Cured product of organophosphorus-modified unsaturated polyester and polyhalide and preparation method thereof

Abstract

The present application provides a cured product of an organophosphorus-modified unsaturated polyester and a polyhalide, and a preparation method thereof. The cured product is a crosslinked polymer of an organophosphorus-modified unsaturated polyester and a polyhalide. The cured product of the organophosphorus-modified unsaturated polyester and the polyhalide of the present invention has good flame retardancy and antibacterial properties.

Description

Technical Field

[0001] This application relates to the field of flame-retardant and antibacterial materials, and particularly to a cured product of an organophosphorus-modified unsaturated polyester and a polyhalide, and a preparation method thereof. Background Art

[0002] Unsaturated polyesters have excellent corrosion resistance, insulation, processability and other characteristics, and are widely used in the fields of aerospace, electrical appliances, transportation, etc. However, their inherent poor flame retardancy, the generation of toxic smoke during combustion, and extremely weak mechanical toughness still remain the biggest limiting conditions for unsaturated polyesters as high-performance engineering materials. Reactive flame retardants directly participate in the polymerization of unsaturated polyester resins as flame-retardant comonomers, so that the molecular chains of unsaturated polyester resins contain flame-retardant components, thereby realizing the flame retardancy of unsaturated polyester resins. Since the flame-retardant comonomer and the unsaturated polyester resin matrix are bonded by chemical bonds, the resulting composite material has better durability and less harmful effects. Phosphorus-based comonomers decompose to generate phosphorus-oxygen free radicals when heated, 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 matrix to dehydrate and form carbon, increasing the char yield, and playing a flame-retardant role in both the gas phase and the condensed phase.

[0003] When unsaturated polyesters are cured, reactive monomers are added. Reactive monomers not only act as reaction monomers but also have the function of 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, can burn the skin, and can cause physical discomfort in severe cases. With the increasingly strict environmental requirements, low-styrene and styrene-free resins have developed rapidly. Summary of the Invention

[0004] One aspect of this application provides a cured product of an organophosphorus-modified unsaturated polyester and a polyhalide.

[0005] The cured product provided by this application is a cross-linked polymer of an organophosphorus-modified unsaturated polyester and a polyhalide.

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

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

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

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

[0010] The method for preparing a cured product of an organophosphorus-modified unsaturated polyester and a polyhalide provided by the present application includes:

[0011] Mixing and curing the organophosphorus-modified unsaturated polyester and the polyhalide to obtain the cured product of the organophosphorus-modified unsaturated polyester and the polyhalide.

[0012] In one embodiment, the molar ratio of the phosphorus group of the organophosphorus-modified unsaturated polyester to the halogen group of the polyhalide is 1:(0.8 - 1.2).

[0013] In one embodiment, the organophosphorus-modified unsaturated polyester is a product formed by an addition reaction of an unsaturated polyester in a solvent with diphenylphosphine.

[0014] In one embodiment, the molar ratio of the double bond group of the unsaturated polyester to the phosphorus group of the diphenylphosphine is 1:(1.2 - 1.5).

[0015] In one embodiment, the polyhalide is one or more of hexanediol chloroacetate, propylene glycol chloroacetate, cetyl alcohol chloroacetate, phytic acid-based chloroacetate, ethylene glycol dichloroacetate, diisopropylamine dichloroacetate, chloro-2-phenyl-1,3-propylene glycol ester, chloro-2-ethyl-2-phenyl-1,3-propylene glycol acetate, 1,5-dimethyl 2-chloro-4-(2-chloro-2-phenylethyl) glutarate, 1,4-bis(4-chlorobutyl) terephthalic acid, 1,1-(1,4-phenylene) bis(2-chloroacetate).

[0016] In one embodiment, the solvent is one or more of chloroform, tetrahydrofuran, dimethyltetrahydrofuran.

[0017] The cured product of the organophosphorus-modified unsaturated polyester and the polyhalide of the present invention has good flame retardant properties and antibacterial properties. Description of the Drawings

[0018] Figure 1 The proton nuclear magnetic resonance spectrum of the unsaturated polyester prepared in Example 1 is shown;

[0019] Figure 2 The proton nuclear magnetic resonance spectrum of the organophosphorus-modified unsaturated polyester prepared in Example 1 is shown;

[0020] Figure 3a The physical picture of the cured product of the organophosphorus-modified unsaturated polyester and polyhalide prepared in Example 1 is shown;

[0021] Figure 3b The physical picture of the cured product of the organophosphorus-modified unsaturated polyester and polyhalide prepared in Example 2 is shown;

[0022] Among them, Figure 3a and Figure 3b The text in the background of is used to show the light transmittance of the sample. Detailed implementation manners

[0023] One aspect of the present application provides a cured product of an organophosphorus-modified unsaturated polyester and a polyhalide.

