JPH0912694A - High-molecular polyester flame retardant and its production - Google Patents

Abstract

PURPOSE: To improve the heat resistance, the compatibility with resins, and the wash-fastness of a fabric by using a specific high-molecular weight polyester flame retardant in the fabric.

CONSTITUTION: This flame retardant has a structure represented by formula I (wherein R'₁, R''₁, and R₂ each represent a C_2-10 alkylene or an aromatic group, R' represents a C_2-12 trivalent aliphatic saturated hydrocarbon group or aromatic group, A represents R or OR in which R denotes a C_1-12 alkyl or aromatic group, and (m) and (n) are each 1 to 10). In producing the flame retardant, a metal complex functioning as a catalyst (e.g. H₂PtCl₆), an unsaturated dicarboxylic acid (e.g. itaconic acid) or its derivative, a saturated dicarboxylic acid (e.g. terephthalic acid) or its derivative, a diol (e.g. ethylene glycol) and a phosphorus compound represented by formula II, wherein A and R have the same meanings as in formula I (e.g. triphenylphosphite) are fed into a reaction vessel in a single batch or two batches and they are reacted at 80 to 120°C to obtain a phosphorus-containing dicarboxylic acid. Then the temperature is elevated to 170 to 270°C to start the esterification reaction and the polymerization is carried out at 245 to 285°C under a pressure of 1.5mmHg.

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high molecular weight phosphorus-containing polyester type flame retardant and a method for producing the same.

[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. Moreover, the poor compatibility of the polymeric resin with the flame retardant often causes migration of the flame retardant, especially when the mixture is treated 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.

It is an object of the present invention to provide a new flame retardant which solves these problems and a method for producing the same.

[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.)
A method for producing a high molecular weight polyester type flame retardant represented by the following: (a) a metal complex functioning as a catalyst, an unsaturated dicarboxylic acid and its derivative, a saturated dicarboxylic acid and its derivative, a diol and 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) increasing the temperature of the reactor to 170 to 270 ° C. to start the esterification reaction, and subsequently (c) temperature 245 to 245 285 ° C and 1.5 mmHg
And a step of preparing a high molecular weight polyester type flame retardant by polymerizing under a lower pressure, and a general formula (I):

[0013]

[Chemical 6]

[0014] (wherein, R _'1 is an alkylene group or an aromatic group having 2 to 10 carbon atoms, R _"1 represents an alkylene group or an aromatic group having 2 to 10 carbon atoms, R ₂ is 2 to 10 carbon atoms Alkylene group or aromatic group, R'is trivalent aliphatic saturated hydrocarbon group or aromatic group having 2 to 12 carbon atoms, A is R or OR, R is alkyl group or aromatic group having 1 to 12 carbon atoms , M is an integer of 1 to 10, and n is an integer of 1 to 10)
The present invention relates to a high molecular weight polyester type flame retardant.

[0015]

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):

[0016]

Embedded image

(In the formula, A is R or OR, and R is 1 carbon atom.
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, reactive dicarboxylic acids having a phosphorus-containing group in the side chain, such as 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 have selected a suitable metal complex that acts as a catalyst, and then send a phosphorus compound, an unsaturated dicarboxylic acid, a saturated dicarboxylic acid and a diol into one reactor to obtain a high molecular weight phosphorus compound. It has been found that a 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 its derivative, a saturated dicarboxylic acid or its derivative, a diol and a phosphorus compound represented by the general formula (II) are reacted in a single batch or two batches. The phosphorus-containing dicarboxylic acid is fed into the reactor and reacted at a temperature of 80 to 120 ° C., and then the temperature of the reactor is adjusted to 17
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 which acts as a catalyst is an efficient catalyst and therefore contains phosphorus in the presence of saturated dicarboxylic acid and diol at low temperature without any by-products. Dicarboxylic acids can be prepared with high conversion. 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 retardants of the present invention have good compatibility with polyesters, polycarbonates and polyamides, so that they can be washed directly after addition to those resins. Flame-retardant fibers, woven fabrics with good fastness and heat resistance,
It can be a film, an adhesive or the like.

It is also possible to prepare a flame retardant polyurethane and urea resin by adding the flame retardant of the present invention to polyurethane or an unsaturated urea resin.

