Solidified product of unsaturated polyester modified by phosphonium styrene group and preparation method thereof

Abstract

The present application provides a solidified product of a phosphonium-modified unsaturated polyester and a preparation method thereof. The solidified product is a cross-linked polymer of a phosphonium-modified unsaturated polyester and a reactive diluent; the phosphonium-modified unsaturated polyester is a cross-linked polymer of an organic phosphine-modified unsaturated polyester and 4-chloromethylstyrene. The solidified product of the phosphonium-modified unsaturated polyester has a significant flame retardant effect.

Description

Technical Field

[0001] The present application relates to the field of flame retardant and antibacterial materials, and in particular to a cured product of a phosphonium-modified styrene-based unsaturated polyester and a preparation method thereof. Background Art

[0002] Unsaturated polyester coatings are composed of unsaturated resins, curing systems and additives. They have the advantages of heat resistance, high gloss, good hardness, wear resistance, water resistance, and good chemical resistance. They are widely used in the furniture industry, agricultural industry, transportation and other fields, and are one of the important film-forming resins for coatings. Unsaturated polyester resins are cheap raw materials, simple synthesis and processing technology, and excellent thermomechanical properties. They are widely used in various applications. Itaconic acid has the advantages of bio-based raw materials, renewability, and simple preparation process, and has become a good polyester synthesis monomer. However, unsaturated polyester is mainly composed of carbon and hydrogen elements, and its limiting oxygen index (LOI) is only 19.6%. It is very easy to burn, and its flame retardant and heat resistance are poor. It will produce a lot of harmful smoke when burning, and the resin itself has a poor carbon-forming ability, and the residual carbon rate at 700°C is only 1.16%. The diols, dibasic acids, acid anhydrides, cross-linking agents, etc. used in the synthesis and curing process of unsaturated polyester resins are chemically modified to introduce flame retardant elements or groups into their molecular structures. Then, through chemical reactions such as esterification and cross-linking, the flame retardant elements or groups directly constitute a part of the main chain or side chain of the unsaturated polyester resin. Since the interaction between the flame retardant elements or groups and the unsaturated polyester resin is a chemical bond, the force is strong, which fundamentally solves the shortcomings of poor stability, easy loss and poor compatibility of the flame retardant structure. Therefore, the reactive unsaturated polyester resin has a better flame retardant effect.

[0003] Quaternary phosphonium salts were first introduced abroad in the late 1980s. They are highly effective and broad-spectrum fungicides. After ionization in water, quaternary phosphonium salts carry positive charges and can be adsorbed on the surface of negatively charged microorganisms and penetrate into the interior of microorganisms, changing the properties of the native membrane, making it impossible for bacteria to move normally. The hydrophobic base dissolves the fat wall on the surface of the bacteria, causing the bacteria to die. Quaternary phosphonium salts are effective against Gram-negative bacteria, Gram-positive bacteria, molds, and algae. Quaternary phosphonium salts have the advantages of low toxicity, low foaming, and low dosage, and can be quickly decomposed in the environment without biological accumulation. Summary of the invention

[0004] The present application provides a cured product of a phosphonium-modified styrene-based unsaturated polyester and a preparation method thereof.

[0005] In one aspect of the present application, the cured product of phosphonium-modified styrene-based unsaturated polyester is a cross-linked polymer of phosphonium-modified styrene-based unsaturated polyester and a reactive diluent; the phosphonium-modified styrene-based unsaturated polyester is a cross-linked polymer of an organic phosphine-modified unsaturated polyester and 4-chloromethylstyrene.

[0006] In one embodiment, the active diluent is one or more of styrene, divinyl styrene, 4-acetoxy-3-methoxy styrene, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, butyl methacrylate, epoxylated soybean oil, glycidyl methacrylate, acrylates, and 4-vinylguaiacol glycidyl ether.

