KR20190102680A - Method for preparing phosphor-nitrogen flame retardant - Google Patents

Abstract

The present invention relates to a method for producing a phosphorus-nitrogen flame retardant and, more specifically, to a method for producing a phosphorus-nitrogen flame retardant, which comprises the steps of: firstly performing esterification reaction of bis-cyclic phosphate and phosphorus chloride; synthesizing a bis-type flame retardant by adding a nitrogen compound to a product synthesized by four-ester esterification reaction and performing secondary amination reaction; atomizing the synthesized bis-type flame retardant; and washing the same with an aqueous solvent. The method for producing a phosphorus-nitrogen flame retardant is excellent in yield, shortens the reaction time and can significantly reduce the residual amount of chlorine.

Description

Production method of phosphorus-nitrogen flame retardant {METHOD FOR PREPARING PHOSPHOR-NITROGEN FLAME RETARDANT}

The present invention relates to a method for preparing a phosphorus-nitrogen flame retardant, and more specifically, to a phosphorus-nitrogen flame retardant for synthesizing a phosphate amide compound by a secondary amine reaction after a primary ester reaction and removing chlorine in a post-treatment process. It relates to a manufacturing method of.

Fires can cause many property and casualties. Toxic gas generated during fire is considered to be the main cause of combustion of synthetic resins used for interior and exterior materials in buildings, vehicles, furniture, etc.As a result, fire is spread quickly by giving flame resistance to synthetic resins to solve these problems. At the same time, technologies have been developed to minimize human injury by reducing the generation of toxic gases.

In general, a method of adding a flame-retardant bromine (Br) or the like or a flame retardant is added to the flame retardant of the synthetic resin during chemical production. The flame retardant added at this time is classified into halogen-based, phosphorus-based, nitrogen-based, composite-based, and inorganic-based according to the composition to be included. Many organic halogen-based compounds have been used in the conventional flame retardant, and especially when bromine-based flame retardants and antimony-based flame retardants are used together, it is known that the flame retardant effect is further improved. However, when halogen-based flame retardants are burned, they generate toxic gas, causing asphyxiation, and antimony-based flame retardants are also causing carcinogenicity. In addition, the flame retardant containing a high content of chlorine (Cl) component of the halogen element has a problem that the difference in physical properties occurs due to the difference in reaction rate when applied to a solvent-free urethane, when applied to electronic components It is difficult to apply it because there is a problem of deteriorating stability by causing a fatal problem such as a short circuit of the product due to corrosion of the PCB substrate during weather resistance measurement to confirm.

Halogen-based flame retardants have been widely used in Korea because of their excellent flame retardancy and economic efficiency.However, due to the above-mentioned problems and international concerns about the impact of the use of halogen-containing materials on the environment and stability, demand for the development of non-halogen-based flame retardants is increasing. The trend is increasing. Halogen-free products typically require a sum of bromine and chlorine (Cl) content of no greater than 1500 ppm and chlorine alone of no greater than 1000 ppm.

Non-halogen flame retardants have a lot of efforts to develop a new flame retardant with excellent flame retardant performance and economic efficiency due to the problem of significantly lower flame retardant performance or higher manufacturing cost than brominated flame retardant. Examples of such non-halogen flame retardants include phosphorus-based, nitrogen-based, silicon-based, and boron-based, and research and development on phosphorus-based flame retardants has been actively conducted. However, the organic phosphate flame retardant which is a representative phosphorus flame retardant has a problem in that the quality of the product is lowered due to volatile components when applied to a polymer product.

Phosphorus-nitrogen-based flame retardants exhibit a flame retardant effect by controlling the combustion by pyrolysis by making nitrogen gas porous by the char generated by heat operation. It is widely known as an intumescent flame retardant having excellent flame retardancy and hydrolysis resistance, and is mainly used as an additive type. The best structure to form such a foam layer is known to form the best foam layer in the carbon source: polyphosphoric acid: N ratio 1: 2: 1 structure (Perstorp, sweden).

Conventional flame retardant synthesis is purified by water washing, solvent extraction after synthesis of flame retardant compounds to remove impurities generated during the synthesis reaction, and then solidified by spray drying or vacuum drying. However, such a conventional manufacturing method has a problem of increasing the manufacturing cost, such as washing, atomization, polarization during the process, and has a problem that significantly increases the production cost in the process, such as drying, dry mill, polarization, thereby greatly reducing the product economy.

KR 1020150082359 A

An object of the present invention is to provide a method for producing a halogen-free phosphorus-nitrogen-based flame retardant that can be applied to high-strength flame-retardant polymer material, artificial leather, textile materials and electronic components to excellent flame retardancy.

In addition, it is an object of the present invention to provide a method for producing a phosphorus-nitrogen flame retardant which can reduce the reaction time, improve the yield by using a catalyst, and can control the particle size by a simplified synthesis process.

It is another object of the present invention to provide a phosphorus-nitrogen flame retardant prepared by the above production method.

