A trapezoidal phosphorus-containing polyborosiloxane flame retardant, a preparation method and application thereof

Abstract

The application discloses a ladder-shaped phosphorus-containing polyborosiloxane flame retardant and a preparation method and application thereof, and belongs to the technical field of epoxy resins.The structural general formula of the flame retardant is shown in the following formula (I): wherein p and m are independently selected from integers between 1 and 20, q and n are independently selected from integers between 1 and 6, and R is selected from one or more of the following: The ladder-shaped phosphorus-containing polyborosiloxane flame retardant can obviously improve the flame retardant performance of an epoxy resin cured product, improves the mechanical properties and heat resistance of the epoxy resin cured product, reduces the maximum thermal decomposition rate of the resin cured product, and can also improve the carbon residue rate of the resin cured product at high temperatures, and has a wide application prospect in the fields of adhesive materials, composite materials, copper-clad plate materials and electronic packaging materials.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of epoxy resin, in particular to a ladder-shaped phosphorus-containing polyborosiloxane flame retardant, a preparation method and application thereof. BACKGROUND

[0002] Epoxy resin, as a typical thermosetting resin, has been widely concerned due to its good adhesion, low price, low shrinkage, good electrical insulation and good process performance. However, the flammability of epoxy resin makes it produce a large amount of heat and toxic gas during combustion, which threatens people's life safety and property loss. Therefore, it is of great practical significance to modify the flame retardant of epoxy resin.

[0003] Halogen flame retardants, as a kind of traditional efficient flame retardant, will produce a large amount of toxic gas in the process of flame retardant, causing great pollution. Phosphorus, silicon, nitrogen, boron and other halogen-free flame retardants are widely concerned due to their green environmental protection and certain flame retardant effect. However, when a single flame-retardant element is used for flame-retardant epoxy resin, the demand for its addition is large, and it will affect the other properties of the material, and the improvement of the flame retardant degree is very limited. Therefore, through the synergistic construction of multiple flame-retardant elements, efficient flame retardant of epoxy resin can be realized.

[0004] Polysiloxane is a polymer with a main chain composed of siloxane bonds, which has excellent comprehensive performance, such as high thermal stability, excellent flexibility, excellent flame retardancy and strong hydrophobicity. It is an excellent modifier of epoxy resin. Polysiloxane with reactive functional groups (hydroxyl, carboxyl, amino, aliphatic epoxy group) can participate in the curing of epoxy resin matrix, which can effectively avoid the phase separation phenomenon. Moreover, polysiloxane often plays a major role in the condensed phase in the process of flame retardant. However, the single silicon element has low flame-retardant efficiency. Boron-based flame retardant also mainly plays a flame-retardant role in the condensed phase. The combination of silicon-based flame retardant and boron-based flame retardant has synergistic effect. Phosphorus-based flame retardant is an ideal substitute for halogen-containing flame retardant, which has the advantages of high efficiency, low smoke, low toxicity and low volatility. It can produce a large amount of phosphorus-containing free radicals (such as ·P and ·PO) to quench the high-energy free radicals of combustible materials, and the flame-retardant efficiency is very high. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a ladder-shaped phosphorus-containing polyborosiloxane flame retardant, a preparation method and application thereof. The ladder-shaped phosphorus-containing polyborosiloxane flame retardant of the present application significantly improves the flame retardant performance of the epoxy resin cured product, and at the same time improves the mechanical properties and heat resistance of the epoxy resin cured product, reduces the maximum thermal decomposition rate of the resin cured product, and also can improve the carbon residue rate of the resin cured product at high temperature. It has wide application prospect in the fields of adhesive materials, composite materials, copper-clad plate materials and electronic packaging materials.

[0006] The technical scheme of the present application is as follows:

[0007] The present application provides a ladder-shaped phosphorus-containing polysiloxane flame retardant, and the structural general formula of the ladder-shaped phosphorus-containing polysiloxane flame retardant is shown in the following formula (I):

[0008]

[0009] Among them,

[0010] The p and m are independently selected from integers between 1 and 20, and the q and n are independently selected from integers between 1 and 6.

[0011] The R is selected from one or more of

[0012] Preferably, in the ladder-shaped phosphorus-containing polysiloxane flame retardant, the mass fraction of phosphorus element is 0.84wt%-11.74wt%.

[0013] Preferably, in the ladder-shaped phosphorus-containing polysiloxane flame retardant, the mass fraction of boron element is 0.26wt%-1.31wt%.

[0014] The present application provides a preparation method of the ladder-shaped phosphorus-containing polysiloxane flame retardant.

[0015] (1) After mixing water, anhydrous potassium carbonate and solvent I until the anhydrous potassium carbonate is dissolved, adding boric acid, mixing, and then adding silane monomer dropwise, reacting under a nitrogen atmosphere, removing residual solvent I after the reaction is completed to obtain a crude product, and then treating to obtain an epoxy group-containing polysiloxane;

[0016] (2) Mixing a phosphorus-containing monomer, a catalyst, solvent II and the epoxy group-containing ladder-shaped polysiloxane of step (1), condensing and refluxing, concentrating after the reaction is completed, drying the obtained precipitate to obtain a ladder-shaped phosphorus-containing polysiloxane flame retardant.

[0017] Preferably, in step (1), the molar ratio of the water to the anhydrous potassium carbonate is 800-900:1, and the volume ratio of the water to the solvent I is 1:1-2.

[0018] The solvent I includes one or more of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, acetone and 2-butanone.

[0019] Preferably, in step (1), the molar ratio of the water, the boric acid and the silane monomer is 30:1-3:10. ​

[0020] The silane monomer comprises trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane;

[0021] The temperature of the reaction is 25-80℃, and the time is 6-72h.

[0022] The post-treatment comprises dissolving the crude product with dichloromethane, washing, drying, filtering, removing the solvent I, and vacuum drying for 10-24h.

[0023] Preferably, in step (2), the phosphorus-containing monomer comprises one or more of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-hydroxide, diphenyl phosphine oxide, diethyl phosphite, and diphenyl phosphite.

[0024] The catalyst comprises one or more of triphenylphosphine, N,N-dimethylbenzylamine, and tetrabutylammonium bromide.

[0025] The solvent II comprises one or more of toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,4-dioxane.

[0026] The amount of the solvent II is to ensure that the total concentration of the epoxy-based ladder polysiloxane and the phosphorus-containing monomer is 1-5g / mL.

[0027] The molar ratio of the epoxy group in the epoxy-based ladder polysiloxane to the phosphorus-containing monomer is 10:1-9.

[0028] The amount of the catalyst is 0.5-2.5% of the mass of the phosphorus-containing monomer.

[0029] The temperature of the condensation reflux reaction is 90-120℃, and the time is 6-12h; the drying is vacuum drying, the temperature of the drying is 40-60℃, and the time is 12-24h.

[0030] The third aspect of the present application provides an epoxy composition, which comprises the following raw materials in parts by weight:

[0031]

[0032]

[0033] The ladder phosphorus-containing polyborosiloxane is the ladder phosphorus-containing polyborosiloxane flame retardant described in the first aspect above, or the ladder phosphorus-containing polyborosiloxane flame retardant prepared by the preparation method described in the second aspect above.

[0034] Preferably, the epoxy resin comprises one or more of bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol aldehyde type epoxy resin, aliphatic glycidyl ether epoxy resin, aliphatic epoxy resin;

[0035] The curing agent comprises an acid anhydride type curing agent or an amine type curing agent;

[0036] The curing accelerator comprises one or more of N,N-dimethylbenzylamine, 2,4,6-tris(dimethylaminomethyl)phenol, acetylacetone metal salt, triphenylphosphine and its phosphonium salt, substituted urea, addition product of aryl isocyanate and imidazole compound, active chromium tris(2-ethylhexanoate), organic acid salt-amine complex, 1,8-diaza-bicyclo(5,4,0)-7-undecene, 2-mercaptobenzothiazole, peroxide, thiourea and its derivatives, cycloalkylimidazoline, 2-phenylimidazoline, epoxy group-containing aromatic tertiary amine, titanate accelerator, ferrocenyl accelerator, chromium halide-acid anhydride complex.

[0037] The fourth aspect of the present application provides an application of the epoxy resin of the third aspect, the epoxy resin is used as an adhesive, and the adhesive is used in adhesive materials, composite materials, copper-clad plates and electronic packaging materials.

[0038] The present application has the beneficial technical effects that:

[0039] The ladder-shaped phosphorus-containing polyborosiloxane flame retardant of the present application can significantly improve the flame retardant performance of the epoxy resin cured product, and is expected to be applied in the fields of adhesive materials, composite materials, copper-clad plate materials and electronic packaging materials. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 It is the 1H NMR curve of the ladder-shaped epoxy-based polyborosiloxane in Example 1 of the present application.

[0041] Figure 2 It is the 1H NMR curve of the ladder-shaped epoxy-based polyborosiloxane in Example 1 of the present application. 29 Si NMR curve.

[0042] Figure 3 It is the Fourier transform infrared spectrogram of the ladder-shaped epoxy-based polyborosiloxane in Example 1 of the present application.

[0043] Figure 4 It is the Fourier transform infrared spectrogram of the ladder-shaped phosphorus-containing polyborosiloxane in Example 1 of the present application. DETAILED DESCRIPTION

[0044] The present application will be described in detail below in combination with examples.

