Organic phosphonate containing olefin structure as well as preparation method and application of organic phosphonate
By using organic phosphonates containing olefin structure in polymer materials, the problems of high pollution and high toxicity in the synthesis of polymer flammable and flame retardant are solved, and good flame retardant performance and mechanical and electrical properties are achieved at low additive amounts. Retained, expanding the scope of application.
Patent Information
- Application Number
- CN202411315159.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-20
- Publication Date
- 2024-12-27
AI Technical Summary
Existing polymer materials are flammable, and existing flame retardants use high-pollution, highly toxic substances or lead to a decrease in thermal stability during the synthesis process.
Using an olefin structure, the organic phosphonate with a dihydrocarbonylphosphinic acid/dihydrocarbonylphosphinate reacts with a halogen element under ultraviolet light, and then reacts with an excess of strong alkali to neutralize and purify, to obtain a carbon-carbon double bond Organic phosphonates and used to synthesize flame retardants.
This method avoids the use of high-pollution and high-toxic substances, provides good flame retardant properties, and retains the mechanical and electrical properties of the material at low addition amounts, while widening the application scenarios.
Smart Images
Figure CN119192230A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of flame retardants, and in particular to an organic phosphonate containing an olefin structure and a preparation method and application thereof. Background Art
[0002] Organic polymers are a type of material that is used in large quantities in the current material market. Organic compounds are generally divided into rubbers with lower hardness and greater elongation, plastics with higher hardness and greater strength, as well as synthetic fibers, coatings and other materials. However, polymer molecules contain a large amount of C, H, O, and N elements, which are flammable materials and will continue to burn when on fire, posing a great risk to people's lives and property safety, especially for electronic appliances, wires and cables and other electrical-related polymers. Once burned, they will spread rapidly. At the same time, with the stricter and halogen-free flame retardant standards of various countries, regions and some companies such as REACH regulations, California Act 65, and Sony flame retardant standards, higher requirements have been put forward for the performance of flame retardants. Summary of the invention
[0003] The purpose of the present invention is to solve the deficiencies of the above-mentioned technology and to provide an organic phosphonate containing an olefin structure and a preparation method and application thereof.
[0004] To this end, the present invention provides a method for preparing an organic phosphonate containing an olefin structure, comprising the following steps:
[0005] (1) reacting a dialkylphosphinic acid / dialkylphosphinic salt solution with a halogen element under ultraviolet light to obtain a halogenated dialkylphosphinic acid / halogenated dialkylphosphinic salt;
[0006] The reaction formula is:
[0007]
[0008] Alternatively, a dialkylphosphinic acid / dialkylphosphinic acid salt solution is reacted with a hydrogen halide or a halogen salt under the action of an oxidant and ultraviolet light to obtain a halogenated dialkylphosphinic acid / halogenated dialkylphosphinic acid salt;
[0009] The reaction formula is:
[0010]
[0011] (2) dissolving the halogenated dialkyl phosphinic acid / halogenated dialkyl phosphinic acid salt obtained by the reaction in alcohol, adding an excess of a strong base and heating to boiling reflux until the reaction is completed, cooling after the reaction is completed, neutralizing and purifying to obtain the organic phosphonate containing an olefin structure;
[0012] The reaction formula is:
[0013]
[0014] Alternatively, the halogenated dialkyl phosphinate obtained by the reaction is heated to boiling reflux with an excess of a strong base, and after the reaction is completed and neutralized to neutrality, a strong acid containing an equimolar amount of hydrogen ions to the halogenated dialkyl phosphinate is added, followed by purification, and then a catalyst is added to remove hydroxyl groups at 100-300° C., and then the temperature is lowered to below 100° C. for neutralization and purification to obtain the organic phosphonate containing an olefin structure.
