Organic phosphine modified unsaturated polyester and epoxy resin condensate and preparation method thereof

Abstract

The invention provides a cured product of organic phosphine modified unsaturated polyester and epoxy resin and a preparation method of the cured product. The cured product is a cross-linked polymer of organic phosphine modified unsaturated polyester and epoxy resin. A cured product of the organic phosphine modified unsaturated polyester and epoxy resin has good flame retardance and antibacterial property.

Description

Technical Field

[0001] The present application relates to the field of flame retardant and antibacterial materials, and specifically to a cured product of an organic phosphine-modified unsaturated polyester and an epoxy resin and a preparation method thereof. Background Art

[0002] Unsaturated polyester resin is one of the most important thermosetting resins in the modern plastics industry. It is one of the most commonly used resins in the fields of construction, maritime, transportation and wind energy industries because of its excellent mechanical properties, good corrosion resistance, low cost, low density and high strength-to-weight ratio. However, due to the molecular structure and chemical composition of the unsaturated polyester resin itself, it is extremely easy to burn, and a large amount of toxic gas and smoke will be produced during the combustion process. In order to expand the application range of unsaturated polyester resin, especially to meet the requirements of some special fields, it is necessary to modify the unsaturated polyester resin to be flame retardant and maintain the comprehensive application performance of the unsaturated polyester resin. Flame retardant elements or flame retardant comonomers are introduced into the molecular structure of unsaturated polyester resin by chemical modification, so that it has the characteristics of intrinsic flame retardancy. Among them, phosphorus-containing flame retardant comonomers are widely used in the research of reactive flame retardant unsaturated polyester because they are green and environmentally friendly and can play a flame retardant role in both gas phase and condensed phase. Summary of the invention

[0003] The present application provides a cured product of an organic phosphine-modified unsaturated polyester and an epoxy resin and a preparation method thereof.

[0004] On one hand, the cured product of an organic phosphine-modified unsaturated polyester and an epoxy resin provided in the present application is a cross-linked polymer of an organic phosphine-modified unsaturated polyester and an epoxy resin.

[0005] In one embodiment, the molar ratio of the phosphine groups of the organic phosphine-modified unsaturated polyester to the epoxy groups of the epoxy resin is 1:(0.8-1.2).

[0006] In one embodiment, the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol C epoxy resin and bisphenol fluorene epoxy resin.

[0007] In one embodiment, the organic phosphine-modified unsaturated polyester is an addition reaction product of an unsaturated polyester and diphenylphosphine.

[0008] Another aspect of the present invention provides a method for preparing a cured product of an organic phosphine-modified unsaturated polyester and an epoxy resin, comprising: The organic phosphine-modified unsaturated polyester and the epoxy resin are mixed and cured to obtain a cured product of the organic phosphine-modified unsaturated polyester and the epoxy resin.

[0009] In one embodiment, the molar ratio of the phosphine groups of the organic phosphine-modified unsaturated polyester to the epoxy groups of the epoxy resin is 1:(0.8-1.2).

[0010] In one embodiment, the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol C epoxy resin and bisphenol fluorene epoxy resin.

[0011] In one embodiment, the organic phosphine-modified unsaturated polyester is a product generated by an addition reaction between an unsaturated polyester in a solvent and diphenylphosphine.

[0012] In one embodiment, the molar ratio of the double bond groups of the unsaturated polyester to the phosphine groups of the diphenylphosphine is 1:(1.2-1.5).

[0013] In one embodiment, the solvent is one or more of chloroform, tetrahydrofuran, dimethyltetrahydrofuran, and N,N-dimethylformamide.

