A flame-retardant anti-dripping agent, a flame-retardant polypropylene containing the anti-dripping agent, and a method for preparing the same
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HEFEI GENIUS NEW MATERIALS CO LTD
- Filing Date
- 2024-12-30
- Publication Date
- 2026-06-30
AI Technical Summary
Pure powdered polytetrafluoroethylene anti-dripping agents are prone to stickiness and agglomeration, and have poor dispersibility, making them unsuitable for effective application in polypropylene resins.
A flame-retardant and anti-dripping agent is formed by mixing polytetrafluoroethylene and polyperfluoroalkoxy, adding sodium perfluorononenoxybenzenesulfonate, and processing through a twin-screw extruder. This agent is used to prepare flame-retardant polypropylene.
It improves the dispersibility and anti-dripping effect of anti-dripping agents, and broadens their application scope, including applications in the fields of new energy vehicle battery components, 5G or 6G communication equipment, laptops, capacitors, TVs/monitors, power shields and insulating spacers, etc.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of flame retardant modification of polymer materials, and particularly to a flame retardant and anti-dripping agent, flame retardant polypropylene containing the anti-dripping agent, and a method for preparing the same. Background Technology
[0002] Anti-drip agents are added to flame-retardant plastics primarily because they effectively prevent molten plastic from dripping during combustion, thus reducing the spread and expansion of a fire. Without anti-drip agents, molten plastic material could drip onto other combustibles, igniting new fire points and causing the fire to spread rapidly. Anti-drip agents prevent this dripping by increasing melt strength and flexural modulus, thereby reducing the risk of fire. Furthermore, anti-drip agents can improve the flame-retardant properties of plastics, helping thermoplastic materials achieve higher flame-retardant standards and further enhancing their safety. Therefore, the application of anti-drip agents in flame-retardant plastics is crucial; it not only reduces the spread of fire but also improves the flame-retardant effect of the material, protecting people's safety.
[0003] The most common and cost-effective anti-dripping agent on the market is polytetrafluoroethylene (PTFE). High molecular weight PTFE (around 4-5 million molecules) undergoes fiberization under the shear force of a screw, forming a network structure that prevents dripping. PTFE anti-dripping agents are mainly divided into three categories: coated, emulsion, and pure powder.
[0004] Coated PTFE antidrip agents consist of a polymer coating on the outside of PTFE particles, resulting in better dispersibility during mixing with plastic resins. The outer shell polymer is typically polyacrylonitrile, polystyrene, or polymethyl methacrylate. Compared to pure powder and emulsion antidrip agents, coated antidrip agents offer advantages such as better dispersibility, ease of use, no clumping at room temperature, easy storage, no crystalline points on the product surface, and high surface smoothness. However, coated antidrip agents are currently only applicable to a few polymers such as polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), and polystyrene (PS), and cannot be used in polypropylene resins. Furthermore, the outer coating polymer is considered an impurity in the final product, which can significantly impact compatibility and performance.
[0005] Emulsion-type PTFE anti-drip agents are produced by dispersing PTFE in water with a dispersant to form a PTFE dispersion emulsion. Because the emulsion contains a large amount of water, its use requires sophisticated equipment and technical expertise. Currently, it cannot be practically applied in the plastics industry.
[0006] The advantage of pure powdered PTFE anti-dripping agents is that they contain 100% PTFE, introduce no other impurities, and can be added in relatively large quantities. However, pure powdered PTFE is still prone to agglomeration and has poor dispersibility after sintering. Summary of the Invention
[0007] One objective of this invention is to provide a flame retardant and anti-dripping agent; another objective is to provide a flame retardant polypropylene containing an anti-dripping agent and its preparation method, to solve the problems of pure powdered polytetrafluoroethylene being prone to sticking, agglomeration, and poor dispersibility.
