JP2703871B2 - Method for producing high molecular weight polyester type flame retardant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing a high molecular weight phosphorus-containing polyester-type flame retardant agent.

[0002]

2. Description of the Related Art A flame-retardant high-temperature-resistant polymer resin is obtained by incorporating a flame-retardant comonomer (flame retardant) into a polymer main chain during copolymerization. Because the flame retardant is chemically bonded to the polymer backbone, it does not migrate to the surface of the polymer resin during processing such as extrusion or injection molding, and the flame retardant effect and physical properties are affected Not receive. When the polymer resin is woven into a woven or non-woven fabric, the washing fastness is improved. However, this method has a disadvantage that the processing cost on the producer side increases.

[0003] As another method, there is a method of treating on the consumer side, in which a layer of a flame retardant is applied on a woven fabric of a polymer resin. For example, if a flame retardant is applied on a textile, the textile exhibits flame retardancy. However, with repeated washing, the flame retardant effect will gradually decrease. That is, the wash fastness of such treated fabrics is generally not satisfactory.

[0004] Polymer modification is one method of improving the flame retardancy of a polymer resin. According to such a method, the flame retardant is mixed with the polymer resin before finishing the polymer resin into a molded article such as a fiber or a filament. This method has the advantage of being easy to manufacture. However, organic flame retardants generally cannot withstand high temperature processing. For example, polyester and polyamide resins are typically extruded into filaments at temperatures higher than 290 ° C., which often degrades the quality of the organic flame retardant, resulting in filament breakage.
When polymer resin is mixed with inorganic flame retardant, during spinning,
The spinneret is clogged. This affects the filling pressure during spinning, which results in the filaments breaking and becoming shorter. In addition, poor compatibility between the polymeric resin and the flame retardant often causes migration of the flame retardant when the mixture is treated, especially at elevated temperatures. In the case of textiles made from flame-retardant fibers by polymer modification, their washing fastness is also unsatisfactory.

[0005] Recently, polymeric flame retardants containing phosphorus have been developed, replacing conventional halogen containing flame retardants. This flame retardant also satisfies the requirements of low toxicity, low smoke emission during combustion, and low mobility in terms of environmental protection and public safety. For example, a flame retardant manufactured by Daihachi Chemical Industry Co., Ltd., trade name: CR733 and a fire retardant manufactured by Akzo (AKZO), trade name: RDP, have a degree of polymerization of less than 15 and a phosphorus having a molecular weight of less than 2,000. It is an acid ester flame retardant. However, the heat resistance of these phosphate ester flame retardants is still insufficient, and those treated at a relatively low temperature in addition to the polymer resin, such as polyurethane sponge, polyurethane leather, polyurethane paint and soft polyurethane Only suitable for applications such as vinyl chloride (PVC). Phosphonic anhydride flame retardant manufactured by Hoechst Celanese Corp. and manufactured by Toyobo Co., Ltd., trade name:
GH flame retardants also do not have satisfactory heat resistance. Since they are reactive flame retardants, they are added to the polyester resin and copolymerized. As a result, the resulting copolyester contains 0.4-0.7% by weight of phosphorus and is suitable for being spun into flame-retardant fibers or filaments. The high molecular weight ammonium polyphosphate containing flame retardant is available from Monsanto and Hoechst.
Hoechst Celanese Cor
p.), these ammonium polyphosphate-containing flame retardants have low compatibility with polyester,
It only withstands a temperature of 00 ° C.

[0006]

The conventional flame retardant has low heat resistance, low compatibility with the resin, and has a problem of migration in the resin.

An object of the present invention is to provide a method for producing the new flame retardant agent that solves these problems.

