Composition, flame retardant, preparation method of flame retardant, polycarbonate composition, and preparation method and application of polycarbonate composition

Abstract

The invention relates to the technical field of high polymer materials, and discloses a composition for preparing a flame retardant, the flame retardant and a preparation method thereof, and a polycarbonate composition and a preparation method and application thereof. The composition for preparing the flame retardant is prepared from the following components in parts by mole: 1 to 1.5 parts of a triazine compound, 1.5 to 3.5 parts of sulfydryl sulfonate and 1.5 to 3.5 parts of allyl silane. The flame retardant prepared from the composition with the variety and content has good flame retardant property. The polycarbonate composition prepared by using the flame retardant has proper limit oxygen index, vertical combustion performance and impact strength.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a composition for preparing a flame retardant, a method for preparing a flame retardant, a flame retardant, a polycarbonate composition containing the flame retardant, a method for preparing the polycarbonate composition, and applications of the polycarbonate composition. Background Art

[0002] Polycarbonate is a thermoplastic engineering plastic with excellent properties such as creep resistance, good dimensional stability, high temperature resistance, low water absorption, and non-toxicity. It has good flame retardancy and can reach UL94 V2 level. It is widely used in electronic appliances, automotive accessories, telecommunications industry components, optical components and lighting fields. With the development of the times, the requirements for the flame retardant properties of plastic materials are getting higher and higher. Therefore, technicians usually add flame retardants to polycarbonate to improve the flame retardant properties of polycarbonate. The flame retardants used mainly follow two flame retardant mechanisms.

[0003] One is the gas phase flame retardant mechanism, which is characterized by delaying or preventing gas chain combustion. The other is the condensed phase flame retardant mechanism, which is characterized by generating a carbon layer by itself or forming a carbon layer through interaction, which can reduce the thermal degradation ability of the polymer.

[0004] The flame retardants used in the prior art often use only gas phase flame retardancy mechanism or condensed phase flame retardancy mechanism to achieve flame retardancy, and their flame retardancy effect is not good. How to obtain a flame retardant with both gas phase flame retardancy and condensed phase flame retardancy is of great significance in improving the flame retardancy of polycarbonate, and is an important research direction of polycarbonate. Summary of the invention

[0005] The purpose of the present invention is to overcome the problem that the flame retardant in the prior art has a single flame retardant mechanism and poor flame retardant effect, and to provide a composition for preparing a flame retardant, a method for preparing a flame retardant, a flame retardant, a polycarbonate composition containing the flame retardant, a method for preparing the polycarbonate composition, and the application of the polycarbonate composition. The flame retardant has both gas phase flame retardant effect and condensed phase flame retardant effect, and has important application value in the polycarbonate composition. The polycarbonate composition not only has excellent flame retardant performance, but also has good toughness.

[0006] The first aspect of the present invention provides a composition for preparing a flame retardant, wherein the composition comprises: 1-1.5 mole parts of a triazine compound, 1.5-3.5 mole parts of a mercaptosulfonate, and 1.5-3.5 mole parts of allylsilane.

[0007] A second aspect of the present invention provides a method for preparing a flame retardant, the method comprising the following steps: (1) A solution 1 containing a triazine compound and a solution 2 containing allylsilane are mixed and reacted under alkaline conditions, and then concentrated to obtain an intermediate 1; (2) mixing a solution 3 containing mercaptosulfonate with a solution 4 containing an intermediate 1 and a catalyst 1, allowing them to react, and then drying to obtain an intermediate 2; (3) The solution 5 containing the intermediate 2 is mixed with an oxidant and a catalyst 2 to react, and then concentrated and crystallized to obtain a flame retardant.

[0008] The third aspect of the present invention provides a flame retardant prepared by the method described in the second aspect.

[0009] A fourth aspect of the present invention provides a polycarbonate composition, the polycarbonate composition comprising a polycarbonate resin, a flame retardant and a layered silicate; Wherein, the flame retardant is the flame retardant described in the third aspect.

[0010] A fifth aspect of the present invention provides a method for preparing a polycarbonate composition, the method comprising the following steps: The polycarbonate resin, the flame retardant and the layered silicate are mixed and pelletized to obtain the polycarbonate composition.

[0011] A sixth aspect of the present invention provides an application of the polycarbonate composition described in the fourth aspect in the field of flame retardant materials.

[0012] The flame retardant provided by the present invention not only contains S and N elements, but also creatively introduces Si element. On the one hand, under the condition of heating, the flame retardant can generate SO 2 and NH 3 Non-flammable gases such as Si can not only dilute the concentration of combustible gases and oxygen, but also absorb heat and reduce the ambient temperature of the material. On the other hand, during the combustion process, the Si element migrates to the surface of the material, which can further improve the density of the carbon layer and better block oxygen exchange and heat transfer, thereby protecting the matrix under the carbon layer, so that the flame retardant has both gas phase flame retardant effect and condensed phase flame retardant effect.