[0008] The flame retardant and anti-dripping agent is composed of polytetrafluoroethylene and perfluoroalkoxy, with a mixing mass ratio of polytetrafluoroethylene to perfluoroalkoxy of (3-5):(1).
[0009] The polyfluoroalkoxy group is an ultrafine white powder with an average particle size D50 ≤ 10 μm.
[0010] A flame-retardant polypropylene containing an anti-dripping agent is made from the following components in parts by weight:
[0011]
[0012] The polypropylene has a melt index of 20-50 g / 10 min at a temperature of 230°C and a load of 2.16 kg.
[0013] The flame retardant is selected from at least one of halogenated flame retardants and halogen-free flame retardants.
[0014] The halogen-free flame retardant is selected from at least one of phosphorus-based flame retardants, nitrogen-based flame retardants, and inorganic flame retardants.
[0015] Preferably, the flame retardant is selected from at least one of decabromodiphenyl ethane, antimony trioxide, melamine cyanurate (MCA), aluminum diethylphosphonate, melamine polyphosphate (MPP), and ammonium polyphosphate (APP).
[0016] The sodium perfluorononenoxybenzenesulfonate is a white or slightly yellow powder with a melting point of 250-260℃.
[0017] The antioxidants mentioned are selected from one or more of hindered amines (HALS), hindered phenols, thiolated compounds, and phosphites.
[0018] Furthermore, the antioxidant is one or more of antioxidant 1098, antioxidant 1076, antioxidant 1010, antioxidant 9228, antioxidant 300, antioxidant TH-412S, antioxidant DLTDP, antioxidant DSTP, or antioxidant 168.
[0019] A method for preparing flame-retardant polypropylene containing an anti-dripping agent includes the following steps: first, 80-100 parts of polypropylene, 0.5-2 parts of flame-retardant and anti-dripping agent, and 0.1-0.5 parts of sodium perfluorononenoxybenzenesulfonate are mixed evenly; then, 0.5-2 parts of antioxidant and 5-20 parts of flame retardant are added, and the mixture is mixed evenly to obtain a mixture.
[0020] The mixture is fed into the feed port of a twin-screw extruder, and the final product is obtained after extrusion and pelletizing. Preferably, the temperature of the twin-screw extruder is 130-160℃ in zone one, 160-190℃ in zone two, 180-210℃ in zone three, 190-220℃ in zone four, 200-220℃ in zone five, and 200-220℃ at the die head. The beneficial effects of this invention are:
[0021] 1. The composite anti-dripping agent of this invention, compared with polytetrafluoroethylene (PTFE), does not agglomerate, has excellent dispersibility, and further improves the anti-dripping effect; compared with anti-dripping agents coated with PTFE, it can be applied to polypropylene resin, further improving the anti-dripping effect. This invention further broadens the application range of PTFE powder.
[0022] 2. The addition of sodium perfluorononenoxybenzenesulfonate to the composition in this invention can better disperse the composite anti-dripping agent evenly in the polypropylene matrix, thereby further improving the flame retardant properties of the composition.
[0023] 3. The product of this invention can be widely used in fields including new energy vehicle battery components, 5G or 6G communications, laptops, capacitors, televisions / monitors, power shields, insulating sheets, and other electronic appliances and relays. Detailed Implementation
[0024] Unless otherwise specified, all raw materials used in this invention are commercially available or prepared according to conventional methods in the art. Unless otherwise defined or stated, all technical and scientific terms used herein have the same meaning as are familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to the methods of this invention. Other aspects of this invention will be apparent to those skilled in the art from the disclosure herein. The invention is further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.
[0025] Unless otherwise specified, experimental methods in the following examples are generally performed according to national standards. If no corresponding national standard exists, general international standards, standard conditions, or conditions recommended by the manufacturer are followed. Unless otherwise stated, all parts are parts by weight, and all percentages are weight percentages.
[0026] It should be noted that those skilled in the art can make various changes and improvements without departing from the concept of this invention. These all fall within the scope of protection of this invention.
