A pyrophosphoric acid piperazine coating and a preparation method and application thereof

Abstract

The application discloses a pyrophosphoric acid piperazine coating and a preparation method and application thereof, and belongs to the technical field of flame retardants. The pyrophosphoric acid piperazine coating comprises a pyrophosphoric acid piperazine core and a coating layer coated on the surface of the pyrophosphoric acid piperazine core; the coating layer comprises bis-palmitoyl tartaric acid diester and a coupling agent, and the coupling agent is a titanate coupling agent and / or a zirconate coupling agent. The pyrophosphoric acid piperazine coating improves the water resistance, chemical stability and anti-precipitation performance of the pyrophosphoric acid piperazine coating by coating the coating layer comprising bis-palmitoyl tartaric acid diester and the coupling agent on the surface of the pyrophosphoric acid piperazine.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of flame retardants, in particular to a piperazine pyrophosphate coating and a preparation method and application thereof. BACKGROUND

[0002] Piperazine pyrophosphate (PAPP) is a high-efficiency nitrogen-phosphorus halogen-free flame retardant. It is widely used in the field of flame retardation of plastics, rubbers, fibers and other materials due to its excellent thermal stability, high flame retardation efficiency and environmental friendliness. When the material burns, it can form a stable carbon layer to effectively block the transfer of heat and oxygen, thereby achieving the effect of flame retardation.

[0003] Piperazine pyrophosphate has a significant defect: the hydrophilic group in its molecular structure leads to high water solubility (solubility at room temperature can reach 2-3 g / 100 mL). The high water solubility of piperazine pyrophosphate is closely related to the precipitation problem. When the material containing piperazine pyrophosphate is in a humid environment or contacts moisture, due to its water solubility characteristics, piperazine pyrophosphate molecules will gradually interact with water molecules and dissolve out of the original material matrix. With the evaporation of water or the change of the environment in the material system, the piperazine pyrophosphate dissolved in water will reach a supersaturated state, and then precipitate from the solution in the form of crystals; this precipitation not only affects the appearance of the material, causing phenomena such as surface whitening and blooming, but also causes the precipitated piperazine pyrophosphate to accumulate on the surface of the material, which cannot play a flame-retardant role in the interior of the material, further exacerbating the decline of the material's flame-retardant performance. At the same time, the precipitated substance may also affect the subsequent processing performance of the material, such as in the injection molding process, the precipitate may block the flow channel of the mold, affecting the molding quality. These problems seriously restrict its application in the field of electronic appliances, automobile parts and other fields with strict requirements on durability. In addition, the loss of piperazine pyrophosphate by dissolution may also pose a potential pollution risk to the environment. SUMMARY

[0004] The purpose of the present disclosure is to overcome the shortcomings of the prior art and provide a piperazine pyrophosphate coating and a preparation method and application thereof.

[0005] To achieve the above-mentioned purpose, the technical solution adopted by the present disclosure is as follows: in a first aspect, a piperazine pyrophosphate coating is provided, which comprises a piperazine pyrophosphate core and a coating layer coated on the surface of the piperazine pyrophosphate core.

[0006] The coating layer comprises a bis-palmitoyl tartaric acid diester and a coupling agent, and the coupling agent is a titanate coupling agent and / or a zirconate coupling agent.

[0007] In some embodiments, the mass ratio of the piperazine pyrophosphate and the coating layer is 1: (0.3-1).

[0008] In some embodiments, the mass ratio of the dipalmitoyl tartrate and the coupling agent is 1: (0.5-1.2).

[0009] In some embodiments, the coupling agent is a titanate coupling agent and a zirconate coupling agent; the mass ratio of the titanate coupling agent and the zirconate coupling agent is (2-8):1.

[0010] In some embodiments, the titanate coupling agent includes a monoalkoxy type titanate and / or a neoalkoxy type titanate.

[0011] In some embodiments, the monoalkoxy type titanate includes at least one of isopropoxy triisostearyl acyloxy titanate, bis(dioctylpyrophosphoryloxy) ethylene titanate acrylamide chelate, tetraoctyloxy bis(dilauryl phosphite oxy) titanate, triethanolamine chelate of bis(dioctylpyrophosphoryloxy) ethylene titanate, isopropoxy tri(dodecylbenzenesulfonyloxy) titanate, tetraisopropyl bis(dioctyl phosphite oxy) titanate, bis(dioctylpyrophosphoryloxy) ethylene titanate, isopropyl tri(branched and linear dioctyl phosphite oxy) titanate, isopropoxy dioleic acyloxy (dioctyl phosphite oxy) titanate, propoxy titanium tristearate, isopropoxy trioleic acyloxy titanate, isopropoxy tri(ethylenediamine-N-ethoxy) titanate.

[0012] In some embodiments, the neoalkoxy type titanate includes at least one of neoalkoxy tri(p-aminophenoxy) titanate, neoalkoxy tri(dioctylpyrophosphoryloxy) titanate acrylamide chelate, neoalkoxy tri(dioctyl phosphite oxy) titanate, neoalkoxy tri(neodecanoic acyloxy) titanate, neoalkoxy tri(dioctylpyrophosphoryloxy) titanate, neoalkoxy tri(dioctyl phosphite oxy) titanate.

[0013] In some embodiments, the zirconate coupling agent includes at least one of neoalkoxy tri(dioctyl phosphite oxy) zirconate, neoalkoxy tri(dodecylbenzenesulfonyloxy) zirconate, neoalkoxy tri(neodecanoic acyloxy) zirconate, neoalkoxy tri(dioctylpyrophosphoryloxy) zirconate.

[0014] In some embodiments, the piperazine pyrophosphate core is formed from piperazine pyrophosphate, and the average particle size of the piperazine pyrophosphate is 10-50 μm.

[0015] In a second aspect, a preparation method of the piperazine pyrophosphate coating is provided, including the following steps:

[0016] preparing a first dispersion liquid containing piperazine pyrophosphate;

[0017] Preparation of the second dispersion liquid of dipalmitoyl tartrate diester and coupling agent;

[0018] The second dispersion liquid is added to the first dispersion liquid, ultrasonic dispersion is performed, and after a heating reaction of the obtained suspension, solid-liquid separation and drying are performed to obtain the piperazine pyrophosphate coating.

[0019] In some embodiments, the heating reaction is performed at a temperature of 60-80 h for 3-6 h.

[0020] In some embodiments, the ultrasonic dispersion is performed at a power of 200-400 W for 10-30 min.

[0021] In a third aspect, a flame-retardant composition is provided, which comprises the piperazine pyrophosphate coating or the piperazine pyrophosphate coating prepared by the preparation method.

