Phosphorus-nitrogen synergistic high-CTI (comparative tracking index) flame-retardant epoxy resin composition and preparation method thereof

Abstract

The invention discloses a phosphorus-nitrogen synergistic high-CTI (comparative tracking index) flame-retardant epoxy resin composition and a preparation method thereof. The phosphorus-nitrogen synergistic high-CTI flame-retardant epoxy resin composition is characterized by being prepared by mixing 30-50 parts by mass of phosphorus-containing epoxy resin, 10-30 parts by mass of nitrogen-containing epoxy resin, 3-6 parts by mass of novolac epoxy resin, 2-5 parts by mass of tetraphenol ethane epoxy resin, 2-8 parts by mass of bisphenol A solid epoxy resin and 10-20 parts by mass of solvent butanone. The preparation method comprises the following steps: preparing phosphorus-containing epoxy resin, preparing nitrogen-containing epoxy resin, and preparing the phosphorus-nitrogen synergistic high-CTI flame-retardant epoxy resin composition. The phosphorus-nitrogen synergistic high-CTI flame-retardant epoxy resin composition disclosed by the invention has the advantages of high CTI, excellent moisture resistance, flame retardance and chemical stability, environment friendliness, low production cost and the like, is suitable for production of copper-clad plates, and is high in practicability.

Description

Technical Field

[0001] The present invention belongs to a composition of a polymer compound and its preparation, and relates to a phosphorus-nitrogen synergistic high CTI (CTI, i.e., resistance to tracking, comparative tracking index) flame-retardant epoxy resin composition and its preparation method. The phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition (prepared) of the present invention is suitable for the production of copper-clad laminates. Background Art

[0002] In recent years, due to environmental protection requirements, the application of halogen flame retardants has been restricted. With the rapid development of the electronics industry and the export of domestic high-speed rail and rail transit industries, the trend of halogen-free flame retardant has become more obvious. At the same time, in humid and easily polluted environments, the requirements for material resistance to leakage tracking have become more stringent. Therefore, the development of environmentally friendly halogen-free flame retardant and high resistance to leakage tracking materials has become a trend.

[0003] In the prior art, halogen-free flame retardant additives mainly include phosphorus compounds, nitrogen flame retardants, metal hydroxides and silicon flame retardants. Phosphorus is modified epoxy with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short). The modified epoxy resin has excellent flame retardancy, excellent physical and mechanical properties, and no pollution to the environment, but it also has many disadvantages: poor moisture resistance, heat resistance, chemical stability, etc.: moisture resistance, because it contains this resin as the matrix resin, after curing, its system contains a small amount of heterocyclic compounds, which will absorb moisture from humid air. When moisture accumulates in the system, it will cause confusion in the subsequent heating processing of the board, reduce the life of the board or even scrap it; nitrogen flame retardants are mainly melamine and its derivatives. Melamine resin has the advantages of high nitrogen content, low toxicity, low smoke generation, etc., and is favored by the market; but it also has the problem of insufficient heat resistance.

[0004] In the prior art, the "method for preparing melamine-modified epoxy resin glass cloth laminate" disclosed in CN111572129A utilizes melamine-modified epoxy resin to coat alkali-free glass fiber cloth, and solves the problem of high resistance to leakage tracking after baking, lamination and hot pressing. However, the disadvantage is that the heat resistance is low, which affects the use of the board and is prone to bursting. Summary of the invention

[0005] The purpose of the present invention is to overcome the deficiencies in the above-mentioned prior art and provide a phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition and a preparation method thereof. The present invention redesigns the product structure, introduces DOPO derivatives into the main chain structure of the epoxy resin, utilizes its rigid structure to improve the heat resistance of the system, and improves the tracking resistance of the system through the synergistic effect of melamine-modified epoxy, introduces multifunctional phenolic epoxy, thereby providing a phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition with excellent flame retardancy, heat resistance and high tracking resistance and a preparation method thereof, thereby effectively solving the deficiencies and defects of heat resistance in the prior art.

[0006] The content of the present invention is: a phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition, which is characterized in that: the phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition is composed of 30 to 50 parts by mass of phosphorus-containing epoxy resin, 10 to 30 parts by mass of nitrogen-containing epoxy resin, 3 to 6 parts by mass of phenolic epoxy resin, 2 to 5 parts by mass of tetraphenol ethane epoxy resin, 2 to 8 parts by mass of bisphenol A solid epoxy resin and 10 to 20 parts by mass of solvent butanone (it can also be a mixture of butanone and propylene glycol methyl ether, acetone, or a mixture of acetone and propylene glycol methyl ether).

[0007] In the context of the present invention: the preparation method of the phosphorus-containing epoxy resin is:

[0008] 10 to 20 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short), 5 to 10 parts by weight of quinones, and 30 to 50 parts by weight of bisphenol A epoxy resin or / and bisphenol F epoxy resin are added to a reactor, heated to 60 to 100° C. under stirring, maintained at the temperature for reaction for 2.0 to 4.0 hours, then heated to 100 to 150° C., added with 0.01 to 0.1 parts by weight of catalyst A, kept warm for reaction for 30 minutes, then heated to 160 to 190° C. (warm) for reaction for 3 to 6 hours, then cooled to 100 to 120° C., added with 20 to 40 parts by weight of solvent A, mixed evenly (until dissolved and transparent), to obtain a phosphorus-containing epoxy resin;

[0009] The quinone substance may be one or a mixture of p-benzoquinone and naphthoquinone;

[0010] The catalyst A can be one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethylbenzylammonium chloride, tetrabutylammonium bromide, and butyltriphenylphosphonium bromide;

[0011] The solvent A is any one of butanone, acetone, a mixture of butanone and propylene glycol methyl ether (can be a mixture in any proportion), or a mixture of acetone and propylene glycol methyl ether (can be a mixture in any proportion).

[0012] In the content of the present invention: the product production and providing enterprise and model of the bisphenol A type epoxy resin is one of NPEL128 of Nan Ya (Nan Ya is the abbreviation of Nan Ya Plastics Industry Co., Ltd., the same below), NPEL127 of Nan Ya, EMTE128 of Shandong Aimonte (Shandong Aimonte is the abbreviation of Shandong Aimonte New Materials Co., Ltd., the same below) or a mixture of two thereof, and the product production and providing enterprise and model of the bisphenol F type epoxy resin is Nan Ya NPEF170.

[0013] In the context of the present invention: the preparation method of the nitrogen-containing epoxy resin is:

[0014] 2-4 parts by mass of melamine, 4-8 parts by mass of paraformaldehyde (the product manufacturer is Nantong Jiangtian Chemical Co., Ltd.), 10-20 parts by mass of propylene glycol methyl ether, and 40-60 parts by mass of bisphenol A epoxy resin are added into a reactor, heated to 60°C-70°C with stirring, and the temperature is maintained for reaction for 1.0-2.0 hours, and then 0.05-0.2 parts by mass of catalyst B are added, and the temperature is increased to 80°C-100°C and kept for reaction for 2.0-4.0 hours, and 20-40 parts by mass of solvent A are added and mixed (until dissolved and transparent) to obtain a nitrogen-containing epoxy resin.

