CN116217620A - Phosphorus-containing porphyrin and preparation method and application thereof - Google Patents

Phosphorus-containing porphyrin and preparation method and application thereof Download PDF

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CN116217620A
CN116217620A CN202310036604.0A CN202310036604A CN116217620A CN 116217620 A CN116217620 A CN 116217620A CN 202310036604 A CN202310036604 A CN 202310036604A CN 116217620 A CN116217620 A CN 116217620A
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phosphorus
containing porphyrin
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杨伟
周宇
朱三娥
卫春祥
鲁红典
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Hefei University
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    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
    • C07F9/65616—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings containing the ring system having three or more than three double bonds between ring members or between ring members and non-ring members, e.g. purine or analogs
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    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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Abstract

A phosphorus-containing porphyrin and a preparation method and application thereof, wherein the chemical structural formula is as follows:
Figure DDA0004047506560000011
firstly, dissolving a benzaldehyde derivative, potassium carbonate and triethylamine in a solvent, slowly dropwise adding organic phosphonyl chloride and the solvent, and then carrying out heat preservation reaction to obtain an intermediate product; mixing the intermediate product with propionic acid and propionic anhydride, then dripping pyrrole and propionic acid into the mixed solution, and carrying out heat preservation reaction to obtain the phosphorus-containing porphyrin. The phosphorus-containing porphyrin has good compatibility with polymer materials and high molecular materialsThere is a strong intermolecular force between them, so that it can strengthen and toughen the polymer. Has better ultraviolet absorption performance and can obviously improve the ultraviolet aging resistance of the polymer material. The polymer material has excellent thermal stability, and can effectively enhance the thermal stability of the polymer material in nitrogen and air atmosphere. The flame retardant coating has a good flame retardant function on the polymer, can obviously inhibit the heat release of the polymer, promotes the self-extinguishing function of the polymer material, and prevents the spread of fire.

Description

Phosphorus-containing porphyrin and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polymer composite material performance modification aids, and particularly relates to phosphorus-containing porphyrin, and a preparation method and application thereof.
Background
The polymer has the advantages of excellent chemical resistance, easy processing and the like, and is widely applied to the fields of buildings, packaging, electronic appliances and the like. However, some polymers (e.g., polylactic acid, epoxy, etc.) still have some drawbacks that limit their further development and use: (1) poor toughness. Most of the current polymers are easily cracked due to stress due to the special molecular structure, so that the toughness is poor. (2) poor aging resistance. The polylactic acid and other materials are very sensitive to ultraviolet rays, and after the ultraviolet rays are irradiated, molecular chains are broken, so that the mechanical properties of the polylactic acid and other materials are seriously affected, and the service life of the materials is reduced. (3) flammability. Most polymers are very flammable, emit a lot of heat during combustion and melt and drip, resulting in further spread of fire and endangering human lives.
Aiming at the three defects of the polymer, a toughening agent, an ultraviolet light absorber, a flame retardant and the like are required to be added respectively to improve the comprehensive performance of the polymer. For example, chinese patent CN 115521469A is used to improve the flame retardant property of polylactic acid by synthesizing a triazine ring-containing flame retardant, which has a larger molecular weight and better compatibility with polylactic acid. Chinese patent CN 102093681a uses lignin and elastomer grafted maleic anhydride based tougheners for fillers to improve the toughness of polylactic acid. Patent CN112341775a discloses a titanium dioxide nano material with ultraviolet light absorption functional groups on the surface, which can be uniformly dispersed in a polylactic acid matrix, so that the ultraviolet absorption and ultraviolet shielding performance of the polylactic acid are remarkably improved, and the excellent ultraviolet aging resistance of the material is provided.