[0013] The present invention also provides a polycarbonate composition containing the flame retardant. Since the flame retardant provided by the present invention decomposes and releases sulfur oxides with a higher valence state under heat, the polycarbonate ester group is more likely to break and undergo Fries rearrangement, thereby making it easier to obtain a carbon layer with a cross-linked structure.

[0014] In addition, the polycarbonate composition provided by the present invention further contains layered silicate. Under the combined action of the flame retardant and the layered silicate, the material distribution in the polycarbonate composition is more uniform, and the toughness of the polycarbonate composition is stronger. DETAILED DESCRIPTION

[0015] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0016] The first aspect of the present invention provides a composition for preparing a flame retardant, wherein the composition comprises: 1-1.5 molar parts of a triazine compound, 1.5-3.5 molar parts of a mercaptosulfonate, and 1.5-3.5 molar parts of allylsilane.

[0017] According to the present invention, the content of the triazine compound is 1-1.5 parts by mole, for example, it can be 1.1, 1.2, 1.3, 1.4, 1.5 parts by mole or a range therebetween.

[0018] According to the present invention, the content of mercaptosulfonate is 1.5-3.5 parts by mole. For example, it can be 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5 parts by mole or the like or a range therebetween.

[0019] According to the present invention, the content of allylsilane is 1.5-3.5 parts by mole. For example, it can be 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5 parts by mole or the like specific content or the range therebetween.

[0020] The triazine compound contains N element, so that the prepared flame retardant can decompose non-combustible gas containing N element when heated, thereby playing the role of diluting the concentration of combustible gas and oxygen, absorbing heat and reducing the ambient temperature of the material.

[0021] The mercaptosulfonate contains the S element, so that the prepared flame retardant can decompose the non-combustible gas containing the S element when heated, thereby playing the role of diluting the concentration of combustible gas and oxygen, absorbing heat and reducing the ambient temperature of the material.

[0022] The allylsilane contains Si element, and during the combustion process, Si element will migrate to the surface of the material, thereby further improving the density of the carbon layer, better blocking oxygen exchange and heat transfer, and protecting the matrix under the carbon layer.

[0023] According to a preferred embodiment of the present invention, the triazine compound content is 1.2-1.5 parts by mole, the mercaptosulfonate content is 2.5-3.5 parts by mole, and the allylsilane content is 2.5-3.5 parts by mole. The composition within the above preferred range can make the flame retardant prepared subsequently have a more suitable Si content and S content, thereby further improving the flame retardant performance of the flame retardant.

[0024] According to a preferred embodiment of the present invention, the triazine compound is selected from one or more of cyanuric fluoride, cyanuric chloride, and melamine; more preferably, the triazine compound is selected from cyanuric fluoride and / or cyanuric chloride. The use of the above-mentioned more preferred type of triazine compound can further promote the flame retardant to decompose the non-flammable gas containing the N element under heating, thereby further improving the flame retardancy of the flame retardant.

[0025] According to a preferred embodiment of the present invention, the mercaptosulfonate is selected from one or more of 3-mercapto-1-propanesulfonate, 2,3-dimercaptopropanesulfonate, and 2-mercaptoethanesulfonate; more preferably, the mercaptosulfonate is selected from 3-mercapto-1-propanesulfonate and / or 2,3-dimercaptopropanesulfonate. The use of the above more preferred types of mercaptosulfonates can further promote the flame retardant to decompose the non-combustible gas containing the S element when heated, thereby further improving the flame retardancy of the flame retardant.

[0026] According to a preferred embodiment of the present invention, the allylsilane is selected from allyltrimethylsilane, allyltriisopropylsilane, and allyltrimethoxysilane; more preferably, the allylsilane is selected from allyltrimethylsilane and / or allyltriisopropylsilane. The use of the above-mentioned more preferred types of allylsilane can further promote the migration of Si elements in the flame retardant to the surface of the material, thereby improving the flame retardant properties of the flame retardant.

[0027] A second aspect of the present invention provides a method for preparing a flame retardant, the method comprising the following steps: (1) A solution 1 containing a triazine compound and a solution 2 containing allylsilane are mixed and reacted under alkaline conditions, and then concentrated to obtain an intermediate 1; (2) mixing a solution 3 containing mercaptosulfonate with a solution 4 containing an intermediate 1 and a catalyst 1, allowing them to react, and then drying to obtain an intermediate 2; (3) The solution 5 containing the intermediate 2 is mixed with an oxidant and a catalyst 2 to react, and then concentrated and crystallized to obtain a flame retardant.

