CN115181023B - Spiro active plasticizer and preparation method thereof - Google Patents
Spiro active plasticizer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a spiro active plasticizer and a preparation method thereof, wherein the spiro and active alkynyl spiro active plasticizer, namely spiro [3.3] heptane-2-propynyl formate, is successfully prepared through substitution reaction, cyclization reaction, hydrolysis reaction, decarboxylation reaction and esterification reaction. The plasticizer can fundamentally solve the migration problem of the plasticizer through the click chemistry activity between the alkynyl and the azido while maintaining the energy.
Description
Technical Field
The invention relates to the technical field of plasticizers, in particular to a spiro active plasticizer and a preparation method thereof.
Background
The energetic plasticizer is used as one of important auxiliary agents for preparing the composite solid propellant, and can remarkably improve the processing performance, mechanical property, energy level and the like. Conventional energetic plasticizers are typically incorporated into composite solid propellants by physical blending, however, mechanical movement, temperature, and the like can cause migration and precipitation of the energetic plasticizer.
The problem of migration of energetic plasticizers has been of great concern because the energetic materials are highly sensitive substances, and migration of energetic plasticizers reduces the mechanical integrity of the materials and the safe storage properties of the weapon equipment, which can easily lead to the failure of safe and effective transportation and storage of the munitions equipment, which prevents the improvement of national defence.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a spiro active plasticizer which contains a novel active plasticizer with high-energy spiro and active alkynyl groups, and can fundamentally solve the migration problem of the plasticizer through the click chemistry activity between the alkynyl groups and the azido groups while maintaining the energy of the novel active plasticizer.
According to a first aspect of the object of the present invention, there is provided a spiro-reactive plasticizer comprising a spiro ring and a reactive alkynyl group, the spiro-reactive plasticizer having the molecular structural formula of formula i;
preferably, the spiro reactive plasticizer has the formula C 11 H 14 O 2 。
According to a second aspect of the object of the present invention, there is provided a process for the preparation of a spiro reactive plasticizer comprising the steps of:
s1, dissolving 1, 1-cyclobutane dimethanol, p-toluenesulfonyl chloride, pyridine and 4-dimethylaminopyridine in a first organic solvent, and stirring for reaction to obtain a first solution;
extracting the first solution by using a saturated sodium chloride solution, drying an organic phase obtained by extraction, filtering and concentrating to obtain 1, 1-cyclobutane dimethyl p-toluenesulfonate;
s2, adding the dimethyl 1, 1-cyclobutane p-toluenesulfonate obtained in the step S1 into a second organic solvent containing diethyl malonate and metallic sodium, and carrying out reflux reaction to obtain a second solution;
cooling the second solution to room temperature, extracting the second solution by adopting saturated sodium bicarbonate solution, drying an organic phase obtained by extraction, filtering, concentrating, and separating by a column chromatography to obtain spiro [3.3] heptane-1, 1-diethyl dicarboxylate;
s3, blending and refluxing the diethyl spiro [3.3] heptane-1, 1-dicarboxylic acid obtained in the step S2 with a third organic solvent, water and potassium hydroxide to obtain a third solution, cooling the temperature of the third solution to room temperature after the reaction, and adjusting the pH to be acidic to obtain a fourth solution;
extracting the fourth solution by using ethyl acetate, drying an organic phase obtained by extraction, filtering, and concentrating to obtain crude spiro [3.3] heptane-1, 1-dicarboxylic acid;
adding spiro [3.3] heptane-1, 1-dicarboxylic acid into pyridine for reflux, drying the organic phase after reflux, filtering, and concentrating to obtain spiro [3.3] heptane carboxylic acid;
s4, dissolving the spiro [3.3] heptane carboxylic acid obtained in the step S3, p-toluenesulfonic acid and propargyl alcohol in a fourth organic solvent, and heating for reaction to obtain a fifth solution;
and (3) cooling the fifth solution to room temperature, extracting the fifth solution by using saturated sodium bicarbonate solution, drying, filtering, concentrating an organic phase obtained by extraction, and separating by using a column chromatography to obtain spiro [3.3] heptane-2-propynylformate, namely the spiro active plasticizer.
