.
[0046] A method for preparing a halogen-free flame retardant masterbatch includes the following steps: S1, accurately measured activated modified aluminum diethyl phosphite, melamine resin microcapsules coated with ammonium polyphosphate, melamine polyphosphate, and organic modified montmorillonite are mixed evenly to prepare a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is vacuum dried at 110-120℃ for 3-4 hours. S2, add carrier resin, coupling-dispersion composite additive, antioxidant, lubricant and nucleating agent into a high-speed mixer, and premix for 5-10 minutes at 80-100℃ and 800-1200rpm to obtain resin premix; S3, the halogen-free flame retardant composition dried in step S1 is added to the twin-screw extruder via side feeding, and the resin premix in S2 is added to the twin-screw extruder via main feeding. The screw length-to-diameter ratio L / D = 40-48, the screw speed is 200-400 rpm, and the vacuum degree is ≤-0.08MPa. When the carrier resin is PET: the extrusion temperature is set as follows: Zone 1 220-240℃, Zone 2 230-250℃, Zone 3 240-260℃, Zones 4 to 7 250-285℃, and the die head 270-290℃. When the carrier resin is PP: the extrusion temperature is set as follows: Zone 1 160-165℃, Zone 2 180-185℃, Zone 3 200-210℃, Zones 4 to 7 210-220℃, and the die head 220-230℃. When the carrier resin is PE: the extrusion temperature is set as follows: Zone 1 140-150℃, Zone 2 160-170℃, Zone 3 175-180℃, Zones 4 to 7 185-200℃, and the die head 200-210℃. When the carrier resin is PP / PE: the extrusion temperature is set as follows: Zone 1 160-185℃, Zone 2 170-175℃, Zone 3 185-190℃, Zones 4 to 7 200-230℃, and the die head 230-240℃. The melt output from the die head of the twin-screw extruder is water-cooled, stretched, and pelletized, and then dried in a fluidized bed at 90-110℃ for 1-2 hours to obtain halogen-free flame retardant masterbatch with a particle size of 2-4 mm and a moisture content of ≤0.05 wt%.
[0047] The resulting halogen-free flame retardant masterbatch has a limiting oxygen index of ≥31%, a vertical burning rating of UL-94V-0, and a melt flow rate (MFR) of ≥6g / 10min at 230℃ / 2.16kg.
[0048] Preferably, in S3, the screw's length-to-diameter ratio (L / D) is 44-48, and the screw assembly adopts a high-mixing-strength design: 2-3 sets of 90° kneading blocks and toothed discs are alternately arranged after the flame retardant-side feed port to ensure uniform dispersion of the highly filled halogen-free flame retardant system. The screw speed is 250-350 rpm, and the vacuum degree is -0.085 to -0.095 MPa.
[0049] Preferably, if the carrier resin is PE, the extrusion temperature is set as follows: Zone 1 140℃, Zone 2 160℃, Zone 3 170℃, Zone 4 185℃, Zone 5 190℃, Zone 6 195℃, Zone 7 200℃, and die head 200℃.
[0050] Preferably, if the carrier resin is PP, the extrusion temperature is set as follows: Zone 1 160℃, Zone 2 180℃, Zone 3 200℃, Zone 4 220℃, Zone 5 230℃, Zone 6 230℃, Zone 7 235℃, and die head 235℃.
[0051] Preferably, if the carrier resin is PET, the extrusion temperature is set as follows: Zone 1 230℃, Zone 2 240℃, Zone 3 250℃, Zone 4 260℃, Zone 5 265℃, Zone 6 275℃, Zone 7 280℃, and die head 280℃.
[0052] Preferably, if the carrier resin is PP / PE, the extrusion temperature is set as follows: Zone 1 165℃, Zone 2 180℃, Zone 3 185℃, Zone 4 200℃, Zone 5 210℃, Zone 6 220℃, Zone 7 230℃, and die head 235℃.
[0053] Application of halogen-free flame retardant masterbatch: After mixing halogen-free flame retardant masterbatch with matrix resin at a mass ratio of 1:(4-9), flame retardant products are obtained by injection molding or extrusion molding. The matrix resin is at least one of PET, PP, and PE, and the matrix resin is the same as or compatible with the carrier resin in the halogen-free flame retardant masterbatch.
[0054] When the base resin is PET, the barrel temperature is 265-275℃ and the mold temperature is 15℃. When the base resin is PP, the barrel temperature is 200-220℃ and the mold temperature is 40℃. When the base resin is PE, the barrel temperature is 190-210℃ and the mold temperature is 30℃.
[0055] Preparation Example 1: The preparation method of activated modified aluminum diethylphosphite is as follows: The median particle size D... 50 Aluminum diethylphosphite with a particle size of 2.5 μm (Clariant Chemicals Ltd. Exolit OP1230, CAS: 225789-38-8) was added to a high-speed mixer and heated to 80±5℃. An aminosilane KH540 / anhydrous ethanol mixture was added dropwise at 0.5 wt% of the aluminum diethylphosphite mass, with the mass ratio of aminosilane to anhydrous ethanol in the KH540 / anhydrous ethanol mixture being 1:1. The speed was adjusted to 1200 rpm and stirred for 5 min. Then, the temperature was raised to 120℃ and stirred for 10 min to allow the ethanol to completely evaporate, thus obtaining the activated and modified aluminum diethylphosphite.
