TW201506054A - Phosphorus-containing compound, phosphorus-containing polyester and manufacturing method thereof - Google Patents

Abstract

A phosphorus-containing compound, a phosphorus-containing polyester and a manufacturing method thereof are provided. The phosphorus-containing compound has an acetoxy group and a carboxyl group. The phosphorus-containing compound can undergo a condensation reaction so as to obtain the phosphorus-containing polyester featured with high glass transition temperature.

Description

Phosphorous compound, phosphorus polyester and preparation method thereof

The present invention relates to a phosphorus-based compound and a phosphorus-based polyester thereof, and a preparation method thereof, and particularly to a phosphorus-based compound having an ethoxylated group and a carboxyl group, and a phosphorus-based polyester formed therefrom Preparation.

Polyester is a general term for polymers obtained by polycondensation of polybasic acids or anhydrides with polyols. Although there are many types, polyethylene terephthalate (PET) is still commercially available. The bulk of the ester. PET is a semi-crystalline polymer having excellent properties such as heat resistance, chemical resistance, toughness, electrical insulation, safety, and the like. At the same time, because of its low price, it is widely used in fiber, container, product packaging, electrical parts or composite materials made of glass fiber. However, PET itself is flammable, and the glass transition temperature is not high, so the application is still relatively limited. Therefore, how to make PET no longer limited to these limitations is an urgent problem to be solved.

In the past, methods to improve the flammability of PET, for example, Toyo in 1973 Toyobo Co., Ltd. added 7-9% of oligomeric sulfonylbisphenol phenylphosphonate to PET. For example, in 1978, Toyobo Co., Ltd. added itaconic acid with 9 ,10-dihydro-9-oxA-I0-phosphaphenanthrene 10-oxide (DOPO) reaction to synthesize a novel phosphorus-containing diester, and This new phosphorus-containing diester is introduced into PET. For example, in 2004, some scholars added a novel nitrogen-phosphorus additive to PET.

However, although the above method can improve the flame retardancy of PET, it cannot effectively increase the glass transition temperature of PET. Furthermore, the foregoing methods are all additive physical mixing, so that uneven distribution or phase separation often occurs, which adversely affects the mechanical properties of PET. Therefore, there is still a lack of technical solutions for effectively increasing the transfer temperature of PET glass, and the application range of PET is difficult to break through.

An object of the present invention is to provide a phosphorus-based compound having an ethoxylated group and a carboxyl group, and the phosphorus-based compound can form a phosphorus-based polyester having an excellent glass transition temperature via a condensation reaction.

According to one embodiment of the structural aspect of the present invention, a phosphorus-based compound having a structure as shown in the formula (A) is proposed: (A); wherein R is an alkyl group having 1 to 6 carbon atoms, a phenyl group or a hydrogen atom.

According to the foregoing embodiment, R may be a methyl group, and the structure of the phosphorus compound is as shown in the formula (A1):

According to the foregoing embodiment, R may be a phenyl group, and the structure of the phosphorus compound is as shown in the formula (A2):

According to the foregoing embodiment, R may be a hydrogen atom, and the structure of the phosphorus compound is as shown in the formula (A3):

According to one embodiment of the method aspect of the present invention, a method for preparing a phosphorus compound having the structure of formula (A) is proposed, which comprises the following steps. First, a first intermediate having the structure of formula (II) is provided, specifically This step is a catalytic reaction of DOPO, a compound of the formula (I) and a phenol (Phenol) with an acidic catalyst to form a first intermediate. Next, a second intermediate having the structure of formula (III) is provided. Specifically, this step is a reaction of the first intermediate with acetic anhydride to form a second intermediate. Further, the second intermediate is oxidized. Specifically, this step is to oxidize the methyl group of the second intermediate to a carboxyl group to form a phosphorus compound, wherein the formula (I) is as follows: Formula (II) is as follows: Formula (III) is as follows:

According to the foregoing embodiment, in the step of providing the first intermediate of the formula (II), the acidic catalyst may be p-methylbenzoic acid. (p-Toluenesulfonic acid, PTSA), sulfuric acid (Sulfuric acid) or oxalic acid (Oxalic acid), and the amount of the acidic catalyst may be from 1% by weight to 4% by weight of the DOPO. Alternatively, this step can be carried out at 120 ° C to 180 ° C for 12 to 24 hours and can be carried out under a nitrogen atmosphere.