[0022] Compared with the prior art, the piperazine pyrophosphate coating has the following advantages:

[0023] (1) The piperazine pyrophosphate coating of the present application improves the water resistance, chemical stability and anti-precipitation performance of the piperazine pyrophosphate coating by coating a coating layer comprising dipalmitoyl tartrate diester and a coupling agent on the surface of the piperazine pyrophosphate. The long-chain alkyl group in the dipalmitoyl tartrate diester molecule is adsorbed on the surface of the piperazine pyrophosphate by van der Waals force to form a hydrophobic outer membrane. The polar end (tartrate ester group) is combined with the polar group (such as pyrophosphate group, residual hydroxyl group) on the surface of the piperazine pyrophosphate by hydrogen bond and / or dipole interaction. The long-chain alkyl group in the coupling agent and the long-chain alkyl group in the dipalmitoyl tartrate diester are intertwined by hydrophobic interaction to form an interpenetrating network structure, which together constitutes a “double-layer hydrophobic barrier” to improve the water resistance of the piperazine pyrophosphate coating.

[0024] (2) In the present application, the second dispersion liquid containing dipalmitoyl tartrate diester and a coupling agent is added to the first dispersion liquid containing piperazine pyrophosphate. Through a heating reaction, the dipalmitoyl tartrate diester and the coupling agent self-assemble into a coating layer on the surface of the piperazine pyrophosphate. The coating layer has good chemical stability and water resistance, which can effectively improve the water resistance and anti-precipitation performance of the piperazine pyrophosphate coating.

[0025] (3) The preparation method of the piperazine pyrophosphate coating of the present application uses non-toxic and harmless raw materials and solvents. After the heating reaction, the residual impurities and unreacted substances in the piperazine pyrophosphate coating can be effectively removed by solid-liquid separation, which improves the purity of the piperazine pyrophosphate coating and reduces the pollution to the environment. In addition, the stability and water resistance of the piperazine pyrophosphate coating are high, which reduces the secondary pollution caused by precipitation. DETAILED DESCRIPTION

[0026] For the purposes of understanding the present disclosure, a more complete description of the disclosure will be presented. However, the present disclosure can be realized in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and fully convey the disclosure to those skilled in the art.

[0027] As used herein the terms "a," "an," or "the" mean one or more.

[0028] "Made from" is synonymous with "comprising." The terms "comprising," "including," "having" or any other open terminology indicates that the item includes the listed elements but not excluding others. For example, a composition, a step, a method, an article, or an apparatus that comprises an item includes components, elements, or steps that are not expressly listed or inherent to such composition, step, method, article, or apparatus.

[0029] The conjunctive term "consisting of limits whatever is not specified to be excluded from the claim. If used in the claims, this phrase shall mean that the claims are closed such that no materials other than those explicitly recited are to be considered included in the claims. When the phrase "consisting of appears in the body of a claim, it should be construed in accordance with the definition found in the Manual of Patent Examining Procedure, Section 2111.03.

[0030] When equivalent, concentration, or other values or parameters are expressed in ranges, preferred ranges, or a series of upper preferred values and lower preferred values defining a range, it should be understood that all ranges formed by any pair of any upper range limit or preferred value and any lower range limit or preferred value, whether or not the range is expressly disclosed, are specifically disclosed. For example, where a range "1-5" is disclosed, the described range should be interpreted to include ranges "1-4," "1-3," "1-2," "1-2 and 4-5," "1-3 and 5," etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include the endpoints and all integers and fractions within that range.

[0031] In these embodiments, the parts and percentages described are by mass, unless otherwise indicated.

[0032] "Mass parts" refers to a basic unit of measurement that represents the proportional relationship of the mass of multiple components, 1 part can represent any unit of mass, such as 1 g, 2.689 g, etc. If we say that the mass parts of component A is a parts, and the mass parts of component B is b parts, it means that the mass ratio of component A to component B is a:b. It should not be misunderstood that unlike the mass percentage, the sum of the mass parts of all components is not limited to 100 parts.

[0033] "and / or" is used to indicate one or both of the stated conditions can occur, for example A and / or B includes (A and B) and (A or B).

[0034] In a first aspect of the present application, a pyrophosphoryl piperazine coating is provided, comprising a pyrophosphoryl piperazine core and a coating layer coated on the surface of the pyrophosphoryl piperazine core;

[0035] The coating layer comprises bis-palmitoyl tartaric acid diester and a coupling agent, and the coupling agent is a titanate coupling agent and / or a zirconate coupling agent.

[0036] In the pyrophosphoryl piperazine coating of the present application, by coating a coating layer comprising bis-palmitoyl tartaric acid diester and a coupling agent on the surface of pyrophosphoryl piperazine, the water resistance, thermal stability and anti-precipitation performance of the pyrophosphoryl piperazine coating are improved. In the bis-palmitoyl tartaric acid diester molecule, the long-chain alkyl group is adsorbed on the surface of pyrophosphoryl piperazine by van der Waals force, forming a hydrophobic outer membrane; the polar end (tartaric acid ester group) is combined with the polar group (such as pyrophosphoric acid group, residual hydroxyl group) on the surface of pyrophosphoryl piperazine through hydrogen bond and / or dipole interaction; the long-chain alkyl group in the coupling agent and the long-chain alkyl group in the bis-palmitoyl tartaric acid diester are intertwined through hydrophobic interaction to form an interpenetrating network structure, which together constitutes a "double-layer hydrophobic barrier", improving the water resistance and thermal stability of the pyrophosphoryl piperazine coating.

[0037] In some embodiments, the mass ratio of the pyrophosphoryl piperazine and the coating layer is 1:(0.3-1), which can be but is not limited to 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1.0, preferably 1:(0.5-0.8).

[0038] The applicant found that when the mass ratio of pyrophosphoryl piperazine and coating layer is 1:(0.3-1), the water resistance, hydrophobic durability, mechanical properties and thermal stability of the obtained pyrophosphoryl piperazine coating are higher.

[0039] When the mass ratio of pyrophosphoryl piperazine and coating layer is <0.3, it is easy to cause insufficient coating and insufficient crosslinking of the coupling agent, resulting in defects in the coating layer, incomplete coverage of the surface of the pyrophosphoryl piperazine core, and poor water resistance and hydrophobic durability of the pyrophosphoryl piperazine coating; when the mass ratio of pyrophosphoryl piperazine and coating layer is >1, the coating is excessive, the coating layer is physically stacked in multiple layers, and the mechanical properties of the pyrophosphoryl piperazine coating are decreased; when the mass ratio is 1:(0.3-1), the coating layer is a single-layer structure, the long-chain alkyl group in the coupling agent is woven with the bis-palmitoyl C16 chain, and a dense coating layer is obtained, thereby improving the water resistance, hydrophobic durability, mechanical properties and thermal stability of the pyrophosphoryl piperazine coating.

