Environment-friendly halogen-free efficient flame-retardant composition, flame retardant, preparation method and application

Abstract

The invention discloses an environment-friendly halogen-free efficient flame-retardant composition, a flame retardant, a preparation method and application, and relates to the field of flame retardants, and the environment-friendly halogen-free efficient flame-retardant composition specifically comprises piperazine pyrophosphate, melamine cyanurate, organic phosphonate and polytetrafluoroethylene. The flame-retardant efficiency is improved. By introducing the silane coupling agent, the compatibility of the flame-retardant composition and polyolefin is improved, the processability of the flame retardant and a polyolefin substrate is improved, the precipitation of the flame retardant is reduced, and the flame-retardant composition can continuously and stably exist in a double-85 environment for more than 1000 hours without precipitation. The halogen-free flame retardant prepared by the method can reduce the use cost, solves the problem that most of the halogen-free flame retardants of the scorched piperidine system in the market are easy to separate out, is high in universality, and has a better flame-retardant effect in flame retardance of various types of polyolefins such as polypropylene and polyethylene.

Description

Technical Field

[0001] This invention relates to the field of flame retardancy, specifically to an environmentally friendly, halogen-free, high-efficiency flame retardant composition and flame retardant, its preparation method, and its application. Background Technology

[0002] With technological advancements, the requirements for flame retardants are becoming increasingly stringent, especially in high-temperature and high-humidity environments. Existing flame retardants often exhibit precipitation issues, which reduce their flame-retardant effectiveness. To meet these requirements, the amount of flame retardant added is typically increased to improve flame retardancy, but this increases costs and reduces the compatibility between the flame retardant and the substrate. Therefore, developing a flame retardant with high flame-retardant efficiency, low addition amount, and resistance to high-temperature and high-humidity environments is crucial.

[0003] Chinese invention patent application CN118005997A discloses a halogen-free flame-retardant bonding microparticle and its flame-retardant polyolefin material. This invention utilizes an in-situ bonding method to achieve rapid reaction of different halogen-free flame-retardant components at the micro-nano level. The aggregated flame-retardant bonding microparticles exert a synergistic flame-retardant effect both within and between the microparticles, resulting in a concentrated release of the flame-retardant effects of different halogen-free components. This improves performance such as limiting oxygen index, vertical burning grade, and glow ignition temperature, while reducing peak heat and smoke release rates. However, it does not possess high-temperature and high-humidity resistance. Chinese invention patent application CN111484520A discloses an aluminum ethylenediaminetetramethylenephosphonate flame retardant, its preparation method, and its uses. The additive in the flame-retardant composition is at least one of aluminum diethylphosphonate, piperazine pyrophosphate, melamine cyanurate, guanidine, and dicyandiamide. The synthesis process is simple, with high yield, and easy for industrial production. However, it cannot achieve high-efficiency flame retardancy in 85°C environments. Summary of the Invention

[0004] In order to develop a flame retardant with high flame retardant efficiency, low addition amount, and resistance to high temperature and high humidity environments, the first aspect of the present invention provides an environmentally friendly halogen-free high-efficiency flame retardant composition comprising piperazine pyrophosphate, melamine cyanurate, organophosphonate and polytetrafluoroethylene.

[0005] In one embodiment, the weight ratio of piperazine pyrophosphate, melamine cyanurate, organophosphonate and polytetrafluoroethylene is (60-75):(20-30):(1-15):(0.1-2).

[0006] In one embodiment, the weight ratio of piperazine pyrophosphate, melamine cyanurate, organophosphonate and polytetrafluoroethylene is (66-71):(21-28):(4-10):(0.5-1.5).

[0007] In one embodiment, the weight ratio of piperazine pyrophosphate, melamine cyanurate, organophosphonate and polytetrafluoroethylene is (66.41-70.15):(22.14-23.38):(4.97-9.95):1.

[0008] In one embodiment, the weight ratio of piperazine pyrophosphate, melamine cyanurate, organophosphonate and polytetrafluoroethylene is 70.15:23.38:4.97:1.