Another object of the present invention is to provide a polymer material, artificial leather, textile material or electronic component having excellent flame retardancy by being processed with the phosphorus-nitrogen flame retardant.

According to an aspect of the present invention, a first step of reacting by adding a bis-cyclic phosphate, phosphorus chloride (POCl ₃ ) and a catalyst to a hydrophilic solvent; Adding a nitrogen compound and reacting to synthesize a bis type flame retardant; A third step of atomizing the bis type flame retardant synthesized in the second step; And a fourth step of washing the bis type flame retardant finely divided in the third step with a water-soluble solvent.

In addition, the bicyclic phosphate may be neopentyl glycol, ethyl butyl glycol or a mixture thereof.

In addition, the catalyst may be anhydrous magnesium chloride (anhydride MgCl ₂ ) or anhydrous aluminum chloride (anhydride AlCl ₃ ).

In the first step, a biscyclic phosphate and a catalyst are first added to a hydrophilic solvent, and phosphorus oxychloride is added dropwise for 1 to 2 hours with stirring at 45 to 55 ° C., and the temperature is increased to 70 to 80 ° C. to 2 to 4 It may be carried out by aging for time.

In addition, the catalyst may be added in an amount of 0.05 to 0.2 moles based on 1 mole of the biscyclic phosphate.

In addition, the second step may be performed at 20 to 30 ℃ for 4 to 6 hours.

In addition, solvent atomization may be further performed with water or DMF (N, N-dimethylformamide) before atomizing the bis type flame retardant synthesized in the second step.

According to another aspect of the present invention, there is provided a phosphorus-nitrogen flame retardant prepared by the above production method.

According to another aspect of the invention, there is provided a two-component urethane resin comprising the phosphorus-nitrogen-based flame retardant.

In addition, an electronic component including the phosphorus-nitrogen flame retardant is provided.

According to the production method according to an aspect of the present invention, it is possible to manufacture a halogen-free phosphorus-nitrogen flame retardant excellent in flame retardancy.

In addition, the phosphorus-nitrogen-based flame retardant can be manufactured with high productivity through a simplified manufacturing process and short synthesis time.

In addition, even if chlorine is removed and applied to a solvent-free urethane or electronic components it can be produced a phosphorus-nitrogen-based flame retardant that can exhibit excellent flame resistance without loss of the application material.

1 is a result of analyzing the physical properties of the phosphorus-nitrogen-based flame retardant synthesized according to one manufacturing example,
2 is a result of analyzing the particle size distribution by solvent-substituted phosphorus-nitrogen flame retardant synthesized according to one manufacturing example,
3 is a result of analyzing the particle size distribution of the phosphorus-nitrogen flame retardant synthesized according to an embodiment of the present invention,
Figure 4 is a ¹ H-NMR analysis of the phosphorus-nitrogen flame retardant synthesized according to an embodiment of the present invention,
5 is an FT-IR analysis result of the phosphorus-nitrogen flame retardant synthesized according to an embodiment of the present invention,
6 is a result of TGA analysis of a phosphorus-nitrogen flame retardant synthesized according to an embodiment of the present invention,
7 is a result of HPLC analysis of a phosphorus-nitrogen flame retardant synthesized according to an embodiment of the present invention,
Figure 8 is a result of confirming the flame retardant performance after processing the phosphorus-nitrogen-based flame retardant synthesized in accordance with an embodiment of the present invention to the fiber material.

The present invention comprises the steps of primary esterification of bis-cyclic phosphate and phosphorus chloride; Synthesizing a bis type flame retardant by adding a nitrogen compound to the product synthesized by the esterification reaction and performing secondary amination reaction; Atomizing the synthesized bis type flame retardant; And it relates to a method for producing a phosphorus-nitrogen flame retardant comprising the step of washing with a water-soluble solvent and a phosphorus-nitrogen flame retardant prepared accordingly.

Hereinafter, the present invention will be described in detail.

According to one aspect of the present invention, a method for preparing a phosphorus-nitrogen flame retardant is provided.

The method for preparing a phosphorus-nitrogen flame retardant according to an aspect of the present invention includes a step (S1) of adding a catalyst to bis-cyclic phosphate and phosphorus chloride.

As the biscyclic phosphate, a glycol-based compound may be selected and used. The use of linear glycols and triol-type glycols can lead to the formation of low melting point compounds that cannot be used as final products, so branched to produce cyclic primary phosphate ester compounds to produce high melting point compounds. It is preferred that the glycol compound of branch type, specifically branched diol type, be selected. Preferably, neopentyl glycol, ethyl butyl glycol or a mixture thereof is selected as the biscyclic phosphate. More preferably, neopentylglycol having excellent solubility in various solvents such as alcohols, ketones, esters, and hydrophilic solvents and having excellent utility and easy reaction control may be selected. In the case of using a compound having no structural symmetry, for example, ethyl butylpentanediol, a reaction may not occur or a difficult reaction control may occur. In addition, when using an ester compound may cause a problem of lowering the content of phosphorus.

