Organophosphine Oxides and Their Preparation Methods and Applications

Abstract

The present invention provides an organophosphorus oxide compound, a preparation method and an application thereof. The organophosphorus oxide compound has a structure shown in formula (I): wherein R and R1 are each independently selected from: phenyl, alkyl-substituted phenyl, phenoxy, alkyl-substituted phenoxy, alkoxy. The present invention also uses these organophosphorus oxide compounds as starting materials to prepare a series of bisphenol A structure compounds or bisphenol A structure polymers. The preparation method is simple and the process controllability is strong. The obtained bisphenol A structure compounds or bisphenol A structure polymers are added to a synthetic resin, and it is confirmed that the synthetic resin after addition has excellent low dielectric constant, low hygroscopicity and high glass transition temperature, and good flame retardancy. These bisphenol A structure compounds or bisphenol A structure polymers can be widely used for preparing curing agents, flame retardants, membrane materials, adhesives, insulating materials, chip packaging materials, copper clad laminates.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to an organic phosphine oxide compound and a preparation method and application thereof. Background Art

[0002] Synthetic resins are widely used in industrial and consumer electronics due to their outstanding chemical resistance, mechanical strength and electrical properties. For example, synthetic resins can be used as protective films, adhesive materials or insulating materials, such as inner insulating films, in the electronics industry. In order to be used for these purposes, synthetic resins need to provide convenient operability and certain necessary physical, thermal, electrical insulation and moisture resistance properties. For example, synthetic resins are required to have low insulation constants and low hygroscopicity and high glass transition temperatures (Tg) to match the high standards of electronic application directions. However, most of the common synthetic resins currently have a certain degree of flammability, although different methods have been adopted to give synthetic resins (e.g., epoxy resins) the required degree of flame retardancy, such as the use of halogen-containing flame retardant compounds. However, such compounds are expressly prohibited from use in many directions because of their many potential hazards, and various halogen-free flame retardant compounds are difficult to provide synthetic resins with the required degree of flame retardancy, so there are still many problems in electronic applications that need to be solved, such as performance compatibility with electronic products, flame retardancy, etc., which are important problems that need to be solved.

[0003] Organic phosphine oxide compounds are important chemical synthesis intermediates and are widely used in industrial production. The types of organic phosphine oxide compounds currently developed are limited. The present invention aims to expand the application of organic oxygen phosphorus compounds and the preparation of new synthetic resins with good flame retardant properties. Summary of the invention

[0004] The purpose of the present invention is to provide an organic phosphine oxide compound and a preparation method and application thereof. On the one hand, a new organic phosphine oxide compound structure is explored and the problems of low yield and high by-product of the organic phosphine oxide compound are solved. On the other hand, the obtained organic phosphine oxide compound is used to explore the preparation of a series of bisphenol A structure compounds or bisphenol A structure polymers, as well as their use performance.

[0005] In order to achieve the above technical objectives, the technical solutions adopted in this application are as follows:

[0006] In a first aspect, the present invention provides an organic phosphine oxide compound having a structure shown in formula (I):

[0007] Wherein, R and R1 are independently selected from: phenyl, alkyl-substituted phenyl, phenoxy, alkyl-substituted phenoxy, and alkoxy.

[0008] Preferably, R and R1 are each independently selected from: phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl, methoxy, ethoxy.

[0009] More preferably, R is selected from phenyl, and R1 is selected from phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl; or,

[0010] R is selected from tolyl, and R1 is selected from phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl; or,

[0011] R is selected from xylyl, and R1 is selected from xylyl, phenoxy, ethylphenyl, diethylphenyl; or,

[0012] R is selected from phenoxy, and R1 is selected from phenoxy, ethylphenyl, diethylphenyl; or,

[0013] R is selected from methoxy, and R1 is selected from methoxy, ethoxy; or,

[0014] R is selected from ethoxy, and R1 is selected from ethoxy.

[0015] Even more preferably, the compound is selected from the following structures:

[0016]

[0017] In a second aspect, the present invention provides a method for preparing the organic phosphine oxide compound, comprising: under anhydrous and anaerobic conditions, reacting one or two of the compounds containing phenyl, alkyl-substituted phenyl, phenoxy, alkyl-substituted phenoxy, alkoxy with phosphorus trichloride under the action of a catalyst. Preferably, the catalyst is selected from one of magnesium chloride, aluminum chloride, iron chloride, and zinc chloride.

[0018] Preferably, the molar ratio of the compound containing phenyl, alkyl-substituted phenyl, phenoxy, alkyl-substituted phenoxy, alkoxy to phosphorus trichloride is 2:1; preferably, the compound containing phenyl, alkyl-substituted phenyl, phenoxy, alkyl-substituted phenoxy, alkoxy and phosphorus trichloride are first reacted in a molar ratio of 1:1 under the action of a catalyst for the first reaction, and then the remaining compound containing phenyl, alkyl-substituted phenyl, phenoxy, alkyl-substituted phenoxy, alkoxy is further added for the second reaction; more preferably, the reaction temperature is 50-150 °C, the first reaction time is 2-8 h, and the second reaction time is 8-16 h.

[0019] Preferably, it further comprises: after the reaction is completed, quenching the reaction solution with water, followed by extraction, alkali washing, and drying to obtain the organic phosphine oxide compound.

[0020] In a third aspect, the present invention provides the use of the organic phosphine oxide compound in the preparation of a bisphenol A structure compound substituted with a phosphine oxide group or a polymer of a bisphenol A structure substituted with a phosphine oxide group.

[0021] In a fourth aspect, the present invention provides a bisphenol A structure compound substituted with a phosphine oxide group having the structure shown in formula (II):

[0022] Wherein, R and R1 are each independently selected from: phenyl, alkyl-substituted phenyl, phenoxy, alkyl-substituted phenoxy, alkoxy.

[0023] Preferably, R and R1 are each independently selected from: phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl, methoxy, ethoxy.

[0024] More preferably, R is selected from phenyl, and R1 is selected from phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl; or,

[0025] R is selected from tolyl, and R1 is selected from phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl; or,

[0026] R is selected from xylyl, and R1 is selected from xylyl, phenoxy, ethylphenyl, diethylphenyl; or,

[0027] R is selected from phenoxy, and R1 is selected from phenoxy, ethylphenyl, diethylphenyl; or,

[0028] R is selected from methoxy, and R1 is selected from methoxy, ethoxy; or,

[0029] R is selected from ethoxy, and R1 is selected from ethoxy.

[0030] Even more preferably, the bisphenol A structure compound is selected from the following structures:

[0031]

[0032]

[0033]

[0034] In a fifth aspect, the present invention provides a method for synthesizing the bisphenol A structure compound, which is obtained by mixing an alcohol-etherified bisphenol A compound with the organic phosphine oxide compound according to any one of claims 1 to 4 and then heating and reacting, wherein the alcohol-etherified bisphenol A compound has the structure shown in formula (III):

[0035] Wherein, R2 is selected from: C1-C8 alkyl.