Preferably, in the step S1, the concentration of the tosyl chloride is 0.8 to 1.2M; the mol ratio of 1, 1-cyclobutane dimethanol to p-toluenesulfonyl chloride is 1 (2.0-2.5); the mass ratio of the 1, 1-cyclobutane dimethanol to the pyridine is 1 (2.5-3.0); the molar ratio of the 4-dimethylaminopyridine to the p-toluenesulfonyl chloride is 1 (8-12); the first organic solvent is dichloromethane or chloroform.
Preferably, in the step S1, the reaction temperature for obtaining the first solution is 20-30 ℃, and the reaction time is 12-24 hours.
Preferably, in the step S2, the concentration of the dimethyl 1, 1-cyclobutane-p-toluenesulfonate is 0.4-0.6M; the molar ratio of the 1, 1-cyclobutane dimethyl tosylate to the diethyl malonate is 1:2.0-3.0; the molar ratio of diethyl malonate to sodium is 1:1-1.2; the second organic solvent is xylene.
Preferably, the xylene is ortho-xylene or meta-xylene.
Preferably, in the step S2, the reaction temperature for obtaining the second solution is 120-138 ℃, and the reaction time is 24-48 hours;
the conditions for column chromatography separation were: silica gel is adopted for 200-300 meshes, and the volume ratio of ethyl acetate to normal hexane is 1:10-12.
Preferably, in the step S3, the mol ratio of the diethyl spiro [3.3] heptane-1, 1-dicarboxylic acid to the potassium hydroxide is 1:3.0-4.0; the mass ratio of the potassium hydroxide to the third organic solvent is 1:8-12; the mass ratio of the water to the third organic solvent is 1:2-3; the third organic solvent is ethanol or methanol.
Preferably, in the step S3, the reaction temperature for obtaining the third solution is 80-100 ℃, and the reaction time is 6-12 hours; and regulating the pH value of the third solution to 1-3 to obtain a fourth solution.
Preferably, in the step S4, the concentration of spiro [3.3] heptanoic acid is 0.25 to 0.30M; the mole ratio of the spiro [3.3] heptane carboxylic acid to the p-toluene sulfonic acid is 1:0.1-0.3; the molar ratio of the spiro [3.3] heptane carboxylic acid to the propargyl alcohol is 1:1-1.3; the fourth organic solvent is toluene or xylene.
Preferably, in the step S4, the reaction temperature of the fifth solution is 110-138 ℃ and the reaction time is 8-12 hours;
the conditions for column chromatography separation were: silica gel is adopted for 200-300 meshes, and the volume ratio of ethyl acetate to normal hexane is 1:10-12.
Compared with the prior art, the invention has the beneficial effects that:
1. the spiro active plasticizer has high-energy spiro and active alkynyl, wherein the spiro is a substance which has ring tension energy and can be stably stored in a ring-shaped molecular structure, has a more compact space structure compared with a linear molecule, can remarkably improve the energy density of the substance, the combustion heat and the specific impulse of a propellant, has lower sensitivity than the traditional energetic group, and keeps the energy; the molecular design that the electron-withdrawing group is close to the alkynyl is introduced while the energy is kept, and the click chemical reaction activity between the alkynyl and the azido is accelerated under the condition of no catalyst, so that the active plasticizer is quickly linked to the side chain of the macromolecule through chemical reaction to form a grafted space configuration, the migration problem of the plasticizer is fundamentally solved, and the safe and effective storage and transportation of weapons are ensured.
2. The spiro [3.3] heptane-2-propynyl formate is successfully prepared through substitution reaction, cyclization reaction, hydrolysis reaction, decarboxylation reaction and esterification reaction, and the whole preparation process has the advantages of low cost, high yield, high safety and the like aiming at the design of a complex spiro molecular structure, and is beneficial to batch production.
Drawings
FIG. 1 is a schematic representation of the preparation of spiro reactive plasticizers of the present invention.
FIG. 2 shows a spiro reactive plasticizer according to the invention 1 HNMR spectra.
FIG. 3 is an FT-IR spectrum of a spiro active plasticizer according to the invention.
FIG. 4 is a DSC of a mixture of a spiro-reactive Plasticizer (PSHC) and a Glycidyl Azide (GAP) according to the present invention.
Detailed Description
For a better understanding of the technical content of the present invention, specific examples are set forth below, along with the accompanying drawings.
