Phosphorus-based compound, preparation method therefor, flame-retardant polyphenylene oxide resin composition and cured product

Abstract

To provide a phosphorus-based compound having high compatibility with polyphenylene oxide and capable of preparing a flame-retardant polyphenylene oxide resin cured product, and also to provide a preparation method for a phosphorus-based compound having low production cost.SOLUTION: Provided is a phosphorus-based compound having a structure shown in formula (I).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a phosphorus-based compound, a method for preparing the same, a flame-retardant polyphenylene oxide resin composition, and a cured product thereof, and more particularly to a phosphorus-based compound having phenyl methacrylate and a vinylbenzyl ether functional group, a method for preparing the same, a flame-retardant polyphenylene oxide resin composition, and a cured product thereof. [Background technology]

[0002] In high-frequency communication substrates, polyphenylene oxide is often used as an insulating layer resin and is manufactured into printed circuit boards together with flame retardants, rubber, glass fiber, and copper foil laminates. However, since the insulating layer resin and rubber are flammable materials, a flame retardant must be added separately to improve the flame retardancy of the entire printed circuit board.

[0003] In recent years, with growing awareness of environmental protection, the use of halogen-containing flame retardants has been banned, and the development of halogen-free flame retardants has begun. Typical halogen-free flame retardants are phosphorus-based flame retardants, of which 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) derivative-type phosphorus flame retardants have superior thermal and chemical stability compared to common organic phosphate esters, and furthermore have the characteristics of a high glass transition temperature and long-lasting flame retardancy. Summary of the Invention [Problem to be solved by the invention]

[0004] However, there are compatibility issues between common flame retardants and polyphenylene oxide resins, and some flame retardants can only be dispersed in the resin by processing means, which results in problems such as uneven distribution or precipitation of the flame retardant after curing, which are disadvantageous for practical application.

[0005] In view of this, the goal of those in the related art is to synthesize phosphorus compounds that are highly compatible with polyphenylene oxide at low cost. [Means for solving the problem]

[0006] One object of the present invention is to provide a phosphorus-based compound and a method for preparing the same. The phosphorus-based compound of the present invention uses low-cost raw materials, which contributes to reducing production costs and further expands the range of applications.

[0007] Another object of the present invention is to provide a flame-retardant polyphenylene oxide resin composition and a cured product thereof which are prepared using the above-mentioned phosphorus-based compound and have thermal and chemical stability.

[0008] One embodiment of the present invention provides a phosphorus-based compound having the structure shown in formula (I): [ka] In the formula, R1 and R2 each independently represent a hydrogen atom, a C1-C6 alkyl group, a trifluoromethyl group, an unsubstituted phenyl group, a substituted phenyl group, an unsubstituted C3-C 10 cycloalkyl groups, substituted C3-C 10 a cycloalkyl group, a fluorenyl group, or a halogen atom. R3, R4, R5 and R6 are each independently hydrogen, a C1 to C6 alkyl group, a trifluoromethyl group, an unsubstituted phenyl group, a substituted phenyl group, an unsubstituted C3 to C6 alkyl ... 10 cycloalkyl groups, substituted C3-C 10 a cycloalkyl group, a halogen atom, or a nitro group. X is a structure shown in formula (i), formula (ii), formula (iii), or formula (iv). [ka] wherein R7, R8, and R9 are each independently hydrogen, a C1-C6 alkyl group, an unsubstituted phenyl group, a substituted phenyl group, or a halogen atom; R 10 is a C1-C6 alkylene group or an unsubstituted C3-C 10 is a cycloalkylene group of the formula:

[0009] Another embodiment of the present invention provides a method for preparing a phosphorus-based compound, comprising the steps of: conducting a synthesis reaction, a catalytic reaction, and a substitution reaction, in which an organic phosphorus-containing compound represented by formula (1) is reacted with a carbonyl group-containing compound represented by formula (2) to obtain a hydroxy group-containing compound represented by formula (3). [ka] In the catalytic reaction, a hydroxyl group-containing compound represented by formula (3) and a phenolic compound represented by formula (4) are reacted in the presence of an acid catalyst to obtain a phosphorus-based hydroxyl group compound represented by formula (5). [ka] In the substitution reaction, the phosphorus-based hydroxy compound represented by formula (5) is reacted with the compound represented by formula (6), formula (7), formula (8), or formula (9) to obtain the phosphorus-based compound according to the above embodiment. [ka]

[0010] According to the method for preparing phosphorus-based compounds described in the preceding paragraph, the acid catalyst may be acetic acid, methanesulfonic acid, oxalic acid, sulfuric acid, p-toluenesulfonic acid, or a combination thereof.

