Organic phosphine modified unsaturated polyester and polyhalide condensate and preparation method thereof

Abstract

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

Description

Technical Field

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

[0002] Unsaturated polyester has excellent corrosion resistance, insulation, processability and other characteristics and is widely used in aerospace, electrical appliances, transportation and other fields. However, its inherent poor flame retardancy, toxic smoke generated during combustion and extremely weak mechanical toughness are still the biggest limiting conditions for unsaturated polyester as a high-performance engineering material. Reactive flame retardants directly participate in the polymerization of unsaturated polyester resin as flame retardant comonomers, so that the unsaturated polyester resin molecular chain contains flame retardant components, thereby achieving flame retardancy of unsaturated polyester resin. Since the flame retardant comonomer and the unsaturated polyester resin matrix are chemically bonded, the resulting composite material has better durability and less harmful effects. Phosphorus-based comonomers decompose when heated to produce phosphorus oxygen free radicals, and at the same time release strong acids such as phosphoric acid, metaphosphoric acid, and pyrophosphoric acid, which can not only capture and quench the active free radicals generated in the combustion chain reaction, but also promote the dehydration of the matrix into carbon, increase the residual carbon yield, and play a flame retardant role in both the gas phase and the condensed phase.

[0003] Reactive monomers are added when unsaturated polyester is cured. In addition to being used as reactive monomers, reactive monomers also act as diluents, so they are called reactive diluents. Styrene is widely used because of its low price and easy copolymerization with polyester. However, styrene has a strong odor and can burn the skin. In severe cases, it can also cause physical discomfort. As environmental requirements become more and more stringent, low-styrene and styrene-free resins are developing rapidly. Summary of the invention

[0004] One aspect of the present application provides a cured product of an organic phosphine-modified unsaturated polyester and a polyhalide.

[0005] The solidified material provided in the present application is a cross-linked polymer of an unsaturated polyester modified by an organic phosphine and a polyhalide.

[0006] In one embodiment, the molar ratio of the phosphine groups of the organic phosphine-modified unsaturated polyester to the halogen groups of the polyhalide is 1:(0.8-1.2).

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

[0008] In one embodiment, the polyhalide is one or more of hexanediol chloroacetate, propylene glycol chloroacetate, hexadecanol chloroacetate, phytyl chloroacetate, ethylene glycol dimonochloroacetate, diisopropylamine dichloroacetate, chloro-2-phenyl-1,3-propanediyl ester, chloro-2-ethyl-2-phenyl-1,3-propanediyl acetate, 1,5-dimethyl 2-chloro-4-(2-chloro-2-phenylethyl) glutarate, 1,4-bis(4-chlorobutyl) terephthalic acid, and 1,1-(1,4-phenyl)bis(2-chloroacetate).

[0009] Another aspect of the present application provides a method for preparing a solid product of an organic phosphine-modified unsaturated polyester and a polyhalide.

[0010] The method for preparing a solidified product of an organic phosphine-modified unsaturated polyester and a polyhalide provided in the present application comprises: The organic phosphine-modified unsaturated polyester and the polyhalide are mixed and cured to obtain a cured product of the organic phosphine-modified unsaturated polyester and the polyhalide.

[0011] In one embodiment, the molar ratio of the phosphine groups of the organic phosphine-modified unsaturated polyester to the halogen groups of the polyhalide is 1:(0.8-1.2).

[0012] 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.

[0013] 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).

[0014] In one embodiment, the polyhalide is one or more of hexanediol chloroacetate, propylene glycol chloroacetate, hexadecanol chloroacetate, phytyl chloroacetate, ethylene glycol dimonochloroacetate, diisopropylamine dichloroacetate, chloro-2-phenyl-1,3-propanediyl ester, chloro-2-ethyl-2-phenyl-1,3-propanediyl acetate, 1,5-dimethyl 2-chloro-4-(2-chloro-2-phenylethyl) glutarate, 1,4-bis(4-chlorobutyl) terephthalic acid, and 1,1-(1,4-phenyl)bis(2-chloroacetate).

