A ferrocenylcyanoporphyrin burning rate catalyst and its preparation method and application

Abstract

The invention discloses a ferrocenylcyanoporphyrin burning rate catalyst and a preparation method and application thereof. The method comprises the following steps: 3-ferrocenylethynylbenzaldehyde is catalyzed by trifluoroacetic acid, and 2,3-dichloro-5,6-dicyanobenzoquinone is oxidized to obtain 5,15-diphenylporphyrin and 5,10,15,20-tetraphenylporphyrin in which the meta-position of the benzene ring is substituted by ferrocenylacetylene, respectively. The two porphyrins are then reacted with acetates of zinc, nickel, ketone and cobalt to obtain corresponding metalloporphyrins. The two series of porphyrins containing alkynyl groups are reacted with tetracyanoethylene to obtain cyanoferrocenyl functionalized porphyrin and metalloporphyrin. The ferrocenylcyanoporphyrin and metalloporphyrin provided by the present invention not only have good catalytic properties for the thermal degradation of AP, but also have the advantage of non-migration as a burning rate catalyst of a composite solid propellant. Therefore, the cyanoferrocene functionalized porphyrin and metalloporphyrin provided by the present invention have good practical prospects in the field of solid rocket propellant burning rate catalysts.

Description

Technical Field

[0001] The invention belongs to the technical field of burning rate catalysts for composite solid propellants, and specifically relates to a ferrocenylcyanoporphyrin burning rate catalyst and a preparation method and application thereof. Background Art

[0002] Composite solid propellant (HTPB) is the main raw material for missiles and rocket engines. Currently, the most widely used oxidizer in composite solid propellant is ammonium perchlorate (AP). However, since AP itself has a very high decomposition temperature and incomplete decomposition, this greatly affects the combustion rate of the propellant. Adding a burning rate catalyst has become the simplest and most commonly used method to adjust the burning rate.

[0003] Ferrocene derivatives, as burning rate catalysts for composite solid propellants, can significantly increase the burning rate of fuels, and their performance exceeds that of other transition metal compounds. However, ferrocene burning rate catalysts, such as commercial 2,2'-di(ethylferrocene) (Cat.), tert-butylferrocene and n-butylferrocene, have the disadvantages of easy migration and volatility during the storage of propellants, which will lead to propellant aging and non-renewability. In order to solve these problems, many scholars have made a lot of modifications to burning rate catalysts, such as introducing active groups that can react with butyl hydroxy rubber into ferrocene molecules; preparing ferrocene ion compounds, polymers or complexes, etc. Although these methods have played a certain role in reducing the volatility and mobility of ferrocene burning rate catalysts, the mobility problem has not been completely solved. Moreover, since these burning rate catalyst molecules often contain only one ferrocene group, the ferrocene content is low, and the burning rate catalytic effect is limited.

[0004] The periphery of porphyrin can not only connect multiple ferrocene molecules, but the center can also coordinate with various metal ions. When applied to the field of burning rate catalysts, such a structure can not only meet the requirements of increasing molecular weight and iron content, but also increase redox and catalytic centers through coordinated metals, thereby achieving the effect of improving burning rate catalytic performance. We have tried to use ferrocene-modified porphyrin as a burning rate catalyst for composite solid propellants, connecting long-chain alkyl ferrocene to the periphery of porphyrin and metal porphyrin through ester bonds and ether bonds, and found that such compounds hardly migrate. However, since such catalysts contain multiple long alkyl chains, the ferrocene content is not high, and the burning rate catalytic performance needs to be further improved. Therefore, it is urgent to develop a new type of burning rate catalyst that can greatly improve the burning rate catalytic effect and does not migrate. Summary of the invention

[0005] In view of the drawbacks of current burning rate catalysts, the present invention provides a ferrocenylcyanoporphyrin burning rate catalyst and a preparation method thereof, and applies the catalyst to composite solid propellants to solve the problems of low catalytic efficiency and easy migration of the burning rate catalyst.