[0027] In the following examples and comparative examples, some raw material specifications and sources are described, but not limited to these materials:
[0028] The polypropylene used is BX3800 from SK Corporation of South Korea, with a melt flow index of 30 g / 10 min.
[0029] Polytetrafluoroethylene is in powder form, Daikin M-112 from Japan.
[0030] Coated polytetrafluoroethylene, Dongguan Xingyuan Chemical Co., Ltd. XY3300.
[0031] The polyfluoroalkoxy powder has an average particle size of 800 mesh, 2000 mesh, and 3000 mesh. It is produced by Hengtai Plastics in Zhangmutou, Dongguan City.
[0032] The suppliers of decabromodiphenyl ethane, antimony trioxide, ammonium polyphosphate, and pentaerythritol are all Shandong Chenxu New Material Co., Ltd.
[0033] The supplier of melamine cyanurate (MCA) is Jinan Jinyingtai Chemical Co., Ltd.
[0034] Sodium perfluorononenoxybenzenesulfonate is a white powder, supplied by Wuhan Shuer Biotechnology Co., Ltd.
[0035] Both antioxidants 1010 and 168 are supplied by Cytec Chemicals, Inc.
[0036] In the embodiments and comparative examples of the present invention, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 mixed in a mass ratio of 1:1.
[0037] Example 1
[0038] In this embodiment, the mass ratio of the flame retardant and anti-dripping agent: polytetrafluoroethylene to polyperfluoroalkoxy is (3): (1); the mass ratio of the flame retardant: decabromodiphenyl ethane to antimony trioxide is (3): (1).
[0039] First, mix 80 parts of polypropylene, 0.5 parts of flame retardant and anti-dripping agent, and 0.1 parts of sodium perfluorononenoxybenzenesulfonate evenly; then add 0.5 parts of antioxidant and 8 parts of flame retardant, and mix evenly to obtain a mixture.
[0040] The mixture is fed into the feed port of a twin-screw extruder, and the final product is obtained after extrusion and pelletizing. Preferably, the temperature of the twin-screw extruder is 130°C in zone one, 160°C in zone two, 180°C in zone three, 190°C in zone four, 200°C in zone five, and 205°C at the die head.
[0041] Example 2
[0042] In this embodiment, the flame retardant and anti-dripping agent is a mixture of polytetrafluoroethylene and polyperfluoroalkoxy in a mass ratio of (3):(1). Flame retardant: melamine cyanurate.
[0043] First, mix 90 parts of polypropylene, 1 part of flame retardant and anti-dripping agent, and 0.2 parts of sodium perfluorononenoxybenzenesulfonate evenly; then add 1 part of antioxidant and 12 parts of flame retardant, and mix evenly to obtain a mixture.
[0044] The mixture is fed into the feed port of a twin-screw extruder, and the final product is obtained after extrusion and pelletizing. Preferably, the temperature of the twin-screw extruder is 140°C in zone one, 170°C in zone two, 190°C in zone three, 200°C in zone four, 210°C in zone five, and 220°C at the die head.
[0045] Example 3
[0046] In this embodiment, the flame retardant and anti-dripping agent is a mixture of polytetrafluoroethylene and polyperfluoroalkoxy in a mass ratio of (4):(1). The flame retardant is a mixture of ammonium polyphosphate and pentaerythritol in a mass ratio of (3):(1).
[0047] First, mix 100 parts of polypropylene, 2 parts of flame retardant and anti-dripping agent, and 0.5 parts of sodium perfluorononenoxybenzenesulfonate evenly; then add 1.5 parts of antioxidant and 18 parts of flame retardant, and mix evenly to obtain a mixture.
[0048] The mixture is fed into the feed port of a twin-screw extruder, and the final product is obtained after extrusion and pelletizing. Preferably, the temperature of the twin-screw extruder is 160°C in zone one, 190°C in zone two, 210°C in zone three, 220°C in zone four, 220°C in zone five, and 220°C at the die head.