[0015] In one embodiment, the solvent is one or more of chloroform, tetrahydrofuran, and dimethyltetrahydrofuran.

[0016] The cured product of the organic phosphine-modified unsaturated polyester and the polyhalide has good flame retardant and antibacterial properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1The 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 The actual image of the solidified product of the organic phosphine-modified unsaturated polyester and polyhalide prepared in Example 1 is shown; Figure 3b The actual image of the solidified product of the organic phosphine-modified unsaturated polyester and polyhalide 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

[0018] One aspect of the present application provides a cured product of an organic phosphine-modified unsaturated polyester and a polyhalide.

[0019] The solidified material provided by the present application is a cross-linked polymer of an unsaturated polyester modified by an organic phosphine and a polyhalide. The introduction of phosphorus and chlorine elements makes the solidified material have good flame retardant and antibacterial properties. At the same time, the styrene-free unsaturated polyester resin reduces the volatility and toxicity of the unsaturated polyester curing process.

[0020] The present application uses organic phosphine to modify unsaturated polyester and polyhalide to undergo quaternary phosphonium reaction and cross-linking to solidify into a cross-linked polymer. The molecular structure of quaternary phosphonium salt is relatively stable and does not react with general redox agents and acids and bases. Quaternary phosphonium salt can be adsorbed onto the surface of negatively charged bacteria, diffuse through the cell wall, and combine with the cytoplasmic membrane to rupture it, and the bacteria die due to the release of the contents. The atomic radius of the phosphorus atom is greater than the atomic radius of nitrogen, which makes the electronegativity of phosphorus lower, the polarization effect is stronger, it is easier to adsorb on the cell membrane, and the bactericidal ability is stronger. Therefore, the introduction of organic phosphine makes the cured product have good flame retardant and antibacterial properties.

[0021] In one embodiment, the molar ratio of the phosphine groups of the organic phosphine-modified unsaturated polyester to the halogen groups of the polyhalide is 1:(0.8-1.2).

[0022] In one embodiment, the polyhalide is one or more of hexanediol chloroacetate, propylene glycol chloroacetate, hexadecanol chloroacetate, phytyl chloroacetate, ethylene glycol dimonochloroacetate, diisopropylamine dichloroacetate, chloro-2-phenyl-1,3-propanediyl ester, chloro-2-ethyl-2-phenyl-1,3-propanediyl acetate, 1,5-dimethyl 2-chloro-4-(2-chloro-2-phenylethyl) glutarate, 1,4-bis(4-chlorobutyl) terephthalic acid, and 1,1-(1,4-phenyl)bis(2-chloroacetate).

[0023] In one embodiment, the organic phosphine-modified unsaturated polyester is an addition reaction product of the unsaturated polyester and the diphenylphosphine.

[0024] Another aspect of the present application provides a method for preparing a solid product of an organic phosphine-modified unsaturated polyester and a polyhalide.

[0025] The method for preparing a solidified product of an organic phosphine-modified unsaturated polyester and a polyhalide provided in the present application comprises: The organic phosphine-modified unsaturated polyester and the polyhalide are mixed and cured to obtain a cured product of the organic phosphine-modified unsaturated polyester and the polyhalide.

[0026] In one embodiment, the molar ratio of the phosphine groups of the organic phosphine-modified unsaturated polyester to the halogen groups of the polyhalide is 1:(0.8-1.2).

[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] Specifically, in an inert atmosphere, unsaturated polyester is reacted with diphenylphosphine in a solvent at 50-90° C. After the reaction, the solvent is removed, and the organic phosphine-modified unsaturated polyester is obtained through 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 polyhalide is one or more of hexanediol chloroacetate, propylene glycol chloroacetate, hexadecanol chloroacetate, phytyl chloroacetate, ethylene glycol dimonochloroacetate, diisopropylamine dichloroacetate, chloro-2-phenyl-1,3-propanediyl ester, chloro-2-ethyl-2-phenyl-1,3-propanediyl acetate, 1,5-dimethyl 2-chloro-4-(2-chloro-2-phenylethyl) glutarate, 1,4-bis(4-chlorobutyl) terephthalic acid, and 1,1-(1,4-phenyl)bis(2-chloroacetate).