[0056] Preparation Example 2: A method for preparing organically modified montmorillonite (OMMT), comprising the following steps: Step 1: Mix 5 parts sodium montmorillonite (Zhejiang Fenghong SM-P), 45 parts ethanol and 50 parts deionized water at room temperature to obtain suspension A; Meanwhile, 2.7 parts of hexadecyltributylphosphine bromide (HTPB, Shandong Yaotong Industry, CAS: 14937-45-2) were dissolved in 20 parts of acetone and 25 parts of deionized water to obtain solution B; Step 2: Add solution B to suspension A, heat to 70°C, adjust the speed to 1200 rpm, and mechanically stir for 8 hours to obtain suspension C; Step 3: Filter the suspension C obtained in Step 2, and wash the filter cake 5 times alternately with ethanol and deionized water until the bromide ions Br in the filtrate are removed. - The concentration is 0. The method for detecting bromide ions in the filtrate is as follows: Adding acidified silver nitrate to the filtrate results in no pale yellow precipitate, indicating the absence of bromide ions (Br). - The filter cake was then placed in an oven and dried at 80°C for 24 hours. The resulting solid material was then ground and sieved through a 300-mesh sieve to obtain the sieved material, which is quaternary phosphate intercalated modified montmorillonite. Step 4: Mix 5 parts of the quaternary phosphate salt intercalated modified montmorillonite prepared in Step 3, 45 parts of ethanol and 50 parts of deionized water at room temperature to obtain suspension D. Simultaneously, 5 parts of hexadecyltrimethoxysilane (HTDMS, Wuhan Yardoma Biotechnology Co., Ltd., CAS: 16415-12-6), 40 parts of ethanol and 5 parts of deionized water were mixed evenly, and the pH of the system was adjusted to 4.5 with glacial acetic acid. The mixture was stirred evenly at room temperature to obtain solution E. Step 5: Add solution E to suspension D, heat to 50°C, adjust the speed to 1200 rpm, and mechanically stir for 24 hours to obtain suspension F; Step six: Filter the suspension F obtained in step five, and wash the filter cake five times alternately with ethanol and deionized water until the bromide ions Br in the filtrate are removed. - The concentration is 0. The method for detecting bromide ions in the filtrate is as follows: Adding acidified silver nitrate to the filtrate results in no pale yellow precipitate, indicating the absence of bromide ions (Br). - The filter cake was then placed in an oven and dried at 80°C for 24 hours. The resulting solid material was then ground and sieved through a 300-mesh screen to obtain the screened material, which is the organically modified montmorillonite (OMMT).
[0057] Example 1: A halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 30 parts PET resin (Yizheng Chemical Fiber Co., Ltd., CAS: 25038-59-9, grade: FG600; intrinsic viscosity IV = 0.675 ± 0.010 dL / g), 40 parts activated and modified aluminum diethyl phosphite as in Example 1, 15 parts melamine resin microcapsule-coated ammonium polyphosphate (Procefu EPFR-APP231H), and 10 parts melamine polyphosphate (BASF Melapur® 200, CAS: 218768-84-4, median diameter D). 50 =5μm), 5 parts of the organically modified montmorillonite from Preparation Example 2, 3 parts of the coupling-dispersion composite additive, 0.3 parts of antioxidant 1010 (Shanghai Jinghong Chemical Technology Co., Ltd., CAS: 6683-19-8), 0.3 parts of antioxidant 168 (Dongguan Kangjin New Material Technology Co., Ltd., CAS: 31570-04-4), and 0.4 parts of polyethylene wax (Honeywell AC-6A, CAS: 9002-88-4, M W =3500g / mol), 0.2 parts of sodium benzoate (Shandong Tianxiang Chemical Co., Ltd., CAS:532-32-1).
[0058] The 3 parts of coupling-dispersing composite additive are compounded from 1 part of γ-glycidyl etheroxypropyltrimethoxysilane KH-560 (Yamaichi Plastics Co., Ltd., CAS: 2530-83-8) and 2 parts of bis-stearamide EBS (Kao Corporation, Japan, CAS: 110-30-5).
[0059] The halogen-free flame retardant system comprises the following raw materials in parts by weight:
[0060] A method for preparing a halogen-free flame retardant masterbatch includes the following steps: S1, accurately measured 40 parts of activated modified aluminum diethylphosphite from Preparation Example 1, 15 parts of melamine resin microcapsules encapsulating ammonium polyphosphate (Procefu EPFR-APP231H), and 10 parts of melamine polyphosphate (BASF Melapur® 200, CAS: 218768-84-4, median diameter D) 50 =5μm), 5 portions of the organic modified montmorillonite from Preparation Example 2 were added to a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition was then vacuum dried at 120℃ for 4.0 h. Before use, PET resin FG600 is pre-crystallized at 130 ℃ for 2 h, and then vacuum dried at 140 ℃ for 6 h. S2, add 30 parts of dried PET resin FG600, 1 part of γ-glycidyl etheroxypropyltrimethoxysilane KH-560, 2 parts of bis-stearamide EBS, 0.3 parts of antioxidant 1010, 0.3 parts of antioxidant 168, 0.4 parts of polyethylene wax AC-6A, and 0.2 parts of sodium benzoate to a high-speed mixer and premix for 5 minutes at 90°C and 1000 rpm to obtain resin premix; S3. The halogen-free flame-retardant composition dried in step S1 is fed into a twin-screw extruder via side feeding. At the same time, the resin premix from S2 is fed into the twin-screw extruder via main feeding. The total feed rate is maintained at 30 kg / h, the screw length-to-diameter ratio L / D = 44, and the extrusion temperature is set as follows: Zone 1 230℃, Zone 2 240℃, Zone 3 250℃, Zone 4 260℃, Zone 5 265℃, Zone 6 275℃, Zone 7 280℃, and Die head 280℃. The screw speed is 300 rpm, and the vacuum degree is -0.08 MPa. The melt is water-cooled, stretched, and pelletized, and then dried in a fluidized bed at 100℃ for 2 hours to obtain halogen-free flame-retardant PET masterbatch with a particle size range of 2-4 mm and a moisture content of ≤0.05 wt%.
[0061] The difference between Example 2 and Example 1 is that the halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 30 parts PET resin FG600, 35 parts activated modified aluminum diethylphosphite from Example 1, 18 parts melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 8 parts melamine polyphosphate Melapur® 200, 4 parts organic modified montmorillonite from Example 2, 2.5 parts coupling-dispersion composite additive, 0.25 parts antioxidant 1010, 0.25 parts antioxidant 168, 0.3 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate. The coupling-dispersion composite additive is a compound of γ-glycidyl etheroxypropyltrimethoxysilane KH-560 and bis-stearamide EBS in a mass ratio of 1:2.5.
[0062] The difference between Example 3 and Example 1 is that: a halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 32 parts LLDPE resin (Maoming Petrochemical Company, CAS: 9002-88-4, grade: DNDA7042; melt flow rate MFR=2.0g / 10min at 190℃ / 2.16kg), 38 parts activated modified aluminum diethyl phosphite from Preparation Example 1, 16 parts melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 9 parts melamine polyphosphate Melapur® 200, 5 parts organic modified montmorillonite from Preparation Example 2, 3 parts coupling-dispersion composite additive, 0.3 parts antioxidant 1010, 0.3 parts antioxidant 168, 0.3 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate. The coupling-dispersing composite additive is composed of γ-glycidyl etheroxypropyltrimethoxysilane KH-560 and bis-stearamide EBS in a mass ratio of 1:2.5.