[0049] Example 4
[0050] In this embodiment, the flame retardant and anti-dripping agent is a mixture of polytetrafluoroethylene and polyperfluoroalkoxy in a mass ratio of (4):(1). The flame retardant is a mixture of ammonium polyphosphate and pentaerythritol in a mass ratio of (3):(1).
[0051] First, mix 100 parts of polypropylene, 1.2 parts of flame retardant and anti-dripping agent, and 0.5 parts of sodium perfluorononenoxybenzenesulfonate evenly; then add 1.5 parts of antioxidant and 18 parts of flame retardant, and mix evenly to obtain a mixture.
[0052] The mixture is fed into the feed port of a twin-screw extruder, and the final product is obtained after extrusion and pelletizing. Preferably, the temperature of the twin-screw extruder is 160°C in zone one, 190°C in zone two, 210°C in zone three, 220°C in zone four, 220°C in zone five, and 220°C at the die head.
[0053] Example 5
[0054] In this embodiment, the flame retardant and anti-dripping agent is a mixture of polytetrafluoroethylene and polyperfluoroalkoxy in a mass ratio of (5):(1). The flame retardant is a mixture of ammonium polyphosphate and pentaerythritol in a mass ratio of (3):(1).
[0055] First, mix 100 parts of polypropylene, 2 parts of flame retardant and anti-dripping agent, and 0.5 parts of sodium perfluorononenoxybenzenesulfonate evenly; then add 1.5 parts of antioxidant and 18 parts of flame retardant, and mix evenly to obtain a mixture.
[0056] The mixture is fed into the feed port of a twin-screw extruder, and the final product is obtained after extrusion and pelletizing. Preferably, the temperature of the twin-screw extruder is 160°C in zone one, 190°C in zone two, 210°C in zone three, 220°C in zone four, 220°C in zone five, and 220°C at the die head.
[0057] Each comparative example is compared with Example 3.
[0058] Comparative Example 1
[0059] In this embodiment, the flame retardant and anti-dripping agent is a mixture of polytetrafluoroethylene and polyperfluoroalkoxy in a mass ratio of (6):(1). The flame retardant is a mixture of ammonium polyphosphate and pentaerythritol in a mass ratio of (3):(1).
[0060] First, mix 100 parts of polypropylene, 1.2 parts of flame retardant and anti-dripping agent, and 0.5 parts of sodium perfluorononenoxybenzenesulfonate evenly; then add 1.5 parts of antioxidant and 18 parts of flame retardant, and mix evenly to obtain a mixture.
[0061] The mixture is fed into the feed port of a twin-screw extruder, and the final product is obtained after extrusion and pelletizing. Preferably, the temperature of the twin-screw extruder is 160°C in zone one, 190°C in zone two, 210°C in zone three, 220°C in zone four, 220°C in zone five, and 220°C at the die head.
[0062] Comparative Example 2
[0063] In this embodiment, the flame retardant and anti-dripping agent is a mixture of polytetrafluoroethylene and polyperfluoroalkoxy in a mass ratio of (2):(1). The flame retardant is a mixture of ammonium polyphosphate and pentaerythritol in a mass ratio of (3):(1).
[0064] First, mix 100 parts of polypropylene, 1.2 parts of flame retardant and anti-dripping agent, and 0.5 parts of sodium perfluorononenoxybenzenesulfonate evenly; then add 1.5 parts of antioxidant and 18 parts of flame retardant, and mix evenly to obtain a mixture.
[0065] The mixture is fed into the feed port of a twin-screw extruder, and the final product is obtained after extrusion and pelletizing. Preferably, the temperature of the twin-screw extruder is 160°C in zone one, 190°C in zone two, 210°C in zone three, 220°C in zone four, 220°C in zone five, and 220°C at the die head.