[0045] In the present application, the prepared flame retardant contains a large number of flexible network Si-O-Si structures in the main chain structure, compared with ordinary polysiloxane, ladder polysiloxane has more excellent heat resistance, oxidation resistance and the like, after being added to resin and cured, it can significantly enhance the mechanical properties of resin cured product and maintain good heat resistance, can significantly improve the bending strength and impact strength. At the same time, the phosphorus-containing structure can promote the dehydration and carbonization of the matrix resin in the early stage to quickly form a carbon layer, and the silicon-containing structure and the boron-containing structure also help to form a stable and dense carbon layer, which can effectively reduce heat transfer and play a protective role for the matrix resin, so it can significantly reduce the maximum thermal decomposition rate R max of the resin cured product, and at the same time can improve the carbon residue rate of the resin cured product at 800℃.

[0046] The present application will be further described below through examples and the like.

[0047] Example 1:

[0048] A kind of ladder phosphorus-containing polyborosiloxane flame retardant, its preparation method is:

[0049] (1) 89.8 mg (0.65 mmol) of potassium carbonate is dissolved in a mixed solution of 9.7 mL (0.54 mol) of deionized water and 12.9 mL of tetrahydrofuran and stirred uniformly to form a mixed solution, 1.1 g (0.0175 mol) of boric acid is added and dissolved thoroughly, 43.0 g (0.175 mol) of trimethoxy[2-(7-oxabicyclo[4.1.0]heptane 3-3yl)ethyl]silane is added dropwise to the above mixed solution under nitrogen atmosphere, and stirred at 25℃ for 72h; after the reaction is completed, the residual solvent is removed to obtain a crude product, the crude product is redissolved with dichloromethane, washed, dried, filtered, and after removing the solvent, vacuum drying for 10-24h to obtain an epoxy group-containing polyborosiloxane LASQ, which is a ladder polysiloxane containing silicon and boron at the same time, and the molar ratio of silicon atoms to boron atoms is 10:1.

[0050] (2) 31.47 g (containing 0.173 mol of epoxy groups) of epoxy group-containing polysiloxane, 31.59 g (0.156 mol) of diphenyl phosphorus oxide, 0.71 g of triphenylphosphine and 144.2 mL of N,N-dimethylformamide are added to a flask at one time, and reacted at 100℃ for 10h. The solution after the reaction is completed is concentrated, then precipitated in anhydrous ether, and the precipitate is vacuum dried at 60℃ for 24h to obtain a ladder phosphorus-containing polyborosiloxane flame retardant FR1-91 in which 90% of the epoxy groups are replaced by phosphorus-containing monomers, which is a ladder polysiloxane flame retardant containing phosphorus, silicon and boron at the same time, and the molar ratio of silicon atoms to boron atoms is 10:1, the phosphorus-containing structure (diphenyl phosphorus oxide) in the side group accounts for 90% (90% of the total number of side groups, the same below), and the epoxy group accounts for 10%.

[0051] Example 2:

[0052] A ladder-shaped phosphorus-containing polysiloxane flame retardant is prepared by:

[0053] (1) 89.8 mg of potassium carbonate is dissolved in a mixed solution of 9.7 mL of deionized water and 12.9 mL of tetrahydrofuran and stirred uniformly to form a mixed solution, 2.2 g (0.035 mol) of boric acid is added and dissolved thoroughly, 43.0 g of trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-3-yl)ethyl]silane is added dropwise to the above mixed solution under a nitrogen atmosphere, and stirred at 25°C for 72 h; after the reaction is completed, the residual solvent is removed to obtain a crude product, the crude product is redissolved with dichloromethane, washed, dried, filtered, and vacuum dried for 10-24 h after the solvent is removed, to obtain an epoxy group-containing polysiloxane LASQ, a ladder-shaped polysiloxane containing silicon and boron, wherein the molar ratio of silicon atoms to boron atoms is 10:2.

[0054] (2) 31.47 g (containing 0.173 mol of epoxy groups) of the epoxy group-containing polysiloxane, 31.59 g (0.156 mol) of diphenyl phosphoroxide, 0.71 g of triphenylphosphine, and 144.2 mL of N,N-dimethylformamide are added at one time to a flask, and reacted at 100°C for 10 h. The solution after the reaction is completed is concentrated, then precipitated in anhydrous diethyl ether, and the precipitate is vacuum dried at 60°C for 24 h, to obtain a phosphorus-containing polysiloxane flame retardant FR1-92 in which 90% of the epoxy groups are substituted with phosphorus-containing monomers, a ladder-shaped polysiloxane containing phosphorus, silicon, and boron, wherein the molar ratio of silicon atoms to boron atoms is 10:2, and the phosphorus structure (diphenyl phosphoroxide) in the side group accounts for 90%, and the epoxy group accounts for 10%.

[0055] Example 3:

[0056] A ladder-shaped phosphorus-containing polysiloxane flame retardant is prepared by:

[0057] (1) 89.8 mg of potassium carbonate is dissolved in a mixed solution of 9.7 mL of deionized water and 12.9 mL of tetrahydrofuran and stirred uniformly to form a mixed solution, 2.2 g (0.035 mol) of boric acid is added and dissolved thoroughly, 43.0 g of trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-3-yl)ethyl]silane is added dropwise to the above mixed solution under a nitrogen atmosphere, and stirred at 25°C for 72 h; after the reaction is completed, the residual solvent is removed to obtain a crude product, the crude product is redissolved with dichloromethane, washed, dried, filtered, and vacuum dried for 10-24 h after the solvent is removed, to obtain an epoxy group-containing polysiloxane LASQ, a ladder-shaped polysiloxane containing silicon and boron, wherein the molar ratio of silicon atoms to boron atoms is 10:2.

[0058] (2) 31.47 g of epoxy group-containing polysiloxane (containing 0.173 mol of epoxy groups), 17.55 g (0.0865 mol) of diphenyl phosphine oxide, 0.51 g of triphenylphosphine, and 103.4 mL of N,N-dimethylformamide were added at one time into a flask, and reacted at 100°C for 10 h. The solution after the reaction was completed was concentrated, and then precipitated in anhydrous diethyl ether, and the precipitate was vacuum-dried at 60°C for 24 h to obtain a ladder-shaped phosphorus-containing polyborosiloxane flame retardant FR1-53 having a molar ratio of 30% of boron-containing structures in the main chain in which 50% of the epoxy groups were substituted with phosphorus-containing monomers, a ladder-shaped polysiloxane flame retardant containing phosphorus, silicon, and boron, in which the molar ratio of silicon atoms to boron atoms was 10:3, and the phosphorus-containing structure (diphenyl phosphine oxide) in the side group was 50%, and the epoxy groups were 50%.

[0059] Example 4:

[0060] A ladder-shaped phosphorus-containing polysiloxane flame retardant was prepared by:

[0061] (1) 89.8 mg of potassium carbonate was dissolved in a mixed solution of 9.7 mL of deionized water and 12.9 mL of tetrahydrofuran and stirred uniformly to form a mixed solution, 3.2 g of boric acid was added and dissolved thoroughly, and 43.0 g of trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-3-yl)ethyl]silane was added dropwise into the above mixed solution under a nitrogen atmosphere, and stirred at 25°C for 72 h; after the reaction was completed, the residual solvent was removed to obtain a crude product, the crude product was redissolved with dichloromethane, washed, dried, filtered, and vacuum-dried for 10-24 h after removing the solvent to prepare an epoxy group-containing polyborosiloxane LASQ, a ladder-shaped polysiloxane containing silicon and boron, in which the molar ratio of silicon atoms to boron atoms was 10:3.

[0062] (2) 31.47 g of epoxy group-containing polysiloxane (containing 0.173 mol of epoxy groups), 17.55 g (0.0865 mol) of diphenyl phosphine oxide, 0.51 g of triphenylphosphine, and 103.4 mL of N,N-dimethylformamide were added at one time into a flask, and reacted at 100°C for 10 h. The solution after the reaction was completed was concentrated, and then precipitated in anhydrous diethyl ether, and the precipitate was vacuum-dried at 60°C for 24 h to obtain a ladder-shaped phosphorus-containing polyborosiloxane flame retardant FR1-53 having a molar ratio of 30% of boron-containing structures in the main chain in which 50% of the epoxy groups were substituted with phosphorus-containing monomers, a ladder-shaped polysiloxane flame retardant containing phosphorus, silicon, and boron, in which the molar ratio of silicon atoms to boron atoms was 10:3, and the phosphorus-containing structure (diphenyl phosphine oxide) in the side group was 50%, and the epoxy groups were 50%.

[0063] Example 5:

[0064] A ladder-shaped phosphorus-containing polyborosiloxane flame retardant was prepared by:

[0065] (1) 89.8 mg of potassium carbonate was dissolved in a mixed solution of 9.7 mL of deionized water and 12.9 mL of tetrahydrofuran and stirred uniformly to form a mixed solution, 3.2 g of boric acid was added and dissolved thoroughly, 43.0 g of trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-3-yl)ethyl]silane was added dropwise to the above mixed solution under a nitrogen atmosphere, and the reaction was stirred at 25°C for 72 h; after the reaction was completed, the residual solvent was removed to obtain a crude product, the crude product was redissolved with dichloromethane, washed, dried, filtered, and vacuum dried for 10-24 h after removing the solvent to prepare an epoxy group-containing polyborosiloxane LASQ, and a ladder-shaped polysiloxane containing silicon and boron, in which the molar ratio of silicon atoms to boron atoms was 10:3.