[0015] The reaction formula is:
[0016]
[0017]
[0018] A method for preparing an organic phosphonate containing an olefin structure comprises the following steps:
[0019] (1) reacting a dialkyl phosphinate solution with a halogen element or a hydrogen halide or a halogen salt in the presence of an oxidant and ultraviolet light to obtain a halogenated dialkyl phosphinate;
[0020] The reaction formula is:
[0021]
[0022] (2) dissolving the halogenated dialkyl phosphinate obtained by the reaction in alcohol, adding an excess of a strong base and heating to boiling reflux until the reaction is completed, neutralizing and purifying after the reaction to obtain the organic phosphonate containing an olefin structure, then adding a strong alkaline solution for azeotropic hydrolysis, and separating and purifying to obtain the organic phosphonate containing an olefin structure.
[0023] The reaction formula is:
[0024]
[0025]
[0026] Preferably, the halogen element in step (1) is chlorine or bromine, and the halogen salt is any one of the water-soluble metal salts of chlorine or bromine.
[0027] Preferably, the oxidant in step (1) is any one of potassium permanganate, hydrogen peroxide, hypochlorous acid, sodium hypochlorite, potassium hypochlorite, sodium perchlorate, potassium perchlorate, perchloric acid, and dichromic acid.
[0028] Preferably, the alcohol in step (2) is any one of methanol, ethanol, propanol, isopropanol, n-butanol and isobutanol; the catalyst is a dehydration catalyst, which is any one of concentrated sulfuric acid, phosphorus pentoxide, phosphoric acid, aluminum oxide and aluminum chloride; and the strong base is any one of the hydroxides of Group IA or Group IIA metal elements.
[0029] Preferably, the molar ratio of the halogen in the halogen element, hydrogen halide or halogen salt to the phosphorus in the dialkylphosphinic acid / dialkylphosphinic acid salt / dialkylphosphinic acid ester solution is 1:1-1:6.
[0030] Preferably, the reaction time of step (1) is 0.5-24 hours, and in step (2), the reflux time with alcohol and strong base is 1-24 hours, the hydrolysis reaction time with strong alkaline aqueous solution is 1-24 hours, and the dehydration reaction time with catalyst is 1-24 hours.
[0031] An organic phosphonate containing an olefin structure is prepared by the method.
[0032] Preferably, the organic phosphonate containing an olefin structure has the following structure:
[0033]
[0034] In the structural formula I, R1 and R2 may be the same or different, and R1 and R2 are selected from a C1-C18 aliphatic olefin carbon chain structure or ring structure or a C8-C18 aromatic olefin structure; m is an integer of 1-2, and M is a Group IA or Group IIA metal element.
[0035] Preferably, R1 and R2 are selected from any two of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, vinyl, propenyl, allyl, (1-vinyl) 1'-ethyl, 2-cyclopentenyl, 3-cyclopentenyl, (1-methyl) allyl, 2-cyclohexenyl, and 3-cyclohexenyl, and not both are saturated groups.
[0036] Preferably, M is selected from any one of lithium, sodium, potassium, beryllium, magnesium and calcium.
[0037] Preferably, when dialkyl hypophosphorous acid or dialkyl hypophosphite is used as the initiator, the dialkyl phosphinic acid or dialkyl hypophosphite is selected from any one of diethyl phosphinic acid, methyl ethyl phosphinic acid, methyl propyl phosphinic acid, methyl isopropyl phosphinic acid, methyl n-butyl hypophosphorous acid, methyl cyclohexyl phosphinic acid, methyl phenylethyl phosphinic acid, ethyl propyl phosphinic acid, ethyl isopropyl phosphinic acid, ethyl n-butyl phosphinic acid, ethyl cyclohexyl phosphinic acid, ethyl cyclopentyl phosphinic acid, ethyl (1-phenyl-propyl) phosphinic acid, propyl butyl phosphinic acid, propyl phenyl phosphinic acid, propyl phenylethyl phosphinic acid, propyl cyclohexyl phosphinic acid, and propyl cyclopentyl phosphinic acid, and the dialkyl hypophosphite is selected from their IA or IIA Group metal salts.