[0009] In one embodiment, the weight ratio of piperazine pyrophosphate, melamine cyanurate, organophosphonate and polytetrafluoroethylene is 66.41:22.14:9.95:1.

[0010] A second aspect of the present invention provides an environmentally friendly, halogen-free, high-efficiency flame retardant, comprising the above-described environmentally friendly, halogen-free, high-efficiency flame retardant composition and a silane coupling agent.

[0011] As one embodiment, the weight ratio of the environmentally friendly halogen-free high-efficiency flame retardant composition to the silane coupling agent is (91-115):(0.1-1).

[0012] In one embodiment, the weight ratio of the environmentally friendly halogen-free high-efficiency flame retardant composition to the silane coupling agent is (91-115):0.5.

[0013] In one embodiment, the silane coupling agent includes at least one of methylsilane coupling agents, aminosilane coupling agents, vinylsilane coupling agents, or epoxysilane coupling agents.

[0014] In one embodiment, the silane coupling agent is an aminosilane coupling agent.

[0015] In one embodiment, the silane coupling agent is 3-aminopropyltriethoxysilane.

[0016] In one embodiment, the organophosphonate includes at least one of aluminum diethylphosphonate, aluminum dipropylphosphonate, aluminum dibutylphosphonate, aluminum ethylbutylphosphonate, or aluminum hypophosphite.

[0017] In one embodiment, the organophosphonate is aluminum diethylphosphonate.

[0018] In one embodiment, the raw materials for preparing piperazine pyrophosphate include at least phosphoric acid and piperazine, and the molar ratio of phosphoric acid to piperazine in piperazine pyrophosphate is 1:(1-1.5).

[0019] In one embodiment, the molar ratio of phosphoric acid to piperazine in the piperazine pyrophosphate is 1:1.2.

[0020] A third aspect of this invention provides a method for preparing an environmentally friendly, halogen-free, high-efficiency flame retardant, comprising the following steps: Preparation of piperazine pyrophosphate; The prepared piperazine pyrophosphate, melamine cyanurate, organophosphonate and polytetrafluoroethylene are mixed in proportion at a speed of 20-40 rpm, heated to 40-60℃, and silane coupling agent is intermittently sprayed in and mixed for 5-7 minutes to obtain an environmentally friendly halogen-free high-efficiency flame retardant.

[0021] As one embodiment, the method for preparing piperazine pyrophosphate includes the following steps: Phosphoric acid and piperazine are fed in a molar ratio and reacted at 50-95℃ for 2-5 hours to produce piperazine diphosphate; piperazine diphosphate is dehydrated at 250-260℃ to produce piperazine pyrophosphate, and then ball-milled to obtain piperazine pyrophosphate powder.

[0022] In one embodiment, the D50 particle size of the piperazine pyrophosphate powder is 1-10 μm.

[0023] In one embodiment, the D50 particle size of the piperazine pyrophosphate powder is 5 μm.

[0024] A fourth aspect of the present invention provides an application of an environmentally friendly, halogen-free, high-efficiency flame retardant in polyolefin products.

[0025] In one embodiment, the polyolefin includes, but is not limited to, at least one of homopolymer polyolefin, copolymer polyolefin, or homopolymer / copolymer blend polyolefin.

[0026] In one embodiment, the polyolefin product includes, but is not limited to, at least one of film, sheet, plate or pipe.

[0027] As one implementation method, the amount of the environmentally friendly halogen-free high-efficiency flame retardant added to the polyolefin product is 15-25 wt%.

[0028] Compared with the prior art, the present invention has the following beneficial effects: (1) The environmentally friendly halogen-free high-efficiency flame retardant composition of the present invention uses piperazine pyrophosphate, melamine cyanurate, organophosphonate and polytetrafluoroethylene in a weight ratio of (60-75):(20-30):(1-15):(0.1-2). Excellent flame retardant effect can be achieved with a small amount of addition, thus improving flame retardant efficiency.