[0066] (2) 31.47 g of an epoxy group-containing polysiloxane (containing 0.173 mol of an epoxy group), 31.59 g (0.156 mol) of diphenyl phosphine oxide, 0.71 g of triphenylphosphine, and 144.2 mL of N,N-dimethylformamide were added at once to a flask, and the reaction was performed at 100°C for 10 h. The solution after the reaction was completed was concentrated, and then precipitated in anhydrous diethyl ether, and the precipitate was vacuum dried at 60°C for 24 h to obtain a ladder-shaped phosphorus-containing polyborosiloxane flame retardant FR1-93 in which 90% of the epoxy groups were substituted with a phosphorus-containing monomer, and the molar ratio of boron structures in the main chain was 30%, and a ladder-shaped polysiloxane containing phosphorus, silicon, and boron, in which the molar ratio of silicon atoms to boron atoms was 10:3, and the phosphorus structure (diphenyl phosphine oxide) in the side group was 90%, and the epoxy group was 10%.

[0067] Example 6:

[0068] A ladder-shaped phosphorus-containing polyborosiloxane flame retardant was prepared by:

[0069] (1) 89.8 mg of potassium carbonate was dissolved in a mixed solution of 9.7 mL of deionized water and 12.9 mL of tetrahydrofuran and stirred uniformly to form a mixed solution, 3.2 g of boric acid was added and dissolved thoroughly, 43.0 g of trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-3-yl)ethyl]silane was added dropwise to the above mixed solution under a nitrogen atmosphere, and the reaction was stirred at 25°C for 72 h; after the reaction was completed, the residual solvent was removed to obtain a crude product, the crude product was redissolved with dichloromethane, washed, dried, filtered, and vacuum dried for 10-24 h after removing the solvent to prepare an epoxy group-containing polyborosiloxane LASQ, and a ladder-shaped polysiloxane containing silicon and boron, in which the molar ratio of silicon atoms to boron atoms was 10:3.

[0070] (2) 31.47 g of an epoxy group-containing polysiloxane (containing 0.173 mol of an epoxy group), 31.59 g (0.156 mol) of diphenyl phosphine oxide, 0.71 g of triphenylphosphine, and 144.2 mL of N,N-dimethylformamide were added at once to a flask, and the reaction was performed at 100°C for 10 h. The solution after the reaction was completed was concentrated, and then precipitated in anhydrous diethyl ether, and the precipitate was vacuum dried at 60°C for 24 h to obtain a ladder-shaped phosphorus-containing polyborosiloxane flame retardant FR1-93 in which 90% of the epoxy groups were substituted with a phosphorus-containing monomer, and the molar ratio of boron structures in the main chain was 30%, and a ladder-shaped polysiloxane containing phosphorus, silicon, and boron, in which the molar ratio of silicon atoms to boron atoms was 10:3, and the phosphorus structure (diphenyl phosphine oxide) in the side group was 90%, and the epoxy group was 10%.

[0071] 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-hydrogen, 0.74 g of triphenylphosphine and 148.4 mL of N,N-dimethylformamide were added at once into a flask, and reacted at 100°C for 10 h. The solution after the reaction was completed was concentrated, and then precipitated in anhydrous diethyl ether, and the precipitate was vacuum-dried at 60°C for 24 h to obtain ladder phosphorus-containing polyborosiloxane flame retardant FR2-93 having a boron structure in the main chain in a molar ratio of 30% and having 90% of the epoxy groups substituted with a phosphorus-containing monomer, which is a ladder polysiloxane flame retardant containing phosphorus, silicon and boron, in which the molar ratio of silicon atoms to boron atoms is 10:3, and the phosphorus-containing structure (DOPO) in the side group is 90% and the epoxy group is 10%.

[0072] Example 7:

[0073] A ladder phosphorus-containing polyborosiloxane flame retardant was prepared by:

[0074] (1) 89.8 mg of potassium carbonate was dissolved in a mixed solution of 9.7 mL of deionized water and 12.9 mL of tetrahydrofuran and stirred uniformly to form a mixed solution, 3.2 g of boric acid was added and dissolved thoroughly, 43.0 g of trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-3-yl)ethyl]silane was added dropwise to the above mixed solution under a nitrogen atmosphere, and stirred at 25°C for 72 h. After the reaction was completed, the residual solvent was removed to obtain a crude product, the crude product was redissolved with dichloromethane, washed, dried, filtered, and vacuum-dried for 10-24 h after removing the solvent to obtain epoxy group-containing polyborosiloxane LASQ, which is a ladder polysiloxane containing silicon and boron, in which the molar ratio of silicon atoms to boron atoms is 10:3.

[0075] (2) 31.47 g (containing 0.173 mol of epoxy groups) of epoxy group-containing polysiloxane, 17.20 g (0.156 mol) of dimethyl phosphite, 0.53 g of triphenylphosphine and 53.5 mL of N,N-dimethylformamide were added at once into a flask, and reacted at 100°C for 10 h. The solution after the reaction was completed was concentrated, and then precipitated in anhydrous diethyl ether, and the precipitate was vacuum-dried at 60°C for 24 h to obtain ladder phosphorus-containing polyborosiloxane flame retardant FR3-93 having a boron structure in the main chain in a molar ratio of 30% and having 90% of the epoxy groups substituted with a phosphorus-containing monomer, which is a ladder polysiloxane flame retardant containing phosphorus, silicon and boron, in which the molar ratio of silicon atoms to boron atoms is 10:3, and the phosphorus-containing structure (dimethyl phosphite) in the side group is 90% and the epoxy group is 10%.

[0076] Example 8:

[0077] A ladder phosphorus-containing polyborosiloxane flame retardant was prepared by:

[0078] (1) 89.8 mg of potassium carbonate was dissolved in a mixed solution of 9.7 mL of deionized water and 12.9 mL of tetrahydrofuran and stirred uniformly to form a mixed solution, 3.2 g of boric acid was added and dissolved thoroughly, 43.0 g of trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-3-yl)ethyl]silane was added dropwise to the above mixed solution under a nitrogen atmosphere, and the reaction was stirred at 25°C for 72 h; after the reaction was completed, the residual solvent was removed to obtain a crude product, the crude product was redissolved with dichloromethane, washed, dried, filtered, and vacuum dried for 10-24 h after removing the solvent to prepare an epoxy-containing polyborosiloxane LASQ, a ladder-shaped polysiloxane containing silicon and boron, in which the molar ratio of silicon atoms to boron atoms is 10:3.

[0079] (2) 31.47 g (containing 0.173 mol of epoxy groups) of an epoxy-containing polysiloxane, 21.57 g (0.156 mol) of diethyl phosphite, 0.59 g of triphenylphosphine, and 59.2 mL of N,N-dimethylformamide were added at once to a flask, and the reaction was performed at 100°C for 10 h. The solution after the reaction was completed was concentrated, and then precipitated in anhydrous diethyl ether, and the precipitate was vacuum dried at 60°C for 24 h to obtain a ladder-shaped phosphorus-containing polyborosiloxane flame retardant FR4-93 in which 90% of the epoxy groups were substituted with a phosphorus-containing monomer, and the molar fraction of the boron-containing structure in the main chain was 30%, a ladder-shaped polysiloxane flame retardant containing phosphorus, silicon, and boron, in which the molar ratio of silicon atoms to boron atoms was 10:3, and the phosphorus-containing structure (diethyl phosphite) in the side group was 90%, and the epoxy group was 10%.

[0080] Example 9:

[0081] A ladder-shaped phosphorus-containing polyborosiloxane flame retardant, the preparation method of which is:

[0082] (1) 89.8 mg of potassium carbonate was dissolved in a mixed solution of 9.7 mL of deionized water and 12.9 mL of tetrahydrofuran and stirred uniformly to form a mixed solution, 3.2 g of boric acid was added and dissolved thoroughly, 43.0 g of trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-3-yl)ethyl]silane was added dropwise to the above mixed solution under a nitrogen atmosphere, and the reaction was stirred at 25°C for 72 h; after the reaction was completed, the residual solvent was removed to obtain a crude product, the crude product was redissolved with dichloromethane, washed, dried, filtered, and vacuum dried for 10-24 h after removing the solvent to prepare an epoxy-containing polyborosiloxane LASQ, a ladder-shaped polysiloxane containing silicon and boron, in which the molar ratio of silicon atoms to boron atoms is 10:3.

[0083] (2) 31.47 g (containing 0.173 mol of epoxy groups) of epoxy-containing polysiloxane, 36.62 g (0.156 mol) of diphenyl phosphite, 0.79 g of triphenylphosphine and 78.6 mL of N,N-dimethylformamide were added into a flask at one time, and reacted at 100°C for 10 h. The solution after the reaction was completed was concentrated, then precipitated in anhydrous diethyl ether, and the precipitate was vacuum dried at 60°C for 24 h to obtain phosphorus-containing polysiloxane flame retardant FR5-93 containing 30% of boron-containing structures in the main chain, in which 90% of the epoxy groups were replaced by phosphorus-containing monomers, and the ladder-shaped polysiloxane flame retardant containing phosphorus, silicon and boron, in which the molar ratio of silicon atoms to boron atoms was 10:3, and the phosphorus-containing structure (diethyl phosphite) in the side group was 90%, and the epoxy group was 10%.