[0038] Preferably, when using dialkyl phosphinate as initiator, the dialkyl phosphinate is selected from methyl ethyl phosphinate, methyl ethyl phosphinate ethyl, methyl ethyl phosphinate propyl, methyl ethyl phosphinate butyl, methyl ethyl phosphinate pentyl, diethyl phosphinate methyl, diethyl phosphinate propyl, diethyl phosphinate butyl, diethyl phosphinate phenyl, diethyl phosphinate phenyl, diethyl phosphinate benzyl, diethyl phosphinate naphthyl, methyl propyl phosphinate methyl, methyl propyl phosphinate ethyl, methyl propyl phosphinate butyl, dipropyl phosphinate methyl, dipropyl phosphinate ethyl, dipropyl phosphinate butyl, dipropyl phosphinate pentyl, dipropyl phosphinate cyclopentyl, dipropyl phosphinate cyclohexyl, dipropyl phosphinate phenyl, dibutyl phosphinate methyl, dibutyl phosphinate ethyl.
[0039] The above-mentioned organic phosphonates containing olefin structures can be used to synthesize organic phosphate flame retardants containing olefin structures, and can also be used to synthesize organic phosphonates in polymer form; they can also be added as reactive flame retardants to polymers containing double bonds, or added as reactive units during the polymerization process and polymerized, participating in the reaction as reactive units while providing flame retardancy.
[0040] Preferably, the organic phosphonate containing an olefin structure directly reacts with a metal cation or first forms an acid and then reacts with melamine to prepare an organic phosphate flame retardant, and the obtained organic phosphate flame retardant containing an olefin structure is a salt containing a metal element of Group IIIB to Group IIIA or a melamine salt.
[0041] More preferably, the metal element of Group IIIB to Group IIIA used as the flame retardant is any one of zinc, titanium, iron, copper, silver, gold, platinum, aluminum, germanium, manganese, scandium, and vanadium.
[0042] Preferably, the polymer selected is polyethylene terephthalate (PET), polyamide (PA), polybutylene terephthalate (PBT), polycarbonate (PC), thermoplastic elastomer (TPR), polyurethane (PU), epoxy resin, unsaturated polyester resin, silicone resin, natural rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, and silicone rubber.
[0043] The present invention provides an organic phosphonate containing an olefin structure and a preparation method and application thereof, which have the following beneficial effects:
[0044] (1) Compared with the organic phosphonates with olefin structures synthesized in the prior art, either phosphorus trichloride is used as an initiator or hypophosphite and diene are used as initiators, and the synthesis is carried out under the action of an initiator. When phosphorus trichloride is used as an initiator, due to the high toxicity of phosphorus trichloride, there is a greater risk of damage to the environment; and when diene and sodium hypophosphite are reacted, diene self-polymerization is easily caused, resulting in the inability to completely react the active hydrogen on the hypophosphite, resulting in a decrease in thermal stability. The organic phosphonate containing a carbon-carbon double bond synthesized by the present invention is not only simple in structure and convenient to synthesize, but also avoids the use of highly polluting and highly toxic substances, and the synthetic structure is clear, and the active hydrogen on phosphorus will not be left to affect the temperature resistance.
[0045] (2) The organic phosphonate containing carbon-carbon double bonds synthesized by the present invention can react with the resin to directly connect the entire flame retardant molecule into the resin molecular chain, and provide better flame retardant properties when added in a low amount. In addition, due to the low addition amount, the resin also has a higher retention rate of mechanical properties and electrical properties. The organic phosphonate containing carbon-carbon double bonds synthesized by the present invention can also undergo copolymerization with active olefins containing double bonds such as styrene, acrylic acid, and maleic anhydride, thereby broadening the application scenarios of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS
[0046] Figure 1 It is the infrared image of ethyl vinyl phosphinate prepared by the present invention. DETAILED DESCRIPTION
[0047] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments to help understand the content of the present invention. The methods used in the present invention are all conventional methods unless otherwise specified; the raw materials and devices used are all conventional commercial products unless otherwise specified.
[0048] Example 1
[0049] Take 121g of diethylphosphinic acid (1mol) and dissolve it in 1L of deionized water, then add 79g (0.5mol) of potassium permanganate and 238g (2mol) of potassium bromide, react under ultraviolet light at 0-5°C for 24 hours, after the reaction, add 320g of potassium hydroxide, then raise the temperature to 100°C and reflux for 24 hours, after the reflux, neutralize the solution and add 0.5mol of sulfuric acid, purify to obtain di(hydroxyethyl)phosphinic acid, mix with 1mol of P2O5, heat to 300°C and dehydrate under nitrogen atmosphere, then lower the temperature to room temperature, add 1L of deionized water, neutralize with potassium hydroxide, and purify to obtain potassium divinylphosphinate.