The phosphorus-containing porphyrin, which is a heterocyclic compound, has good biocompatibility and has been widely applied to the fields of biology, catalysis and the like. In addition, the phosphorus-containing porphyrin has good ultraviolet absorptivity, and the terminal groups of the phosphorus-containing porphyrin can be connected with different groups, so that the design of the phosphorus-containing porphyrin with different structures can be carried out according to the needs. Therefore, based on the excellent property and special structure of the phosphorus-containing porphyrin, the phosphorus-containing porphyrin additive with multifunctional characteristics is developed to improve the heat stability, ageing resistance, mechanical property, flame retardance and other various composite properties of the polymer, and is a hot spot and a difficult point in the research and development field of the multifunctional polymer additive at present.
Disclosure of Invention
The invention aims to overcome the defects of poor toughness, poor ageing resistance, inflammability and the like of the existing polymer (such as polylactic acid, epoxy resin and the like), and provides phosphorus-containing porphyrin and a preparation method thereof, wherein the phosphorus-containing porphyrin is added into a polymer composite material to obviously improve the comprehensive performance of the polymer.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a phosphorus-containing porphyrin having the chemical structural formula:
Figure BDA0004047506540000021
wherein R1 is
Figure BDA0004047506540000022
Or->
Figure BDA0004047506540000023
R2 is H or O-CH 3 。
The invention provides a preparation method of phosphorus-containing porphyrin, which comprises the following specific steps:
1) Firstly, mixing and dissolving benzaldehyde derivative, potassium carbonate and triethylamine in a solvent according to a certain proportion;
2) Slowly adding the mixed solution of the organic phosphonic chloride and the solvent into the solution in the step 1), and dropwise adding the mixed solution to finish the heat-preserving reaction;
3) Filtering and purifying the product after the reaction in the step 2), and then drying to obtain light yellow powder which is an intermediate product;
4) Mixing the intermediate product obtained in the step 3) with propionic acid and propionic anhydride, and then dripping a mixture of pyrrole and propionic acid in a certain proportion into the mixed solution, wherein the dripping is completed with heat preservation reaction;
5) Filtering the product after the reaction in the step 4), removing the solvent, and purifying and drying to obtain purple powder which is the phosphorus-containing porphyrin.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
step 1) mixing a benzaldehyde derivative, potassium carbonate and triethylamine, adding a solvent, and introducing nitrogen at room temperature for protection and mixing for 5-30 min until the mixture is completely dissolved; the molar ratio of the benzaldehyde derivative, the potassium carbonate and the triethylamine added in the step 1) is 1:1-1.5:1-3; the benzaldehyde derivative is vanillin or parahydroxybenzaldehyde.
Step 2), firstly stirring the solution in the step 1) at 60 ℃, then slowly adding the mixed solution of the organic phosphonyl chloride and the organic solvent, and dropwise adding the mixed solution to complete the thermal insulation reaction; the molar ratio of the benzaldehyde derivative added in the step 1) to the organic phosphonic acid chloride added in the step 2) is 1:2-3.5; the organic phosphonic chloride is diphenyl phosphinic chloride or diphenyl chlorophosphonate; and 2) carrying out heat preservation reaction for 4-6 h.
The solvent added in step 1) and step 2) is 1, 4-dioxane, ethyl acetate or tetrahydrofuran.
In the step 4), firstly mixing the intermediate product obtained in the step 3) with propionic acid and propionic anhydride, heating to 140-160 ℃, simultaneously slowly dripping a mixed solution of propionic acid and pyrrole, and then keeping the temperature for continuous reaction for 3-4 hours; the molar ratio of the benzaldehyde derivative added in the step 1) to the pyrrole added in the step 4) is 10:2-4.
The invention also discloses application of the phosphorus-containing porphyrin as a multifunctional additive of the polymer material, in particular to preparation of a composite material by mixing phosphorus-containing porphyrin and the polymer material, wherein the mass percentage of the phosphorus-containing porphyrin in the prepared composite material is 1-7%.