[0063] A method for preparing a halogen-free flame retardant masterbatch includes the following steps: S1, 38 parts of activated modified aluminum diethyl phosphite from Preparation Example 1, 16 parts of melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 9 parts of melamine polyphosphate Melapur® 200, and 5 parts of organic modified montmorillonite from Preparation Example 2 were added to a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition was vacuum dried at 120°C for 4.0 h. Before use, LLDPE resin DNDA7042 should be dried at 90℃ for 2 hours using a forced-air drying method. S2, 32 parts of dried LLDPE resin DNDA7042, 3 parts of coupling-dispersion composite additive, 0.3 parts of antioxidant 1010, 0.3 parts of antioxidant 168, 0.3 parts of polyethylene wax AC-6A, and 0.2 parts of sodium benzoate were added to a high-speed mixer and premixed for 5 minutes at 90℃ and 1000rpm to obtain resin premix; S3. The halogen-free flame-retardant composition dried in step S1 is fed into a twin-screw extruder via side feeding. At the same time, the resin premix from S2 is fed into the twin-screw extruder via main feeding, maintaining a total feed rate of 30 kg / h, a screw length-to-diameter ratio of L / D = 44, and extrusion temperature settings: Zone 1 140℃, Zone 2 160℃, Zone 3 170℃, Zone 4 185℃, Zone 5 190℃, Zone 6 195℃, Zone 7 200℃, and die head 200℃. The screw speed is 300 rpm, and the vacuum degree is -0.085 MPa. The melt is water-cooled, stretched, and pelletized, and then dried in a fluidized bed at 90℃ for 2 hours to obtain halogen-free flame-retardant LLDPE masterbatch with a particle size range of 2-4 mm and a moisture content of ≤0.05 wt%.
[0064] The difference between Example 4 and Example 3 is that the halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 15 parts LLDPE resin (Maoming Petrochemical Company, CAS: 9002-88-4, grade: DNDA7042; melt flow rate MFR = 2.0 g / 10 min at 190℃ / 2.16 kg), and 15 parts PP resin (Maoming Petrochemical Company, CAS: 9003-07-0, grade: PPB-M02D; melt flow rate MFR = 2.0 g / 10 min at 230℃ / 2.16 kg). The composition of the mixture is as follows: melt flow rate (MFR) = 1.5 g / 10 min (kg); 45 parts of activated modified aluminum diethyl phosphite from Preparation Example 1; 15 parts of melamine resin microcapsule-encapsulated ammonium polyphosphate EPFR-APP231H; 10 parts of melamine polyphosphate Melapur® 200; 5 parts of organic modified montmorillonite from Preparation Example 2; 3 parts of coupling-dispersion composite additive; 0.3 parts of antioxidant 1010; 0.3 parts of antioxidant 168; 0.4 parts of polyethylene wax AC-6A; and 0.2 parts of sodium benzoate. The 3 parts of coupling-dispersion composite additive are composed of 1 part of γ-glycidyl etheroxypropyltrimethoxysilane KH-560 and 2 parts of bis-stearamide EBS.
[0065] A method for preparing a halogen-free flame retardant masterbatch includes the following steps: S1, 45 parts of activated modified aluminum diethyl phosphite from Preparation Example 1, 15 parts of melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 10 parts of melamine polyphosphate Melapur® 200, and 5 parts of organic modified montmorillonite from Preparation Example 2 were added to a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition was vacuum dried at 120°C for 4.0 h. LLDPE resin DNDA7042 and PP resin PPB-M02D should be dried at 90℃ for 2 hours before use. S2, 15 parts of dried LLDPE resin DNDA7042, 15 parts of PP resin PPB-M02D, 3 parts of coupling-dispersion composite additive, 0.3 parts of antioxidant 1010, 0.3 parts of antioxidant 168, 0.4 parts of polyethylene wax AC-6A, and 0.2 parts of sodium benzoate are added to a high-speed mixer and premixed for 5 minutes at 90℃ and 1000rpm to obtain resin premix. In step S3, the halogen-free flame-retardant composition dried in step S1 is fed into a twin-screw extruder via side feeding. Simultaneously, the resin premix from step S2 is fed into the twin-screw extruder via main feeding, maintaining a total feed rate of 30 kg / h, a screw length-to-diameter ratio (L / D) of 44, and extrusion temperature settings: zone 1 165℃, zone 2 180℃, zone 3 185℃, zone 4 200℃, zone 5 210℃, zone 6 220℃, zone 7 230℃, and die head 235℃. The screw speed is 300 rpm, and the vacuum degree is -0.085 MPa. The melt is water-cooled, stretched, and pelletized, and then dried in a fluidized bed at 90℃ for 2 hours to obtain halogen-free flame-retardant LLDPE / PP composite masterbatch with a particle size range of 2-4 mm and a moisture content ≤0.05 wt%.
[0066] The difference between Example 5 and Example 1 is that the halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 35 parts PP resin (Maoming Petrochemical Company, CAS: 9003-07-0, grade: PPB-M02D; melt flow rate MFR=1.5g / 10min at 230℃ / 2.16 kg), 42 parts activated modified aluminum diethyl phosphite from Preparation Example 1, 15 parts melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 10 parts melamine polyphosphate Melapur® 200, 2.5 parts organic modified montmorillonite from Preparation Example 2, 3 parts coupling-dispersion composite additive, 0.25 parts antioxidant 1010, 0.25 parts antioxidant 168, 0.3 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate. The coupling-dispersing composite additive is composed of γ-glycidyl etheroxypropyltrimethoxysilane KH-560 and bis-stearamide EBS in a mass ratio of 1:2.5.
