Organophosphorus hybrid alpha-ZrP flame-retardant material and preparation method thereof

Abstract

The present invention relates to an organophosphorus hybrid alpha-ZrP flame-retardant material and a preparation method thereof, alpha-ZrP is used as a substrate, a small molecule amine is used for supporting in advance to reduce alpha-ZrP inter-laminate force and increase interlayer spacing, then a silane coupling agent is inserted between layers, the small molecule amine for supporting in advance is removed by heat treatment, and the organophosphorus hybrid alpha-ZrP flame-retardant material can be prepared by the effect of formation of chemical bonding of a terminal group of the silane coupling agent and organophosphorus, wherein the initial decomposition temperature of the organophosphorus hybrid alpha-ZrP is 340-450 DEG C, the interlayer spacing is 1.60-2.50nm, the grafting ratio of the silane coupling agent is 6 to 18%, and the organophosphorus content is 1 to 15%. The organophosphorus hybrid alpha-ZrP flame-retardant material has high thermal stability, grafting ratio, interlayer spacing and organophosphorus content, has stronger nonpolar organic substance affinity, can be uniformly dispersed in a hydrophobic organic polymer material, may be added into most polymer materials (PET, PBT, PP, and the like) processed by melting for e preparation of flame-retardant materials, and has excellent flame retardant properties.

Description

technical field [0001] The invention belongs to the technical field of material modification, and relates to an organophosphorus hybrid α-ZrP flame-retardant material and a preparation method thereof. Background technique [0002] α-zirconium phosphate (α-ZrP) is a layered phosphate with remarkable features such as high ion exchange performance (7meq / g, MMT is 1meq / g), controllable area ratio, high thermal and chemical stability , compared with other layered nanofillers, it is easier to be intercalated or exfoliated in the polymer matrix, and it is widely used in catalysts, fuel cells, photochemistry, environmental protection, flame retardants and other fields. α-ZrP, as a new type of inorganic flame retardant with nano-scale layered structure, when introduced into the polymer system, due to the barrier effect of inorganic nano-sheets, can make the free radicals generated by decomposition "lifetime" between inorganic sheets. "Prolonging, delaying the degradation process of ...

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Problems solved by technology

However, the product prepared by this method has low bonding fastness and poor thermal stability, and cannot adapt to the higher processing temperature of hydrophobic thermoplastic polymers. It is applied to polymer modification, and it decomposes during the spinning process of polymers. The small molecular amines produced will affect the spinnability and mechanical properties of the polymer, making fiber processing difficult

[0004] Covalent graft modification requires the modifier to have reactive functional groups such as isocyanate, acid chloride bond, etc., and these groups can chemically react with P-OH on the surface of α-ZrP to establish a covalent bond with high thermal stability, which can It is suitable for further processing, in which the silane coupling agent has a special structure, and each molecule contains two or more different reactive groups, one of which is methoxy or ethoxy, which can Combined with inorganic materials, such as glass, metal, silica sand, etc.; another reactive group is vinyl, epoxy, amino, methacryloxy or mercapto, which can form chemical bonds with organic materials, silane coupling Agent modifiers can play a very good bridge role in the preparation of organic-inorganic composite materials. At present, there are few studies on the application of silane coupling agents to the modification of zirconium phosphate. Kevin DalPont made a preliminary attempt to use γ-aminopropyl Modified α-ZrP with trimethoxysilane, and compounded it with styrene-butadiene rubber (SBR) to prepare a new type of nanocomposite (PontKD, GerardJ. 1051-1059.), however, like other covalent grafting modifiers, silane coupling agents are often difficult to intercalate directly into the interior of the α-ZrP sheet due to their large molecules, and only interact with the P-OH on the outer surface of the sheet. Reverse reaction, so that the number of modifiers grafted on the surface of α-ZrP is small, and its hydrophilic properties are not changed much (Mosby BM, Agustín Díaz. Surface Functionalization of Zirconium Phosphate Nanoplatelets for the Design of Polymer Fillers [J]. Appl. Mater. Interfaces, 2014 (6): 585 -592.)

[0005] α-ZrP is a very good inorganic flame retardant. At present, there are few studies on the synergistic flame retardancy of α-ZrP dispersion and organic phosphorus integration. CharlesA et al. modified α -ZrP, and melt-blended the modified α-ZrP with EVA and PS respectively, it was found that the use of α-ZrP alone basically did not play a role in flame retardancy, but when used together with other flame retardants, it was able to Exhibits the effect of a flame retardant synergist

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