The phosphorus chloride is preferably used a compound capable of stable room temperature reaction. Preferably, phosphorus oxychloride (POCl ₃ ) having a high boiling point of 105.8 ° C. is selected.

The catalyst is added to reduce the reaction time and improve the yield. The catalyst may be at least one selected from the group consisting of metal chloride anhydride, triethanolamine, triethanolamine, ethylenediamine, pyridine, piperazine, and platinum (Pt), but is not limited thereto. It is not. Preferably, the metal chloride anhydride excellent in product yield improvement in the first reaction is selected. More preferably, aluminum chloride anhydride (AlCl ₃ anhydride) or magnesium chloride anhydride (MgCl ₂ anhydride) may be selected.

This step (S1) is carried out to produce a primary phosphate ester compound, is carried out by the esterification reaction by adding the bis cyclic phosphate, the phosphorus chloride and the catalyst to a hydrophilic solvent. Specifically, first adding and dissolving the bis cyclic phosphate and the catalyst in a hydrophilic solvent; Adding dropwise addition of the phosphorus chloride while stirring; And it may be carried out including the step of raising the temperature to mature. The bis cyclic phosphate and the catalyst are first added and dissolved in a hydrophilic solvent, which may be performed by dissolving until the solution is completely transparent, and may be performed at 50 to 70 ° C. The dropping is preferably carried out at 45 to 55 ° C. with stirring for 2 hours, preferably 1 to 2 hours. By performing the reaction as described above, it is possible to optimize the reaction to reduce side reactions and to improve the yield of the first reaction. The step of aging by raising the temperature is preferably performed for 2 to 4 hours by raising the temperature to 70 to 80 ℃. The biscyclic phosphate and the phosphorus chloride may be used in a mole ratio of 1: 0.8 to 1.2, preferably 1: 1. The bis cyclic phosphate and the catalyst may be used in a molar ratio of 1: 0.05 to 0.2. An example of the preferred chemical reaction carried out in this step (S1) is shown in Scheme 1 below.

Scheme 1

The hydrophilic solvent may be selected in consideration of the physical properties of the bis cyclic phosphate, ease of reflux, reaction yield and the application target of the flame retardant prepared. For example, at least one selected from the group consisting of 1,4-dioxane, THF, MEK, DMF, acetone and IPA can be used. Preferably, 1,4-dioxane or DMF rather than a low boiling point solvent is used in consideration of boiling point to facilitate solvent reflux during the reaction.

The method for preparing a phosphorus-nitrogen-based flame retardant according to an aspect of the present invention includes a step (S2) of adding a nitrogen compound to the product synthesized through the first reaction to perform a second reaction.

The nitrogen compound is added to provide a nitrogen component to the flame retardant to be synthesized. The nitrogen compound is a structure for bridging the primary phosphate ester compound, and may be selected in consideration of cost and flame retardancy. For example, ethylenediamine or piperazine may be used, but is not limited thereto. Preferably, ethylenediamine having an ideal symmetry among diamines containing nitrogen is used.

This step (S2) is carried out to synthesize a phosphate-based flame retardant compound by the amine reaction connecting the reaction product synthesized in the first step, the first step to the diamine. A bis type flame retardant is synthesized by adding and reacting the nitrogen compound to the reaction product synthesized in the first reaction. The nitrogen compound may be adjusted in consideration of the number of moles of the reaction product and the reaction product produced in the previous step, preferably 1: 0.8 to 1.2, preferably 1: based on the bis cyclic phosphate reacted in the previous step. It can be used with a mole ratio of 1. This step (S2) can be carried out at 20 to 30 ℃ for 4 to 6 hours. An example of the preferred chemical reaction carried out in this step (S2) is shown in Scheme 2 below.

Scheme 2

Hydrochloric acid (HCl) gas generated during the first and second reactions can be collected and removed using at least one selected from the group consisting of nitrogen (N2) gas, potassium hydroxide (KOH) and sodium hydroxide (NaOH). have. For example, neutralization may be performed by continuing to add sodium hydroxide using an acid wash bottle throughout the reaction.

If necessary, the method for preparing a phosphorus-nitrogen-based flame retardant according to an aspect of the present invention comprises the steps of solvent-substituted with water or DMF (N, N-dimethylformamide) in the flame retardant synthesized through the first and second reactions before atomization It may further include (S3).

This step (S3) can be carried out to improve the conventional flame retardant slurry solidification method that is economically lowered by reducing the number of manufacturing process steps and to control the particle size of the flame retardant produced. By solidifying the flame retardant slurry using a solvent replacement method which proceeds in the direction of washing, atomizing, harmfulness and risk, it is possible to improve the stability and economics in the production of flame retardants. In the case of applying the solvent replacement method, the flame retardant solidification method may first perform purification and atomization, and finally solidification may be performed using spray drying or the like.