[0066] Comparative Example 3
[0067] In this embodiment, the flame retardant and anti-dripping agent is polytetrafluoroethylene powder. The mass ratio of the flame retardant ammonium polyphosphate to pentaerythritol is (3):(1).
[0068] First, mix 100 parts of polypropylene, 1.2 parts of flame retardant and anti-dripping agent, and 0.5 parts of sodium perfluorononenoxybenzenesulfonate evenly; then add 1.5 parts of antioxidant and 18 parts of flame retardant, and mix evenly to obtain a mixture.
[0069] The mixture is fed into the feed port of a twin-screw extruder, and the final product is obtained after extrusion and pelletizing. Preferably, the temperature of the twin-screw extruder is 160°C in zone one, 190°C in zone two, 210°C in zone three, 220°C in zone four, 220°C in zone five, and 220°C at the die head.
[0070] Comparative Example 4
[0071] In this embodiment, the flame retardant and anti-dripping agent is polytetrafluoroethylene powder coated with polytetrafluoroethylene. The mass ratio of the flame retardant ammonium polyphosphate to pentaerythritol is (3):(1).
[0072] First, mix 100 parts of polypropylene, 1.2 parts of flame retardant and anti-dripping agent, and 0.5 parts of sodium perfluorononenoxybenzenesulfonate evenly; then add 1.5 parts of antioxidant and 18 parts of flame retardant, and mix evenly to obtain a mixture.
[0073] The mixture is fed into the feed port of a twin-screw extruder, and the final product is obtained after extrusion and pelletizing. Preferably, the temperature of the twin-screw extruder is 160°C in zone one, 190°C in zone two, 210°C in zone three, 220°C in zone four, 220°C in zone five, and 220°C at the die head.
[0074] Comparative Example 5
[0075] In this embodiment, the flame retardant and anti-dripping agent is polytetrafluoroethylene powder coated with polytetrafluoroethylene. The mass ratio of the flame retardant ammonium polyphosphate to pentaerythritol is (3):(1).
[0076] First, mix 100 parts of polypropylene and 1.2 parts of flame retardant and anti-dripping agent evenly; then add 1.5 parts of antioxidant and 18 parts of flame retardant, mix evenly to obtain a mixture.
[0077] The mixture is fed into the feed port of a twin-screw extruder, and the final product is obtained after extrusion and pelletizing. Preferably, the temperature of the twin-screw extruder is 160°C in zone one, 190°C in zone two, 210°C in zone three, 220°C in zone four, 220°C in zone five, and 220°C at the die head.
[0078] Comparative Example 6
[0079] In this embodiment, the flame retardant and anti-dripping agent is a mixture of polytetrafluoroethylene and polyperfluoroalkoxy in a mass ratio of (4):(1). The flame retardant is a mixture of ammonium polyphosphate and pentaerythritol in a mass ratio of (3):(1).
[0080] Mix 100 parts polypropylene, 2 parts flame retardant and anti-dripping agent, 0.5 parts sodium perfluorononenoxybenzenesulfonate, 1.5 parts antioxidant, and 18 parts flame retardant evenly to obtain a mixture.
[0081] The mixture is fed into the feed port of a twin-screw extruder, and the final product is obtained after extrusion and pelletizing. Preferably, the temperature of the twin-screw extruder is 160°C in zone one, 190°C in zone two, 210°C in zone three, 220°C in zone four, 220°C in zone five, and 220°C at the die head.
[0082] Flame retardant test methods for each embodiment and comparative example: Tested according to UL-94 standard.
[0083] The test piece (1.6 mm thick) was placed vertically, and the flame height was adjusted to 20 ± 1 mm. The first burn lasted 10 seconds, and the flame was removed until it extinguished. The time and other phenomena were recorded. The second burn lasted 10 seconds, and the flame was removed until it extinguished. The time and other phenomena were recorded again, while observing whether dripping or cotton burning occurred. Specific test results are shown in Table 1.