[0014] The cured product of the organic phosphine-modified unsaturated polyester and epoxy resin of the present application can resist oxidation and has good thermal stability and exhibits good flame retardancy because phosphoric acid can cover the carbon layer during combustion. At the same time, the cured product of the organic phosphine-modified unsaturated polyester and epoxy resin of the present application has antibacterial properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 The hydrogen nuclear magnetic resonance spectrum of the unsaturated polyester prepared in Example 1 is shown; Figure 2 The hydrogen nuclear magnetic resonance spectrum of the organic phosphine-modified unsaturated polyester prepared in Example 1 is shown; Figure 3a A physical picture of the cured product of the organic phosphine-modified unsaturated polyester and epoxy resin prepared in Example 1 is shown; Figure 3b A physical picture of the cured product of the organic phosphine-modified unsaturated polyester and epoxy resin prepared in Example 2 is shown; in, Figure 3a and Figure 3b The text in the background is used to show the transmittance of the sample. DETAILED DESCRIPTION

[0016] The present application provides a cured product of an organic phosphine-modified unsaturated polyester and an epoxy resin and a preparation method thereof.

[0017] On one hand, the cured product of an organic phosphine-modified unsaturated polyester and an epoxy resin provided in the present application is a cross-linked polymer of an organic phosphine-modified unsaturated polyester and an epoxy resin.

[0018] The present invention introduces organic phosphine into unsaturated polyester, and then performs ring-opening copolymerization with epoxy resin. The phosphorus-containing groups in the system undergo ring-opening reaction with the epoxy groups of the resin, thereby increasing the crosslinking degree of the system and improving the thermal stability of the heat-curing epoxy resin. At the same time, the introduction of organic phosphine improves the flame retardant and antibacterial properties of the epoxy resin.

[0019] In one embodiment, the molar ratio of the phosphine groups of the organic phosphine-modified unsaturated polyester to the epoxy groups of the epoxy resin is 1:(0.8-1.2).

[0020] Epoxy resin is a high-performance synthetic resin with excellent mechanical properties, adhesive properties, electrical properties and electrical insulation properties after curing. At the same time, it has good chemical stability and product dimensional stability, easy molding, good stress transfer and low cost. However, due to the molecular structure characteristics of epoxy resin, its flame retardant performance is poor and it is easy to catch fire and burn under the action of flame. The oxygen index (LOI) of general epoxy resin is about 19.8%, which is a flammable material. In order to improve its fire safety and expand its application range, flame retardant modification is required. Phosphorus-containing groups are introduced into the molecular structure of the curing agent, and the active groups of the phosphorus-containing compounds are used to react with the epoxy groups or active epoxides of the resin to undergo a ring-opening reaction, thereby improving the flame retardancy and thermal stability of the cured epoxy resin system.

[0021] In one embodiment, the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol C epoxy resin and bisphenol fluorene epoxy resin.

[0022] In one embodiment, the organic phosphine-modified unsaturated polyester is an addition reaction product of an unsaturated polyester and diphenylphosphine.

[0023] The quaternary phosphonium salt group with a long-chain alkyl group has strong antibacterial properties. The organic polymer compound with the antibacterial group has the advantages of no residue, easy processing, good chemical stability, etc., and the polymer antibacterial agent will not penetrate into human skin, and has better antibacterial properties than small molecule antibacterial agents. The present application introduces organic phosphine into the unsaturated polyester resin system through a quaternary phosphonium reaction with an epoxy group, which effectively improves the antibacterial properties of the system.

[0024] Another aspect of the present invention provides a method for preparing a cured product of an organic phosphine-modified unsaturated polyester and an epoxy resin, comprising: The organic phosphine-modified unsaturated polyester and the epoxy resin are mixed and cured to obtain a cured product of the organic phosphine-modified unsaturated polyester and the epoxy resin.

[0025] In one embodiment, the molar ratio of the phosphine groups of the organic phosphine-modified unsaturated polyester to the epoxy groups of the epoxy resin is 1:(0.8-1.2).

[0026] In one embodiment, the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol C epoxy resin and bisphenol fluorene epoxy resin.

[0027] In one embodiment, the organic phosphine-modified unsaturated polyester is a product generated by an addition reaction between an unsaturated polyester in a solvent and diphenylphosphine.