[0028] In the present invention, the concentration range of the solution 1 is relatively wide, as long as it can react with the solution 2 after being mixed, and those skilled in the art can select it according to actual needs.

[0029] In the present invention, the concentration range of the solution 2 is relatively wide, as long as it can react with the solution 1 after being mixed, and those skilled in the art can select it according to actual needs.

[0030] In the present invention, the mixing ratio of the solution 1 and the solution 2 is not particularly limited, and the concentration of the two after mixing is not particularly limited, as long as they can react to generate the intermediate 1; preferably, the concentration of the solution 1 after mixing with the solution 2 is 0.5-0.75 mol / L, and the concentration of the solution 2 after mixing with the solution 1 is 0.75-1.75 mol / L.

[0031] In the present invention, the solvent of the solution 1 is not particularly limited, as long as it can dissolve the triazine compound, and those skilled in the art can select it according to actual needs. Preferably, the solvent of the solution 1 is selected from one or more of acetonitrile, ethanol, and tetrahydrofuran; more preferably, the solvent of the solution 1 is tetrahydrofuran.

[0032] In the present invention, the solvent of the solution 2 is not particularly limited, as long as it can dissolve allylsilane, and those skilled in the art can select it according to actual needs. Preferably, the solvent of the solution 2 is selected from one or more of acetonitrile, ethanol, and tetrahydrofuran; more preferably, the solvent of the solution 2 is tetrahydrofuran.

[0033] In the present invention, the solvents of the solution 1 and the solution 2 may be the same or different, and are preferably the same.

[0034] In the present invention, the triazine compound undergoes a nucleophilic substitution reaction with allylsilane to prepare an intermediate 1, and N and Si elements are introduced. The prepared flame retardant can decompose non-combustible gas containing N element under heating, thereby playing the role of diluting the concentration of combustible gas and oxygen, absorbing heat, and reducing the ambient temperature of the material; during the combustion process, Si element migrates to the surface of the material, thereby further improving the density of the carbon layer, better blocking oxygen exchange and heat transfer, and playing the role of protecting the matrix under the carbon layer.

[0035] In the present invention, the concentration range of the solution 3 is relatively wide, as long as it can react with the solution 4 after being mixed, and those skilled in the art can select it according to actual needs.

[0036] In the present invention, the concentration range of the solution 4 is relatively wide, as long as it can react with the solution 3 after being mixed, and those skilled in the art can select it according to actual needs.

[0037] In the present invention, the mixing ratio of the solution 3 and the solution 4 is not particularly limited, and the concentration of the two after mixing is not particularly limited, as long as they can react to generate the intermediate 2; preferably, the concentration of the solution 3 after mixing with the solution 4 is 0.06-0.14 mol / L, and after the solution 4 is mixed with the solution 3, the concentration of the intermediate 1 is 0.04-0.06 mol / L, and the concentration of the catalyst 1 is 1.64-1.84 g / L.

[0038] In the present invention, the solvent of the solution 3 is not particularly limited, as long as it can dissolve the mercaptosulfonate, and those skilled in the art can select it according to actual needs. Preferably, the solvent of the solution 3 is selected from one or more of ethanol and methanol; more preferably, the solvent of the solution 3 is methanol.

[0039] In the present invention, the solvent of the solution 4 is not particularly limited, as long as it can dissolve the intermediate 1 and the catalyst 1, and those skilled in the art can select it according to actual needs. Preferably, the solvent of the solution 4 is selected from one or more of ethanol and methanol; more preferably, the solvent of the solution 4 is methanol.

[0040] In the present invention, the solvents of solution 3 and solution 4 may be the same or different, and are preferably the same.

[0041] In the present invention, the preparation order of solution 1, solution 2 and solution 3 is not particularly limited and can be adjusted according to actual conditions.

[0042] In the present invention, the concentration range of the solution 5 is relatively wide, as long as it can react after being mixed with the oxidant and the catalyst, and those skilled in the art can select it according to actual needs.

[0043] In the present invention, the amount of the solution 5 is not particularly limited, and the concentration after mixing with the oxidant and the catalyst 2 is not particularly limited, as long as the reaction can occur after mixing, and those skilled in the art can select according to actual needs. Preferably, after the solution 5 is mixed with the oxidant and the catalyst 2, the concentration of the intermediate 2 is 0.1-0.2 mol / L.

[0044] According to a preferred embodiment of the present invention, the oxidant is selected from one or more of sodium hypochlorite, sodium periodate and hydrogen peroxide, more preferably hydrogen peroxide.