[0040] In some embodiments, the mass ratio of the dipalmitoyl tartrate diester and the coupling agent is 1:(0.5-1.2), which can be, but is not limited to, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.39, 1:1.0, 1:1.1, 1:1.2; preferably 1:(0.7-1).

[0041] The applicant found that when the mass ratio of the dipalmitoyl tartrate diester and the coupling agent is 1:(0.5-1.2), the water resistance, hydrophobic durability, mechanical properties and thermal stability of the resulting pyrophosphazine coating are higher.

[0042] In some embodiments, the coupling agent is a titanate coupling agent and a zirconate coupling agent; the mass ratio of the titanate coupling agent and the zirconate coupling agent is (2-8):1, which can be, but is not limited to, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1; preferably (4-6):1.

[0043] The applicant found that when the mass ratio of the titanate coupling agent and the zirconate coupling agent is (2-8):1, the water resistance, hydrophobic durability, mechanical properties and thermal stability of the resulting pyrophosphazine coating are higher.

[0044] When the mass ratio of the titanate coupling agent and the zirconate coupling agent is <2:1, the excess of zirconate leads to large branched steric hindrance, which easily leads to too strong rigidity of the coating layer, a decrease in impact strength, and the long chain of the titanate is bound, so that the hydrophobic network cannot fully stretch, thereby leading to a decrease in the hydrophobic performance of the pyrophosphazine coating. When the mass ratio of the titanate coupling agent and the zirconate coupling agent is >8:1, the proportion of the titanate is too high, at which time the hydrolysis side reaction is dominant, the Ti-OH group absorbs water, and the unreacted titanate catalyzes the decomposition of the pyrophosphazine, leading to a decrease in the thermal stability of the pyrophosphazine coating.

[0045] In some embodiments, the titanate coupling agent includes a monoalkoxy type titanate and / or a neoalkoxy type titanate.

[0046] In some embodiments, the monoalkoxy titanate includes at least one of isopropoxy triisostearyl acyloxy titanate, bis(dioctylpyrophosphato) ethylene titanate acrylamide chelate, tetraoctyloxy bis(dilauryl phosphite acyloxy) titanate, triethanolamine chelate of bis(dioctylpyrophosphato) ethylene titanate, isopropoxy tridodecylbenzenesulfonyloxy titanate, tetraisopropyl bis(dioctyl phosphite acyloxy) titanate, bis(dioctylpyrophosphato) ethylene titanate, isopropyl tris( branched and linear dioctyl phosphite acyloxy) titanate, isopropoxy dioleic acyloxy (dioctyl phosphite acyloxy) titanate, propoxy titanium tristearate, isopropoxy trioleic acyloxy titanate, isopropoxy tri(ethylenediamine-N-ethoxy) titanate.

[0047] In some embodiments, the neoalkoxy titanate includes at least one of neoalkoxy tri(p- aminophenoxy) titanate, neoalkoxy tri(dioctylpyrophosphato) titanate acrylamide chelate, neoalkoxy tri(dioctylphosphato) titanate, neoalkoxy tri(neodecanoato) titanate, neoalkoxy tri(dioctylpyrophosphato) titanate, neoalkoxy tri(dioctylphosphato) titanate.

[0048] In some embodiments, the zirconate coupling agent includes at least one of neoalkoxy tri(dioctylphosphato) zirconate, neoalkoxy tridodecylbenzenesulfonyloxy zirconate, neoalkoxy tri(neodecanoato) zirconate, neoalkoxy tri(dioctylpyrophosphato) zirconate.

[0049] Preferably, the titanate coupling agent is at least one of bis(dioctylpyrophosphato) ethylene titanate acrylamide chelate, triethanolamine chelate of bis(dioctylpyrophosphato) ethylene titanate, bis(dioctylpyrophosphato) ethylene titanate, neoalkoxy tri(dioctylpyrophosphato) titanate acrylamide chelate, neoalkoxy tri(dioctylphosphato) titanate, neoalkoxy tri(dioctylpyrophosphato) titanate, neoalkoxy tri(dioctylphosphato) titanate.

[0050] Preferably, the zirconate coupling agent includes at least one of neoalkoxy tri(dioctylphosphato) zirconate, neoalkoxy tri(dioctylpyrophosphato) zirconate.

[0051] In some embodiments, the molecular structure of the titanate coupling agent and the zirconate coupling agent both comprise pyrophosphoric acyloxy groups, when the molecular structure of the titanate coupling agent and the zirconate coupling agent both comprise pyrophosphoric acyloxy groups, the pyrophosphoric acyloxy groups are partially hydrolyzed in a solvent (such as ethanol) to generate active hydroxyl groups, the active hydroxyl groups condense with the hydroxyl groups or pyrophosphoric groups on the surface of the piperazine pyrophosphate to form covalent bonds, thereby improving the stability of the piperazine pyrophosphate, and thus improving the water resistance, hydrophobic durability, mechanical properties and thermal stability of the piperazine pyrophosphate coating.

[0052] In some embodiments, the piperazine pyrophosphate inner core is formed by piperazine pyrophosphate, and the average particle size of the piperazine pyrophosphate is 10-50 μm, for example, but not limited to, 10 μm, 12 μm, 15 μm, 17 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 43 μm, 45 μm, 48 μm, 50 μm; preferably 20-40 μm.

[0053] The applicant found that when the average particle size of the piperazine pyrophosphate is 10-50 μm, the water resistance, hydrophobic durability, mechanical properties and thermal stability of the obtained piperazine pyrophosphate coating are higher.

[0054] Specifically, the average particle size of the piperazine pyrophosphate is tested according to the following method: dispersing the piperazine pyrophosphate in an aqueous solution, using a scanning electron microscope (SEM) to characterize the morphology of the piperazine pyrophosphate, and counting 100 piperazine pyrophosphate particles to obtain the average particle size of the piperazine pyrophosphate.

[0055] In a second aspect of the present application, a preparation method of the piperazine pyrophosphate coating is provided, comprising the following steps:

[0056] Preparation of a first dispersion liquid containing piperazine pyrophosphate;

[0057] Preparation of a second dispersion liquid containing dipalmitoyl tartrate and a coupling agent;

[0058] Adding the second dispersion liquid containing dipalmitoyl tartrate and a coupling agent to the first dispersion liquid containing piperazine pyrophosphate, ultrasonic dispersion, and then heating the obtained suspension to perform a reaction, followed by solid-liquid separation and drying to obtain the piperazine pyrophosphate coating.