According to the foregoing embodiment, the step of providing the second intermediate having the structure of the formula (III) can be carried out at 100 ° C to 140 ° C for 1 to 24 hours, and can be carried out under a nitrogen atmosphere.

According to the foregoing embodiment, the step of oxidizing the second intermediate may be carried out at 100 ° C to 120 ° C for 12 to 24 hours, and may be carried out under an oxygen atmosphere.

According to another embodiment of the structural aspect of the present invention, a phosphorus-based polyester having a structure as shown in the formula (PA) is proposed: Wherein R is an alkyl group having 1 to 6 carbon atoms, a phenyl group or a hydrogen atom, and n is an integer of 10 to 50.

According to another embodiment of the aspect of the invention, there is provided a method for producing a phosphorus-based polyester comprising the steps of first providing a phosphorus-based compound having a structure as shown in the above formula (A). Next, a condensation reaction is carried out to form a phosphorus-based polyester.

According to the foregoing embodiment, the step of performing the condensation reaction may be a diphenyl sulfone as a solvent, and may provide manganese acetate (manganese (II) acetate, Mn (OAc) ₂ ) and acetic anhydride as a touch. The medium wherein the manganese acetate is used in an amount of from 0.5% by weight to 5% by weight based on the amount of the phosphorus compound, and the acetic anhydride is used in an amount of from 5 to 15% by weight based on the amount of the phosphorus compound. Further, this step can be carried out at 180 ° C to 280 ° C for 7 to 12 hours, or under a nitrogen atmosphere.

Fig. ^{1 is a 1} H-NMR spectrum chart of a first intermediate according to a first embodiment of the present invention.

Fig. ^{2 is a 1} H-NMR spectrum chart of a second intermediate according to the first embodiment of the present invention.

Fig. ^{3 is a 1} H-NMR spectrum chart of a phosphorus-based compound according to a first embodiment of the present invention.

In order to clarify and clarify the description of the embodiment, the structural formula of each chemical substance is immediately after each chemical substance. For example, "phosphorus compound (A)" represents "a phosphorus compound, and its structure is as follows." (A), for example, "phosphorus-based polyester (PA)" stands for "a kind of phosphorus-based polyester, and its structure is as shown in formula (PA)".

The present invention provides a phosphorus compound (A): Wherein R is an alkyl group having 1 to 6 carbon atoms, a phenyl group or a hydrogen atom.

When R is a methyl group, a phosphorus compound (A1) can be obtained:

When R is a phenyl group, a phosphorus compound (A2) can be obtained:

When R is a hydrogen atom, a phosphorus compound (A3) can be obtained: (A3).

The phosphorus compound (A) can be produced by the method shown in the following reaction formula 1: In the reaction formula 1, the preparation method of the phosphorus compound (A) roughly comprises three steps, the first step is to provide the first intermediate (II), in particular, the first step is to DOPO, the compound (I) and The excess phenol is reacted under the catalysis of an acidic catalyst to form a first intermediate (II). The first step can be carried out under a nitrogen atmosphere at a temperature of from 120 ° C to 180 ° C for 12 to 24 hours, preferably 130. The reaction is carried out at ° C to 150 ° C for 12 to 15 hours. The second step is to provide a second intermediate (III). Specifically, the second step is to react the first intermediate (II) with acetic anhydride to react the hydroxyl group of the first intermediate (II) into an ethoxy group. To form a second intermediate (III), the second step can be carried out under a nitrogen atmosphere at a temperature of from 100 ° C to 140 ° C for from 1 to 24 hours, preferably from 110 ° C to 130 ° C for from 8 to 12 hours. The third step is to oxidize the second intermediate (III). Specifically, the third step can be carried out at a temperature of from 100 ° C to 120 ° C for 12 to 24 hours, preferably in an oxygen atmosphere and catalytic catalyst. The reaction may be carried out at 110 ° C to 120 ° C for 12 to 15 hours to oxidize the methyl group of the second intermediate to a carboxyl group to form a phosphorus compound (A).

The phosphorus compound (A) can undergo a condensation reaction to form a phosphorus polyester (PA): Wherein n is an integer from 10 to 50.