[0011] Yet another embodiment of the present invention provides a method for preparing a phosphorus-based compound, comprising the steps of: conducting a catalytic reaction; and conducting a substitution reaction. In the catalytic reaction, an organic phosphorus-containing compound represented by formula (1) is reacted with a bisphenol compound represented by formula (10) in the presence of an acid catalyst to obtain a phosphorus-based hydroxy compound represented by formula (5). [ka] In the substitution reaction, the phosphorus-based hydroxy compound represented by formula (5) is reacted with the compound represented by formula (6), formula (7), formula (8), or formula (9) to obtain the phosphorus-based compound according to the above embodiment. [ka]

[0012] According to the method for preparing phosphorus-based compounds described in the preceding paragraph, the acid catalyst may be acetic acid, methanesulfonic acid, oxalic acid, sulfuric acid, p-toluenesulfonic acid, or a combination thereof.

[0013] Yet another embodiment of the present invention provides a flame-retardant polyphenylene oxide resin composition comprising the above-described phosphorus-based compound and a polyphenylene oxide resin.

[0014] According to the flame-retardant polyphenylene oxide resin composition described in the preceding paragraph, the phosphorus content of the phosphorus-based compound in the flame-retardant polyphenylene oxide resin composition may be 0.05% to 8%.

[0015] Yet another embodiment of the present invention provides a flame-retardant cured polyphenylene oxide resin obtained by mixing the above-described flame-retardant polyphenylene oxide resin composition with a double bond initiator and curing the mixture by heating.

[0016] According to the flame-retardant cured polyphenylene oxide resin described in the preceding paragraph, the double bond initiator may be dicumyl peroxide, benzoyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, or a combination thereof.

[0017] According to the flame-retardant polyphenylene oxide resin cured product described in the preceding paragraph, the content of the double bond initiator may be 0.1 wt % to 1.5 wt % of the total weight of the flame-retardant polyphenylene oxide resin composition. [Effects of the Invention]

[0018] Therefore, the phosphorus-based compound of the present invention can be prepared in at most three steps, which simplifies the process and reduces production costs. Furthermore, the phosphorus-based compound of the present invention can be added to polyphenylene oxide resin, and the cured product prepared therefrom has low dielectric properties and good flame retardancy and can be used as a manufacturing material for base plates, copper foil substrates, or printed circuit boards. [Brief explanation of the drawings]

[0019] To make the above and other objects, features, advantages and embodiments of the present invention more clear and understandable, reference is made to the accompanying drawings as follows. [Figure 1] 1 is a process flow chart illustrating a method for preparing a phosphorus-based compound according to one embodiment of the present invention. [Figure 2] 1 is a process flow chart illustrating a method for preparing a phosphorus-based compound according to another embodiment of the present invention. [Figure 3] 1 shows a 1H-NMR spectrogram of Example 1. [Figure 4] 1 shows the 1H-NMR spectrogram of Example 2. [Figure 5] 1 shows the 1H-NMR spectrogram of Example 5. [Figure 6] 1 shows the 1H-NMR spectrogram of Example 7. DETAILED DESCRIPTION OF THE INVENTION

[0020] Each embodiment of the present invention will be discussed in more detail below. However, the embodiments may be applications of various inventive concepts and may be specifically implemented within a variety of different specific scopes. The specific embodiments are merely illustrative and are not limited to the scope disclosed.

[0021] In the present invention, the term "C X " indicates that the group has X carbon atoms.

[0022] In the present invention, the structure of a compound may be expressed by a skeleton formula, and in this expression, carbon atoms, hydrogen atoms, and carbon-hydrogen bonds may be omitted. When functional groups are clearly depicted in the structural formula, the depicted groups are used as the basis.

[0023] In the present invention, for the sake of brevity and fluency, the "phosphorus compound having the structure shown in formula (I)" may be referred to as the phosphorus compound shown in formula (I) or phosphorus compound (I), and other compounds or groups are represented in this manner.