[0008]

According to the present invention, there is provided a compound represented by the general formula (I):

[0009]

Embedded image

Wherein R ′ ₁ is an alkylene group or aromatic group having 2 to 10 carbon atoms, R ″ ₁ is an alkylene group or aromatic group having 2 to 10 carbon atoms, and R ₂ is Alkylene group or aromatic group, R ′ is a trivalent aliphatic saturated hydrocarbon group or aromatic group having 2 to 12 carbon atoms, A is R or OR, and R is an alkyl group or aromatic group having 1 to 12 carbon atoms. , M represents an integer of 1 to 10, and n represents an integer of 1 to 10.)
And (a) a metal complex, an unsaturated dicarboxylic acid and its derivative, a saturated dicarboxylic acid and its derivative, a diol, and a metal complex that function as a catalyst in a single batch or in two batches. General formula (II):

[0011]

Embedded image

(Wherein A and R are the same as described above) are fed into a reactor, and a temperature of 80 to
Reacting at 120 ° C. to prepare a phosphorus-containing dicarboxylic acid; (b) elevating the temperature of the reactor to 170-270 ° C. to start the esterification reaction; 285 ° C. and is polymerized at a pressure lower than 1.5mmHg characterized by comprising a step of preparing a high molecular weight polyester type flame retardant, the metal complex
The body is represented by the general formula: MX ₄ , H ₂ MX ₆ or MX ₂ (wherein M
Is a metal element of Group VIIIB of the periodic table, and X is a halogen atom
Group, sulfur atom-containing group, oxygen atom-containing group or silicon source
It relates to the production how the high molecular weight polyester-type flame retardant is a compound represented by showing the child-containing group).

[0013]

Action and Examples In order to achieve the above object of the present invention, as a result of various studies, the present inventors have found that unsaturated dicarboxylic acids have the general formula (II):

[0014]

Embedded image

Wherein A is R or OR, and R is carbon atom 1
To 12 alkyl groups or aromatic groups), by incorporating a phosphorus-containing dicarboxylic acid, which is a reaction product of a phosphorus compound represented by
It has been found that compatibility can be improved and migration problems can be reduced. This means that the resulting phosphorus-containing dicarboxylic acid is a reactive dicarboxylic acid, in which the phosphorus-containing group is grafted to the side chain, even if O = P-O
Even if the bond breaks, the physical properties of the remaining flame retardant are not affected.

However, a reactive dicarboxylic acid having a phosphorus-containing group in the side chain, for example, 6H-dibenzo [1,
2] Derivatives of oxaphospholin-6-ylmethylbutanedicarboxylic acid p-oxide (hereinafter referred to as DOP),
Derivatives of phosphonic acid, dimethyl phosphite, and the like cannot be obtained as commercial products, and therefore must be synthesized in advance. This requires additional capital investment for the synthesis of the reactive dicarboxylic acid and for the separation and purification of the obtained reactive dicarboxylic acid.

However, the present inventors, when selecting an appropriate metal complex acting as a catalyst, feed a phosphorus compound, an unsaturated dicarboxylic acid, a saturated dicarboxylic acid and a diol into a single reactor to obtain a high molecular weight phosphorus. It has been found that a polyester containing polyester can be produced.

The present invention has been completed based on such findings.

According to the method of the present invention, a metal complex, an unsaturated dicarboxylic acid or a derivative thereof, a saturated dicarboxylic acid or a derivative thereof, a diol and a phosphorus compound represented by the general formula (II) are reacted in a single batch or two batches. The mixture was fed into a vessel, and reacted at a temperature of 80 to 120 ° C. to prepare a phosphorus-containing dicarboxylic acid.
0 to 270 ° C. to start the esterification reaction,
Subsequently, polymerization is carried out at a temperature of 245 to 285 ° C. and a pressure lower than 1.5 mmHg.

According to one embodiment of the present invention, the metal complex acting as a catalyst is an efficient catalyst and does not produce any by-products at low temperatures and contains phosphorus in the presence of a saturated dicarboxylic acid and a diol. Dicarboxylic acids can be prepared at high conversions. Therefore, it becomes possible to feed all the reaction raw materials into one reactor and synthesize a flame retardant having a high phosphorus content.

According to another embodiment of the present invention, the high molecular weight polyester type flame retardant obtained according to the present invention comprises:
Good compatibility with polyesters, polycarbonates and polyamides, so that after being directly added to those resins, it can be made into flame-retardant fibers, fabrics, films, adhesives, etc. with good washing fastness and heat resistance .

Further, by adding the flame retardant obtained according to the present invention to a polyurethane or unsaturated urea resin, a flame-retardant polyurethane and urea resin can be prepared.

The invention can be better understood with reference to the following more detailed description.