[0028] In one embodiment, in an inert atmosphere, the unsaturated polyester in a solvent is reacted with diphenylphosphine at 50-90° C. After the reaction, the solvent is removed, and the organic phosphine-modified unsaturated polyester is obtained by precipitation and drying.

[0029] In one embodiment, the molar ratio of the double bond groups of the unsaturated polyester to the phosphine groups of the diphenylphosphine is 1:(1.2-1.5).

[0030] In one embodiment, the solvent is one or more of chloroform, tetrahydrofuran, dimethyltetrahydrofuran, and N,N-dimethylformamide.

[0031] In one embodiment, the unsaturated polyester is obtained by the following process: In an inert atmosphere, unsaturated acid or anhydride, dicarboxylic acid or anhydride, and diol are reacted at 140-180° C. in the presence of an esterification catalyst and a polymerization inhibitor; and then a polycondensation reaction is carried out at 140-180° C. and 0.05-0.09 MPa in the presence of a polycondensation catalyst.

[0032] In one embodiment, the unsaturated acid or anhydride is itaconic acid or itaconic anhydride.

[0033] Bio-based unsaturated polyester resins have sustainable resources, and most of them are biodegradable and biocompatible. The main raw materials for bio-based unsaturated polyester resins are itaconic acid, isosorbide, furan compounds and vegetable oils. Itaconic acid, also known as methylene succinic acid, contains a carbon-carbon double bond and two carboxyl groups in its molecular structure, which is very similar to maleic acid. It can replace maleic acid or maleic anhydride and polycondense with diols to synthesize bio-based unsaturated polyester resins. At present, itaconic acid is mainly made of agricultural and sideline products such as wine lees, starch, beets, sugarcane, straw, etc., and suitable fermentation strains (Candida, Aspergillus itachius, Aspergillus terreus, etc.) are selected for large-scale fermentation production, and it is widely used in the synthesis of bio-based unsaturated polyester resins.

[0034] In one embodiment, the dicarboxylic acid or anhydride is oxalic acid, succinic acid, adipic acid, sebacic acid, phthalic acid, phthalic acid, phthalic anhydride, isophthalic acid, biphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, chloro-bridged anhydride or bromo-bridged anhydride.

[0035] In one embodiment, the diol is 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol, 1,4-butanediol, pentanediol, 1,6-hexanediol, cyclohexanediol, dihexanediol, diethylene glycol, methylpropylene glycol, 3-chloropropylene glycol, 4-chloro-1,3-butanediol, dibromoneopentyl glycol, 2,3-dibromopropanol, 4-bromo-1,2-butanediol or dibromobutylene glycol.

[0036] In one embodiment, the esterification catalyst is one or more of p-toluenesulfonic acid, manganese acetate, stannous chloride, dibutyltin oxide, stannous oxalate, zinc acetate, cobalt acetate, and titanium butoxide.

[0037] In one embodiment, the polymerization inhibitor is one or more of hydroquinone, trimethyl hydroquinone, p-tert-butylcatechol, tert-butyl hydroquinone, toluene hydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper cyclohexane, and copper chloride.

[0038] In one embodiment, the polycondensation catalyst is one or more of dibutyltin dilaurate, antimony trioxide, antimony acetate, antimony glycol, titanium dioxide, tetraisopropyl titanate, tetra-n-butyl titanate, titanium glycol, tetraphenyl titanate, titanium acetylacetonate, germanium dioxide, stannous oxalate, dibutyltin oxide, stannous octoate, tin acetylacetonate, aluminum phosphate, aluminum sulfate, aluminum nitrate, and aluminum chloride.