[0024] <Phosphorus compounds>

[0025] The present invention provides a phosphorus-based compound having the structure shown in formula (I): [ka] In the formula, R1 and R2 each independently represent a hydrogen atom, a C1-C6 alkyl group, a trifluoromethyl group, an unsubstituted phenyl group, a substituted phenyl group, an unsubstituted C3-C 10 cycloalkyl groups, substituted C3-C 10 a cycloalkyl group, a fluorenyl group, or a halogen atom. R3, R4, R5 and R6 are each independently hydrogen, a C1 to C6 alkyl group, a trifluoromethyl group, an unsubstituted phenyl group, a substituted phenyl group, an unsubstituted C3 to C6 alkyl ... 10 cycloalkyl groups, substituted C3-C 10 a cycloalkyl group, a halogen atom, or a nitro group. X is a structure shown in formula (i), formula (ii), formula (iii), or formula (iv). [ka] In the formula, R7, R8, and R9 are each independently a hydrogen atom, a C1-C6 alkyl group, an unsubstituted phenyl group, a substituted phenyl group, or a halogen atom; 10is a C1-C6 alkylene group or an unsubstituted C3-C 10 is a cycloalkylene group of the formula:

[0026] The aforementioned "substituted phenyl group" means that hydrogen on the phenyl group can be substituted with a monovalent organic group or a halogen atom, and the monovalent organic group may be a C1 to C6 alkyl group or a trifluoromethyl group, and the halogen atom may be -F, -Cl, or -Br.

[0027] The aforementioned "substituted cycloalkyl group" means that hydrogen on the cycloalkyl group can be substituted with a monovalent organic group or a halogen atom, and the monovalent organic group may be a C1 to C6 alkyl group or a trifluoromethyl group, and the halogen atom may be -F, -Cl, or -Br.

[0028] As a result, the cost of the raw materials used in the phosphorus-based compound of the present invention is low, which contributes to reducing the production cost and further expands the range of application.

[0029] <Method for preparing phosphorus-based compounds>

[0030] Please refer to Figure 1, which is a process flow diagram illustrating a method 100 for preparing a phosphorus-based compound according to one embodiment of the present invention. In Figure 1, the method 100 for preparing a phosphorus-based compound includes steps 110, 120, and 130.

[0031] In step 110, an organic phosphorus-containing compound represented by formula (1) is reacted with a carbonyl group-containing compound represented by formula (2) to perform a synthesis reaction to obtain a hydroxy group-containing compound represented by formula (3). [ka] For definitions of R1 and R2, please refer to the above and they will not be explained separately here.

[0032] In step 120, a hydroxyl group-containing compound represented by formula (3) and a phenolic compound represented by formula (4) are reacted in the presence of an acid catalyst to form a phosphorus-based hydroxyl group compound represented by formula (5). [ka] For the definitions of R1, R2, R3, R4, R5 and R6, please refer to the above and will not be explained separately here, but the acid catalyst may be, but is not limited to, acetic acid, methanesulfonic acid, oxalic acid, sulfuric acid, p-toluenesulfonic acid or a combination thereof.

[0033] In step 130, a phosphorus-based hydroxy compound represented by formula (5) is reacted with a compound represented by formula (6), formula (7), formula (8), or formula (9) to carry out a substitution reaction to obtain a phosphorus-based compound represented by formula (I). [ka] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 The definitions of and X are given above and will not be explained separately here.

[0034] Specifically, the phosphorus-based compounds obtained by reacting the phosphorus-based hydroxy group compound represented by formula (5) with the compound represented by formula (6), formula (7), formula (8), or formula (9) have the structures represented by formula (I-1), formula (I-2), formula (I-3), or formula (I-4), respectively, and the reaction formulas are as shown in Table 1 below. [Table 1]

[0035] 2, which is a process flow diagram illustrating a method 200 for preparing a phosphorus-based compound according to another embodiment of the present invention. In FIG. 2, the method 200 for preparing a phosphorus-based compound includes steps 210 and 220.

[0036] In step 210, an organic phosphorus-containing compound represented by formula (1) and a bisphenol compound represented by formula (10) are reacted with an acid catalyst to produce a phosphorus-based hydroxy group compound represented by formula (5). [ka] The definitions of R1, R2, R3, R4, R5 and R6 and the type of acid catalyst are as described above and will not be explained here.

[0037] In step 220, a phosphorus-based hydroxy compound represented by formula (5) is reacted with a compound represented by formula (6), formula (7), formula (8), or formula (9) to perform a substitution reaction to obtain a phosphorus-based compound represented by formula (I). [ka] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 The definitions and reaction formulas for and X are given above and will not be explained here separately.

[0038] <Flame-retardant polyphenylene oxide resin composition>

[0039] The present invention provides a flame-retardant polyphenylene oxide resin composition obtained by mixing the above-mentioned phosphorus-based compound with a polyphenylene oxide resin, and the phosphorus content of the phosphorus-based compound in the flame-retardant polyphenylene oxide resin composition may be 0.05% to 8%. For the description of the phosphorus-based compound, please refer to the above, and no separate description will be given here.