[0059] In the present application, the second dispersion liquid containing dipalmitoyl tartrate and a coupling agent is added to the first dispersion liquid containing piperazine pyrophosphate, and through a heating reaction, the dipalmitoyl tartrate and the coupling agent self-assemble into a coating layer on the surface of the piperazine pyrophosphate. The coating layer has good chemical stability and water resistance, and can effectively improve the water resistance, hydrophobic durability, mechanical properties and thermal stability of the piperazine pyrophosphate coating.

[0060] The preparation method of the pyrophosphate piperazine coating uses non-toxic and harmless raw materials and solvents, and after the heating reaction, the residual impurities and unreacted substances in the pyrophosphate piperazine coating can be effectively removed through solid-liquid separation, thereby improving the purity of the pyrophosphate piperazine coating and reducing environmental pollution. In addition, in the application process, the pyrophosphate piperazine coating has high thermal stability and water resistance, thereby reducing secondary pollution caused by precipitation.

[0061] In some embodiments, the heating reaction has a temperature of 60-80℃, which can be, but is not limited to, 60℃, 62℃, 65℃, 67℃, 70℃, 73℃, 75℃, 78℃, or 80℃, and a time of 3-6h, which can be, but is not limited to, 3h, 4h, 5h, or 6h.

[0062] The preparation method of the pyrophosphate piperazine coating is simple, the reaction conditions are mild, no complex equipment and harsh reaction environment are required, the production time is short, the production efficiency is greatly improved, the production cycle is shortened, the production energy consumption is reduced, and the economic benefits are improved.

[0063] In some embodiments, the ultrasonic dispersion has a power of 200-400W and a time of 10-30min.

[0064] Specifically, the step of preparing the first dispersion liquid containing pyrophosphate piperazine is as follows:

[0065] The pyrophosphate piperazine is added to the first solvent and uniformly dispersed to obtain the first dispersion liquid; the first solvent is at least one selected from water, ethanol, and methanol.

[0066] Specifically, the step of preparing the second dispersion liquid containing the dipalmitoyl tartrate and the coupling agent is as follows:

[0067] The dipalmitoyl tartrate and the coupling agent are added to the second solvent and uniformly dispersed to obtain the second dispersion liquid; the second solvent is at least one selected from water, ethanol, and methanol.

[0068] In order to improve the dispersibility of the dipalmitoyl tartrate and the coupling agent, the preparation method of the second dispersion liquid is as follows:

[0069] First, the dipalmitoyl tartrate is added to the first solvent, heated and dissolved, and then the coupling agent is added and uniformly stirred to obtain the second dispersion liquid.

[0070] Specifically, the heating and dissolving temperature is 50-60℃, which can be, but is not limited to, 50℃, 52℃, 54℃, 56℃, 58℃, or 60℃.

[0071] Specifically, the dipalmitoyl tartrate can be purchased on the market or prepared by using a preparation method known in the art.

[0072] For example, 10.5 g of palmitic acid is added into a round bottom flask, 10 mL of thionyl chloride is added dropwise, after the dropwise addition is completed, the temperature is raised to 75-95°C for 2-4 h until the solution is transparent, the excess thionyl chloride is removed by rotary evaporation under reduced pressure, 5 mL of methyl tert-butyl ether is added and rotary evaporation is continued, to obtain a brownish yellow palmitoyl chloride;

[0073] The palmitoyl chloride is dissolved in dichloromethane and transferred into a three-necked flask, 16.8 mL of triethylamine is added under ice water bath condition; 3.0 g of tartaric acid is weighed, dissolved by heating with acetone and added dropwise into the three-necked flask, after the dropwise addition is completed, the temperature is raised to room temperature for overnight reaction; the obtained reaction product is suction filtered, the filtrate is rotary evaporated under reduced pressure to obtain a paste-like solid crude product, which is recrystallized twice with acetone and dried to obtain a bis-palmitoyl tartaric acid diester.

[0074] In a third aspect, the present application provides a flame-retardant composition comprising the pyrophosphoric acid piperazine coating or the pyrophosphoric acid piperazine coating prepared by the preparation method of the pyrophosphoric acid piperazine coating.

[0075] Specifically, the flame-retardant composition comprises a resin matrix; the pyrophosphoric acid piperazine coating is added into the resin matrix, the organic end (such as isopropoxy) of the coupling agent in the pyrophosphoric acid piperazine coating is connected with the resin matrix, the dispersibility of the pyrophosphoric acid piperazine in the resin matrix is improved, thereby improving the flame retardancy and mechanical properties of the flame-retardant product.

[0076] As specific examples of the resin base, there can be mentioned polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polybutene-1, α-olefin polymers such as poly-3-methylpentene or ethylene-vinyl acetate copolymers, polyolefins such as ethylene-propylene copolymers and copolymers thereof, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, chloroethylene-vinyl acetate copolymers, chloroethylene-ethylene copolymers, chloroethylene-vinylidene chloride copolymers, chloroethylene-vinylidene chloride-vinyl acetate terpolymers, chloroethylene-acrylate copolymers, chloroethylene-maleate copolymers, chloroethylene-cyclohexylmaleimide copolymers and other halogen-containing resins, petroleum resins, coumarone resins, polystyrene, polyvinyl acetate, acrylic resins, copolymers of styrene and / or α-methylstyrene with other monomers (e.g., maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) (e.g., AS resins, ABS resins, MBS resins, heat-resistant ABS resins, etc.), polymethyl methacrylate, polyvinyl alcohol, polyvinyl methylene, polyvinyl butylene, linear polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyphenylene ether, polyamides such as polycaprolactam and polyhexamethylene adipamide, polycarbonates, polycarbonate / ABS resins, branched polycarbonates, polyacetals, polyphenylene sulfide, polyurethane, cellulose-based resins and other thermoplastic resins, and mixtures thereof or thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyester resins, and the like, with preference particularly given to polypropylene resins.

