CN107459673A - A kind of synthetic method of the fire-retardant carbon forming agent of ethylenediamine phosphorus borate - Google Patents

Abstract

A kind of synthetic method of ethylenediamine phosphorus borate, is related to a kind of fire retardant and preparation method thereof, and this method is Ethylene diamine phosphate and boric acid Hybrid Heating solid phase reaction, you can obtains fire retardant.Obtained fire retardant is phosphorous, three kinds of boron, nitrogen ignition-proof elements, and good into carbon, flame retardant effect is notable, and the boron element contained may also function as suppression cigarette effect, can be used for the carbon forming agent of TPO flame-retardant formulations, can also be used alone as fire retardant to use.Preparation method is simple, and three wastes produce, environmental protection.

Description

A kind of synthetic method of ethylenediamine phosphate borate flame retardant carbon forming agent

technical field

The invention belongs to the field of chemistry, and in particular relates to the application and synthesis method of an ethylenediamine phosphate borate flame retardant carbon forming agent.

Background technique

Intumescent flame retardants are usually composed of inorganic acid source, carbon source (also known as carbon forming agent) and gas source (also known as blowing agent). In commercially available products, there is a lack of a single substance with the above three functions at the same time, so the addition of flame retardants can only be increased to ensure better mixing between the various components in order to meet the flame retardant requirements. In addition, for different polymer materials, it is also necessary to adjust the composition and ratio of acid source, carbon source and gas source, so as to meet the different flame retardant requirements of different materials. Considering the heat resistance of the polymer and the flame retardant itself, it is usually impossible to fully mix the components of the flame retardant through long-term melt mixing during processing. Commercially available products that can maintain high temperature stability for a long time are not very common. For example, melamine polyphosphate (MPP) and dipentaerythritol with high decomposition temperature can provide better flame retardancy protection, but need to add more High dosage.

In recent years, some phosphates of organic amines, such as piperazine phosphate, piperazine pyrophosphate, and ethylenediamine phosphate (EDAP), have attracted the attention of researchers, mainly because of the simplicity and low cost of the manufacturing process. For example, the piperazine pyrophosphate developed by Adeka in Japan can be used in conjunction with melamine pyrophosphate and used in polyolefin flame retardancy. It only needs 25-30% addition to reach the V-0 standard. It overcomes the disadvantage of poor water resistance of the ammonium polyphosphate system. However, in terms of the current manufacturing process, the synthesis of piperazine pyrophosphate is complicated and the yield is low. Korea Douben Co., Ltd. disclosed a series of phosphate double salts in Chinese patent ^{201180067852.7} to reduce costs and simplify the manufacturing process. Salt. Ethylenediamine phosphate (EDAP) is an inexpensive and readily available flame retardant with excellent expansion properties. However, due to the two disadvantages of poor heat resistance and poor water resistance, the application of EDAP in polyolefins is limited. US0109514 reported that sodium pyrophosphate solution and ethylenediamine salt were used for metathesis reaction to obtain ethylenediamine pyrophosphate. US2002038855 and CN 1599772 reported that the compound obtained from imines such as ethylenediamine and diethylenetriamine with paraformaldehyde and polyphosphoric acid in water has good heat resistance, and there will be no obvious heat resistance when heated at 250 degrees for 10 minutes. The quality is reduced, but the problem of water solubility is still prominent. Similar to the idea of metal ion piperazine phosphate double salt, "Plastic Additives" 2013pp26, CN201310588575.5 reported ethylenediamine phosphate zinc double salt flame retardant for polyolefin flame retardancy.

Phosphorus borate has attracted the attention of researchers in the field of flame retardant in recent years. Zhao Aiming and others reported the synthesis of melamine phosphate borate flame retardant. CN 102482452A discloses the use of borophosphates, borophosphates and metal borophosphates as flame retardant additives for plastics. Bastian Ewald et al. systematically reviewed the structural chemistry of borophosphates and metal borophosphates in journal articles, but there is no systematic report on the research on the compounds suitable for use as flame retardants among hundreds of borophosphates.

Contents of the invention

The object of the present invention is to provide a kind of synthetic method and application of ethylenediamine phosphate borate flame retardant carbon forming agent. The ethylenediamine phosphonium borate flame retardant carbon forming agent prepared by this method solves the shortcomings of the traditional carbon forming agent EDAP that it is not resistant to water and high temperature by introducing borate bridged phosphate, and overcomes the shortcomings of the flame retardant in the polymer. Easy to migrate, easy to precipitate during processing, and has excellent durability. The preparation method is simple, the conditions are easy to realize, there is no three wastes, and it is environment-friendly.