[0024] The cured product provided by the present application is a cross-linked polymer of an organophosphorus-modified unsaturated polyester and a polyhalide. The introduction of phosphorus and chlorine elements endows the cured product with good flame retardancy and antibacterial properties. At the same time, the styrene-free unsaturated polyester resin reduces the volatility and toxicity during the curing process of the unsaturated polyester.

[0025] In the present application, the organophosphorus-modified unsaturated polyester and the polyhalide undergo a quaternization reaction to crosslink and cure into a cross-linked polymer. The molecular structure of the quaternary phosphonium salt is relatively stable and does not react with general oxidizing and reducing agents, acids, and bases. The quaternary phosphonium salt can adsorb on the surface of negatively charged bacteria, diffuse through the cell wall, and bind to 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 larger than that of the nitrogen atom, making the electronegativity of phosphorus lower and the polarization effect stronger, and it is easier to adsorb on the cell membrane, with stronger bactericidal ability. Therefore, the introduction of organophosphorus endows the cured product with good flame retardancy and antibacterial properties.

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

[0027] In one embodiment, the polyhalide is one or more of hexanediol chloroacetate, propylene glycol chloroacetate, cetyl alcohol chloroacetate, phytic acid-based chloroacetate, ethylene glycol dichloroacetate, diisopropylamine dichloroacetate, chloro-2-phenyl-1,3-propylene ester, chloro-2-ethyl-2-phenyl-1,3-propylene acetate, 1,5-dimethyl 2-chloro-4-(2-chloro-2-phenylethyl) glutarate, 1,4-bis(4-chlorobutyl) terephthalic acid, 1,1-(1,4-phenylene) bis(2-chloroacetate).

[0028] In one embodiment, the organophosphorus-modified unsaturated polyester is an addition reaction product of the unsaturated polyester and the diphenylphosphine.

[0029] Another aspect of the present application provides a method for preparing a cured product of an organophosphorus-modified unsaturated polyester and a polyhalide.

[0030] The method for preparing a cured product of an organophosphorus-modified unsaturated polyester and a polyhalide provided by the present application includes:

[0031] Mixing and curing the organophosphorus-modified unsaturated polyester and the polyhalide to obtain the cured product of the organophosphorus-modified unsaturated polyester and the polyhalide.

[0032] In one embodiment, the molar ratio of the phosphorus group of the organophosphorus-modified unsaturated polyester to the halogen group of the polyhalide is 1:(0.8 - 1.2).

[0033] In one embodiment, the organophosphorus-modified unsaturated polyester is a product formed by an addition reaction of an unsaturated polyester and diphenylphosphine in a solvent.

[0034] Specifically, in an inert atmosphere, the unsaturated polyester and diphenylphosphine are reacted in a solvent at 50 - 90 °C. After the reaction is completed, the solvent is removed, and the organophosphorus-modified unsaturated polyester is obtained by precipitation and drying.

[0035] In one embodiment, the molar ratio of the double bond group of the unsaturated polyester to the phosphorus group of the diphenylphosphine is 1:(1.2 - 1.5).

[0036] In one embodiment, the polyhalide is one or more of hexanediol chloroacetate, propylene glycol chloroacetate, cetyl alcohol chloroacetate, phytic acid-based chloroacetate, ethylene glycol dichloroacetate, diisopropylamine dichloroacetate, chloro-2-phenyl-1,3-propylene ester, chloro-2-ethyl-2-phenyl -1,3-propylene acetate, 1,5-dimethyl 2-chloro-4-(2-chloro-2-phenylethyl) glutarate, 1,4-bis(4-chlorobutyl) terephthalic acid, 1,1-(1,4-phenylene) bis(2-chloroacetate).

[0037] In one embodiment, the solvent is one or more of chloroform, tetrahydrofuran, and dimethyltetrahydrofuran.

[0038] In one embodiment, the unsaturated polyester is obtained by the following method:

[0039] Reacting an unsaturated acid or anhydride, a dicarboxylic acid or anhydride, and a diol at 140 - 180°C in the presence of an esterification catalyst and a polymerization inhibitor under an inert atmosphere; then carrying out a polycondensation reaction at 140 - 180°C and 0.05 - 0.09 MPa in the presence of a polycondensation catalyst.