[0029] (2) The environmentally friendly halogen-free high-efficiency flame retardant of the present invention improves the compatibility of the flame retardant composition with polyolefin by introducing a silane coupling agent, improves the processability of the flame retardant and the polyolefin substrate, and reduces the precipitation of the flame retardant.

[0030] (3) The environmentally friendly halogen-free high-efficiency flame retardant of the present invention uses a weight ratio of (91-115):(0.1-1) for the flame retardant composition and silane coupling agent, which further improves the compatibility between the flame retardant and the polyolefin substrate. It can be continuously and stably present for more than 1000 hours without precipitation in a double 85 environment.

[0031] (4) The environmentally friendly halogen-free high-efficiency flame retardant described in this invention can be applied to polyolefins to prepare products in various forms. It can be processed at high temperatures to meet different processing temperature requirements, thus improving its wide applicability in polyolefins.

[0032] (5) The environmentally friendly halogen-free high-efficiency flame retardant of the present invention has high flame retardant efficiency, low addition amount and high temperature resistance, which can reduce the cost of use, solve the problem of easy precipitation of most halogen-free flame retardants in the market, and has strong versatility. It has good flame retardant effect in various types of polypropylene, polyethylene and other polyolefin flame retardants.

[0033] (6) The environmentally friendly halogen-free high-efficiency flame retardant described in this invention has strong versatility. In both glass fiber reinforced and non-glass fiber reinforced systems, the flame retardant ratings of different thicknesses (above 0.3mm) of UL94 V0 / 5VA / 5VB can be achieved by adjusting the amount added, thereby meeting the flame retardant requirements of customers for different products such as films, sheets, plates, pipes, etc. Detailed Implementation

[0034] The polymer used in the application examples and comparative examples is polypropylene, which is a mixture of Lotte PD701 from South Korea and Yangzi Petrochemical YPJ-1215C in a 1:1 weight ratio.

[0035] Example 1 An environmentally friendly, halogen-free, high-efficiency flame-retardant composition comprising piperazine pyrophosphate, melamine cyanurate, organophosphonate, and polytetrafluoroethylene in a weight ratio of 70.15:23.38:4.97:1.

[0036] An environmentally friendly, halogen-free, high-efficiency flame retardant comprises the above-mentioned environmentally friendly, halogen-free, high-efficiency flame retardant composition and a silane coupling agent, with a weight ratio of 99.5:0.5.

[0037] The silane coupling agent is 3-aminopropyltriethoxysilane.

[0038] The organophosphonate is aluminum diethylphosphonate.

[0039] The molar ratio of phosphoric acid to piperazine in the piperazine pyrophosphate is 1:1.2.

[0040] The CAS number for melamine cyanurate is 37640-57-6.

[0041] A method for preparing an environmentally friendly, halogen-free, high-efficiency flame retardant includes the following steps: Preparation of piperazine pyrophosphate; Piperazine pyrophosphate, melamine cyanurate, organophosphonate and polytetrafluoroethylene were mixed at 30 rpm in a certain proportion, heated to 50°C, and silane coupling agent was intermittently sprayed in. After mixing for 6 min, an environmentally friendly halogen-free high-efficiency flame retardant was obtained.

[0042] The preparation method of the piperazine pyrophosphate includes the following steps: Phosphoric acid and piperazine were fed in a molar ratio and reacted at 85°C for 3.5 h to produce piperazine diphosphate; piperazine diphosphate was dehydrated at 255°C to produce piperazine pyrophosphate, and then ball-milled to obtain piperazine pyrophosphate powder.

[0043] The D50 particle size of the piperazine pyrophosphate powder is 5 μm.

[0044] Example 2 An environmentally friendly, halogen-free, high-efficiency flame retardant composition, flame retardant, and preparation method are disclosed. The specific implementation method is the same as in Example 1, except that the weight ratio of piperazine pyrophosphate, melamine cyanurate, organophosphonate, and polytetrafluoroethylene is 66.41:22.14:9.95:1.

[0045] Comparative Example 1 An environmentally friendly, halogen-free, high-efficiency flame retardant composition, flame retardant, and preparation method are disclosed. The specific implementation method is the same as in Example 1, except that the environmentally friendly, halogen-free, high-efficiency flame retardant composition comprises a combination of piperazine pyrophosphate and melamine polyphosphate in a weight ratio of 2:1.