[0006] The technical solution of the present invention is as follows:

[0007] A ferrocenylcyanoporphyrin-based burning rate catalyst, the structure of which is shown in the following general formula (I) or general formula (II). They are 5,15-diphenylporphyrin and its metal porphyrin in which the meta position of the benzene ring is substituted by ferrocenyltetracyanobutadiene, and tetraphenylporphyrin and its metal porphyrin in which the meta position of the benzene ring is substituted by ferrocenyltetracyanobutadiene;

[0008] ;

[0009] Wherein, M is two hydrogens 2H or one of the metal elements Zn, Ni, Cu, and Co.

[0010] The preparation method of the ferrocenylcyanoporphyrin burning rate catalyst represented by the general formula (I) comprises the following steps:

[0011] Porphyrin was synthesized by 3-ferrocenylethynylbenzaldehyde and bispyrromethane with trifluoroacetic acid (TFA) as catalyst, and then oxidized with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) to obtain free porphyrin 3a, which was then coordinated with the corresponding acetate to obtain metal porphyrins 3b~3e. 3a~3e were reacted with click reagent tetracyanoethylene (TCNE) in dichloromethane (DCM) solution to obtain porphyrins Ia~Ie;

[0012] .

[0013] The preparation method of the ferrocenylcyanoporphyrin burning rate catalyst represented by the general formula (II) comprises the following steps:

[0014] The free porphyrin 4a was prepared by reacting 3-ferrocenylethynylbenzaldehyde with pyrrole, and then coordinated with metal ions to obtain metal porphyrins 4b~4e. 4a~4e were click-reacted with TCNE in DCM solution to obtain porphyrins IIa~IIe;

[0015] .

[0016] This type of catalyst is added to AP at a certain amount to test its promoting effect on AP thermal degradation. This type of catalyst simulates the formula content of the actual composite solid propellant burning rate catalyst, and is mixed with other components in the propellant in proportion and loaded into a glass tube to test its anti-migration property.

[0017] Beneficial effects of the present invention:

[0018] The present invention constructs ferrocene functionalized porphyrin and metalloporphyrin containing multiple cyano groups through the Click reaction of TCNE and alkyne porphyrin. The ferrocene cyanoporphyrin and metalloporphyrin compounds provided by the present invention have not been reported in the literature. This type of compound has a significant catalytic effect on the thermal degradation of AP, and the catalytic performance of some catalysts is better than that of catocten. The cyano group is a group with a large polarity. Multiple large polar cyano groups can form hydrogen bonds with the butyl hydroxy rubber of the propellant. Such compounds are used as burning rate catalysts of composite solid propellants to simulate anti-migration experiments. The results show that this type of catalyst does not migrate. Therefore, the cyano ferrocene functionalized porphyrin and metalloporphyrin provided by the present invention have good application prospects in the field of solid rocket propellant burning rate catalysts. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 . UV-visible absorption spectra of porphyrins Ia and IIa.

[0020] Figure 2 . Fluorescence spectra of porphyrins IIa~IIe.

[0021] Figure 3 . DTA curves of pure AP, 4% tetraphenylporphyrin TPP, Cat, and porphyrin IIa~IIe added to AP respectively.

[0022] Figure 4 . Picture of the anti-migration experiment of porphyrin Id. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative improvements are within the scope of protection of the present invention.

[0024] Example 1

[0025] Preparation of compound 3a:

[0026] In a 200 mL Schlenk reaction bottle, 73.1 mg (0.5 mmol) of bispyrromethane and 157.1 mg (0.5 mmol) of 3-ferrocenylethynylbenzaldehyde were added, and 100 mL of DCM was added to dissolve the mixture. Subsequently, 22.3 μL (0.0342 mmol) of TFA was added, and the mixture was reacted at room temperature for 21 h under N2 protection and in the dark. After the reaction, 0.2078 g (0.75 mmol) of DDQ was added for oxidation for 1 h, and then 2.5 mL of triethylamine was added and stirred for 20 min to quench the reaction. The mixture was purified by silica gel column chromatography with petroleum ether PE:DCM=1:1 as the eluent, and recrystallized from DCM / MeOH to obtain 103.7 mg of compound 3a with a yield of 47.1%. 1 H NMR (600 MHz, CDCl3) δ, ppm: 10.35 (s, 2H), 9.43 (d, J = 4.5 Hz, 4H), 9.12 (d, J = 4.4 Hz, 4H), 8.41 (s, 2H), 8.21 (d, J= 6.2 Hz, 2H), 7.95 (d, J = 7.8 Hz, 2H), 7.77 (t, J = 8.1 Hz, 2H), 4.56 (s,4H), 4.27 (d, J = 8.2 Hz, 14H), -3.14 (s, 2H).