[0036] Preferably, the process of the heating reaction includes: raising the temperature of the system to 90 - 100 °C and holding for 1 - 2 h; then further raising the temperature to 110 - 120 °C and holding for 1 - 2 h; and then further raising the temperature to 130 - 140 °C and maintaining under vacuum for 2 - 3 h. More preferably, the vacuum is a vacuum degree below 0.01 MPa. After the heating reaction is completed, the bisphenol A structure compound is obtained by vacuum distillation. Preferably, the temperature of the vacuum distillation is 130 - 140 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min.

[0037] In the sixth aspect, the present invention provides a bisphenol A structure polymer substituted with a phosphine oxide group having the structure shown in formula (IV):

[0038] Wherein, R and R1 are each independently selected from: phenyl, alkyl-substituted phenyl, phenoxy, alkyl-substituted phenoxy, alkoxy; n = 1 - 5.

[0039] Preferably, R and R1 are each independently selected from: phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl, methoxy, ethoxy.

[0040] More preferably, R is selected from phenyl, and R1 is selected from phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl; or,

[0041] R is selected from tolyl, and R1 is selected from phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl; or,

[0042] R is selected from xylyl, and R1 is selected from xylyl, phenoxy, ethylphenyl, diethylphenyl; or,

[0043] R is selected from phenoxy, and R1 is selected from phenoxy, ethylphenyl, diethylphenyl; or,

[0044] R is selected from methoxy, and R1 is selected from methoxy, ethoxy; or,

[0045] R is selected from ethoxy, and R1 is selected from ethoxy.

[0046] More preferably, the bisphenol A structure polymer is selected from the following structures:

[0047]

[0048]

[0049]

[0050] Seventh aspect, the present invention provides a method for synthesizing the bisphenol A-structured polymer, which is obtained by mixing an alcohol-etherified bisphenol A polymer with the organophosphine oxide compound according to any one of claims 1 to 4 and then heating and reacting, wherein the alcohol-etherified bisphenol A polymer has a structure shown in formula (V):

[0051] wherein, R2 is selected from: C1-C8 alkyl, and n = 1-5.

[0052] Preferably, the process of the heating reaction includes: raising the temperature of the system to 100-110 °C and keeping warm for 1-2 h; then further raising the temperature to 120-130 °C and keeping warm for 1-2 h; further raising the temperature to 140-150 °C and maintaining under vacuum for 2-3 h. More preferably, the vacuum is a vacuum degree below 0.01 MPa; after the heating reaction is completed, the bisphenol A-structured compound is obtained by vacuum distillation. Preferably, the temperature of the vacuum distillation is 140-150 °C, the pressure is 0.05-0.1 MPa, and the time is 30-60 min.

[0053] Eighth aspect, the present invention provides the application of the bisphenol A-structured compound and / or the bisphenol A-structured polymer in the preparation of one of the following materials: curing agent, flame retardant, film material, adhesive, insulating material, chip packaging material, copper clad laminate.

[0054] Ninth aspect, the present invention provides the application of the bisphenol A-structured compound and / or the bisphenol A-structured polymer in improving the flame retardant performance of synthetic resin materials.

[0055] Preferably, the application includes: compounding the bisphenol A-structured compound and / or the bisphenol A-structured polymer with the synthetic resin material according to the mass content of phosphorus element in the synthetic resin being 2-3%.

[0056] The beneficial effects compared with the prior art are as follows:

[0057] The present invention obtains a series of organophosphine oxide compounds, and this series of organophosphine oxide compounds are simple to prepare, with mild conditions, high yield, and few side reaction products, greatly simplifying the process flow, shortening the process time, and reducing the cost. The present invention also uses these organophosphine oxide compounds as starting materials to prepare a series of bisphenol A-structured compounds or bisphenol A-structured polymers, and the preparation method is simple and the process controllability is strong. The obtained bisphenol A-structured compounds or bisphenol A-structured polymers are added to the synthetic resin, and it is confirmed that the synthetic resin after addition has excellent low dielectric constant, low hygroscopicity, high glass transition temperature, and good flame retardant performance. These bisphenol A-structured compounds or bisphenol A-structured polymers can be widely used in the preparation of curing agents, flame retardants, film materials, adhesives, insulating materials, chip packaging materials, and copper clad laminates. Description of the Drawings

[0058] Figure 1 It is the carbon nuclear magnetic spectrum of Compound 1'.

[0059] Figure 2 It is the phosphorus nuclear magnetic spectrum of Compound 1'.

[0060] Figure 3 It is the hydrogen nuclear magnetic spectrum of Compound 1'.

[0061] Figure 4 It is the carbon nuclear magnetic spectrum of Compound 2'.

[0062] Figure 5 It is the phosphorus nuclear magnetic spectrum of Compound 2'.

[0063] Figure 6 It is the hydrogen nuclear magnetic spectrum of Compound 2'. Detailed Description of the Invention

[0064] In the description of the present invention, it should be noted that for those not specified in the examples, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. For the reagents or instruments not specified in the manufacturer, they are all conventional products that can be obtained by purchasing in the market.

[0065] In some embodiments of the present invention, the organophosphine oxide compound has the structure shown in formula (I):

[0066] Wherein, R and R1 are each independently selected from: phenyl, alkyl-substituted phenyl, phenoxy, alkyl-substituted phenoxy, alkoxy. The alkyl-substituted phenyl may be: tolyl; xylyl, including o-xylyl, m-xylyl, p-xylyl; mesityl; ethylphenyl; n-propylphenyl; isopropylphenyl; n-butylphenyl; isobutylphenyl; sec-butylphenyl; diethylphenyl, including o-diethylphenyl, m-diethylphenyl, p-diethylphenyl; methylethylphenyl: including o-methylethylphenyl, m-methylethylphenyl, p-methylethylphenyl; triethylphenyl, including mesityltriethylphenyl; 1,3,5-triisopropylphenyl. The alkyl-substituted phenoxy may be: C1-C4 alkyl-substituted phenoxy: including ortho, para, and meta mono-substituted alkyl. The alkoxy may be: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy.

[0067] In some preferred cases of the present invention, R and R1 are each independently selected from: phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl, methoxy, ethoxy.

[0068] In some more preferred embodiments of the present invention, R is selected from phenyl, and R1 is selected from: phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl; or, R is selected from tolyl, and R1 is selected from phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl; or, R is selected from xylyl, and R1 is selected from xylyl, phenoxy, ethylphenyl, diethylphenyl; or, R is selected from phenoxy, and R1 is selected from phenoxy, phenyl, tolyl, ethylphenyl, xylyl, diethylphenyl; or, R is selected from methoxy, and R1 is selected from methoxy, ethoxy; or, R is selected from ethoxy, and R1 is selected from methoxy, ethoxy.