[0040] In one embodiment, the molar ratio of the total number of hydroxyl groups of the unsaturated acid or anhydride, the dicarboxylic acid or anhydride, and the diol to the total number of carboxyl groups is 1:1:1.

[0041] The formation reaction of the unsaturated polyester is mainly a dehydration polycondensation reaction of alcohol and acid, which is a reversible equilibrium stepwise reaction. Whether in an acidic, basic, or neutral environment, the ester bond can be broken, which means that the cured product of the organophosphorus-modified unsaturated polyester containing an ester bond and a polyhalide has application potential in terms of recycling.

[0042] In one embodiment, the unsaturated acid or anhydride is itaconic acid or itaconic anhydride.

[0043] In one embodiment, the dicarboxylic acid or anhydride is oxalic acid, succinic acid, adipic acid, sebacic acid, phthalic acid, o-phthalic acid, o-phthalic anhydride, m-phthalic acid, biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, chlorendic anhydride, or bromendic anhydride.

[0044] In one embodiment, the diol is 1,2-propanediol, 1,3-propanediol, ethylene glycol, 1,4-butanediol, pentanediol, 1,6-hexanediol, cyclohexanediol, dihexanediol, diethylene glycol, methylpropanediol, chloropropanediol, 4-chloro-1,3-butanediol, dibromoneopentyl glycol, 2,3-dibromopropanol, 4-bromo-1,2-butanediol, or dibromobutenediol.

[0045] 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.

[0046] In one embodiment, the polymerization inhibitor is hydroquinone, trimethylhydroquinone, p-tert-butylcatechol, tert-butylhydroquinone, tolylhydroquinone, p-benzoquinone, naphthoquinone, methylhydroquinone, phenothiazine, copper naphthenate, or copper chloride.

[0047] In one embodiment, the polycondensation catalyst is tin dibutyl dilaurate, antimony trioxide, antimony acetate, antimony glycolate, titanium dioxide, tetraisopropyl titanate, tetrabutyl titanate, titanium glycolate, tetraphenyl titanate, titanium acetylacetonate, germanium dioxide, stannous oxalate, dibutyltin oxide, stannous octanoate, tin acetylacetonate, aluminum phosphate, aluminum sulfate, aluminum nitrate or aluminum chloride.

[0048] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below 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. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts fall within the protection scope of the present invention.

[0049] In the following embodiments, the experimental methods are conventional methods unless otherwise specified; the reagents and materials can be obtained from commercial sources unless otherwise specified.

[0050] Example 1:

[0051] Put itaconic acid (33.64 mmol), phthalic anhydride (33.64 mmol) and 1,3-propanediol (67.28 mmol) into a four-necked flask, add p-toluenesulfonic acid (1%) and hydroquinone (0.02%), connect a water separator, a stirrer and a thermometer, and react at 180 °C for 2 hours in a nitrogen atmosphere until no more water is produced in the water separator, then the esterification reaction ends. Add tin dibutyl dilaurate (1%) and reduce the pressure to 0.05 MPa, and carry out a polycondensation reaction at 180 °C for 3 hours to obtain an unsaturated polyester. Figure 1 The nuclear magnetic resonance hydrogen spectrum of the prepared unsaturated polyester is shown.

[0052] In a nitrogen atmosphere, dissolve the unsaturated polyester (the number of moles of double bonds contained is 7.577 mmol) in dimethyltetrahydrofuran (10 ml), add diphenylphosphine (11.37 mmol), and stir the mixture at 90 °C for 8 hours until the reaction ends. After the reaction ends, remove the solvent, and obtain an organophosphorus-modified unsaturated polyester through precipitation and drying. Figure 2 The nuclear magnetic resonance hydrogen spectrum of the prepared organophosphorus-modified unsaturated polyester is shown.

[0053] Mix the organophosphorus-modified unsaturated polyester (the number of moles of phosphorus groups contained is 2.101 mmol) and hexanediol chloroacetate (1.261 mmol) evenly and pour them into a mold, and cure at 120 °C for 1 hour to obtain a cured product of the organophosphorus-modified unsaturated polyester and a polyhalide. Figure 3a The physical picture of the cured product of the prepared organophosphorus-modified unsaturated polyester and a polyhalide is shown.