[0050] Example 2
[0051] Take 1 mol of methyl ethyl phosphinate and dissolve it in 1L of deionized water, then add 2 mol of potassium bromide, and dropwise add 380g of 20% hydrogen peroxide solution (2 mol) at 0-5°C and turn on ultraviolet light illumination at the same time. After the dropwise addition is completed, continue to stir and react for 20 hours. After the reaction is completed, add 320g of potassium hydroxide, and raise the temperature to 50°C and reflux for 15 hours. After the reflux is completed, the solution is neutralized and purified, and then the product is added to potassium methoxide-methanol solution and boiled and refluxed for 15 hours to obtain potassium methyl vinyl phosphinate after purification.
[0052] Example 3
[0053] Take 136g of diethyl methyl hypophosphite (1mol) and dissolve it in 1L of deionized water, then add 58.5g of sodium chloride (1mol), add 200g (1mol) of 10% hydrogen peroxide at 25°C, and react for 12 hours under ultraviolet light. After the reaction is completed, rotary evaporation and drying are performed to obtain chloroethyl (ethyl) methyl hypophosphite, and then 500g of 20% sodium hydroxide methanol solution is added to azeotrope for 8 hours, then methanol is distilled off, and 500g of 20% sodium hydroxide aqueous solution is added to azeotrope for 6 hours. After the reaction is completed, it is neutralized with sulfuric acid to neutrality, and purified to obtain sodium vinyl ethyl phosphinate.
[0054] Example 4
[0055] 1 mol of sodium dipropylphosphinate was dissolved in 1 L of deionized water, and then 1 mol of hydrogen bromide was added, and then 1 mol of sodium hypochlorite was added dropwise to the solution, and the mixture was reacted for 16 hours under ultraviolet light. After the reaction was completed, the mixture was dried to remove water and impurities, and then 500 g of 20% sodium hydroxide methanol solution was added to azeotrope for 4 hours, and then the methanol was evaporated, neutralized with sulfuric acid to neutrality, and purified to obtain sodium vinylethylphosphinate.
[0056] Example 5
[0057] 1 mol of methylethyl phosphinate was dissolved in 2L of deionized water, and then 1 mol of potassium chloride was added, and then a solution of 1 mol of sodium hypochlorite dissolved in 1L of water was added dropwise, and the mixture was reacted for 1 hour under ultraviolet light. After the reaction was completed, the mixture was dried to remove water and impurities, and then 500g of 20% sodium hydroxide methanol solution was added to azeotrope for 1 hour, and then the methanol was distilled off, and then 500g of 20% sodium hydroxide aqueous solution was added to azeotrope for 1 hour. After the reaction was completed, the mixture was neutralized with sulfuric acid to neutrality, and purified to obtain sodium methyl vinyl phosphinate.
[0058] Example 6
[0059] 1 mol of butyl methylethylphosphinate was dissolved in 2 L of deionized water, and then 1 mol of chlorine was slowly introduced, and ultraviolet light was turned on at the same time. When the yellow-green color of the solution disappeared, the reaction was completed. After the reaction was completed, the solution was dried to remove water and impurities, and then 500 g of 20% sodium hydroxide methanol solution was added to azeotrope for 1 hour, and then the methanol was distilled off, and 500 g of 20% sodium hydroxide aqueous solution was added to azeotrope for 1 hour. After the reaction was completed, it was neutralized with sulfuric acid to neutrality, and purified to obtain sodium methylvinylphosphinate;
[0060] Example 7
[0061] 1 mol of ethylphenylphosphinate was dissolved in 2L of deionized water, and then 1 mol of potassium chloride was added, and then a solution of 1 mol of sodium hypochlorite dissolved in 1L of water was added dropwise, and the mixture was reacted for 0.5 hour under ultraviolet light. After the reaction was completed, the mixture was dried to remove water and impurities, and then 500 g of 20% sodium hydroxide methanol solution was added to azeotrope for 4 hours, and then the methanol was distilled off, and then 500 g of 20% sodium hydroxide aqueous solution was added to azeotrope for 3 hours. After the reaction was completed, the mixture was neutralized with sulfuric acid to neutrality, and purified to obtain sodium vinylphenylphosphinate.