[0015] The catalyst B is one or both of ethanolamine and triethanolamine;

[0016] The solvent A is any one of butanone, acetone, a mixture of butanone and propylene glycol methyl ether (can be a mixture in any proportion), or a mixture of acetone and propylene glycol methyl ether (can be a mixture in any proportion).

[0017] In the content of the present invention: the product production and providing enterprise and model of the bisphenol A epoxy resin are one of NPEL128 of Nanya, NPEL127 of Nanya, EMTE128 of Shandong Aimonte, or a mixture of two thereof.

[0018] In the content of the present invention: the phenolic epoxy resin is any one of Shandong Aimonte EMT638, Nan Ya NPPN638S, Shandong Deyuan (Shandong Deyuan is the abbreviation of Shandong Deyuan Epoxy Technology Co., Ltd., the same below) 638 epoxy resin; the tetraphenol ethane epoxy resin is any one of Cologne (Cologne is the Cologne Group (KOLON) of South Korea) 4131A70 and Nan Ya NPPN431; the bisphenol A solid epoxy resin is any one of Sinopec (Sinopec is the abbreviation of Sinopec Baling Petrochemical Co., Ltd., the same below) CYD011 and Nan Ya NPES901.

[0019] In the content of the present invention: the physicochemical data of the phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition are: solid content 60% to 80%, viscosity 200 to 2000 mPa·s, epoxy equivalent 240 to 320 g / eq, phosphorus content 2% to 3%, nitrogen content 1% to 2%, glass transition temperature 150°C to 170°C, and a reddish-brown transparent liquid.

[0020] Another aspect of the present invention is: a method for preparing a phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition, characterized in that the steps are:

[0021] a. Preparation of phosphorus-containing epoxy resin:

[0022] 10 to 20 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short), 5 to 10 parts by weight of quinones, and 30 to 50 parts by weight of bisphenol A epoxy resin or / and bisphenol F epoxy resin are added to a reactor, heated to 60 to 100° C. under stirring, maintained at the temperature for reaction for 2.0 to 4.0 hours, then heated to 100 to 150° C., added with 0.01 to 0.1 parts by weight of catalyst A, kept warm for reaction for 30 minutes, then heated to 160 to 190° C. (warm) for reaction for 3 to 6 hours, then cooled to 100 to 120° C., added with 20 to 40 parts by weight of solvent A, mixed evenly (until dissolved and transparent), to obtain a phosphorus-containing epoxy resin;

[0023] The quinone substance may be one or a mixture of p-benzoquinone and naphthoquinone;

[0024] The catalyst A can be one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethylbenzylammonium chloride, tetrabutylammonium bromide, and butyltriphenylphosphonium bromide;

[0025] The solvent A is any one of butanone, acetone, a mixture of butanone and propylene glycol methyl ether (can be a mixture in any proportion), or a mixture of acetone and propylene glycol methyl ether (can be a mixture in any proportion);

[0026] b. Preparation of nitrogen-containing epoxy resin:

[0027] 2-4 parts by weight of melamine, 4-8 parts by weight of paraformaldehyde, 10-20 parts by weight of propylene glycol methyl ether and 40-60 parts by weight of bisphenol A epoxy resin are added into a reactor, heated to 60-70°C with stirring, maintained at the temperature for reaction for 1.0-2.0 hours, then 0.05-0.2 parts by weight of catalyst B are added, heated to 80-100°C and maintained for reaction for 2.0-4.0 hours, 20-40 parts by weight of solvent A are added, mixed evenly (until dissolved and transparent), and a nitrogen-containing epoxy resin is obtained.

[0028] The catalyst B is one or both of ethanolamine and triethanolamine;

[0029] The solvent A is any one of butanone, acetone, a mixture of butanone and propylene glycol methyl ether (can be a mixture in any proportion), or a mixture of acetone and propylene glycol methyl ether (can be a mixture in any proportion);

[0030] c. Preparation of phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition: Take the raw materials of each component in a mass ratio of 30-50 parts by mass of phosphorus-containing epoxy resin, 10-30 parts by mass of nitrogen-containing epoxy resin, 3-6 parts by mass of phenolic epoxy resin, 2-5 parts by mass of tetraphenol ethane epoxy resin, 2-8 parts by mass of bisphenol A solid epoxy resin and 10-20 parts by mass of solvent butanone, stir and mix evenly to obtain a phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition.

[0031] In the preparation method of the phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition described in another aspect of the present invention, the bisphenol A epoxy resin product production and providing enterprise and model is one of NPEL128 of Nan Ya (Nan Ya is the abbreviation of Nan Ya Plastics Industry Co., Ltd., the same below), NPEL127 of Nan Ya, EMTE128 of Shandong Aimonte (Shandong Aimonte is the abbreviation of Shandong Aimonte New Materials Co., Ltd., the same below) or a mixture of two;

[0032] The bisphenol F epoxy resin product manufacturer and model is Nanya NPEF170;

[0033] The phenolic epoxy resin is any one of Shandong Aimonte EMT638, Nanya NPPN638S, Shandong Deyuan (Shandong Deyuan is the abbreviation of Shandong Deyuan Epoxy Technology Co., Ltd., the same below) 638 epoxy resin;

[0034] The tetraphenol ethane epoxy resin is any one of KOLON (KOLON is the abbreviation of KOLON Group of South Korea, the same below) 4131A70 and Nanya NPPN431;

[0035] The bisphenol A solid epoxy resin is any one of Sinopec (Sinopec is the abbreviation of Sinopec Baling Petrochemical Co., Ltd., the same below) CYD011 and Nanya NPES901.

[0036] In another aspect of the present invention: the physicochemical data of the prepared phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition are: solid content 60% to 80%, viscosity 200 to 2000 mPa·s, epoxy equivalent 240 to 320 g / eq, phosphorus content 2% to 3%, nitrogen content 1% to 2%, glass transition temperature 150°C to 170°C, and a reddish-brown transparent liquid.

[0037] The definition of "solid content" described in this article is: the percentage of the mass of non-volatile matter in the total mass of 1g sample (i.e., the phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition) after baking in an oven at 160°C for 1 hour, and the solid content finally determined by calculating the mass of the solvent added based on the mass of the non-volatile matter.

[0038] The definition of "phosphorus content" described herein is: the percentage of phosphorus content in the total solid mass of the phosphorus-nitrogen synergistic high CTI flame retardant epoxy resin composition.