[0054] Example 2:

[0055] Put itaconic acid (33.64 mmol), phthalic anhydride (33.64 mmol) and 1,2 - propanediol (67.28 mmol) into a four - necked flask, and add p - toluenesulfonic acid (0.5%) and hydroquinone (0.01%). Connect a water separator, a stirrer and a thermometer. Under a nitrogen atmosphere, react at 140 °C for 3 hours until no more water is produced in the water separator, then the esterification reaction ends. Add dibutyltin dilaurate (0.5%) and reduce the pressure to 0.09 MPa, and carry out a polycondensation reaction at 140 °C for 5 hours to obtain an unsaturated polyester.

[0056] Under a nitrogen atmosphere, dissolve the unsaturated polyester (the number of moles of double bonds contained is 7.577 mmol) in tetrahydrofuran (10 ml), add diphenylphosphine (9.092 mmol), and stir the mixture at 50 °C for 24 hours until the reaction ends. After the reaction ends, remove the solvent, and obtain the organophosphorus - modified unsaturated polyester through precipitation and drying.

[0057] Mix the organophosphorus - modified unsaturated polyester (the number of moles of phosphorus groups contained is 2.101 mmol) and hexanediol chloroacetate (0.8405 mmol) evenly and pour them into a mold, and cure at 30 °C for 24 hours to obtain a cured product of the organophosphorus - modified unsaturated polyester and the polyhalide. Figure 3b The physical picture of the cured product of the prepared organophosphorus - modified unsaturated polyester and the polyhalide is shown.

[0058] Example 3:

[0059] Put itaconic acid (33.64 mmol), terephthalic anhydride (33.64 mmol) and 1,4 - butanediol (67.28 mmol) into a four - necked flask, and add manganese acetate (0.5%) and trimethylhydroquinone (0.01%). Connect a water separator, a stirrer and a thermometer. Under a nitrogen atmosphere, react at 160 °C for 2 hours until no more water is produced in the water separator, then the esterification reaction ends. Add antimony trioxide (1%) and reduce the pressure to 0.05 MPa, and carry out a polycondensation reaction at 160 °C for 4 hours to obtain an unsaturated polyester.

[0060] Under a nitrogen atmosphere, dissolve the unsaturated polyester (the number of moles of double bonds contained is 7.577 mmol) in tetrahydrofuran (10 ml), add diphenylphosphine (11.37 mmol), and stir the mixture at 60 °C for 24 hours until the reaction ends. After the reaction ends, remove the solvent, and obtain the organophosphorus - modified unsaturated polyester through precipitation and drying.

[0061] The organophosphorus-modified unsaturated polyester (with the molar amount of phosphorus groups being 2.101 mmol) and propylene glycol chloroacetate (0.9455 mmol) were mixed evenly and then poured into a mold, and cured at 80 °C for 4 hours to obtain a cured product of the organophosphorus-modified unsaturated polyester and the polyhalide.

[0062] Example 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. A water separator, a stirrer and a thermometer were connected. In a nitrogen atmosphere, the reaction was carried out at 160 °C for 2 hours until no more water was produced in the water separator, and then the esterification reaction ended. Titanium dioxide (1%) was added and 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.

[0064] In a nitrogen atmosphere, the unsaturated polyester (with the molar amount of double bonds being 7.577 mmol) was dissolved in tetrahydrofuran (10 ml), and diphenylphosphine (11.37 mmol) was added. The mixture was stirred at 60 °C for 24 hours until the reaction ended. After the reaction ended, the solvent was removed, and the organophosphorus-modified unsaturated polyester was obtained through precipitation and drying.

[0065] The organophosphorus-modified unsaturated polyester (with the molar amount of phosphorus groups being 2.101 mmol) and 2-phenyl-1,3-propylene dichloride (0.9455 mmol) were mixed evenly and then poured into a mold, and cured at 80 °C for 4 hours to obtain a cured product of the organophosphorus-modified unsaturated polyester and the polyhalide.

[0066] Example 5:

[0067] 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. A water separator, a stirrer and a thermometer were connected. In a nitrogen atmosphere, the reaction was carried out at 160 °C for 2 hours until no more water was produced in the water separator, and then the esterification reaction ended. Antimony glycolate (1%) was added and 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, the unsaturated polyester (with the molar amount of double bonds being 7.577 mmol) was dissolved in dimethyltetrahydrofuran (10 ml), and diphenylphosphine (11.37 mmol) was added. The mixture was stirred at 60 °C for 24 hours until the reaction ended. After the reaction ended, the solvent was removed, and the organophosphorus-modified unsaturated polyester was obtained through precipitation and drying.