As a preferred technical scheme of the application, the steps of preparing the composite material by melt blending are as follows:
taking 0.3-9 g of phosphorus-containing porphyrin and 21-29.7 g of polylactic acid (PLA), and carrying out melt blending for 10-20 min at 185-190 ℃ to obtain the PLA/phosphorus-containing porphyrin composite material. Or, taking 0.3-9 g of phosphorus-containing porphyrin and 21-29.7 g of epoxy monomer and curing agent, and curing for 6h at 180-220 ℃ to obtain the epoxy resin/phosphorus-containing porphyrin composite material.
Compared with the prior art, the invention has the following advantages:
1) The phosphorus-containing porphyrin has good compatibility with polymer materials (such as polylactic acid, epoxy resin and the like), and has stronger intermolecular force (such as hydrogen bond and pi-pi interaction) with the polymer materials, thereby playing a role in reinforcing and toughening the polymer.
2) The phosphorus-containing porphyrin has good ultraviolet absorption performance, and can obviously improve the ultraviolet aging resistance of the polymer material.
3) The phosphorus-containing porphyrin has excellent thermal stability, and can effectively enhance the thermal stability of the polymer material in nitrogen and air atmosphere.
4) The phosphorus-containing porphyrin has a better flame-retardant function on the polymer, can obviously inhibit the heat release of the polymer, promotes the self-extinguishing function of the polymer material, and prevents the spread of fire.
5) The phosphorus-containing porphyrin has wide sources of raw materials, relatively low cost, environmental friendliness and wide application prospect.
Drawings
FIG. 1 shows a nuclear magnetic resonance hydrogen spectrum (a) of the target product VPR prepared in example 1 and a thermal pyrolysis curve (b) under nitrogen atmosphere.
FIG. 2 is a graph showing the thermal decomposition curves of the target product of the composite material prepared by the target product prepared in example 7 in an air atmosphere (a) and a nitrogen atmosphere (b).
FIG. 3 is a graph showing the tensile properties of the target product prepared in example 7.
FIG. 4 is a graph showing the impact strength of the target product prepared in example 7.
FIG. 5 is a graph showing the tensile curve properties of the target product prepared in example 7 after ultraviolet aging.
FIG. 6 is a graph of the burn performance of composite PLA/3VPR prepared in example 7 and PLA prepared in comparative example 1 including Heat Release Rate (HRR) (a), total Heat Release (THR) (b) and CO 2 And CO gas release profiles (c, d).
FIG. 7 is a nuclear magnetic resonance hydrogen spectrum of the target product PPR prepared in example 4.
FIG. 8 is a graph showing the tensile properties of the target product prepared in example 8.
FIG. 9 is a graph showing the impact strength of the objective product prepared in example 8.
FIG. 10 is a graph of the combustion performance of the composite EP/PPR prepared in example 8 and EP prepared in comparative example 2, including Heat Release Rate (HRR) (a), total Heat Release (THR) (b), smoke release rate (c), total smoke release (d), CO and CO 2 Gas release profiles (e, f).
Detailed Description
Example 1
1) 15g (0.1 mol) of vanillin, 20.4g (0.147 mol) of K are reacted at room temperature 2 CO 3 And 30mL (0.216 mol) of triethylamine were dissolved in 450mL of tetrahydrofuran, and the dissolution was accelerated for 15min under nitrogen protection with stirring to complete dissolution.
2) Slowly adding the mixed solution of diphenyl phosphoryl chloride and tetrahydrofuran into the solution in the step 1), wherein the mol ratio of the added vanillin to the diphenyl phosphoryl chloride is 1:2.5, and dropwise adding the mixture for heat-preserving reaction for 6h (60 ℃ and N) 2 Protection), the reaction equation is as follows:
Figure BDA0004047506540000041
3) Filtering and purifying the product after the reaction in the step 2), and then drying to obtain light yellow powder which is the intermediate product 1.