[0069] The present invention also provides a method for preparing an organophosphine oxide compound, comprising: under anhydrous and anaerobic conditions, reacting one or two of the compounds containing phenyl, alkyl-substituted phenyl, phenoxy, alkyl-substituted phenoxy, alkoxy with phosphorus trichloride under the action of a Lewis acid catalyst, and the catalyst is selected from Lewis acid catalysts such as magnesium chloride, aluminum chloride, iron chloride, zinc chloride. The molar ratio of the compound containing phenyl, alkyl-substituted phenyl, phenoxy, alkyl-substituted phenoxy, alkoxy to phosphorus trichloride is 2:1. The starting materials can be added for reaction by a one-pot method, or can be reacted in two steps in a one-pot experiment. The latter is preferred, and the specific operation is: first react the compound containing phenyl, alkyl-substituted phenyl, phenoxy, alkyl-substituted phenoxy, alkoxy with phosphorus trichloride in a molar ratio of 1:1 under the action of a Lewis acid catalyst, and then further add the remaining compound containing phenyl, alkyl-substituted phenyl, phenoxy, alkoxy for the second reaction, and the Lewis acid does not need to be replenished. The preferred reaction temperature is 50-150 °C, and the total reaction time is within 24 h; when reacting in two steps, the first reaction time is 2-8 h, and the second reaction time is 8-16 h. After the reaction is completed, the reaction solution is quenched with water, and after extraction, alkali washing, and drying, an organophosphine oxide compound is obtained.

[0070] In some other embodiments of the present invention, the bisphenol A structure compound substituted with a phosphine oxide group has the structure shown in formula (II): Among them, R and R1 are each independently selected from: phenyl, alkyl-substituted phenyl, phenoxy, alkyl-substituted phenoxy, alkoxy. The alkyl-substituted phenyl may be: tolyl; xylyl, including o-xylyl, m-xylyl, p-xylyl; mesityl; ethylphenyl; n-propylphenyl; isopropylphenyl; n-butylphenyl; isobutylphenyl; sec-butylphenyl; diethylphenyl, including o-diethylphenyl, m-diethylphenyl, p-diethylphenyl; methylethylphenyl: including o-methylethylphenyl, m-methylethylphenyl, p-methylethylphenyl; triethylphenyl, including mesityltriethylphenyl; 1,3,5-triisopropylphenyl. The alkyl-substituted phenoxy may be: C1-C4 alkyl-substituted phenoxy: including ortho, para, and meta mono-substituted alkyl. The alkoxy may be: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy.

[0071] In some preferred embodiments of the present invention, R and R1 are each independently selected from: phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl, methoxy, ethoxy.

[0072] In some more preferred embodiments of the present invention, R is selected from phenyl, and R1 is selected from: phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl; or R is selected from tolyl, and R1 is selected from phenyl, tolyl, xylyl, phenoxy, ethylphenyl, diethylphenyl; or R is selected from xylyl, and R1 is selected from xylyl, phenoxy, ethylphenyl, diethylphenyl; or R is selected from phenoxy, and R1 is selected from phenoxy, phenyl, tolyl, ethylphenyl, xylyl, diethylphenyl; or R is selected from methoxy, and R1 is selected from methoxy, ethoxy; or R is selected from ethoxy, and R1 is selected from methoxy, ethoxy.

[0073] The present invention also provides a method for synthesizing a bisphenol A structure compound, which is obtained by heating and reacting an alcohol-etherified bisphenol A compound with the organic phosphine oxide compound. Among them, the alcohol-etherified bisphenol A compound has the structure shown in formula (III):

[0074] Among them, R2 is selected from: C1-C8 alkyl groups. Specifically, it can be selected from: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 4,4-dimethylpentyl, 3,4-dimethylpentyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 5,5-dimethylhexyl, 3-methylhexyl, 4,5-dimethylhexyl, 2-methylhexyl, 1-methylhexyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methylheptyl, 3,3-dimethylbutyl. This alcohol-etherified bisphenol A compound can be obtained commercially or prepared by oneself. In the specific embodiments of the present invention, mainly the butanol-etherified bisphenol A compound is used as the starting material, and this product is a commercially available product.

[0075] In the above reaction process, the process of heating the reaction includes: raising the temperature of the system to 90-100°C and maintaining the temperature for 1-2 h; then further raising the temperature to 110-120°C and maintaining the temperature for 1-2 h; and then further raising the temperature to 140°C and maintaining under vacuum for 2-3 h. This way of gradient heating reaction can make the viscosity of the reaction system continuously increase during the smooth progress of the reaction, thereby preventing the raw materials from volatilizing away after reaching the boiling point in the subsequent high-temperature reaction, and preventing the self-polymerization of the butanol-etherified bisphenol A compound, ensuring the full progress of the alcohol-etherified bisphenol A compound and the organic phosphine oxide compound.

[0076] In the above reaction process, the vacuum is a vacuum degree below 0.01 MPa; after the heating reaction is completed, the bisphenol A structure compound is obtained by vacuum distillation. Preferably, the temperature of the vacuum distillation is 140°C, the pressure is 0.1 MPa, and the time is 30-60 min.

[0077] In some other embodiments of the present invention, the bisphenol A structure polymer substituted with a phosphine oxide group has the structure shown in formula (IV):

[0078] Among them, R and R1 are each independently selected from: phenyl, alkyl-substituted phenyl, phenoxy, alkyl-substituted phenoxy, alkoxy; n = 1 to 5. The alkyl-substituted phenyl can be: tolyl; xylenyl, including o-xylenyl, m-xylenyl, p-xylenyl; mesityl, including 1,3,5-trimethylphenyl; ethylphenyl; n-propylphenyl; isopropylphenyl; n-butylphenyl; isobutylphenyl; sec-butylphenyl; diethylphenyl, including o-diethylphenyl, m-diethylphenyl, p-diethylphenyl; methylethylphenyl: including o-methylethylphenyl, m-methylethylphenyl, p-methylethylphenyl; triethylphenyl, including 1,3,5-triethylphenyl; 1,3,5-triisopropylphenyl. The alkyl-substituted phenoxy can be: C1-C4 alkyl-substituted phenoxy: including ortho, para, and meta-monosubstituted alkyl. The alkoxy can be: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy.

[0079] In some preferred embodiments of the present invention, R and R1 are each independently selected from: phenyl, tolyl, xylenyl, phenoxy, ethylphenyl, diethylphenyl, methoxy, ethoxy.

[0080] In some more preferred embodiments of the present invention, R is selected from phenyl, and R1 is selected from: phenyl, tolyl, xylenyl, phenoxy, ethylphenyl, diethylphenyl; or R is selected from tolyl, and R1 is selected from phenyl, tolyl, xylenyl, phenoxy, ethylphenyl, diethylphenyl; or R is selected from xylenyl, and R1 is selected from xylenyl, phenoxy, ethylphenyl, diethylphenyl; or R is selected from phenoxy, and R1 is selected from phenoxy, phenyl, tolyl, ethylphenyl, xylenyl, diethylphenyl; or R is selected from methoxy, and R1 is selected from methoxy, ethoxy; or R is selected from ethoxy, and R1 is selected from methoxy, ethoxy.