[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 application provides a method for preparing a cured product of a phosphonium-modified styrene-based unsaturated polyester, comprising:

[0009] Under an inert atmosphere, an organic phosphine-modified unsaturated polyester and 4-chloromethylstyrene in a solvent are reacted at 40-80° C. to obtain a phosphonium-modified styrene-modified unsaturated polyester;

[0010] In the presence of an initiator, the phosphonium-modified styrene-based unsaturated polyester is mixed with a reactive diluent and cured to obtain a cured product of the phosphonium-modified styrene-based unsaturated polyester.

[0011] In one embodiment, the molar ratio of the phosphine groups of the organic phosphine-modified unsaturated polyester to the chlorine groups of 4-chloromethylstyrene is 1:(1.2-1.5).

[0012] In one embodiment, the mass ratio of the phosphonium styrene-modified unsaturated polyester to the reactive diluent is 10:(2-8).

[0013] In one embodiment, the active diluent is one or more of styrene, divinyl styrene, 4-acetoxy-3-methoxy styrene, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, butyl methacrylate, epoxylated soybean oil, glycidyl methacrylate, acrylates, and 4-vinylguaiacol glycidyl ether.

[0014] In one embodiment, the organic phosphine-modified unsaturated polyester is an addition reaction product of an unsaturated polyester and diphenylphosphine.

[0015] 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).

[0016] The cured product of the phosphonium-modified styrene-based unsaturated polyester of the present application (when burning, the charcoal layer can resist oxidation and has good thermal stability because phosphoric acid can cover the charcoal layer) exhibits good flame retardancy. The cured product of the phosphonium-modified styrene-based unsaturated polyester provided by the present application has more significant flame retardant and antibacterial effects than traditional styrene unsaturated polyester. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The hydrogen nuclear magnetic resonance spectrum of the unsaturated polyester prepared in Example 1 is shown;

[0018] Figure 2 The hydrogen nuclear magnetic resonance spectrum of the organic phosphine-modified unsaturated polyester prepared in Example 1 is shown;

[0019] Figure 3 The hydrogen nuclear magnetic resonance spectrum of the phosphonium-modified styrene-based unsaturated polyester prepared in Example 1 is shown;

[0020] Figure 4a A physical picture of the phosphonium-modified styrene-based unsaturated polyester resin prepared in Example 1 is shown;

[0021] Figure 4b A physical picture of the phosphonium-modified styrene-based unsaturated polyester resin prepared in Example 2 is shown;

[0022] in, Figure 4a and Figure 4b The text in the background is used to show the transmittance of the sample. DETAILED DESCRIPTION

[0023] 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.

[0024] On the one hand, the present application provides a solidified material of a phosphonium-modified unsaturated polyester, which is a cross-linked polymer of a phosphonium-modified unsaturated polyester and a reactive diluent; the phosphonium-modified unsaturated polyester is a cross-linked polymer of an organic phosphine-modified unsaturated polyester and 4-chloromethylstyrene.

[0025] In one embodiment, the active diluent is one or more of styrene, divinyl styrene, 4-acetoxy-3-methoxy styrene, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, butyl methacrylate, epoxylated soybean oil, glycidyl methacrylate, acrylates, and 4-vinylguaiacol glycidyl ether.

[0026] In one embodiment, the organic phosphine-modified unsaturated polyester is an addition reaction product of an unsaturated polyester and diphenylphosphine.

[0027] On the other hand, the present application provides a method for preparing a cured product of a phosphonium-modified styrene-based unsaturated polyester, comprising:

[0028] Under an inert atmosphere, an organic phosphine-modified unsaturated polyester and 4-chloromethylstyrene in a solvent are reacted at 40-80° C. to obtain a phosphonium-modified styrene-modified unsaturated polyester;

[0029] In the presence of an initiator, the phosphonium-modified styrene-based unsaturated polyester is mixed with a reactive diluent and cured to obtain a cured product of the phosphonium-modified styrene-based unsaturated polyester.

[0030] In one embodiment, the active diluent is one or more of styrene, divinyl styrene, 4-acetoxy-3-methoxy styrene, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, butyl methacrylate, epoxylated soybean oil, glycidyl methacrylate, acrylates, and 4-vinylguaiacol glycidyl ether.