[0067] A method for preparing a halogen-free flame retardant masterbatch includes the following steps: S1, 42 parts of activated modified aluminum diethyl phosphite from Preparation Example 1, 15 parts of melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 10 parts of melamine polyphosphate Melapur® 200, and 3 parts of organic modified montmorillonite from Preparation Example 2 were added to a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition was vacuum dried at 120°C for 4.0 h. Before use, PP resin PPB-M02D should be dried at 90℃ for 2 hours using a forced-air drying method. S2, add 35 parts of dried PP resin PPB-M02D, 2.5 parts of coupling-dispersion composite additive, 0.25 parts of antioxidant 1010, 0.25 parts of antioxidant 168, 0.3 parts of polyethylene wax AC-6A, and 0.2 parts of sodium benzoate to a high-speed mixer and premix for 5 minutes at 90℃ and 1000rpm to obtain resin premix; S3. The halogen-free flame-retardant composition dried in step S1 is fed into a twin-screw extruder via side feeding. At the same time, the resin premix from S2 is fed into the twin-screw extruder via main feeding, maintaining a total feed rate of 30 kg / h, a screw length-to-diameter ratio of L / D = 44, and extrusion temperature settings: Zone 1 160℃, Zone 2 180℃, Zone 3 200℃, Zone 4 220℃, Zone 5 230℃, Zone 6 230℃, Zone 7 235℃, and die head 235℃. The screw speed is 300 rpm, and the vacuum degree is -0.085 MPa. The melt is water-cooled, stretched, and pelletized, and then dried in a fluidized bed at 90℃ for 2 hours to obtain halogen-free flame-retardant PP masterbatch with a particle size range of 2-4 mm and a moisture content of ≤0.05 wt%.
[0068] The difference between Example 6 and Example 3 is that: a halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 32 parts LLDPE resin (Maoming Petrochemical Company, CAS: 9002-88-4, grade: DNDA7042; melt flow rate MFR=2.0g / 10min at 190℃ / 2.16kg), 40 parts activated modified aluminum diethyl phosphite from Preparation Example 1, 14 parts melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 11 parts melamine polyphosphate Melapur® 200, 5 parts organic modified montmorillonite from Preparation Example 2, 3 parts coupling-dispersion composite additive, 0.3 parts antioxidant 1010, 0.3 parts antioxidant 168, 0.3 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate. The coupling-dispersing composite additive is composed of γ-glycidyl etheroxypropyltrimethoxysilane KH-560 and bis-stearamide EBS in a mass ratio of 1:2.5.
[0069] The difference between Comparative Example 1-A and Example 1 is that the halogen-free flame retardant composition does not contain the organically modified montmorillonite OMMT of Preparation Example 2. The halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 30 parts PET resin FG600, 45 parts activated modified aluminum diethylphosphite of Preparation Example 1, 15 parts melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 10 parts melamine polyphosphate Melapur® 200, 3 parts coupling-dispersion composite additive, 0.3 parts antioxidant 1010, 0.3 parts antioxidant 168, 0.4 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate.
[0070] The difference in preparation method is as follows: S1, 45 parts of activated modified aluminum diethyl hypophosphite from Preparation Example 1, 15 parts of melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, and 10 parts of melamine polyphosphate Melapur®200 are put into a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is then vacuum dried at 120°C for 4.0 h; the remaining steps are the same.
[0071] The difference between Comparative Example 1-B and Example 1 is that the organic modified montmorillonite OMMT in Preparation Example 2 of the halogen-free flame retardant composition was replaced with commercially available organic montmorillonite DK1N (Zhejiang Fenghong New Material Co., Ltd.).
[0072] The halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 30 parts PET resin FG600, 40 parts activated and modified aluminum diethylphosphite as in Preparation Example 1, 15 parts melamine resin microcapsule-encapsulated ammonium polyphosphate EPFR-APP231H, 10 parts melamine polyphosphate Melapur® 200, 5 parts organomontmorillonite DK1N (Zhejiang Fenghong New Material Co., Ltd.), 3 parts coupling-dispersion composite additive, 0.3 parts antioxidant 1010, 0.3 parts antioxidant 168, 0.4 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate.
[0073] The difference in preparation method is as follows: S1, 40 parts of activated modified aluminum diethyl phosphite from Preparation Example 1, 15 parts of melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 10 parts of melamine polyphosphate Melapur®200, and 5 parts of organomontmorillonite DK1N (Zhejiang Fenghong New Material Co., Ltd.) are put into a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is then vacuum dried at 120℃ for 4.0 h; the remaining steps are the same.
[0074] The difference between Comparative Example 2 and Example 2 is that the halogen-free flame retardant composition does not contain melamine resin microcapsule-encapsulated ammonium polyphosphate EPFR-APP231H, but uses unencapsulated ammonium polyphosphate APP [(EPFR-APP(II), Jinan Xinnuo Chemical Co., Ltd.]]. The halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 30 parts PET resin FG600, 35 parts activated modified aluminum diethylphosphite from Preparation Example 1, 18 parts ammonium polyphosphate APP, 8 parts melamine polyphosphate Melapur® 200, 4 parts organic modified montmorillonite from Preparation Example 2, 2.5 parts coupling-dispersion composite additive, 0.25 parts antioxidant 1010, 0.25 parts antioxidant 168, 0.3 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate.
[0075] The difference in preparation method is as follows: S1, 35 parts of activated modified aluminum diethylphosphite from Preparation Example 1, 18 parts of ammonium polyphosphate APP, 8 parts of melamine polyphosphate Melapur® 200, and 4 parts of organic modified montmorillonite from Preparation Example 2 are put into a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is then vacuum dried at 120°C for 4.0 h; the remaining steps are the same.
[0076] The difference between Comparative Example 3 and Example 3 is that: a halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 32 parts LLDPE resin DNDA7042, 45 parts activated modified aluminum diethyl phosphite from Preparation Example 1, 9 parts melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 9 parts melamine polyphosphate Melapur® 200, 5 parts organic modified montmorillonite from Preparation Example 2, 3 parts coupling-dispersion composite additive, 0.3 parts antioxidant 1010, 0.3 parts antioxidant 168, 0.3 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate.
[0077] The difference in preparation method is as follows: S1, 45 parts of activated modified aluminum diethyl phosphite from Preparation Example 1, 9 parts of melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 9 parts of melamine polyphosphate Melapur® 200, and 5 parts of organic modified montmorillonite from Preparation Example 2 are put into a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is then vacuum dried at 120°C for 4.0 h; the remaining steps are the same.
[0078] The difference between Comparative Example 4 and Example 1 is that the halogen-free flame retardant composition does not contain melamine resin microcapsule-encapsulated ammonium polyphosphate EPFR-APP231H.
[0079] The halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 30 parts PET resin FG600, 55 parts activated modified aluminum diethyl phosphite from Preparation Example 1, 10 parts melamine polyphosphate Melapur® 200, 5 parts organic modified montmorillonite from Preparation Example 2, 3 parts coupling-dispersion composite additive, 0.3 parts antioxidant 1010, 0.3 parts antioxidant 168, 0.4 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate.