[0081] The present invention also provides a method for synthesizing a bisphenol A structural polymer, which is obtained by mixing an alcohol-etherified bisphenol A polymer with the organophosphine oxide compound according to any one of claims 1 to 4 and then heating and reacting, wherein the alcohol-etherified bisphenol A polymer has the structure shown in formula (V): Among them, R2 is selected from: C1-C6 alkyl, specifically, it can be selected: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 4,4-dimethylpentyl, 3,4-dimethylpentyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 5,5-dimethylhexyl, 3-methylhexyl, 4,5-dimethylhexyl, 2-methylhexyl, 1-methylhexyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methylheptyl, 3,3-dimethylbutyl, n = 1 to 5.

[0082] Among them, the process of the heating reaction includes: raising the temperature of the system to 90 - 100 °C and holding for 1 - 2 h; then further raising the temperature to 110 - 120 °C and holding for 1 - 2 h; then further raising the temperature to 140 °C and maintaining under vacuum for 2 - 3 h. This way of gradient temperature rise reaction can make the viscosity of the reaction system continuously increase during the smooth progress of the reaction, so as to prevent the raw materials from volatilizing away after reaching the boiling point in the subsequent high-temperature reaction, and ensure the full progress of the alcohol etherification bisphenol A polymer and the organic phosphine oxide compound.

[0083] Preferably, the vacuum is a vacuum degree below 0.01 MPa; after the heating reaction is completed, the bisphenol A structural compound is obtained by vacuum distillation. Preferably, the temperature of the vacuum distillation is 130 - 150 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min.

[0084] Furthermore, the present invention details the preparation processes of some compounds:

[0085] 1) Organic phosphine oxide compounds 1 - 10, the structural formulas are as follows:

[0086]

[0087]

[0088] Synthesis of compound 1: Under anhydrous and anaerobic conditions, add half of the benzene into a three-necked flask, successively add phosphorus trichloride and aluminum chloride, introduce nitrogen, stir at high speed and raise the temperature to 60 - 90 °C. After reacting for 6 - 8 hours, add the remaining benzene and react for another 14 - 16 hours. After the reaction is completed, drop the reaction solution into water for quenching, then extract, wash with alkali, remove water and dry to obtain organic phosphine oxide compound 1.

[0089] Synthesis of compound 2: Under anhydrous and anaerobic conditions, add benzene into a three-necked flask, successively add phosphorus trichloride and aluminum chloride, introduce nitrogen, stir at high speed and raise the temperature to 80 - 100 °C. After reacting for 6 - 8 hours, add toluene and react for another 8 - 10 hours. After the reaction is completed, drop the reaction solution into water for quenching, then extract, wash with alkali, remove water and dry to obtain organic phosphine oxide compound 2.

[0090] Synthesis of compound 3: Under anhydrous and anaerobic conditions, add benzene into a three-necked flask, successively add phosphorus trichloride and aluminum chloride, introduce nitrogen, stir at high speed and raise the temperature to 120 - 150 °C. After reacting for 2 - 5 hours, add o-xylene and react for another 8 - 10 hours. After the reaction is completed, drop the reaction solution into water for quenching, then extract, wash with alkali, remove water and dry to obtain organic phosphine oxide compound 3.

[0091] Synthesis of Compound 4: Under anhydrous and anaerobic conditions, toluene was added to a three-necked flask, phosphorus trichloride and zinc chloride were added successively, nitrogen was introduced, and the mixture was stirred at high speed and heated to 60 - 80 °C. After reacting for 5 - 8 hours, o-xylene was added, and the reaction continued for 13 - 16 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, washing with alkali, dehydration, and drying to obtain the organophosphine oxide compound 4.

[0092] Synthesis of Compound 5: Under anhydrous and anaerobic conditions, o-xylene was added to a three-necked flask, phosphorus trichloride and zinc chloride were added successively, nitrogen was introduced, and the mixture was stirred at high speed and heated to 80 - 100 °C. After reacting for 3 - 6 hours, o-xylene was added, and the reaction continued for 12 - 13 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, washing with alkali, dehydration, and drying to obtain the organophosphine oxide compound 5.

[0093] Synthesis of Compound 6: Under anhydrous and anaerobic conditions, toluene was added to a three-necked flask, phosphorus trichloride and zinc chloride were added successively, nitrogen was introduced, and the mixture was stirred at high speed and heated to 100 - 120 °C. After reacting for 4 - 6 hours, toluene was added, and the reaction continued for 10 - 12 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, washing with alkali, dehydration, and drying to obtain the organophosphine oxide compound 6.

[0094] Synthesis of Compound 7: Under anhydrous and anaerobic conditions, toluene was added to a three-necked flask, phosphorus trichloride and magnesium chloride were added successively, nitrogen was introduced, and the mixture was stirred at high speed and heated to 80 - 100 °C. After reacting for 6 - 9 hours, phenol was added, and the reaction continued for 8 - 10 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, washing with alkali, dehydration, and drying to obtain the organophosphine oxide compound 7.

[0095] Synthesis of Compound 8: Under anhydrous and anaerobic conditions, benzene was added to a three-necked flask, phosphorus trichloride and magnesium chloride were added successively, nitrogen was introduced, and the mixture was stirred at high speed and heated to 80 - 100 °C. After reacting for 8 - 9 hours, phenol was added, and the reaction continued for 14 - 16 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, washing with alkali, dehydration, and drying to obtain the organophosphine oxide compound 8.

[0096] Synthesis of Compound 9: Under anhydrous and anaerobic conditions, o-xylene was added to a three-necked flask, phosphorus trichloride and ferric chloride were added successively, nitrogen was introduced, and the mixture was stirred at high speed and heated to 130 - 150 °C. After reacting for 2 - 3 hours, phenol was added, and the reaction continued for 8 - 9 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, washing with alkali, dehydration, and drying to obtain the organophosphine oxide compound 9.

[0097] Synthesis of Compound 10: Under anhydrous and anaerobic conditions, phenol was added to a three-necked flask, followed by the addition of phosphorus trichloride and magnesium chloride. Nitrogen was introduced, and the mixture was stirred at high speed and heated to 50 - 80 °C. After reacting for 2 - 4 hours, phenol was added again, and the reaction continued for 11 - 14 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, washing with alkali, and dehydration and drying to obtain the organophosphine oxide compound 10.

[0098] The yields of Compounds 1 - 3 and 10 are between 85 - 90%, the yields of Compounds 4 - 6 are between 75 - 85%, and the yields of Compounds 7 - 9 are between 50 - 70%. The purity of all compounds can reach over 98%.

