KR102049441B1 - Flame retardant and method for manufacturing the same - Google Patents

Abstract

상기 화학식 (1)에서, n 은 0 이상 100 이하인 정수이다.The present invention relates to a flame retardant and a method for producing the flame retardant. The flame retardant is a compound represented by the following general formula (1). The method for preparing a flame retardant includes: a mixing step of preparing phosphate-urea mixture by adding urea to phosphoric acid, a synthesis step of heating the phosphoric acid-urea mixture to produce a phosphorus-based flame retardant, and a granulation of crushing and pulverizing the phosphorus-based flame retardant Steps.
<Formula (1)>

In the said General formula (1), n is an integer of 0 or more and 100 or less.

Description

Flame retardant and manufacturing method thereof {FLAME RETARDANT AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a flame retardant and a method for producing the same.

Flame retardants are additives added to improve the flame resistance of plastics. Flame retardants are used in all areas of society such as electronics, cables, wire coverings, home interior products, building materials and interior materials, polymer resin flame retardants, coating and paint additives, and transportation equipment.

The main flame retardants include metal hydrate inorganic flame retardants such as antimony oxide, magnesium hydroxide and aluminum trihydrate, halogen flame retardants containing bromine or chlorine, phosphorus flame retardants based on phosphate esters and melamine cyanurate Nitrogen-based flame retardants such as;

Depending on the method of imparting flame retardancy, it may be divided into additive type and reactive flame retardant.Additional flame retardant is added as an additive during compounding process and used as a simple mixing method.Reactive flame retardant may impart flame retardancy to the main chain of a polymer. A flame retardant polymer may be prepared by introducing a monomer capable of producing a flame retardant polymer or by introducing a reactive group into a polymer to chemically bond a flame retardant to a terminal or side chain of the polymer.

Based on the total amount of flame retardants used, inorganic flame retardants are used in the largest amount and are applied in the order of halogen flame retardants and phosphorus flame retardants. Halogen-based flame retardants have been regulated globally due to the controversy of hazards, discussions are underway to regulate them, and there is a growing need to develop new flame retardants to replace halogen-based flame retardants.

Recently, the development of suitable materials with high flame retardancy has been strongly demanded, and attention has been focused on the development of products having high flame retardancy, low harmfulness, low smoke resistance, low corrosion resistance and heat resistance, and take over eco-friendly and high performance in Korea. / Nitrogen / nano composite flame retardant development is in progress.

 The present invention seeks to provide a novel flame retardant and a method for producing the same having an environmentally friendly and high performance.

The flame retardant which concerns on this invention is a compound represented by following General formula (1).

<Formula (1)>

In the said General formula (1), n is an integer of 0 or more and 100 or less.

The method for preparing a flame retardant according to the present invention includes a mixing step of adding urea to phosphoric acid to prepare a phosphoric acid-urea mixture, a synthesis step of heating the phosphoric acid-urea mixture to prepare a phosphorus-based flame retardant, and particles to crush and grind the phosphorus-based flame retardant. Includes anger step.

The invention can provide flame retardant with environmentally friendly and high performance.

The invention can provide a method for producing a flame retardant with environmentally friendly and high performance.

1 is an FT-IR spectrum of a flame retardant according to one embodiment.
FIG. 2 is a result of thermogravimetric analysis (TGA) of the flame retardant of FIG. 1.
FIG. 3 is a differential scanning calorimetry (DSC) result of the flame retardant of FIG. 1.
FIG. 4 is a comparative image showing a combustion state over time according to whether the flame retardant of FIG. 1 is coated.
5 is a comparative image showing a combustion state over time according to the presence or absence of coating of a flame retardant according to another embodiment.
FIG. 6 is a comparison image of the results of the presence or absence of the coating of the flame retardant of FIG. 5, confirmed using a scanning electron microscope. FIG.
7A and 7B illustrate a ¹ H-NMR spectrum and a FR-IR spectrum of a flame retardant according to another embodiment.

Hereinafter, the present invention will be described in more detail with reference to the following examples and drawings. The following examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

The flame retardant which concerns on this invention is represented by following General formula (1), and n is an integer which is 0 or more and 100 or less in following formula (1).

<Formula (1)>

The flame retardant according to the present invention may be used as a flame retardant coating agent or a flame retardant additive, and has a hydrophilic group (-OH) at the end thereof, and thus has an advantage of higher addition efficiency than conventional phosphorus-based flame retardants.

In addition, the flame retardant according to the invention is composed of an oxygen element (O), phosphorus element (P), hydrogen element (H), it is an environmentally friendly and less harmful than the halogen-based flame retardant.

Flame retardant according to the invention can be prepared through the following manufacturing method. The method for producing a flame retardant according to the invention includes a mixing step, a synthesis step and a granulation step.

The mixing step is the addition of urea to phosphoric acid to produce a phosphoric acid-urea mixture, the synthesis step is heating the phosphoric acid-urea mixture to produce a phosphorus flame retardant, and the granulation step is the crushing and grinding of the phosphorus flame retardant. .

In the mixing step, the content of urea may be in the range of 30 parts by weight to 70 parts by weight based on 100 parts by weight of phosphoric acid.

In the synthesis step, the heating of the phosphate-urea mixture is carried out in a temperature range from room temperature of about 20 ° C. to 25 ° C. to 145 ° C., complete dissolution of urea as the temperature rises, and synthesis starts at 120 ° C. It is finished at 占 폚.

By adding urea to phosphoric acid to make ammonium phosphate, and only a two-step process of heating to 145 ℃, the flame retardant represented by the formula (1) can be synthesized, the method of producing a flame retardant according to the present invention, the price is competitive There is an advantage that can provide an excellent phosphorous flame retardant.