[0046] An environmentally friendly, halogen-free, high-efficiency flame retardant, comprising the above-mentioned environmentally friendly, halogen-free, high-efficiency flame retardant composition, without silane coupling agents.

[0047] Comparative Example 2 An environmentally friendly, halogen-free, high-efficiency flame retardant composition, flame retardant, and preparation method are disclosed. The specific implementation method is the same as in Example 1, except that the environmentally friendly, halogen-free, high-efficiency flame retardant composition comprises a combination of piperazine pyrophosphate and melamine cyanurate in a weight ratio of 1:1.

[0048] An environmentally friendly, halogen-free, high-efficiency flame retardant, comprising the above-mentioned environmentally friendly, halogen-free, high-efficiency flame retardant composition, without silane coupling agents.

[0049] Comparative Example 3 An environmentally friendly, halogen-free, high-efficiency flame retardant composition, flame retardant, and preparation method are disclosed. The specific implementation method is the same as that of Comparative Example 2, except that the weight ratio of piperazine pyrophosphate to melamine cyanurate is 2:1.

[0050] An environmentally friendly, halogen-free, high-efficiency flame retardant, comprising the above-mentioned environmentally friendly, halogen-free, high-efficiency flame retardant composition, without silane coupling agents.

[0051] Comparative Example 4 An environmentally friendly, halogen-free, high-efficiency flame retardant composition, flame retardant, and preparation method are disclosed. The specific implementation method is the same as that of Comparative Example 2, except that the weight ratio of piperazine pyrophosphate to melamine cyanurate is 3:1.

[0052] An environmentally friendly, halogen-free, high-efficiency flame retardant, comprising the above-mentioned environmentally friendly, halogen-free, high-efficiency flame retardant composition, without silane coupling agents.

[0053] Comparative Example 5 An environmentally friendly, halogen-free, high-efficiency flame retardant composition, flame retardant, and preparation method are disclosed. The specific implementation method is the same as that of Comparative Example 2, except that the weight ratio of piperazine pyrophosphate to melamine cyanurate is 4:1.

[0054] An environmentally friendly, halogen-free, high-efficiency flame retardant, comprising the above-mentioned environmentally friendly, halogen-free, high-efficiency flame retardant composition, without silane coupling agents.

[0055] Comparative Example 6 An environmentally friendly halogen-free high-efficiency flame retardant composition, flame retardant, and preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that the environmentally friendly halogen-free high-efficiency flame retardant composition includes piperazine pyrophosphate, melamine cyanurate, and polytetrafluoroethylene in a weight ratio of 74.25:24.75:1.

[0056] An environmentally friendly, halogen-free, high-efficiency flame retardant, comprising the above-mentioned environmentally friendly, halogen-free, high-efficiency flame retardant composition, without silane coupling agents.

[0057] Comparative Example 7 An environmentally friendly halogen-free high-efficiency flame retardant composition, flame retardant and preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that the environmentally friendly halogen-free high-efficiency flame retardant composition includes piperazine pyrophosphate, melamine cyanurate and polytetrafluoroethylene in a weight ratio of 79.2:19.8:1.

[0058] An environmentally friendly, halogen-free, high-efficiency flame retardant, comprising the above-mentioned environmentally friendly, halogen-free, high-efficiency flame retardant composition, without silane coupling agents.

[0059] Comparative Example 8 An environmentally friendly, halogen-free, high-efficiency flame retardant composition, flame retardant, and preparation method are disclosed. The specific implementation method is the same as in Example 1, except that the environmentally friendly, halogen-free, high-efficiency flame retardant composition includes piperazine pyrophosphate, melamine cyanurate, organophosphonate, and polytetrafluoroethylene in a weight ratio of 70.5:23.5:5:1.

[0060] An environmentally friendly, halogen-free, high-efficiency flame retardant, comprising the above-mentioned environmentally friendly, halogen-free, high-efficiency flame retardant composition, without silane coupling agents.