[0099] 2) Bisphenol A-structured Compounds 1' - 10', with the structural formulas shown as follows:

[0100]

[0101]

[0102] Taking butanol-etherified bisphenol A as an example, as the starting material, the synthesis of bisphenol A-structured Compounds 1' - 10' is as follows:

[0103] Synthesis of Compound 1': Butanol-etherified bisphenol A reacts with organophosphine oxide compound 1. The temperature of the system is raised to 90 - 100 °C and kept warm for 1 - 2 h; then the temperature is further raised to 110 - 120 °C and kept warm for 1 - 2 h; then the temperature is further raised to 130 - 140 °C and kept under vacuum for 2 - 3 h with a vacuum degree below 0.01 MPa. Then, vacuum distillation is carried out at a temperature of 130 - 140 °C, a pressure of 0.05 - 0.1 MPa, and a time of 30 - 60 min to obtain bisphenol A-structured Compound 1'.

[0104] Synthesis of Compound 2': Butanol-etherified bisphenol A reacts with organophosphine oxide compound 3. The temperature of the system is raised to 90 - 100 °C and kept warm for 1 - 2 h; then the temperature is further raised to 110 - 120 °C and kept warm for 1 - 2 h; then the temperature is further raised to 130 - 140 °C and kept under vacuum for 2 - 3 h with a vacuum degree below 0.01 MPa. Then, vacuum distillation is carried out at a temperature of 130 - 140 °C, a pressure of 0.05 - 0.1 MPa, and a time of 30 - 60 min to obtain bisphenol A-structured Compound 2'.

[0105] Synthesis of Compound 3': Butanol-etherified bisphenol A reacts with organic phosphine oxide compound 4. Raise the temperature of the system to 90 - 100 °C and keep it for 1 - 2 h; then further raise the temperature to 110 - 120 °C and keep it for 1 - 2 h; then further raise the temperature to 130 - 140 °C and keep it under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then carry out vacuum distillation. The temperature of vacuum distillation is 130 - 140 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min to obtain bisphenol A-structured compound 3'.

[0106] Synthesis of Compound 4': Butanol-etherified bisphenol A reacts with organic phosphine oxide compound 5. Raise the temperature of the system to 90 - 100 °C and keep it for 1 - 2 h; then further raise the temperature to 110 - 120 °C and keep it for 1 - 2 h; then further raise the temperature to 130 - 140 °C and keep it under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then carry out vacuum distillation. The temperature of vacuum distillation is 130 - 140 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min to obtain bisphenol A-structured compound 4'.

[0107] Synthesis of Compound 5': Butanol-etherified bisphenol A reacts with organic phosphine oxide compound 6. Raise the temperature of the system to 90 - 100 °C and keep it for 1 - 2 h; then further raise the temperature to 110 - 120 °C and keep it for 1 - 2 h; then further raise the temperature to 130 - 140 °C and keep it under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then carry out vacuum distillation. The temperature of vacuum distillation is 130 - 140 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min to obtain bisphenol A-structured compound 5'.

[0108] Synthesis of Compound 6': Butanol-etherified bisphenol A reacts with organic phosphine oxide compound 2. Raise the temperature of the system to 90 - 100 °C and keep it for 1 - 2 h; then further raise the temperature to 110 - 120 °C and keep it for 1 - 2 h; then further raise the temperature to 130 - 140 °C and keep it under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then carry out vacuum distillation. The temperature of vacuum distillation is 130 - 140 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min to obtain bisphenol A-structured compound 6'.

[0109] Synthesis of Compound 7': Butanol-etherified bisphenol A reacts with organic phosphine oxide compound 8. Raise the temperature of the system to 90 - 100 °C and keep it for 1 - 2 h; then further raise the temperature to 110 - 120 °C and keep it for 1 - 2 h; then further raise the temperature to 130 - 140 °C and keep it under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then carry out vacuum distillation. The temperature of vacuum distillation is 130 - 140 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min to obtain bisphenol A-structured compound 7'.

[0110] Synthesis of Compound 8': Butanol-etherified bisphenol A reacts with organophosphine oxide compound 10. Raise the temperature of the system to 90 - 100 °C and keep it warm for 1 - 2 h; then further raise the temperature to 110 - 120 °C and keep it warm for 1 - 2 h; then further raise the temperature to 130 - 140 °C and keep it under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then perform vacuum distillation. The temperature of vacuum distillation is 130 - 140 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min to obtain bisphenol A-structured compound 8'.

[0111] Synthesis of Compound 9': Butanol-etherified bisphenol A reacts with organophosphine oxide compound 7. Raise the temperature of the system to 90 - 100 °C and keep it warm for 1 - 2 h; then further raise the temperature to 110 - 120 °C and keep it warm for 1 - 2 h; then further raise the temperature to 130 - 140 °C and keep it under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then perform vacuum distillation. The temperature of vacuum distillation is 130 - 140 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min to obtain bisphenol A-structured compound 9'.

[0112] Synthesis of Compound 10': Butanol-etherified bisphenol A reacts with organophosphine oxide compound 9. Raise the temperature of the system to 90 - 100 °C and keep it warm for 1 - 2 h; then further raise the temperature to 110 - 120 °C and keep it warm for 1 - 2 h; then further raise the temperature to 130 - 140 °C and keep it under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then perform vacuum distillation. The temperature of vacuum distillation is 130 - 140 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min to obtain bisphenol A-structured compound 10'.

[0113] The yields of Compounds 1' - 10' are above 98%, and the purities of all compounds can reach above 98%.

[0114] 3) Bisphenol A-structured polymers 1" - 10", with the structural formulas as follows:

[0115]

[0116]

[0117]

[0118] Taking butanol-etherified bisphenol A resin (purchased from Axalta Coating Systems, PR 411 / 75B, with a molecular weight of 1000 - 1500) as an example, as the starting material, the synthesis of bisphenol A-structured polymers 1" - 10" is carried out as follows:

[0119] Synthesis of "Compound 1": The butanol-etherified bisphenol A resin reacts with the organic phosphine oxide compound 1. The temperature of the system is raised to 100 - 110 °C and kept warm for 1 - 2 h; then it is further heated to 120 - 130 °C and kept warm for 1 - 2 h; then it is further heated to 140 - 150 °C and kept under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then vacuum distillation is carried out. The temperature of the vacuum distillation is 140 - 150 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min, to obtain the bisphenol A-structured polymer "Compound 1".

[0120] Synthesis of "Compound 2": The butanol-etherified bisphenol A resin reacts with the organic phosphine oxide compound 3. The temperature of the system is raised to 100 - 110 °C and kept warm for 1 - 2 h; then it is further heated to 120 - 130 °C and kept warm for 1 - 2 h; then it is further heated to 140 - 150 °C and kept under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then vacuum distillation is carried out. The temperature of the vacuum distillation is 140 - 150 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min, to obtain the bisphenol A-structured polymer "Compound 2".

[0121] Synthesis of "Compound 3": The butanol-etherified bisphenol A resin reacts with the organic phosphine oxide compound 4. The temperature of the system is raised to 100 - 110 °C and kept warm for 1 - 2 h; then it is further heated to 120 - 130 °C and kept warm for 1 - 2 h; then it is further heated to 140 - 150 °C and kept under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then vacuum distillation is carried out. The temperature of the vacuum distillation is 140 - 150 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min, to obtain the bisphenol A-structured polymer "Compound 3".