[0084] Comparative Example 1:

[0085] A ladder-shaped phosphorus-containing polysiloxane flame retardant was prepared by the following method:

[0086] (1) 89.8 mg of potassium carbonate was dissolved in a mixed solution of 9.7 mL of deionized water and 12.9 mL of tetrahydrofuran and stirred uniformly to form a mixed solution, and 43.0 g of trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-3-yl)ethyl]silane was added dropwise into the above mixed solution under a nitrogen atmosphere, and stirred at 25°C for 72 h; after the reaction was completed, the residual solvent was removed to obtain a crude product, which was redissolved with dichloromethane, washed, dried, filtered, and vacuum dried for 10-24 h after removing the solvent to obtain epoxy-containing polysiloxane LASQ (ladder-shaped polysiloxane not containing boron).

[0087] (2) 31.0 g of epoxy-containing polysiloxane, 31.59 g of diphenyl phosphorus oxide, 0.71 g of triphenylphosphine and 144.2 mL of N,N-dimethylformamide were added into a flask at one time, and reacted at 100°C for 10 h. The solution after the reaction was completed was concentrated, then precipitated in anhydrous diethyl ether, and the precipitate was vacuum dried at 60°C for 24 h to obtain ladder-shaped phosphorus-containing polysiloxane flame retardant FR1-9, which was a ladder-shaped polysiloxane flame retardant containing only phosphorus and silicon, in which the phosphorus-containing structure (diphenyl phosphorus oxide) in the side group was 90%, and the epoxy group was 10%.

[0088] Comparative Example 2:

[0089] A ladder-shaped phosphorus-containing polysiloxane flame retardant was prepared by the following method:

[0090] (1) 89.8 mg of potassium carbonate was dissolved in a mixed solution of 9.7 mL of deionized water and 12.9 mL of tetrahydrofuran and stirred uniformly to form a mixed solution, and 43.0 g of trimethoxy[2-(7-oxabicyclo[4.1.0]heptane 3-3-yl)ethyl]silane was added dropwise to the mixed solution under a nitrogen atmosphere, and the reaction was stirred at 25°C for 72 h. After the reaction was completed, the residual solvent was removed to obtain a crude product, which was dissolved again with dichloromethane, washed, dried, filtered, and vacuum dried for 10 to 24 h after removing the solvent to prepare an epoxy group-containing polysiloxane LASQ (ladder siloxane containing only silicon).

[0091] (2) 31.0 g of the epoxy group-containing polysiloxane, 33.75 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-hydrate, 0.74 g of triphenylphosphine, and 148.4 mL of N,N-dimethylformamide were added at once to a flask, and the reaction was performed at 100°C for 10 h. The solution after the reaction was completed was concentrated, and then precipitated in anhydrous diethyl ether, and the precipitate was vacuum dried at 60°C for 24 h to obtain a ladder phosphorus-containing polysiloxane flame retardant FR2-9 in which 90% of the epoxy groups were substituted with the phosphorus-containing monomer, a ladder siloxane flame retardant containing only phosphorus and silicon, and a phosphorus structure (DOPO) in the side group accounted for 90%, and an epoxy group accounted for 10%.

[0092] Comparative Example 3:

[0093] A ladder phosphorus-containing polysiloxane flame retardant was prepared by the following method:

[0094] (1) 89.8 mg of potassium carbonate was dissolved in a mixed solution of 9.7 mL of deionized water and 12.9 mL of tetrahydrofuran and stirred uniformly to form a mixed solution, and 43.0 g of trimethoxy[2-(7-oxabicyclo[4.1.0]heptane 3-3-yl)ethyl]silane was added dropwise to the mixed solution under a nitrogen atmosphere, and the reaction was stirred at 25°C for 72 h. After the reaction was completed, the residual solvent was removed to obtain a crude product, which was dissolved again with dichloromethane, washed, dried, filtered, and vacuum dried for 10 to 24 h after removing the solvent to prepare an epoxy group-containing polysiloxane LASQ (ladder siloxane containing only silicon).

[0095] (2) 31.0 g of the epoxy group-containing polysiloxane, 17.20 g of dimethyl phosphite, 0.53 g of triphenylphosphine, and 53.5 mL of N,N-dimethylformamide were added at once to a flask, and the reaction was performed at 100°C for 10 h. The solution after the reaction was completed was concentrated, and then precipitated in anhydrous diethyl ether, and the precipitate was vacuum dried at 60°C for 24 h to obtain a ladder phosphorus-containing polysiloxane flame retardant FR3-9 in which 90% of the epoxy groups were substituted with the phosphorus-containing monomer, a ladder siloxane flame retardant containing only phosphorus and silicon, and a phosphorus structure (dimethyl phosphite) in the side group accounted for 90%, and an epoxy group accounted for 10%.

[0096] Comparative Example 4:

[0097] A ladder phosphorus-containing polysiloxane flame retardant is prepared by the process of:

[0098] (1) 89.8 mg of potassium carbonate is dissolved in a mixed solution of 9.7 mL of deionized water and 12.9 mL of tetrahydrofuran and stirred uniformly to form a mixed solution, and 43.0 g of trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-3-yl)ethyl]silane is added dropwise to the mixed solution under a nitrogen atmosphere, and the reaction is stirred at 25°C for 72 h; after the reaction is completed, the residual solvent is removed to obtain a crude product, the crude product is redissolved with dichloromethane, washed, dried, filtered, and vacuum dried for 10-24 h after the solvent is removed to prepare an epoxy group-containing polysiloxane LASQ (ladder polysiloxane containing only silicon).

[0099] (2) 31.0 g of the epoxy group-containing polysiloxane, 21.57 g of diethyl phosphite, 0.59 g of triphenylphosphine, and 59.2 mL of N,N-dimethylformamide are added at one time to a flask, and the reaction is carried out at 100°C for 10 h. The solution after the reaction is completed is concentrated, and then precipitated in anhydrous diethyl ether, and the precipitate is vacuum dried at 60°C for 24 h to obtain a ladder phosphorus-containing polysiloxane flame retardant FR4-9 in which 90% of the epoxy groups are substituted with phosphorus-containing monomers, a ladder phosphorus-silicon-containing polysiloxane flame retardant, and the phosphorus structure (diethyl phosphite) in the side group accounts for 90%, and the epoxy group accounts for 10%.

[0100] Comparative Example 5:

[0101] A ladder phosphorus-containing polysiloxane flame retardant is prepared by the process of:

[0102] (1) 89.8 mg of potassium carbonate is dissolved in a mixed solution of 9.7 mL of deionized water and 12.9 mL of tetrahydrofuran and stirred uniformly to form a mixed solution, and 43.0 g of trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-3-yl)ethyl]silane is added dropwise to the mixed solution under a nitrogen atmosphere, and the reaction is stirred at 25°C for 72 h; after the reaction is completed, the residual solvent is removed to obtain a crude product, the crude product is redissolved with dichloromethane, washed, dried, filtered, and vacuum dried for 10-24 h after the solvent is removed to prepare an epoxy group-containing polysiloxane LASQ (ladder polysiloxane containing only silicon).

[0103] (2) 31.0 g of epoxy group-containing polysiloxane, 36.62 g of diphenyl phosphite, 0.79 g of triphenylphosphine and 78.6 mL of N,N-dimethylformamide were added at one time into a flask and reacted at 100°C for 10 h. The solution after the reaction was completed was concentrated, then precipitated in anhydrous diethyl ether, and the precipitate was vacuum-dried at 60°C for 24 h to obtain ladder phosphorus-containing polysiloxane flame retardant FR5-9 in which 90% of the epoxy groups were substituted with phosphorus-containing monomers, a ladder polysiloxane flame retardant containing only phosphorus and silicon, and a phosphorus structure (diphenyl phosphite) in the side group accounted for 90% and an epoxy group accounted for 10%.

[0104] Application Example 1:

[0105] An epoxy resin cured product, the content of each component of the components contained therein is shown in the preparation method,

[0106] The preparation method of the above epoxy resin cured product is: 100 g of epoxy resin (E51, epoxy equivalent EEW = 196 g·eq -1 ) and 33.00 g of ladder phosphorus-containing polysiloxane flame retardant FR1-91 obtained in Example 1 were uniformly mixed at 120°C, then cooled to 60°C, 87.01 g of curing agent methylhexahydrophthalic anhydride and 1 g of curing accelerator N,N-dimethylbenzylamine were uniformly mixed and poured into the epoxy resin. And continue to stir for 30 min. After the resin and the curing agent were uniformly mixed, they were placed in a vacuum oven at 60°C for 20 min to degas, poured into a preheated mold, degassed for another 20 min, and then placed in a high-temperature oven for stage curing. The curing program was 80°C x 1 h, 100°C x 1 h, 120°C x 1 h, and 140°C x 4 h. After curing, cooling and demolding, the epoxy resin cured product with FR1-91 addition amount of 15 wt% was obtained.

[0107] Application Example 2:

[0108] An epoxy resin cured product, the content of each component of the components contained therein is shown in the preparation method,

[0109] The preparation method of the above epoxy resin cured product is: 100 g of epoxy resin (E51, epoxy equivalent EEW = 196 g·eq -1The 46.90g of the trapezoidal phosphorus-containing polyborosiloxane flame retardant FR1-91 obtained in Example 1 was melted and mixed uniformly at 120°C, then cooled to 60°C. 87.60g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed uniformly and poured into the epoxy resin, and stirring was continued for 30 minutes. After the resin and curing agent were mixed uniformly, the mixture was placed in a 60°C vacuum oven for degassing for 20 minutes, poured into a preheated mold, and degassed again for 20 minutes. Then, it was placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80°C × 1h, 100°C × 1h, 120°C × 1h, and 140°C × 4h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR1-91 added at 20wt%.

[0110] Application Example 3:

[0111] An epoxy resin cured product, the contents of which are described in the preparation method.