When the condensation reaction is carried out with the phosphorus compound (A1), a phosphorus polyester (PA1) can be formed:

When the condensation reaction is carried out with the phosphorus compound (A2), a phosphorus polyester (PA2) can be formed:

When the condensation reaction is carried out with the phosphorus compound (A3), a phosphorus polyester (PA3) can be formed:

The above condensation reaction can be carried out at a temperature of from 180 ° C to 280 ° C for 7 to 12 hours under a nitrogen atmosphere, preferably at 220 ° C to 260 ° C for 8 to 12 hours.

Hereinafter, the phosphorus-based compound, the phosphorus-based polyester, the method for producing the phosphorus-based compound, and the method for preparing the phosphorus-based polyester of the present invention will be further described by way of examples.

<First Example> Preparation of a phosphorus-based compound (A1)

The preparation method of the phosphorus compound (A1) is as shown in the reaction equation 2:

First, a first intermediate (II-1) is provided which is obtained from 20 g (92.5 mmole) of DOPO, 12.41 g (92.5 mmole) of 4-methylacetophenone, and 43.5352 g (92.5 x 5). The mmole) phenol and the acidic catalyst (4 wt% based on DOPO) were placed in a three-necked round bottom flask, and nitrogen gas was introduced and heated to 130 ° C, and the reaction was continuously stirred for 12 hours. After the reaction, methanol was poured and stirring was continued for a while, and then a white powder was precipitated. Then, suction filtration was carried out, and the filter cake was placed in a vacuum oven and vacuum-dried at 100 ° C to obtain a product in which the yield was 50%, and the product was subjected to differential scanning calorimetry (DSC). The measurement revealed that the melting point was 294 °C. Referring to Fig. 1, which is a ¹ H-NMR spectrum of the above product, it can be confirmed from Fig. 1 that the above product is the first intermediate (II-1).

Next, a second intermediate (III-1) is provided which is obtained by placing 15 g (35.2 mmole) of the first intermediate (II-1), 0.15 g of sodium acetate, and 50 mL of acetic anhydride. The mixture was stirred in a three-necked round bottom flask, purged with nitrogen and heated to 130 ° C, and the reaction was continuously stirred for 12 hours. After the reaction was completed, the material was precipitated by cooling, and then the precipitate was obtained by filtration and washed several times with deionized water. Then, suction filtration was carried out, and the filter cake was placed in a vacuum oven and dried under vacuum at 140 ° C to obtain a product as a white powder, wherein the yield was 92%, and the product was found to have a melting point of 216 by DSC measurement. °C. Referring to Fig. 2, which is a ¹ H-NMR spectrum of the above product, it can be confirmed from Fig. 2 that the above product is the second intermediate (III-1).

Further, the second intermediate (III-1) is oxidized, which is 15 g (32.0 mmole) of the second intermediate (III-1), 0.15 g of sodium bromide (NaBr), 0.15 g of Cobalt acetate (Cobalt(II) acetate, Co(OAc) ₂ ), 0.15 g of manganese acetate, and 0.30 g of dicumyl peroxide were placed in a three-necked round bottom bottle, stirred, and heated with oxygen. The reaction was continuously stirred for 12 hours at 110 °C. After the reaction was completed, the material was precipitated by cooling, and then the precipitate was obtained by filtration and washed several times with deionized water. Then, suction filtration was carried out, and the filter cake was placed in a vacuum oven and dried under vacuum at 140 ° C to obtain a product as a white powder, wherein the yield was 80%. Referring to Fig. 3, which is a ¹ H-NMR spectrum of the above product, it can be confirmed from Fig. 3 that the above product is a phosphorus compound (A1).

<Second embodiment> Preparation of phosphorus compound (A2)

The preparation method of the phosphorus compound (A2) is as shown in the reaction formula 3:

First, a first intermediate (II-2) is provided which is obtained by taking 20 g (92.5 mmole) of DOPO, 18.16 g (92.5 mmole) of 4-methylbenzophenone, 43.5352 g (92.5). The phenol and the acidic catalyst (4 wt% based on DOPO) were stirred in a three-necked round bottom flask, purged with nitrogen and heated to 130 ° C, and the reaction was stirred for 12 hours. After the reaction, methanol was poured and stirring was continued for a while, and then a white powder was precipitated. Then, suction filtration was carried out, and the filter cake was placed in a vacuum oven and vacuum-dried at 100 ° C to obtain a product in which the yield was 50%, and the product was found to have a melting point of 290 ° C by DSC measurement. That is, the first intermediate (II-2).