This step (S3) is prepared by preparing a concentrated flame retardant slurry by concentrating the flame retardant slurry synthesized through the first and second reactions with a concentrator, and adding the micelle auxiliary to water or DMF solvent to the concentrated solution By dispersing the prepared flame retardant slurry. The micelle adjuvant added to the mixed solution may be a dispersant or a surfactant. In preparing the mixed solution, the micelle adjuvant may be used in an amount of 1 to 3% (w / w). The concentrated flame retardant slurry may be 30 to 60% (w / w), but is not limited thereto. The concentrated flame retardant slurry is preferably used after slowly cooling to room temperature. The room temperature is 15 to 25 ℃ in the usual sense.

The method for preparing a phosphorus-nitrogen-based flame retardant according to an aspect of the present invention includes a step (S4) of atomizing the flame retardant synthesized through the first and second reactions.

This step (S4) is carried out to control the particle size of the flame retardant to be manufactured to nanonization, it is preferable to be carried out by a wet milling method in order to reduce the manufacturing cost and simplify the process. The wet milling may be performed by a known method, for example, atomization of the flame retardant slurry may be performed using a ball mill.

The method for preparing a phosphorus-nitrogen-based flame retardant according to an aspect of the present invention includes washing the atomized flame retardant with a water-soluble solvent (S5).

This step (S5) is carried out to remove residual chlorine (Cl), it can be carried out by adding a water-soluble solvent to the atomized flame retardant slurry in the previous step (S4) and dispersion washing. The dispersion washing may be performed by controlling the number of times in consideration of the residual chlorine removal rate and process productivity, and may be performed 3 to 5 times.

If necessary, solidification of the washed flame retardant slurry can be carried out. The solidification may be carried out using a known method, for example, it may be carried out by spray drying, atmospheric pressure drying or reduced pressure drying. Preferably carried out by spray drying.

The production method according to an aspect of the present invention can shorten the reaction time for the synthesis of flame retardants, and by grinding the synthesized flame retardant slurry to have a particle size of 1 ㎛ or less and wash with an aqueous solvent to remove the residual chlorine concentration to 50 ppm or less have.

Phosphorus-nitrogen flame retardant prepared by the manufacturing method according to an aspect of the present invention is a bis (bis) compound containing at least 17% P, N 13% or more, and has a N-P complex structure of the formula (1).

The flame retardant of Chemical Formula 1 is a structure capable of imparting flame retardancy by forming a foam layer (intumescent) by the best thermal decomposition of the phosphorus-nitrogen-based flame retardant by using a small amount. In order to form an intumescent layer, it is most advantageous to have a carbon source, polyphosphoric acid, and a blowing agent in one body. As mentioned above, the phosphorus-nitrogen-based flame retardant is thermally decomposed so that Neopentyl glycol serves as a carbon source, PO ₂ polyphosphoric acid ( Condensation reaction), N foaming agent. In addition, in the phosphorus-nitrogen flame retardant structure, it can be seen that the polyhydric alcohol 2, N 2, PO ₂ 4.2 structure is very close to the ideal structure for forming the intumescent (intumescent) structure.

The flame retardant prepared according to the method of the present invention has an average particle size of 300 to 500 nm, and has excellent flame retardancy as a halogen-free flame retardant from which chlorine is removed. Since the residual chlorine concentration is 50ppm or less, even if it is applied to electronic parts without affecting urethane reactivity, it does not cause corrosion problems due to chlorine, and thus, it may be applied to reactive urethane resins and electronic parts.

The flame retardant prepared according to the method of the present invention may be applied to the product in the form of a dry powder or applied to the product in the form of a slurry dispersed in a solvent without drying. For example, it may be applied in the form of dry powder to the production of environmentally friendly solvent-free adhesives, polymer products or flame retardant yarn. When applied in the form of a slurry, it may be applied to the solvent type (DMF) or aqueous type products, depending on the dispersion solvent, and may be applied to artificial leather, textile products or furniture.

Hereinafter, the present invention will be described in more detail with reference to the following Examples and Comparative Examples in order to help the understanding of the present invention. However, these examples are merely illustrative of the present invention and are not intended to limit the appended claims, it will be apparent to those skilled in the art that various changes and modifications to the embodiments are possible within the scope and spirit of the present invention. Naturally, such modifications and variations fall within the scope of the appended claims.