Aspects of the invention are described in this disclosure with reference to the drawings, in which are shown a number of illustrative embodiments. The embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be appreciated that the various concepts and embodiments described above, as well as those described in more detail below, may be implemented in any of a wide variety of ways.
According to an exemplary embodiment of the present invention, there is provided a spiro-reactive plasticizer comprising a spiro ring and a reactive alkynyl group, the spiro-reactive plasticizer having a molecular structural formula of formula i;
in a preferred embodiment, the spiro reactive plasticizer has the formula C 11 H 14 O 2 。
As shown in fig. 1, according to another exemplary embodiment of the present invention, there is provided a method for preparing a spiro reactive plasticizer, comprising the steps of:
s1, dissolving 1, 1-cyclobutane dimethanol, p-toluenesulfonyl chloride, pyridine and 4-dimethylaminopyridine in a first organic solvent, and stirring for reaction to obtain a first solution;
extracting the first solution by using a saturated sodium chloride solution, drying an organic phase obtained by extraction, filtering and concentrating to obtain 1, 1-cyclobutane dimethyl p-toluenesulfonate;
s2, adding the dimethyl 1, 1-cyclobutane p-toluenesulfonate obtained in the step S1 into a second organic solvent containing diethyl malonate and metallic sodium, and carrying out reflux reaction to obtain a second solution;
cooling the second solution to room temperature, extracting the second solution by adopting saturated sodium bicarbonate solution, drying an organic phase obtained by extraction, filtering, concentrating, and separating by a column chromatography to obtain spiro [3.3] heptane-1, 1-diethyl dicarboxylate;
s3, blending and refluxing the diethyl spiro [3.3] heptane-1, 1-dicarboxylic acid obtained in the step S2 with a third organic solvent, water and potassium hydroxide to obtain a third solution, cooling the temperature of the third solution to room temperature after the reaction, and adjusting the pH to be acidic to obtain a fourth solution;
extracting the fourth solution by using ethyl acetate, drying an organic phase obtained by extraction, filtering, and concentrating to obtain crude spiro [3.3] heptane-1, 1-dicarboxylic acid;
adding spiro [3.3] heptane-1, 1-dicarboxylic acid into pyridine for reflux, drying the organic phase after reflux, filtering, and concentrating to obtain spiro [3.3] heptane carboxylic acid;
s4, dissolving the spiro [3.3] heptane carboxylic acid obtained in the step S3, p-toluenesulfonic acid and propargyl alcohol in a fourth organic solvent, and heating for reaction to obtain a fifth solution;
and (3) cooling the fifth solution to room temperature, extracting the fifth solution by using saturated sodium bicarbonate solution, drying, filtering, concentrating an organic phase obtained by extraction, and separating by using a column chromatography to obtain spiro [3.3] heptane-2-propynylformate, namely the spiro active plasticizer.
In a preferred embodiment, in the step S1, the concentration of the tosyl chloride is 0.8 to 1.2M; the mol ratio of 1, 1-cyclobutane dimethanol to p-toluenesulfonyl chloride is 1 (2.0-2.5); the mass ratio of the 1, 1-cyclobutane dimethanol to the pyridine is 1 (2.5-3.0); the molar ratio of the 4-dimethylaminopyridine to the p-toluenesulfonyl chloride is 1 (8-12); the first organic solvent is dichloromethane or chloroform.
In a preferred embodiment, in the step S1, the reaction temperature for obtaining the first solution is 20 to 30 ℃ and the reaction time is 12 to 24 hours.
In a preferred embodiment, in the step S2, the concentration of dimethyl 1, 1-cyclobutane-p-toluenesulfonate is 0.4 to 0.6M; the molar ratio of the 1, 1-cyclobutane dimethyl tosylate to the diethyl malonate is 1:2.0-3.0; the molar ratio of diethyl malonate to sodium is 1:1-1.2; the second organic solvent is xylene.
In a more preferred embodiment, the xylene is ortho-xylene or meta-xylene.
In a preferred embodiment, in the step S2, the reaction temperature for obtaining the second solution is 120-138 ℃ and the reaction time is 24-48 hours;
the conditions for column chromatography separation were: silica gel is adopted for 200-300 meshes, and the volume ratio of ethyl acetate to normal hexane is 1:10-12.