[0027] Example 2

[0028] Preparation of compound 3b:

[0029] 74.7 mg (0.085 mmol) of compound 3a was added to a 250 mL three-necked flask and dissolved in 75 mL of chloroform. 186.6 mg (0.85 mmol) of zinc acetate dihydrate was added and dissolved in 14 mL of methanol solution. The mixture was refluxed for 5 h under nitrogen protection. After the reaction was completed, the mixture was washed with water, extracted with DCM, and the organic phases were combined and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure and the mixture was eluted with silica gel column chromatography using PE:DCM=3:2 to obtain 60.8 mg of compound 3b with a yield of 75.8%. 1 H NMR (600 MHz, CDCl3) δ, ppm: 10.37 (s,2H), 9.48 (d, J = 4.9 Hz, 4H), 9.18 (d, J = 5.0 Hz, 4H), 8.41 (s, 2H), 8.21(s, 2H), 7.94 (d, J = 8.9 Hz, 2H), 7.78 – 7.73 (m, 2H), 4.56 (s, 4H), 4.27(d, J = 8.0 Hz, 14H).

[0030] Example 3

[0031] Preparation of compounds 3d~3e:

[0032] 111.8 mg (0.13 mmol) of compound 3a was added to a 250 mL three-necked flask and dissolved in 120 mL of chloroform. 259.5 mg (1.3 mmol) of cupric acetate dihydrate dissolved in 20 mL of methanol solution was added and refluxed for 37 h under nitrogen protection. After the reaction was completed, the mixture was washed with water, extracted with DCM, and the organic phases were combined and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure and the mixture was eluted with silica gel column chromatography using PE:DCM=3:2 to obtain 85.6 mg of compound 3d with a yield of 70.0%.

[0033] Compounds 3c and 3e were synthesized by the same method.

[0034] Example 4

[0035] Preparation of compounds Ia~Ie:

[0036] Compound 3 (0.066 mmol) and 42.4 mg (0.33 mmol) of TCNE were added to a 100 mL Schlenk reaction bottle. 40 mL of DCM was added under nitrogen protection and the reaction was refluxed for 12 h. After the reaction was completed, the solvent was evaporated under reduced pressure, and the mixture was eluted with DCM:MeOH=500:1 on a silica gel column. The mixture was recrystallized from DCM / Hexane to obtain compound I.

[0037] The characterization data of parts Ia~Ie are listed below, which will help to understand the present invention, but are not limited to the contents of the invention.

[0038] Ia, yield 25.8%. 1 H NMR (600 MHz, CDCl3) δ, ppm: 10.37 (t, J = 7.6 Hz, 2H), 9.58 – 9.38 (m, 4H), 9.04 – 8.80 (m, 4H), 8.60 – 8.41 (m, 4H), 8.23 ​​– 7.98(m, 4H), 5.42 (s, 2H), 5.06 (s, 2H), 4.96 (s, 2H), 4.82 (s, 2H), 4.33 (s,10H), -3.19 (s, 2H). 1313C NMR (151 MHz, CDCl3) δ, ppm: 172.55, 166.65, 143.31, 139.58, 134.47, 130.68, 128.66, 127.73, 116.20, 113.58, 113.12, 111.76, 111.58, 106.19, 79.01, 75.96, 75.22, 74.99, 72.80, 72.53, 71.64. HRMS(C 68 H 38 Fe2N 12 ) calcd 1134.2051 [M - , found 1134.2066 [M - .