[0039] The definition of "nitrogen content" described herein is: the percentage of nitrogen content in the total solid mass of the phosphorus-nitrogen synergistic high CTI flame retardant epoxy resin composition.

[0040] Compared with the prior art, the present invention has the following characteristics and beneficial effects:

[0041] (1) The present invention adopts the addition reaction of quinone substances and phosphorus-containing compounds to introduce phosphorus into the main chain of the molecule, and utilizes the rigid structure of quinone substances to improve the flame retardancy of epoxy resin, thereby being used for the preparation of high-performance copper-clad laminates;

[0042] (2) The present invention adopts melamine-modified epoxy resin, introduces a nitrogen-containing structure into the main chain structure of the epoxy resin, and improves the CTI (tracking resistance, comparative tracking index) of the system by introducing bisphenol A type solid epoxy resin;

[0043] (3) The preparation process of the present invention is simple, and the obtained phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition has good product performance, high CTI, excellent moisture resistance, flame retardancy and chemical stability, and is environmentally friendly, easy to operate, fast in reaction speed, and low in production cost. It is suitable for the production of copper clad laminates and has strong practicality. DETAILED DESCRIPTION

[0044] The following embodiments are intended to further illustrate the present invention, but should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by technicians in this field based on the above-mentioned contents of the present invention still fall within the scope of protection of the present invention.

[0045] In the following embodiments, the specific unit of "parts by mass" is "kilogram (kg)".

[0046] Part I Preparation of Phosphorus-Containing Epoxy Resin

[0047] Example 1-1:

[0048] 30 parts by weight of bisphenol A epoxy resin NPEL127, 15 parts by weight of NPEF170, 5 parts by weight of quinone compound (p-benzoquinone), and 10 parts by weight of DOPO were added to the reactor and heated to 60°C (T 1 , the same as in the subsequent examples), keep the temperature for 2h (t 1 , the same as in the subsequent embodiments), then the temperature was raised to 100°C, 0.01 mass parts of catalyst A triphenylphosphine was added, the temperature was kept for reaction for 30 minutes, and then the temperature was raised to 160°C (heating, T 2 , the same as in the subsequent examples) and reacted for 3h (t 2 , the same as in the subsequent examples), then cooled to 100°C, 25 parts by mass of solvent A (a mixture of butanone and propylene glycol methyl ether) were added dropwise, and mixed until it was dissolved and transparent, thus obtaining a phosphorus-containing epoxy resin. The product had a phosphorus content of 2.0% and an epoxy equivalent of 280 g / eq.

[0049] Embodiment 1-2:

[0050] 30 parts by weight of bisphenol A epoxy resin NPEL127, 15 parts by weight of NPEF170, 5.5 parts by weight of quinone compounds (p-benzoquinone), and 11 parts by weight of DOPO were added to a reactor, heated to 70°C with stirring, maintained at this temperature for 2 hours, then heated to 100°C and added with 0.01 parts by weight of catalyst A triphenylphosphine, kept warm for 30 minutes, then heated to 160°C for 3 hours (then cooled to 100°C, 26 parts by weight of solvent A (a mixture of butanone and propylene glycol methyl ether) were added dropwise, and mixed until it was dissolved and transparent, thereby obtaining a phosphorus-containing epoxy resin. The product has a phosphorus content of 2.08% and an epoxy equivalent of 285 g / eq.

[0051] Embodiment 1-3:

[0052] 30 parts by weight of bisphenol A epoxy resin NPEL127, 15 parts by weight of NPEF170, 6 parts by weight of quinone compounds (para-benzoquinone), and 12 parts by weight of DOPO were added to a reactor, heated to 70°C with stirring, maintained at this temperature for 3 hours, then heated to 100°C and added with 0.015 parts by weight of catalyst A triphenylphosphine, kept warm for 30 minutes, then heated to 170°C for 3 hours (then cooled to 100°C, and 26 parts by weight of solvent A (a mixture of butanone and propylene glycol methyl ether) were added dropwise, and mixed until it was dissolved and transparent, thereby obtaining a phosphorus-containing epoxy resin. The product has a phosphorus content of 2.1% and an epoxy equivalent of 288 g / eq.

[0053] Embodiment 1-4:

[0054] 30 parts by weight of bisphenol A epoxy resin NPEL127, 15 parts by weight of NPEF170, 6.5 parts by weight of quinone compound (p-benzoquinone), and 13 parts by weight of DOPO were added to a reactor, heated to 80°C under stirring, maintained at this temperature for 3 hours, then heated to 100°C and added with 0.015 parts by weight of catalyst A triphenylphosphine, kept warm for 30 minutes, then heated to 170°C and reacted for 4 hours (then cooled to 100°C, 27 parts by weight of solvent A (butanone) was added dropwise, and mixed until it was dissolved and transparent, thereby obtaining a phosphorus-containing epoxy resin. The product has a phosphorus content of 2.12% and an epoxy equivalent of 294 g / eq.

[0055] Embodiment 1-5:

[0056] 30 parts by weight of bisphenol A epoxy resin NPEL127, 15 parts by weight of NPEF170, 7 parts by weight of quinone compound (p-benzoquinone), and 14 parts by weight of DOPO were added to a reactor, heated to 80°C under stirring, maintained at this temperature for 3 hours, then heated to 100°C and added with 0.02 parts by weight of catalyst A triphenylphosphine, kept warm for 30 minutes, then heated to 180°C and reacted for 4 hours (then cooled to 100°C, 27 parts by weight of solvent A (butanone) was added dropwise, and mixed until it was dissolved and transparent, thereby obtaining a phosphorus-containing epoxy resin. The product has a phosphorus content of 2.18% and an epoxy equivalent of 300 g / eq.

[0057] Embodiment 1-6:

[0058] 30 parts by weight of bisphenol A epoxy resin NPEL127, 15 parts by weight of NPEF170, 7.5 parts by weight of quinone compound (p-benzoquinone), and 15 parts by weight of DOPO were added to a reactor, heated to 90°C under stirring, maintained at this temperature for 4 hours, then heated to 100°C and added with 0.02 parts by weight of catalyst A triphenylphosphine, kept warm for 30 minutes, then heated to 180°C and reacted for 5 hours (then cooled to 100°C, 28 parts by weight of solvent A (acetone) were added dropwise, and mixed and dissolved until transparent, thereby obtaining a phosphorus-containing epoxy resin. The product has a phosphorus content of 2.22% and an epoxy equivalent of 310 g / eq.