[0077] When the pyrophosphoryl piperazine coating of the present application is used as a flame retardant, the amount of the pyrophosphoryl piperazine coating to be added is preferably 20 to 60 parts by weight per 100 parts by weight of the above-mentioned resin base. In addition, in combination with the pyrophosphoryl piperazine coating of the present application, other flame retardants such as melamine pyrophosphate, polyphosphoryl piperazine, polyphosphoryl melamine, polyphosphoryl amide, phosphate ester, phosphate ester amide, and the like, as well as compounding agents such as polysiloxane compounds, metal oxides, silica, higher aliphatic carboxylic acids, and the like, can be used. In this case, the amount of the other flame retardants to be added is preferably 50 to 400 parts by weight per 100 parts by weight of the pyrophosphoryl piperazine coating of the present application, and the amount of the compounding agents to be added is preferably 0.05 to 20 parts by weight per 100 parts by weight of the above-mentioned resin base. In addition, they can be premixed as a flame retardant composition and added to the above-mentioned resin base.

[0078] The above-mentioned flame-retardant composition containing the resin base and the pyrophosphoryl piperazine coating is molded into a molded body by a molding method such as general injection molding, extrusion molding, gas-assisted molding, and the like. Such a molded body is also one mode of the present application. As the molded body of the present application, there is no limitation on the shape, and examples that can be given are power plug, connector, bushing, box, wire covering, tape base material, tube, sheet, film, and the like.

[0079] In addition, in the case of obtaining an injection-molded product such as an electric wire member, the injection molding can be performed at a temperature of about 190°C for the material tube and at a temperature of about 190°C for the tube head. The molding can be performed using an injection molding machine that is generally used for molding of PVC resin and the like as the injection molding device.

[0080] The raw materials used in the examples and comparative examples are described below, but are not limited to these materials:

[0081] Piperazine pyrophosphate was self-made. The preparation method was as follows: 40 mL of deionized water and 43.07 g (0.5 mol) of anhydrous piperazine were added to a 250 mL three-necked flask equipped with a stirrer, a thermometer, a condenser and a dropping funnel, heated to about 40°C, stirred and dissolved, and after complete dissolution, 115.3 g (1.0 mol) of a phosphoric acid solution with a concentration of 85% was added dropwise, which was completed in about 1 h, and the temperature was increased to 85°C for 2 h of reaction. The material was cooled to room temperature, filtered, and the filter cake was washed with deionized ice water for 3 times, each time with 30 mL of water. The washed filter cake was dried under vacuum until the mass was constant, to obtain piperazine diphosphate.

[0082] 100 g of piperazine diphosphate and 4.5 g of a catalyst were added to a 500 mL beaker with stirring and a thermometer, and the material was heated to 200°C by an oil bath for 5 h of reaction, and then cooled to room temperature. The crude product was crushed by a universal crusher. The crushed crude product and methanol were added to a beaker at a mass ratio of 1:1, stirred at room temperature for 0.5 h, vacuum filtered, and the filter cake was washed with a small amount of methanol. The washed filter cake was dried under vacuum until the mass was constant, to obtain piperazine pyrophosphate.

[0083] Dipalmitoyl tartrate was self-made. The preparation method was as follows: 10.3 g of palmitic acid was taken in a round-bottom flask, and 10 mL of thionyl chloride was added dropwise at a rate of 1 s / drop under stirring. After the addition was completed, the temperature was increased to 80°C for 3 h of reaction until the solution became transparent. The excess thionyl chloride was removed by rotary evaporation under reduced pressure, and then 5 mL of methyl tert-butyl ether was added for further rotary evaporation, to obtain brownish yellow palmitoyl chloride. The obtained palmitoyl chloride was dissolved in dichloromethane and transferred to a three-necked flask, and 16.8 mL of triethylamine was added under ice water bath. 3.0 g of tartaric acid was weighed, dissolved in acetone by heating, and added dropwise to the three-necked flask. After the addition was completed, the temperature was increased to 25°C for overnight reaction. Filtration was performed, and the filtrate was rotary evaporated under reduced pressure to form a paste-like solid crude product. The crude product was recrystallized twice with acetone, and dried to obtain a white solid, which was the target product, dipalmitoyl tartrate.

[0084] Titanate coupling agent and zirconate coupling agent were purchased from Nanjing Nengxin New Material Technology Co., Ltd.

[0085] Example 1

[0086] The present embodiment provides a pyrophosphoryl piperazine coating, comprising a pyrophosphoryl piperazine core and a coating layer coated on the surface of the pyrophosphoryl piperazine core;

[0087] The coating layer comprises a bis-palmitoyl tartrate diester and a coupling agent, and the coupling agent is isopropoxy trioleic acyloxy titanate;

[0088] The weight parts of the bis-palmitoyl tartrate diester is 2.5 parts, and the weight parts of the coupling agent is 2.5 parts, based on 10 parts by weight of the pyrophosphoryl piperazine;

[0089] The average particle size of the pyrophosphoryl piperazine is 20 μm.

[0090] The present embodiment provides a pyrophosphoryl piperazine coating, comprising a pyrophosphoryl piperazine core and a coating layer coated on the surface of the pyrophosphoryl piperazine core;

[0091] 10 parts by weight of pyrophosphoryl piperazine with an average particle size of 20 μm is added to 100 parts by volume of an ethanol / water solution, the volume ratio of ethanol to water in the ethanol / water solution is 1:1, and the mixture is stirred uniformly to obtain a first dispersion;

[0092] 2.5 parts by weight of bis-palmitoyl tartrate diester is added to 50 parts by volume of ethanol, and the mixture is stirred and dissolved at a temperature of 50°C and a rotation speed of 800 rpm, then 2.5 parts by weight of a coupling agent is added, and the mixture is stirred at a rotation speed of 800 rpm for 35 min to obtain a second dispersion;

[0093] The second dispersion is added to the first dispersion, and the mixture is ultrasonically dispersed at an ultrasonic power of 200 W for 15 min to obtain a suspension; the suspension is reacted at a temperature of 60°C and a rotation speed of 800 rpm for 4 h, the product obtained by the reaction is centrifuged, the precipitate obtained by centrifugation is washed with ethanol for 3 times, and then dried in a vacuum drying oven at 60°C for 12 h to obtain the pyrophosphoryl piperazine coating.

[0094] Examples 2-21 and Comparative Examples 1-3 refer to Example 1, and the differences between them are shown in Tables 1 and 2.

[0095] Table 1

[0096]

[0097] Table 2

[0098]

[0099] Comparative Example 4

[0100] The present embodiment provides a pyrophosphoryl piperazine coating, comprising a pyrophosphoryl piperazine core and a coating layer coated on the surface of the pyrophosphoryl piperazine core;

[0101] The coating layer includes bis-palmitoyl tartaric acid diester and a coupling agent, and the coupling agent is isopropyl tri(dioctyl pyrophosphoryloxy) titanate;

[0102] The weight parts of bis-palmitoyl tartaric acid diester is 2.5 parts, and the weight parts of the coupling agent is 2.5 parts, based on 10 weight parts of piperazine pyrophosphate;

[0103] The average particle size of piperazine pyrophosphate is 20 μm.