[0040] <Flame-retardant cured polyphenylene oxide resin>

[0041] The present invention provides a flame-retardant polyphenylene oxide resin cured product obtained by mixing the aforementioned flame-retardant polyphenylene oxide resin composition with a double bond initiator, followed by heating and curing. The double bond initiator may be, but is not limited to, dicumyl peroxide, benzoyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, or a combination thereof, and the content of the double bond initiator is 0.1 wt% to 1.5 wt% of the total weight of the flame-retardant polyphenylene oxide resin composition.

[0042] Specifically, adding the aforementioned phosphorus-based compound to a polyphenylene oxide resin by physical mixing can impart flame retardancy to the final product, i.e., the final product is a flame-retardant cured polyphenylene oxide resin. The polyphenylene oxide resin refers to a polyphenylene oxide resin having double bonds, and the double bonds of the resin undergo copolymerization (hereinafter referred to as addition polymerization) by addition reaction with the terminal double bonds of the phosphorus-based compound. The addition polymerization may be carried out under heat curing conditions, and a double bond initiator may be added depending on actual needs. The use of a double bond initiator to open double bonds and cause polymerization is a conventional technique and will not be described in detail here.

[0043] The present invention will now be further illustrated by specific examples, which are provided to enable those skilled in the art to fully utilize and practice the present invention without undue interpretation. These examples should not be construed as limitations on the scope of the present invention, but are used to explain how to implement the materials and methods of the present invention.

[0044] <Synthesis example>

[0045] Synthesis Example 1: 10 grams of DOPO monomer and 50 grams of acetone were placed in a 250 ml three-neck reactor, and the mixture was stirred magnetically in a sealed nitrogen atmosphere. The reaction temperature was controlled at 50°C and the reaction was carried out for 6 hours. After the reaction was completed, the white precipitate was filtered, and the filter cake was baked to obtain the product. The filtrate was allowed to stand to yield transparent crystals, with a yield of 98%. The reaction scheme for Synthesis Example 1 is shown in Table 2 below. [Table 2]

[0046] Synthesis Example 2: 10 grams of Synthesis Example 1, 17.16 grams of phenol, and 0.4 grams of p-toluenesulfonic acid were placed in a 250 ml three-neck reactor and stirred magnetically under a nitrogen atmosphere. The reaction temperature was controlled at 110 ° C and the reaction was carried out for 6 hours. After the reaction was completed, the reactor was cooled to room temperature and then poured into water and stirred continuously to obtain a precipitate, which was then washed with boiling water several times. After filtration, the precipitate was baked in a vacuum oven at 75 ° C to obtain a white powder with a yield of 81%. The reaction formula for Synthesis Example 2 is shown in Table 3 below. [Table 3]

[0047] Synthesis Example 3: 30 grams of DOPO monomer, 15.8 grams of bisphenol A, and 1.2 grams of p-toluenesulfonic acid were placed in a 100 ml three-neck reactor and stirred magnetically under a nitrogen atmosphere. The reaction temperature was controlled at 130°C and the reaction was allowed to proceed for 12 hours. After the reaction was complete, the reactor was cooled to room temperature and poured into methanol / water (volume ratio 1 / 1) to precipitate the product. The product was washed multiple times with methanol / water, filtered, and baked in a vacuum oven at 75°C to obtain a white powder with a yield of 80%. The reaction scheme for Synthesis Example 3 is shown in Table 4 below. [Table 4]

[0048] Synthesis Example 4: 30 grams of DOPO monomer, 19.74 grams of tetramethylbisphenol A, and 1.2 grams of p-toluenesulfonic acid were placed in a 100 ml three-neck reactor and stirred magnetically under a nitrogen atmosphere. The reaction temperature was controlled at 140°C and the reaction was allowed to proceed for 12 hours. After the reaction was complete, the reactor was cooled to room temperature and poured into methanol / water (volume ratio 1 / 1) to precipitate the product. The product was washed multiple times with methanol / water, filtered, and baked in a vacuum oven at 75°C to obtain a white powder with a yield of 92%. The reaction scheme for Synthesis Example 4 is shown in Table 5 below. [Table 5]

