CN110078616B - Fullerene phenolic ester derivative and preparation method and application thereof - Google Patents

Fullerene phenolic ester derivative and preparation method and application thereof Download PDF

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CN110078616B
CN110078616B CN201910392460.6A CN201910392460A CN110078616B CN 110078616 B CN110078616 B CN 110078616B CN 201910392460 A CN201910392460 A CN 201910392460A CN 110078616 B CN110078616 B CN 110078616B
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fullerene
phenolic ester
reaction
phenyl
mixed solution
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CN110078616A (en
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金波
彭汝芳
赵杨
张青春
黄琪
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Southwest University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/006—Stabilisers (e.g. thermal stabilisers)
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/04—Formic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/21—Acetic acid esters of hydroxy compounds with more than three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/33—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with hydroxy compounds having more than three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2604/00—Fullerenes, e.g. C60 buckminsterfullerene or C70
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a fullerene phenolic ester derivative shown as a formula (I) and a preparation method thereof. The fullerene phenolic ester derivative is synthesized by using optimized Friedel-Crafts alkylation reaction and hexachlorofullerene and phenolic ester as raw materials. The fullerene derivative can be used as a novel fullerene stabilizer to be applied to a solid rocket propellant.
Figure DDA0002056105770000011
In the formula: r is-H, -CH 3 ，‑CH 3 CH 2 ，‑CH(CH 3 ) 2 ，‑CH 2 CH 2 CH 3 ，‑CH 2 CH 2 CH 2 CH 3 。