Example

Catalytic Reaction Design to Improve First Reaction Yield

In the one-step ester reaction, experiments were conducted to confirm the reaction and yield of glycol and phosphorus oxychloride by the catalyst. In 1000 ml four-neck top-down reactor equipped with a reflux condenser, thermometer, stirrer, and pressure equalization funnel, add 208.4 g (2 mol) of neopentyl glycol and 1,4-dioxane 73 g and heat the reaction to 50 ° C. After complete dissolution until, the catalyst was added. 307 g (2 mol) of phosphorus oxychloride was dropped over 1 hour through a pressure equilibration dropping funnel with stirring at a temperature of 70-80 ° C. in the separation reactor. After dropping, the temperature was raised to 80 ° C. for 2 hours, and HCl was recovered using an acid wash bottle in the reaction. To select a catalyst for the first reaction, synthesis was performed using AlCl ₃ anhydride, MgCl ₂ anhydride, and platinum (Pt) as catalysts, respectively, and the type of catalyst used, the amount of catalyst used, and the reaction results thereof are shown in Table 1 below. Indicated. In the following Table 1, the yield result shows the result of measuring the non-volatile content of water after drying the liquid and washing twice with water after the additional reaction. All reagents performed in the experiment were purchased from DAEJUNG CHEMICALS.

No. POCl ₃
(mole) Neopentyl
glycol
(mole) catalyst Drip time
(70 ℃) menstruum yield
(%) B 2 2 - 1hr 1,4-dioxane 27.3 A-1 2 2 0.05 1hr 1,4-dioxane 44.1 A-2 2 2 0.1 1hr 1,4-dioxane 50.1 A-3 2 2 0.2 1hr 1,4-dioxane 73.2 M-1 2 2 0.05 1hr 1,4-dioxane 42.1 M-2 2 2 0.1 1hr 1,4-dioxane 60.1 M-3 2 2 0.2 1hr 1,4-dioxane 75.1 P-1 2 2 0.05 1hr 1,4-dioxane 38.1 P-2 2 2 0.1 1hr 1,4-dioxane 49.1 P-3 2 2 0.2 1hr 1,4-dioxane 58.2

* B: Blank, A: AlCl ₃ Anhydrous, M: MgCl ₂ Anhydrous, P: Pt catalyst

Looking at Table 1, when the catalyst is not used (B) it can be seen that the reaction rate is very slow, the results when the reaction using the AlCl ₃ anhydride and MgCl ₂ anhydride as a catalyst is confirmed to be excellent. In addition, it can be seen that the reaction progress occurs differently even with the same catalyst depending on the amount of the catalyst used.

Experiment for selecting optimal solvent

An experiment was conducted to evaluate the efficiency performance of the synthesis of phosphorus-nitrogen flame retardant using a representative hydrophilic solvent. In 1000 ml of a four-neck upper and lower separation reactor equipped with a reflux condenser, thermometer, stirrer, and pressure equilibration funnel, 208.4 g (2 mol) of neopentyl glycol, 100 ml of solvent, and a catalyst were dissolved at 50 ° C, and then the temperature of the separation reactor was 70-80 ° C. Under stirring, 307 g (2 mol) of phosphorus oxychloride was dropped over 1 hour through a pressure equilibration dropping funnel. After dropping, the temperature was raised to 80 ° C. for 2 hours, and the reaction was carried out by recovering HCl using an acid wash bottle in the reaction and refluxing the solvent with a reflux condenser. The solvent was carried out under different conditions as shown in Table 2.

No. POCl ₃
(mole) Neopentyl glycol (mole) catalyst
(MgCl ₂ ) Drip time
(70 ℃) menstruum yield
(%) S-1 2 2 0.2 1hr 1,4-dioxane 75.4 S-2 2 2 0.2 1hr THF 68 S-3 2 2 0.2 1hr MEK 72.5 S-4 2 2 0.2 1hr DMF 78

Yield results showed no problems in reaction rate or product formation by hydrophilic solvents, but reflux was not easy when low boiling point solvents such as Acetone, THF, and MEK were used.

The boiling point of 1,4-Dioxane is similar to water, so it is easy to wash with water and solvent replacement, which has the advantage of reducing the risk of accidents caused by organic solvents during drying. In addition, since water is easily applied to the nano-sol synthesis or nanomaterial dispersion used for the application of composite flame retardant, it seems to be easy to use, and since the solvent applied to the impregnation process of artificial leather is DMF, it is nano-composite Since it is considered to be easy to prepare the composite phosphate amide flame retardant slurry, it is easy to replace the solvent by the difference of 1,4-dioxane and the non-point difference. Therefore, 1,4-dioxane is selected as the optimal solvent for the flame retardant synthesis process. It became.

<Selection of optimum synthesis condition for phosphorus-nitrogen flame retardant>

After dissolving neopentyl glycol 208.4g (2mol), 1,4-dioxane 73g and catalyst in 1000 ml of four-neck upper and lower reactor equipped with a reflux condenser, thermometer, stirrer, and pressure equilibration funnel, the catalyst was completely dissolved at a temperature of 50 to 70 ° C. 307 g (2 mol) of phosphorus oxychloride was slowly added dropwise through a pressure equilibration dropping funnel under stirring at a temperature of 45-55 ° C. After dropping, the temperature was raised to 80 ° C. to evaluate the reactivity according to the additional reaction time. Throughout the reaction, HCl was recovered using an pickling bottle and the solvent was refluxed with a reflux condenser to proceed with the reaction. At this time, the recovery of HCl was easily performed by using a pressure reduction device using water. As a result of reaction product analysis, the dropping time was adjusted to 2 hours, the reaction temperature was lowered by 10 ° C., and the recovery of HCl was facilitated using an aspirator. One-step reaction conditions and results are shown in Table 3 below.