[0069] The organophosphorus-modified unsaturated polyester (with the molar amount of phosphorus groups being 2.101 mmol) and hexadecyl chloroacetate (0.9455 mmol) were mixed evenly and then poured into a mold, and cured at 80 °C for 4 hours to obtain a cured product of the organophosphorus-modified unsaturated polyester and the polyhalide.

[0070] Example 6:

[0071] Itaconic acid (33.64 mmol), sebacic acid (33.64 mmol) and methylpropanediol (67.28 mmol) were placed in a four-necked flask, and stannous oxalate (0.5%) and p-tolylhydroquinone (0.01%) were added. A water separator, a stirrer and a thermometer were connected. Under a nitrogen atmosphere, the reaction was carried out at 160 °C for 2 hours until no more water was produced in the water separator, and then the esterification reaction ended. Titanium acetylacetonate (1%) was added, and 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.

[0072] Under a nitrogen atmosphere, the unsaturated polyester (with the molar amount of double bonds being 7.577 mmol) was dissolved in dimethyltetrahydrofuran (10 ml), and diphenylphosphine (11.37 mmol) was added. The mixture was stirred at 60 °C for 24 hours until the reaction ended. After the reaction ended, the solvent was removed, and the organophosphorus-modified unsaturated polyester was obtained through precipitation and drying.

[0073] The organophosphorus-modified unsaturated polyester (with the molar amount of phosphorus groups being 2.101 mmol) and hexadecyl chloroacetate (0.9455 mmol) were mixed evenly and then poured into a mold, and cured at 100 °C for 2 hours to obtain a cured product of the organophosphorus-modified unsaturated polyester and the polyhalide.

[0074] Example 7:

[0075] Itaconic acid (33.64 mmol), 2,6-naphthalenedicarboxylic acid (33.64 mmol) and chloropropanediol (67.28 mmol) were placed in a four-necked flask, and titanium butoxide (0.5%) and p-benzoquinone (0.01%) were added. A water separator, a stirrer and a thermometer were connected. Under a nitrogen atmosphere, the reaction was carried out at 160 °C for 2 hours until no more water was produced in the water separator, and then the esterification reaction ended. Stannous oxalate (1%) was added, and 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.

[0076] Under a nitrogen atmosphere, the unsaturated polyester (with the molar amount of double bonds being 7.577 mmol) was dissolved in dimethyltetrahydrofuran (10 ml), and diphenylphosphine (11.37 mmol) was added. The mixture was stirred at 60 °C for 24 hours until the reaction ended. After the reaction ended, the solvent was removed, and the organophosphorus-modified unsaturated polyester was obtained through precipitation and drying.

[0077] The organophosphorus-modified unsaturated polyester (with the molar number of phosphorus groups being 2.101 mmol) and phytic acid-based chloroacetate (0.9455 mmol) were mixed evenly and then poured into a mold, and cured at 100 °C for 2 hours to obtain a cured product of the organophosphorus-modified unsaturated polyester and the polyhalide.

[0078] Example 8:

[0079] Itaconic acid (33.64 mmol), chlorendic 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. A water separator, a stirrer and a thermometer were connected. Under a nitrogen atmosphere, the reaction was carried out at 160 °C for 2 hours until no more water was produced in the water separator, and the esterification reaction ended. Dibutyltin oxide (1%) was added, and 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.

[0080] Under a nitrogen atmosphere, the unsaturated polyester (with the molar number of double bonds being 7.577 mmol) was dissolved in chloroform (10 ml), and diphenylphosphine (11.37 mmol) was added. The mixture was stirred at 60 °C for 24 hours until the reaction ended. After the reaction ended, the solvent was removed, and the organophosphorus-modified unsaturated polyester was obtained through precipitation and drying.

[0081] The organophosphorus-modified unsaturated polyester (with the molar number of phosphorus groups being 2.101 mmol) and 1,1-(1,4-phenylene)bis(2-chloroacetate) (0.9455 mmol) were mixed evenly and then poured into a mold, and cured at 100 °C for 2 hours to obtain a cured product of the organophosphorus-modified unsaturated polyester and the polyhalide.

[0082] Example 9:

[0083] Itaconic acid (33.64 mmol), chlorendic anhydride (33.64 mmol) and 2,3-dibromobutenediol (67.28 mmol) were placed in a four-necked flask, and zinc acetate (0.5%) and tert-butylhydroquinone (0.01%) were added. A water separator, a stirrer and a thermometer were connected. Under a nitrogen atmosphere, the reaction was carried out at 160 °C for 2 hours until no more water was produced in the water separator, and the esterification reaction ended. Tetraphenyl titanate (1%) was added, and 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.