The present invention is achieved through the following technical solutions:

A kind of ethylenediamine phosphorus borate flame retardant carbon forming agent is characterized in that, the chemical formula of this flame retardant carbon forming agent is:

[NH ₃ CH ₂ CH ₂ NH ₃ ] ₂ [B ₂ P ₄ O ₁₅ ], where NH ₃ CH ₂ CH ₂ NH ₃ is the protonated ion of ethylenediamine; as mentioned above, phosphoborate is a large The composition and structure of polyacids are very complex. B ₂ P ₄ O ₁₅ ^4- is also one of them. In fact, the acid group is a polyanion.

A method for synthesizing an ethylenediamine phosphate borate flame retardant carbon forming agent, the method comprising the following steps: uniformly mixing ethylenediamine phosphate borate EDAP, boric acid and silicone oil, and performing a solid phase reaction at 150-270°C for 1- After 6 hours, the flame retardant carbon forming agent was obtained after discharging;

The ethylenediamine phosphate EDAP can be prepared by using commercially available EDAP, or by neutralizing phosphoric acid and ethylenediamine in water or an organic solvent.

The synthetic method of described a kind of ethylenediamine phosphate borate flame retardant carbon forming agent, the molar ratio of ethylenediamine phosphate EDAP and boric acid is 1:0.8-1:1.3; The mass of silicone oil and ethylenediamine phosphate 0.2-5%. Among them, the solid phase reactor can be Henschel mixer, rake dryer, double cone dryer, hot air drying oven, vacuum drying oven, kneader, screw extruder, internal mixer; The phase reacts for 1-6 hours, and the flame retardant carbon forming agent can be obtained after discharging.

Preferably, the molar ratio of ethylenediamine phosphate EDAP to boric acid is 1:0.93-1:1.1;

Preferably, the mass ratio of silicone oil to ethylenediamine phosphate is 0.5-2.5%;

Preferably, the solid-phase reaction device is a rake dryer, a kneader and an internal mixer; wherein the temperature of the solid-phase reaction is preferably 180-220°C.

The present invention has the following advantages:

(1) Raw materials are readily available. The raw materials used in the invention are all commercially available products with a wide range of sources.

(2) The production process is simple and environmentally friendly. The target product can be obtained by simply mixing and then heating; only a small amount of water is generated during the production process.

(3) The thermal stability of the product is good and the carbon residue rate is high. The 5% decomposition temperature of the sample is 332°C, the temperature at the maximum decomposition rate is 410°C, and the carbon residue rate at 800°C is 53%. High decomposition temperature enables it to be used in most polymer resins.

Description of drawings

The influence of reaction temperature on the product phase in Fig. 1 embodiment 1.

The thermal stability curve of Fig. 2 embodiment 5 products.

detailed description

Below in conjunction with embodiment the present invention is described in detail:

Example 1

Take 1.28Kg of commercially available EDAP (ethylenediamine phosphate), place it in a 5L kneader with 310g of boric acid, stir and mix at room temperature for 30min, add 15g of methylphenyl silicone oil and continue stirring for 30min, raise the temperature to 190°C for 3hr, and unload , to obtain flame retardant products.

In order to further study the influence of reaction temperature, the formation of products at different reaction temperatures were studied, and the phases of products were tracked by X-ray powder diffraction technology. It was found that when the reaction temperature exceeded 190°C, the target product was obtained (Fig. 1). Taking the reaction product at 210°C for thermal stability study, it was found that the 5% decomposition temperature was 332°C, the temperature at the maximum decomposition rate was 410°C, and the carbon residue rate was 53% at 800°C.

Example 2

Take 1.28Kg of commercially available EDAP, place it in a 5L kneader with 310g of boric acid, stir and mix at room temperature for 30 minutes, add 15g of methylphenyl silicone oil and continue to stir for 30 minutes, feed in nitrogen, raise the temperature to 190°C for 3 hours, discharge the material, and obtain the resistance fuel products.