[0049] Synthesis Example 5: 30 grams of DOPO monomer, 24.31 grams of bisphenol fluorene, and 1.2 grams of p-toluenesulfonic acid were placed in a 100 ml three-neck reactor and stirred magnetically under a nitrogen atmosphere. The reaction temperature was controlled at 140°C and the reaction was allowed to proceed for 12 hours. After the reaction was complete, the reactor was cooled to room temperature and poured into methanol / water (volume ratio 1 / 1) to precipitate the product. The product was then washed several times with methanol / water, filtered, and baked in a vacuum oven at 75°C to obtain a white powder with a yield of 90%. The reaction scheme for Synthesis Example 5 is shown in Table 6 below. [Table 6]

[0050] Synthesis Example 6: 30 grams of DOPO monomer, 18.62 grams of bisphenol Z, and 1.2 grams of p-toluenesulfonic acid were placed in a 100 ml three-neck reactor and stirred magnetically under a nitrogen atmosphere. The reaction temperature was controlled at 130°C and the reaction was allowed to proceed for 12 hours. After the reaction was complete, the reactor was cooled to room temperature and poured into methanol / water (volume ratio 1 / 1) to precipitate the product. The product was then washed several times with methanol / water, filtered, and baked in a vacuum oven at 75°C to obtain a white powder with a yield of 80%. The reaction scheme for Synthesis Example 6 is shown in Table 7 below. [Table 7]

[0051] <Example>

[0052] Example 1: 10 grams of Synthesis Example 2 or Synthesis Example 3, 13.2 grams of methacrylic anhydride, 0.264 grams of sodium acetate, and 30 milliliters of dimethylacetamide were placed in a 100 milliliter three-neck reactor and stirred magnetically under a nitrogen atmosphere. The reaction temperature was controlled at 80°C and the reaction was allowed to proceed for 24 hours. After the reaction was completed, the reactor was cooled to room temperature, poured into deionized water to precipitate, and washed several times with deionized water. After filtration, the mixture was baked in a vacuum oven at 75°C to obtain a white powder with a yield of 80%. The reaction scheme for Example 1 is shown in Table 8 below. [Table 8]

[0053] Example 2: 10 grams of Synthesis Example 2 or Synthesis Example 3, 5.21 grams of 4-chlorostyrene, 0.072 grams of potassium carbonate, and 30 milliliters of dimethylacetamide were placed in a 100 milliliter three-neck reactor and stirred magnetically under a nitrogen atmosphere. The reaction temperature was controlled at 80°C and the reaction was allowed to proceed for 24 hours. After the reaction was completed, the reactor was cooled to room temperature, poured into deionized water to precipitate, and washed several times with deionized water. After filtration, the mixture was baked in a vacuum oven at 75°C to obtain a white powder with a yield of 80%. The reaction scheme for Example 2 is shown in Table 9 below. [Table 9]

[0054] Example 3: 10 grams of Synthesis Example 4, 6.111 grams of methacrylic anhydride, 0.12 grams of sodium acetate, and 30 milliliters of dimethylacetamide were placed in a 100 milliliter three-neck reactor and stirred magnetically under a nitrogen atmosphere. The reaction temperature was controlled at 80°C and the reaction was allowed to proceed for 24 hours. After the reaction was completed, the reactor was cooled to room temperature, poured into deionized water to precipitate, and washed several times with deionized water. After filtration, the mixture was baked in a vacuum oven at 75°C to obtain a white powder with a yield of 80%. The reaction scheme for Example 3 is shown in Table 10 below. [Table 10]

[0055] Example 4: 10 grams of Synthesis Example 4, 5.63 grams of 4-chlorostyrene, 0.078 grams of potassium carbonate, and 30 milliliters of dimethylacetamide were placed in a 100 milliliter three-neck reactor and stirred magnetically under a nitrogen atmosphere. The reaction temperature was controlled at 80°C and the reaction was allowed to proceed for 24 hours. After the reaction was completed, the reactor was cooled to room temperature, poured into deionized water to precipitate, and washed several times with deionized water. After filtration, the mixture was baked in a vacuum oven at 75°C to obtain a white powder with a yield of 80%. The reaction scheme for Example 4 is shown in Table 11 below. [Table 11]

[0056] Example 5: 10 grams of Synthesis Example 5, 4.89 grams of methacrylic anhydride, 0.098 grams of sodium acetate, and 30 milliliters of dimethylacetamide were placed in a 100 milliliter three-neck reactor and stirred magnetically under a nitrogen atmosphere. The reaction temperature was controlled at 80°C and the reaction was allowed to proceed for 24 hours. After the reaction was completed, the reactor was cooled to room temperature, poured into deionized water to precipitate, and washed several times with deionized water. After filtration, the mixture was baked in a vacuum oven at 75°C to obtain a white powder with a yield of 80%. The reaction scheme for Example 5 is shown in Table 12 below. [Table 12]