[0084] Table 1 Flame retardant properties
[0085] Test Project Example 1: UL-94 Flame Retardant Rating The sum of t1+t2 for 5 splines (in seconds) Example 1 V0 31 Example 2 V0 26 Example 3 V0 8 Example 4 V0 13 Example 5 V0 25 Comparative Example 1 V1 56 Comparative Example 2 V1 62 Comparative Example 3 V2 165 Comparative Example 4 V1 110 Comparative Example 5 V1 84 Comparative Example 6 V0 45
[0086] As can be seen from the above embodiments and comparative examples, the composite anti-dripping agent of the present invention, compared with pure polytetrafluoroethylene (PTFE), does not agglomerate, has good dispersibility, and further improves the anti-dripping effect; compared with the anti-dripping agent coated with PTFE, it can be applied to polypropylene resin, and the anti-dripping effect is further improved. The product of the present invention further broadens the application range of PTFE powder.
[0087] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. 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 present invention without departing from the essence and scope of the technical solutions of the present invention.
Claims
1. A flame retardant and anti-dripping agent, characterized in that, It is made of polytetrafluoroethylene and perfluoroalkoxy in a mass ratio of (3-5):(1).
2. The flame retardant and anti-dripping agent as described in claim 1, characterized in that, The polyfluoroalkoxy group is an ultrafine white powder with an average particle size D50 ≤ 10 μm.
3. A flame-retardant polypropylene containing the anti-dripping agent as described in claim 1, characterized in that, It is made from the following components in parts by weight:
4. The flame-retardant polypropylene as described in claim 3, characterized in that, The polypropylene has a melt index of 20-50 g / 10 min at a temperature of 230℃ and a load of 2.16 kg; the sodium perfluorononenoxybenzenesulfonate is a white or slightly yellow powder with a melting point of 250-260℃.
5. The flame-retardant polypropylene as described in claim 3, characterized in that, The flame retardant is selected from at least one of halogenated flame retardants and halogen-free flame retardants.
6. The flame-retardant polypropylene as described in claim 5, characterized in that, The halogen-free flame retardant is selected from at least one of phosphorus-based flame retardants, nitrogen-based flame retardants, and inorganic flame retardants.
7. The flame-retardant polypropylene as described in claim 5, characterized in that, The flame retardant is selected from at least one of decabromodiphenyl ethane, antimony trioxide, melamine cyanurate (MCA), aluminum diethylphosphonate, melamine polyphosphate (MPP), and ammonium polyphosphate (APP).
8. The flame-retardant polypropylene as described in claim 3, characterized in that, The antioxidant is selected from one or more of hindered amines (HALS), hindered phenols, thiolated compounds, and phosphites; the antioxidant is one or more of antioxidant 1098, antioxidant 1076, antioxidant 1010, antioxidant 9228, antioxidant 300, antioxidant TH-412S, antioxidant DLTDP, antioxidant DSTP, or antioxidant 168.
9. A method for preparing flame-retardant polypropylene containing the anti-dripping agent as described in claim 1, comprising the following steps: First, mix 80-100 parts of polypropylene, 0.5-2 parts of flame retardant and anti-dripping agent, and 0.1-0.5 parts of sodium perfluorononenoxybenzenesulfonate evenly; then add 0.5-2 parts of antioxidant and 5-20 parts of flame retardant, and mix evenly to obtain a mixture. The mixture is fed into the feed port of a twin-screw extruder, and after extrusion and pelletizing, the final product is obtained.
10. The method for preparing flame-retardant polypropylene as described in claim 9, characterized in that, The twin-screw extruder has the following temperature zones: Zone 1: 130-160℃; Zone 2: 160-190℃; Zone 3: 180-210℃; Zone 4: 190-220℃; Zone 5: 200-220℃; and Die head temperature: 200-220℃.