According to the present invention, the metal complex has the general formula: M
X _4, H ₂ MX ₆ or MX ₂ (where, M is the Periodic Table VII
X is a metal element belonging to Group IB, and X represents a halogen atom or sulfur atom-containing group, an oxygen atom-containing group and a silicon atom-containing group. In addition, as M in the metal complex, for example, a platinum atom, a nickel atom, and a palladium atom are preferably used. Examples of the metal complex include PtCl ₄ , NiCl ₄ , PdCl ₄ , H ₂ PtCl
₆ , PtBr ₄ , PtS ₄ , Pt (OOCCH ₃ ) ₂ , platinum divinyltetramethyldisiloxane and platinum-cyclovinylmethylsiloxane complex,
It is not limited to these. These metal complexes can be used alone or as a mixture. The amount of the metal complex is 0.003 to 0.040% by weight, preferably 0.005 to 0.015% by weight, based on the total weight of the phosphorus compound and the unsaturated dicarboxylic acid.

The phosphorus compound suitable in the present invention has the general formula (II):

[0026]

Embedded image

(Wherein, A and R are the same as defined above). Usually, R represents a phenyl group, a naphthyl group or a biphenyl group.

The unsaturated dicarboxylic acids suitable in the present invention include, but are not limited to, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, aconic acid and the like.

The preferred saturated dicarboxylic acids and derivatives thereof in the present invention include terephthalic acid, isophthalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, hexahydroterephthalic acid, dimethylterephthalic acid, dimethylisophthalic acid, dimethyl Examples include, but are not limited to, sodium salts of 5-sulfoisophthalic acid esters, sodium salts of bis (2-hydroxyethyl) -5-sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, and diesters thereof. Not something.

The diols which can be suitably used in the present invention include ethylene glycol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanediol, polyethylene ether glycol, polytetramethylene ether glycol and their diols. Examples thereof include mixtures, but are not limited thereto.

In the present invention, the addition reaction between the phosphorus compound and the unsaturated dicarboxylic acid can be carried out in the presence of a saturated dicarboxylic acid and a diol. Therefore, all of the starting materials and metal complexes are fed into one reactor, alone or in two batches. The molar ratio of the phosphorus compound to the unsaturated dicarboxylic acid ranges from 1: 1 to 1: 1.
05, preferably 1: 1.02.
The molar ratio of the saturated dicarboxylic acid to the phosphorus compound is 5:
The ratio is desirably 95 to 55:45. The molar ratio of the diol to the total weight of the saturated dicarboxylic acid and the phosphorus-containing dicarboxylic acid is 2: 1 to 10: 1, preferably 3: 2.
It is desirable that the ratio be 1 to 6: 1. The addition reaction is 80-
120 ° C., preferably 85-105 ° C., preferably 3
The reaction is carried out for up to 5 hours, particularly preferably for 3.5 to 4 hours. After the phosphorus-containing dicarboxylic acid is formed, a catalyst for the esterification reaction, that is, a metal oxide catalyst such as titanium oxide, aluminum oxide, lead oxide, germanium oxide, or tin oxide is used at 170 to 270 ° C., preferably 180 to 270 ° C.
It is desirable to carry out the esterification by adding at 50 ° C.
The amount of the metal oxide catalyst is 0.0
Preferably it is 2 to 0.3% by weight. When the conversion of the esterification reaction reaches preferably 90% by weight, particularly preferably 95% by weight, a temperature of 245 to 285 ° C.,
Polymerization is performed under a pressure lower than 1.5 mmHg to complete the treatment.

The thus prepared high molecular weight phosphorus-containing polyester type flame retardant has the general formula (I):

[0033]

Embedded image

(Wherein R ′ ₁ is an alkylene group or aromatic group having 2 to 10 carbon atoms, R ″ ₁ is an alkylene group or aromatic group having 2 to 10 carbon atoms, and R ₂ is an alkylene group or an aromatic group having 2 to 10 carbon atoms. Alkylene group or aromatic group, R 'is a trivalent aliphatic saturated hydrocarbon group or aromatic group having 2 to 12 carbon atoms, A and R are the same as above, m is an integer of 1 to 10, n is 1 to It represents an integer of 10.)

Hereinafter, the present invention will be described in more detail with reference to specific examples.