The reaction scheme is shown in the following formula (1). With reference to the following formula (1), it will be described in more detail a method for producing a flame retardant according to the invention.

<Equation (1)>

With respect to 100 parts by weight of 75% phosphoric acid, in the range of 30 parts by weight to 70 parts by weight, urea is added and heated, the urea is completely dissolved at 100 ° C. and synthesis starts at 120 ° C.

When the synthesis starts at 120 ° C., the volume of the solution expands 8 times to 10 times and expands and contracts repeatedly, and ammonia gas is generated. When the temperature reaches 145 ° C., the chemical reaction is completed. When it is crushed and pulverized, a flame retardant according to the invention can be prepared.

The method for preparing a flame retardant according to the present invention may further include an addition synthesis step of preparing a modified phosphorus-based flame retardant by adding a crosslinking agent or a chain extender to the phosphorus-based flame retardant prepared in the synthesis step before the granulation step.

In the following formulas (2) to (4), phosphorus-based flame retardants prepared through this addition step are represented.

The flame retardant according to the invention may be represented by the following general formula (2), in the following general formula (2), n, m, o may be a natural number of 1 or more and 100 or less, respectively.

<Formula (2)>

In addition, the flame retardant according to the invention may be represented by the following formula (3), in the formula (3), n, m may be a natural number of 1 or more and 100 or less, respectively.

<Formula (3)>

In following formula (2), the reaction scheme of the flame retardant represented by the said General formula (3) is shown.

<Expression (2)>

Referring to the formula (2), by adding and reacting ethylene glycol to the phosphorus-based flame retardant prepared in the synthesis step, a flame retardant represented by the formula (3) can be prepared. In Formula (2), n may be a natural number of 1 or more and 50 or less.

In addition, the flame retardant according to the invention may be represented by the following general formula (4), in the following general formula (4), n may be a natural number of 1 or more and 100 or less.

<Formula 4>

In the following formulas (3-1) and (3-2), a reaction scheme of the flame retardant represented by the general formula (4) is shown.

<Expression (3-1)>

<Expression (3-2)>

Referring to the formulas (3-1) and (3-2), a flame retardant represented by the formula (4) is prepared by adding and reacting acryloyl chloride to the phosphorus flame retardant prepared in the synthesis step. Can be.

<Example 1>

100 g of 75% phosphoric acid was added to the reactor, and 50 g of water and urea # 50 were added thereto, followed by stirring. Thereafter, the temperature of the reactor was raised to 145 ° C to synthesize a compound represented by the formula (1), and then the reaction was terminated. Thereafter, the reaction product was ground and crushed to prepare a powdery phosphorus flame retardant.

<Example 2>

A siloxane was added to the reaction product of Example 1 to synthesize a compound represented by the formula (2), and the composite was ground and crushed to prepare a phosphorus-based flame retardant.

<Example 3>

Ethylene glycol was added to the reaction product of Example 1 to synthesize a compound represented by the formula (3), and the composite was pulverized and crushed to prepare a phosphorus-based flame retardant.

Experimental Example 1

The structural analysis of the phosphorus-based flame retardant of Example 1 was performed. FIG. 1 shows the FT-IR spectrum of the phosphorous flame retardant of Example 1, FIG. 2 shows the results of thermogravimetric analysis (TGA) of the phosphorous flame retardant of Example 1, and FIG. Differential scanning calorimetry (DSC) results of phosphorus-based flame retardants are shown.

Experimental Example 2

The combustion state of the experimental group coated with the phosphorus-based flame retardant of Example 1 and the control group not coated with the phosphorus-based flame retardant of Example 1 was observed. Figure 4 shows a comparative image of the combustion state over time, with or without the coating of the phosphorus-based flame retardant of Example 1.

Referring to Figure 4, compared to the non-coating paper, a control paper consisting of wood, the phosphorous flame retardant coated in Example 1 (coating) is less paper, coated with wood, flame retardant of Example 1 From the combustion, it was found that the phosphorus-based flame retardant of Example 1 had excellent flame retardant performance.

Experimental Example 3

The combustion state of the experimental group coated with the phosphorus-based flame retardant of Example 2 and the control group not coated with the phosphorus-based flame retardant of Example 2 was observed. FIG. 5 is a comparative image of a combustion state with time according to the presence or absence of coating of the phosphorus-based flame retardant of Example 2. FIG.

Referring to FIG. 5, since the experimental group composed of the fabric coated with the phosphorous flame retardant of Example 2 was less burned than the control composed of the fabric not coated with the phosphorous flame retardant of Example 2, the phosphorous flame retardant of Example 2 was It was found to have excellent flame retardant performance.

Experimental Example 4

The control group and the experimental group of Experimental Example 3 were observed using a scanning electron microscope. 6 shows scanning electron microscopy images of the control group before and after combustion (before combustion: a, after combustion: b) and scanning electron micrographs before and after the combustion of the experimental group (before combustion: c, after combustion: d).

Experimental Example 5

The structural analysis of the phosphorus-based flame retardant of Example 3 was performed. FIG. 7A shows the ¹ H-NMR spectrum of the phosphorus flame retardant of Example 3, and FIG. 7B shows the FR-IR spectrum of the phosphorus flame retardant of Example 3. FIG.

The specific parts of the present invention have been described in detail above, and it is apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. something to do. Therefore, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (8)

delete Flame retardant, characterized by the following formula (2):
<Formula (2)>

In the above formula (2),
n, m, o are each a natural number of 1 or more and 100 or less. Flame retardant characterized by the following formula (3):
<Formula (3)>

In the above formula (3),
n and m are natural numbers of 1 or more and 100 or less, respectively. delete delete delete delete delete

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