Next, a second intermediate (III-2) is provided which is obtained by placing 15 g (30.7 mmole) of the first intermediate (II-2), 0.15 g of sodium acetate and 50 mL of acetic anhydride in a three-necked round bottom. The flask was stirred, purged with nitrogen and heated to 130 ° C, and the reaction was stirred for 12 hours. After the reaction was completed, the material was precipitated by cooling, and then the precipitate was obtained by filtration and washed several times with deionized water. Then, suction filtration is carried out, and the filter cake is placed in a vacuum oven and dried at 140 ° C in vacuum, that is, The product was obtained as a white powder, wherein the yield was 92%, and the product was found to have a melting point of 206 ° C as measured by DSC, and this product was the second intermediate (III-2).

Further, the second intermediate (III-2) is oxidized, which is 15 g (28.3 mmole) of the second intermediate (III-2), 0.15 g of sodium bromide, 0.15 g of cobalt acetate, 0.15 g of Manganese acetate and 0.30 g of dicumyl peroxide were placed in a three-necked round bottom flask, and oxygen was introduced and heated to 110 ° C, and the reaction was continuously stirred for 12 hours. After the reaction was completed, the material was precipitated by cooling, and then the precipitate was obtained by filtration and washed several times with deionized water. Then, suction filtration was carried out, and the filter cake was placed in a vacuum oven and vacuum-dried at 140 ° C to obtain a white powder product in which the yield was 80%, and the product was a phosphorus compound (A2).

<Third Example> Preparation of phosphorus compound (A3)

The preparation method of the phosphorus compound (A3) is as shown in the reaction formula 4:

First, a first intermediate (II-3) is provided, which is taken as 20 g (92.5 MME), DOPO, 11.12 g (92.5 mmole) of 4-methylbenzaldehyde, 43.5352 g (92.5×5 mmole) of phenol and acidic catalyst (4 wt% based on DOPO) were placed in a three-necked circle The bottom bottle was stirred, purged with nitrogen and heated to 130 ° C, and the reaction was continuously stirred for 12 hours. After the reaction, methanol was poured and stirring was continued for a while, and then a white powder was precipitated. Then, suction filtration was carried out, and the filter cake was placed in a vacuum oven and vacuum-dried at 100 ° C to obtain a product in which the yield was 50%, and the product was found to have a melting point of 286 ° C by DSC measurement. That is, the first intermediate (II-3).

Next, a second intermediate (III-3) is provided which is obtained by placing 15 g (36.4 mmole) of the first intermediate (II-3), 0.15 g of sodium acetate and 50 mL of acetic anhydride in a three-necked round bottom. The flask was stirred, purged with nitrogen and heated to 130 ° C, and the reaction was stirred for 12 hours. After the reaction was completed, the material was precipitated by cooling, and then the precipitate was obtained by filtration and washed several times with deionized water. Then, suction filtration was carried out, and the filter cake was placed in a vacuum oven and dried under vacuum at 140 ° C to obtain a product as a white powder, wherein the yield was 92%, and the product was found to have a melting point of 201 by DSC measurement. This product is the second intermediate (III-3) at °C.

Further, the second intermediate (III-3) is oxidized, which is 15 g (33.0 mmole) of the second intermediate (III-3), 0.15 g of sodium bromide, 0.15 g of cobalt acetate, 0.15 g. Manganese acetate and 0.30 g of dicumyl peroxide were placed in a three-necked round bottom flask, and oxygen was introduced and heated to 110 ° C, and the reaction was continuously stirred for 12 hours. After the reaction was completed, the material was precipitated by cooling, and then the precipitate was obtained by filtration and washed several times with deionized water. Then pumping Filtration, and the filter cake was placed in a vacuum oven and dried under vacuum at 140 ° C to obtain a white powder product in which the yield was 80%, and the product was a phosphorus compound (A3).