[0039] Ib, yield 67.4%. 1 1H NMR (600 MHz, CDCl3) δ, ppm: 10.35 (t, J = 10.1 Hz, 2H), 9.53 – 9.39 (m, 4H), 8.99 (t, J = 4.2 Hz, 2H), 8.84 (t, J = 5.4 Hz, 2H), 8.49 (dt, J = 14.4, 7.3 Hz, 4H), 8.18 (t, J = 6.6 Hz, 2H), 7.99 (td, J = 7.8, 2.1 Hz, 2H), 5.37 (s, 2H), 5.06 (s, 2H), 4.97 (s, 2H), 4.86 (s, 2H), 4.26 (s, 10H). 13 13C NMR (150 MHz, CDCl3) δ, ppm: 172.75, 166.87, 149.88, 149.60, 144.71, 139.44, 134.32, 132.73, 131.87, 130.25, 128.29, 127.51, 117.03, 113.15, 111.81, 111.64, 90.28, 78.96, 75.91, 75.24, 75.06, 72.69, 72.43, 71.89. HRMS(C 68 H 36 Fe2N 12 Zn) calcd 1196.1176 [M + , found 1196.1171 [M + .

[0040] Id, yield 20.6%. HRMS (C 68 H 36 CuFe2N 12 ) calcd 1195.1181 [M + ], found1195.1172 [M + ].

[0041] Example 5

[0042] Preparation of compound 4a:

[0043] 0.3142 g (1 mmol) of 3-ferrocenylethynylbenzaldehyde was added to a 200 mL Schlenk reaction bottle. 100 mL of DCM and 0.0692 mL (1 mmol) of pyrrole were added under nitrogen protection and in the dark. After the mixture was fully dissolved, 0.1485 mL (2 mmol) of TFA was added. The mixture was reacted at room temperature for 1.5 h. Subsequently, 0.4155 g (1.5 mmol) of DDQ was added and the mixture was oxidized at room temperature for 3.5 h. After the reaction was completed, 2.4 mL of triethylamine was added and stirred for 10 min to quench the reaction. The mixture was purified by silica gel column chromatography and eluted with DCM. The mixture was recrystallized from DCM / MeOH to obtain 32.2 mg of purple solid 4a with a yield of 8.9%. 1 H NMR (600 MHz, CDCl3) δ, ppm: 8.92 (s, 8H), 8.37 (s, 4H), 8.17 (d, J = 8.5 Hz, 4H), 7.92 (d, J = 7.9 Hz, 4H), 7.73 (t, J = 7.8 Hz, 4H), 4.53 (s, 8H), 4.25 (d, J = 9.5 Hz, 28H), -2.78 (s, 2H).

[0044] Example 6

[0045] Preparation of compound 4b:

[0046] 10 mg (0.0069 mmol) of compound 4a was added to a 25 mL three-necked flask and dissolved in 5 mL of chloroform. 15.1 mg (0.069 mmol) of zinc acetate dihydrate was added and dissolved in 1.4 mL of methanol solution. The mixture was refluxed for 3 h under nitrogen protection. After the reaction was completed, DCM was added to dilute the mixture, and the mixture was washed with water. The organic phases were collected and combined, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The mixture was eluted by silica gel column chromatography with PE:DCM=3:2 to obtain 9.5 mg of compound 4b with a yield of 91.3%. 1H NMR (600 MHz, CDCl3) δ, ppm: 9.02 (d, J =3.3 Hz, 8H), 8.37 (s, 4H), 8.18 (t, J = 6.4 Hz, 4H), 7.91 (d, J = 8.0 Hz,4H), 7.72 (t, J = 7.6 Hz, 4H), 4.52 (s, 8H), 4.23 (d, J = 5.3 Hz, 28H).

[0047] Example 7

[0048] Preparation of compounds 4c~4e:

[0049] 59.3 mg (0.041 mmol) of compound 4a was added to a 100 mL three-necked flask and dissolved in 50 mL of chloroform. 102.0 mg (0.41 mmol) of nickel acetate tetrahydrate was added and dissolved in 15 mL of methanol solution. The mixture was refluxed for 37 h under nitrogen protection. After the reaction was completed, DCM was added to dilute the mixture, washed with water, and the organic phases were combined and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure and the mixture was eluted by silica gel column chromatography with PE:DCM=3:2 to obtain 23.1 mg of compound 4c with a yield of 37.6%. 1 H NMR (600 MHz, CDCl3) δ, ppm: 8.80 (s,8H), 8.16 (s, 4H), 7.96 (d, J = 7.6 Hz, 4H), 7.83 (d, J = 7.9 Hz, 4H), 7.64(t, J = 7.7 Hz, 4H), 4.56 (s, 8H), 4.27 (s, 28H).