[0061] Comparative Example 9 An environmentally friendly halogen-free high-efficiency flame retardant composition, flame retardant, and preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that the environmentally friendly halogen-free high-efficiency flame retardant composition includes piperazine pyrophosphate, melamine cyanurate, organophosphonate, and polytetrafluoroethylene in a weight ratio of 66.75:22.15:10:1.

[0062] An environmentally friendly, halogen-free, high-efficiency flame retardant, comprising the above-mentioned environmentally friendly, halogen-free, high-efficiency flame retardant composition, without silane coupling agents.

[0063] Application Example 1 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene is described. The flame retardant prepared in Example 1 is blended with polypropylene, and the mixture is extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added is 17 wt%.

[0064] Application Example 2 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene: The flame retardant prepared in Example 1 is blended with polypropylene, extruded and granulated using a twin-screw extruder, and then injection molded to obtain polypropylene products. The amount of flame retardant added is 19 wt%.

[0065] Application Example 3 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene: The flame retardant prepared in Example 1 is blended with polypropylene, extruded and granulated using a twin-screw extruder, and then injection molded to obtain polypropylene products. The amount of flame retardant added is 21 wt%.

[0066] Application Example 4 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene: The flame retardant prepared in Example 2 is blended with polypropylene, extruded and granulated using a twin-screw extruder, and then injection molded to obtain polypropylene products. The amount of flame retardant added is 17 wt%.

[0067] Application Example 5 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Example 2 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 19 wt%.

[0068] Application Example 6 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene: The flame retardant prepared in Example 2 is blended with polypropylene, extruded and granulated using a twin-screw extruder, and then injection molded to obtain polypropylene products. The amount of flame retardant added is 21 wt%.

[0069] Application Example 7 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene: The flame retardant prepared in Example 2 is blended with glass fiber and polypropylene, extruded and granulated using a twin-screw extruder, and then injection molded to obtain polypropylene products. The amount of flame retardant added is 24 wt%, and the amount of glass fiber added is 20%.

[0070] Application Comparative Example 1 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 1 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 21 wt%.

[0071] Application Comparative Example 2 An environmentally friendly, halogen-free, and highly efficient flame retardant was applied to polypropylene. The flame retardant prepared in Comparative Example 1 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 23 wt%.

[0072] Application Comparative Example 3 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 2 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 23 wt%.

[0073] Application Comparative Example 4 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 2 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 25 wt%.

[0074] Application Comparative Example 5 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 3 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 23 wt%.

[0075] Application Comparative Example 6 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 3 was blended with polypropylene, and the amount of flame retardant added was 25 wt%.

[0076] Application Comparative Example 7 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 4 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 23 wt%.

[0077] Application Comparative Example 8 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 4 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 25 wt%.

[0078] Application Comparison Example 9 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 5 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 23 wt%.

[0079] Application Comparison Example 10 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 5 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 25 wt%.

[0080] Application Comparative Example 11 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 6 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 23 wt%.

[0081] Application Comparative Example 12 An environmentally friendly, halogen-free, and highly efficient flame retardant was applied to polypropylene. The flame retardant prepared in Comparative Example 6 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 25 wt%.

[0082] Application Comparative Example 13 An environmentally friendly, halogen-free, and highly efficient flame retardant was applied to polypropylene. The flame retardant prepared in Comparative Example 7 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 23 wt%.

[0083] Application Comparative Example 14 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 7 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 25 wt%.

[0084] Application Comparative Example 15 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 8 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 17 wt%.

[0085] Application Comparative Example 16 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 8 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 19 wt%.

[0086] Application Comparative Example 17 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 8 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 21 wt%.

[0087] Application Comparison Example 18 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 9 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 17 wt%.

[0088] Application Comparison Example 19 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 9 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 19 wt%.

[0089] Application Comparative Example 20 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene was described. The flame retardant prepared in Comparative Example 9 was blended with polypropylene, and the mixture was extruded and granulated using a twin-screw extruder and then injection molded to obtain polypropylene products. The amount of flame retardant added was 21 wt%.