[0045] In the present invention, the oxidant can oxidize the sulfide bond in the intermediate 2 into a sulfone group, thereby increasing the valence of the element S. The polycarbonate composition prepared using a flame retardant having a higher valence of the element S can more easily cause the polycarbonate ester group to break and Fries rearrange at high temperatures to form a carbon layer with a cross-linked structure.

[0046] The amount of the oxidant used in the present invention is not particularly limited, as long as an oxidation reaction occurs, and those skilled in the art can select the amount according to actual needs.

[0047] The amount of the oxidant used in the present invention is not particularly limited, as long as the oxidation reaction occurs, and those skilled in the art can select it according to actual needs; preferably, the reaction concentration of the hydrogen peroxide is 2.73-5wt%, that is, after the oxidant, the catalyst 2 and the solution 5 are mixed, the concentration of the oxidant is 2.73-5.00wt%. The above reaction concentration can further increase the degree of oxidation of the intermediate 2, increase the content of the high-valent S element, thereby improving the flame retardant properties of the flame retardant, and can also effectively reduce the consumption of the oxidant and save production costs.

[0048] There is no particular limitation on the type and amount of the catalyst of the present invention, as long as it plays a catalytic role, and those skilled in the art can choose according to actual needs; preferably, the catalyst 2 is selected from molybdenum trioxide; after the oxidant, catalyst 2 and solution 5 are mixed, the concentration of catalyst 2 is 5-10mmol / L.

[0049] In the present invention, the solvent of the solution 5 is not particularly limited, as long as it can dissolve the intermediate 2, and those skilled in the art can select it according to actual needs. Preferably, the solvent 3 is water.

[0050] According to a preferred embodiment of the present invention, in step (1), the alkaline condition is a pH value ≥ 10.

[0051] According to a preferred embodiment of the present invention, in step (1), while stirring solution 1, solution 2 is added dropwise to solution 1. By mixing solution 1 and solution 2 in the above method, agglomeration of allyl silane can be further avoided, allowing allyl silane to react more fully with the triazine compound.

[0052] According to a preferred embodiment of the present invention, the reaction temperature of step (1) is 40-60° C. The above reaction temperature can further reduce the generation of by-products, thereby improving the purity of the flame retardant and improving the flame retardant performance of the flame retardant.

[0053] According to a preferred embodiment of the present invention, the reaction time of step (1) is 45-50 hours.

[0054] According to a preferred embodiment of the present invention, the preparation method further comprises, in step (3), mixing solution 1 and solution 2 before heating, and then reacting them, preferably for 1.5-2.5 hours, and then heating to the reaction temperature. The above reaction method can further reduce the generation of by-products, thereby improving the purity of the flame retardant and improving the flame retardant performance of the flame retardant.

[0055] According to a preferred embodiment of the present invention, in step (1), the concentration method is reduced pressure concentration.

[0056] According to a preferred embodiment of the present invention, in step (1), the concentration method further comprises rotary evaporation, extraction and suction filtration. The rotary evaporation method is not particularly limited, and can achieve evaporation of the solvent; the extraction method is not particularly limited, and can achieve extraction of the solute; the suction filtration method is not particularly limited, and can achieve filtration.

[0057] In the present invention, the catalyst 1 can catalyze the click reaction between the intermediate 1 and the mercaptosulfonate, and introduce the sulfonate into the intermediate 2. The flame retardant prepared subsequently contains the S element, and decomposes the non-combustible gas containing the S element under heating, thereby playing the role of diluting the concentration of the combustible gas and oxygen, absorbing heat, and reducing the ambient temperature of the material.

[0058] According to a preferred embodiment of the present invention, in step (2), the catalyst 1 is azobisisobutyronitrile. Azobisisobutyronitrile can more effectively promote the reaction between the intermediate 1 and the sulfhydryl sulfonate, so that the sulfonate is introduced into the intermediate 2 more quickly.

[0059] The amount of the anti-solvent used in the present invention is not particularly limited, as long as it can play a catalytic role, and those skilled in the art can select it according to actual needs.

[0060] According to a preferred embodiment of the present invention, in step (2), the temperature of the mixing process is 60-80° C. The above reaction temperature can further reduce the generation of by-products, thereby improving the purity of the flame retardant and improving the flame retardant performance of the flame retardant.

[0061] According to a preferred embodiment of the present invention, in step (2), the mixing method is to add solution 4 dropwise into solution 3 while stirring solution 3. By mixing solution 3 and solution 4 in the above method, agglomeration of reactants can be further avoided, so that the reaction between reactants is more complete.

[0062] According to a preferred embodiment of the present invention, in step (2), the drying includes filtering and drying. The filtering method is not particularly limited, as long as it can achieve solid-liquid separation; the drying method is not particularly limited, as long as it can achieve drying of the product.