In a preferred embodiment, in the step S3, the mole ratio of the diethyl spiro [3.3] heptane-1, 1-dicarboxylic acid to the potassium hydroxide is 1:3.0-4.0; the mass ratio of the potassium hydroxide to the third organic solvent is 1:8-12; the mass ratio of the water to the third organic solvent is 1:2-3; the third organic solvent is ethanol or methanol.
In a preferred embodiment, in the step S3, the reaction temperature for obtaining the third solution is 80-100 ℃ and the reaction time is 6-12 hours; and regulating the pH value of the third solution to 1-3 to obtain a fourth solution.
In a preferred embodiment, in the step S4, the concentration of spiro [3.3] heptanoic acid is 0.25 to 0.30M; the mole ratio of the spiro [3.3] heptane carboxylic acid to the p-toluene sulfonic acid is 1:0.1-0.3; the molar ratio of the spiro [3.3] heptane carboxylic acid to the propargyl alcohol is 1:1-1.3; the fourth organic solvent is toluene or xylene.
In a preferred embodiment, in the step S4, the reaction temperature for obtaining the fifth solution is 110-138 ℃ and the reaction time is 8-12 h;
the conditions for column chromatography separation were: silica gel is adopted for 200-300 meshes, and the volume ratio of ethyl acetate to normal hexane is 1:10-12.
The above preparation and the spiro reactive plasticizers prepared are tested in the following experiments in combination with specific examples.
The experimental methods used in the following examples are conventional methods unless otherwise specified. Materials, reagents, and the like used in the embodiments described below are commercially available unless otherwise specified.
[ example 1 ]
10.42g of 1, 1-cyclobutane dimethanol, 37.62g of p-toluenesulfonyl chloride, 28.38g of pyridine and 2.19g of 4-dimethylaminopyridine are dissolved in 180mL of dichloromethane under stirring for reaction for 24 hours, then 100mL of saturated sodium chloride solution is used for extraction for 3 times, the extracts are combined, the organic phase is dried by anhydrous magnesium sulfate for 12 hours, filtered and then subjected to rotary evaporation under reduced pressure for 1 hour at 40-50 ℃ by a rotary evaporator, and white powder 1, 1-cyclobutane dimethyl p-toluenesulfonate can be obtained after concentration, and the yield is 91.1%.
Nuclear magnetic resonance: 1 H NMR(300MHz,CDCl 3 ):δ＝1.92–1.75ppm(m,2H,2H,2H,CH 2 –CH 2 ,CH 2 –C,CH 2 –C),2.45ppm(s,J＝1.4Hz,6H,–CH 3 ),3.93ppm(s,4H,CH 2 –O),7.35ppm(d,J＝7.4Hz,2H,＝CH–C–CH 3 ),7.70ppm(d,J＝8.4Hz,2H,CH＝CH–C). 13 C NMR(75MHz,CDCl 3 ,ppm)δ＝15.15,21.88,25.49,40.82,71.89,128.04,130.12,132.49,145.33。
by analyzing the structural analysis and the configuration of the molecule through nuclear magnetic resonance spectroscopy, the successful synthesis of the product molecule, namely 1, 1-cyclobutane dimethyl p-toluenesulfonate, can be determined according to the results.
Elemental analysis: molecular formula C 20 H 24 O 6 S 2 ,424.53。
Theoretical value (%): c,56.59; h,5.70; o,22.61; s,15.10; measured value (%) C,56.57; h,5.73; o,22.64; s,15.06.
Through elemental analysis tests, the elemental composition and content of the 1, 1-cyclobutane dimethyl p-toluenesulfonate are determined to be close to the theoretical value, and the purity is higher. [ example 2 ]
Under stirring, 32.69g of dimethyl 1, 1-cyclobutane-p-toluenesulfonate was then added to 180mL of a p-xylene solution containing 30.72g of diethyl malonate and 4.41g of metallic sodium, the mixture was refluxed for 24 hours, cooled to room temperature, extracted 3 times with 100mL of saturated sodium bicarbonate solution, the extracts were combined, the organic phase was dried over anhydrous magnesium sulfate for 12 hours, filtered, distilled off under reduced pressure at 60 to 70 ℃ for 2 hours by a rotary evaporator after filtration, and a dark yellow liquid was obtained after concentration, and after separation by column chromatography (silica gel 200 to 300 mesh, ethyl acetate/n-hexane=1/10, v/v), pale yellow spiro [3.3] heptane-1, 1-dicarboxylic acid diethyl ester was obtained in a yield of 83.2%.