The present invention may be better understood with reference to the more detailed description that follows.

According to the 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):

[0028]

Embedded image

A phosphorus compound represented by the formula (wherein A and R are the same as above). Usually, R represents a phenyl group, a naphthyl group or a biphenyl group.

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

Suitable 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 and dimethyl. Examples thereof include sodium salts of 5-sulfoisophthalic acid esters, sodium salts of bis (2-hydroxyethyl) -5-sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid and diesters thereof, but are not limited thereto. Not a thing.

The diols that can be preferably used in the present invention include ethylene glycol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanediol, polyethylene ether glycol, polytetramethylene ether glycol and their mixtures. Examples thereof include, but are not limited to, a mixture and the like.

In the present invention, the addition reaction between the phosphorus compound and the unsaturated dicarboxylic acid can be carried out in the presence of the saturated dicarboxylic acid and 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.
It is desirable that the ratio is 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 diol to the total weight of saturated dicarboxylic acid and phosphorus-containing dicarboxylic acid is 2: 1 to 10: 1, preferably 3 :.
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, and tin oxide is added at 170 to 270 ° C., preferably 180 to 2 ° 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 high molecular weight phosphorus-containing polyester flame retardant thus prepared has the general formula (I):

[0035]

Embedded image

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

The present invention will be described in more detail below by showing specific examples.

In the following examples and comparative examples, the intrinsic viscosity (IV) was measured at 30 ° C. in a mixed solvent of phenol and 1,1,2,2-tetrachloroethane 3: 2 (weight ratio). . 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.
It was obtained by dissolving in a mixed solvent (weight ratio) and titrating with 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, itaconic acid (ITA) 44.98
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 0.0078 g of PtBr ₄ was used as the catalyst for the addition reaction. Table 1 shows the properties of the obtained high molecular weight polyester type flame retardant.

Example 3 12.30 g of dimethylphosphonic acid, 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 to 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), 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 Examples were carried out 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 74.78 g of DOP, 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 Pt (OOCCH ₃ ) ₂ 0.0045 g was used as a catalyst for the addition reaction.
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 No addition reaction catalyst was added and the addition reaction temperature was adjusted to 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 No addition reaction catalyst was added and the addition reaction temperature was adjusted to 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, the high molecular weight polyester flame retardant was prepared in two batches using two reactors.

<Reactor A: Synthesis of phosphorus-containing dicarboxylic acid> DOP 216 g and itaconic acid (ITA) 130 g
Was placed in a 1.5 liter stainless steel reactor equipped with a fractionating tube, a stirrer and a nitrogen gas inlet, and 60
While stirring at rpm and feeding nitrogen gas at a flow rate of 40 ml / min, heat up to a temperature of 160 ° C., and
A crude phosphorus-containing dicarboxylic acid (hereinafter, referred to as TP) was prepared by keeping the state for a time. 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 was 195 ° C., and the conversion rate was 8
It was 0 to 85% by weight.

<Reactor B: Synthesis of high molecular weight polyester type flame retardant> Purified TP124.25 g, terephthalic acid 163 g and ethylene glycol 249.4 g were equipped with a fractionating pipe, a stirrer and a nitrogen gas inlet. It was poured into a stainless steel reactor containing 1.5 liters. The reaction mixture was heated to 180 to 230 ° C. while feeding nitrogen gas at a flow rate of 40 ml / min, and this temperature was maintained until the conversion rate of the esterification reached 90%. Then, a TBT (tetra (butyl orthotitanium)) catalyst 0.3087 g, a heat stabilizer (manufactured by Ciba-Geigy Corp.), trade name: Irganox 101
0) 0.3087 g was added to the reaction system, and the temperature was further adjusted to 2
The temperature was raised to 50 to 260 ° C., the pressure was gradually lowered to less than 1 mmHg within 40 minutes, and the state was kept for 2 hours to prepare a high molecular weight polyester flame retardant. The melting point of the obtained high molecular weight polyester type flame retardant is 180.
C., intrinsic viscosity was 0.64, and acid value was 20.8 equivalent / kg. The conversion was 83.3% by weight, the phosphorus content in the ³¹ P-NMR analysis was 2.75% 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.