[0112] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1 The FR1-92 trapezoidal phosphorus-containing polyboron siloxane flame retardant obtained in Example 2 was melted and mixed uniformly at 120°C, then cooled to 60°C. 87.01g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed uniformly and poured into the epoxy resin, and stirring was continued for 30 minutes. After the resin and curing agent were mixed uniformly, they were placed in a 60°C vacuum oven for degassing for 20 minutes, poured into a preheated mold, and degassed again for 20 minutes. Then, they were placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80°C × 1h, 100°C × 1h, 120°C × 1h, and 140°C × 4h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin with FR1-92 added at 15wt%.

[0113] Application Example 4:

[0114] An epoxy resin cured product, the contents of which are described in the preparation method.

[0115] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1The 46.90g of the trapezoidal phosphorus-containing polyborosiloxane flame retardant FR1-92 obtained in Example 2 was melted and mixed uniformly at 120°C, then cooled to 60°C. 87.60g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed uniformly and poured into the epoxy resin, and stirring was continued for 30 minutes. After the resin and curing agent were mixed uniformly, they were placed in a 60°C vacuum oven for degassing for 20 minutes, poured into a preheated mold, and degassed again for 20 minutes. Then, they were placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80°C×1h, 100°C×1h, 120°C×1h, and 140°C×4h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR1-92 added at 20wt%.

[0116] Application Example 5:

[0117] An epoxy resin cured product, the contents of which are described in the preparation method.

[0118] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1 The trapezoidal phosphorus-containing polyborosiloxane flame retardant FR1-13 obtained in Example 3 was melted and mixed uniformly at 120°C, then cooled to 60°C. 107.00g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed uniformly and poured into the epoxy resin, and stirring was continued for 30 minutes. After the resin and curing agent were mixed uniformly, the mixture was placed in a 60°C vacuum oven for degassing for 20 minutes, poured into a preheated mold, and degassed again for 20 minutes. Then, it was placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80°C × 1h, 100°C × 1h, 120°C × 1h, and 140°C × 4h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR1-13 added at 15wt%.

[0119] Application Example 6:

[0120] An epoxy resin cured product, the contents of which are described in the preparation method.

[0121] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1The trapezoidal phosphorus-containing polyborosiloxane flame retardant FR1-13 obtained in Example 3 was melted and mixed evenly at 120°C, then cooled to 60°C. 117.52g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed evenly and poured into the epoxy resin, and stirring was continued for 30 minutes. After the resin and curing agent were evenly mixed, they were placed in a 60°C vacuum oven for degassing for 20 minutes, poured into a preheated mold, and degassed again for 20 minutes. Then, they were placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80°C × 1h, 100°C × 1h, 120°C × 1h, and 140°C × 4h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR1-13 added at 20wt%.

[0122] Application Example 7:

[0123] An epoxy resin cured product, the contents of which are described in the preparation method.

[0124] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1 The trapezoidal phosphorus-containing polyborosiloxane flame retardant FR1-53 obtained in Example 4 was melted and mixed uniformly at 120°C, then cooled to 60°C. 97.04g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed uniformly and poured into the epoxy resin, and stirring was continued for 30 minutes. After the resin and curing agent were mixed uniformly, the mixture was placed in a 60°C vacuum oven for degassing for 20 minutes, poured into a preheated mold, and degassed again for 20 minutes. Then, it was placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80°C × 1h, 100°C × 1h, 120°C × 1h, and 140°C × 4h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR1-53 added at 15wt%.

[0125] Application Example 8:

[0126] An epoxy resin cured product, the contents of which are described in the preparation method.

[0127] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1) and 50.55 g of the ladder-type phosphorus-containing polyborosiloxane flame retardant obtained in Example 4 were uniformly mixed by melting at 120°C, and then cooled to 60°C. 102.20 g of the curing agent methyl hexahydrophthalic anhydride and 1 g of the curing accelerator N,N-dimethylbenzylamine were uniformly mixed, and then poured into the epoxy resin and stirred for 30 min. After the resin and the curing agent were uniformly mixed, they were placed in a vacuum oven at 60°C for 20 min to remove bubbles, poured into a preheated mold, again removed of bubbles for 20 min, and then placed in a high-temperature oven for stage curing. The curing was performed according to a curing procedure of 80°C x 1 h, 100°C x 1 h, 120°C x 1 h, and 140°C x 4 h. After the curing was completed, the product was cooled and demolded to obtain an epoxy resin cured product with an FR1-53 addition amount of 20 wt%.

[0128] Application Example 9:

[0129] An epoxy resin cured product, the content of each component of which is shown in the preparation method,

[0130] The preparation method of the above epoxy resin cured product is as follows: 100 g of an epoxy resin (E51, epoxy equivalent EEW = 196 g·eq -1 ) and 33.00 g of the ladder-type phosphorus-containing polyborosiloxane flame retardant FR1-93 obtained in Example 5 were uniformly mixed by melting at 120°C, and then cooled to 60°C. 87.01 g of the curing agent methyl hexahydrophthalic anhydride and 1 g of the curing accelerator N,N-dimethylbenzylamine were uniformly mixed, and then poured into the epoxy resin and stirred for 30 min. After the resin and the curing agent were uniformly mixed, they were placed in a vacuum oven at 60°C for 20 min to remove bubbles, poured into a preheated mold, again removed of bubbles for 20 min, and then placed in a high-temperature oven for stage curing. The curing was performed according to a curing procedure of 80°C x 1 h, 100°C x 1 h, 120°C x 1 h, and 140°C x 4 h. After the curing was completed, the product was cooled and demolded to obtain an epoxy resin cured product with an FR1-93 addition amount of 15 wt%.

[0131] Application Example 10:

[0132] An epoxy resin cured product, the content of each component of which is shown in the preparation method,

[0133] The preparation method of the above epoxy resin cured product is as follows: 100 g of an epoxy resin (E51, epoxy equivalent EEW = 196 g·eq -1After melting and mixing 46.90g of the trapezoidal phosphorus-containing polyborosiloxane flame retardant FR1-93 obtained in Example 5 at 120°C, the mixture was cooled to 60°C. 87.60g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed evenly and poured into the epoxy resin, with stirring continued for 30 minutes. After the resin and curing agent were evenly mixed, the mixture was placed in a 60°C vacuum oven for degassing for 20 minutes, poured into a preheated mold, and degassed again for 20 minutes. Then, it was placed in a high-temperature oven for staged curing. Curing was carried out according to a curing program of 80°C × 1h, 100°C × 1h, 120°C × 1h, and 140°C × 4h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR1-93 added at 20wt%.

[0134] Application Example 11:

[0135] An epoxy resin cured product, the contents of which are described in the preparation method.

[0136] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1 The 33.00g of the trapezoidal phosphorus-containing polyborosiloxane flame retardant FR2-93 obtained in Example 6 was melted and mixed uniformly at 120°C, then cooled to 60°C. 87.01g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed uniformly and poured into the epoxy resin, and stirring was continued for 30 minutes. After the resin and curing agent were mixed uniformly, they were placed in a 60°C vacuum oven for degassing for 20 minutes, poured into a preheated mold, and degassed again for 20 minutes. Then, they were placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80°C × 1h, 100°C × 1h, 120°C × 1h, and 140°C × 4h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin with FR2-93 added at 15wt%.

[0137] Application Example 12:

[0138] An epoxy resin cured product, the contents of which are described in the preparation method.

[0139] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1The 46.90g of the trapezoidal phosphorus-containing polyborosiloxane flame retardant FR2-93 obtained in Example 6 was melted and mixed uniformly at 120°C, then cooled to 60°C. 87.60g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed uniformly and poured into the epoxy resin, and stirring was continued for 30 minutes. After the resin and curing agent were mixed uniformly, the mixture was placed in a 60°C vacuum oven for degassing for 20 minutes, poured into a preheated mold, and degassed again for 20 minutes. Then, it was placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80°C × 1h, 100°C × 1h, 120°C × 1h, and 140°C × 4h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR2-93 added at 20wt%.

[0140] Application Example 13:

[0141] An epoxy resin cured product, the contents of which are described in the preparation method.

[0142] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1 The 47.01g of the trapezoidal phosphorus-containing polyborosiloxane flame retardant FR3-93 obtained in Example 7 was melted and mixed uniformly at 120°C, then cooled to 60°C. 88.04g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed uniformly and poured into the epoxy resin, and stirring was continued for 30 minutes. After the resin and curing agent were mixed uniformly, the mixture was placed in a 60°C vacuum oven for degassing for 20 minutes, poured into a preheated mold, and degassed again for 20 minutes. Then, it was placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80°C × 1h, 100°C × 1h, 120°C × 1h, and 140°C × 4h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR3-93 added at 20wt%.

[0143] Application Example 14:

[0144] An epoxy resin cured product, the contents of which are described in the preparation method.

[0145] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1The trapezoidal phosphorus-containing polyborosiloxane flame retardant FR4-93 obtained in Example 8 was melted and mixed uniformly at 120°C, then cooled to 60°C. 87.88g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed uniformly and poured into the epoxy resin, and stirring was continued for 30 minutes. After the resin and curing agent were mixed uniformly, they were placed in a 60°C vacuum oven for degassing for 20 minutes, poured into a preheated mold, and degassed again for 20 minutes. Then, they were placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80°C × 1h, 100°C × 1h, 120°C × 1h, and 140°C × 4h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR4-93 added at 20wt%.

[0146] Application Example 15:

[0147] An epoxy resin cured product, the contents of which are described in the preparation method.