[0080] The difference in preparation method is as follows: S1, 55 parts of activated modified aluminum diethylphosphite from Preparation Example 1, 10 parts of melamine polyphosphate Melapur® 200, and 5 parts of organic modified montmorillonite from Preparation Example 2 are put into a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is then vacuum dried at 120°C for 4.0 h; the remaining steps are the same.
[0081] The difference between Comparative Example 5 and Example 1 is that the halogen-free flame retardant composition does not contain melamine polyphosphate Melapur® 200.
[0082] The halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 30 parts PET resin FG600, 50 parts activated modified aluminum diethyl phosphite from Preparation Example 1, 15 parts melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 5 parts organic modified montmorillonite from Preparation Example 2, 3 parts coupling-dispersion composite additive, 0.3 parts antioxidant 1010, 0.3 parts antioxidant 168, 0.4 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate.
[0083] The difference in preparation method is as follows: S1, 50 parts of activated modified aluminum diethyl phosphite from Preparation Example 1, 15 parts of melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, and 5 parts of organic modified montmorillonite from Preparation Example 2 are put into a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is then vacuum dried at 120℃ for 4.0 h; the remaining steps are the same.
[0084] The difference between Comparative Example 6 and Example 1 is that the halogen-free flame retardant composition does not contain the activated modified aluminum diethylphosphite as in Preparation Example 1.
[0085] The halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 35 parts PET resin FG600, 35 parts melamine resin microcapsule-encapsulated ammonium polyphosphate EPFR-APP231H, 30 parts melamine polyphosphate Melapur® 200, 5 parts organic modified montmorillonite from Preparation Example 2, 3 parts coupling-dispersion composite additive, 0.3 parts antioxidant 1010, 0.3 parts antioxidant 168, 0.4 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate.
[0086] The difference in preparation method is as follows: S1, 35 parts of melamine resin microcapsules coated with ammonium polyphosphate EPFR-APP231H, 30 parts of melamine polyphosphate Melapur®200, and 5 parts of the organic modified montmorillonite from Preparation Example 2 are put into a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is then vacuum dried at 120°C for 4.0 h; the remaining steps are the same.
[0087] The difference between Comparative Example 7 and Example 1 is that the activated modified aluminum diethylphosphite in Preparation Example 1 was replaced with unmodified aluminum diethylphosphite (Clariant Chemicals Ltd. Exolit OP1230, CAS: 225789-38-8) in the halogen-free flame retardant composition.
[0088] The halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 30 parts PET resin FG600, 40 parts aluminum diethyl phosphite (Clariant Chemicals Ltd. Exolit OP1230, CAS: 225789-38-8), 15 parts melamine resin microcapsule-encapsulated ammonium polyphosphate EPFR-APP231H, 10 parts melamine polyphosphate Melapur® 200, 5 parts organic modified montmorillonite from Preparation Example 2, 3 parts coupling-dispersion composite additive, 0.3 parts antioxidant 1010, 0.3 parts antioxidant 168, 0.4 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate.
[0089] The difference between Comparative Example 8 and Example 1 is that the halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 30 parts PET resin FG600, 32 parts activated modified aluminum diethyl phosphite from Preparation Example 1, 23 parts melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 10 parts melamine polyphosphate Melapur® 200, 5 parts organic modified montmorillonite from Preparation Example 2, 3 parts coupling-dispersion composite additive, 0.3 parts antioxidant 1010, 0.3 parts antioxidant 168, 0.4 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate.
[0090] The difference in preparation method is as follows: S1, 32 parts of activated modified aluminum diethyl phosphite from Preparation Example 1, 23 parts of melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 10 parts of melamine polyphosphate Melapur® 200, and 5 parts of organic modified montmorillonite from Preparation Example 2 are put into a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is then vacuum dried at 120°C for 4.0 h; the remaining steps are the same.
[0091] The difference between Comparative Example 9 and Example 1 is that the halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 30 parts PET resin FG600, 47 parts activated modified aluminum diethyl phosphite from Preparation Example 1, 15 parts melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 3 parts melamine polyphosphate Melapur® 200, 5 parts organic modified montmorillonite from Preparation Example 2, 3 parts coupling-dispersion composite additive, 0.3 parts antioxidant 1010, 0.3 parts antioxidant 168, 0.4 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate.
[0092] The difference in preparation method is as follows: S1, 47 parts of activated modified aluminum diethyl phosphite from Preparation Example 1, 8 parts of melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 10 parts of melamine polyphosphate Melapur® 200, and 5 parts of organic modified montmorillonite from Preparation Example 2 are put into a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is then vacuum dried at 120°C for 4.0 h; the remaining steps are the same.
[0093] The difference between Comparative Example 10 and Example 1 is that the halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 30 parts PET resin FG600, 30 parts activated modified aluminum diethylphosphite from Preparation Example 1, 15 parts melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 20 parts melamine polyphosphate Melapur® 200, 5 parts organic modified montmorillonite from Preparation Example 2, 3 parts coupling-dispersion composite additive, 0.3 parts antioxidant 1010, 0.3 parts antioxidant 168, 0.4 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate.
[0094] The difference in preparation method is as follows: S1, 41 parts of activated modified aluminum diethyl phosphite from Preparation Example 1, 9 parts of melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 20 parts of melamine polyphosphate Melapur® 200, and 5 parts of organic modified montmorillonite from Preparation Example 2 are put into a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is then vacuum dried at 120°C for 4.0 h; the remaining steps are the same.
[0095] The difference between Comparative Example 11 and Example 1 is that the halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 30 parts PET resin FG600, 44 parts activated modified aluminum diethyl phosphite from Preparation Example 1, 15 parts melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 10 parts melamine polyphosphate Melapur® 200, 1 part organic modified montmorillonite from Preparation Example 2, 3 parts coupling-dispersion composite additive, 0.3 parts antioxidant 1010, 0.3 parts antioxidant 168, 0.4 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate.
[0096] The difference in preparation method is as follows: S1, 44 parts of activated modified aluminum diethyl phosphite from Preparation Example 1, 15 parts of melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 10 parts of melamine polyphosphate Melapur® 200, and 1 part of organic modified montmorillonite from Preparation Example 2 are put into a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is then vacuum dried at 120°C for 4.0 h; the remaining steps are the same.