[0039] In order to make the purpose, technical scheme and advantages of the present invention more clear, the present invention is further described in detail in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0040] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0041] Embodiment 1: Itaconic acid (33.64 mmol), phthalic anhydride (33.64 mmol) and 1,3-propylene glycol (67.28 mmol) were placed in a four-necked flask, and p-toluenesulfonic acid (1%) and hydroquinone (0.02%) were added. The mixture was connected to a water separator stirrer and a thermometer. The esterification reaction was completed at 180°C for 2 hours in a nitrogen atmosphere until no more water was produced in the water separator. Dibutyltin dilaurate (1%) was added, the pressure was reduced to 0.05 MPa, and the polycondensation reaction was carried out at 180°C for 3 hours to obtain an unsaturated polyester. Figure 1 The H NMR spectrum of the unsaturated polyester is shown.

[0042] In a nitrogen atmosphere, an unsaturated polyester (containing 7.577 mmol of double bonds) was dissolved in dimethyltetrahydrofuran (10 ml), and diphenylphosphine (11.37 mmol) was added and stirred at 90°C for 8 hours until the reaction was completed. After the reaction was completed, the solvent was removed, and the organic phosphine-modified unsaturated polyester was obtained by precipitation and drying. Figure 2 The hydrogen nuclear magnetic resonance spectrum of the organic phosphine-modified unsaturated polyester is shown.

[0043] The organic phosphine-modified unsaturated polyester (the molar number of the phosphine group contained is 2.101 mmol) and the epoxy resin E51 (the molar number of the epoxy group contained is 2.521 mmol) are mixed evenly and poured into a mold, and cured at 120° C. for 1 hour to obtain a cured product of the organic phosphine-modified unsaturated polyester and the epoxy resin. Figure 3a The actual picture shows the cured product of the unsaturated polyester modified with organic phosphine and epoxy resin.

[0044] Embodiment 2: Itaconic acid (33.64 mmol), phthalic anhydride (33.64 mmol) and 1,2-propylene glycol (67.28 mmol) were placed in a four-necked flask, and p-toluenesulfonic acid (0.5%) and hydroquinone (0.01%) were added. The mixture was connected to a water separator stirrer and a thermometer. The esterification reaction was completed at 140°C for 3 hours in a nitrogen atmosphere until no more water was produced in the water separator. Dibutyltin dilaurate (0.5%) was added, the pressure was reduced to 0.09 MPa, and the polycondensation reaction was carried out at 140°C for 5 hours to obtain an unsaturated polyester.

[0045] In a nitrogen atmosphere, an unsaturated polyester (containing 7.577 mmol of double bonds) was dissolved in tetrahydrofuran (10 ml), and diphenylphosphine (9.092 mmol) was added and stirred at 50°C for 24 hours until the reaction was completed. After the reaction was completed, the solvent was removed, and the organic phosphine-modified unsaturated polyester was obtained by precipitation and drying.

[0046] The organic phosphine-modified unsaturated polyester (the molar number of the phosphine group contained is 2.101 mmol) and the epoxy resin E51 (the molar number of the epoxy group contained is 1.681 mmol) are mixed evenly and poured into a mold, and cured at 30° C. for 24 hours to obtain a cured product of the organic phosphine-modified unsaturated polyester and the epoxy resin. Figure 3b The actual picture shows the cured product of the organic phosphine-modified unsaturated polyester and epoxy resin.

[0047] Embodiment 3: Itaconic acid (33.64 mmol), terephthalic anhydride (33.64 mmol) and 1,4-butanediol (67.28 mmol) were placed in a four-necked flask, and manganese acetate (0.5%) and trimethylhydroquinone (0.01%) were added. The mixture was connected to a water separator stirrer and a thermometer. The esterification reaction was completed at 160°C in a nitrogen atmosphere for 2 hours until no more water was produced in the water separator. Antimony trioxide (1%) was added, the pressure was reduced to 0.05 MPa, and the polycondensation reaction was carried out at 160°C for 4 hours to obtain an unsaturated polyester.

[0048] In a nitrogen atmosphere, an unsaturated polyester (containing 7.577 mmol of double bonds) was dissolved in tetrahydrofuran (10 ml), and diphenylphosphine (11.37 mmol) was added and stirred at 60°C for 24 hours until the reaction was completed. After the reaction was completed, the solvent was removed, and the organic phosphine-modified unsaturated polyester was obtained by precipitation and drying.