In the following Examples and Comparative Examples, the intrinsic viscosity (IV) was measured at 30 ° C. in a 3: 2 (weight ratio) mixed solvent of phenol and 1,1,2,2-tetrachloroethane. . Phosphorus content is determined by heating the sample in a mixture of sulfuric acid and perchloric acid to decompose it and developing its color using ammonium molybdate and ferric ammonium sulfate. Was measured. The acid value was determined by dividing the sample into phenol and chloroform at 3: 2.
(Weight ratio) and obtained by titration with a 0.1N-KOH phenyl alcohol solution using phenol red as an indicator. Melting point (T
m) is from -40 to 30 at a rate of 20 ° C./min using a differential scanning calorimeter (990 DSC manufactured by DuPont) for 5 to 8 mg of the sample.
Obtained by heating with increasing temperature to 0 ° C. Flame retardancy is represented by the limiting oxygen index (LOI), and the limiting oxygen index of each sample was determined according to ASTM D2
It was measured according to the standard test of 863. The proportion of phosphorus contained in the polymer chain was confirmed using ³¹ P-NMR.

Example 1 74.78 g of DOP, 44.98 of itaconic acid (ITA)
g, terephthalic acid (TPA) 163 g, ethylene glycol (EG) 249 g and H ₂ PtCl ₆ 0.0078
g into a 1.5 liter stainless steel reactor equipped with a fractionating tube, a stirrer and a nitrogen gas inlet, and stirring and feeding nitrogen gas at a flow rate of 30 ml / min. And maintained for 4 hours. After the addition reaction is completed, the temperature is increased to 190-2.
The temperature was raised to 30 ° C. to carry out an esterification reaction. After the conversion reaches 90% by weight, the RSnO catalyst ((C ₄ H ₉ )
₂ SnO) 0.3087 g, triphenyl phosphite (hereinafter referred to as TPP) 0.3087 as a heat stabilizer
g was added to the reaction system and the reaction temperature was further increased to 250-260.
° C, and gradually increase the pressure to 1 mmHg within 40 minutes.
And maintaining the state for 2 hours to prepare a high molecular weight polyester type flame retardant. The melting point of the obtained high molecular weight polyester type flame retardant was 180 ° C., the intrinsic viscosity was 0.63, and the acid value was 21.5 equivalents / kg. The conversion was 98% by weight, and the phosphorus content was 3.23 by ³¹ P-NMR analysis.
By weight, phosphorus had reacted with the polyester backbone. Table 1 shows other properties of the obtained high molecular weight polyester type flame retardant.

Example 2 The same procedure and reaction conditions as in Example 1 were repeated except that the catalyst for the addition reaction was 0.0078 g of PtBr ₄ . Table 1 shows the properties of the obtained high molecular weight polyester type flame retardant.

Example 3 12.30 g of dimethylphosphonic acid and itaconic acid (IT
A) 17.0 g, terephthalic acid (TPA) 122.56
g, 265.36 g of ethylene glycol (EG) and 0.0045 g of PtBr _{4 are} placed in a 1.5 liter stainless steel reactor equipped with a fractionating tube, a stirrer and a nitrogen gas inlet, stirring and flow rate. While supplying nitrogen gas at a rate of 30 ml / min, the mixture was heated to a temperature of 95 to 100 ° C. and kept there for 4 hours. After the addition reaction was completed, the temperature was raised to 185 to 225 ° C to perform the esterification reaction. After the conversion reaches 90% by weight, RS
0.2872 g of nOZ catalyst, TPP as heat stabilizer
0.2872 g was added to the reaction system, and the reaction temperature was further increased by 2
A high molecular weight polyester type flame retardant was prepared by raising the pressure to 45 to 255 ° C., gradually lowering the pressure to less than 1 mmHg within 45 minutes, and maintaining the state for 2.5 hours. The melting point of the obtained high molecular weight polyester type flame retardant is 1
98.5 ° C., the intrinsic viscosity was 0.65, and the acid value was 18.6 equivalents / kg. The conversion was 96% by weight, the phosphorus content was 2.11% by weight in ³¹ P-NMR analysis, and phosphorus had reacted with the polyester main chain. Table 1 shows other properties of the obtained high molecular weight polyester type flame retardant.