[0062] Example 8
[0063] Take 1 mol of butylphenylphosphinic acid and dissolve it in 2L of deionized water, then add 0.5 mol of potassium bromide and 1.25 mol of sulfuric acid, and then add 2 mol of hydrogen peroxide dropwise, and use ultraviolet light to accelerate the reaction. The reaction is carried out for 6 hours. After the reaction is completed, it is dried to remove water and impurities, and then 500g of 20% sodium hydroxide aqueous solution is added for azeotropic 8 hours. After neutralization, 0.5 mol of sulfuric acid is added and purified to obtain butylhydroxyphenylphosphinic acid, which is then mixed with 1 mol of P2O5, heated for dehydration, and then P2O5 is removed by nitrogen protection, and neutralized to obtain (2-alkenyl)-1-butylphenylphosphinic acid potassium.
[0064] like Figure 1 Shown is an infrared image of vinyl ethyl phosphinate prepared by the present invention.
[0065] Example 9 Group
[0066] 1 mol of the sodium vinyl ethyl hypophosphite prepared in Example 3 was added to 500 ml of chloroform and stirred to form a suspension, followed by dropwise addition of thionyl chloride, and reacted at 40° C. for 6 hours to obtain vinyl ethyl hypophosphite chloride, which was then reacted with methanol at 60° C. to produce vinyl ethyl hypophosphite methyl ester, and then 1 mol of vinyl ethyl hypophosphite methyl ester was reacted with 10-3 mol of ammonium persulfate at 60° C. for 4 hours, and then the temperature was raised to 80° C. and the reaction was continued for 2 hours to obtain a flame retardant poly (ethyl methyl phosphate) ethylene, and the flame retardant was added to 30% GF enhanced PBT system at 15% for blending, extrusion and granulation to obtain enhanced flame retardant PBT, and then injection molding was performed to obtain standard specimens to test their mechanical properties and flame retardant properties, as shown in Table 1;
[0067] Example 10 Group
[0068] The implementation process was the same as that of Example 9 except that 1 mol of potassium (2-alkenyl)-1-butylphenylphosphinate prepared in Example 8 was used instead of 1 mol of sodium vinylethylphosphinate. The mechanical properties are shown in Table 1.
[0069] Example 11 Group
[0070] The implementation process is the same as that of Example 9 except that 1 mol of sodium vinyl phenyl phosphinate prepared in Example 7 is substituted for 1 mol of sodium vinyl ethyl phosphinate. The mechanical properties and flame retardant properties are shown in Table 1.
[0071] Example 12 Group
[0072] The vinyl ethyl sodium hypophosphite prepared in Example 3 was mixed with an unsaturated polyester resin in a ratio of 1:10, and then a proper amount of curing agent was added. After degassing, the mixture was heated to a curing temperature and cured to obtain a flame-retardant polyester resin. The mechanical properties and flame-retardant properties of the resin are shown in Table 1.