[0104] The preparation method of the piperazine pyrophosphate coating of the present comparative example includes the following steps:

[0105] 10 weight parts of piperazine pyrophosphate with an average particle size of 20 μm, 2.5 weight parts of bis-palmitoyl tartaric acid diester and 2.5 weight parts of a coupling agent are added to 100 parts by volume of an ethanol / water solution, the volume ratio of ethanol to water in the ethanol / water solution is 1:1, stirring is carried out at a temperature of 20°C and a rotation speed of 800 rpm for 4 h, the product obtained by the reaction is centrifuged, the precipitate obtained by centrifugation is washed with ethanol for 3 times, and then dried in a vacuum drying oven at 60°C for 12 h to obtain the piperazine pyrophosphate coating.

[0106] Comparative Example 5

[0107] The present comparative example provides a piperazine pyrophosphate coating including a piperazine pyrophosphate inner core and a coating layer coated on the surface of the piperazine pyrophosphate inner core;

[0108] The coating layer includes bis-palmitoyl tartaric acid diester and a coupling agent, and the coupling agent is isopropyl tri(dioctyl pyrophosphoryloxy) titanate;

[0109] The weight parts of bis-palmitoyl tartaric acid diester is 2.5 parts, and the weight parts of the coupling agent is 2.5 parts, based on 10 weight parts of piperazine pyrophosphate;

[0110] The average particle size of piperazine pyrophosphate is 20 μm.

[0111] The preparation method of the piperazine pyrophosphate coating of the present comparative example includes the following steps:

[0112] 10 weight parts of piperazine pyrophosphate with an average particle size of 20 μm, 2.5 weight parts of bis-palmitoyl tartaric acid diester and 2.5 weight parts of a coupling agent are added to 100 parts by volume of an ethanol / water solution, the volume ratio of ethanol to water in the ethanol / water solution is 1:1, stirring is carried out at a temperature of 20°C and a rotation speed of 800 rpm for 4 h, the product obtained by the reaction is centrifuged, the precipitate obtained by centrifugation is washed with ethanol for 3 times, and then dried in a vacuum drying oven at 60°C for 12 h to obtain the piperazine pyrophosphate coating.

[0113] 2.5 weight parts of bis-palmitoyl tartaric acid diester is added to 50 parts by volume of ethanol, stirring and dissolving at a temperature of 50°C and a rotation speed of 800 rpm, and then 2.5 weight parts of a coupling agent is added, stirring at a rotation speed of 800 rpm for 35 min to obtain a second dispersion liquid;

[0114] The second dispersion liquid was added to the first dispersion liquid, and ultrasonic dispersion was performed at an ultrasonic power of 200 W for 15 min to obtain a suspension; the suspension was stirred at a temperature of 25°C and a rotation speed of 800 rpm for 4 h, and the reaction product was centrifuged; the precipitate obtained by centrifugation was washed with ethanol for 3 times, and then dried in a vacuum drying oven at 60°C for 12 h to obtain the pyrazophosphoric acid-coated substance.

[0115] Application Example 1

[0116] The application example provides a flame-retardant composition, which comprises the following components in parts by weight: 38.3 parts of copolymerized PP K8009, 39 parts of homopolymerized PP T30S, 22 parts of the pyrazophosphoric acid-coated substance of Example 1, 0.3 parts of ethylene bis-stearamide (EBS), 0.2 parts of antioxidant B215, and 0.2 parts of anti-dripping agent M532.

[0117] The application example provides a preparation method of the flame-retardant composition, which comprises the following steps:

[0118] The components are uniformly mixed in proportion to obtain a premix;

[0119] The premix is added into a double-screw extruder, uniformly mixed and melt-extruded and granulated to obtain the flame-retardant composition; during the melt-extrusion and granulation, the temperature settings of the double-screw extruder from the feeding port to the die head are as follows: the temperature of zone 1 is 160°C, the temperature of zone 2 is 180°C, the temperature of zone 3 is 190°C, the temperature of zone 4 is 190°C, the temperature of zone 5 is 190°C, the temperature of zone 6 is 190°C, and the temperature of the die head is 200°C; the rotation speed of the screw is 150 rpm, and the length-diameter ratio of the double-screw extruder is 42.

[0120] Application Examples 2-21 and Comparative Application Examples 1-6

[0121] The flame-retardant compositions of Application Examples 2-21 and Comparative Application Examples 1-6 are composed of the components as in Application Example 1, and the only difference between them and Application Example 1 is that the pyrazophosphoric acid-coated substances of Examples 2-21 and Comparative Examples 1-6 are used to replace the pyrazophosphoric acid-coated substance of Example 1 in Application Example 1, that is, the pyrazophosphoric acid-coated substance of Example 2 is used to replace the pyrazophosphoric acid-coated substance of Example 1 in Application Example 2, the pyrazophosphoric acid-coated substance of Example 3 is used to replace the pyrazophosphoric acid-coated substance of Example 1 in Application Example 3, and so on; wherein Comparative Example 6 is pyrazophosphoric acid with an average particle size of 20 μm without any treatment;

[0122] The preparation methods of the flame-retardant compositions of Application Examples 2-21 and Comparative Application Examples 1-6 are the same as those of the flame-retardant composition of Application Example 1.

[0123] Performance test

[0124] The performance tests were carried out on the pyrophosphoryl piperazine coating obtained in the examples and comparative examples, the flame-retardant composition obtained in the application examples and comparative application examples, and the test methods were as follows:

[0125] (1) Water resistance: characterized by the solubility of the pyrophosphoryl piperazine coating in water, 10 g of the pyrophosphoryl piperazine coating was placed in 100 mL of water, stirred at 300 rpm for 20 min, then centrifuged at a speed of 2000 r / min for 20 min, the supernatant was filtered, and V of the supernatant was taken from the filtrate with a pipette and placed in two beakers. The beaker containing the supernatant was placed in a 135℃ oven, and after 2.5 h, the beaker was taken out and placed in a desiccator. The mass of the beaker was weighed on a constant weight analysis balance.

[0126] The mass fraction W of water-soluble was calculated according to the formula, and the value was expressed in grams per 100 milliliters (g / 100 mL):

[0127] W = (m2-m1) / V x 100;

[0128] m1--the value of the weight of the small beaker dried to a constant weight, in grams (g);

[0129] m2--the value of the total weight of the filtrate in the dried small beaker, in grams (g);

[0130] V--the volume of the filtrate, in milliliters (mL).