[0031] In one embodiment, the organic phosphine-modified unsaturated polyester is an addition reaction product of an unsaturated polyester and diphenylphosphine. Specifically, the organic phosphine-modified unsaturated polyester is obtained by reacting an unsaturated polyester with diphenylphosphine at 50-90° C. under an inert atmosphere.

[0032] In one embodiment, the molar ratio of the phosphine groups of the organic phosphine-modified unsaturated polyester to the chlorine groups of 4-chloromethylstyrene is 1:(1.2-1.5).

[0033] In one embodiment, the mass ratio of the phosphonium styrene-modified unsaturated polyester to the reactive diluent is 10:(2-8).

[0034] 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).

[0035] In one embodiment, the solvent is one or more of chloroform, tetrahydrofuran, dimethyltetrahydrofuran, and N,N-dimethylformamide.

[0036] In one embodiment, the initiator is a photoinitiator or a thermal initiator. The photoinitiator is one or more of diphenoxybenzophenone, thioxanthone, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzil dimethyl ketal bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexyl benzophenone, benzoin diethyl ether, 4-benzoyl-4-methyldiphenyl sulfide. The thermal initiator is one or more of azoisobutyronitrile, cyclohexanone peroxide, dibenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, dodecyl peroxide, diacetyl peroxide, 4-bromomethylbenzoyl peroxide, tert-butyl perbenzoate, tert-butyl peroxide diethyl acetate, and tert-butyl peroctanoate.

[0037] In one embodiment, the unsaturated polyester can be obtained by the following method: unsaturated acid or anhydride, dicarboxylic acid or anhydride, and diol are reacted at 40-180° C. in the presence of an esterification catalyst and an inhibitor under an inert atmosphere, and then polycondensed at 140-180° C. and 0.05-0.09 MPa in the presence of a polycondensation catalyst.

[0038] 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.

[0039] In one embodiment, the unsaturated acid or anhydride is itaconic acid or itaconic anhydride.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in conjunction with specific embodiments.

[0046] 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.

[0047] Embodiment 1:

[0048] 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.

[0049] 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 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.

[0050] In a nitrogen atmosphere, an organic phosphine-modified unsaturated polyester (containing 3.948 mmol of phosphine groups) and 4-chloromethylstyrene (5.922 mmol) were dissolved in dimethyltetrahydrofuran and reacted at 80°C for 8 hours. After the reaction was completed, the solvent was removed, and the unsaturated polyester modified with phosphonium styrene was obtained by precipitation and drying; Figure 3The hydrogen nuclear magnetic resonance spectrum of the prepared phosphonium-modified unsaturated polyester is shown.

[0051] The phosphonium-modified styrene-based unsaturated polyester (1.672 g), styrene (0.3344 g), and cyclohexanone peroxide (10.03 mg) were mixed evenly and poured into a mold, and the mixture was heated to 120° C. and cured for 1 hour to obtain a phosphonium-modified styrene-based unsaturated polyester resin; Figure 4a A physical picture of the prepared phosphonated styrene-based unsaturated polyester resin is shown.

[0052] Embodiment 2:

[0053] 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.

[0054] 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.

[0055] In a nitrogen atmosphere, an organic phosphine-modified unsaturated polyester (containing 3.948 mmol of phosphine groups) and 4-chloromethylstyrene (4.738 mmol) were dissolved in chloroform and reacted at 40°C for 12 hours. After the reaction was completed, the solvent was removed, and the unsaturated polyester modified with phosphonium styrene was obtained by precipitation and drying.

[0056] The phosphonium-modified styrene-based unsaturated polyester (1.672 g), styrene (1.338 g), and cyclohexanone peroxide (60.19 mg) were mixed evenly and poured into a mold, and the mixture was heated to 60° C. and cured for 8 hours to obtain a phosphonium-modified styrene-based unsaturated polyester resin; Figure 4b A physical picture of the prepared phosphonated styrene-based unsaturated polyester resin is shown.