No. POCl ₃
(mole) Neopentyl
glycol
(mole) EthylButyl pentane
diol
(mole) catalyst
(MgCl ₂ ) Drip time
(45-55 ℃) menstruum Reaction time yield APT07 2 2 - 0.2 2hr 1,4-dioxane 2hr 88% APT07-1 2 - 2 0.2 2hr 1,4-dioxane 2hr 60%

Next, a two step reaction was carried out on the one step product. After the amount of HCl generated in the washing bottle was not visible, EDA was added over about 2 hours, and the reaction was continued for 4 hours after the temperature was raised. The reaction proceeded to the point where no HCl was detected, and the results are shown in Table 4 below. In the case of pickling, it was neutralized by continuously adding 24% (w / v) NaOH to the washing bottle.

No. Primary product Drip time
(30 ℃) menstruum Reaction time yield APT07 421 g 2hr 1,4-dioxane 4hr 72.5% APT07-1 370 g 3hr 1,4-dioxane 4hr 53%

After filtering the sample obtained in step 2 with a filter, a water washing step of stirring for 30 minutes at a solid content: water = 1: 1 ratio and filtration was performed at least 7 times, and dried at 120 ℃ for 1 hour after the final filtration to 189g flame retardant composite Obtained.

The reaction for the synthesis of phosphorus-nitrogen compounds was divided into 1st and 2nd phases, and sufficient time and temperature conditions were changed for each step, and OH-peak using FT-IR was measured in the reaction slurry state for each step. Synthesis was performed to minimize errors occurring during the drying process. Physical properties of the synthesized flame retardant were evaluated using IR (Thermo scientific iD5), DSC (Scinco DSC N-650), NMR, TGA and ICP and the results are shown in Table 5 and FIG. 1. The limiting oxygen index (LOI) index was evaluated according to JIS-K-7210, and when evaluated, the LOI was measured three times in the form of a film by adding a flame retardant (APT07) synthesized to an existing adhesive layer resin to a 20% weight ratio. Notation. Hydrolyzability was measured by flame retardant and exposed to 121 ℃ / 0.2MPa, 100% RH, 96 hr condition and dispersed in water for 10 minutes, filtered by 0.1 μm glass filter under reduced pressure and dried Was measured. Alkaline solubility was measured by adding 10 g of flame retardant prepared in 100 ml of aqueous solution prepared at pH 10 using ammonia water, filtering under reduced pressure under a 0.1 μm glass filter after 10 minutes of forced stirring, and measuring the solubility (%). . The fogging test was carried out by the MS 300-54 test method after placing 2 g of the sample on the specimen. In Figure 1, (A) is FT-IR analysis results, (B) differential scanning calorimetry (DSC) analysis results, (C) thermal gravitational analysis (TGA) analysis results, (D) H-NMR analysis results .

No. Yield Hydrolysis resistance 90 ℃ Solubility alkali
Solubility LOI Index APT07 72.5% 1.72% 0.62% 0.6% 26.5 APT07-1 53% 1.28% 0.32% 0.4% 25.3

The flame retardant having a melting point of 270 ~ 280 ℃ according to the product design by the manufacturing method as described above could be synthesized. From the results of evaluation of the properties of the synthesized flame retardant, impurities were not analyzed on FT-IR and DSC, and it was confirmed that about 5% of impurities appeared during NMR analysis. This was analyzed by dissolving in DMSO during the pretreatment of the analyte, and the excessive melting of impurities not present in TGA, DSC, and FT-IR. In the case of APT07-1 than APT07, the hydrophobic Alkyl group was higher, resulting in better water resistance, alkali solubility, and hydrolysis resistance. Appeared to be not high. Therefore, it was confirmed that APT07 was more excellent in mass production of the product.

Residual chlorine was detected more than 2000ppm by washing with an existing solvent or by volatilization by a decompression process, making it difficult to apply to urethane resins or electronic components, and experiments were performed to remove halogen elements by varying post-process conditions. .

Samples were prepared by performing different post-processes on the synthesized flame retardants and analyzed for the presence or absence of halogen elements. The post-process conditions were carried out in three parts of 15 hours heat treatment, 24 hours heat treatment and 5 times of general water washing (once / 30 minutes) at 120 ° C. for 1 hour heat treatment, and the results are shown in Table 6 below. Halogen containing assays were performed using Combustion-Ion Chromatography assays.