Description

Fullerene phenolic ester derivative and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic chemistry, and relates to a fullerene phenolic ester derivative and a preparation technology thereof.
Technical Field
With the development of aerospace industry and the continuous improvement of the requirements of national defense science and technology on high, fine and sharp weapons, the high-performance propellant becomes a hot problem of research. The stabilizer is one of indispensable components for maintaining the thermal stability of the solid propellant, and is a very critical functional material in the formulation of the solid propellant. The search for stabilizers with excellent performance has become a main direction for improving the performance of the propellant under the condition that the main components of the existing propellant are not changed.
As the leading energy source in modern rocket and missile engines, aromatic amine compounds containing nitrogen atoms (such as diphenylamine, N-methyl-4-nitroaniline, N '-dimethyl-N, N' -diphenylurea and 3-methyl-1, 1-diphenylurea) are usually selected as stabilizers for bi-or modified bi-based propellants, and the stabilizers and thermal decomposition products of the propellants have different degrees of reaction activity, can delay the autocatalytic decomposition of the main components of the propellants and have obvious effect on prolonging the safe storage life of the propellants.
However, these compounds also have two significant disadvantages, namely, poor stability and not very durable stabilizing effect; secondly, the compatibility with other components in the propellant is poor, and the comprehensive performance of the propellant cannot be improved.
In view of this, efforts are being made to find stabilizers which have a longer-lasting stabilizing effect and better suitability and which can provide the propellant with better overall properties.
Disclosure of Invention
The invention aims to overcome the problems of poor stability and adaptability and the like of the existing solid rocket propellant stabilizer, and provides a fullerene phenolic ester derivative and a preparation method thereof.
The technical scheme for realizing the purpose of the invention is as follows:
a fullerene phenolic ester derivative having a chemical structure represented by the following formula (I):
Figure BDA0002056105750000021
in the formula: r is-H, -CH 3 ，-CH 3 CH 2 ，-CH(CH 3 ) 2 ，-CH 2 CH 2 CH 3 ，-CH 2 CH 2 CH 2 CH 3 。
The fullerene phenolic ester derivative is used as a stabilizer for a solid rocket propellant.
The preparation method of the fullerene phenolic ester derivative comprises the step of synthesizing the fullerene phenolic ester derivative by using hexachlorofullerene and phenolic ester.
The specific steps for synthesizing the fullerene phenolic ester derivative are that hexachlorofullerene is dissolved in an organic solvent at room temperature of 25 ℃, the mass of the solvent is 10-20 times of the sum of the mass of reactants, the mixed solution is stirred for at least 2 hours under the protection of nitrogen, after the hexachlorofullerene is completely dissolved, phenolic ester and a catalyst are added into the mixed solution, and the molar ratio of hexachlorofullerene to the catalyst is as follows: 1:90, adjusting the reaction temperature to 100 ℃, stirring the mixture to react under the protection of nitrogen until the thin layer chromatography shows that the reactants are completely consumed, and changing the reaction liquid from orange to dark brown; after the reaction is finished, removing redundant solvent through rotary evaporation to obtain a reddish brown crude product; and dissolving the crude product by using a small amount of organic solvent, and separating by using a silica gel column chromatography to obtain an orange-red product, namely the product.
The phenolic ester is one of phenyl formate, phenyl acetate, phenyl propionate and phenyl n-butyrate; the catalyst is one of anhydrous aluminum trichloride, anhydrous ferric trichloride and titanium tetrachloride; the organic solvent is one of chlorobenzene, nitrobenzene and carbon disulfide.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
fullerene C 60 Is an allotrope of carbon, has a plurality of conjugated olefins, and has higher reaction activity with free radicals. Therefore, the phenol ether group is introduced into the fullerene ball, a brand-new cage-shaped stabilizer, namely p-alkoxy phenyl fullerene can be obtained, the heat stabilization effect can be achieved, and the fullerene-based stabilizer with excellent comprehensive performance is provided for the low-characteristic signal double-base propellant.
The p-alkoxy phenyl fullerene provided by the invention is obtained by Friedel-Crafts alkylation reaction of hexachlorofullerene and alkoxy benzene, and a single crystal structure is obtained, so that the performance is very stable and excellent. The fullerene stabilizer is adopted to replace the traditional stabilizer, the thermal stability of the propellant is improved, the storage period of the rocket is prolonged more durably, the fullerene stabilizer has good compatibility with other components of the propellant, and the abundant carbon component in the fullerene in the stabilizer can be used as a combustion improver to improve the specific impulse of the propellant, so that the comprehensive performance of the propellant is further improved.
The phenyl alkoxy fullerene provided by the invention can absorb free radicals and nitrogen oxides to achieve the stabilizing effect, is a mono-base propellant stabilizer with potential application value, and has good development potential and market prospect in the aerospace field and the national defense field such as rocket propellant;
the preparation method of the product is simple and convenient, the reaction condition is mild, the separation and purification are easy, the yield is high, and the method is suitable for industrial production.
Drawings
FIG. 1 is a hydrogen spectrum of a phenylformate-based fullerene
FIG. 2 is a hydrogen spectrum diagram of a phenylacetate-based fullerene
Detailed Description
The following examples are intended to illustrate the invention further, but should not be construed as limiting the scope of the invention, and many insubstantial modifications and adaptations of the invention by those skilled in the art based on the teachings set forth herein should be made without departing from the scope of the invention.
Example 1:
the preparation method of the benzoate fullerene (a) comprises the following steps:
0.05mmol of hexachlorofullerene is dissolved in 20mL of nitrobenzene at room temperature and 25 ℃, and the mixed solution is stirred and dissolved for 2 hours under the protection of nitrogen. After complete dissolution, 15mmol of phenyl formate and 4.55mmol of titanium tetrachloride were added to the mixed solution, and the oil bath temperature was raised to 100 ℃. The reaction was stirred under nitrogen until thin layer chromatography showed complete consumption of the reactants and the reaction turned from orange to dark brown. After the reaction was completed, the excess solvent was removed by distillation under reduced pressure to obtain a reddish brown crude product. The crude product was dissolved with a small amount of carbon disulfide and separated by silica gel column chromatography to give an orange-red product, the eluent was ethyl acetate/carbon disulfide (1/1).
Example 2:
the preparation method of the benzoate fullerene (a) comprises the following steps:
0.05mmol of hexachlorofullerene was dissolved in 20mL of nitrobenzene at room temperature and 25 ℃, and the mixed solution was dissolved under stirring under nitrogen for 2 hours. After complete dissolution, 15mmol of phenyl formate and 6mmol of anhydrous aluminum trichloride are added into the mixed solution, and the oil bath temperature is raised to 100 ℃. The reaction was stirred under nitrogen until thin layer chromatography showed complete consumption of the reactants and the reaction turned from orange to dark brown. After the reaction was completed, the excess solvent was removed by distillation under reduced pressure to obtain a reddish brown crude product. The crude product was dissolved in a small amount of carbon disulfide and separated by silica gel column chromatography to give an orange-red product, the eluent being ethyl acetate/carbon disulfide (1/1).
Example 3:
the preparation method of the phenyl acetate-based fullerene (b) comprises the following steps:
0.05mmol of hexachlorofullerene is dissolved in 20mL of nitrobenzene at room temperature and 25 ℃, and the mixed solution is stirred and dissolved for 2 hours under the protection of nitrogen. After complete dissolution, 15mmol of phenyl acetate and 4.55mmol of titanium tetrachloride were added to the mixed solution, and the oil bath temperature was raised to 100 ℃. The reaction was stirred under nitrogen until thin layer chromatography showed complete consumption of the reactants and the reaction turned from orange to dark brown. After the reaction was completed, the excess solvent was removed by distillation under reduced pressure to obtain a reddish brown crude product. The crude product was dissolved in a small amount of carbon disulfide and separated by silica gel column chromatography to give an orange-red product, the eluent being ethyl acetate/carbon disulfide (1/3).
Example 4:
the preparation method of the propionate-based fullerene (c) comprises the following steps:
0.05mmol of hexachlorofullerene is dissolved in 20mL of nitrobenzene at room temperature and 25 ℃, and the mixed solution is stirred and dissolved for 2 hours under the protection of nitrogen. After complete dissolution, 15mmol of phenyl propionate and 6mmol of anhydrous ferric chloride are added into the mixed solution, and the oil bath temperature is raised to 100 ℃. The reaction was stirred under nitrogen until thin layer chromatography showed complete consumption of the reaction and the reaction turned from orange to dark brown. After the reaction was completed, the excess solvent was removed by distillation under reduced pressure to obtain a reddish brown crude product. Dissolving the crude product with small amount of carbon disulfide, and separating by silica gel column chromatography to obtain orange red product, wherein the eluent is ethyl acetate/n-hexane (1/2).
Example 5:
the preparation method of the n-butyl benzene ester based fullerene (d) comprises the following steps:
0.05mmol of hexachlorofullerene is dissolved in 20mL of nitrobenzene at room temperature and 25 ℃, and the mixed solution is stirred and dissolved for 2 hours under the protection of nitrogen. After complete dissolution, 15mmol of phenyl propionate and 6mmol of anhydrous ferric chloride are added into the mixed solution, and the oil bath temperature is raised to 100 ℃. The reaction was stirred under nitrogen until thin layer chromatography showed complete consumption of the reaction and the reaction turned from orange to dark brown. After the reaction was completed, the excess solvent was removed by distillation under reduced pressure to obtain a reddish brown crude product. Dissolving the crude product with small amount of carbon disulfide, and separating by silica gel column chromatography to obtain orange red product, wherein the eluent is ethyl acetate/n-hexane (1/3).
The nuclear magnetic hydrogen spectra of the obtained fullerene phenolic ester derivatives are shown in figures 1 and 2, and the stabilizing effect of the fullerene phenolic ester derivatives (a and b) and traditional stabilizers (DPA, C2 and AKII) on nitrocotton is shown in table 1.
TABLE 1 time taken for the color change of methyl violet test paper of nitrocotton samples doped with different stabilizers in the methyl violet test
Figure BDA0002056105750000071
Further examples can be written with any of the catalysts, organic solvents and leachates defined in the claims, with the principle of the invention, with any of the groups in any position, but without space and without enumeration.