[0057] Embodiment 3:

[0058] 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.

[0059] 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.

[0060] In a nitrogen atmosphere, an organic phosphine-modified unsaturated polyester (containing 3.948 mmol of phosphine groups) and 4-chloromethylstyrene (5.922 mmol) were dissolved in tetrahydrofuran and reacted at 60°C for 12 hours. After the reaction was completed, the solvent was removed, and the unsaturated polyester modified with phosphonium styrene was obtained by precipitation and drying.

[0061] The phosphonium-modified styrene-based unsaturated polyester (1.672 g), 4-acetoxy-3-methoxystyrene (0.5016 g), and azoisobutyronitrile (21.74 mg) were mixed evenly and poured into a mold. The mixture was heated to 80° C. and cured for 4 hours to obtain a phosphonium-modified styrene-based unsaturated polyester resin.

[0062] Embodiment 4:

[0063] 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.

[0064] 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.

[0065] In a nitrogen atmosphere, an organic phosphine-modified unsaturated polyester (containing 3.948 mmol of phosphine groups) and 4-chloromethylstyrene (5.922 mmol) were dissolved in tetrahydrofuran and reacted at 60°C for 12 hours. After the reaction was completed, the solvent was removed, and the unsaturated polyester modified with phosphonium styrene was obtained by precipitation and drying.

[0066] The phosphonium-modified styrene-based unsaturated polyester (1.672 g), 4-acetoxy-3-methoxystyrene (0.5016 g), and azoisobutyronitrile (21.74 mg) were mixed evenly and poured into a mold. The mixture was heated to 100° C. and cured for 2 hours to obtain a phosphonium-modified styrene-based unsaturated polyester resin.

[0067] Embodiment 5:

[0068] 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.

[0069] 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.

[0070] In a nitrogen atmosphere, an organic phosphine-modified unsaturated polyester (containing 3.948 mmol of phosphine groups) and 4-chloromethylstyrene (5.922 mmol) were dissolved in dimethyltetrahydrofuran and reacted at 60°C for 12 hours. After the reaction was completed, the solvent was removed, and the unsaturated polyester modified with phosphonium styrene was obtained by precipitation and drying.

[0071] The phosphonium-modified styrene-modified unsaturated polyester (1.672 g), hydroxyethyl methacrylate (1.3376 g), and 2,4-dichlorobenzoyl peroxide (30.10 mg) were mixed evenly and poured into a mold. The mixture was heated to 80° C. and cured for 4 hours to obtain a phosphonium-modified styrene-modified unsaturated polyester resin.

[0072] Embodiment 6:

[0073] 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.

[0074] 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.

[0075] In a nitrogen atmosphere, an organic phosphine-modified unsaturated polyester (containing 3.948 mmol of phosphine groups) and 4-chloromethylstyrene (5.922 mmol) were dissolved in dimethyltetrahydrofuran and reacted at 60°C for 12 hours. After the reaction was completed, the solvent was removed, and the unsaturated polyester modified with phosphonium styrene was obtained by precipitation and drying.

[0076] The phosphonium-modified styrene-based unsaturated polyester (1.672 g), hydroxyethyl methacrylate (1.3376 g), and 2,4-dichlorobenzoyl peroxide (30.10 mg) were mixed evenly and poured into a mold. The mixture was heated to 100° C. and cured for 2 hours to obtain a phosphonium-modified styrene-based unsaturated polyester resin.

[0077] Embodiment 7:

[0078] 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, and 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. 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.

[0079] 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.

[0080] In a nitrogen atmosphere, an organic phosphine-modified unsaturated polyester (containing 3.948 mmol of phosphine groups) and 4-chloromethylstyrene (5.922 mmol) were dissolved in dimethyltetrahydrofuran and reacted at 60°C for 12 hours. After the reaction was completed, the solvent was removed, and the unsaturated polyester modified with phosphonium styrene was obtained by precipitation and drying.