[0063] According to a preferred embodiment of the present invention, in step (3), the mixing method is to slowly add the oxidant and the catalyst into the solution 5 while stirring the solution 5.

[0064] According to a preferred embodiment of the present invention, in step (3), the concentration includes filtering and concentration. The filtering method is not particularly limited, as long as it can achieve solid-liquid separation; the concentration method is not particularly limited, as long as it can achieve liquid concentration.

[0065] According to a preferred embodiment of the present invention, in step (3), the crystallization method is to drop the concentrated solution into an anti-solvent to produce crystals.

[0066] In the present invention, the type of the anti-solvent is not particularly limited, as long as it can produce crystals, and those skilled in the art can select it according to their needs. Preferably, the anti-solvent is acetone.

[0067] The amount of the anti-solvent used in the present invention is not particularly limited, as long as it can cause the solution to crystallize, and those skilled in the art can select the amount according to actual needs.

[0068] According to the method provided by the present invention, the selection range of the types of triazine compounds, mercaptosulfonates, and silanes can be the same as the selection range described in the first aspect above, and the present invention will not be repeated here.

[0069] According to a preferred embodiment of the present invention, the amount of the triazine compound is 1-1.5 molar parts, the amount of the allyl silane is 1.5-3.5 molar parts, and the amount of the mercaptosulfonate is 1.5-3.5 molar parts relative to 1 molar part of the intermediate 1. More preferably, the amount of the triazine compound is 1.2-1.5 molar parts, the amount of the mercaptosulfonate is 2.5-3.5 molar parts, and the amount of the allyl silane is 2.5-3.5 molar parts relative to 1 molar part of the intermediate 1. The flame retardant is prepared by taking the above preferred range of amounts, so that the prepared flame retardant has a more suitable Si content and S content, thereby further improving the flame retardant properties of the flame retardant.

[0070] The third aspect of the present invention provides a flame retardant prepared by the method described in the second aspect.

[0071] The flame retardant contains N, S and Si elements. On the one hand, the prepared flame retardant can decompose non-combustible gas containing N and S elements when heated, thereby playing the role of diluting the concentration of combustible gas and oxygen, absorbing heat and reducing the ambient temperature of the material; on the other hand, during the combustion process, Si element will migrate to the surface of the material, thereby further improving the density of the carbon layer, better blocking oxygen exchange and heat transfer, and playing the role of protecting the matrix under the carbon layer.

[0072] A fourth aspect of the present invention provides a polycarbonate composition, the polycarbonate composition comprising a polycarbonate resin, a flame retardant and a layered silicate; Wherein, the flame retardant is the flame retardant described in the third aspect.

[0073] The polycarbonate composition containing the flame retardant, on the one hand, can decompose non-combustible gas containing S and N elements when heated, thereby playing the role of diluting the concentration of combustible gas and oxygen, absorbing heat, and reducing the ambient temperature of the material. In addition, the S element released by the flame retardant when decomposed by heat has a higher valence state, which can make it easier for the polycarbonate ester group to break and Fries rearrange at high temperature to form a carbon layer with a cross-linked structure; on the other hand, during the combustion process, Si elements will migrate to the surface of the material, which can further improve the density of the carbon layer, better block oxygen exchange and heat transfer, and thus protect the matrix under the carbon layer. The flame retardant has a condensed phase flame retardant effect while having a gas phase flame retardant effect.

[0074] According to a preferred embodiment of the present invention, the content of the flame retardant is 0.1-1 parts by weight, preferably 0.5-0.7 parts by weight, relative to 100 parts by weight of the polycarbonate resin. The use of the flame retardant in the preferred range can further improve the flame retardant properties of the polycarbonate composition, further effectively avoid the agglomeration of the flame retardant, and improve the toughness of the polycarbonate composition.

[0075] According to a preferred embodiment of the present invention, the content of the layered silicate is 1-5 parts by weight, preferably 2.5-4 parts by weight, relative to 100 parts by weight of the polycarbonate resin. The use of the layered silicate in the preferred range can further play the role of the surfactant while better avoiding agglomeration, making the layered silicate more evenly dispersed, thereby improving the toughness of the polycarbonate composition; in addition, the use of the layered silicate in the preferred range can further improve the compactness of the carbon layer, thereby better improving the flame retardant properties of the polycarbonate composition.

[0076] The use of a flame retardant within a preferred range and a layered silicate within a preferred range simultaneously can allow the flame retardant and the layered silicate to have a better synergistic effect, further improving the flame retardancy and toughness of the polycarbonate composition.

[0077] According to a preferred embodiment of the present invention, the layered silicate is selected from one or more of mica, illite, montmorillonite and talc, preferably talc.