[0053]

[Table 1]

Experimental Example High molecular weight polyester type flame retardant (UCL-P-FR01) prepared in Example 1, 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.

Regarding the thermal stability, a microbalance (TGA900 manufactured by DuPont) was used to measure 80 mg of the sample first 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 Td (decomposition temperature) was also measured by heating 80 mg of a sample with TGA900 manufactured by DuPont at a temperature rising rate of 20 ° C./minute from room temperature to 850 ° C.
Td was recorded.

[0057]

[Table 2]

High molecular weight polyester type flame retardants of the present invention (UCL-P-FR01 and UCL-P-FR02).
Table 3 shows a comparison of the thermal properties of CRDP and CR-733 or RDP.
Shown in

[0059]

[Table 3]

[0060]

EFFECTS OF THE INVENTION According to the high molecular weight polyester type flame retardant of the present invention and the method for producing the same, the washing fastness, heat resistance and compatibility with resin are improved.

Claims (14)

[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
0 is an integer, and n is an integer of 1 to 10).
(A) In a single batch or in two batches, a metal complex functioning as a catalyst, unsaturated dicarboxylic acid or its derivative, saturated dicarboxylic acid or its derivative, diol and general formula (II): A step of feeding a phosphorus compound represented by the formula (wherein A and R are the same as above) into a reactor and reacting at a temperature of 80 to 120 ° C. to prepare a phosphorus-containing dicarboxylic acid;
(B) a step of increasing the temperature of the reactor to 170 to 270 ° C. to carry out an esterification reaction, followed by (c) polymerizing at a temperature of 245 to 285 ° C. and a pressure lower than 1.5 mmHg to obtain a high molecular weight A method for producing a high molecular weight polyester flame retardant, comprising the step of preparing a polyester flame retardant. 2. A metal complex having a general formula: MX ₄ , H ₂ MX ₆
Or a compound represented by MX ₂ (wherein M represents a metal element of Group VIIIB of the Periodic Table, X represents a halogen atom, a sulfur atom-containing group, an oxygen atom-containing group or a silicon atom-containing group). Manufacturing method. 3. The metal complex is PtCl ₄ , NiCl ₄ , P
dCl ₄ , H ₂ PtCl ₆ , PtBr ₄ , PtS ₄ , Pt
The method according to claim 2, wherein the compound is a compound selected from the group consisting of (OOCCH ₃ ) ₂ , platinum divinyl tetramethyl disiloxane and platinum-cyclovinyl methyl siloxane complex. 4. 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. 5. The saturated dicarboxylic acid and its derivative are
Terephthalic acid, isophthalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, hexahydroterephthalic acid, dimethyl terephthalic acid ester, dimethyl isophthalic acid ester, sodium salt of dimethyl 5-sulfoisophthalic acid ester, bis (2-hydroethyl) ) -5-Sulfoisophthalic acid sodium salt, a compound selected from the group consisting of 2,6-naphthalenedicarboxylic acid and their diesters.
The manufacturing method as described. 6. The diol is ethylene glycol, neopentyl glycol, 1,6-hexanediol, 1,
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. 7. The addition reaction of step (a) is carried out at 85-105.
2. The method according to claim 1, wherein the method is carried out at a temperature of 0. 8. The esterification reaction of step (b) is carried out using 180
The method according to claim 1, which is carried out at a temperature of from 250 to 250 ° C. 9. In the esterification reaction of 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. 10. The molar ratio of the phosphorus compound represented by the general formula (II) to the unsaturated dicarboxylic acid is 1: 1 to 1: 1.
2. The method according to claim 1, wherein the ratio is 1.05. 11. The molar ratio of the phosphorus compound represented by the general formula (II) to the unsaturated dicarboxylic acid is 1: 1.02.
The manufacturing method according to claim 10, wherein 12. The esterification reaction of 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. 13. The amount of the metal oxide catalyst is 0.02 to 0.3% by weight based on the phosphorus-containing dicarboxylic acid.
2. The production method according to 2. 14. General formula (I): 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, 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
A high molecular weight polyester type flame retardant represented by an integer of 0 and n is an integer of 1 to 10.