Example 4 The same procedure and reaction conditions as in Example 3 were repeated, except that the catalyst for the addition reaction was 0.0078 g of H ₂ PtCl ₆ . Table 1 shows the properties of the obtained high molecular weight polyester type flame retardant.

Example 5 16.46 g of dimethyl phosphite, 12.74 g of itaconic acid (ITA) and 13 of terephthalic acid (TPA)
7.43 g, 286.8 g ethylene glycol (EG)
And 0.0034 g of PtS ₄ were placed in a 1.5 liter stainless steel reactor equipped with a fractionating tube, a stirrer and a nitrogen gas inlet, while stirring and introducing nitrogen gas at a flow rate of 30 ml / min. It was heated to a temperature of 90-95 ° C and kept there for 4 hours. After the addition reaction was completed, the temperature was raised to 180 to 230 ° C to perform the esterification reaction. After the conversion reaches 90% by weight, RS
0.1713 g of nO catalyst, TPP0.
1713 g was added to the reaction system, and the reaction temperature was further increased to 245.
To 260 ° C., and gradually increase the pressure to 1 within 40 minutes.
The high molecular weight polyester type flame retardant was prepared by keeping the temperature lower than mmHg and maintaining the state for 2.5 hours. The melting point of the obtained high molecular weight polyester type flame retardant is 221.
C, the intrinsic viscosity was 0.70, and the acid value was 17.5 equivalents / kg. The conversion was 97.5% by weight, the phosphorus content was 1.494% by weight in ³¹ P-NMR analysis, and phosphorus had reacted with the polyester main chain. Table 1 shows other properties of the obtained high molecular weight polyester type flame retardant.

Examples 6 to 8 Except that the molar ratio of the phosphorus-containing dicarboxylic acid to the total amount of the saturated dicarboxylic acid (TPA) and the phosphorus-containing dicarboxylic acid was 5 mol%, 12 mol% or 15 mol%, respectively. The same procedure and reaction conditions as in Example 1 were repeated. Table 1 shows the properties of the obtained high molecular weight polyester type flame retardant.

Example 9 DOP 74.78 g, itaconic acid (ITA) 44.98
g, 150 g of ethylene glycol (EG) and H ₂ P
0.0078 g of tCl _{6 was} placed in a 1.5 liter stainless steel reactor equipped with a fractionating tube, a stirrer and a nitrogen gas inlet, while stirring and sending nitrogen gas at a flow rate of 30 ml / min. It was heated to a temperature of 100-105 ° C. and kept there for 4 hours to form a phosphorus-containing dicarboxylic acid. Thereafter, 163 g of terephthalic acid, 100 g of ethylene glycol, 0.3087 g of RSnOZ catalyst and 0.3087 g of TPP as a heat stabilizer were added, and the temperature was raised to 190 to 230 ° C. to carry out an esterification reaction. After the conversion reaches 95% by weight, the reaction temperature is further raised to 250-260 ° C., the pressure is gradually lowered to less than 1 mmHg within 45 minutes, and the state is reduced to 2.5%.
By keeping the time, a high molecular weight polyester type flame retardant was prepared. The melting point of the obtained high molecular weight polyester type flame retardant was 181 ° C., the intrinsic viscosity was 0.62, and the acid value was 22.5 equivalents / kg. Conversion is 98% by weight, ³¹ P-NMR
As a result of analysis, the phosphorus content was 3.23% by weight, and phosphorus was reacted with the polyester main chain. Table 1 shows other properties of the obtained high molecular weight polyester type flame retardant.

Example 10 The catalyst for the addition reaction was 0.0045 g of Pt (OOCCH ₃ ) ₂ .
And the same procedure and reaction conditions as in Example 9 were repeated. Table 1 shows the properties of the obtained high molecular weight polyester type flame retardant.

Comparative Example 1 An addition reaction catalyst was not added, and the addition reaction temperature was 160
The same procedure and reaction conditions as in Example 1 were repeated except that the temperature was changed to ° C. Table 1 shows the properties of the obtained high molecular weight polyester type flame retardant.

Comparative Example 2 An addition reaction catalyst was not added, and the addition reaction temperature was 160
The same procedure and reaction conditions as in Example 3 were repeated except that the temperature was changed to ° C. Table 1 shows the properties of the obtained high molecular weight polyester type flame retardant.