4) Intermediate 1 obtained in step 3) was mixed with 200mL of propionic acid and 20mL of propionic anhydride, and then 1.38mL (0.02 mol) of pyrrole (addedThe molar ratio of vanillin to pyrrole is 10:2) and 3mL propionic acid are added into the mixed solution dropwise, and the reaction is carried out for 4h (150 ℃ C., N) 2 Protection), the reaction equation is shown below;
Figure BDA0004047506540000051
5) Filtering the product after the reaction in the step 4), removing the solvent, and purifying and drying to obtain purple powder which is the product biomass phosphorus porphyrin (VPR) with the yield of 16.3%.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of phosphorus-containing porphyrin prepared in example 1 1 H NMR (400 MHz, deuterated chloroform) was specifically analyzed as follows (δ, ppm): delta 8.74 (d, j=4.0 hz, 8H), 8.21-8.16 (m, 16H), 7.79-7.60 (m, 36H), 3.88 (s, 12H), 2.92 (s, 2H).
Example 2
The preparation process is the same as in example 1, except that the molar ratio of vanillin to pyrrole is 10:3, and the prepared purple powder is the product biomass phosphorus porphyrin (VPR) with a yield of 20.1%.
Example 3
The preparation process is the same as in example 1, except that the molar ratio of vanillin to pyrrole is 10:4, and the prepared purple powder is the product biomass phosphorus porphyrin (VPR) with a yield of 17.3%.
Example 4
1) 10g (0.08 mol) of p-hydroxybenzaldehyde, 13.6g (0.098 mol) of K are reacted at room temperature 2 CO 3 And 15mL (0.108 mol) of triethylamine were dissolved in 100mL of 1, 4-dioxane, and the dissolution was accelerated for 15min under nitrogen protection with stirring to complete dissolution.
2) Slowly adding a mixed solution of diphenyl chlorophosphate and 1, 4-dioxane into the solution in the step 1), wherein the molar ratio of the added p-hydroxybenzaldehyde to the diphenyl chlorophosphate is 1:2.2, and dropwise adding the mixture for thermal insulation reaction for 6h (60 ℃ C., N) 2 Protection), the reaction equation is as follows:
Figure BDA0004047506540000052
3) Filtering and purifying the product after the reaction in the step 2), and then drying to obtain a light yellow viscous fluid which is the intermediate product 2.
4) Mixing the intermediate 2 obtained in the step 3) with 200mL of propionic acid and 20mL of propionic anhydride, then dropwise adding 1.1mL (0.016 mol) of pyrrole (the molar ratio of added p-hydroxybenzaldehyde to pyrrole is 10:2) and 2mL of propionic acid into the mixed solution, and carrying out thermal insulation reaction for 4h (150 ℃ C., N) 2 Protection), the reaction equation is as follows:
Figure BDA0004047506540000061
5) Filtering the product after the reaction in the step 4), removing the solvent, and purifying and drying to obtain purple powder, namely the product Phosphorus Porphyrin (PPR) with the yield of 17.3%.
FIG. 7 is a nuclear magnetic resonance spectrum of example 4 for preparing phosphorus-containing porphyrin PPR 1 H NMR (400 MHz, deuterated chloroform) was specifically analyzed as follows (δ, ppm): δ8.84 (s, 8H), 8.19 (d, j=8.3 hz, 8H), 7.65 (d, j=8.3 hz, 8H), 7.49-7.43 (m, 32H), 7.30 (t, j=6.6 hz, 8H), -2.87 (s, 2H).
Example 5
The preparation process is the same as in example 4, except that the molar ratio of added p-hydroxybenzaldehyde to pyrrole is 10:3, and the prepared purple powder is the product Phosphorus Porphyrin (PPR) with the yield of 18.6%.
Example 6
The preparation process is the same as in example 4, except that the molar ratio of added p-hydroxybenzaldehyde to pyrrole is 10:4, and the prepared purple powder is the product Phosphorus Porphyrin (PPR) with the yield of 20.2%.