[0031] In one embodiment, the solvent is one or more of chloroform, tetrahydrofuran, and dimethyltetrahydrofuran.

[0032] 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.

[0033] In one embodiment, the ratio of the total molar number of hydroxyl groups to the total molar number of carboxyl groups of the unsaturated acid or anhydride, the dicarboxylic acid or anhydride and the diol is 1:1:1.

[0034] The formation reaction of unsaturated polyester is mainly based on the dehydration polycondensation of alcohol and acid, which is a reversible equilibrium step-by-step reaction. Whether in an acidic, alkaline or neutral environment, the ester bond can be broken, which means that the organic phosphine-modified unsaturated polyester containing ester bonds and the solidified products of polyhalides have application potential in recycling.

[0035] In one embodiment, the unsaturated acid or anhydride is itaconic acid or itaconic anhydride.

[0036] 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.

[0037] 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, dibromobutylene glycol.

[0038] In one embodiment, the esterification catalyst is p-toluenesulfonic acid, manganese acetate, stannous chloride, dibutyltin oxide, stannous oxalate, zinc acetate, cobalt acetate or titanium butoxide.

[0039] In one embodiment, the polymerization inhibitor is hydroquinone, trimethyl hydroquinone, p-tert-butylcatechol, tert-butyl hydroquinone, toluene hydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate or copper chloride.

[0040] In one embodiment, the polycondensation catalyst is dibutyltin dilaurate, antimony trioxide, antimony acetate, antimony glycolate, titanium dioxide, tetraisopropyl titanate, tetra-n-butyl titanate, titanium glycolate, tetraphenyl titanate, titanium acetylacetonate, germanium dioxide, stannous oxalate, dibutyltin oxide, stannous octoate, tin acetylacetonate, aluminum phosphate, aluminum sulfate, aluminum nitrate or aluminum chloride.

[0041] 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.

[0042] 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.

[0043] 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 hydrogen nuclear magnetic resonance spectrum of the prepared unsaturated polyester is shown.

[0044] 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 prepared organic phosphine-modified unsaturated polyester is shown.

[0045] The organic phosphine-modified unsaturated polyester (containing 2.101 mmol of phosphine groups) and hexanediol chloroacetate (1.261 mmol) were uniformly mixed 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 polyhalide. Figure 3a The actual pictures of the prepared organic phosphine-modified unsaturated polyester and the cured product of the polyhalide are shown.

[0046] 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.

[0047] 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.

[0048] The organic phosphine-modified unsaturated polyester (containing 2.101 mmol of phosphine groups) and hexanediol chloroacetate (0.8405 mmol) were uniformly mixed 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 polyhalide. Figure 3b The actual pictures of the prepared organic phosphine-modified unsaturated polyester and the cured product of the polyhalide are shown.

[0049] 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.

[0050] 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.

[0051] The organic phosphine-modified unsaturated polyester (containing 2.101 mmol of phosphine groups) and propylene glycol chloroacetate (0.9455 mmol) were uniformly mixed 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 polyhalide.

[0052] 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.

[0053] 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.

[0054] The organic phosphine-modified unsaturated polyester (the molar number of the phosphine group contained is 2.101 mmol) and chloro-2-phenyl-1,3-propanediyl ester (0.9455 mmol) are uniformly mixed 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 polyhalide.

[0055] 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 reaction was carried out at 160°C for 2 hours in a nitrogen atmosphere until no more water was produced in the water separator. The esterification reaction was completed. Antimony glycol (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.

[0056] 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.

[0057] The organic phosphine-modified unsaturated polyester (containing 2.101 mmol of phosphine groups) and hexadecanol chloroacetate (0.9455 mmol) were uniformly mixed 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 polyhalide.

[0058] 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.

[0059] 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.

[0060] The organic phosphine-modified unsaturated polyester (containing 2.101 mmol of phosphine groups in moles) and hexadecanol chloroacetate (0.9455 mmol) were uniformly mixed and poured into a mold, and cured at 100° C. for 2 hours to obtain a cured product of the organic phosphine-modified unsaturated polyester and the polyhalide.