[0050] Compounds 4d~4e were synthesized by the same method.

[0051] Example 8

[0052] Preparation of compound IIa:

[0053] In a 25 mL Schlenk reaction bottle, 12.7 mg (0.0088 mmol) of compound 4a and 11.3 mg (0.088 mmol) of TCNE were added, and 7 mL of DCM was added under nitrogen protection. The reaction was refluxed for 12 h. After the reaction was completed, the solvent was evaporated under reduced pressure, and the mixture was eluted with silica gel column chromatography using DCM:MeOH=250:1 to obtain 12.8 mg of compound IIa with a yield of 74.4%. 1H NMR (600 MHz, CDCl3) δ, ppm: 9.17 – 7.76 (m, 24H), 5.92 – 3.88 (m, 36H), -2.90 (s, 2H). 13 C NMR (151MHz, CDCl3) δ, ppm: 172.56, 166.60, 143.55, 139.36, 134.05, 130.52, 128.59,128.05, 118.13, 114.61, 113.63, 113.23, 111.75, 111.53, 87.72, 74.90, 72.74,72.67, 71.78. HRMS (C 116 H 62 4N 20 ) calcd 1959.2906 [M - ], found 1959.2918 [M - ].

[0054] Compounds IIb~IIe were synthesized using the same method.

[0055] IIb, yield 91.3 %. 1 H NMR (600 MHz, CDCl3) δ, ppm: 8.94 – 7.81 (m, 24H), 5.50 – 4.06 (m, 36H). 13 C NMR (151 MHz, CDCl3) δ, ppm: 172.58, 166.77, 150.09,144.30, 139.38, 133.94, 132.61, 132.32, 130.32, 128.32, 127.78, 125.07,118.91, 113.58, 111.72, 111.49, 87.35, 74.95, 72.55, 72.51, 71.80. HRMS(C 116 H 60 4N 20 Zn) calcd 2022.2036 [M - ], found 2022.2046 [M - ].

[0056] IIc, yield 85.1%. 1H NMR (600 MHz, CDCl3) δ, ppm: 9.01 – 7.66 (m, 24H), 5.68 – 3.97 (m, 36H). 13 C NMR (150 MHz, CDCl3) δ, ppm: 172.48, 166.42, 142.59,142.29, 138.33, 133.23, 132.68, 130.66, 128.77, 127.91, 116.92, 113.63,113.26, 111.68, 111.51, 87.54, 78.52, 76.41, 75.53, 74.67, 72.88, 72.70,71.53. HRMS (C 116 H 60 4N 20 Ni) calcd 2015.2102 [M - ], found 2015.2115 [M - ].

[0057] IId, yield 61.6 %. HRMS (C 116 H 60 CuFe4N 20 ) calcd 2020.2048 [M - ], found2020.2038 [M - ].

[0058] IIe, yield 80.9%. HRMS (C 116 H 60 CoFe4N 20 ) calcd 2016.2092 [M - ], found2016.2081 [M - ].

[0059] The UV-visible absorption spectra of porphyrins Ia and IIa are shown in the attached Figure 1 The maximum absorption of the Soret band of Ia and IIa are located at 408 nm and 422 nm, respectively. Compared with Ia, the maximum absorption of the Soret band of IIa is red-shifted by 24 nm due to the increase of the conjugated system, and the absorption below 400 nm is significantly enhanced.

[0060] The fluorescence spectra of porphyrin IIa and its metalloporphyrins IIb~IIe are shown in the attached Figure 2Due to the electron exchange between ferrocene and porphyrin, and the strong electron-withdrawing effect of cyanide, these porphyrins all emit weak fluorescence at 600-800 nm, and the fluorescence quenching of metal porphyrin is more intense than that of free porphyrin.