[0049] The organic phosphine-modified unsaturated polyester (the molar number of the phosphine group contained is 2.101 mmol) and the epoxy resin E35 (the molar number of the epoxy group contained is 1.681 mmol) are mixed evenly and poured into a mold, and cured at 80° C. for 4 hours to obtain a cured product of the organic phosphine-modified unsaturated polyester and the epoxy resin.

[0050] Embodiment 4: Itaconic acid (33.64 mmol), isophthalic acid (33.64 mmol) and pentanediol (67.28 mmol) were placed in a four-necked flask, and stannous chloride (0.5%) and trimethylhydroquinone (0.01%) were added. The mixture was connected to a water separator stirrer and a thermometer. The esterification reaction was completed at 160°C for 2 hours in a nitrogen atmosphere until no more water was produced in the water separator. Titanium dioxide (1%) was added and the pressure was reduced to 0.05 MPa. The polycondensation reaction was carried out at 160°C for 4 hours to obtain an unsaturated polyester.

[0051] In a nitrogen atmosphere, an unsaturated polyester (containing 7.577 mmol of double bonds) was dissolved in tetrahydrofuran (10 ml), and diphenylphosphine (11.37 mmol) was added and stirred at 60°C for 24 hours until the reaction was completed. After the reaction was completed, the solvent was removed, and the organic phosphine-modified unsaturated polyester was obtained by precipitation and drying.

[0052] The organic phosphine-modified unsaturated polyester (the molar number of the phosphine group contained is 2.101 mmol) and the epoxy resin E44 (the molar number of the epoxy group contained is 1.681 mmol) are mixed evenly and poured into a mold, and cured at 80° C. for 4 hours to obtain a cured product of the organic phosphine-modified unsaturated polyester and the epoxy resin.

[0053] Embodiment 5: Itaconic acid (33.64 mmol), adipic acid (33.64 mmol) and 1,6-hexanediol (67.28 mmol) were placed in a four-necked flask, and dibutyltin oxide (0.5%) and p-tert-butylcatechol (0.01%) were added. The mixture was connected to a water separator stirrer and a thermometer. The esterification reaction was completed at 160°C for 2 hours in a nitrogen atmosphere until no more water was produced in the water separator. Ethylene glycol antimony (1%) was added, the pressure was reduced to 0.05 MPa, and the polycondensation reaction was carried out at 160°C for 4 hours to obtain an unsaturated polyester.

[0054] In a nitrogen atmosphere, an unsaturated polyester (containing 7.577 mmol of double bonds) was dissolved in dimethyltetrahydrofuran (10 ml), and diphenylphosphine (11.37 mmol) was added and stirred at 60°C for 24 hours until the reaction was completed. After the reaction was completed, the solvent was removed, and the organic phosphine-modified unsaturated polyester was obtained by precipitation and drying.

[0055] The organic phosphine-modified unsaturated polyester (the molar number of the phosphine group contained is 2.101 mmol) and the epoxy resin E44 (the molar number of the epoxy group contained is 1.681 mmol) are mixed evenly and poured into a mold, and cured at 80° C. for 4 hours to obtain a cured product of the organic phosphine-modified unsaturated polyester and the epoxy resin.

[0056] Embodiment 6: Itaconic acid (33.64 mmol), sebacic acid (33.64 mmol) and methyl propanediol (67.28 mmol) were placed in a four-necked flask, and stannous oxalate (0.5%) and p-toluene hydroquinone (0.01%) were added. The mixture was connected to a water separator stirrer and a thermometer. The esterification reaction was completed at 160°C for 2 hours in a nitrogen atmosphere until no more water was produced in the water separator. Titanium acetylacetonate (1%) was added and the pressure was reduced to 0.05 MPa. The mixture was subjected to polycondensation reaction at 160°C for 4 hours to obtain an unsaturated polyester.