[0059] Embodiment 1-7:

[0060] 30 parts by weight of bisphenol A epoxy resin NPEL127, 15 parts by weight of NPEF170, 8 parts by weight of quinone compounds (para-benzoquinone), and 16 parts by weight of DOPO were added to a reactor, heated to 90°C with stirring, maintained at this temperature for 4 hours, then heated to 100°C and added with 0.025 parts by weight of catalyst A triphenylphosphine, kept warm for 30 minutes, then heated to 190°C and reacted for 6 hours (then cooled to 100°C, 28 parts by weight of solvent A (a mixture of acetone and propylene glycol methyl ether) were added dropwise, and mixed and dissolved until transparent, thereby obtaining a phosphorus-containing epoxy resin. The product has a phosphorus content of 2.35% and an epoxy equivalent of 320 g / eq.

[0061] The specific ratios of raw materials and specific process parameters for preparing phosphorus-containing epoxy resins in Examples 1-1 to 1-7 are shown in Table 1 below:

[0062] Table 1: Raw material ratios and process parameters for preparing phosphorus-containing epoxy resins in Examples 1-1 to 1-7:

[0063]

[0064] In Examples 1-1 to 1-7: the solvent A is one of butanone, acetone, a mixture of butanone and propylene glycol methyl ether (can be a mixture in any proportion), and a mixture of acetone and propylene glycol methyl ether (can be a mixture in any proportion).

[0065] Part II Preparation of Nitrogen-Containing Epoxy Resins

[0066] Example 2-1:

[0067] 40 parts by mass of bisphenol A epoxy resin NPEL127, 15 parts by mass of NPEF170, 2 parts by mass of melamine, 4 parts by mass of paraformaldehyde were added to the reactor, and 10 parts by mass of propylene glycol methyl ether were added to the reactor, and the temperature was raised to 60°C (T 1 , the same as in the subsequent examples) add 0.05 mass parts of catalyst B triethanolamine, keep the temperature for reaction for 1h (t 1 , the same as in the subsequent embodiments), and then heated to 80°C (keeping temperature T 2 , the same as in the subsequent examples) and reacted for 2h (t 2 , the same as in the subsequent examples), then cooled to 60°C, added 16 parts by mass of solvent A (a mixture of butanone and propylene glycol methyl ether), and mixed until it was dissolved and transparent, thus obtaining a nitrogen-containing epoxy resin. The product had a nitrogen content of 2.18% and an epoxy equivalent of 215 g / eq.

[0068] Example 2-2:

[0069] 40 parts by weight of bisphenol A epoxy resin NPEL127, 15 parts by weight of NPEF170, 2.5 parts by weight of melamine, 5 parts by weight of paraformaldehyde are added to a reactor, and 10 parts by weight of propylene glycol methyl ether are added to the reactor, and the temperature is raised to 60°C under stirring, and 0.05 parts by weight of catalyst B triethanolamine is added, and the temperature is maintained for reaction for 1 hour, and then the temperature is raised to 80°C for reaction for 2 hours, and then cooled to 60°C, and 17 parts by weight of solvent A (butanone) is added, and the mixture is mixed and dissolved until transparent, and the nitrogen-containing epoxy resin is obtained. The product has a nitrogen content of 2.50% and an epoxy equivalent of 220 g / eq.

[0070] Embodiment 2-3:

[0071] 40 parts by weight of bisphenol A epoxy resin NPEL127, 15 parts by weight of NPEF170, 3 parts by weight of melamine, and 6 parts by weight of paraformaldehyde are added to a reactor, and 10 parts by weight of propylene glycol methyl ether are added to the reactor, and the temperature is raised to 70°C under stirring, and 0.05 parts by weight of catalyst B triethanolamine is added, and the temperature is maintained for reaction for 2 hours, and then the temperature is raised to 90°C for reaction for 3 hours, and then cooled to 60°C, and 17 parts by weight of solvent A (acetone) are added, and the mixture is mixed and dissolved until transparent, and a nitrogen-containing epoxy resin is obtained. The product has a nitrogen content of 2.98% and an epoxy equivalent of 225 g / eq.

[0072] Embodiment 2-4:

[0073] 40 parts by weight of bisphenol A epoxy resin NPEL127, 15 parts by weight of NPEF170, 3.5 parts by weight of melamine, and 7 parts by weight of paraformaldehyde are added to a reactor, and 10 parts by weight of propylene glycol methyl ether are added to the reactor, and the temperature is raised to 70°C under stirring, and 0.1 parts by weight of catalyst B triethanolamine is added, and the temperature is maintained for reaction for 2 hours, and then the temperature is raised to 90°C for reaction for 3 hours, and then cooled to 60°C, and 18 parts by weight of solvent A (a mixture of acetone and propylene glycol methyl ether) is added, and the mixture is mixed and dissolved until transparent, and a nitrogen-containing epoxy resin is obtained. The product has a nitrogen content of 3.48% and an epoxy equivalent of 235 g / eq.

[0074] Embodiment 2-5:

[0075] 40 parts by weight of bisphenol A epoxy resin NPEL127, 15 parts by weight of NPEF170, 4 parts by weight of melamine, and 8 parts by weight of paraformaldehyde are added to a reactor, and 10 parts by weight of propylene glycol methyl ether are added to the reactor, and the temperature is raised to 70°C under stirring, and 0.1 parts by weight of catalyst B triethanolamine is added, and the temperature is maintained for reaction for 2 hours, and then the temperature is raised to 100°C for reaction for 4 hours, and then cooled to 60°C, and 19 parts by weight of solvent A (a mixture of acetone and propylene glycol methyl ether) is added, and the mixture is mixed and dissolved until transparent, and a nitrogen-containing epoxy resin is obtained. The product has a nitrogen content of 4.0% and an epoxy equivalent of 245 g / eq.

[0076] The specific ratios of raw materials and specific process parameters for preparing nitrogen-containing epoxy resins in Examples 2-1 to 2-5 are shown in Table 2 below:

[0077] Table 2: Raw material ratios and process parameters for preparing nitrogen-containing epoxy resins in Examples 2-1 to 2-5:

[0078]

[0079]

[0080] In Examples 2-1 to 2-5: the solvent A is one of butanone, acetone, a mixture of butanone and propylene glycol methyl ether (can be a mixture in any proportion), and a mixture of acetone and propylene glycol methyl ether (can be a mixture in any proportion).