[0061] Example 9

[0062] Catalytic performance test of catalyst

[0063] The prepared catalyst was added to AP at a mass percentage of 4% of AP, and then ground evenly in an agate mortar. The catalytic performance of the catalyst on the thermal degradation of AP was tested by TG-DTA thermal analyzer. The temperature range was 30~700 ℃, the heating rate was 10 ℃ / min, nitrogen protection, and the nitrogen flow rate was 20 mL / min. Figure 3 The DTA curves of pure AP and 4% TPP, Cat, and porphyrin IIa~IIe added to AP. Figure 3 It can be seen that IIa~IIe have a good catalytic effect on the thermal degradation of AP. After adding 4% porphyrin IIa~IIe to AP, the high-temperature thermal degradation temperature of AP is advanced by 70~120 ℃, and the high-temperature thermal degradation exothermic enthalpy is also increased from 910 J / g of pure AP to 1069~1321 J / g. Among them, the catalytic effect of porphyrin IId is equivalent to that of catoctin Cat, while the catalytic performance of cobalt porphyrin IIe is better than that of catoctin.

[0064] Example 10

[0065] Catalyst migration resistance test

[0066] The anti-migration test of the catalyst in the propellant was carried out using the common protocol in the literature (Z. Anorg. Allg. Chem. 2022, 648, e202200053). Figure 4 The figure is a test picture of the anti-migration property of porphyrin Id. The formula content of the catalyst representing the burning rate of porphyrin Id simulating the actual solid propellant was mixed with other components in the propellant in proportion and put into a glass tube, placed at room temperature, and photographed and measured the migration distance every seven days. It was found that there was no migration after 16 weeks, indicating that the catalyst provided by the present invention not only has excellent catalytic performance, but also does not migrate.

[0067] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A ferrocenylcyanoporphyrin-based burning rate catalyst, characterized in that: Its structure is shown in general formula (I) or general formula (II): ， Wherein, M is two hydrogens 2H or one of the metal elements Zn, Ni, Cu, and Co.

2. The method for preparing a ferrocenylcyanoporphyrin burning rate catalyst according to claim 1, characterized in that: The preparation method of the burning rate catalyst described in general formula (I) comprises the following steps: ， (1) Under nitrogen protection, 3-ferrocenylethynylbenzaldehyde and bispyrromethene were reacted in dichloromethane (DCM) with trifluoroacetic acid (TFA) as a catalyst, and the reaction was carried out at room temperature in the dark for 21 h. The free porphyrin 3a was then obtained by oxidation with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) for 1 h. The molar ratio of each material was: 3-ferrocenylethynylbenzaldehyde:bispyrromethene:TFA:DDQ = 1:1:0.6:1.5; (2) Then, the chloroform solution of 3a was refluxed with the corresponding methanol solution of acetate under nitrogen protection to obtain metalloporphyrins 3b~3e, wherein 3b required reflux for 5 h, and 3c~3e required reflux for 37 h. The molar ratio of material 3a to acetate was 1:10; (3) Under nitrogen protection, 3a~3e were respectively reacted with the click reagent tetracyanoethylene (TCNE) in DCM solution for reflux for 12 h to obtain porphyrins Ia~Ie. The molar ratio of materials 3a~3e to TCNE was 1:

5.

3. The method for preparing a ferrocenylcyanoporphyrin burning rate catalyst according to claim 1, characterized in that: The preparation method of the burning rate catalyst described in general formula (II) comprises the following steps: ， (1) Under nitrogen protection, 3-ferrocenylethynylbenzaldehyde and pyrrole were reacted in DCM with TFA as the catalyst, and the reaction was carried out at room temperature in the dark for 1.5 h, followed by oxidation with DDQ for 3.5 h to obtain free porphyrin 4a. The molar ratio of each material was: 3-ferrocenylethynylbenzaldehyde:pyrrole:TFA:DDQ = 1:1:2:1.5; (2) Then, the chloroform solution of 4a was refluxed with the corresponding methanol solution of acetate under nitrogen protection to prepare metalloporphyrins 4b~4e, wherein 4b needed to be refluxed for 3 h, and 4c~4e needed to be refluxed for 37 h. The molar ratio of material 4a to acetate was 1:10; (3) Under nitrogen protection, 4a~4e were refluxed with TCNE in DCM solution for 12 h to obtain porphyrins IIa~IIe. The molar ratio of materials 4a~4e to TCNE was 1:

5.

4. Use of the ferrocenylcyanoporphyrin burning rate catalyst according to claim 1 in composite solid propellant.

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