[0084] Under a nitrogen atmosphere, the unsaturated polyester (with the molar number of double bonds being 7.577 mmol) was dissolved in chloroform (10 ml), and diphenylphosphine (11.37 mmol) was added. The mixture was stirred at 60 °C for 24 hours until the reaction ended. After the reaction ended, the solvent was removed, and the organophosphorus-modified unsaturated polyester was obtained through precipitation and drying.

[0085] The organophosphorus-modified unsaturated polyester (the number of moles of phosphorus groups contained is 2.101 mmol) and diisopropylamine dichloroacetate (0.9455 mmol) were mixed evenly and then poured into a mold, and cured at 80 °C for 4 hours to obtain a cured product of the organophosphorus-modified unsaturated polyester and the polyhalide.

[0086] Flame retardancy test

[0087] To verify the flame retardancy, the cured products of the organophosphorus-modified unsaturated polyester and the polyhalide prepared in Examples 1-9 were tested according to the vertical burning test in the UL94 flame retardant rating test standard of the American Standard.

[0088] Table 1

[0089]

[0090] 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 burning material dripping or the dripping material cannot ignite absorbent cotton during the test.

[0091] From the test results in Table 1, it can be seen that the UL-94 of the cured products of the organophosphorus-modified unsaturated polyester and the polyhalide prepared in Examples 1-9 are all V-0.

[0092] 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 conflict. 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 replacements, improvements, etc. made within the spirit and principle of this application shall be included within 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 unsaturated polyester modified by an organic phosphine and a polyhalide; The organic phosphine-modified unsaturated polyester is an addition reaction product of an unsaturated polyester and diphenylphosphine; The unsaturated polyester is obtained by reacting an unsaturated acid or anhydride, a dicarboxylic acid or anhydride, and a diol at 140-180° C. in an inert atmosphere in the presence of an esterification catalyst and a polymerization inhibitor; and then performing a polycondensation reaction at 140-180° C. and 0.05-0.09 MPa in the presence of a polycondensation catalyst; The unsaturated acid or anhydride is itaconic acid or itaconic anhydride; The dicarboxylic acid or anhydride is oxalic acid, succinic acid, adipic acid, sebacic acid, phthalic acid, phthalic anhydride, isophthalic acid, biphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, chloro-bridged anhydride, or bromo-bridged anhydride; The diols are 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol, 1,4-butanediol, pentanediol, 1,6-hexanediol, cyclohexanediol, dihexanediol, diethylene glycol, methyl propanediol, 3-chloropropylene glycol, 4-chloro-1,3-butanediol, dibromoneopentyl glycol, 2,3-dibromopropanol, 4-bromo-1,2-butanediol, and dibromobutylene glycol.

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 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).

4. A method for preparing a solid product of an organic phosphine-modified unsaturated polyester and a polyhalide, comprising: Mixing and curing an organic phosphine-modified unsaturated polyester and a polyhalide to obtain a cured product of the organic phosphine-modified unsaturated polyester and the polyhalide; The organic phosphine-modified unsaturated polyester is a product generated by an addition reaction between an unsaturated polyester in a solvent and diphenylphosphine; The unsaturated polyester is obtained by reacting an unsaturated acid or anhydride, a dicarboxylic acid or anhydride, and a diol at 140-180° C. in an inert atmosphere in the presence of an esterification catalyst and a polymerization inhibitor; and then performing a polycondensation reaction at 140-180° C. and 0.05-0.09 MPa in the presence of a polycondensation catalyst; The unsaturated acid or anhydride is itaconic acid or itaconic anhydride; The dicarboxylic acid or anhydride is oxalic acid, succinic acid, adipic acid, sebacic acid, phthalic acid, phthalic anhydride, isophthalic acid, biphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, chloro-bridged anhydride, or bromo-bridged anhydride; The diols are 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol, 1,4-butanediol, pentanediol, 1,6-hexanediol, cyclohexanediol, dihexanediol, diethylene glycol, methyl propanediol, 3-chloropropylene glycol, 4-chloro-1,3-butanediol, dibromoneopentyl glycol, 2,3-dibromopropanol, 4-bromo-1,2-butanediol, and dibromobutylene glycol.

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

6. The method according to claim 4 or 5, 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).

7. The method according to claim 4 or 5, 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).

8. The method according to claim 4 or 5, characterized in that: The solvent is one or more of chloroform, tetrahydrofuran and dimethyltetrahydrofuran.

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