Comparative Example 3 The same procedure and reaction conditions as in Comparative Example 1 were repeated, except that DOP and itaconic acid (ITA) were not added. Table 1 shows the properties of the obtained high molecular weight polyester type flame retardant.

Comparative Example 4 In this comparative example, a high molecular weight polyester flame retardant was prepared in two batches using two reactors.

<Reactor A: Synthesis of Phosphorus-Containing Dicarboxylic Acid> 216 g of DOP and 130 g of itaconic acid (ITA)
Were placed in a fractionation tube,撹拌 machine and a stainless steel reactor 1.5 liter equipped with a nitrogen gas inlet, 60
While feeding a nitrogen gas at撹拌 and a flow rate of 40ml / min rpm, heated to a temperature of 160 ° C., 1.5 hours the crude phosphorus-containing dicarboxylic acid retained its status (hereinafter,
TP) was prepared. The crude TP was crushed, added to acetone, and purified by refluxing at 60 ° C. for 2 hours. The crude TP was also dissolved in acetone and subsequently purified by recrystallization. The melting point of the obtained white purified phosphorus-containing dicarboxylic acid is 195 ° C., and the conversion is 80 to 80%.
It was 85% by weight.

[0050] <reactor B: Synthesis of high molecular weight polyester type flame retardant> purified TP124.25G, terephthalic acid 163g and ethylene glycol 249.4G, fractionating tube,撹拌 <br/> machines and nitrogen gas inlet Poured into a 1.5 liter stainless steel reactor equipped with a mouth. While the reaction mixture is being fed with nitrogen gas at a flow rate of 40 ml / min.
Heat to 230 ° C. and convert this esterification to 90%
This temperature was maintained until the temperature reached. Then, 0.3087 g of TBT (tetra (butyl orthotitanium)) catalyst,
Heat stabilizer (Ciba-Geigy Corporation (Ci)
ba-Geigy Corp. Product name: Irganox 1010) 0.3087 g
Was added to the reaction system, the temperature was further increased to 250 to 260 ° C., and the pressure was gradually lowered to less than 1 mmHg within 40 minutes, and the state was maintained for 2 hours to prepare a high molecular weight polyester type flame retardant. . The obtained high molecular weight polyester type flame retardant has a melting point of 180 ° C. and an intrinsic viscosity of 0.6.
4. The acid value was 20.8 eq / kg. Conversion is 8
3.3% by weight, ³¹ P-NMR analysis indicates a phosphorus content of 2.75.
By weight, phosphorus had reacted with the polyester backbone. Table 1 shows other properties of the obtained high molecular weight polyester type flame retardant.

[0051]

[Table 1]

Experimental Example The high molecular weight polyester type flame retardant (UCL-P-FR01) prepared in Example 1, the high molecular weight polyester type flame retardant (UCL-P-FR02) prepared in Example 3,
Daihachi Chemical Industry Co., Ltd., trade name: CR-733 and Akzo Co., Ltd., trade name: RDP, the thermal stability of the flame retardant, Td (decomposition temperature), weight loss rate and char%
Was measured for Table 2 shows the results.

The thermal stability was measured by using a microbalance (TGA900 manufactured by DuPont) to first measure 80 mg of the sample at a heating rate of 20%.
The temperature was raised from room temperature to 100 ° C. at 0 ° C./min and heated for 30 minutes.
Heated for 0 minutes and indicated the percent weight loss of the sample at 290 ° C.

The measurement of Td (decomposition temperature) was carried out by heating 80 mg of a sample from room temperature to 850 ° C. at a heating rate of 20 ° C./min using TGA900 manufactured by DuPont.
Td was recorded.

[0055]

[Table 2]

The high molecular weight polyester type flame retardants (UCL-P-FR01 and UCL-P-) obtained by the present invention.
Table 3 shows a comparison of thermal properties between FR02) and CR-733 or RDP.

[0057]

[Table 3]

[0058]

According to the present invention a high molecular weight polyester-type flame retardant agent of the present invention
According to the production method, a high-molecular-weight polyester-type flame retardant having good washing fastness, heat resistance and compatibility with resin is selected.
It is .