[0131] (2) Izod impact strength: the flame-retardant compositions of application examples 1-21 and comparative application example 1-6 were injection molded into samples with a size of 80 mm x 10 mm x 4 mm, and tested according to the standard ASTM D256-24, with a temperature of 25℃, a notch depth of 2 mm, and an impact energy of 2.75 J.

[0132] (3) Hydrophobic durability: the same mass of the flame-retardant compositions of application examples 1-21 and comparative application example 1-6 were placed in a constant temperature and humidity test chamber with a temperature of 85℃ and a humidity of 85%, and the water absorption rate after 100 h was tested;

[0133] (4) Thermal stability: 5-10 mg of the pyrophosphoryl piperazine coating was weighed, the heating rate was set to 20℃ / min, the air atmosphere was set, and the temperature was raised from room temperature to 800℃. The carbon residue rate at 800℃ was calculated, and the higher the carbon residue rate, the better the thermal stability.

[0134] The test results are shown in Table 3.

[0135] Table 3

[0136]

[0137] From the experimental data of Table 3, it can be seen that the solubility of the pyrophosphate piperazine coating in water is ≤0.25 g / 100 mL, the carbon residue rate at 800°C is 24-41%, the Izod impact strength of the flame-retardant composition containing the pyrophosphate piperazine coating is ≥67 J / m, and the water absorption rate after being placed in an environment of 85% humidity and 85°C for 100 h is ≤0.45%, indicating that the pyrophosphate piperazine coating has high water resistance, mechanical properties, hydrophobic durability and thermal stability.

[0138] From the experimental data of Examples 1-5, it can be seen that when the molecular structure of the titanate coupling agent contains a pyrophosphate acyloxy group, the solubility of the obtained pyrophosphate piperazine coating in water is ≤0.11 g / 100 mL, the carbon residue rate at 800°C is 33.1-35.2%, the Izod impact strength of the flame-retardant composition containing the pyrophosphate piperazine coating is ≥105 J / m, and the water absorption rate after being placed in an environment of 85% humidity and 85°C for 100 h is ≤0.17%, indicating that when the molecular structure of the titanate coupling agent contains a pyrophosphate acyloxy group, the pyrophosphate piperazine coating has high water resistance, mechanical properties, hydrophobic durability and thermal stability.

[0139] From the experimental data of Examples 6-7, it can be seen that when the molecular structure of the zirconate coupling agent contains a pyrophosphate acyloxy group, the solubility of the obtained pyrophosphate piperazine coating in water is 0.14 g / 100 mL, the carbon residue rate at 800°C is 30.5%, the Izod impact strength of the flame-retardant composition containing the pyrophosphate piperazine coating is 163 J / m, and the water absorption rate after being placed in an environment of 85% humidity and 85°C for 100 h is 0.26%, indicating that when the molecular structure of the zirconate coupling agent contains a pyrophosphate acyloxy group, the pyrophosphate piperazine coating has high water resistance, mechanical properties, hydrophobic durability and thermal stability.

[0140] From the experimental data of Example 4 and Examples 8-10, it can be seen that when the mass ratio of pyrophosphate piperazine to coating layer is 1:(0.3-1), the solubility of the obtained pyrophosphate piperazine coating in water is ≤0.18 g / 100 mL, the carbon residue rate at 800°C is 28.5-38%, the Izod impact strength of the flame-retardant composition containing the pyrophosphate piperazine coating is ≥135 J / m, and the water absorption rate after being placed in an environment of 85% humidity and 85°C for 100 h is ≤0.3%, indicating that when the mass ratio of pyrophosphate piperazine to coating layer is 1:(0.3-1), the pyrophosphate piperazine coating has higher water resistance, mechanical properties, hydrophobic durability and thermal stability.

[0141] From the experimental data of Example 9 and Examples 11-13, when the mass ratio of dipalmitoyl tartaric acid diester and coupling agent is 1:(0.7-1), the solubility of the obtained pyrophosphazine coating in water is ≤0.12 g / 100 mL, the carbon residue rate at 800°C is 35-38%, the Izod impact strength of the flame-retardant composition containing the pyrophosphazine coating is ≥168 J / m, and the water absorption rate after being placed in an environment of 85% humidity and 85°C for 100 h is ≤0.12%, indicating that when the mass ratio of dipalmitoyl tartaric acid diester and coupling agent is 1:(0.7-1), the obtained pyrophosphazine coating has higher water resistance, mechanical properties, hydrophobic durability, and thermal stability.

[0142] From the experimental data of Example 9, Examples 14-18, when the coupling agent is a titanate coupling agent and a zirconate coupling agent; and the mass ratio of the titanate coupling agent and the zirconate coupling agent is (2-8):1, the solubility of the obtained pyrophosphazine coating in water is ≤0.09 g / 100 mL, the carbon residue rate at 800°C is 39-41%, the Izod impact strength of the flame-retardant composition containing the pyrophosphazine coating is 165-175 J / m, and the water absorption rate after being placed in an environment of 85% humidity and 85°C for 100 h is ≤0.11%; indicating that when the coupling agent is a titanate coupling agent and a zirconate coupling agent; and the mass ratio of the titanate coupling agent and the zirconate coupling agent is (2-8):1, the obtained pyrophosphazine coating has higher water resistance, mechanical properties, hydrophobic durability, and thermal stability.

[0143] From the experimental data of Example 9 and Examples 19-21, when the average particle size of pyrophosphazine is 20-40 μm, the solubility of the obtained pyrophosphazine coating in water is ≤0.2 g / 100 mL, the carbon residue rate at 800°C is 27-38%, the Izod impact strength of the flame-retardant composition containing the pyrophosphazine coating is 165-180 J / m, and the water absorption rate after being placed in an environment of 85% humidity and 85°C for 100 h is ≤0.29%; indicating that when the average particle size of pyrophosphazine is 20-40 μm, the obtained pyrophosphazine coating has higher water resistance, mechanical properties, hydrophobic durability, and thermal stability.

[0144] From the experimental data of Example 9 and Comparative Examples 1-6, it can be seen that the preparation method of the coating layer using only dipalmitoyl tartrate or a coupling agent, or using other types of coupling agents, or the pyrophosphazine coating is not within the protection scope of the present application, the solubility of the obtained pyrophosphazine coating in water is ≥0.4 g / 100 mL, the carbon residue rate at 800°C is ≤28%, the Izod impact strength of the flame-retardant composition containing the pyrophosphazine coating is ≤50 J / m, and the water absorption rate after being placed in an environment of 85% humidity and 85°C for 100 h is ≥0.85%; it is indicated that only the coating layer composed of dipalmitoyl tartrate and a specific type of coupling agent, and the pyrophosphazine coating prepared by the preparation method of the present application, can obtain the pyrophosphazine coating with water resistance, mechanical properties, hydrophobic durability and thermal stability.