[0090] Application Comparative Example 21 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene involves blending Japanese Idico 2500S flame retardant with polypropylene, followed by extrusion granulation using a twin-screw extruder and injection molding to obtain polypropylene products. The amount of flame retardant added is 21 wt%.

[0091] Application Comparative Example 22 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene involves blending Japanese Idico 2500S flame retardant with polypropylene, followed by extrusion granulation using a twin-screw extruder and injection molding to obtain polypropylene products. The amount of flame retardant added is 23 wt%.

[0092] Application Comparative Example 23 An environmentally friendly, halogen-free, and highly efficient flame retardant was applied to polypropylene. The flame retardant, Guangdong Qingyuan Procyfu 110DNT, was blended with polypropylene, extruded and granulated using a twin-screw extruder, and then injection molded to obtain polypropylene products. The amount of flame retardant added was 21 wt%.

[0093] Application Comparative Example 24 An environmentally friendly, halogen-free, and highly efficient flame retardant was applied to polypropylene. The flame retardant, Guangdong Qingyuan Procyfu 110DNT, was blended with polypropylene, extruded and granulated using a twin-screw extruder, and then injection molded to obtain polypropylene products. The amount of flame retardant added was 23 wt%.

[0094] Application Comparison Example 25 An environmentally friendly, halogen-free, and highly efficient flame retardant is applied to polypropylene. The flame retardant, Guangdong Qingyuan Prosefu 110DNT, is blended with polypropylene, extruded and granulated using a twin-screw extruder, and then injection molded to obtain polypropylene products. The amount of flame retardant added is 25wt%.

[0095] Application Comparison Example 26 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene: Guangdong Qingyuan Procyfu 100DK flame retardant is blended with polypropylene, extruded and granulated using a twin-screw extruder, and then injection molded to obtain polypropylene products. The amount of flame retardant added is 26wt%.

[0096] Application Comparative Example 27 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene: Guangdong Qingyuan Procyfu 100DK flame retardant is blended with polypropylene, extruded and granulated using a twin-screw extruder, and then injection molded to obtain polypropylene products. The amount of flame retardant added is 28wt.

[0097] Application Comparative Example 28 An application of an environmentally friendly, halogen-free, and highly efficient flame retardant in polypropylene: Guangdong Qingyuan Procyfu 100DK flame retardant is blended with polypropylene, extruded and granulated using a twin-screw extruder, and then injection molded to obtain polypropylene products. The amount of flame retardant added is 30wt.

[0098] Performance testing 1. Flame retardant performance: The flame retardant performance of polypropylene products in the application examples and comparative examples were tested according to the UL94 standard for testing the flame retardant performance of plastic materials. The flame retardant rating and afterflame time of the polypropylene products were tested.

[0099] The limiting oxygen index of polypropylene products tested according to GB / T2406-93 application examples and application comparison examples is shown in Table 1.

[0100] 2. Extraction Time: Three polypropylene injection-molded sheets (80mm×80mm×0.8mm) from both the application examples and comparative examples were placed and tested in a constant temperature and humidity test chamber at 85℃ and 85%RH (relative humidity). The initial time was recorded, and the initial state was photographed. The injection-molded sheets were then suspended and clamped in the constant temperature and humidity test chamber to observe the extraction state of the flame retardant and record the extraction time. The test results are shown in Table 1.

[0101] Table 1

[0102] The flame retardant in this application is highly versatile. In both glass fiber reinforced and non-glass fiber reinforced systems, adjusting the addition amount can achieve UL94 V0 / 5VA / 5VB flame retardant ratings for different thicknesses (above 0.3mm), thus meeting the flame retardant requirements of customers for various products such as films, sheets, plates, and pipes. The flame retardant in this embodiment showed no precipitation after 1000 hours of continuous testing. This solves the problem of easy precipitation in most halogen-free flame retardants in the market, such as piperazine pyrophosphate, melamine polyphosphate, and ammonium polyphosphate systems.