<Fourth embodiment> Preparation of phosphorus-based polyester (PA1)

The preparation method of the phosphorus-based polyester (PA1) is as shown in the reaction formula:

First, a phosphorus compound (A1) is provided, and secondly, a phosphorus compound (A1) is subjected to a condensation reaction. In this embodiment, 3 g (6.02 mmole) of the phosphorus compound (A1), 0.003 g of manganese acetate, 0.2 mL of acetic anhydride, and 15 g of diphenyl hydrazine are placed in a three-necked round bottom bottle and stirred. Nitrogen gas was introduced and heated to 250 ° C, and the reaction was continuously stirred for 7 hours. After the reaction, the material was precipitated by cooling, and then the precipitate was obtained by filtration and washed several times with methanol. Then, the filter cake was taken by suction filtration, and the filter cake was placed in a vacuum oven and dried under vacuum at 140 ° C to obtain a product as a white powder. The product was measured by DSC, and the glass transition temperature of the product was 215 ° C. That is, a phosphorus-based polyester (PA1). As a result of measurement by DSC, it is known that the phosphorus-based polyester (PA1) has a relatively high glass transition temperature.

<Fifth embodiment> Modification of polyester (C) with phosphorus compound (A1)

First, a phosphorus compound (A1) and a polyester (C) are provided, Among them, the phosphorus compound (A1) is as described above, the polyester (C) is commercially available PET, and m represents the number of repeating units.

Thereafter, Example 5-1, Example 5-2, and Example 5-3 were prepared, and Example 5-1, Example 5-2, and Example 5-3 were a phosphorus compound (A1) and a polyester ( C) three different molar ratios of 3:1, 1:1 and 1:3, respectively, placed in a separate reactor, stirred and mixed, while passing nitrogen and heated to 275 ° C and stirring for 0.5 hours, such as complete melting Thereafter, the temperature was raised to 280 to 300 ° C, and the nitrogen gas was turned off, and the vacuum was continuously stirred for 4 hours to carry out acid hydrolysis and condensation reaction of the phosphorus compound (A1) and the polyester (C). Then, the dark red solid which was cooled after the reaction was crushed and taken out, placed in a vacuum oven, and dried under vacuum at 140 ° C, and the obtained khaki powder was a phosphorus-based copolyester (A1-C). Wherein x and y are composition fractions of the phosphorus-based compound (A1) and the polyester (C) in the phosphorus-based copolyester (A1-C), respectively, and x and y are both greater than 0 and the sum of x and y is 1.

Comparative Example 1 is a polyester (C) which does not contain a phosphorus compound (A1).

Examples 5-1 to 5-3 and Comparative Example 1 were analyzed by DSC and Thermogravimetric Analysis (TGA) to examine the respective heat of glass transition temperature (Tg) and thermal decomposition temperature (Td). The stability properties and the flame retardancy test were also carried out. The results of the above analysis and test are shown in Table 1 below.

As is clear from Table 1, the polyester (C) of Comparative Example 1 had a glass transition temperature of 77 ° C and was flammable. When the polyester (C) is modified with the phosphorus compound (A1), that is, the phosphorus compound (A1) is introduced into the polyester (C) to form a phosphorus-based copolyester (A1-C), as in Example 5. -1~5-3, the phosphorus-based copolyester (A1-C) has flame retardancy, and the higher the content of the phosphorus-based compound (A1) in the phosphorus-based copolyester (A1-C), the phosphorus-based The glass transition temperature of the polyester (A1-C) is also higher. When the molar ratio of the phosphorus compound (A1) to the polyester (C) is 3:1, the glass transition temperature can be as high as 184 °C.

<Sixth embodiment> Modification of polyester (C) with phosphorus compound (A2)

First, a phosphorus compound (A2) and a polyester (C) are provided, and a phosphorus compound is provided. Both the substance (A2) and the polyester (C) are the same as described above.