[0081] Part III Preparation of phosphorus-nitrogen synergistic high CTI flame retardant epoxy resin composition

[0082] Embodiments 3-1 to 3-7:

[0083] The raw materials of each component are mixed in a proportion of 30-50 parts by mass of phosphorus-containing epoxy resin, 10-30 parts by mass of nitrogen-containing epoxy resin, 3-6 parts by mass of phenolic epoxy resin, 2-5 parts by mass of tetraphenol ethane epoxy resin, 2-8 parts by mass of bisphenol A solid epoxy resin and 10-20 parts by mass of butanone solvent, and stirred and mixed evenly. Specifically, the raw materials of each component are mixed at room temperature (25° C.-30° C.) and stirred at high speed for 30 minutes. After the materials are mixed evenly, a phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition is obtained; wherein:

[0084] The phosphorus-containing epoxy resins used in Examples 3-1 to 3-7 are the phosphorus-containing epoxy resins prepared in Examples 1-1 to 1-7, respectively, that is, the phosphorus-containing epoxy resin used in Example 3-1 is the phosphorus-containing epoxy resin prepared in Example 1-1, the phosphorus-containing epoxy resin used in Example 3-2 is the phosphorus-containing epoxy resin prepared in Example 1-2, the phosphorus-containing epoxy resin used in Example 3-3 is the phosphorus-containing epoxy resin prepared in Example 1-3, ... the phosphorus-containing epoxy resin used in Example 3-7 is the phosphorus-containing epoxy resin prepared in Example 1-7;

[0085] The nitrogen-containing epoxy resins used in Examples 3-1 to 3-7 are the nitrogen-containing epoxy resins prepared in Examples 2-1 to 2-5, that is, the nitrogen-containing epoxy resin used in Example 3-1 is the nitrogen-containing epoxy resin prepared in Example 2-1, the nitrogen-containing epoxy resin used in Example 3-2 is the nitrogen-containing epoxy resin prepared in Example 2-2, the nitrogen-containing epoxy resins used in Examples 3-3 to 3-4 are the nitrogen-containing epoxy resins prepared in Example 2-3, the nitrogen-containing epoxy resins used in Examples 3-5 to 3-6 are the nitrogen-containing epoxy resins prepared in Example 2-4, and the nitrogen-containing epoxy resins used in Example 3-7 are the nitrogen-containing epoxy resins prepared in Example 2-5;

[0086] The specific mass proportions of the raw materials (or materials) of each component for preparing the phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition of Examples 3-1 to 3-7 are shown in Table 3 below:

[0087] Table 3: Material ratio table of phosphorus-nitrogen synergistic high CTI epoxy resin composition of Examples 3-1 to 3-7:

[0088]

[0089] In the above-mentioned embodiments 3-1 to 3-7:

[0090] The tetraphenol ethane epoxy resin is: Cologne-4131A70;

[0091] The phenolic epoxy resin is: Nan Ya NPPN638S;

[0092] The bisphenol A solid epoxy resin is: Nan Ya NPES901;

[0093] The performance results of the copper clad laminates prepared by the phosphorus-nitrogen synergistic high CTI flame retardant epoxy resin compositions of Examples 3-1 to 3-7 are shown in Table 4 below:

[0094] Table 4:

[0095]

[0096]

[0097] Embodiment 4:

[0098] A phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition is prepared by mixing 30 parts by mass of phosphorus-containing epoxy resin, 10 parts by mass of nitrogen-containing epoxy resin, 3 parts by mass of phenolic epoxy resin, 2 parts by mass of tetraphenol ethane epoxy resin, 2 parts by mass of bisphenol A solid epoxy resin and 10 parts by mass of butanone solvent.

[0099] Embodiment 5:

[0100] A phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition is prepared by mixing 50 parts by mass of phosphorus-containing epoxy resin, 30 parts by mass of nitrogen-containing epoxy resin, 6 parts by mass of phenolic epoxy resin, 5 parts by mass of tetraphenol ethane epoxy resin, 8 parts by mass of bisphenol A solid epoxy resin and 20 parts by mass of butanone solvent.

[0101] Embodiment 6:

[0102] A phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition is prepared by mixing 40 parts by mass of phosphorus-containing epoxy resin, 20 parts by mass of nitrogen-containing epoxy resin, 4.5 parts by mass of phenolic epoxy resin, 3.5 parts by mass of tetraphenol ethane epoxy resin, 5 parts by mass of bisphenol A solid epoxy resin and 15 parts by mass of butanone solvent.

[0103] Embodiment 7:

[0104] A phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition, wherein the preparation method of the phosphorus-containing epoxy resin is:

[0105] 10 parts by mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short), 5 parts by mass of quinones, and 30 parts by mass of bisphenol A epoxy resin or / and bisphenol F epoxy resin are added to a reactor, heated to 60°C with stirring, maintained at this temperature for 4.0 hours, then heated to 100°C, added with 0.01 parts by mass of catalyst A, kept warm for 30 minutes, then heated to 160°C for 6 hours, then cooled to 100°C, added with 20 parts by mass of solvent A, mixed (until dissolved and transparent), to obtain a phosphorus-containing epoxy resin; the rest is the same as any one of Examples 4-6 and omitted.

[0106] Embodiment 8:

[0107] A phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition, wherein the preparation method of the phosphorus-containing epoxy resin is:

[0108] 20 parts by mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short), 10 parts by mass of quinones, and 50 parts by mass of bisphenol A epoxy resin or / and bisphenol F epoxy resin are added to a reactor, heated to 100° C. with stirring, maintained at this temperature for reaction for 2.0 hours, then heated to 150° C., added with 0.1 parts by mass of catalyst A, kept warm for reaction for 30 minutes, then heated to 190° C. (warm) for reaction for 3 hours, then cooled to 120° C., added with 40 parts by mass of solvent A, mixed evenly (until dissolved and transparent), to obtain a phosphorus-containing epoxy resin; the rest is the same as any one of Examples 4-6 and omitted.

[0109] Embodiment 9:

[0110] A phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition, wherein the preparation method of the phosphorus-containing epoxy resin is:

[0111] 15 parts by mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short), 7.5 parts by mass of quinones, and 40 parts by mass of bisphenol A epoxy resin or / and bisphenol F epoxy resin are added to a reactor, heated to 80° C. with stirring, maintained at this temperature for reaction for 3.0 hours, then heated to 125° C., added with 0.05 parts by mass of catalyst A, kept warm for reaction for 30 minutes, then heated to 175° C. (warm) for reaction for 4.5 hours, then cooled to 110° C., added with 30 parts by mass of solvent A, mixed evenly (until dissolved and transparent), to obtain a phosphorus-containing epoxy resin; the rest is the same as any one of Examples 4-6 and omitted.

[0112] In the above-mentioned embodiments 7-9:

[0113] The quinone substance may be one or a mixture of p-benzoquinone and naphthoquinone;

[0114] The catalyst A can be one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethylbenzylammonium chloride, tetrabutylammonium bromide, and butyltriphenylphosphonium bromide;

[0115] The solvent A is butanone, acetone, a mixture of butanone and propylene glycol methyl ether, or a mixture of acetone and propylene glycol methyl ether;

[0116] The product production and providing enterprise and model of the bisphenol A epoxy resin is one of Nan Ya's NPEL128, Nan Ya's NPEL127, Shandong Aimonte's EMTE128 or a mixture of two thereof, and the product production and providing enterprise and model of the bisphenol F epoxy resin is Nan Ya's NPEF170.