[0148] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1 The trapezoidal phosphorus-containing polyborosiloxane flame retardant FR5-93 obtained in Example 9 was melted and mixed uniformly at 120°C, then cooled to 60°C. 87.36g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed uniformly and poured into the epoxy resin, and stirring was continued for 30 minutes. After the resin and curing agent were mixed uniformly, they were placed in a 60°C vacuum oven for degassing for 20 minutes, poured into a preheated mold, and degassed again for 20 minutes. Then, they were placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80°C × 1h, 100°C × 1h, 120°C × 1h, and 140°C × 4h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin with FR5-93 added at 20wt%.

[0149] Application Example 16:

[0150] An epoxy resin cured product, the contents of which are described in the preparation method.

[0151] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1The 6.63g of the trapezoidal phosphorus-containing polyborosiloxane flame retardant FR1-92 obtained in Example 2 was melted and mixed uniformly at 120°C, then cooled to 100°C. 25.97g of the curing agent diaminodiphenylmethane was added to the epoxy resin, and the mixture was vacuum degassed using an oil pump while stirring. After the resin and curing agent were mixed uniformly, the mixture was poured into a preheated mold, degassed for another 20 minutes, and then placed in a high-temperature oven for staged curing. Curing was carried out according to a curing program of 120°C × 2h, 140°C × 2h, 160°C × 2h, and 180°C × 1h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with 5wt% FR1-92.

[0152] Application Example 17:

[0153] An epoxy resin cured product, the contents of which are described in the preparation method.

[0154] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1 The 6.63g of the trapezoidal phosphorus-containing polyborosiloxane flame retardant FR1-93 obtained in Example 5 was melted and mixed uniformly at 120°C, then cooled to 100°C. 25.97g of the curing agent diaminodiphenylmethane was added to the epoxy resin, and the mixture was vacuum degassed using an oil pump while stirring. After the resin and curing agent were mixed uniformly, the mixture was poured into a preheated mold, degassed for another 20 minutes, and then placed in a high-temperature oven for staged curing. Curing was carried out according to a curing program of 120°C × 2h, 140°C × 2h, 160°C × 2h, and 180°C × 1h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with 5wt% FR1-93.

[0155] Application Example 18:

[0156] An epoxy resin cured product, the contents of which are described in the preparation method.

[0157] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1The trapezoidal phosphorus-containing polyborosiloxane flame retardant FR2-93 obtained in Example 6 was melted and mixed uniformly at 120°C, then cooled to 100°C. 25.97g of curing agent diaminodiphenylmethane was added to the epoxy resin, and the mixture was vacuum degassed using an oil pump while stirring. After the resin and curing agent were mixed uniformly, the mixture was poured into a preheated mold, degassed for another 20 minutes, and then placed in a high-temperature oven for staged curing. Curing was carried out according to a curing program of 120°C × 2h, 140°C × 2h, 160°C × 2h, and 180°C × 1h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR2-93 added at 5wt%.

[0158] Application Example 19:

[0159] An epoxy resin cured product, the contents of which are described in the preparation method.

[0160] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1 The trapezoidal phosphorus-containing polyborosiloxane flame retardant FR3-93 obtained in Example 7 was melted and mixed uniformly at 120°C, then cooled to 100°C. 25.97g of curing agent diaminodiphenylmethane was added to the epoxy resin, and the mixture was vacuum degassed using an oil pump while stirring. After the resin and curing agent were mixed uniformly, the mixture was poured into a preheated mold, degassed for another 20 minutes, and then placed in a high-temperature oven for staged curing. Curing was carried out according to a curing program of 120°C × 2h, 140°C × 2h, 160°C × 2h, and 180°C × 1h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with 5wt% FR3-93.

[0161] Application Example 20:

[0162] An epoxy resin cured product, the contents of which are described in the preparation method.

[0163] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1The 6.63g of the trapezoidal phosphorus-containing polyborosiloxane flame retardant FR4-93 obtained in Example 8 was melted and mixed uniformly at 120°C, then cooled to 100°C. 25.97g of the curing agent diaminodiphenylmethane was added to the epoxy resin, and the mixture was vacuum degassed using an oil pump while stirring. After the resin and curing agent were mixed uniformly, the mixture was poured into a preheated mold, degassed for another 20 minutes, and then placed in a high-temperature oven for staged curing. Curing was carried out according to a curing program of 120°C × 2h, 140°C × 2h, 160°C × 2h, and 180°C × 1h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with 5wt% FR4-93.

[0164] Application Example 21:

[0165] An epoxy resin cured product, the contents of which are described in the preparation method.

[0166] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1 The trapezoidal phosphorus-containing polyborosiloxane flame retardant FR5-93 obtained in Example 9 was melted and mixed uniformly at 120°C, then cooled to 100°C. 25.97g of curing agent diaminodiphenylmethane was added to the epoxy resin, and the mixture was vacuum degassed using an oil pump while stirring. After the resin and curing agent were mixed uniformly, the mixture was poured into a preheated mold, degassed for another 20 minutes, and then placed in a high-temperature oven for staged curing. Curing was carried out according to a curing program of 120°C × 2h, 140°C × 2h, 160°C × 2h, and 180°C × 1h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR5-93 added at 5wt%.

[0167] Application Example 22:

[0168] An epoxy resin cured product, the contents of which are described in the preparation method.

[0169] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (F51, epoxy equivalent EEW = 196g·eq) is added. -1After melting and mixing 3.89g of the trapezoidal phosphorus-containing polyborosiloxane flame retardant FR1-92 obtained in Example 2 at 120°C until homogeneous, the mixture was cooled to 100°C. 25.90g of the curing agent diaminodiphenylmethane was added to the epoxy resin, and the mixture was vacuum degassed using an oil pump while stirring. After the resin and curing agent were thoroughly mixed, the mixture was poured into a preheated mold and degassed for another 20 minutes. Then, it was placed in a high-temperature oven for staged curing. Curing was performed according to a curing procedure of 120°C × 2h, 140°C × 2h, 160°C × 2h, and 180°C × 1h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR1-92 added at 3wt%.

[0170] Application Example 23:

[0171] An epoxy resin cured product, the contents of which are described in the preparation method.

[0172] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1 After melting and mixing 3.89g of the trapezoidal phosphorus-containing polyborosiloxane flame retardant FR1-93 obtained in Example 5 at 120°C, the mixture was cooled to 100°C. 25.90g of the curing agent diaminodiphenylmethane was added to the epoxy resin, and the mixture was vacuum degassed using an oil pump while stirring. After the resin and curing agent were thoroughly mixed, the mixture was poured into a preheated mold and degassed for another 20 minutes. Then, it was placed in a high-temperature oven for staged curing. Curing was performed according to a curing procedure of 120°C × 2h, 140°C × 2h, 160°C × 2h, and 180°C × 1h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR1-93 added at 3wt%.

[0173] Application Example 24:

[0174] An epoxy resin cured product, the contents of which are described in the preparation method.

[0175] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1The 3.89g of the trapezoidal phosphorus-containing polyborosiloxane flame retardant FR2-93 obtained in Example 6 was melted and mixed uniformly at 120°C, then cooled to 100°C. 25.90g of the curing agent diaminodiphenylmethane was added to the epoxy resin, and the mixture was vacuum degassed using an oil pump while stirring. After the resin and curing agent were mixed uniformly, the mixture was poured into a preheated mold, degassed for another 20 minutes, and then placed in a high-temperature oven for staged curing. Curing was carried out according to a curing program of 120°C × 2h, 140°C × 2h, 160°C × 2h, and 180°C × 1h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR2-93 added at 3wt%.

[0176] Application Example 25:

[0177] An epoxy resin cured product, the contents of which are described in the preparation method.

[0178] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1 The 3.89g of the trapezoidal phosphorus-containing polyborosiloxane flame retardant FR3-93 obtained in Example 7 was melted and mixed uniformly at 120°C, then cooled to 100°C. 25.90g of the curing agent diaminodiphenylmethane was added to the epoxy resin, and the mixture was vacuum degassed using an oil pump while stirring. After the resin and curing agent were mixed uniformly, the mixture was poured into a preheated mold, degassed for another 20 minutes, and then placed in a high-temperature oven for staged curing. Curing was carried out according to a curing program of 120°C × 2h, 140°C × 2h, 160°C × 2h, and 180°C × 1h. After curing, the mixture was cooled, demolded, and sampled to obtain a cured epoxy resin product with FR3-93 added at 3wt%.

[0179] Application Example 26:

[0180] An epoxy resin cured product, the contents of which are described in the preparation method.

[0181] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1) and 3.89 g of the ladder-type phosphorus-containing polyborosiloxane flame retardant FR4-93 obtained in Example 8 were uniformly melt-mixed at 120°C, cooled to 100°C, and then 25.90 g of the curing agent, diaminodiphenyl methane, was added to the epoxy resin, and the mixed resin was vacuum degassed with an oil pump while stirring. After the resin and the curing agent were uniformly mixed, the mixture was poured into a preheated mold, degassed for 20 min, and then placed in a high-temperature oven for stage curing. The curing was performed according to a curing program of 120°C x 2 h, 140°C x 2 h, 160°C x 2 h, and 180°C x 1 h. After the curing was completed, the product was cooled and demolded to obtain an epoxy resin cured product with 3 wt% of the FR4-93.