Example 7
The biomass phosphorus-containing porphyrin (VPR) prepared in example 1 was mixed with PLA in a total mass percentage of 1%,2% and 3%, respectively, and then melt-mixed in an internal mixer at 190℃for 15min, and after the completion of the mixing, further processing was performed to prepare composite materials designated PLA/1VPR, PLA/2VPR and PLA/3VPR, respectively.
Example 8
The phosphorus-containing porphyrin (PPR) prepared in example 4 was mixed with epoxy monomer DGEBA and curing agent DDM in an amount of 1%,3%,5% and 7% by mass, poured into a mold, and cured for 2 hours at 180 ℃,200 ℃ and 220 ℃ banburying temperatures, respectively. The composites were prepared with the designations EP/1PPR, EP/3PPR, EP/5PPR and EP/7PPR, respectively.
Comparative example 1
And (3) banburying the pure polylactic acid in an internal mixer at 190 ℃ for 15min to obtain a blended sample, and pressing the blended sample into test bars through a die, wherein the material is marked as PLA.
Comparative example 2
Mixing epoxy monomer DGEBA and curing agent DDM, pouring into a mould, and sequentially curing for 2h at the banburying temperatures of 180 ℃,200 ℃ and 220 ℃. The composite is labeled EP.
FIG. 1 (b) is a thermal decomposition curve of the target product VPR prepared in example 1, from which it can be seen that the thermal decomposition temperature of VPR is 399.2 ℃. After its addition to PLA, the decomposition temperature of PLA/VPR was raised up to 349.8 ℃ (air atmosphere), as shown in fig. 2 and table 1, demonstrating that the addition of VPR enhances the thermal stability of PLA.
TABLE 1
Figure BDA0004047506540000071
In the table: t (T) -5％ : a temperature corresponding to 5% weight loss; t (T) max : temperature corresponding to the maximum value of the weight loss rate.
Fig. 3, 4 and table 2 are tensile property test curves and impact strength performance parameters for PLA and its composites. The tensile stress and elongation at break of PLA were 58.8MPa and 9.3%, respectively. After VPR is added, the mechanical property is effectively improved, and the tensile stress and the elongation at break of PLA/3VPR are 61.7MPa and 17.5 percent respectively. The tensile stress and elongation at break increases by 4.9% and 88.2% with only 3wt% compared to PLA, indicating that VPR has good propertiesToughening effect. Furthermore, the impact strength of PLA/3VPR reaches 18.89kJ/m 2 An increase of 104.2% compared to PLA, indicating an extreme toughening effect of VPR on PLA.
TABLE 2
Figure BDA0004047506540000081
Fig. 5 and table 2 demonstrate the change in mechanical properties of PLA and its composites after 50h uv aging. The ultraviolet light aging test conditions are as follows: a 500W power ultraviolet lamp, 50 hours of test time, 50 ℃ of temperature, 100% of humidity, 20cm of sample distance from the light source and 340nm of light wavelength. The mechanical properties of PLA were significantly reduced after uv aging, and the strength and elongation at break were reduced by 51.4% and 48.4%, respectively. As the phosphorus-containing porphyrin is added, the strength and the elongation at break of the PLA/3VPR sample are reduced by only 1.5 percent and 8.6 percent respectively, which shows that the ultraviolet aging resistance of the polylactic acid can be effectively improved by adding the phosphorus-containing porphyrin.
TABLE 3 Table 3
Figure BDA0004047506540000082
In the table: TTI: ignition time; time to flame out: heating to burn off; burning time: combustion time, equal to Time to flame out minus TTI; PHRR: peak heat release rate; THR: total heat release; PCOP: a CO production rate peak; PCO (prestressed concrete cylinder pipe) 2 P：CO 2 Generating a rate peak.