Sample name element Measurement result (mg / kg) LOQ (mg / kg) APTO7
(15 hours heat treatment) Cl 6,472 0.5 Br LOQ or less 0.5 APTO7
(24 hours heat treatment) Cl 7,030 0.5 Br LOQ or less 0.5 APTO7
(Five times of water washing, 120 degrees Celsius one hour heat treatment) Cl LOQ or less 0.5 Br LOQ or less 0.5

LOQ: Limit of quantification

Cl detected in the synthesized flame retardant was analyzed to be due to Cl of the hydrochloric acid as a synthetic by-product. Referring to Table 6, the sample that was subjected to heat treatment only did not remove Cl regardless of treatment time, and the sample was dried after washing with water. Only Cl was found not to be detected.

<Solidization of Nano-type Flame Retardant Slurries Using Solvent Substitution Method>

100 g of a 50% flame retardant slurry was prepared by concentrating the solvent in the synthesized flame retardant (APT07) using a concentrator. 100 g of a mixed solution of a surfactant mixed with DMF or water as a solvent was prepared and dispersed by adding a concentrated flame retardant slurry while stirring, and particle size and viscosity were measured. The surfactant was applied to LA-2, LA-7, LA-15, and LA-30, each having different HLB (hydrophile-Lipophile-balance), and the results of the substitution using DMF as the solvent are shown in Table 7. And the result of having substituted with water as a solvent were shown in Table 8. Viscosity was measured by Brookfield RVT 4 # 20rpm conditions, particle size was measured by Particle size Analyzer (Marvern, USA).

ITEM LA-2 (HLB: 6.2) LA-7 (HLB: 12.3) LA-15 (HLB: 15.4) LA-30 (HLB: 17.6) Granularity More than 200㎛ More than 150㎛ 200 μm More than 200㎛ Viscosity
(cps) 2000 1500 1800 1200

ITEM LA-2 (HLB: 6.2) LA-7 (HLB: 12.3) LA-15 (HLB: 15.4) LA-30 (HLB: 17.6) Granularity More than 150㎛ More than 200㎛ 200 μm More than 300㎛ Viscosity
(cps) 1200 1000 1120 900

When the primary dispersant was added, it was helpful for dispersibility but not effective in controlling particle size and viscosity. Secondly, BYK (Germany) dispersant, which is a polymeric dispersant, was added. BYK A (102), BYK B (182) was used to proceed to the solvent type, aqueous and amphoteric and the results are shown in Table 9 below. In addition, in order to confirm the difference in particle size distribution according to the presence or absence of a dispersant during the solvent replacement, experiments were performed by using water as a solvent and varying the application of BYK B, and the results are shown in FIG. 2. In FIG. 2, (A) is a flame retardant having a solvent-substituted dispersant without applying a dispersant, and a D50 value is 150 µm, and (B) is a flame retardant having been solvent-substituted by applying BYK B as a dispersant, and a D50 value is 9 µm.

ITEM BYK A (DMF) BYK B (DMF) BYK A (Water) BYK B (Water) Granularity 10 μm 15 μm 12㎛ 9㎛ Viscosity 300 200 250 300 Slurry concentration 55% 60% 35% 33%

Referring to Table 9 and Figure 2, the average particle size after the solvent replacement was found to be significantly reduced compared to the unused case when using a dispersant. Through this, it is possible to confirm the applicability of the particle size management at the same time as the solvent replacement by the addition of the micelle supplement.

<Wet milling for nano type flame retardant slurry>

Solvent replacement alone has a limitation in controlling the particle size, and after solvent replacement, atomization of the flame retardant slurry using a ball mill was performed. The slurry was prepared by applying solvent dispensing process using water to which BYK B was applied as a dispersant. After applying the solvent substituting process, a ball mill (0.5 μm of zirconia beads) was processed for 24 hours to prepare a nano-type flame retardant slurry. . The atomized flame retardant slurry was solidified by spray dry after three to five dispersion washings with water. After wet milling, the particle size of the nano-type flame retardant slurry was analyzed by a particle size analyzer (NanoPlus, USA) according to the ISO-13320 standard. The results are shown in FIG. 3, and the results of analyzing the presence or absence of a halogen compound are shown in Table 10 below. As a result of FIG. 3, the particle size (mean size) was analyzed to be 322.2 nm.

element Measurement result (mg / kg) L.O.Q. (mg / kg) Cl L.O.Q. Below 0.5 Br L.O.Q. Below 0.5 S L.O.Q. Below 0.5

Referring to FIG. 3, the particle size analysis result shows that the particle size (mean size) is analyzed as 322.2 nm and nanoparticles are formed in the particle size. Also, in Table 10, all of the halogen elements are L.O.Q. Measured below, it can be confirmed that Cl has been removed.