[0117] Embodiment 10:

[0118] A phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition, wherein the preparation method of the nitrogen-containing epoxy resin is:

[0119] 2 parts by mass of melamine, 4 parts by mass of paraformaldehyde, 10 parts by mass of propylene glycol methyl ether and 40 parts by mass of bisphenol A epoxy resin are added into a reactor, heated to 60°C with stirring, maintained at this temperature for reaction for 2.0 hours, then 0.05 parts by mass of catalyst B are added, the temperature is raised to 80°C and kept for reaction for 4.0 hours, 20 parts by mass of solvent A are added, and the mixture is mixed and dissolved until it becomes transparent, thereby obtaining a nitrogen-containing epoxy resin; the rest is the same as any one of Examples 4-9 and is omitted.

[0120] Embodiment 11:

[0121] A phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition, wherein the preparation method of the nitrogen-containing epoxy resin is:

[0122] 4 parts by mass of melamine, 8 parts by mass of paraformaldehyde, 20 parts by mass of propylene glycol methyl ether and 60 parts by mass of bisphenol A epoxy resin are added into a reactor, heated to 70°C with stirring, maintained at this temperature for reaction for 1.0h, then 0.2 parts by mass of catalyst B are added, the temperature is raised to 100°C and kept for reaction for 2.0h, 40 parts by mass of solvent A are added, and the mixture is mixed and dissolved until it becomes transparent, thereby obtaining a nitrogen-containing epoxy resin; the rest is the same as any one of Examples 4-9 and is omitted.

[0123] Embodiment 12:

[0124] A phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition, wherein the preparation method of the nitrogen-containing epoxy resin is:

[0125] 3 parts by mass of melamine, 6 parts by mass of paraformaldehyde, 15 parts by mass of propylene glycol methyl ether and 50 parts by mass of bisphenol A epoxy resin were added into a reactor, heated to 65°C with stirring, maintained at this temperature for 1.5 hours, then 0.1 parts by mass of catalyst B were added, the temperature was raised to 90°C and kept for 3.0 hours, 30 parts by mass of solvent A were added, and the mixture was mixed and dissolved until it became transparent, thereby obtaining a nitrogen-containing epoxy resin; the rest was the same as any one of Examples 4-9 and omitted.

[0126] In the above-mentioned embodiments 10-12:

[0127] The catalyst B is one or both of ethanolamine and triethanolamine;

[0128] The solvent A is butanone, acetone, a mixture of butanone and propylene glycol methyl ether, or a mixture of acetone and propylene glycol methyl ether;

[0129] The bisphenol A epoxy resin is produced by a manufacturer and a model thereof is one of Nanya's NPEL128, Nanya's NPEL127, and Shandong Aimonte's EMTE128, or a mixture of two of them.

[0130] In the above embodiments 4-12: the phenolic epoxy resin is any one of Shandong Aimonte EMT638, Nan Ya NPPN638S, and Shandong Deyuan 638 epoxy resins; the tetraphenol ethane epoxy resin is any one of Cologne 4131A70 and Nan Ya Electronics NPPN431; the bisphenol A solid epoxy resin is any one of Sinopec CYD011 and Nan Ya Electronics NPES901.

[0131] Embodiment 13:

[0132] A method for preparing a phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition, comprising the following steps:

[0133] a. Preparation of phosphorus-containing epoxy resin:

[0134] 10 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short), 5 parts by weight of quinones, and 30 parts by weight of bisphenol A epoxy resin or / and bisphenol F epoxy resin are added to a reactor, heated to 60° C. under stirring, kept at this temperature for reaction for 2.0 hours, then heated to 100° C., added with 0.01 parts by weight of catalyst A, kept at this temperature for reaction for 30 minutes, then heated to 160° C. for reaction for 3 hours, then cooled to 100° C., added with 20 parts by weight of solvent A, mixed evenly (until dissolved and transparent), to obtain a phosphorus-containing epoxy resin;

[0135] The quinone substance may be one or a mixture of p-benzoquinone and naphthoquinone;

[0136] The catalyst A can be one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethylbenzylammonium chloride, tetrabutylammonium bromide, and butyltriphenylphosphonium bromide;

[0137] The solvent A is butanone, acetone, a mixture of butanone and propylene glycol methyl ether, or a mixture of acetone and propylene glycol methyl ether;

[0138] b. Preparation of nitrogen-containing epoxy resin:

[0139] 2 parts by mass of melamine, 4 parts by mass of paraformaldehyde, 10 parts by mass of propylene glycol methyl ether and 40 parts by mass of bisphenol A epoxy resin are added into a reactor, heated to 60°C with stirring, maintained at this temperature for reaction for 1.0 hour, then 0.2 parts by mass of catalyst B are added, the temperature is raised to 80°C and kept for reaction for 2.0 hours, 20 parts by mass of solvent A are added, and the mixture is mixed and dissolved until it becomes transparent, thereby obtaining a nitrogen-containing epoxy resin.

[0140] The catalyst B is one or both of ethanolamine and triethanolamine;

[0141] The solvent A is butanone, acetone, a mixture of butanone and propylene glycol methyl ether, or a mixture of acetone and propylene glycol methyl ether;

[0142] c. Preparation of phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition: Take the raw materials of each component in a mass ratio of 30 parts by mass of phosphorus-containing epoxy resin, 10 parts by mass of nitrogen-containing epoxy resin, 3 parts by mass of phenolic epoxy resin, 2 parts by mass of tetraphenol ethane epoxy resin, 2 parts by mass of bisphenol A solid epoxy resin and 10 parts by mass of solvent butanone, stir and mix evenly to obtain a phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition.

[0143] Embodiment 14:

[0144] A method for preparing a phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition, comprising the following steps:

[0145] a. Preparation of phosphorus-containing epoxy resin:

[0146] 20 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short), 10 parts by weight of quinones, and 50 parts by weight of bisphenol A epoxy resin or / and bisphenol F epoxy resin are added to a reactor, heated to 100° C. under stirring, maintained at the temperature for reaction for 4.0 hours, then heated to 150° C., added with 0.1 parts by weight of catalyst A, kept at the temperature for reaction for 30 minutes, then heated to 190° C. (keeping the temperature) for reaction for 6 hours, then cooled to 120° C., added with 40 parts by weight of solvent A, mixed evenly (until dissolved and transparent), to obtain a phosphorus-containing epoxy resin;

[0147] The quinone substance may be one or a mixture of p-benzoquinone and naphthoquinone;

[0148] The catalyst A can be one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethylbenzylammonium chloride, tetrabutylammonium bromide, and butyltriphenylphosphonium bromide;

[0149] The solvent A is butanone, acetone, a mixture of butanone and propylene glycol methyl ether, or a mixture of acetone and propylene glycol methyl ether;

[0150] b. Preparation of nitrogen-containing epoxy resin:

[0151] 4 parts by mass of melamine, 8 parts by mass of paraformaldehyde, 20 parts by mass of propylene glycol methyl ether and 60 parts by mass of bisphenol A epoxy resin are added into a reactor, heated to 70°C with stirring, kept at this temperature for reaction for 2.0 hours, then 0.2 parts by mass of catalyst B are added, heated to 100°C and kept at this temperature for reaction for 4.0 hours, 40 parts by mass of solvent A are added, and the mixture is mixed and dissolved until it becomes transparent, thereby obtaining a nitrogen-containing epoxy resin;

[0152] The catalyst B is one or both of ethanolamine and triethanolamine;

[0153] The solvent A is butanone, acetone, a mixture of butanone and propylene glycol methyl ether, or a mixture of acetone and propylene glycol methyl ether;

[0154] c. Preparation of phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition: Take the raw materials of each component in a ratio of 50 parts by mass of phosphorus-containing epoxy resin, 30 parts by mass of nitrogen-containing epoxy resin, 6 parts by mass of phenolic epoxy resin, 5 parts by mass of tetraphenol ethane epoxy resin, 8 parts by mass of bisphenol A solid epoxy resin and 20 parts by mass of solvent butanone, stir and mix evenly to obtain a phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition.

[0155] Embodiment 15:

[0156] A method for preparing a phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition, comprising the following steps:

[0157] a. Preparation of phosphorus-containing epoxy resin:

[0158] 15 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short), 8 parts by weight of quinones, and 40 parts by weight of bisphenol A epoxy resin or / and bisphenol F epoxy resin are added to a reactor, heated to 80° C. under stirring, kept at this temperature for reaction for 3.0 hours, then heated to 130° C., added with 0.06 parts by weight of catalyst A, kept at this temperature for reaction for 30 minutes, then heated to 180° C. (keeping temperature) for reaction for 5 hours, then cooled to 110° C., added with 30 parts by weight of solvent A, mixed evenly (until dissolved and transparent), to obtain a phosphorus-containing epoxy resin;

[0159] The quinone substance may be one or a mixture of p-benzoquinone and naphthoquinone;

[0160] The catalyst A can be one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethylbenzylammonium chloride, tetrabutylammonium bromide, and butyltriphenylphosphonium bromide;

[0161] The solvent A is butanone, acetone, a mixture of butanone and propylene glycol methyl ether, or a mixture of acetone and propylene glycol methyl ether;

[0162] b. Preparation of nitrogen-containing epoxy resin:

[0163] 3 parts by mass of melamine, 6 parts by mass of paraformaldehyde, 15 parts by mass of propylene glycol methyl ether, and 50 parts by mass of bisphenol A epoxy resin are added into a reactor, heated to 65°C with stirring, and kept at this temperature for reaction for 1.5 hours, then 0.13 parts by mass of catalyst B are added, and the temperature is raised to 90°C and kept for reaction for 3.0 hours, and 30 parts by mass of solvent A are added, and the mixture is mixed and dissolved until transparent, thereby obtaining a nitrogen-containing epoxy resin;

[0164] The catalyst B is one or both of ethanolamine and triethanolamine;

[0165] The solvent A is butanone, acetone, a mixture of butanone and propylene glycol methyl ether, or a mixture of acetone and propylene glycol methyl ether;

[0166] c. Preparation of phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition: Take the raw materials of each component in a ratio of 40 parts by mass of phosphorus-containing epoxy resin, 20 parts by mass of nitrogen-containing epoxy resin, 5 parts by mass of phenolic epoxy resin, 4 parts by mass of tetraphenol ethane epoxy resin, 5 parts by mass of bisphenol A solid epoxy resin and 15 parts by mass of solvent butanone, stir and mix evenly to obtain a phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition.

[0167] In the above-mentioned embodiments 13-15:

[0168] The bisphenol A epoxy resin is produced by one of the following companies and models: NPEL128 from Nanya, NPEL127 from Nanya, EMTE128 from Shandong Aimonte, or a mixture of two thereof;

[0169] The bisphenol F epoxy resin product manufacturer and model is Nanya NPEF170;

[0170] The phenolic epoxy resin is any one of Shandong Aimonte EMT638, Nanya NPPN638S, and Shandong Deyuan 638 epoxy resin;

[0171] The tetraphenol ethane epoxy resin is any one of Cologne 4131A70 and Nan Ya NPPN431; the bisphenol A solid epoxy resin is any one of Sinopec CYD011 and Nan Ya NPES901.

[0172] The physical and chemical data of the phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition described (prepared) in the above Examples 4-15 are in the following ranges: solid content 60% to 80%, viscosity 200 to 2000 mPa·s, epoxy equivalent 240 to 320 g / eq, phosphorus content 2% to 3%, nitrogen content 1% to 2%, glass transition temperature 150°C to 170°C, and a reddish-brown transparent liquid.

[0173] In the above embodiments: the percentages used, unless otherwise specified, are all mass (weight) percentages or percentages known to those skilled in the art; the proportions used, unless otherwise specified, are all mass (weight) proportions; and the weights may be in grams or kilograms.

[0174] In the above embodiments, the process parameters (temperature, time, etc.) in each step and the numerical values ​​of the amounts of each component are ranges, and any point can be applied.

[0175] The technical contents not specifically described in the present invention and the above embodiments are the same as the prior art, and the raw materials are all commercially available products.

[0176] The present invention is not limited to the above embodiments, and all the contents of the present invention can be implemented and have the above good effects.

Claims

1. A phosphorus-nitrogen synergistic high CTI flame retardant epoxy resin composition, characterized in that: The phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition is prepared by mixing 30-50 parts by weight of phosphorus-containing epoxy resin, 10-30 parts by weight of nitrogen-containing epoxy resin, 3-6 parts by weight of phenolic epoxy resin, 2-5 parts by weight of tetraphenol ethane epoxy resin, 2-8 parts by weight of bisphenol A solid epoxy resin and 10-20 parts by weight of butanone solvent.

2. The phosphorus-nitrogen synergistic high CTI flame retardant epoxy resin composition according to claim 1, characterized in that: The preparation method of the phosphorus-containing epoxy resin is: 10 to 20 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 5 to 10 parts by weight of quinones, and 30 to 50 parts by weight of bisphenol A epoxy resin or / and bisphenol F epoxy resin are added to a reactor, heated to 60 to 100° C. under stirring, kept at the temperature for reaction for 2.0 to 4.0 hours, then heated to 100 to 150° C., added with 0.01 to 0.1 parts by weight of catalyst A, kept at the temperature for reaction for 30 minutes, then heated to 160 to 190° C. for reaction for 3 to 6 hours, then cooled to 100 to 120° C., added with 20 to 40 parts by weight of solvent A, and mixed well to obtain a phosphorus-containing epoxy resin; The quinone substance is a mixture of one or both of benzoquinone and naphthoquinone; The catalyst A is one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethylbenzylammonium chloride, tetrabutylammonium bromide, and butyltriphenylphosphonium bromide; The solvent A is any one of butanone, acetone, a mixture of butanone and propylene glycol methyl ether, or a mixture of acetone and propylene glycol methyl ether.