[0057] In a nitrogen atmosphere, an unsaturated polyester (containing 7.577 mmol of double bonds) was dissolved in dimethyltetrahydrofuran (10 ml), and diphenylphosphine (11.37 mmol) was added and stirred at 60°C for 24 hours until the reaction was completed. After the reaction was completed, the solvent was removed, and the organic phosphine-modified unsaturated polyester was obtained by precipitation and drying.

[0058] The organic phosphine-modified unsaturated polyester (the molar number of the phosphine group contained is 2.101 mmol) and the bisphenol S epoxy resin (the molar number of the epoxy group contained is 1.891 mmol) are mixed evenly and poured into a mold, and cured at 100° C. for 3 hours to obtain a cured product of the organic phosphine-modified unsaturated polyester and the epoxy resin.

[0059] Embodiment 7: Itaconic acid (33.64 mmol), 2,6-naphthalene dicarboxylic acid (33.64 mmol) and 3-chloropropanediol (67.28 mmol) were placed in a four-necked flask, and titanium butoxide (0.5%) and p-benzoquinone (0.01%) were added. The water separator agitator and a thermometer were connected. The esterification reaction was completed at 160°C in a nitrogen atmosphere for 2 hours until no more water was produced in the water separator. Stannous oxalate (1%) was added and the pressure was reduced to 0.05 MPa. The polycondensation reaction was carried out at 160°C for 4 hours to obtain an unsaturated polyester.

[0060] In a nitrogen atmosphere, an unsaturated polyester (containing 7.577 mmol of double bonds) was dissolved in dimethyltetrahydrofuran (10 ml), and diphenylphosphine (11.37 mmol) was added and stirred at 60°C for 24 hours until the reaction was completed. After the reaction was completed, the solvent was removed, and the organic phosphine-modified unsaturated polyester was obtained by precipitation and drying.

[0061] The organic phosphine-modified unsaturated polyester (the molar number of the phosphine group contained is 2.101 mmol) and the bisphenol S epoxy resin (the molar number of the epoxy group contained is 1.891 mmol) are mixed evenly and poured into a mold, and cured at 100° C. for 3 hours to obtain a cured product of the organic phosphine-modified unsaturated polyester and the epoxy resin.

[0062] Embodiment 8: Itaconic acid (33.64 mmol), chlorohydric anhydride (33.64 mmol) and 4-chloro-1,3-butanediol (67.28 mmol) were placed in a four-necked flask, and cobalt acetate (0.5%) and naphthoquinone (0.01%) were added. The water separator agitator and a thermometer were connected. The esterification reaction was completed at 160°C in a nitrogen atmosphere for 2 hours until no more water was produced in the water separator. Dibutyltin oxide (1%) was added and the pressure was reduced to 0.05 MPa. The polycondensation reaction was carried out at 160°C for 4 hours to obtain an unsaturated polyester.

[0063] In a nitrogen atmosphere, an unsaturated polyester (containing 7.577 mmol of double bonds) was dissolved in chloroform (10 ml), and diphenylphosphine (11.37 mmol) was added and stirred at 60°C for 24 hours until the reaction was completed. After the reaction was completed, the solvent was removed, and the organic phosphine-modified unsaturated polyester was obtained by precipitation and drying.

[0064] The organic phosphine-modified unsaturated polyester (the molar number of the phosphine group contained is 2.101 mmol) and the bisphenol F epoxy resin (the molar number of the epoxy group contained is 1.891 mmol) are mixed evenly and poured into a mold, and cured at 100° C. for 3 hours to obtain a cured product of the organic phosphine-modified unsaturated polyester and the epoxy resin.