[0057] Example 6: 10 grams of Synthesis Example 5, 7.03 grams of 4-chlorostyrene, 0.097 grams of potassium carbonate, and 30 milliliters of dimethylacetamide were placed in a 100 milliliter three-neck reactor and stirred magnetically under a nitrogen atmosphere. The reaction temperature was controlled at 80°C and the reaction was allowed to proceed for 24 hours. After the reaction was completed, the reactor was cooled to room temperature, poured into deionized water to precipitate, and washed several times with deionized water. After filtration, the mixture was baked in a vacuum oven at 75°C to obtain a white powder with a yield of 80%. The reaction scheme for Example 6 is shown in Table 13 below. [Table 13]

[0058] Example 7: 10 grams of Synthesis Example 6, 5.92 grams of methacrylic anhydride, 0.118 grams of sodium acetate, and 30 milliliters of dimethylacetamide were placed in a 100 milliliter three-neck reactor and stirred magnetically under a nitrogen atmosphere. The reaction temperature was controlled at 80°C and the reaction was allowed to proceed for 24 hours. After the reaction was completed, the reactor was cooled to room temperature, poured into deionized water to precipitate, and washed several times with deionized water. After filtration, the mixture was baked in a vacuum oven at 75°C to obtain a white powder with a yield of 80%. The reaction scheme for Example 7 is shown in Table 14 below. [Table 14]

[0059] Example 8: 10 grams of Synthesis Example 6, 7.03 grams of 4-chlorostyrene, 0.097 grams of potassium carbonate, and 30 milliliters of dimethylacetamide were placed in a 100 milliliter three-neck reactor and stirred magnetically under a nitrogen atmosphere. The reaction temperature was controlled at 80°C and the reaction was allowed to proceed for 24 hours. After the reaction was completed, the reactor was cooled to room temperature, poured into deionized water to precipitate, and washed several times with deionized water. After filtration, the mixture was baked in a vacuum oven at 75°C to obtain a white powder with a yield of 80%. The reaction scheme for Example 8 is shown in Table 15 below. [Table 15]

[0060] In Examples 1, 2, 5 and 7 1 H-NMR analysis was performed to confirm the structure of the phosphorus-based compound synthesized in the present invention. Please refer to Figures 3, 4, 5 and 6. Figure 3 shows the structure of the phosphorus-based compound synthesized in Example 1. 1 4 shows the H-NMR spectrogram of Example 2. 1 5 shows the H-NMR spectrogram of Example 5. 1 6 shows the H-NMR spectrogram of Example 7. 1 3 to 6 show H-NMR spectrograms. As can be seen from the results of Figures 3 to 6, it was confirmed that the phosphorus-based compounds of Examples 1, 2, 5 and 7 were successfully synthesized in the present invention.

[0061] <Flame-retardant polyphenylene oxide resin composition>

[0062] The flame-retardant polyphenylene oxide resin compositions of Examples 9 to 20 of the present invention were composed of the polyphenylene oxide resins of Examples 1 and 2, respectively, and commercially available polyphenylene oxide resins. The polyphenylene oxide resins were SA9000 from SABIC and OPE-2st from Mitsubishi Chemical, respectively. Specifically, Examples 1 and 2 were mixed with the polyphenylene oxide resins described above, each with a different phosphorus content, and a double bond initiator was added. The content of the double bond initiator was 1.0 wt% of the flame-retardant polyphenylene oxide resin composition. Finally, the mixture was blended with xylene to form a solution with a solids content of 20%. Comparative Examples 1 and 2 were also composed of the commercially available polyphenylene oxide resins described above, and the blending method was the same as that of Examples 9 to 20. The conditions for the flame-retardant polyphenylene oxide resin compositions of Examples 9 to 20 and Comparative Examples 1 and 2 are shown in Table 16 below. [Table 16]

[0063] <Flame-retardant cured polyphenylene oxide resin>

[0064] The flame-retardant polyphenylene oxide resin cured products of Examples 21 to 32 and Comparative Examples 3 and 4 of the present invention were prepared by uniformly mixing the flame-retardant polyphenylene oxide resin compositions of Examples 9 to 20 and Comparative Examples 1 and 2, pouring them into a mold, and curing them by heating them in a nitrogen environment. The heating conditions were 60°C (4 hours), 80°C (4 hours), 120°C (2 hours), 180°C (2 hours), 200°C (2 hours), and 220°C (2 hours). After demolding, the flame-retardant polyphenylene oxide resin cured products of Examples 21 to 32 and Comparative Examples 3 and 4 were obtained.