[0122] Synthesis of "Compound 4": The butanol-etherified bisphenol A resin reacts with the organic phosphine oxide compound 5. The temperature of the system is raised to 100 - 110 °C and kept warm for 1 - 2 h; then it is further heated to 120 - 130 °C and kept warm for 1 - 2 h; then it is further heated to 140 - 150 °C and kept under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then vacuum distillation is carried out. The temperature of the vacuum distillation is 140 - 150 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min, to obtain the bisphenol A-structured polymer "Compound 4".

[0123] Synthesis of Compound 5": The butanol-etherified bisphenol A resin reacts with the organic phosphine oxide compound 6. The temperature of the system is raised to 100 - 110 °C and kept at this temperature for 1 - 2 h; then the temperature is further raised to 120 - 130 °C and kept at this temperature for 1 - 2 h; then the temperature is further raised to 140 - 150 °C and kept under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then vacuum distillation is carried out. The temperature of the vacuum distillation is 140 - 150 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min to obtain the bisphenol A-structured polymer 5".

[0124] Synthesis of Compound 6": The butanol-etherified bisphenol A resin reacts with the organic phosphine oxide compound 2. The temperature of the system is raised to 100 - 110 °C and kept at this temperature for 1 - 2 h; then the temperature is further raised to 120 - 130 °C and kept at this temperature for 1 - 2 h; then the temperature is further raised to 140 - 150 °C and kept under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then vacuum distillation is carried out. The temperature of the vacuum distillation is 140 - 150 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min to obtain the bisphenol A-structured polymer 6".

[0125] Synthesis of Compound 7": The butanol-etherified bisphenol A resin reacts with the organic phosphine oxide compound 7. The temperature of the system is raised to 100 - 110 °C and kept at this temperature for 1 - 2 h; then the temperature is further raised to 120 - 130 °C and kept at this temperature for 1 - 2 h; then the temperature is further raised to 140 - 150 °C and kept under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then vacuum distillation is carried out. The temperature of the vacuum distillation is 140 - 150 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min to obtain the bisphenol A-structured polymer 7".

[0126] Synthesis of Compound 8": The butanol-etherified bisphenol A resin reacts with the organic phosphine oxide compound 9. The temperature of the system is raised to 100 - 110 °C and kept at this temperature for 1 - 2 h; then the temperature is further raised to 120 - 130 °C and kept at this temperature for 1 - 2 h; then the temperature is further raised to 140 - 150 °C and kept under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then vacuum distillation is carried out. The temperature of the vacuum distillation is 140 - 150 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min to obtain the bisphenol A-structured polymer 8".

[0127] Synthesis of Compound 9": The butanol-etherified bisphenol A resin reacts with the organophosphine oxide compound 8. The temperature of the system is raised to 100 - 110 °C and kept at this temperature for 1 - 2 h; then the temperature is further raised to 120 - 130 °C and kept at this temperature for 1 - 2 h; then the temperature is further raised to 140 - 150 °C and kept under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then vacuum distillation is carried out. The temperature of the vacuum distillation is 140 - 150 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min to obtain the bisphenol A-structured polymer 9".

[0128] Synthesis of Compound 10": The butanol-etherified bisphenol A resin reacts with the organophosphine oxide compound 10. The temperature of the system is raised to 100 - 110 °C and kept at this temperature for 1 - 2 h; then the temperature is further raised to 120 - 130 °C and kept at this temperature for 1 - 2 h; then the temperature is further raised to 140 - 150 °C and kept under vacuum for 2 - 3 h with the vacuum degree below 0.01 MPa, and then vacuum distillation is carried out. The temperature of the vacuum distillation is 140 - 150 °C, the pressure is 0.05 - 0.1 MPa, and the time is 30 - 60 min to obtain the bisphenol A-structured polymer 10".

[0129] The present invention will be further described in detail below with specific examples, which are explanations of the present invention rather than limitations.

[0130] Example 1

[0131] Synthesis of Compound 1:

[0132] Under anhydrous and anaerobic conditions, 39.06 g of benzene is added to a three-necked flask, and then 68.66 g of phosphorus trichloride and 93.34 g of aluminum chloride are added in sequence. Nitrogen is introduced, and the mixture is stirred at high speed and heated to 60 °C. After reacting for 8 hours, another 39.06 g of benzene is added, and the reaction continues for 16 hours. After the reaction is completed, the reaction solution is dropped into water for quenching, and then extracted, washed with alkali, and dried to remove water, obtaining 89.22 g of the organophosphine oxide compound 1 with a yield of 88% and a purity of 98%.

[0133] Example 2

[0134] Synthesis of Compound 2:

[0135] Under anhydrous and anaerobic conditions, 39.06 g of benzene is added to a three-necked flask, and then 68.66 g of phosphorus trichloride and 93.34 g of aluminum chloride are added in sequence. Nitrogen is introduced, and the mixture is stirred at high speed and heated to 100 °C. After reacting for 6 hours, another 46.07 g of toluene is added, and the reaction continues for 8 hours. After the reaction is completed, the reaction solution is dropped into water for quenching, and then extracted, washed with alkali, and dried to remove water, obtaining 96.15 g of the organophosphine oxide compound 2 with a yield of 89% and a purity of 98%.

[0136] Example 3

[0137] Synthesis of Compound 3:

[0138] Under anhydrous and anaerobic conditions, 39.06 g of benzene was added to a three-necked flask, followed by 68.66 g of phosphorus trichloride and 93.34 g of aluminum chloride. Nitrogen was introduced, and the mixture was stirred at high speed and heated to 150 °C. After reacting for 2 hours, 53.09 g of o-xylene was added, and the reaction continued for 8 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, washing with alkali, dehydration and drying to obtain 101.24 g of organophosphine oxide compound 3 with a yield of 88% and a purity of 98%.

[0139] Example 4

[0140] Synthesis of Compound 4:

[0141] Under anhydrous and anaerobic conditions, 46.07 g of toluene was added to a three-necked flask, followed by 68.66 g of phosphorus trichloride and 95.30 g of zinc chloride. Nitrogen was introduced, and the mixture was stirred at high speed and heated to 60 °C. After reacting for 8 hours, 53.09 g of o-xylene was added, and the reaction continued for 16 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, washing with alkali, dehydration and drying to obtain 96.42 g of organophosphine oxide compound 4 with a yield of 79% and a purity of 98%.

[0142] Example 5

[0143] Synthesis of Compound 5:

[0144] Under anhydrous and anaerobic conditions, 53.09 g of o-xylene was added to a three-necked flask, followed by 68.66 g of phosphorus trichloride and 95.30 g of zinc chloride. Nitrogen was introduced, and the mixture was stirred at high speed and heated to 80 °C. After reacting for 6 hours, 53.09 g of o-xylene was added, and the reaction continued for 12 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, washing with alkali, dehydration and drying to obtain 100.663 g of organophosphine oxide compound 5 with a yield of 78% and a purity of 98%.