Nuclear magnetic resonance: 1 H NMR(300MHz,CDCl 3 ):δ＝1.16ppm(m,6H,CH 3 ),1.69ppm(m,2H,CH 2 –CH 2 ),1.91ppm(t,4H,CH 2 –C–),2.47ppm(t,4H,CH 2 –C–),4.11ppm(m,J＝8.0Hz,4H,O–CH 2 ). 13 C NMR(75MHz,CDCl 3 ,ppm):δ＝14.28,16.27,35.29,38.59,41.63,48.82,61.55,172.17。
from the above results, it was confirmed that the product molecule spiro [3.3] heptane-1, 1-dicarboxylic acid diethyl ester was successfully synthesized by analyzing the structure and configuration of the molecule by nuclear magnetic resonance spectroscopy.
Elemental analysis: molecular formula, C13H20O4,240.30.
Theoretical value (%): c,64.98; h,8.39; o,26.63; measured value (%) C,64.95; h,8.37; o,26.68.
The elemental analysis test shows that the elemental composition and content of the spiro [3.3] heptane-1, 1-dicarboxylic acid diethyl ester are close to the theoretical value, and the purity is higher.
[ example 3]
10.00g of spiro [3.3] heptane-1, 1-dicarboxylic acid diethyl ester, 100mL of ethanol, 50mL of water and 9.34g of potassium hydroxide are mixed and refluxed at the temperature of 24 ℃ under stirring, the reaction is carried out for 12 hours, the temperature is reduced to room temperature and the pH value is adjusted to 3 after the reaction, the mixture is extracted for 3 times by 100mL of ethyl acetate, the extracts are combined, the organic phase is dried by anhydrous magnesium sulfate for 12 hours, filtered and subjected to reduced pressure rotary evaporation for 1 hour at the temperature of 40-50 ℃ by a rotary evaporator, the concentrated solution can be crude to obtain dark brown spiro [3.3] heptane-1, 1-dicarboxylic acid, the spiro [3.3] heptane-1, 1-dicarboxylic acid is added into 100mL of pyridine and refluxed for 24 hours, the organic phase is dried by anhydrous magnesium sulfate for 12 hours, the filtered solution is subjected to reduced pressure rotary evaporation for 2 hours at the temperature of 70-80 ℃ by a rotary evaporator, and the concentrated solution can obtain spiro [3.3] heptane carboxylic acid with the yield of 83.4%.
Nuclear magnetic resonance: 1 HNMR(300MHz,DMSO-d 6 ):δ＝1.71–2.09ppm(m,2H,2H,2H,2H,2H,CH 2 –CH 2 ,CH 2 –C,CH 2 –C,CH 2 –CH,CH 2 –CH),2.84ppm(m,J＝7.0Hz,1H,CH–COOH). 13 CNMR(75MHz,DMSO-d 6 ,ppm):δ＝16.48,32.92,34.78,35.28,38.02,40.20,176.91。
from the above results, it was confirmed that the product molecule spiro [3.3] heptane carboxylic acid had been successfully synthesized by analysis of structural analysis and configuration of the molecule by nuclear magnetic resonance spectroscopy.
Elemental analysis: molecular formula C 8 H 12 O 2 ,140.18。
Theoretical value (%): c,68.54; h,8.63; o,22.83; measured values (%) C,68.52; h,8.64; o,22.84.
The elemental analysis test shows that the elemental composition and content of the spiro [3.3] heptane carboxylic acid are close to the theoretical value, and the purity is higher.
[ example 4 ]
2.54g of spiro [3.3] heptane carboxylic acid, 0.38g of p-toluene sulfonic acid and 1.51g of propargyl alcohol are dissolved in 70mL of toluene under stirring at the temperature of 24 ℃, heated to 110 ℃, reacted for 12 hours, cooled to room temperature after the reaction, extracted with 100mL of saturated sodium bicarbonate solution for 3 times, the extracts are combined, the organic phase is dried for 12 hours by anhydrous magnesium sulfate, filtered and subjected to rotary evaporation under reduced pressure for 2 hours at 70-80 ℃ by a rotary evaporator, concentrated and separated by column chromatography (silica gel 200-300 meshes, ethyl acetate/n-hexane=1/10, v/v) to obtain pale yellow liquid spiro [3.3] heptane-2-propynylformate with the yield of 80.0%.