[0065] <Thermal characteristic evaluation>

[0066] The thermal characteristics of Examples 21 to 32 and Comparative Examples 3 and 4 were evaluated by the following evaluation methods.

[0067] (1) Using a dynamic mechanical analyzer (DMA), the relationship between the storage modulus and tan delta curve of the cured product and temperature, as well as the glass transition temperature (T g ) was measured at a temperature rise rate of 5°C / min in the temperature range of 40°C to 350°C.

[0068] (2) The glass transition temperature and coefficient of thermal expansion (CPE) of the cured product were measured using thermomechanical analysis (TMA), with a heating rate of 5°C / min and a temperature range of 50°C to 150°C.

[0069] (3) The 5% thermal weight loss temperature (T d5% The char yield at 800°C and 800°C is measured. The conditions for thermogravimetric analysis are to measure the weight change of the sample using a thermogravimetric analyzer in a nitrogen atmosphere at a heating rate of 20°C / min. The 5% thermal weight loss temperature refers to the temperature at which the sample's weight loss reaches 5%, and a higher 5% thermal weight loss temperature indicates a higher thermal stability of the sample. The char yield at 800°C refers to the remaining weight of the sample when the heating temperature reaches 800°C, and a higher remaining weight ratio at 800°C indicates a higher thermal stability of the sample.

[0070] The results of the thermal property evaluation of Examples 21 to 32 and Comparative Examples 3 and 4 are shown in Table 17 below. [Table 17]

[0071] As can be seen from the results in Table 17, based on the glass transition temperature measurements by DMA, the cured products of Examples 21 to 32 all had good glass transition temperatures, close to those of Comparative Examples 3 and 4. Furthermore, based on the thermal stability results by TGA, the 5% thermal weight loss temperatures of the cured products of Examples 21 to 32 were all maintained at 350°C or higher. Therefore, from the above thermal property analysis, it can be seen that the addition of a phosphorus-based compound to a polyphenylene oxide resin in the present invention does not affect the thermal properties of the cured product, and maintains thermal stability.

[0072] <Flame retardancy evaluation>

[0073] Examples 21 to 32 and Comparative Examples 3 and 4 were subjected to UL-94 flame retardancy testing. The test method involved wrapping an 8-inch x 2-inch film around a 0.5-inch diameter cylindrical support, then moving the support to wrap a 5-inch film around the support, spreading the remaining film into a cone shape. The prepared sample was then burned with a flame for 3 seconds. The flame source was then moved and the flame burning time was recorded as t1. After the sample cooled, a second burn was conducted, also for 3 seconds. The flame source was then moved and the burning time was recorded as t2. During the burning process, cotton was placed 12 inches below the sample, and dripping was observed. Then repeat the above test method for other samples, record t1 and t2, the test result is that the average t1+t2 is between 10-30 seconds, the sample t1+t2 time should not exceed 50 seconds, and if no sagging or dripping is observed, the sample will be graded as UL-94 VTM-0; the test result is that the average t1+t2 is between 10-30 seconds, and no sagging or dripping is observed, the sample will be graded as UL-94 VTM-1.

[0074] The results of the flame retardancy evaluation of Examples 21 to 32 and Comparative Examples 3 and 4 are shown in Table 18 below. [Table 18]

[0075] As can be seen from the results in Table 18, according to the results of the UL-94 flame retardancy test, the self-extinguishing time of the cured products of Examples 21 to 32 after the addition of the phosphorus-based compound was significantly shorter than that of Comparative Examples 3 and 4. This proves that the addition of the phosphorus-based compound is beneficial to the flame retardancy of the cured products, and that Examples 21 to 32 can all achieve a VTM V0 grade.

[0076] <Electrical characteristic evaluation>

[0077] Electrical properties were evaluated for Examples 21 to 32 and Comparative Examples 3 and 4. The evaluation method involved measuring the dielectric constant and dielectric loss of the cured films at 10 GHz using a dielectric meter, and cutting the cured films into 9 cm x 13 cm pieces. The results of the electrical property evaluation for Examples 21 to 32 and Comparative Examples 3 and 4 are shown in Table 19 below. [Table 19]

[0078] As can be seen from the results in Table 19, the cured products of Examples 21 to 32 retain constant electrical properties at a constant phosphorus content after the phosphorus-based compound is added.

[0079] In summary, the phosphorus-based compound of the present invention can be prepared at the lowest possible cost, effectively reducing production costs, has good compatibility with polyphenylene oxide resins, and the cured product prepared therefrom has a high glass transition temperature, low dielectric properties, high thermal stability, and good flame retardancy, and can be used as a manufacturing material for base plates, copper foil substrates, or printed circuit boards.