FIG. 6 is a graph of the combustion performance test of prepared PLA and its composite PLA/3VPR, including HRR and THR and carbon monoxide and carbon dioxide gas emissions, and the relevant data is summarized in Table 3. PLA/3VPR and PHRR for PLA exhibited similar peaks, but PLA/3VPR exhibited significantly enhanced self-extinguishing behavior during this combustion process. The combustion process of PLA/3VPR lasted 168s, less than 184s for pure PLA. Shorter burning times minimize the spread of fire while reducing the total heat released during the combustion process. PLA/3VPTHR of R is from 48.4MJ/m 2 Down to 40.5MJ/m 2 A 16.3% reduction indicates that the addition of VPR can result in an effective enhancement of flame retardant properties of PLA.
Fig. 8, 9 and table 4 are tensile property test curves and impact strength performance parameters for epoxy resins and their composites. The tensile strength and elongation at break of pure EP were 45.9MPa and 11.1%, respectively, indicating that they are relatively brittle. After addition of PPR, the mechanical properties of EP/PPR gradually improve with increasing PPR content. EP/5PPR has the highest tensile strength (49.6 MPa), an increase of 8.1% compared to pure EP. Furthermore, EP/PPR shows a more pronounced increase in elongation at break, with an elongation at break of 17.7% for EP/7PPR, which is increased by 59.5% compared to pure EP. These results demonstrate that PPR exhibits a significant toughening effect on EP. And the impact strength of EP/7PPR is also obviously improved along with the increase of the PPR content (1.03 kJ/m 2 ) The improvement is 43.1% compared with pure EP.
TABLE 4 Table 4
Sample of Tensile Strength (MPa) Elongation at break (%) Impact Strength (kJ/m) 2 )
EP 45.9±1.3 11.1±0.6 0.72±0.08
EP/1PPR 46.1±3.5 12.9±0.4 0.81±0.03
EP/3PPR 46.2±3.7 13.6±0.5 0.94±0.07
EP/5PPR 49.6±5.3 14.2±1.8 0.95±0.08
EP/7PPR 48.5±3.1 17.7±1.0 1.03±0.09
Fig. 10 is a graph showing the combustion performance test of the prepared epoxy resin and its composite material, and the related data are summarized in table 5. PHRR value of pure EP is 1469kW/m 2 While the PHRR value decreases significantly with the addition of PPR, wherein the PHRR of EP/7PPR is 818kW/m 2 (44.3% reduction compared to EP). THR values show a similar trend as PHRR, from 121MJ/m of EP 2 105MJ/m down to EP/7PPR 2 . Furthermore, the PSPR of pure EP is 0.36m 2 And/s, indicating high toxicity during combustion. After addition of PPR, the PSPR was reduced to 0.28m 2 And/s, 22.2% less. More importantly, the TSP value is also from 31.6m of EP 2 Reduced to 27.0m of EP/7PPR 2 The PPR has good smoke suppression performance. This is due to the excellent catalytic carbonization of PPR. Finally, PCOP and PCO 2 P also decreases substantially with increasing PPR content (29.5% and 39.4% decrease in EP/7PPR, respectively). Therefore, the PPR can obviously improve the flame retardant property of the epoxy resin, reduce the smoke release amount during combustion, and furtherFurther expanding the application range of the epoxy resin.
TABLE 5
Figure BDA0004047506540000101
In the table: TTI: ignition time; PHRR: peak heat release rate; THR: total heat release; PSPR: a smoke release peak; TSP: total smoke release; PCOP: a CO production rate peak; PCO (prestressed concrete cylinder pipe) 2 P：CO 2 Generating a rate peak.
According to the comparison of the performances of the groups, the ultraviolet ageing resistance, the mechanical property, the thermal stability and the flame retardant property of polylactic acid and epoxy can be effectively improved by adding a certain amount of phosphorus-containing porphyrin auxiliary agent. As a high-efficiency functional additive, the phosphorus-containing porphyrin provided by the invention can effectively improve the comprehensive performance of the polymer so as to expand the application range of the polymer.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.