[0145] Example 6

[0146] Synthesis of Compound 6:

[0147] Under anhydrous and anaerobic conditions, 46.07 g of toluene was added to a three-necked flask, followed by 68.66 g of phosphorus trichloride and 95.30 g of zinc chloride. Nitrogen was introduced, and the mixture was stirred at high speed and heated to 120 °C. After reacting for 4 hours, another 46.07 g of toluene was added, and the reaction continued for 10 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, alkali washing, water removal and drying to obtain 96.63 g of organophosphine oxide compound 6, with a yield of 84% and a purity of 98%.

[0148] Example 7

[0149] Synthesis of compound 7:

[0150] Under anhydrous and anaerobic conditions, 46.07 g of toluene was added to a three-necked flask, followed by 68.66 g of phosphorus trichloride and 66.65 g of magnesium chloride. Nitrogen was introduced, and the mixture was stirred at high speed and heated to 100 °C. After reacting for 6 hours, 47.05 g of phenol was added, and the reaction continued for 8 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, alkali washing, water removal and drying to obtain 75.43 g of organophosphine oxide compound 7, with a yield of 65% and a purity of 98%.

[0151] Example 8

[0152] Synthesis of compound 8:

[0153] Under anhydrous and anaerobic conditions, 39.06 g of benzene was added to a three-necked flask, followed by 68.66 g of phosphorus trichloride and 66.65 g of magnesium chloride. Nitrogen was introduced, and the mixture was stirred at high speed and heated to 100 °C. After reacting for 8 hours, 47.05 g of phenol was added, and the reaction continued for 16 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, alkali washing, water removal and drying to obtain 61.05 g of organophosphine oxide compound 8, with a yield of 56% and a purity of 98%.

[0154] Example 9

[0155] Synthesis of compound 9:

[0156] Under anhydrous and anaerobic conditions, 53.09 g of o-xylene was added to a three-necked flask, followed by 68.66 g of phosphorus trichloride and 113.54 g of iron chloride. Nitrogen was introduced, and the mixture was stirred at high speed and heated to 130 °C. After reacting for 3 hours, 47.05 g of phenol was added, and the reaction continued for 9 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, alkali washing, water removal and drying to obtain 77.52 g of organophosphine oxide compound 9, with a yield of 63% and a purity of 98%.

[0157] Example 10

[0158] Synthesis of compound 10:

[0159] Under anhydrous and anaerobic conditions, 47.05 g of phenol was added to a three-necked flask, followed by the addition of 68.66 g of phosphorus trichloride and 66.65 g of magnesium chloride. Nitrogen was introduced, and the mixture was stirred at high speed and heated to 50 °C. After reacting for 4 hours, another 47.05 g of phenol was added, and the reaction continued for 14 hours. After the reaction was completed, the reaction solution was dropped into water for quenching, followed by extraction, alkali washing, water removal and drying to obtain 100.64 g of organophosphorus oxide 10, with a yield of 86% and a purity of 98%.

[0160] Example 11

[0161] Synthesis of compound 1':

[0162] 572.83 g of butyl etherified bisphenol A was reacted with 808.70 g of organophosphorus oxide 1. The temperature was raised to 100 °C and maintained for 1 h, then raised to 120 °C and maintained for 1 h, then raised to 140 °C and kept under slightly vacuum for 2 h. Finally, vacuum distillation was carried out at 140 °C for 40 min. The remaining component was compound 1'. 1074.2 g of bisphenol A-structured compound 1' was obtained, with a yield of 99% and a purity of 98%. The carbon NMR spectrum, phosphorus NMR spectrum, and hydrogen NMR spectrum of compound 1' are respectively as Figures 1 - 3 shown, and after comparison, it is the structure of compound 1'.

[0163] Example 12

[0164] Synthesis of compound 2':

[0165] 572.83 g of butyl etherified bisphenol A was reacted with 920.90 g of organophosphorus oxide 3. The temperature was raised to 100 °C and maintained for 1 h, then raised to 120 °C and maintained for 1 h, then raised to 140 °C and kept under slightly vacuum for 2 h. Finally, vacuum distillation was carried out at 140 °C for 60 min. The remaining component was compound 2'. 1185.34 g of bisphenol A-structured compound 2' was obtained, with a yield of 99% and a purity of 98%. The carbon NMR spectrum, phosphorus NMR spectrum, and hydrogen NMR spectrum of compound 2' are respectively as Figures 4 - 6 shown, and after comparison, it is the structure of compound 2'.

[0166] Example 13

[0167] Synthesis of polymer 1":

[0168] 985.50 g of butanol-etherified bisphenol A resin reacts with 1212.55 g of organic phosphine oxide 1. The temperature is raised to 100 °C and maintained for 1 h. Then the temperature is raised to 120 °C and maintained for 1 h. Next, the temperature is raised to 140 °C and maintained under slightly reduced pressure for 2 h. Finally, vacuum distillation is carried out at 140 °C for 60 min. The remaining component is compound 1”. 1753.33 g of compound 1” is obtained. The GPC results are shown in Table 1.

[0169] Table 1 GPC test molecular weight results of compound 1”

[0170]

[0171] Example 22

[0172] Synthesis of polymer 2”:

[0173] 985.50 g of butanol-etherified bisphenol A resin reacts with 1380.50 g of organic phosphine oxide 3. The temperature is raised to 100 °C and maintained for 1 h. Then the temperature is raised to 120 °C and maintained for 1 h. Next, the temperature is raised to 140 °C and maintained under slightly reduced pressure for 2 h. Finally, vacuum distillation is carried out at 140 °C for 60 min. The remaining component is compound 2”. 1922.22 g of compound 2” is obtained. The GPC results are shown in Table 2.

[0174] Table 2 GPC test molecular weight results of compound 2”

[0175]

[0176] Example 23

[0177] Application Example 1

[0178] Performance test of bisphenol A structural compounds:

[0179] After adding bisphenol A structural compounds / bisphenol A structural polymers, epoxy resin E51, aluminum hydroxide, soft silicon, and dicyandiamide curing agent, the specimens are trimmed into standard specimens for limiting oxygen index test: 125.0 mm in length, 13 mm in width, and 1.60 mm in thickness. Five specimens are prepared for each bisphenol A structural compound material. The specimens are flat, smooth, without bubbles inside and subjected to vertical burning test. The component ratios and contents are shown in Table 1.

[0180] The vertical burning test method refers to GB4609 method:

[0181] After installing the specimen as required, light the Bunsen burner, align the lamp flame with the center plane at the lower end of the specimen, and keep the upper end of the lamp tube 10 mm away from the lower end of the specimen. After applying the flame to the specimen for 10 s, move the Bunsen burner to a position at least 150 mm away from the specimen, and simultaneously measure the flaming combustion time t of the specimen. When the flame of the specimen goes out, apply the flame to the specimen again for 10 s, then remove the Bunsen burner, and measure the flaming combustion time t and the non-flaming combustion time t3. In addition, observe whether there is a dripping phenomenon when the specimen is burning and whether the dripping can ignite absorbent cotton. Repeat the above steps to test 5 parallel specimens. The results are shown in Table 2. Specimens 1-4 correspond to bisphenol A structure compounds 1'-2' and bisphenol A structure polymers 1''-2'' respectively. Comparative specimen 1 has no addition of bisphenol A structure compounds, and comparative specimen 2 replaces the bisphenol A structure compounds / bisphenol A structure polymers with SF-600 purchased from Macklin.