Nuclear magnetic resonance: the results are shown in FIG. 2
1 H NMR(300MHz,CDCl 3 ):δ＝1.71–2.22ppm(m,2H,2H,2H,2H,2H,CH 2 –CH 2 ,CH 2 –C–,CH 2 –C,CH 2 –CH,CH 2 –CH),2.45ppm(t,J＝2.9Hz,1H,≡C–H),2.99ppm(m,J＝7.0Hz,1H,CH–COO),4.63ppm(m,J＝2.9Hz,2H,O–CH 2 ). 13 C NMR(75MHz,CDCl 3 ,ppm):δ＝16.37,32.86,34.59,35.28,40.45,52.02,74.94,78.06,174.86。
From the above results, it was confirmed that the product molecule spiro [3.3] heptane-2-carboxylic acid propynyl ester was successfully synthesized by structural analysis and analysis of the molecule by nuclear magnetic resonance spectroscopy.
Infrared spectrum: the results are shown in FIG. 3
IR(neat,cm -1 ):3299(≡C–H),2950(CH 2 ),2868(CH),2122(C≡C),1733(C＝O)。
Characterization of the functional groups in the infrared spectroscopy molecule can confirm that the product molecule has the specified functional groups, further proving that spiro [3.3] heptane-2-propynylformate has been successfully synthesized.
Elemental analysis: molecular formula C 11 H 14 O 2 ,178.10。
Theoretical value (%): c,74.13; h,7.92; o,17.95; measured value (%) C,74.26; h,7.77; o,17.97.
The elemental analysis test shows that the elemental composition and content of the spiro [3.3] heptane-2-propynylformate are close to the theoretical value, and the purity is higher.
DSC test：[3.3]The glass transition temperature of the heptane-2-carboxylic acid propynylester was-110.8 ℃.
As shown in fig. 4, by DSC test of spiro [3.3] heptane-2-carboxylic acid propyne ester (PSHC) and azidoglycidyl ether (GAP) of the present invention, it was found that PSHC has a lower glass transition temperature than GAP, and by blending PSHC and GAP in three mass ratios of 20/80,35/65 and 50/50, superior compatibility of both was determined, contributing to improvement of dispersibility, processability and safety of each component in the composite solid propellant.
Taken together, it can be demonstrated that the present invention successfully produces a spiro reactive plasticizer.
While the invention has been described with reference to preferred embodiments, it is not intended to be limiting. Those skilled in the art will appreciate that various modifications and adaptations can be made without departing from the spirit and scope of the present invention. Accordingly, the scope of the invention is defined by the appended claims.
Claims (11)
1. The spiro active plasticizer is characterized by comprising a spiro and an active alkynyl, and the molecular structural formula of the spiro active plasticizer is shown as a formula I;
formula I.
2. A process for the preparation of a spiro-active plasticizer according to claim 1, comprising the steps of:
s1, dissolving 1, 1-cyclobutane dimethanol, p-toluenesulfonyl chloride, pyridine and 4-dimethylaminopyridine in a first organic solvent, and stirring for reaction to obtain a first solution;
extracting the first solution by using a saturated sodium chloride solution, drying an organic phase obtained by extraction, filtering and concentrating to obtain 1, 1-cyclobutane dimethyl p-toluenesulfonate;
s2, adding the dimethyl 1, 1-cyclobutane p-toluenesulfonate obtained in the step S1 into a second organic solvent containing diethyl malonate and metallic sodium, and carrying out reflux reaction to obtain a second solution;
cooling the second solution to room temperature, extracting the second solution by adopting saturated sodium bicarbonate solution, drying an organic phase obtained by extraction, filtering, concentrating, and separating by a column chromatography to obtain spiro [3.3] heptane-1, 1-diethyl dicarboxylate;
s3, blending and refluxing the diethyl spiro [3.3] heptane-1, 1-dicarboxylic acid obtained in the step S2 with a third organic solvent, water and potassium hydroxide to obtain a third solution, cooling the temperature of the third solution to room temperature after the reaction, and adjusting the pH to be acidic to obtain a fourth solution;
extracting the fourth solution by using ethyl acetate, drying an organic phase obtained by extraction, filtering, and concentrating to obtain crude spiro [3.3] heptane-1, 1-dicarboxylic acid;
adding spiro [3.3] heptane-1, 1-dicarboxylic acid into pyridine for reflux, drying the organic phase after reflux, filtering, and concentrating to obtain spiro [3.3] heptane carboxylic acid;
s4, dissolving the spiro [3.3] heptane carboxylic acid obtained in the step S3, p-toluenesulfonic acid and propargyl alcohol in a fourth organic solvent, and heating for reaction to obtain a fifth solution;
and (3) cooling the fifth solution to room temperature, extracting the fifth solution by using saturated sodium bicarbonate solution, drying, filtering, concentrating an organic phase obtained by extraction, and separating by using a column chromatography to obtain spiro [3.3] heptane-2-propynylformate, namely the spiro active plasticizer.