Claims (1)

1. A preparation method of fullerene phenolic ester derivatives is characterized by comprising the following specific steps:
at room temperature of 25 ℃, dissolving hexachlorofullerene in an organic solvent, wherein the mass of the solvent is 10-20 times of the sum of the mass of reactants, stirring the mixed solution for at least 2 hours under the protection of nitrogen, and after the mixed solution is completely dissolved, adding phenolic ester and a catalyst into the mixed solution, wherein the molar ratio of hexachlorofullerene to the catalyst is as follows: 1:90, adjusting the reaction temperature to 100 ℃, stirring and reacting under the protection of nitrogen until the thin layer chromatography shows that the reactants are completely consumed, and the reaction liquid is changed from orange to dark brown; after the reaction is finished, removing the redundant solvent by rotary evaporation to obtain a reddish brown crude product; dissolving the crude product with a small amount of organic solvent, and separating by silica gel column chromatography to obtain an orange-red product, namely the product;
the phenolic ester is one of phenyl formate, phenyl acetate, phenyl propionate and phenyl n-butyrate; the catalyst is one of anhydrous aluminum trichloride, anhydrous ferric trichloride and titanium tetrachloride; the organic solvent is one of chlorobenzene, nitrobenzene and carbon disulfide;
the fullerene phenolic ester derivative has a chemical structure shown in the following formula (I):
Figure FDA0003733144520000011
in the formula: r is-H, -CH 3 ，-CH 3 CH 2 ，-CH 2 CH 2 CH 3 。
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CN102863595A (en) * 2012-09-06 2013-01-09 西南科技大学 Fullerene itaconic acid metal salt derivative as well as preparation method and application thereof
CN106083626A (en) * 2016-06-03 2016-11-09 厦门大学 One fullerene amino-acid ester self assembly carried medicine sustained-release vesicle material and its preparation method and application

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* Cited by examiner, † Cited by third party
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CN1906149A (en) * 2003-12-15 2007-01-31 Nano-C公司 Higher fullerenes useful as radical scavengers
EP1787987A1 (en) * 2005-10-21 2007-05-23 C Sixty, Inc. Substituted fullerenes and their use as antioxidants
CN102583308A (en) * 2012-01-18 2012-07-18 中国人民解放军63971部队 Method for preparing multi-peroxide-group fullerene derivative
CN102863595A (en) * 2012-09-06 2013-01-09 西南科技大学 Fullerene itaconic acid metal salt derivative as well as preparation method and application thereof
CN106083626A (en) * 2016-06-03 2016-11-09 厦门大学 One fullerene amino-acid ester self assembly carried medicine sustained-release vesicle material and its preparation method and application

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