Claims (9)

1. The phosphorus-containing porphyrin is characterized by having a chemical structural formula:
Figure FDA0004047506530000011
wherein R1 is
Figure FDA0004047506530000012
R2 is H or O-CH 3 。
2. A method for preparing the phosphorus-containing porphyrin according to claim 1, comprising the steps of:
1) Firstly, mixing and dissolving benzaldehyde derivative, potassium carbonate and triethylamine in a solvent according to a certain proportion;
2) Slowly adding the mixed solution of the organic phosphonic chloride and the solvent into the solution in the step 1), and dropwise adding the mixed solution to finish the heat-preserving reaction;
3) Filtering and purifying the product after the reaction in the step 2), and then drying to obtain light yellow powder which is an intermediate product;
4) Mixing the intermediate product obtained in the step 3) with propionic acid and propionic anhydride, and then dripping a mixture of pyrrole and propionic acid in a certain proportion into the mixed solution, wherein the dripping is completed with heat preservation reaction;
5) Filtering the product after the reaction in the step 4), removing the solvent, and purifying and drying to obtain purple powder which is the phosphorus-containing porphyrin.
3. The method according to claim 2, wherein step 1) mixing the benzaldehyde derivative, potassium carbonate and triethylamine and adding the solvent, and introducing nitrogen at room temperature for protection and mixing for 5-30 min until complete dissolution; the molar ratio of the benzaldehyde derivative, the potassium carbonate and the triethylamine added in the step 1) is 1:1-1.5:1-3; the benzaldehyde derivative is vanillin or parahydroxybenzaldehyde.
4. The method according to claim 2, wherein in step 2), the solution in step 1) is stirred at 60 ℃ first, then the mixed solution of the organic phosphonic chloride and the organic solvent is slowly added, and the reaction is completed by dropwise adding; the molar ratio of the benzaldehyde derivative added in the step 1) to the organic phosphonic acid chloride added in the step 2) is 1:2-3.5; the organic phosphonic chloride is diphenyl phosphinic chloride or diphenyl chlorophosphonate; and 2) carrying out heat preservation reaction for 4-6 h.
5. The method of claim 2, wherein the solvent added in step 1) and step 2) is 1, 4-dioxane, ethyl acetate, or tetrahydrofuran.
6. The method of claim 2, wherein in the step 4), the intermediate product obtained in the step 3) is firstly mixed with propionic acid and propionic anhydride, the temperature is raised to 140-160 ℃ for heating, meanwhile, the mixed solution of propionic acid and pyrrole is slowly added dropwise, and then the reaction is continued for 3-4 hours under heat preservation; the molar ratio of the benzaldehyde derivative added in the step 1) to the pyrrole added in the step 4) is 10:2-4.
7. The use of the phosphorus-containing porphyrin as a multifunctional additive for polymer materials according to claim 1, wherein the phosphorus-containing porphyrin and the polymer materials are mixed to prepare a composite material, and the mass percentage of the phosphorus-containing porphyrin in the prepared composite material is 1-7%.
8. The use according to claim 7, wherein 0.3-9 g of phosphorus-containing porphyrin and 21-29.7 g of polylactic acid (PLA) are melt blended for 10-20 min at 185-190 ℃ to obtain the PLA/phosphorus-containing porphyrin composite material.
9. The use according to claim 7, wherein the epoxy resin/phosphorus-containing porphyrin composite material is obtained by taking 0.3 to 9g of phosphorus-containing porphyrin and 21 to 29.7g of epoxy monomer and curing agent and curing the mixture at 180 to 220 ℃ for 6 hours.
CN202310036604.0A 2023-01-10 2023-01-10 Phosphorus-containing porphyrin and preparation method and application thereof Pending CN116217620A (en)

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