[0097] The difference between Comparative Example 12 and Example 1 is that the halogen-free flame retardant masterbatch is made from the following raw materials in parts by weight: 30 parts PET resin FG600, 35 parts activated modified aluminum diethyl phosphite from Preparation Example 1, 15 parts melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 10 parts melamine polyphosphate Melapur® 200, 10 parts organic modified montmorillonite from Preparation Example 2, 3 parts coupling-dispersion composite additive, 0.3 parts antioxidant 1010, 0.3 parts antioxidant 168, 0.4 parts polyethylene wax AC-6A, and 0.2 parts sodium benzoate.
[0098] The difference in preparation method is as follows: S1, 35 parts of activated modified aluminum diethyl phosphite from Preparation Example 1, 15 parts of melamine resin microcapsule-coated ammonium polyphosphate EPFR-APP231H, 10 parts of melamine polyphosphate Melapur® 200, and 10 parts of organic modified montmorillonite from Preparation Example 2 are put into a high-speed mixer and mixed at 800 rpm for 5 min at room temperature to obtain a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is then vacuum dried at 120°C for 4.0 h; the remaining steps are the same.
[0099] To verify the performance of the flame-retardant masterbatches in each example and comparative example, the masterbatches were mixed uniformly with the corresponding pure resin at 10 wt% (for the LLDPE / PP composite carrier masterbatch of Example 4, 10 wt% of the masterbatch was blended with 90 wt% of the (LLDPE:PP=1:1) mixture and extruded at the corresponding processing temperatures: PET: barrel temperature 265-275℃, mold temperature 15℃; PP: barrel temperature 200-220℃, mold temperature 40℃; PE: barrel temperature 190-210℃, mold temperature 30℃. The resulting 1.6 mm test strips can be directly used for performance testing. The test methods include: 1. Limiting Oxygen Index (LOI): Determined according to GB / T2406.2-2020 standard using the top ignition method. Sample size is 150mm × 58mm, thickness is the actual film thickness (e.g., 25μm). Gas flow rate is 40mm / s, and total oxygen / nitrogen mixture flow rate is 10L / min. When the sample combustion time exceeds 3 minutes or the combustion length exceeds 50mm, the oxygen volume fraction at this point is recorded as the LOI value. Five samples are tested for each sample, and the average value is taken. This invention requires an LOI of not less than 30%.
[0100] 2. Vertical Burning (UL-94): Determined according to GB / T2408-2021 (equivalent to UL-94). Sample size is 200mm × 50mm, with 5 samples each in the longitudinal and transverse directions. The test procedure is based on the VTM rating. A flame height of 20mm is applied for 3 seconds, and the afterflame time t1 is recorded. A second flame is applied, and the afterflame + afterglow time t2 is recorded. It is observed whether the dripping material ignites the absorbent cotton. The rating is V-0 only if t1 ≤ 10s, t2 ≤ 30s, and no dripping material ignites the cotton.
[0101] 3. Cone Calorimeter According to GB / T 16172-2021 (ISO 5660-1). Radiant power 50 kW / m²; sample size 100 mm × 100 mm × 3 mm. Record the peak heat release rate (PHRR).
[0102] 4. Melt Flow Rate (MFR): Determined according to ISO 1133-1:2011 "Plastics - Determination of melt mass flow rate (MFR) and melt volumetric flow rate (MVR) of thermoplastics". The test temperature was 270℃ for PET and 230℃ for PP / PE, with a load of 2.16 kg for both. The results were taken as the average of 5 measurements, expressed in g / 10 min. 5. Mechanical property retention rate: Tensile strength was tested according to GB / T 1040.2, and impact strength according to GB / T 1043.1. The specimens were strip-shaped, 25 mm wide, with a gauge length of 50 mm. Test conditions were: tensile speed 500 mm / min, clamp spacing 100 mm, ambient temperature 23±2℃, and humidity 50±5%RH. Stress-strain curves were recorded until specimen fracture. Tensile strength was taken as the maximum stress before fracture, and elongation at fracture was taken as the percentage change in gauge length at fracture. Tensile strength was tested for each sample, and outliers were removed according to the standard deviation before taking the average value. Retention rate was calculated based on the corresponding pure resin.
[0103] 6. Smoke density D4: According to GB / T 8323.2-2008. Sample size: 75mm×75mm×1.6 mm. The irradiance was set to 50 kW / m². The maximum specific optical density (D4) of the sample was recorded in static mode after 4 minutes of exposure, and the average value of three tests was taken.
[0104] Preheat for 5 minutes, sample for 10 minutes, and express the results in g / 10 min.
[0105] Table 1: Test parameters of flame retardant masterbatches in Examples 1-5 and Comparative Examples 1-12 Note: The PHRR reduction is calculated based on the corresponding matrix resin.
[0106] Table 2: Test parameters of mechanical strength and smoke density of flame retardant masterbatches in Examples 1-5 and Comparative Examples 1-12 Note: The tensile strength retention rate and elongation retention rate are calculated based on the corresponding matrix resin.
[0107] Combined with Example 1 and Comparative Example 1-A and Table 1-2, it can be seen that the self-made organic modified montmorillonite OMMT, melamine polyphosphate, melamine resin microcapsule-coated ammonium polyphosphate, and activated modified diethyl aluminum hypophosphite are used in synergy to effectively improve the overall flame retardancy and mechanical properties, and the prepared flame retardant masterbatch has good flowability.
[0108] Combined with Example 1 and Comparative Example 1-B and Table 1-2, it can be seen that, compared with commercially available organic montmorillonite DK1N, the use of the self-made organic modified montmorillonite OMMT in this invention, in conjunction with melamine polyphosphate, melamine resin microcapsule-encapsulated ammonium polyphosphate, and activated modified diethyl aluminum hypophosphite, can impart excellent flame retardancy, mechanical properties, and melt flowability to the flame retardant masterbatch.
[0109] Based on Example 2, Comparative Examples 2 and 4, and in conjunction with Table 1-2, it can be seen that melamine resin microcapsule-encapsulated ammonium polyphosphate EPFR-APP231H is an indispensable component of the halogen-free flame retardant system in this invention. Compared with commercially available ammonium polyphosphate APP [(EPFR-APP(II)], melamine resin microcapsule-encapsulated ammonium polyphosphate EPFR-APP231H, when used in conjunction with melamine polyphosphate, self-made organic modified montmorillonite OMMT, and activated modified aluminum diethyl phosphite, can impart excellent flame retardancy, mechanical properties, and melt flowability to the flame retardant masterbatch.