[0061] 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.

[0062] 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.

[0063] The organic phosphine-modified unsaturated polyester (containing 2.101 mmol of phosphine groups) and phytic acid chloroacetate (0.9455 mmol) were uniformly mixed and poured into a mold, and cured at 100° C. for 2 hours to obtain a cured product of the organic phosphine-modified unsaturated polyester and the polyhalide.

[0064] 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.

[0065] 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.

[0066] An organic phosphine-modified unsaturated polyester (containing 2.101 mmol of phosphine groups in moles) and 1,1-(1,4-phenyl)di(2-chloroacetate) (0.9455 mmol) were uniformly mixed and poured into a mold, and cured at 100° C. for 2 hours to obtain a cured product of an organic phosphine-modified unsaturated polyester and a polyhalide.

[0067] 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.

[0068] 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.

[0069] The organic phosphine-modified unsaturated polyester (containing 2.101 mmol of phosphine groups in moles) and diisopropylamine dichloroacetate (0.9455 mmol) were uniformly mixed 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 polyhalide.

[0070] Flame retardant performance test In order to verify the flame retardant performance, the cured products of the organic phosphine-modified unsaturated polyester and the polyhalide prepared in Examples 1-9 were tested according to the vertical burning test in the American standard UL94 flame retardant grade test standard.

[0071] Table 1

[0072] 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.

[0073] From the test results in Table 1, it can be seen that the UL-94 of the organic phosphine-modified unsaturated polyester and the cured product of the polyhalide prepared in Examples 1-9 is V-0.

[0074] 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 solidified product of an organic phosphine-modified unsaturated polyester and a polyhalide, characterized in that: The solidified material is a cross-linked polymer of an organic phosphine-modified unsaturated polyester and a polyhalide.

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 halogen group of the polyhalide is 1:(0.8-1.2).

3. The cured product according to claim 1 or 2, characterized in that: The organic phosphine-modified unsaturated polyester is an addition reaction product of the unsaturated polyester and the diphenylphosphine.

4. The cured product according to claim 1 or 2, characterized in that: The polyhalide is one or more of hexanediol chloroacetate, propylene glycol chloroacetate, hexadecanol chloroacetate, phytyl chloroacetate, ethylene glycol dimonochloroacetate, diisopropylamine dichloroacetate, chloro-2-phenyl-1,3-propanediyl ester, chloro-2-ethyl-2-phenyl-1,3-propanediyl acetate, 1,5-dimethyl 2-chloro-4-(2-chloro-2-phenylethyl) glutarate, 1,4-bis(4-chlorobutyl) terephthalic acid, and 1,1-(1,4-phenyl)bis(2-chloroacetate).

5. A method for preparing a solid product of an organic phosphine-modified unsaturated polyester and a polyhalide, comprising: The organic phosphine-modified unsaturated polyester and the polyhalide are mixed and cured to obtain a cured product of the organic phosphine-modified unsaturated polyester and the polyhalide.

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

7. The method according to claim 5 or 6, characterized in that: The organic phosphine-modified unsaturated polyester is a product generated by an addition reaction between an unsaturated polyester in a solvent and diphenylphosphine.

8. The method according to claim 7, 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).

9. The method according to claim 5 or 6, characterized in that: The polyhalide is one or more of hexanediol chloroacetate, propylene glycol chloroacetate, hexadecanol chloroacetate, phytyl chloroacetate, ethylene glycol dimonochloroacetate, diisopropylamine dichloroacetate, chloro-2-phenyl-1,3-propanediyl ester, chloro-2-ethyl-2-phenyl-1,3-propanediyl acetate, 1,5-dimethyl 2-chloro-4-(2-chloro-2-phenylethyl) glutarate, 1,4-bis(4-chlorobutyl) terephthalic acid, and 1,1-(1,4-phenyl)bis(2-chloroacetate).

10. The method according to claim 7, characterized in that The solvent is one or more of chloroform, tetrahydrofuran and dimethyltetrahydrofuran.

Images