Thereafter, Example 6-1, Example 6-2, and Example 6-3 were prepared, and Example 6-1, Example 6-2, and Example 6-3 were a phosphorus compound (A2) and a polyester (C). 3, 3:1, 1:1 and 1:3 three different molar ratios, respectively, placed in a separate reactor stirred and mixed, while passing nitrogen and heated to 275 ° C and stirring for 0.5 hours, after complete melting It is raised to 280~300 °C, and the nitrogen gas is turned off and the vacuum is continuously stirred for 4 hours to carry out acid hydrolysis and condensation reaction of the phosphorus compound (A2) and the polyester (C). Then, the dark red solid which was allowed to cool after the reaction was crushed and taken out, placed in a vacuum oven, and dried under vacuum at 140 ° C, and the obtained khaki powder was a phosphorus-based copolyester (A2-C). Wherein x and y are composition fractions of the phosphorus-based compound (A2) and the polyester (C) in the phosphorus-based copolyester (A2-C), respectively, wherein x and y are both greater than 0 and the sum of x and y is 1.

Comparative Example 1 is a polyester (C) which does not contain a phosphorus compound (A2).

The physical property analysis test results of the glass transition temperature, the thermal cracking temperature, and the flame retardancy of Examples 6-1 to 6-3 and Comparative Example 1 are shown in Table 2 below.

As is clear from Table 2, the polyester (C) of Comparative Example 1 had a glass transition temperature of 77 ° C and was flammable. When the polyester (C) is modified with the phosphorus compound (A2), that is, the phosphorus compound (A2) is introduced into the polyester (C) to form a phosphorus-based copolyester (A2-C), as in Example 6. -1~6-3, the phosphorus-based copolyester (A2-C) has flame retardancy, and the phosphorus-based copolyester (A2-C) has a higher content of the phosphorus-based compound (A2). The glass transition temperature of the polyester (A2-C) is also higher. When the molar ratio of the phosphorus compound (A2) to the polyester (C) is 3:1, the glass transition temperature can be as high as 192 °C.

<Seventh embodiment> Modification of polyester (C) with phosphorus compound (A3)

First, a phosphorus compound (A3) and a polyester (C) are provided, and the phosphorus compound (A3) and the polyester (C) are the same as described above.

Thereafter, Example 7-1, Example 7-2, and Example 7-3 were prepared, and Example 7-1, Example 7-2, and Example 7-3 were a phosphorus compound (A3) and a polyester ( C) three different molar ratios of 3:1, 1:1 and 1:3, respectively, placed in a separate reactor, stirred and mixed, while passing nitrogen and heated to 275 ° C and stirring for 0.5 hours, such as complete melting Thereafter, the temperature was raised to 280 to 300 ° C, and the nitrogen gas was turned off, and the vacuum was continuously stirred for 4 hours to carry out acid hydrolysis and condensation reaction of the phosphorus compound (A3) and the polyester (C). Next, the dark red solid which was allowed to cool after the reaction was crushed and taken out, placed in a vacuum oven, and dried under vacuum at 140 ° C, and the obtained khaki powder was a phosphorus-based copolyester (A3-C). Wherein x and y are composition fractions of the phosphorus-based compound (A3) and the polyester (C) in the phosphorus-based copolyester (A3-C), respectively, wherein x and y are both greater than 0 and the sum of x and y is 1.

Comparative Example 1 is a polyester (C) which does not contain a phosphorus compound (A3).

The physical property analysis test results of the glass transition temperature, the thermal cracking temperature, and the flame retardancy of Examples 7-1 to 7-3 and Comparative Example 1 are shown in Table 3 below.

As is clear from Table 3, the polyester (C) of Comparative Example 1 had a glass transition temperature of 77 ° C and was flammable. When the polyester (C) is modified with the phosphorus compound (A3), that is, the phosphorus compound (A3) is introduced into the polyester (C) to form a phosphorus-based copolyester (A3-C), as in Example 7. -1~7-3, phosphorus-based copolyester (A3-C) is flame retardant, and phosphorus in phosphorus-based copolyester (A3-C) The higher the content of the compound (A3), the higher the glass transition temperature of the phosphorus-based copolyester (A3-C), when the molar ratio of the phosphorus-based compound (A3) to the polyester (C) is 3:1. The glass transfer temperature can be as high as 185 °C.

It can be seen from the above embodiments that the phosphorus-based compound of the present invention can undergo a condensation reaction to form a phosphorus-based polyester. The glass-based polyester has a glass transition temperature superior to that of a conventional polyester such as PET, and can break the application limit of the conventional polyester. In addition, the phosphorus-based compound of the present invention can also be introduced into a conventional polyester such as PET to improve the flammability of the conventional polyester and the low glass transition temperature, thereby expanding the application range of the conventional polyester.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.