3. The phosphorus-nitrogen synergistic high CTI flame retardant epoxy resin composition according to claim 2, characterized in that: The product production and providing enterprise and model of the bisphenol A epoxy resin is one of Nan Ya's NPEL128, Nan Ya's NPEL127, Shandong Aimonte's EMTE128 or a mixture of two thereof, and the product production and providing enterprise and model of the bisphenol F epoxy resin is Nan Ya's NPEF170.

4. The phosphorus-nitrogen synergistic high CTI flame retardant epoxy resin composition according to claim 1 or 2, characterized in that: The preparation method of the nitrogen-containing epoxy resin is: 2-4 parts by weight of melamine, 4-8 parts by weight of paraformaldehyde, 10-20 parts by weight of propylene glycol methyl ether, and 40-60 parts by weight of bisphenol A epoxy resin are added into a reactor, heated to 60-70°C under stirring, and kept at this temperature for reaction for 1.0-2.0 hours, then 0.05-0.2 parts by weight of catalyst B are added, heated to 80-100°C and kept at this temperature for reaction for 2.0-4.0 hours, and 20-40 parts by weight of solvent A are added and mixed to obtain a nitrogen-containing epoxy resin; The catalyst B is one or both of ethanolamine and triethanolamine; The solvent A is any one of butanone, acetone, a mixture of butanone and propylene glycol methyl ether, or a mixture of acetone and propylene glycol methyl ether.

5. The phosphorus-nitrogen synergistic high CTI flame retardant epoxy resin composition according to claim 4, characterized in that: The bisphenol A epoxy resin is produced by a manufacturer and a model thereof is one of Nanya's NPEL128, Nanya's NPEL127, and Shandong Aimonte's EMTE128, or a mixture of two of them.

6. The phosphorus-nitrogen synergistic high CTI flame retardant epoxy resin composition according to claim 3, characterized in that: The phenolic epoxy resin is any one of Shandong Aimonte EMT638, Nan Ya NPPN638S, and Shandong Deyuan 638 epoxy resins; the tetraphenol ethane epoxy resin is any one of Cologne 4131A70 and Nan Ya Electronics NPPN431; the bisphenol A solid epoxy resin is any one of Sinopec CYD011 and Nan Ya Electronics NPES901.

7. The phosphorus-nitrogen synergistic high CTI flame retardant epoxy resin composition according to claim 1 or 2, characterized in that: The physicochemical data of the phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition are: solid content 60% to 80%, viscosity 200 to 2000 mPa·s, epoxy equivalent 240 to 320 g / eq, phosphorus content 2% to 3%, nitrogen content 1% to 2%, and glass transition temperature 150° C. to 170° C.

8. A method for preparing a phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition, characterized in that the steps are: a. Preparation of phosphorus-containing epoxy resin: 10 to 20 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 5 to 10 parts by weight of quinones, and 30 to 50 parts by weight of bisphenol A epoxy resin or / and bisphenol F epoxy resin are added to a reactor, heated to 60 to 100° C. under stirring, kept at the temperature for reaction for 2.0 to 4.0 hours, then heated to 100 to 150° C., added with 0.01 to 0.1 parts by weight of catalyst A, kept at the temperature for reaction for 30 minutes, then heated to 160 to 190° C. for reaction for 3 to 6 hours, then cooled to 100 to 120° C., added with 20 to 40 parts by weight of solvent A, and mixed well to obtain a phosphorus-containing epoxy resin; The quinone substance is a mixture of one or both of benzoquinone and naphthoquinone; The catalyst A is one or a mixture of two of imidazole, triphenylphosphine, triphenyl phosphate, triethylbenzylammonium chloride, tetrabutylammonium bromide, and butyltriphenylphosphonium bromide; The solvent A is any one of butanone, acetone, a mixture of butanone and propylene glycol methyl ether, or a mixture of acetone and propylene glycol methyl ether; b. Preparation of nitrogen-containing epoxy resin: 2-4 parts by weight of melamine, 4-8 parts by weight of paraformaldehyde, 10-20 parts by weight of propylene glycol methyl ether, and 40-60 parts by weight of bisphenol A epoxy resin are added into a reactor, heated to 60-70°C under stirring, and kept at this temperature for reaction for 1.0-2.0 hours, then 0.05-0.2 parts by weight of catalyst B are added, heated to 80-100°C and kept at this temperature for reaction for 2.0-4.0 hours, and 20-40 parts by weight of solvent A are added and mixed to obtain a nitrogen-containing epoxy resin; The catalyst B is one or both of ethanolamine and triethanolamine; The solvent A is any one of butanone, acetone, a mixture of butanone and propylene glycol methyl ether, or a mixture of acetone and propylene glycol methyl ether; c. Preparation of phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition: Take the raw materials of each component in a mass ratio of 30-50 parts by mass of phosphorus-containing epoxy resin, 10-30 parts by mass of nitrogen-containing epoxy resin, 3-6 parts by mass of phenolic epoxy resin, 2-5 parts by mass of tetraphenol ethane epoxy resin, 2-8 parts by mass of bisphenol A solid epoxy resin and 10-20 parts by mass of solvent butanone, stir and mix evenly to obtain a phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition.

9. The method for preparing the phosphorus-nitrogen synergistic high CTI flame retardant epoxy resin composition according to claim 8, characterized in that: The bisphenol A epoxy resin is produced by a manufacturer and a model thereof is one of Nanya's NPEL128, Nanya's NPEL127, and Shandong Aimonte's EMTE128, or a mixture of two thereof; The bisphenol F epoxy resin product manufacturer and model is Nanya NPEF170; The phenolic epoxy resin is any one of Shandong Aimonte EMT638, Nanya NPPN638S, and Shandong Deyuan 638 epoxy resin; The tetraphenol ethane epoxy resin is any one of Cologne 4131A70 and Nanya NPPN431; The bisphenol A solid epoxy resin is any one of Sinopec CYD011 and Nanya NPES901.

10. The method for preparing the phosphorus-nitrogen synergistic high CTI flame retardant epoxy resin composition according to claim 8 or 9, characterized in that: The physicochemical data of the prepared phosphorus-nitrogen synergistic high CTI flame-retardant epoxy resin composition are: solid content 60%-80%, viscosity 200-2000 mPa·s, epoxy equivalent 240-320 g / eq, phosphorus content 2%-3%, nitrogen content 1%-2%, and glass transition temperature 150°C-170°C.

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