[0073] Example 13 Group
[0074] 1 mol of vinyl ethyl sodium hypophosphite prepared in Example 3 was dissolved in 1 L of water, and then reacted with 10% aluminum sulfate at 80°C to obtain a flame retardant vinyl ethyl aluminum phosphonate. Vinyl ethyl aluminum phosphate and butadiene rubber were added in a ratio of 1:4, and then 20 parts of white carbon black, 10 parts of operating oil, and 5 parts of N330 carbon black were added, and then the rubber was mixed with an internal mixer and an open mixer respectively, and then the rubber was fully cooled and further mixed with an accelerator, sulfur, and an antioxidant to obtain a mixed rubber, and then the mixed rubber was vulcanized to obtain a flame retardant vulcanized butadiene rubber, and its mechanical properties and flame retardant properties are shown in Table 1;
[0075] Comparative Example 1
[0076] 15% of diethyl aluminum hypophosphite was added to the 30% GF reinforced PBT system for blending, extrusion and granulation to obtain reinforced flame retardant PBT, and then injection molding was performed to obtain standard specimens to test their mechanical properties and flame retardant properties, as shown in Table 1;
[0077] Comparative Example 2
[0078] 18% of diethyl aluminum hypophosphite was added to the 30% GF reinforced PBT system for blending, extrusion and granulation to obtain reinforced flame retardant PBT, and then injection molding was performed to obtain standard specimens to test their mechanical properties and flame retardant properties, as shown in Table 1;
[0079] Comparative Example 3
[0080] 12% of diethyl aluminum hypophosphite and 4% of polyphosphate melamine salt were added to the 30% GF reinforced PBT system for blending, extrusion and granulation to obtain reinforced flame retardant PBT, and then injection molding was performed to obtain standard specimens to test their mechanical properties and flame retardant properties, as shown in Table 1;
[0081] Comparative Example 4
[0082] Aluminum diethylphosphinate and butadiene rubber were added in a ratio of 1:4, and then 20 parts of white carbon black, 10 parts of operating oil, and 5 parts of N330 carbon black were added, and then the rubber was mixed with an internal mixer and an open mixer respectively. After the rubber was fully cooled, an accelerator, sulfur, and an antioxidant were added to further mix the rubber to obtain a mixed rubber. The mixed rubber was then vulcanized to obtain a flame-retardant vulcanized butadiene rubber, and its mechanical properties and flame retardant properties are shown in Table 1.
[0083] The experimental performance comparison is as follows:
[0084] Table 1
[0085]
[0086]
[0087] It can be seen from the examples 9-13 and the comparative examples 1-4 that the flame retardant synthesized from the organic phosphonate containing olefin structure, especially the polymeric organic phosphorus flame retardant, can provide a certain toughening effect in addition to the flame retardant effect on the resin, and can also have anti-precipitation property, and can pass the double 85@176h test. At the same time, compared with the traditional diethyl aluminum hypophosphite flame retardant, it has higher flame retardancy at the same addition amount, and its monomer, due to the double bond, can react with the double bond of the unsaturated polyester resin and the double bond in the rubber containing the double bond to form a three-dimensional network structure and provide flame retardancy, which are the properties that the traditional phosphorus flame retardant diethyl hypophosphite and other traditional flame retardants do not have.
[0088] In summary, the organic phosphonate containing carbon-carbon double bonds synthesized by the present invention not only has a simple structure and is convenient to synthesize, but also avoids the use of highly polluting and highly toxic substances, and has a clear synthetic structure, and will not cause residual active hydrogen on phosphorus to affect the heat resistance. At the same time, the organic phosphonate containing carbon-carbon double bonds synthesized by the present invention can react with resins, and provide better flame retardant properties when the addition amount is low, and due to the low addition amount, the resin also has a higher retention rate of mechanical properties and electrical properties; the organic phosphonate containing carbon-carbon double bonds synthesized by the present invention can also be copolymerized with active olefins containing double bonds such as styrene, acrylic acid, maleic anhydride, etc., which broadens the application scenarios of the present invention.
[0089] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement modes and shall be included in the protection of the present invention.
Claims
1. A method for preparing an organic phosphonate containing an olefin structure, characterized in that: The following steps are involved: (1) reacting a dialkylphosphinic acid / dialkylphosphinic salt solution with a halogen element under ultraviolet light to obtain a halogenated dialkylphosphinic acid / halogenated dialkylphosphinic salt; Alternatively, a dialkylphosphinic acid / dialkylphosphinic acid salt solution is reacted with a hydrogen halide or a halogen salt under the action of an oxidant and ultraviolet light to obtain a halogenated dialkylphosphinic acid / halogenated dialkylphosphinic acid salt; (2) dissolving the halogenated dialkyl phosphinic acid / halogenated dialkyl phosphinic acid salt obtained by the reaction in alcohol, adding an excess of a strong base and heating to boiling reflux until the reaction is completed, and neutralizing and purifying after the reaction is completed and cooling to obtain the organic phosphonate containing an olefin structure; Alternatively, the halogenated dialkyl phosphinate obtained by the reaction is heated to boiling reflux with an excess of a strong base, and after the reaction is completed and neutralized to neutrality, a strong acid containing an equimolar amount of hydrogen ions to the halogenated dialkyl phosphinate is added, followed by purification, and then a catalyst is added to remove hydroxyl groups at 100-300° C., and then the temperature is lowered to below 100° C. for neutralization and purification to obtain the organic phosphonate containing an olefin structure.