[0103] Competitor Aidi 2500S from Japan showed precipitation issues after 600 hours of continuous testing with double 85; competitor Guangdong Qingyuan Prosef 110DNT required an addition of over 25% to polypropylene to achieve UL94-1.6mm V0 flame retardant effect, and precipitation occurred after 120 hours of continuous testing with double 85. 100DK required an addition of over 28% to achieve V0, and precipitation occurred after 48 hours.

[0104] The other comparative proportions of flame retardants require a larger amount to meet the flame retardant standards, and they will precipitate during the 85 continuous test.

[0105] 3. High-Temperature Processing Performance Test: The flame retardant prepared in Example 1 was added to polypropylene at an addition ratio of 23-25%, and granulated by twin-screw extrusion. Four temperature gradients were set for the twin-screw extruder: 190-210℃, 210-230℃, 230-250℃, 250-270℃, and 270-290℃. The twin-screw speed was kept constant at 400 RPM. The degree of yellowing of the extruded granules was tested under each of these five temperature conditions. The test results are shown in Table 2.

[0106] Table 2

[0107] The flame retardant in this application greatly improves its applicability in polypropylene and meets customers' needs for different processing temperatures.

Claims

1. An environmentally friendly, halogen-free, high-efficiency flame-retardant composition, characterized in that, It includes piperazine pyrophosphate, melamine cyanurate, organophosphonate and polytetrafluoroethylene, wherein the weight ratio of piperazine pyrophosphate, melamine cyanurate, organophosphonate and polytetrafluoroethylene is (60-75):(20-30):(1-15):(0.1-2).

2. The environmentally friendly halogen-free high-efficiency flame retardant composition according to claim 1, characterized in that, The weight ratio of piperazine pyrophosphate, melamine cyanurate, organophosphonate and polytetrafluoroethylene is (66-71):(21-28):(4-10):(0.5-1.5).

3. The environmentally friendly halogen-free high-efficiency flame retardant composition according to claim 2, characterized in that, The weight ratio of piperazine pyrophosphate, melamine cyanurate, organophosphonate and polytetrafluoroethylene is (66.41-70.15): (22.14-23.38): (4.97-9.95):

1.

4. The environmentally friendly halogen-free high-efficiency flame retardant composition according to claim 1, characterized in that, The raw materials for preparing the piperazine pyrophosphate include at least phosphoric acid and piperazine, and the molar ratio of phosphoric acid to piperazine is 1:(1-1.5).

5. An environmentally friendly, halogen-free, high-efficiency flame retardant, characterized in that, Includes the environmentally friendly halogen-free high-efficiency flame retardant composition and silane coupling agent as described in any one of claims 1-4.

6. The environmentally friendly halogen-free high-efficiency flame retardant according to claim 5, characterized in that, The weight ratio of the environmentally friendly halogen-free high-efficiency flame retardant composition to the silane coupling agent is (91-115):(0.1-1).

7. The environmentally friendly halogen-free high-efficiency flame retardant according to claim 5, characterized in that, The silane coupling agent includes at least one of methylsilane coupling agents, aminosilane coupling agents, vinylsilane coupling agents, or epoxysilane coupling agents.

8. A method for preparing an environmentally friendly halogen-free high-efficiency flame retardant according to any one of claims 5-7, characterized in that, Includes the following steps: Preparation of piperazine pyrophosphate; The prepared piperazine pyrophosphate, melamine cyanurate, organophosphonate and polytetrafluoroethylene are mixed in proportion at a speed of 20-40 rpm, heated to 40-60℃, and silane coupling agent is intermittently sprayed in and mixed for 5-7 minutes to obtain an environmentally friendly halogen-free high-efficiency flame retardant.

9. The application of an environmentally friendly halogen-free high-efficiency flame retardant according to any one of claims 5-7, characterized in that, It is used in polyolefin products.

10. The application of the environmentally friendly halogen-free high-efficiency flame retardant according to claim 9, characterized in that, The environmentally friendly, halogen-free, high-efficiency flame retardant is added to polyolefin products at a rate of 15-25 wt%.

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