Claims (12)

(57) [Claims] 1. A compound of the general formula (I): (Wherein, R ′ ₁ is an alkylene group or aromatic group having 2 to 10 carbon atoms, R ″ ₁ is an alkylene group or aromatic group having 2 to 10 carbon atoms, R ₂ is an alkylene group having 2 to 10 carbon atoms or An aromatic group, R ′ is a trivalent aliphatic saturated hydrocarbon group or an aromatic group having 2 to 12 carbon atoms, A is R or OR, R is an alkyl group or an aromatic group having 1 to 12 carbon atoms, and m is 1 to 1
An integer of 0, and n represents an integer of 1 to 10), comprising: (a) a metal complex which functions as a catalyst in one batch or two batches, and an unsaturated dicarboxylic acid; Acids or derivatives thereof, saturated dicarboxylic acids or derivatives thereof, diols and general formula (II): (Wherein A and R are the same as those described above) into a reactor and react at a temperature of 80 to 120 ° C. to prepare a phosphorus-containing dicarboxylic acid; A step of raising the temperature to 170 to 270 ° C. to carry out an esterification reaction, followed by (c) polymerization at a temperature of 245 to 285 ° C. and a pressure lower than 1.5 mmHg to prepare a high molecular weight polyester type flame retardant The metal complex
The body is represented by the general formula: MX ₄ , H ₂ MX ₆ or MX ₂ (wherein M
Is a metal element of Group VIIIB of the periodic table, and X is a halogen atom
Group, sulfur atom-containing group, oxygen atom-containing group or silicon source
A method for producing a high molecular weight polyester-type flame retardant which is a compound represented by the following formula: 2. The method according to claim 1, wherein the metal complex is PtCl ₄ , NiCl ₄ , P
dCl ₄ , H ₂ PtCl ₆ , PtBr ₄ , PtS ₄ , Pt
(OOCCH _{3) 2,} platinum divinyltetramethyldisiloxane and platinum - The process according to claim 1, wherein a compound selected from the group consisting of cyclovinylmethylsiloxane complex. 3. The method according to claim 1, wherein the unsaturated dicarboxylic acid is a dicarboxylic acid selected from the group consisting of maleic acid, fumaric acid, itaconic acid, traconic acid, mesaconic acid and aconic acid. 4. The method according to claim 1, wherein the saturated dicarboxylic acid and its derivative are
Terephthalic acid, isophthalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, hexahydroterephthalic acid, dimethyl terephthalate, dimethyl isophthalate, sodium salt of dimethyl 5-sulfoisophthalate, bis (2-hydro The method according to claim 1, wherein the compound is a compound selected from the group consisting of sodium salt of (xyethyl) -5-sulfoisophthalic acid ester, 2,6-naphthalenedicarboxylic acid and diesters thereof. 5. The diol according to claim 1, wherein the diol is ethylene glycol, neopentyl glycol, 1,6-hexanediol,
The method according to claim 1, wherein the diol is selected from the group consisting of 4-cyclohexanedimethanediol, polyethylene ether glycol, polytetramethylene glycol, and a mixture thereof. 6. The addition reaction of the step (a) is carried out in a proportion of 85 to 105.
2. The method according to claim 1, wherein the method is carried out at a temperature of 0. 7. The esterification reaction of the step (b) is carried out at 180
The method according to claim 1, which is carried out at a temperature of from 250 to 250 ° C. 8. In the esterification reaction of the step (b),
The method according to claim 1, wherein the molar ratio of the diol to the total weight of the saturated dicarboxylic acid and the phosphorus-containing dicarboxylic acid is 2: 1 to 10: 1. 9. A compound of the general formula (I) for an unsaturated dicarboxylic acid
The molar ratio of the phosphorus compound represented by I) is from 1: 1 to 1:
2. The method according to claim 1, wherein the ratio is 1.05. 10. The molar ratio of the phosphorus compound represented by the general formula (II) to the unsaturated dicarboxylic acid is 1: 1.02.
The method according to claim 9 , wherein 11. The method according to claim 1, wherein the esterification reaction in the step (b) is carried out in the presence of a metal oxide catalyst selected from the group consisting of titanium oxide, aluminum oxide, lead oxide, germanium oxide and tin oxide. Production method. 12. The method of claim 1 the amount of metal oxide catalyst is 0.02 to 0.3 wt% relative to phosphorus-containing dicarboxylic acid
2. The production method according to 1 .