[0081] The phosphonium-modified styrene-based unsaturated polyester (1.672 g), styrene (0.836 g), and diphenoxybenzophenone (25.08 mg) were mixed evenly and poured into a mold, and cured for 40 seconds using a 300 nm UV curing machine to obtain a phosphonium-modified styrene-based unsaturated polyester resin.

[0082] Embodiment 8:

[0083] 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.

[0084] 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.

[0085] In a nitrogen atmosphere, an organic phosphine-modified unsaturated polyester (containing 3.948 mmol of phosphine groups) and 4-chloromethylstyrene (5.922 mmol) were dissolved in dimethyltetrahydrofuran and reacted at 60°C for 12 hours. After the reaction was completed, the solvent was removed, and the unsaturated polyester modified with phosphonium styrene was obtained by precipitation and drying.

[0086] The phosphonium-modified styrene-based unsaturated polyester (1.672 g), divinyl styrene (0.6688 g), and benzoin diethyl ether (23.41 mg) were mixed evenly and poured into a mold, and cured for 60 seconds using a 300 nm UV curing machine to obtain a phosphonium-modified styrene-based unsaturated polyester resin.

[0087] Flame retardant performance test

[0088] In order to verify the flame retardant performance, the phosphonium-containing styrene-based unsaturated polyester resins prepared in Examples 1-8 were tested according to the vertical burning test in the American standard UL94 flame retardant grade test standard.

[0089] Table 1

[0090]

[0091] 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.

[0092] From the test results in Table 1, it can be seen that the UL-94 of the phosphonium-containing styrene-based unsaturated polyester resins prepared in Examples 1-8 are all V-0.

[0093] 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 a phosphonium-modified styrene-based unsaturated polyester, characterized in that: The solidified material is a cross-linked polymer of a phosphonium-modified styrene-based unsaturated polyester and a reactive diluent; The phosphonium-modified styrene-based unsaturated polyester is a cross-linked polymer of an organic phosphine-modified unsaturated polyester and 4-chloromethylstyrene; Wherein, the organic phosphine-modified unsaturated polyester is an addition reaction product of unsaturated polyester and diphenylphosphine.

2. The cured product according to claim 1, characterized in that The active diluent is one or more of styrene, divinyl styrene, 4-acetoxy-3-methoxy styrene, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, butyl methacrylate, epoxylated soybean oil, glycidyl methacrylate, and 4-vinyl guaiacol glycidyl ether.

3. A method for preparing a cured product of a phosphonium-modified styrene-based unsaturated polyester, comprising: Under an inert atmosphere, an organic phosphine-modified unsaturated polyester in a solvent is reacted with 4-chloromethylstyrene at 40-80° C. to obtain a phosphonium-modified styrene-modified unsaturated polyester; In the presence of an initiator, the phosphonium-modified styrene-based unsaturated polyester is mixed with a reactive diluent and cured to obtain a cured product of the phosphonium-modified styrene-based unsaturated polyester; Wherein, the organic phosphine-modified unsaturated polyester is an addition reaction product of unsaturated polyester and diphenylphosphine.

4. The method according to claim 3, characterized in that The active diluent is one or more of styrene, divinyl styrene, 4-acetoxy-3-methoxy styrene, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, butyl methacrylate, epoxylated soybean oil, glycidyl methacrylate, and 4-vinyl guaiacol glycidyl ether.

5. The method according to any one of claims 3 to 4, characterized in that The mass ratio of the phosphonium styrene-modified unsaturated polyester to the active diluent is 10:(2-8).

6. The method according to any one of claims 3 to 4, characterized in that The molar ratio of the phosphine group of the organic phosphine-modified unsaturated polyester to the chlorine group of the 4-chloromethylstyrene is 1:(1.2-1.5).

7. The method according to any one of claims 3 to 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 any one of claims 3 to 4, characterized in that The solvent is one or more of chloroform, tetrahydrofuran, dimethyltetrahydrofuran and N,N-dimethylformamide.

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