[0110] Based on Examples 3 and 3, and referring to Tables 1-2, it can be seen that if the amount of melamine resin microcapsules coated with ammonium polyphosphate in the halogen-free flame retardant system is less than 10 parts, the flame retardancy and mechanical properties of the prepared halogen-free flame retardant masterbatch will be degraded. Therefore, the amount of melamine resin microcapsules coated with ammonium polyphosphate should be controlled to 10-20 parts.
[0111] As can be seen from Example 1 and Comparative Example 5 and Tables 1-2, melamine polyphosphate Melapur® 200 is an indispensable component of the halogen-free flame retardant system in this invention. When used in conjunction with self-made organic modified montmorillonite OMMT, melamine resin microcapsule-coated ammonium polyphosphate, and activated modified diethyl aluminum hypophosphite, it effectively improves the overall flame retardancy, mechanical properties, and melt flowability.
[0112] Based on Example 1 and Comparative Example 6, and in conjunction with Tables 1-2, it can be seen that, compared with the halogen-free flame retardant system of unmodified diethyl aluminum hypophosphite, the self-made activated and modified diethyl aluminum hypophosphite of this invention can be uniformly distributed inside the carrier resin. It forms a more efficient synergistic effect with melamine polyphosphate, melamine resin microcapsule-encapsulated ammonium polyphosphate, and organically modified montmorillonite (OMMT), which can endow the flame retardant masterbatch with superior flame retardancy, mechanical properties, and melt flowability.
[0113] As can be seen from Example 1 and Comparative Example 7 and Tables 1-2, the self-made activated modified aluminum diethylphosphite is an indispensable component of the halogen-free flame retardant system in this invention. When used in conjunction with the self-made organic modified montmorillonite OMMT, melamine resin microcapsule-coated ammonium polyphosphate, and melamine polyphosphate Melapur® 200, it effectively improves the overall flame retardancy, mechanical properties, and melt flowability.
[0114] Based on Examples 1 and 8, and referring to Tables 1-2, it can be seen that in the halogen-free flame retardant system, if the amount of melamine resin microcapsules coating ammonium polyphosphate is greater than 20 parts and the amount of activated modified aluminum diethyl phosphite is less than 35 parts, the flame retardancy (smoke density D4) and mechanical properties of the prepared halogen-free flame retardant masterbatch will be degraded. Therefore, the amount of melamine resin microcapsules coating ammonium polyphosphate in the halogen-free flame retardant system should be controlled at 10-20 parts, and the amount of activated modified aluminum diethyl phosphite should be controlled at 35-45 parts.
[0115] Based on Examples 1 and Comparative Examples 9-10, and referring to Tables 1-2, it can be seen that in the halogen-free flame retardant system, less than 5 parts of melamine polyphosphate Melapur® 200 and more than 45 parts of activated modified aluminum diethyl phosphite will degrade the flame retardancy (smoke density D4) and mechanical properties of the prepared halogen-free flame retardant masterbatch. Furthermore, more than 15 parts of melamine polyphosphate Melapur® 200 and less than 35 parts of activated modified aluminum diethyl phosphite in the halogen-free flame retardant system will also degrade the flame retardancy (smoke density D4) and mechanical properties of the prepared halogen-free flame retardant masterbatch. Therefore, the addition amount of melamine polyphosphate Melapur® 200 in the halogen-free flame retardant system should preferably be controlled at 5-15 parts, and the addition amount of activated modified aluminum diethyl phosphite should preferably be controlled at 35-45 parts.
[0116] Based on Examples 1 and Comparative Examples 11-12, and referring to Tables 1-2, it can be seen that in the halogen-free flame retardant system, if the amount of organically modified montmorillonite added in Preparation Example 2 is less than 3 parts, the flame retardancy (smoke density D4, LOI value) and mechanical properties of the prepared halogen-free flame retardant masterbatch will deteriorate; while if the amount of organically modified montmorillonite added in Preparation Example 2 is greater than 8 parts, the flame retardancy (smoke density D4) and mechanical properties of the prepared halogen-free flame retardant masterbatch will also deteriorate. Therefore, it is advisable to control the amount of organically modified montmorillonite added in Preparation Example 2 of the halogen-free flame retardant system to 3-8 parts.
[0117] In summary, the preferred formulation of the halogen-free flame retardant system is a compound of 30-50 parts of activated and modified aluminum diethylphosphite, 10-20 parts of melamine resin microcapsule-coated ammonium polyphosphate, 5-15 parts of melamine polyphosphate, and 3-8 parts of organically modified montmorillonite. This formulation ensures that the prepared halogen-free flame retardant masterbatch has excellent flame retardancy, mechanical properties, and melt flow properties.
[0118] Examples 1-6 all achieved UL-94V-0, LOI≥30%, PHRR reduction≥40%, and mechanical property retention rate≥80% for 1.6mm PET / PP / PE test strips with a masterbatch addition of 10wt%; while Comparative Examples 1-3, which lacked OMMT, had no APP coating, or used high-filler ADP, could not simultaneously meet V-0 and mechanical requirements, fully verifying the synergistic advantages of the flame retardant system and process of the present invention.
[0119] In summary, the present invention, through the surface activation of diethylaluminum hypophosphite, microcapsule encapsulation of ammonium polyphosphate, and nanolayered barrier modification of montmorillonite combined with melamine polyphosphate, forms a halogen-free flame retardant system that can be uniformly distributed within the carrier resin. This system can effectively improve the overall performance of plastic products with low filler content.
[0120] It should be noted that this specific embodiment is merely an explanation of the technical solution of the present invention and is not intended to limit the present invention. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but as long as they are within the scope of the claims of the present invention, they are protected by patent law.
Claims
1. A halogen-free flame retardant masterbatch, characterized in that: It is made from the following raw materials in parts by weight: 20-40 parts carrier resin, 50-75 parts halogen-free flame retardant system, 2-6 parts coupling-dispersion composite additive, 0.3-1.0 parts antioxidant, 0.2-0.8 parts lubricant, and 0.1-0.5 parts nucleating agent; wherein the carrier resin is selected from at least one of PET, PP, and PE; wherein the halogen-free flame retardant system comprises the following raw materials in parts by weight: 30-50 parts activated modified aluminum diethylphosphite, 10-20 parts melamine resin microcapsule-coated ammonium polyphosphate, 5-15 parts melamine polyphosphate, and 3-8 parts organic modified montmorillonite.