<Structure and Physical Property Analysis of Synthetic Flame Retardant Post-Processing Conditions>

¹ H-NMR and FT-IR analysis of the structure of each compound was carried out for the flame retardant synthesized by performing the two-step reaction, the flame retardant which was further washed with water through the solvent replacement and milling, and the recrystallization using methanol. It was confirmed through and the results are shown in Figures 4 and 5. In addition, to confirm the physical properties of the flame retardant TGA analysis was confirmed the heat resistance and the results are shown in FIG. In addition, HPLC (ACHE 9000, Yeonglin Instruments) analysis was performed for purity analysis of the flame retardant and the results are shown in FIG. HPLC conditions were performed using a flow rate of 0.5 ml / min, an injection amount of 80 µl, a concentration of 100 ppm, a C18 reverse phase column as a fixed phase, and the developing solution was methanol: water = 40: 60. 4 to 7, (A) is a flame retardant immediately after synthesis (APT07), (B) is a solvent-substituted and milled flame retardant, (C) is a flame retardant further recrystallized with methanol for (B) it means.

4 to 7, it can be seen that impurities are removed through purification by solvent substitution, milling and methanol recrystallization, and the purity of the flame retardant is gradually increased. Looking at Figure 6, it can be seen that the heat resistance of the flame retardant is also improved with increasing purity. Referring to FIG. 7, the flame retardant immediately after synthesis can identify a broad impurity peak after a main peak of 3 minutes of retention time, but the impurity peak decreases considerably after a subsequent post-process. Solvent replacement and wet milling post-processing to the synthesized flame retardant to control the average particle size can be atomized, it can be confirmed that improve the purity and reduce Cl.

<Checking Flame Retardant Performance of Synthetic Flame Retardants>

After the synthesis, the wet milling and flushing flame retardant was applied to the fiber material to measure the flame retardant performance. The fabric materials used were cotton (ISO ADJ COTTON, Testfabrics standard white), nylon (ISO ADJ POLYAMIDE, Testfabrics standard white) and polyester (Polyester Adjacent Fabric, SDC Enterprises Limited standard white). 3, 5 and 7% ows respectively Treated with. A flame retardant and polyurethane binder 2PGN-pi were used in a ratio of 1: 1, padded at a pressure of 0.4 MPa and a speed of 7 and dried at 180 ° C. for 2 minutes to process. The pick-up amount of the flame retardant for each fiber material is shown in Table 11 below.

Flame retardant concentration Pick-up (%) Cotton Nylon Polyester 3% ows 91.13 87.12 80.61 5% ows 94.40 112.89 85.40 7% ows 90.91 98.16 85.39

After the synthesis was applied to the wet milling and water-treated flame retardant was applied to the fiber material to measure the flame retardant performance is shown in Figure 8 the results. The flame retardant test for each flame retarded fiber was carried out by MS 300-08, horizontal method.

Looking at Figure 8, it can be seen that the flame retardant of the flame retardant when applied to the fiber material is excellent. When applied to polyester fiber material, even when the flame retardant was treated with a small content of 3% o.w.s., the flame retardant performance was excellent.

Claims (10)

A first step of reacting by adding a bis-cyclic phosphate, phosphorus oxychloride (POCl ₃ ), and a catalyst to a hydrophilic solvent;
Adding a nitrogen compound and reacting to synthesize a bis type flame retardant;
A third step of atomizing the bis type flame retardant synthesized in the second step; And
A method for producing a phosphorus-nitrogen flame retardant comprising a fourth step of washing the bismuth flame retardant atomized in the third step with a water-soluble solvent.
The method of claim 1,
The bis cyclic phosphate is neopentyl glycol, ethyl butyl glycol or a mixture thereof, characterized in that the production method of the phosphorus-nitrogen flame retardant.
The method of claim 1,
The catalyst is an anhydrous magnesium chloride (anhydride MgCl ₂ ) or anhydrous aluminum chloride (anhydride AlCl ₃ ) characterized in that the method for producing a phosphorus-nitrogen flame retardant.
The method of claim 1,
In the first step, a biscyclic phosphate and a catalyst are first added to a hydrophilic solvent, and phosphorus oxychloride is added dropwise for 1 to 2 hours with stirring at 45 to 55 ° C, and the temperature is raised to 70 to 80 ° C for 2 to 4 hours. Process for producing a phosphorus-nitrogen-based flame retardant, characterized in that carried out by aging.
The method of claim 1,
The catalyst is a method for producing a phosphorus-nitrogen-based flame retardant, characterized in that added in an amount of 0.05 to 0.2 moles based on 1 mole of the bis cyclic phosphate.
The method of claim 1,
The second step is a method for producing a phosphorus-nitrogen flame retardant, characterized in that carried out for 4 to 6 hours at 20 to 30 ℃.
The method of claim 1,
The method of preparing a phosphorus-nitrogen flame retardant, characterized in that further performing a solvent-substituted with water or DMF (N, N-dimethylformamide) before atomizing the bis type flame retardant synthesized in the second step.
A phosphorus-nitrogen flame retardant prepared by the method according to any one of claims 1 to 7.
A two-component urethane resin comprising the phosphorus-nitrogen flame retardant of claim 8.
An electronic component comprising the phosphorus-nitrogen flame retardant of claim 8.

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