[0182] In addition, the phosphorus content of specimens 1-4 was tested by an elemental analyzer, and the results are shown in Table 3. The test results of other properties are shown in Tables 4 and 5.

[0183] Table 1 Component ratio in the specimen

[0184]

[0185] Note: The content (%) of bisphenol A structure compounds / bisphenol A structure polymers refers to their addition amount in epoxy resin E51.

[0186] Table 2 Vertical burning test results

[0187]

[0188]

[0189] The results in Table 2 show that specimens 1-4 have excellent flame retardant effects, indicating that the bisphenol A structure compounds / bisphenol A structure polymers of the present invention can be comparable to the performance of a certain commercially available flame retardant that is currently popular.

[0190] Table 3 Phosphorus content of compounds 1'-2' and polymers 1''-2''

[0191] specimen determine phosphorus content theoretical phosphorus content 1 11.3％ 11.4％ 2 10.2％ 10.3％ 3 10.2％ 9.5-10.6％ 4 9.1％ 8.4-9.6％

[0192] The results in Table 3 show that the measured phosphorus content in specimens 1-4 is consistent with the theoretical content.

[0193] Table 4 Test results of related properties of specimens 1-4

[0194] Specimen 1 Specimen 2 Specimen 3 Specimen 4 Comparative Specimen 2 thickness 0.583 0.581 0.582 0.581 0.581 appearance of board surface OK OK OK OK OK Tg (DSC) 180.0 183.9 180.5 180.6 179.9 PCT Pass Pass Pass Pass Pass T288 45、45、45 40、45、45 40、40、45 35、40、45 30、35、40 CTE 2.8％ 2.6％ 2.8％ 2.6％ 2.8％ UD288 > 10 minutes > 10 minutes > 10 minutes > 10 minutes > 10 minutes TGA 364 358 364 358 362 DK 4.49 4.48 4.46 4.42 4.58 DF 0.0091 0.0091 0.0092 0.0091 0.0096

[0195] Table 5 Summary of test methods or instruments for related results in Table 4

[0196]

[0197]

[0198] The results in Table 4 show that Samples 1 to 4 of the present invention have excellent comprehensive properties, indicating that the bisphenol A structure compound / bisphenol A structure polymer of the present invention can be comparable to the performance of a certain commercially available flame retardant that is currently popular.

[0199] In summary, when the bisphenol A structure compound or bisphenol A structure polymer obtained in the present invention is added to a synthetic resin, the resulting synthetic resin has excellent low dielectric constant, low hygroscopicity, and high glass transition temperature, and good flame retardant performance. These bisphenol A structure compounds or bisphenol A structure polymers can be widely used in the preparation of curing agents, flame retardants, film materials, adhesives, insulating materials, chip packaging materials, and copper clad laminates.

[0200] The above-described embodiments merely represent several implementation manners of the present invention, and the description thereof is relatively specific and detailed. However, it should not be construed as a limitation to the scope of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the appended claims.

Claims

1. A bisphenol A structure compound having a flame retardant property and substituted by a phosphine oxygen group, characterized in that: The bisphenol A structural compound is selected from the following structures:

2. The method for synthesizing the bisphenol A structure compound according to claim 1, characterized in that: The alcohol-etherified bisphenol A compound and the organic phosphine oxide compound are mixed and heated to react to obtain the alcohol-etherified bisphenol A compound, wherein the alcohol-etherified bisphenol A compound has a structure as shown in formula (III): Wherein, R2 is selected from: C1-C8 alkyl; the organic phosphine oxide compound has a structure shown in formula (I): Wherein, the definitions of R1 and R correspond to the groups of the bisphenol A structure compound described in claim 1.

3. The synthesis method according to claim 2, characterized in that The heating reaction process includes: raising the system temperature to 90-100°C and keeping it warm for 1-2 hours; then further raising the temperature to 110-120°C and keeping it warm for 1-2 hours; further raising the temperature to 130-140°C and keeping it in vacuum for 2-3 hours; after the heating reaction is completed, obtaining the bisphenol A structure compound through reduced pressure distillation.

4. The synthesis method according to claim 3, characterized in that The vacuum degree is below 0.01 MPa.

5. The synthesis method according to claim 3, characterized in that The temperature of the reduced pressure distillation is 130-140° C., the pressure is 0.05-0.1 MPa, and the time is 30-60 min.

6. A bisphenol A structure polymer substituted with phosphine oxide groups having flame retardant properties, characterized in that: The bisphenol A structural polymer is selected from the following structures:

7. The method for synthesizing the bisphenol A structure polymer according to claim 6, characterized in that: The alcohol-etherified bisphenol A polymer is mixed with an organic phosphine oxide compound and then heated to react to obtain the alcohol-etherified bisphenol A polymer, wherein the alcohol-etherified bisphenol A polymer has a structure as shown in formula (V): Wherein, R2 is selected from: C1-C8 alkyl, n=1-5; the organic phosphine oxide compound has the structure shown in formula (I): Wherein, the definitions of R1 and R correspond to the groups of the bisphenol A structure polymer described in claim 6.

8. The synthesis method according to claim 7, characterized in that The heating reaction process includes: raising the system temperature to 100-110°C and keeping it warm for 1-2 hours; then further raising the temperature to 120-130°C and keeping it warm for 1-2 hours; further raising the temperature to 140-150°C and keeping it in vacuum for 2-3 hours; after the heating reaction is completed, obtaining the bisphenol A structure compound through reduced pressure distillation.

9. The synthesis method according to claim 8, characterized in that The vacuum degree is below 0.01 MPa.

10. The synthesis method according to claim 8, characterized in that The temperature of the reduced pressure distillation is 140-150° C., the pressure is 0.05-0.1 MPa, and the time is 30-60 min.

11. Use of a bisphenol A structure compound and / or a bisphenol A structure polymer as claimed in claim 6 as a flame retardant component in the preparation of one of the following materials: a curing agent, a flame retardant, a film material, an adhesive, an insulating material, a chip packaging material, and a copper clad laminate, wherein the bisphenol A structure compound is selected from the following structures:

12. Use of a bisphenol A structure compound and / or a bisphenol A structure polymer as claimed in claim 6 as a flame retardant component for improving the flame retardant properties of synthetic resin materials, wherein the bisphenol A structure compound is selected from the following structures:

13. The use according to claim 12, characterized in that: The application comprises: compounding the bisphenol A structure compound and / or the bisphenol A structure polymer with a synthetic resin material according to the mass content of phosphorus in the synthetic resin being 2-3%.

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