Claims (20)

A phosphorus compound having the structure shown in formula (A): Wherein R is an alkyl group having 1 to 6 carbon atoms, a phenyl group or a hydrogen atom. The phosphorus-based compound of claim 1, wherein the R is a methyl group, and the structure of the phosphorus-based compound is as shown in the formula (A1): The phosphorus-based compound of claim 1, wherein the R is a phenyl group, and the structure of the phosphorus-based compound is as shown in the formula (A2): The phosphorus-based compound of claim 1, wherein the R is a hydrogen atom, and the structure of the phosphorus-based compound is as shown in the formula (A3): A method for preparing a phosphorus-based compound according to claim 1, comprising: providing a first intermediate having the structure of formula (II), which is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 - an oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, DOPO), a compound of the formula (I) and a phenol (Phenol) are catalytically reacted with an acidic catalyst to form the first An intermediate; providing a second intermediate having the structure of formula (III), reacting the first intermediate with acetic anhydride to form the second intermediate; and oxidizing the second intermediate to make the second The methyl group of the intermediate is oxidized to a carboxyl group to form the phosphorus compound; wherein, the formula (I) is as follows: Formula (II) is as follows: Formula (III) is as follows: The method for producing a phosphorus-based compound according to claim 5, wherein in the step of providing the first intermediate of the formula (II), the acidic catalyst is p-Toluenesulfonic acid (PTSA). ), sulfuric acid (Sulfuric acid) or oxalic acid (Oxalic acid). The method for producing a phosphorus compound according to claim 5, wherein in the step of providing the first intermediate of the formula (II), the acidic catalyst is used in an amount of from 1 to 4% by weight based on the amount of the DOPO. The method for producing a phosphorus-based compound according to claim 5, wherein the step of providing the first intermediate having the structure of the formula (II) is carried out at a temperature of from 120 ° C to 180 ° C for from 12 hours to 24 hours. The method for producing a phosphorus-based compound according to claim 5, wherein the step of providing the first intermediate of the structure of the formula (II) is carried out under a nitrogen atmosphere. The method for producing a phosphorus-based compound according to claim 5, wherein the step of providing the second intermediate having the structure of the formula (III) is carried out at a temperature of from 100 ° C to 140 ° C for from 1 hour to 24 hours. The method for producing a phosphorus-based compound according to claim 5, wherein the step of providing the second intermediate having the structure of the formula (III) is carried out under a nitrogen atmosphere. The method for producing a phosphorus-based compound according to claim 5, wherein the step of oxidizing the second intermediate is carried out at a temperature of from 100 ° C to 120 ° C for from 12 hours to 24 hours. The method for producing a phosphorus-based compound according to claim 5, wherein the step of oxidizing the second intermediate is carried out under an oxygen atmosphere. A phosphorus-based polyester whose structure is as shown in formula (PA): (PA); wherein R is an alkyl group having 1 to 6 carbon atoms, a phenyl group or a hydrogen atom, and n is an integer of 10 to 50. A method for producing a phosphorus-based polyester according to claim 14, comprising: providing a phosphorus-based compound having a structure as shown in the formula (A): A condensation reaction is carried out to form the phosphorus-based polyester. The method for producing a phosphorus-based polyester according to claim 15, wherein the step of performing the condensation reaction is diphenyl sulfone as a solvent. The method for preparing a phosphorus-based polyester according to claim 15, wherein the step of performing the condensation reaction further comprises providing manganese acetate (managed (II) acetate, Mn (OAc) ₂ ) and acetic anhydride as a touch. Media. A method for producing a phosphorus-based polyester according to claim 17, wherein the acetic acid Manganese is used in an amount of from 0.5% by weight to 5% by weight based on the amount of the phosphorus compound, and the acetic anhydride is used in an amount of from 5 to 15% by weight based on the amount of the phosphorus compound. The method for producing a phosphorus-based polyester according to claim 15, wherein the step of performing the condensation reaction is carried out at a temperature of from 180 ° C to 280 ° C for from 7 hours to 12 hours. The method for producing a phosphorus-based polyester according to claim 15, wherein the step of performing the condensation reaction is carried out under a nitrogen atmosphere.