3. The method for preparing a spiro active plasticizer according to claim 2, wherein in the step S1, the concentration of p-toluenesulfonyl chloride is 0.8-1.2M; the mol ratio of the 1, 1-cyclobutane dimethanol to the p-toluenesulfonyl chloride is 1 (2.0-2.5); the mass ratio of the 1, 1-cyclobutane dimethanol to the pyridine is 1 (2.5-3.0); the molar ratio of the 4-dimethylaminopyridine to the p-toluenesulfonyl chloride is 1 (8-12); the first organic solvent is dichloromethane or chloroform.
4. The method for preparing a spiro active plasticizer according to claim 2, wherein in the step S1, the reaction temperature for obtaining the first solution is 20-30 ℃ and the reaction time is 12-24 hours.
5. The method for preparing a spiro active plasticizer according to claim 2, wherein in the step S2, the concentration of 1, 1-cyclobutane dimethyl p-toluenesulfonate is 0.4-0.6M; the molar ratio of the 1, 1-cyclobutane dimethyl tosylate to the diethyl malonate is 1:2.0-3.0; the molar ratio of diethyl malonate to sodium is 1:1-1.2; the second organic solvent is xylene.
6. The process for preparing a spiro active plasticizer according to claim 5, wherein the xylene is o-xylene or m-xylene.
7. The method for preparing a spiro active plasticizer according to claim 2, wherein in the step S2, the reaction temperature for obtaining the second solution is 120-138 ℃ and the reaction time is 24-48 h;
the conditions for column chromatography separation were: silica gel is adopted for 200-300 meshes, and the volume ratio of ethyl acetate to normal hexane is 1:10-12.
8. The method for preparing a spiro active plasticizer according to claim 2, wherein in the step S3, the molar ratio of diethyl spiro [3.3] heptane-1, 1-dicarboxylate to potassium hydroxide is 1:3.0 to 4.0; the mass ratio of the potassium hydroxide to the third organic solvent is 1:8-12; the mass ratio of the water to the third organic solvent is 1:2-3; the third organic solvent is ethanol or methanol.
9. The method for preparing a spiro active plasticizer according to claim 2, wherein in the step S3, the reaction temperature for obtaining the third solution is 80-100 ℃ and the reaction time is 6-12 hours; and adjusting the pH value of the third solution to 1-3 to obtain a fourth solution.
10. The method for preparing a spiro-reactive plasticizer according to claim 2, wherein in the step S4, the concentration of spiro [3.3] heptanoic acid is 0.25-0.30M; the molar ratio of the spiro [3.3] heptane carboxylic acid to the p-toluene sulfonic acid is 1:0.1-0.3; the molar ratio of the spiro [3.3] heptane carboxylic acid to the propargyl alcohol is 1:1-1.3; the fourth organic solvent is toluene or xylene.
11. The method for preparing a spiro active plasticizer according to claim 2, wherein in the step S4, the reaction temperature for obtaining the fifth solution is 110-138 ℃ and the reaction time is 8-12 hours;
the conditions for column chromatography separation were: silica gel is adopted for 200-300 meshes, and the volume ratio of ethyl acetate to normal hexane is 1:10-12.
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