[0145] The reason why the overall performance of the pyrophosphazine coating is reduced when only dipalmitoyl tartrate is used in the coating layer may be that the polar end of the dipalmitoyl tartrate can be combined with the surface of the pyrophosphazine through hydrogen bonds, but the strength of the hydrogen bonds is low and is easily broken in a high-temperature or high-humidity environment, resulting in the peeling of the coating layer; moreover, the single molecular layer lacks a cross-linking structure, and the unreacted dipalmitoyl tartrate monomers and pyrophosphazine decomposition products are easily migrated to the surface of the pyrophosphazine coating, thereby reducing the overall performance of the pyrophosphazine coating.

[0146] The reason why the overall performance of the pyrophosphazine coating is reduced when only a coupling agent is used in the coating layer may be that the hydroxyl groups in the coupling agent react with the hydroxyl groups on the surface of the pyrophosphazine, thereby being coated on the surface of the pyrophosphazine, but the number of the hydroxyl groups on the surface of the pyrophosphazine is limited, the exposed area of the surface of the pyrophosphazine that is not chemically bonded with the coupling agent becomes a water penetration channel, thereby reducing the overall performance of the pyrophosphazine coating.

[0147] The reason why the overall performance of the pyrophosphazine coating is reduced when other types of coupling agents are used in the coating layer may be that the basic coupling agent (such as aminosilane) can destroy the hydrogen bonds of the tartrate ester, and the long-chain alkyl groups in other types of coupling agents cover the surface of the pyrophosphazine, thereby hindering the anchoring of the polar end of the dipalmitoyl tartrate, resulting in the physical mixing layer of the double coating layer; and the viscosity of the dipalmitoyl tartrate (C16 chain) and the long-chain alkyl groups of the coupling agent increases at low temperatures, and it is difficult to spread into a single molecular layer on the surface of the pyrophosphazine, thereby reducing the overall performance of the pyrophosphazine coating.

[0148] Finally, it should be noted that the above examples are used to illustrate the technical solutions of the present disclosure and not to limit the protection scope of the present disclosure. Although the present disclosure has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present disclosure can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present disclosure.

Claims

1. A pyrophosphopiperazine coating, characterized in that, The coating layer comprises bis-palmitoyl tartaric acid diester and a coupling agent, and the coupling agent is a titanate coupling agent and / or a zirconate coupling agent. The coating layer comprises bis-palmitoyl tartaric acid diester and a coupling agent, and the coupling agent is a titanate coupling agent and / or a zirconate coupling agent. The mass ratio of the pyrophosphoric piperazine core and the coating layer is 1:(0.3-1). The mass ratio of the bis-palmitoyl tartaric acid diester and the coupling agent is 1:(0.5-1.2). The preparation method of the pyrophosphoric piperazine coating comprises: adding a second dispersion liquid comprising bis-palmitoyl tartaric acid diester and a coupling agent into a first dispersion liquid comprising pyrophosphoric piperazine, ultrasonic dispersion, and then heating the obtained suspension to obtain the pyrophosphoric piperazine coating.

2. The pyrophosphopiperazine coating of claim 1, wherein, The coupling agent is a titanate coupling agent and a zirconate coupling agent, and the mass ratio of the titanate coupling agent and the zirconate coupling agent is (2-8):

1.

3. The pyrophosphopiperazine coating of claim 1, wherein, The titanate coupling agent comprises at least one of isopropoxy triisostearyl acyloxy titanate, bis(dioctyl phosphato) ethylene titanate acrylamide chelate, tetraoctyloxy bis(dilauryl phosphato) titanate, triethanolamine chelate of bis(dioctyl phosphato) ethylene titanate, isopropoxy tridodecyl benzene sulfonyloxy titanate, tetraisopropyl bis(dioctyl phosphato) titanate, bis(dioctyl phosphato) ethylene titanate, isopropyl tris( branched and linear dioctyl phosphato) titanate, isopropoxy dioleic acyloxy (dioctyl phosphato) titanate, propoxy titanium tristearate, isopropoxy trioleic acyloxy titanate, isopropoxy tri(ethylenediamine-N-ethoxy) titanate, neoalkoxy tri(p-aminophenoxy) titanate, neoalkoxy tri(dioctyl phosphato) titanate acrylamide chelate, neoalkoxy tri(dioctyl phosphato) titanate, neoalkoxy tri(neodecanoic acyloxy) titanate, and neoalkoxy tri(dioctyl phosphato) titanate.

4. The pyrophosphopiperazine coating of claim 1, wherein, The zirconate coupling agent comprises at least one of neoalkoxy tri(dioctyl phosphato) zirconate, neoalkoxy tridodecyl benzene sulfonyloxy zirconate, neoalkoxy tri(neodecanoic acyloxy) zirconate, and neoalkoxy tri(dioctyl phosphato) zirconate.

5. The pyrophosphopiperazine coating of claim 1, wherein, The pyrophosphoric piperazine core is formed by pyrophosphoric piperazine, and the average particle size of the pyrophosphoric piperazine is 10-50 μm.

6. A process for the preparation of a pyrophosphorylazepane coating as claimed in any one of claims 1 to 5, characterized in that, The preparation method comprises the following steps: Preparation of a first dispersion liquid containing pyrophosphoric piperazine; Preparation of a second dispersion liquid containing bis-palmitoyl tartaric acid diester and a coupling agent; Adding the second dispersion liquid into the first dispersion liquid, ultrasonic dispersion, and then heating the obtained suspension to obtain the pyrophosphoric piperazine coating.

7. The method for preparing the piperazine pyrophosphate coated material as described in claim 6, characterized in that, The heating reaction is carried out at a temperature of 60-80 h for 3-6 h. And / or, the ultrasonic dispersion is carried out at a power of 200-400 W for 10-30 min.

8. A flame-retardant composition characterized in that, The flame-retardant composition comprises a pyrophosphoryl piperazine coating as claimed in any one of claims 1 to 5 or a pyrophosphoryl piperazine coating prepared according to the method of any one of claims 6 to 7. The flame-retardant composition comprises a pyrophosphoryl piperazine coating as claimed in any one of claims 1 to 5 or a pyrophosphoryl piperazine coating prepared according to the method of any one of claims 6 to 7.

Images