[0065] Embodiment 9: Itaconic acid (33.64 mmol), chlorohydric anhydride (33.64 mmol) and dibromobutylene glycol (67.28 mmol) were placed in a four-necked flask, and zinc acetate (0.5%) and tert-butyl hydroquinone (0.01%) were added. The mixture was connected to a water separator stirrer and a thermometer. The esterification reaction was completed at 160°C in a nitrogen atmosphere for 2 hours until no more water was produced in the water separator. Tetraphenyl titanate (1%) was added, the pressure was reduced to 0.05 MPa, and the polycondensation reaction was carried out at 160°C for 4 hours to obtain an unsaturated polyester.

[0066] In a nitrogen atmosphere, an unsaturated polyester (containing 7.577 mmol of double bonds) was dissolved in chloroform (10 ml), and diphenylphosphine (11.37 mmol) was added and stirred at 60°C for 24 hours until the reaction was completed. After the reaction was completed, the solvent was removed, and the organic phosphine-modified unsaturated polyester was obtained by precipitation and drying.

[0067] The organic phosphine-modified unsaturated polyester (the molar number of the phosphine group contained is 2.101 mmol) and the bisphenol F epoxy resin (the molar number of the epoxy group contained is 1.891 mmol) are mixed evenly and poured into a mold, and cured at 80° C. for 4 hours to obtain a cured product of the organic phosphine-modified unsaturated polyester and the epoxy resin.

[0068] Flame retardant performance test In order to verify the flame retardant performance, the cured products of the organic phosphine-modified unsaturated polyester and epoxy resin prepared in Examples 1-9 were tested according to the vertical burning test in the American standard UL94 flame retardant grade test standard.

[0069] Table 1

[0070] Note: Definition of V-0 level: When the material is exposed to a flame for 10 seconds twice, and the burning time each time does not exceed 10 seconds, the total burning time does not exceed 50 seconds, and there is no dripping of burning materials during the test or the dripping materials cannot ignite the absorbent cotton.

[0071] From the test results in Table 1, it can be seen that the UL-94 of the cured products of the organic phosphine-modified unsaturated polyester and epoxy resin prepared in Examples 1-9 are all V-0.

[0072] It should be noted that the technical solutions or technical features described in the above embodiments can be combined or supplemented with each other without causing conflicts. The scope of protection of this application is not limited to the precise structures described in the above embodiments and shown in the drawings; all modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of this application should be included in the scope of protection of this application.

Claims

1. A cured product of an organic phosphine-modified unsaturated polyester and an epoxy resin, characterized in that: The solidified material is a cross-linked polymer of an organic phosphine-modified unsaturated polyester and an epoxy resin; the organic phosphine-modified unsaturated polyester is an addition reaction product of an unsaturated polyester and diphenylphosphine.

2. The cured product according to claim 1, characterized in that The molar ratio of the phosphine group of the organic phosphine-modified unsaturated polyester to the epoxy group of the epoxy resin is 1:(0.8-1.2).

3. The cured product according to claim 1 or 2, characterized in that: The epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol C epoxy resin and bisphenol fluorene epoxy resin.

4. A method for preparing a cured product of an organic phosphine-modified unsaturated polyester and an epoxy resin, comprising: Mixing and curing an organic phosphine-modified unsaturated polyester with an epoxy resin to obtain a cured product of the organic phosphine-modified unsaturated polyester and the epoxy resin; The organic phosphine-modified unsaturated polyester is a product generated by an addition reaction between an unsaturated polyester in a solvent and diphenylphosphine.

5. The method according to claim 4, characterized in that The molar ratio of the phosphine group of the organic phosphine-modified unsaturated polyester to the epoxy group of the epoxy resin is 1:(0.8-1.2).

6. The method according to claim 4, characterized in that The epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol C epoxy resin and bisphenol fluorene epoxy resin.

7. The method according to claim 4, characterized in that The molar ratio of the double bond groups of the unsaturated polyester to the phosphine groups of the diphenylphosphine is 1:(1.2-1.5).

8. The method according to claim 4, characterized in that The solvent is one or more of chloroform, tetrahydrofuran, dimethyltetrahydrofuran and N,N-dimethylformamide.

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