[0182] Application Example 27:

[0183] An epoxy resin cured product, the content of each component of which is shown in the preparation method,

[0184] The preparation method of the above epoxy resin cured product is as follows: 100 g of an epoxy resin (E51, epoxy equivalent EEW = 196 g·eq -1 ) and 3.89 g of the ladder-type phosphorus-containing polyborosiloxane flame retardant FR4-93 obtained in Example 8 were uniformly melt-mixed at 120°C, cooled to 100°C, and then 25.90 g of the curing agent, diaminodiphenyl methane, was added to the epoxy resin, and the mixed resin was vacuum degassed with an oil pump while stirring. After the resin and the curing agent were uniformly mixed, the mixture was poured into a preheated mold, degassed for 20 min, and then placed in a high-temperature oven for stage curing. The curing was performed according to a curing program of 120°C x 2 h, 140°C x 2 h, 160°C x 2 h, and 180°C x 1 h. After the curing was completed, the product was cooled and demolded to obtain an epoxy resin cured product with 3 wt% of the FR4-93.

[0185] Comparative Application Example 1:

[0186] An epoxy resin cured product, the content of each component of which is shown in the preparation method,

[0187] The preparation method of the above epoxy resin cured product is as follows: 100 g of an epoxy resin (E51, epoxy equivalent EEW = 196 g·eq -1 ), 85 g of the curing agent, methyl hexahydrophthalic anhydride, and 1.1 g of the curing accelerator, N,N-dimethylbenzylamine, were uniformly melt-mixed at 60°C, degassed in a vacuum oven at 60°C for 20 min, poured into a preheated mold, degassed for 20 min, and then placed in a high-temperature oven for stage curing. The curing was performed according to a curing program of 80°C x 1 h, 100°C x 1 h, 120°C x 1 h, and 140°C x 4 h. After cooling and demolding, the pure epoxy resin cured product was obtained.

[0188] Comparative Application Example 2:

[0189] An epoxy resin cured product, the contents of which are described in the preparation method.

[0190] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1 The trapezoidal phosphorus-containing polysiloxane flame retardant FR1-90 obtained in Comparative Example 1 was melted and mixed uniformly at 120℃, then cooled to 60℃. 87.64g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed uniformly and poured into the epoxy resin, and stirring was continued for 30 min. After the resin and curing agent were mixed uniformly, the mixture was placed in a 60℃ vacuum oven for degassing for 20 min, poured into a preheated mold, and degassed again for 20 min. Then, it was placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80℃×1h, 100℃×1h, 120℃×1h, and 140℃×4h. After curing, the mixture was cooled, demolded, and sampled to obtain the cured epoxy resin with FR1-90 added at 20wt%.

[0191] Compare with example 3:

[0192] An epoxy resin cured product, the contents of which are described in the preparation method.

[0193] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1 The trapezoidal phosphorus-containing polysiloxane flame retardant FR2-90 obtained in Comparative Example 2 was melted and mixed uniformly at 120℃, then cooled to 60℃. 87.56g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed uniformly and poured into the epoxy resin, and stirring was continued for 30 min. After the resin and curing agent were mixed uniformly, the mixture was placed in a 60℃ vacuum oven for degassing for 20 min, poured into a preheated mold, and degassed again for 20 min. Then, it was placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80℃×1h, 100℃×1h, 120℃×1h, and 140℃×4h. After curing, the mixture was cooled, demolded, and sampled to obtain the cured epoxy resin with FR2-90 added at 20wt%.

[0194] Compare with application example 4:

[0195] An epoxy resin cured product, the contents of which are described in the preparation method.

[0196] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1The trapezoidal phosphorus-containing polysiloxane flame retardant FR3-90 obtained in Comparative Example 3 was melted and mixed uniformly at 120℃, then cooled to 60℃. 88.12g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed uniformly and poured into the epoxy resin, and stirring was continued for 30 min. After the resin and curing agent were mixed uniformly, the mixture was placed in a 60℃ vacuum oven for degassing for 20 min, poured into a preheated mold, and degassed again for 20 min. Then, it was placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80℃×1h, 100℃×1h, 120℃×1h, and 140℃×4h. After curing, the mixture was cooled, demolded, and sampled to obtain the cured epoxy resin with FR3-90 added at 20wt%.

[0197] Compare with application example 5:

[0198] An epoxy resin cured product, the contents of which are described in the preparation method.

[0199] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1 The trapezoidal phosphorus-containing polysiloxane flame retardant FR4-90 obtained in Comparative Example 4 was melted and mixed uniformly at 120℃, then cooled to 60℃. 87.96g of curing agent methylhexahydrophthalic anhydride and 1g of curing accelerator N,N-dimethylbenzylamine were mixed uniformly and poured into the epoxy resin, and stirring was continued for 30 minutes. After the resin and curing agent were mixed uniformly, they were placed in a 60℃ vacuum oven for degassing for 20 minutes, poured into a preheated mold, and degassed again for 20 minutes. Then, they were placed in a high-temperature oven for staged curing. Curing was carried out according to the curing program of 80℃×1h, 100℃×1h, 120℃×1h, and 140℃×4h. After curing, the mixture was cooled, demolded, and sampled to obtain the cured epoxy resin with FR4-90 added at 20wt%.

[0200] Comparative application example 6:

[0201] An epoxy resin cured product, the contents of which are described in the preparation method.

[0202] The preparation method of the above-mentioned epoxy resin cured product is as follows: 100g of epoxy resin (E51, epoxy equivalent EEW = 196g·eq) is added. -1) and 46.88 g of ladder-shaped phosphorus-containing polysiloxane flame retardant FR5-90 obtained in Comparative Example 5 were uniformly mixed at 120°C, and then cooled to 60°C. After 87.52 g of a curing agent methyl hexahydrophthalic anhydride and 1 g of a curing accelerator N,N-dimethylbenzylamine were uniformly mixed, they were poured into the epoxy resin and stirred for 30 min. After the resin and the curing agent were uniformly mixed, they were placed in a vacuum oven at 60°C for 20 min to remove bubbles, poured into a preheated mold, and then deaerated for another 20 min. Then, the mixture was placed in a high-temperature oven for stage curing. The curing was performed according to a curing procedure of 80°C x 1 h, 100°C x 1 h, 120°C x 1 h, and 140°C x 4 h. After the curing was completed, the mixture was cooled and demolded to obtain an epoxy resin cured product with a FR4-90 addition amount of 20 wt%.

[0203] Comparative Application Example 7:

[0204] An epoxy resin cured product, which contains components in amounts as described in the preparation method,

[0205] The preparation method of the epoxy resin cured product is as follows: 100 g of an epoxy resin (E51, epoxy equivalent weight EEW = 196 g·eq -1 ) and 25.97 g of a curing agent diamino diphenyl methane were uniformly mixed at 90°C, and the mixed resin was deaerated by an oil pump while stirring. After the resin and the curing agent were uniformly mixed, they were poured into a preheated mold, deaerated for another 20 min, and then placed in a high-temperature oven for stage curing. The curing was performed according to a curing procedure of 120°C x 2 h, 140°C x 2 h, 160°C x 2 h, and 180°C x 1 h. After the curing was completed, the mixture was cooled and demolded to obtain a pure epoxy resin cured product.

[0206] Comparative Application Example 8:

[0207] 100 g of an epoxy resin (F51, epoxy equivalent weight EEW = 196 g·eq -1 ) and 25.80 g of a curing agent diamino diphenyl methane were uniformly mixed at 90°C, and the mixed resin was deaerated by an oil pump while stirring. After the resin and the curing agent were uniformly mixed, they were poured into a preheated mold, deaerated for another 20 min, and then placed in a high-temperature oven for stage curing. The curing was performed according to a curing procedure of 120°C x 2 h, 140°C x 2 h, 160°C x 2 h, and 180°C x 1 h. After the curing was completed, the mixture was cooled and demolded to obtain a pure epoxy resin cured product.

[0208] Test Example:

[0209] The epoxy resin cured products prepared in the application examples and the comparative application examples were subjected to vertical burning performance tests, and the test results are shown in Table 1.

[0210] Table 1 Performance test of epoxy resin cured product of application examples and comparative application examples

[0211]

[0212] As shown in Table 1, the resin and curing agent used in application example 2, application example 4, application example 8, application example 9, application example 10, application example 12, application example 13, application example 14, application example 15, comparative application example 1 and comparative application example 2 are bisphenol A type epoxy resin E51 and methylthiohydantoin. Among them, the addition amount of flame retardant in application example 2, application example 4 and application example 10 is 20wt%, which is different in that the proportion of silicon structure and boron structure in phosphorus-containing ladder-shaped polyborosiloxane is different, which is 10:1, 10:2 and 10:3 respectively, and the test results show that with the increase of the proportion of boron structure, the flame retardant performance of the epoxy resin cured product is obviously improved. The addition amount of flame retardant in application example 8 and application example 10 is 20wt%, which is different in that the proportion of phosphorus structure in the side group of phosphorus-containing ladder-shaped polyborosiloxane is different, which is 50% and 90% respectively, and according to the test results, the more the phosphorus structure in the flame retardant, the better the flame retardant performance of the epoxy cured product under the same addition amount of flame retardant. The addition amount of flame retardant in application example 10, application example 12, application example 13, application example 14 and application example 15 is 20wt%, which is different in that the phosphorus structure in the side group of phosphorus-containing ladder-shaped polyborosiloxane is different, and according to the test results, application example 10, application example 12 and application example 15 all have excellent flame retardant performance, while the flame retardant performance of application example 13 and application example 14 is poor. This is mainly because the phosphorus oxygen free radicals produced by the decomposition of the phosphorus structure in application example 10, application example 12 and application example 15 can quench the combustible free radicals during combustion, and the phosphoric acid substances produced by the decomposition can promote the dehydration of the matrix to form carbon; while the phosphorus structure in application example 13 and application example 14 only plays a role in the condensed phase, and the gas phase effect is very weak, so compared with application example 10, application example 12 and application example 15, the phosphorus monomer used in the flame retardant can provide more effective flame retardant performance for the epoxy resin cured product. Compared with comparative application example 1 (pure epoxy resin cured product, without flame retardant) and comparative application example 2 (without boron in the flame retardant), the addition of flame retardant can significantly improve the flame retardant performance of the epoxy resin cured product, and compared with the flame retardant without boron, the flame retardant with boron can more significantly improve the flame retardant performance of the epoxy resin cured product. This is mainly because in addition to the effect of phosphorus structure, the main body of the flame retardant of the application example is a large number of continuous network Si-O-Si structure, and the silicon-containing fragments produced by the decomposition during combustion will participate in the formation of carbon layer, thereby ensuring the density and stability of the carbon layer; in addition, the borate produced by the thermal decomposition of boron-containing structure will melt at high temperature to seal the surface of the burning material, forming a glassy covering layer to further improve the stability of the carbon layer.