[0078] According to a preferred embodiment of the present invention, the layered silicate is in powder form.

[0079] A fifth aspect of the present invention provides a method for preparing a polycarbonate composition, the method comprising the following steps: The polycarbonate resin, the flame retardant and the layered silicate are mixed and pelletized to obtain the polycarbonate composition.

[0080] According to a preferred embodiment of the present invention, the mixing process is mixing after drying. There is no particular limitation on the drying method, as long as the product can be dried. Preferably, the drying time is 8-15 hours and the drying temperature is 80-120°C. There is no particular limitation on the mixing method, as long as the polycarbonate resin, flame retardant and layered silicate can be mixed.

[0081] The method of mixing after drying can further effectively remove moisture from the polycarbonate resin, flame retardant and layered silicate, thereby improving the mechanical strength of the polycarbonate composition and better avoiding the occurrence of abnormal appearances such as bubbles and silver streaks.

[0082] The granulation method of the present invention is not particularly limited, and those skilled in the art can select it according to actual needs. Preferably, the granulation method is extrusion granulation by a screw extruder.

[0083] A sixth aspect of the present invention provides an application of the polycarbonate composition described in the fourth aspect in the field of flame retardant materials.

[0084] The present invention will be described in detail below through examples.

[0085] In the following examples, unless otherwise specified, the raw materials used were commercially available.

[0086] In the following examples, room temperature refers to 25±5°C.

[0087] The following Examples A1-A16 are used to illustrate the preparation of flame retardants.

[0088] Example A1 (1) Dissolve 13.5 g (0.1 mol) of cyanuric fluoride in 150 ml of tetrahydrofuran to obtain solution 1; dissolve 37.7 g (0.33 mol) of allyltrimethylsilane in 50 ml of tetrahydrofuran to obtain solution 2.

[0089] (2) Stir solution 1 at room temperature, and then add solution 2 dropwise into solution 1; after reacting for 2 hours, raise the temperature to 50°C and continue the reaction for 48 hours; during the reaction, use NaOH solution to maintain the pH value of the reaction solution at 10.5-11.5.

[0090] (3) After the reaction is completed, tetrahydrofuran is removed by rotary evaporation, and then toluene is used for extraction. The obtained extract is filtered and concentrated under reduced pressure to obtain intermediate 1; (4) 5.6 g (0.031 mol) of sodium 3-mercapto-1-propane sulfonate was dissolved in 100 ml of methanol to obtain solution 3; 0.01 mol of intermediate 1 and 0.41 g of azobisisobutyronitrile were dissolved in 150 ml of methanol to obtain solution 4; (5) Stir solution 3 at 70°C, then add solution 4 dropwise into solution 3 and react for 4 h; (6) After the reaction is completed, the mixture is filtered and dried in a vacuum drying oven to obtain intermediate 2; (7) Dissolve 0.012 mol of intermediate 2 in 100 ml of distilled water to obtain solution 5; (8) Stir solution 5 at room temperature, then slowly add 20 ml of 30 wt% hydrogen peroxide solution and 0.07 g of molybdenum trioxide catalyst into the intermediate 2 solution and react for 1.5 h; (9) After the reaction is completed, the filtrate is filtered and concentrated using a rotary evaporator. The concentrated solution is then dropped into acetone to generate crystals. The crystals are filtered and dried to obtain a flame retardant.

[0091] Example A2 The preparation steps are the same as those in Example A1, except that: In step (1), cyanuric fluoride is replaced by cyanuric chloride, and the amount used is changed to 0.15 mol; allyl trimethyl silane is replaced by allyl triisopropyl silane, and the amount used is changed to 0.35 mol.

[0092] In step (4), sodium 3-mercapto-1-propane sulfonate is replaced with 2,3-dimercaptopropane sulfonate, and the amount used is changed to 0.035 mol.

[0093] Example A3 The method of Example A1 was followed, except that the amount of cyanuric fluoride used was 0.12 mol, the amount of allyltrimethylsilane used was 0.28 mol, and the amount of sodium 3-mercapto-1-propane sulfonate used was 0.028 mol.

[0094] Example A4 The preparation steps are the same as those in Example A1, except that in step (2), after reacting for 2 h, the temperature is raised to 40°C.

[0095] Example A5 The preparation steps are the same as those in Example A1, except that in step (2), after reacting for 2 h, the temperature is raised to 60°C.

[0096] Example A6 The preparation steps are the same as those of Example A1, except that in step (5), solution 3 is stirred at 60°C.

[0097] Example A7 The preparation steps are the same as those of Example A1, except that in step (5), solution 3 is stirred at 80°C.