[0080] Although the present invention has been disclosed above by way of embodiments, the embodiments do not limit the present invention, and those skilled in the art may make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention is determined by the content defined in the following claims. [Explanation of symbols]

[0081] 100, 200 Preparation method of phosphorus compounds 110, 120, 130, 210, 220 processes

Claims

1. A phosphorus-based compound having the structure shown in formula (I): 【Chemistry 1】 During the ceremony, R １ and R ２ are each independently hydrogen, C １ ~C ６ an alkyl group of the formula (I), a trifluoromethyl group, an unsubstituted phenyl group, a substituted phenyl group, an unsubstituted C ３ ~C １０ cycloalkyl groups of the formula ３ ~C １０ a cycloalkyl group, a fluorenyl group, or a halogen atom; R ３ , R ４ , R ５ and R ６ are each independently hydrogen, C １ ~C ６ an alkyl group of the formula (I), a trifluoromethyl group, an unsubstituted phenyl group, a substituted phenyl group, an unsubstituted C ３ ~C １０ cycloalkyl groups of the formula ３ ~C １０ a cycloalkyl group, a halogen atom, or a nitro group; X is a structure represented by formula (i), formula (ii), formula (iii), or formula (iv), 【Chemistry 2】 where: R ７ , R ８ and R ９ are each independently hydrogen, C １ ~C ６ an alkyl group, an unsubstituted phenyl group, a substituted phenyl group, or a halogen atom; R １０ is C １ ~C ６ or an unsubstituted C ３ ~C １０ The phosphorus-based compound, wherein the cycloalkylene group is

2. a step of reacting an organic phosphorus-containing compound represented by formula (1) with a carbonyl group-containing compound represented by formula (2) to perform a synthesis reaction to obtain a hydroxy group-containing compound represented by formula (3); 【Transformation 3】 a step of reacting the hydroxy group-containing compound represented by formula (3) with the phenol compound represented by formula (4) in the presence of an acid catalyst to perform a catalytic reaction to obtain a phosphorus-based hydroxy group compound represented by formula (5); 【Chemistry 4】 a step of reacting the phosphorus-based hydroxy group compound represented by formula (5) with a compound represented by formula (6), formula (7), formula (8) or formula (9) to perform a substitution reaction to obtain the phosphorus-based compound according to claim 1; 【Transformation 5】 A method for preparing a phosphorus-based compound, comprising:

3. 3. The method for preparing phosphorus-based compounds according to claim 2, wherein the acid catalyst is acetic acid, methanesulfonic acid, oxalic acid, sulfuric acid, p-toluenesulfonic acid, or a combination thereof.

4. a catalytic reaction step of reacting an organic phosphorus-containing compound represented by formula (1) with a bisphenol compound represented by formula (10) in the presence of an acid catalyst to obtain a phosphorus-based hydroxy group compound represented by formula (5); 【Transformation 6】 a step of reacting the phosphorus-based hydroxy group compound represented by formula (5) with a compound represented by formula (6), formula (7), formula (8) or formula (9) to perform a substitution reaction to obtain the phosphorus-based compound according to claim 1; 【Transformation 7】 A method for preparing a phosphorus-based compound, comprising:

5. 5. The method for preparing phosphorus-based compounds according to claim 4, wherein the acid catalyst is acetic acid, methanesulfonic acid, oxalic acid, sulfuric acid, p-toluenesulfonic acid, or a combination thereof.

6. A flame-retardant polyphenylene oxide resin composition comprising the phosphorus compound according to claim 1 mixed with a polyphenylene oxide resin.

7. 7. The flame-retardant polyphenylene oxide resin composition according to claim 6, wherein the phosphorus content of the phosphorus-based compound in the flame-retardant polyphenylene oxide resin composition is 0.05% to 8%.

8. A flame-retardant cured polyphenylene oxide resin obtained by mixing the flame-retardant polyphenylene oxide resin composition according to claim 6 or 7 with a double bond initiator and curing the mixture by heating.

9. 9. The flame-retardant cured polyphenylene oxide resin according to claim 8, wherein the double bond initiator is dicumyl peroxide, benzoyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, or a combination thereof.

10. 9. The flame-retardant polyphenylene oxide resin cured product according to claim 8, wherein the content of the double bond initiator is 0.1% by weight to 1.5% by weight of the total weight of the flame-retardant polyphenylene oxide resin composition.

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