2. A method for preparing an organic phosphonate containing an olefin structure, characterized in that: The following steps are involved: (1) reacting a dialkyl phosphinate solution with a halogen element or a hydrogen halide or a halogen salt in the presence of an oxidant and ultraviolet light to obtain a halogenated dialkyl phosphinate; (2) dissolving the halogenated dialkyl phosphinate obtained by the reaction in alcohol, adding an excess of a strong base and heating to boiling reflux until the reaction is completed, neutralizing and purifying after the reaction to obtain the organic phosphonate containing an olefin structure, then adding a strong alkaline solution for azeotropic hydrolysis, and separating and purifying to obtain the organic phosphonate containing an olefin structure.
3. The method for preparing an organic phosphonate containing an olefin structure according to claim 1 or 2, characterized in that: In step (1), the halogen element is chlorine or bromine, and the halogen salt is any one of the water-soluble metal salts of chlorine or bromine.
4. The method for preparing an organic phosphonate containing an olefin structure according to claim 1 or 2, characterized in that: The oxidant in step (1) is any one of potassium permanganate, hydrogen peroxide, hypochlorous acid, sodium hypochlorite, potassium hypochlorite, sodium perchlorate, potassium perchlorate, perchloric acid and dichromic acid.
5. The method for preparing an organic phosphonate containing an olefin structure according to claim 1 or 2, characterized in that: The alcohol in step (2) is any one of methanol, ethanol, propanol, isopropanol, n-butanol and isobutanol; the catalyst is a dehydration catalyst, which is any one of concentrated sulfuric acid, phosphorus pentoxide, phosphoric acid, aluminum oxide and aluminum chloride; the strong base is any one of the hydroxides of Group IA or Group IA metal elements.
6. The method for preparing an organic phosphonate containing an olefin structure according to claim 1 or 2, characterized in that: The molar ratio of the halogen in the halogen element, hydrogen halide or halogen salt to the phosphorus in the dialkylphosphinic acid / dialkylphosphinic acid salt / dialkylphosphinic acid ester solution is 1:1-1:
6.
7. The method for preparing an organic phosphonate containing an olefin structure according to claim 1 or 2, characterized in that: The reaction time of step (1) is 0.5-24 hours. In step (2), the reflux time with alcohol and strong base is 1-24 hours, the hydrolysis reaction time with strong alkaline aqueous solution is 1-24 hours, and the dehydration reaction time with catalyst is 1-24 hours.
8. An organic phosphonate containing an olefin structure, characterized in that: The organic phosphonate containing an olefin structure is prepared by the method according to any one of claims 1 to 7.
9. The organic phosphonate containing an olefin structure according to claim 8, characterized in that: The organic phosphonate containing an olefin structure has the following structure: In the structural formula I, R1 and R2 may be the same or different, and R1 and R2 are selected from a C1-C18 aliphatic olefin carbon chain structure or ring structure or a C8-C18 aromatic olefin structure; m is an integer of 1-2, and M is a Group IA or Group IIA metal element.
10. An application of an organic phosphonate containing an olefin structure, characterized in that: The organic phosphonate containing an olefin structure as described in any one of claims 1 to 9 can be used to synthesize an organic phosphate flame retardant containing an olefin structure, and can also be used to synthesize an organic phosphonate in polymer form; it can also be added as a reactive flame retardant to a polymer containing a double bond, or added as a reactive unit during the polymerization process and polymerized, participating in the reaction as a reactive unit while providing flame retardancy.