[0098] Example A8 The preparation steps are the same as those of Example A1, except that in step (8), the amount of hydrogen peroxide solution added is 15 mL.

[0099] Embodiment A9 The preparation steps are the same as those of Example A1, except that in step (8), the amount of hydrogen peroxide solution added is 10 mL.

[0100] Embodiment A10 The preparation steps are the same as those in Example A1, except that in step (2), after reacting for 2 h, the temperature is raised to 35°C.

[0101] Embodiment A11 The preparation steps are the same as those in Example A1, except that in step (2), after reacting for 2 h, the temperature is raised to 65°C.

[0102] Example A12 The preparation steps are the same as those of Example A1, except that in step (5), solution 3 is stirred at 55°C.

[0103] Embodiment A13 The preparation steps are the same as those of Example A1, except that in step (5), solution 3 is stirred at 85°C.

[0104] Embodiment A14 The preparation steps are the same as those of Example A1, except that in step (8), the amount of hydrogen peroxide solution added is 22 mL.

[0105] Embodiment A15 The preparation steps are the same as those of Example A1, except that in step (8), the amount of hydrogen peroxide solution added is 8 mL.

[0106] Comparative Example A1 The preparation steps are the same as those of Example A1, except that allyltrimethylsilane is not used.

[0107] The following Examples B1 and B2 are used to illustrate the preparation of polycarbonate compositions.

[0108] Example B1 (1) The flame retardant, polycarbonate resin and talc prepared in Example A1 are placed in a vacuum drying oven for drying, and then mixed evenly to obtain a premix; (2) Extruding the premix into granules using a twin-screw extruder, the screw speed is 100 r / min, and the temperature range of the twin-screw extruder is 230-240° C.; (3) placing the obtained pellets in a vacuum drying oven for drying; (4) Prepare the experimental specimens using an injection molding machine with a temperature range of 260-270°C.

[0109] The amounts of flame retardant, polycarbonate resin and talcum powder are shown in Table 1.

[0110] Table 1

[0111] Example B2 The preparation steps are the same as those of Example B1, and the addition amount of each substance is the same as that of B1-1, except that the flame retardant is the flame retardant prepared in Examples A1-A15 and Comparative Example A1.

[0112] Comparative Example B1 The preparation steps are the same as those of Example B1, except that the flame retardant is octaphenyl cage silsesquioxane.

[0113] Test Example 1 The polycarbonate composition prepared by the present invention is tested for its limiting oxygen index according to ASTM D2863. Sample size: 120 mm*10 mm*4 mm.

[0114] The polycarbonate compositions obtained in Examples B1, B2 and Comparative Example B1 were tested using the above method. The test results of Example B1 and Comparative Example B1 are shown in Table 2, and the test results of Example B2 are shown in Table 3.

[0115] Test Example 2 The vertical combustion performance of the polycarbonate composition prepared by the present invention is tested according to ASTM D3801-2010. Sample size: 130 mm*13 mm*3.2 mm.

[0116] The test results of Example B1 and Comparative Example B1 are shown in Table 2, and the test results of Example B2 are shown in Table 3.

[0117] Test Example 3 The polycarbonate composition prepared by the present invention is tested for impact strength according to GB / T 1843-2008 standard. Sample size: 80 mm*10 mm*4 mm.

[0118] The test results of Example B1 and Comparative Example B1 are shown in Table 2, and the test results of Example B2 are shown in Table 3.

[0119] Table 2

[0120] Wherein, t1 is the duration of the sample afterflame after the first flame impact; t2 is the duration of the sample afterflame after the second flame impact; t3 is the duration of the sample afterglow after the second flame impact.

[0121] Table 3

[0122] Wherein, t1 is the duration of the sample afterflame after the first flame impact; t2 is the duration of the sample afterflame after the second flame impact; t3 is the duration of the sample afterglow after the second flame impact.

[0123] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A composition for preparing a flame retardant, It is characterized in that The composition comprises: 1-1.5 mole parts of triazine compounds, 1.5-3.5 mole parts of mercaptosulfonate, and 1.5-3.5 mole parts of allyl silane.

2. The composition according to claim 1, in, The triazine compound is selected from one or more of cyanuric fluoride, cyanuric chloride and melamine; preferably, the triazine compound is selected from cyanuric fluoride and / or cyanuric chloride; Preferably, the mercaptosulfonate is selected from one or more of 3-mercapto-1-propanesulfonate, 2,3-dimercaptopropanesulfonate, and 2-mercaptoethanesulfonate; more preferably, the mercaptosulfonate is selected from 3-mercapto-1-propanesulfonate and / or 2,3-dimercaptopropanesulfonate; Preferably, the allylsilane is selected from allyltrimethylsilane, allyltriisopropylsilane, and allyltrimethoxysilane; more preferably, the allylsilane is selected from allyltrimethylsilane and / or allyltriisopropylsilane; Preferably, the content of the triazine compound is 1.2-1.5 parts by mole, the content of the mercaptosulfonate is 2.5-3.5 parts by mole, and the content of the allylsilane is 2.5-3.5 parts by mole.