Example 3

EDAP is prepared according to the following steps: add 10L acetic acid to a reaction kettle with a mechanical stirrer, cooling device and condensing reflux device, then slowly introduce 2.6Kg of 85% phosphoric acid, stir at room temperature for 1 hour, and cool to 0°C. Take 600g of ethylenediamine and dissolve it in 2.5L of methanol. The methanol solution of ethylenediamine was slowly dropped into the acetic acid solution of phosphoric acid, and a large amount of precipitation was obtained immediately. Keep the reaction temperature not exceeding 10°C. After the methanol solution of ethylenediamine was dropped, the reaction was stirred for 3 hours, filtered, and the precipitate was washed with methanol. Dry at 80°C for 12 hours. EDAP product yield 92%.

Take 1.22Kg of self-made EDAP, put it in a rake dryer with 330g of boric acid, stir and mix at room temperature for 30min, add 20g of methylphenyl silicone oil and continue stirring for 30min, raise the temperature to 180°C for 2hr, unload to obtain a flame retardant product.

Example 4

Take 1.30Kg of EDAP, 300g of boric acid, and 20g of methyl phenyl silicone oil, mix them well in a high-mixer, then place them in a hot air drying oven, stir and mix them at room temperature for 30 minutes, then raise the temperature to 230°C for 4 hours, and discharge the materials to obtain the resistance fuel products.

Example 5

Take 1.25Kg of homemade EDAP (the method is the same as in Example 2), place it in an internal mixer with 310g of boric acid, stir and mix at room temperature for 30min, add 40g of methylphenyl silicone oil and continue stirring for 30min, heat up to 210°C for 3hr, and unload , to obtain flame retardant products.

Flame retardant performance test: Taking the PP system as an example, according to the general processing method, the flame retardant performance of the samples of formula 1-4 was tested respectively, and the results are shown in the following table:

Although the embodiment of the present invention has been disclosed as above, it is not limited to the use listed in the specification and implementation, it can be applied to various fields suitable for the present invention, and it can be easily understood by those skilled in the art Therefore, the invention is not limited to the specific details and examples shown and described herein without departing from the general concept defined by the claims and their equivalents.

Claims (7)

1. a kind of ethylenediamine phosphorus borate compound, it is characterised in that the compound is used for fire-retardant carbon forming agent, the fire-retardant carbon forming agent Chemical formula be：[NH₃CH₂CH₂NH₃]₂[B₂P₄O₁₅], NH in formula₃CH₂CH₂NH₃For the ion of ethylenediamine protonation.

2. the synthetic method of a kind of fire-retardant carbon forming agent of ethylenediamine phosphorus borate according to claim 1, it is characterised in that should Method comprises the following steps：

(1) Ethylene diamine phosphate EDAP, boric acid and silicone oil are well mixed；

(2) it is heated to 150-270 DEG C, keeping temperature, solid phase reaction 1-6 hours；

(3) discharging obtains the fire-retardant carbon forming agent.

A kind of 3. synthetic method of fire-retardant carbon forming agent of ethylenediamine phosphorus borate according to claim 2, it is characterised in that second The mol ratio of two amine phosphate EDAP and boric acid is 1:0.8-1:1.3.

A kind of 4. synthetic method of fire-retardant carbon forming agent of ethylenediamine phosphorus borate according to claim 2, it is characterised in that Gu Phase reaction device is Henschel blender, rake type dryer, double cone dryer, hot air drier, vacuum drying chamber, kneader, spiral shell One of bar extruder, banbury.

A kind of 5. synthetic method of fire-retardant carbon forming agent of ethylenediamine phosphorus borate according to claim 2, it is characterised in that Gu The temperature of phase reaction is 150-270 DEG C.

A kind of 6. synthetic method of fire-retardant carbon forming agent of ethylenediamine phosphorus borate according to claim 2, it is characterised in that institute The silicone oil used is methyl phenyl silicone oil, and the mass ratio of silicone oil and Ethylene diamine phosphate is 0.2-5%.

A kind of 7. synthetic method of fire-retardant carbon forming agent of ethylenediamine phosphorus borate according to claim 3-6, it is characterised in that The mol ratio of Ethylene diamine phosphate EDAP and boric acid is 1:0.93-1:1.1；Solid phase reaction device is rake type dryer, kneader And screw extruder；The temperature of solid phase reaction is 180-220 DEG C；The mass ratio of silicone oil and Ethylene diamine phosphate is 0.5-2.5%.