2. The halogen-free flame retardant masterbatch according to claim 1, characterized in that: The activated and modified aluminum diethylphosphite is prepared by pre-activation treatment with 0.3-1.0 wt% aminosilane; the aminosilane is at least one of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropyltriethoxysilane.
3. The halogen-free flame retardant masterbatch according to claim 1, characterized in that: The preparation method of the organically modified montmorillonite is as follows: Step 1: Mix 4-6 parts of sodium montmorillonite, 40-50 parts of ethanol and 40-60 parts of deionized water at room temperature to obtain suspension A; Simultaneously, dissolve 2.5-3.0 parts of hexadecyltributylphosphine bromide in 15-30 parts of acetone and 20-30 parts of deionized water to obtain solution B; Step 2: Add solution B to suspension A, heat to 65-75℃, and mechanically stir for 6-10 hours to obtain suspension C; Step 3: Filter the suspension C obtained in Step 2, wash the filter cake with ethanol and deionized water at least 3 times alternately until the bromide ion content in the filtrate is 0, dry for 20-24 hours, grind and sieve to obtain quaternary phosphate intercalated modified montmorillonite. Step 4: Mix 4-6 parts of the quaternary phosphate salt intercalated modified montmorillonite prepared in Step 3, 40-50 parts of ethanol and 40-60 parts of deionized water at room temperature to obtain suspension D. Simultaneously, 4-6 parts of hexadecyltrimethoxysilane, 35-45 parts of ethanol and 4-8 parts of deionized water are mixed evenly, and the pH of the system is adjusted to 4-5 with glacial acetic acid. The mixture is stirred and mixed evenly at room temperature to obtain solution E. Step 5: Add solution E to suspension D, heat to 48-52℃, and mechanically stir for 20-24 hours to obtain suspension F; Step 6: Filter the suspension F obtained in Step 5, wash the filter cake with ethanol and deionized water alternately at least 3 times until the bromide ion content in the filtrate is 0, dry for 20-24 hours, grind and sieve to obtain organic modified montmorillonite OMMT.
4. The halogen-free flame retardant masterbatch according to claim 3, characterized in that: When the carrier resin is PET, the intrinsic viscosity (IV) of PET is 0.70-0.85 dL / g; when the carrier resin is copolymer polypropylene, the melt flow rate (MFR) of copolymer polypropylene at 230℃ / 2.16kg is 5-15 g / 10min; when the carrier resin is linear low-density polyethylene (LLDPE), the density is 0.918-0.93 g / cm³.
5. The halogen-free flame retardant masterbatch according to claim 3, characterized in that: The coupling-dispersing composite agent is composed of γ-glycidoxypropyltrimethoxysilane and bis-stearamide; the mass ratio of γ-glycidoxypropyltrimethoxysilane to bis-stearamide is 1:(1-3).
6. The halogen-free flame retardant masterbatch according to claim 3, characterized in that: The halogen-free flame retardant system comprises the following raw materials in parts by weight: 35-45 parts of activated modified aluminum diethylphosphite, 12-18 parts of melamine resin microcapsule-coated ammonium polyphosphate, 8-12 parts of melamine polyphosphate, and 4-6 parts of organically modified montmorillonite.
7. The halogen-free flame retardant masterbatch according to claim 6, characterized in that: The antioxidant is a mixture of hindered phenolic antioxidants and phosphite antioxidants in a mass ratio of 1:(0.5-2); the lubricant is a polyethylene wax with a molecular weight of 2000-5000 g / mol; and the nucleating agent is sodium benzoate and / or sorbitol acetal nucleating agent.
8. The halogen-free flame retardant masterbatch according to claim 7, characterized in that: The halogen-free flame retardant masterbatch has a limiting oxygen index ≥31%, a vertical burning rating of UL-94V-0, and a melt flow rate (MFR) ≥6g / 10min at 230℃ / 2.16kg.
9. A method for preparing a halogen-free flame retardant masterbatch according to any one of claims 1-8, characterized in that: Includes the following steps: S1, accurately measured activated modified aluminum diethyl phosphite, melamine resin microcapsules coated with ammonium polyphosphate, melamine polyphosphate, and organic modified montmorillonite are mixed evenly to prepare a halogen-free flame retardant composition. The obtained halogen-free flame retardant composition is vacuum dried at 110-120℃ for 3-4 hours. S2, add carrier resin, coupling-dispersion composite additive, antioxidant, lubricant and nucleating agent into a high-speed mixer, and premix for 5-10 minutes at 80-100℃ and 800-1200rpm to obtain resin premix; S3: The halogen-free flame-retardant composition dried in step S1 is fed into a twin-screw extruder via side feeding. Simultaneously, the resin premix from S2 is fed into the twin-screw extruder via main feeding. The screw length-to-diameter ratio (L / D) is 40-48, the screw speed is 200-400 rpm, and the vacuum degree is ≤-0.08 MPa. When the carrier resin is PET, the extrusion temperature is set as follows: Zone 1 220-240℃, Zone 2 230-250℃, Zone 3 240-260℃, Zones 4-7 250-285℃, and the die head 270-290℃. When the carrier resin is PP, the extrusion temperature is set as follows: Zone 1 160-165℃, Zone 2 180-185℃, Zone 3 200-290℃, Zone 4-7 250-285℃, and the die head 270-290℃. The extrusion temperature is set as follows: Zone 1: 140-150℃, Zone 2: 160-170℃, Zone 3: 175-180℃, Zones 4-7: 185-200℃, Die head: 200-210℃. When the carrier resin is PE, the extrusion temperature is set as follows: Zone 1: 160-185℃, Zone 2: 170-175℃, Zone 3: 185-190℃, Zones 4-7: 200-230℃, Die head: 230-240℃. The melt is water-cooled, stretched, pelletized, and dried to obtain flame-retardant masterbatch with a particle size of 2-4mm and a moisture content of ≤0.05wt%.
10. The application of a halogen-free flame retardant masterbatch according to any one of claims 1-8, characterized in that: The halogen-free flame retardant masterbatch of any one of claims 1-8 is mixed with the matrix resin at a mass ratio of 1:(4-9), and then injection molded or extruded to obtain a flame retardant product; the matrix resin is at least one of PET, PP, and PE, and the matrix resin is the same as or compatible with the carrier resin in the halogen-free flame retardant masterbatch of any one of claims 1-8.