[0213] The resin and curing agent used in application example 16, application example 17, application example 18, application example 21 and comparative application example 7 are bisphenol A type epoxy resin E51 and diamino diphenyl methane respectively, wherein the flame retardant additive amount in application example 16, application example 17, application example 18 and application example 21 is 5wt%, and the resin curing product in comparative application example 7 does not contain flame retardant; the resin and curing agent used in application example 22, application example 23, application example 24, application example 27 and comparative application example 8 are phenolic epoxy resin F51 and diamino diphenyl methane respectively, wherein the flame retardant additive amount in application example 22, application example 23, application example 24 and application example 27 is 3wt%, and the resin curing product in comparative application example 8 does not contain flame retardant. As can be seen from table 1, the flame retardant performance test results have the same trend as the epoxy resin E51 / methyl hexahydrophthalic anhydride resin system, that is, the pure resin curing product does not have flame retardant performance, and after adding the flame retardants in example 1, example 2, example 5, example 6 and example 9, good flame retardant effect can be achieved.

[0214] The experiment of the present application also found that under the condition of a single variable, the more the flame retardant additive amount, the better the flame retardant performance of the resin curing product; the more the proportion of boron element in the flame retardant, the better the flame retardant performance of the prepared epoxy curing product; the more the proportion of phosphorus element in the side group, the better the flame retardant performance of the prepared resin curing product; the performance of the flame retardant prepared from DOPO, diphenyl phosphorus oxide and diphenyl phosphite is better than that of the flame retardant prepared from dimethyl phosphite and diethyl phosphite. Therefore, the above application examples and comparative application examples are used for illustration, and the remaining unlisted application examples also have relatively good comprehensive performance and are also within the protection scope of the present application.

[0215] In addition, since the flame retardant contains a large amount of continuous network Si-O-Si structure with flexibility and high heat resistance, and the reaction position of the phosphorus-containing group is on the side chain of the flame retardant, the mechanical properties of the resin curing product can be significantly enhanced and good heat resistance can be maintained after being added to the resin and cured, so the bending strength and impact strength are significantly improved, and the initial thermal decomposition temperature T 5％ of the resin curing product does not decrease obviously. And since the phosphoric acid substances produced by the thermal decomposition of the phosphorus-containing structure can promote the dehydration and carbonization of the matrix resin in the early stage to quickly form a carbon layer, the silicon-containing structure and boron-containing structure also help to form a stable and dense carbon layer, which can effectively reduce heat transfer and play a protective role for the matrix resin, so the maximum thermal decomposition rate R max of the resin curing product can be significantly reduced, and at the same time the carbon residue rate of the resin curing product at 800℃ can be improved.

[0216] In summary, the present application successfully prepares a ladder-shaped phosphorus-containing polyborosiloxane flame retardant, which is applied to the epoxy resin system to obtain an epoxy resin curing product with excellent flame retardant performance.

[0217] The above merely describes the preferred embodiments of the present application, and the present application is not limited to the above embodiments. It can be understood that other improvements and changes directly derived or thought by those skilled in the art without departing from the spirit and concept of the present application shall be considered to be within the protection scope of the present application.

Claims

1. A ladder phosphorus-containing polyborosiloxane flame retardant, characterized in that, The structural general formula of the ladder-shaped phosphorus-containing polyborosiloxane flame retardant is shown in the following formula (I): （Ⅰ）； wherein, The p, m are independently selected from integers between 1-20, The q, n are independently selected from integers between 1-6; The R is selected from one or more of , , , , .

2. The trapezoidal phosphorus-containing polyborosiloxane flame retardant according to claim 1, characterized in that, In the ladder-shaped phosphorus-containing polyborosiloxane flame retardant, the mass fraction of phosphorus element is 0.84 wt%-11.74 wt%.

3. The trapezoidal phosphorus-containing polyborosiloxane flame retardant according to claim 1, characterized in that, In the ladder-shaped phosphorus-containing polyborosiloxane flame retardant, the mass fraction of boron element is 0.26 wt%-1.31 wt%.

4. A process for the preparation of the trapezoidal phosphorus-containing polysiloxane flame retardant according to any one of claims 1 to 3, characterized in that, The preparation method comprises the following steps: (1) mixing water, anhydrous potassium carbonate and solvent I until the anhydrous potassium carbonate is dissolved, then adding boric acid, mixing, and then adding silane monomer dropwise, reacting under nitrogen atmosphere, removing residual solvent I after the reaction is completed to obtain a crude product, and post-treating to obtain an epoxy group ladder-shaped polyborosiloxane; (2) mixing a phosphorus-containing monomer, a catalyst, solvent II, and the epoxy group ladder-shaped polysiloxane of step (1), condensing and refluxing, concentrating after the reaction is completed, drying the obtained precipitate to obtain a ladder-shaped phosphorus-containing polysiloxane flame retardant.

5. The preparation method according to claim 4, characterized in that, In step (1), the molar ratio of the water to the anhydrous potassium carbonate is 800-900:1; the volume ratio of the water to the solvent I is 1:1-2; The solvent I comprises one or more of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, acetone, and 2-butanone.

6. The preparation method according to claim 4, characterized in that, In step (1), the molar ratio of the water, the boric acid, and the silane monomer is 30:1-3:10; The silane monomer comprises trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane; The reaction temperature is 25-80℃, and the reaction time is 6-72h; The post-treatment comprises dissolving the crude product with dichloromethane, washing, drying, filtering, removing the solvent I, and vacuum drying for 10-24h.

7. The preparation method according to claim 4, characterized in that, In step (2), the phosphorus-containing monomer comprises one or more of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-hydroxide, diphenyl phosphoroxide, diethyl phosphite, and diphenyl phosphite; The catalyst comprises one or more of triphenylphosphine, N,N-dimethylbenzylamine, and tetrabutylammonium bromide; The solvent II comprises one or more of toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,4-dioxane; The amount of the solvent II is to ensure that the total concentration of the epoxy group ladder-shaped polysiloxane and the phosphorus-containing monomer is 1-5g / mL; The molar ratio of the epoxy group in the epoxy group ladder-shaped polysiloxane to the phosphorus-containing monomer is 10:1-9; The amount of the catalyst is 0.5-2.5% of the mass of the phosphorus-containing monomer; The condensation and refluxing temperature is 90-120℃, and the condensation and refluxing time is 6-12h; the drying is vacuum drying, the drying temperature is 40-60℃, and the drying time is 12-24h.

8. An epoxy composition, characterized by, The epoxy composition comprises the following raw materials in parts by weight: ladder-shaped phosphorus-containing polyborosiloxane 15-21 parts epoxy resin 35-55 parts curing agent 25-50 parts curing accelerator 0-0.5 parts. The ladder phosphorus-containing polyborosiloxane is a ladder phosphorus-containing polyborosiloxane flame retardant as claimed in any one of claims 1-3, or a ladder phosphorus-containing polyborosiloxane flame retardant prepared by the preparation method as claimed in any one of claims 4-7.

9. The epoxy resin composition according to claim 8, characterized in that, The epoxy resin comprises one or more of bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol aldehyde type epoxy resin, aliphatic epoxy resin; The curing agent comprises an acid anhydride type curing agent or an amine type curing agent; The curing accelerator comprises one or more of N,N-dimethylbenzylamine, 2,4,6-tris(dimethylaminomethyl)phenol, acetylacetone metal salt, triphenylphosphine and its phosphonium salt, substituted urea, addition product of aryl isocyanate and imidazole compound, active chromium tris(2-ethylhexanoate), organic acid salt-amine complex, 1,8-diaza-bicyclo(5,4,0)-7-undecene, 2-mercaptobenzothiazole, peroxide, thiourea, cycloalkylimidazoline, 2-phenylimidazoline, epoxy group-containing aromatic tertiary amine, titanate accelerator, ferrocenyl accelerator, halogenated chromium-acid anhydride complex.

10. The epoxy resin composition according to claim 9, characterized in that The aliphatic epoxy resin comprises an aliphatic glycidyl ether epoxy resin.

11. Use of the epoxy resin composition according to any one of claims 8 to 10, characterized in that The epoxy resin composition is used as an adhesive.

12. Use according to claim 11, characterized in that, The adhesive is used for copper-clad plates, electronic packaging materials.

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