3. A method for preparing a flame retardant, It is characterized in that The method comprises the following steps: (1) mixing a solution 1 containing a triazine compound and a solution 2 containing allylsilane, reacting them under alkaline conditions, and then concentrating them to obtain an intermediate 1; (2) mixing a solution 3 containing mercaptosulfonate with a solution 4 containing an intermediate 1 and a catalyst 1, allowing them to react, and then drying to obtain an intermediate 2; (3) The solution 5 containing the intermediate 2 is mixed with an oxidant and a catalyst 2 to react, and then concentrated and crystallized to obtain a flame retardant.

4. The method according to claim 3, in, The solvents of solution 1 and solution 2 are independently selected from one or more of acetonitrile, ethanol, and tetrahydrofuran, more preferably tetrahydrofuran; Preferably, the solvent of solution 1 is the same as that of solution 2; Preferably, the solvents of solution 3 and solution 4 are independently selected from one or more of ethanol and methanol, more preferably methanol; Preferably, the solvent of solution 3 is the same as that of solution 4; Preferably, the solvent of solution 5 is water; Preferably, in step (1), the alkaline condition is a pH value ≥ 10; Preferably, the reaction temperature of step (1) is 40-60°C, and the preferred reaction time is 45-50h; Further preferably, before heating, solution 1 and solution 2 are mixed and reacted first, preferably for 1.5-2.5 hours, and then heated to the reaction temperature; Preferably, in step (2), the catalyst 1 is azobisisobutyronitrile; Preferably, in step (2), the temperature of the mixing process is 60-80°C; Preferably, in step (3), the crystallization method comprises dropping the concentrated solution into an anti-solvent to produce crystals; Preferably, the anti-solvent is acetone; Preferably, in step (3), the oxidant is selected from one or more of sodium hypochlorite, sodium periodate, and hydrogen peroxide, more preferably hydrogen peroxide; Preferably, the reaction concentration of the oxidant is 2.73-5wt%.

5. The method according to claim 3 or 4, in, The triazine compound is used in an amount of 1-1.5 molar parts, the allylsilane is used in an amount of 1.5-3.5 molar parts, and relative to 1 molar part of the intermediate 1, the mercaptosulfonate is used in an amount of 1.5-3.5 molar parts; Preferably, the triazine compound is used in an amount of 1.2-1.5 molar parts, the mercaptosulfonate is used in an amount of 2.5-3.5 molar parts, and the allylsilane is used in an amount of 2.5-3.5 molar parts relative to 1 molar part of the intermediate 1; Preferably, the triazine compound is selected from one or more of cyanuric fluoride, cyanuric chloride and melamine; more preferably, the triazine compound is selected from cyanuric fluoride and / or cyanuric chloride; Preferably, the mercaptosulfonate is selected from one or more of 3-mercapto-1-propanesulfonate, 2,3-dimercaptopropanesulfonate, and 2-mercaptoethanesulfonate; more preferably, the mercaptosulfonate is selected from 3-mercapto-1-propanesulfonate and / or 2,3-dimercaptopropanesulfonate; Preferably, the allylsilane is selected from one or more of allyltrimethylsilane, allyltriisopropylsilane and allyltrimethoxysilane; more preferably, the allylsilane is selected from allyltrimethylsilane and / or allyltrimethoxysilane.

6. The flame retardant prepared by the method according to any one of claims 3 to 5.

7. A polycarbonate composition, It is characterized in that The polycarbonate composition contains a polycarbonate resin, a flame retardant and a layered silicate; Wherein, the flame retardant is the flame retardant according to claim 6.

8. The polycarbonate composition according to claim 7, in, Relative to 100 parts by weight of the polycarbonate resin, the content of the flame retardant is 0.1-1 parts by weight, and the content of the layered silicate is 1-5 parts by weight; Preferably, relative to 100 parts by weight of the polycarbonate resin, the content of the flame retardant is 0.5-0.7 parts by weight, and the content of the layered silicate is 2.5-4 parts by weight.

9. A method for preparing the carbonate composition according to claim 7 or 8, It is characterized in that The method comprises the following steps: The polycarbonate resin, the flame retardant and the layered silicate are mixed and pelletized to obtain the polycarbonate composition.

10. Use of the polycarbonate composition according to claim 7 or 8 in the field of flame retardant materials.

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