CN115611772A - Synthesis method of alpha-n-octyl cyanoacrylate - Google Patents
Synthesis method of alpha-n-octyl cyanoacrylate Download PDFInfo
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- CN115611772A CN115611772A CN202211384410.1A CN202211384410A CN115611772A CN 115611772 A CN115611772 A CN 115611772A CN 202211384410 A CN202211384410 A CN 202211384410A CN 115611772 A CN115611772 A CN 115611772A
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- alpha
- octyl
- cyanoacrylate
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- dichloroethane
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for synthesizing alpha-n-octyl cyanoacrylate, which comprises the following steps: the method comprises the steps of taking paraformaldehyde and n-octyl cyanoacetate as raw materials, taking dichloroethane, ethyl acetate and other composite solvents as reaction media, carrying out polycondensation reaction at 50-90 ℃ under the catalytic action of a catalyst to obtain a prepolymerization reactant of the alpha-n-octyl cyanoacrylate, drying water in the prepolymerization reactant by a dryer after the reaction is finished, adding a polymerization inhibitor, carrying out reduced pressure distillation cracking to obtain an alpha-n-octyl cyanoacrylate crude monomer, and purifying the alpha-n-octyl cyanoacrylate crude monomer to obtain the alpha-n-octyl cyanoacrylate high-purity monomer.
Description
Technical Field
The invention relates to the technical field of glue preparation, in particular to a synthesis method of alpha-n-octyl cyanoacrylate.
Background
Alpha-cyanoacrylate is currently the most widely used and effective one and has been approved by the U.S. Food and Drug Administration (FDA) for use in clinical medicine. The alpha-cyanoacrylate adhesive has the advantages of one-step operation, stable storage, strong reactivity and the like, can be quickly crosslinked under various environmental conditions, can fill the defect part of the tissue and stimulate the growth of granulation tissue, is often used for skin injury, and is an attractive hemostatic material. In addition, the alpha-cyanoacrylate has certain hemostatic and bacteriostatic properties. At present, the synthesis method of alpha-cyanoacrylate is mainly a formaldehyde condensation method, wherein cyanoacetate and formaldehyde are used as raw materials, and the alpha-cyanoacrylate is synthesized through a condensation polymerization reaction. Although the prior formaldehyde condensation method process is always optimized, the traditional process for preparing the n-octyl alpha-cyanoacrylate needs to firstly prepare methanol solution of formaldehyde as a synthetic raw material, so that the operation steps are increased, and the methanol solution of the formaldehyde is easy to volatilize, has strong pungent smell, is harmful to human bodies and cannot prepare the medical grade n-octyl alpha-cyanoacrylate.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a synthesis method of alpha-n-octyl cyanoacrylate, which has the advantages of good adhesive strength, moderate curing speed and reduced whitening.
In order to achieve the purpose, the technical scheme provided by the invention is as follows: a synthetic method of n-octyl alpha-cyanoacrylate comprises the following steps:
1) Performing polycondensation reaction at 50-90 ℃ under the action of an alkaline catalyst by taking paraformaldehyde and n-octyl cyanoacetate as raw materials and a composite solvent of dichloroethane and ethyl acetate as a reaction medium to obtain a prepolymerization reactant of the alpha-n-octyl cyanoacrylate;
2) After the reaction is finished, the compound solvent of dichloroethane and ethyl acetate is recycled by a distillation condensation method, and is dried for 24 hours by a dryer until the moisture in the prepolymer is completely dried out, and then a polymerization inhibitor is added for reduced pressure distillation to obtain the coarse monomer of the alpha-n-octyl cyanoacrylate;
3) And purifying the coarse alpha-n-octyl cyanoacrylate monomer to obtain the high-purity alpha-n-octyl cyanoacrylate monomer.
The dosage ratio of the paraformaldehyde to the n-octyl cyanoacetate is 1g:1-1.5g.
The dosage ratio of the paraformaldehyde to the dichloroethane is 1g:3-4g.
The dosage ratio of the paraformaldehyde to the ethyl acetate is 1g:5-6g.
And 2) recovering ethyl acetate and dichloroethane in the reaction mixture in the step 2) until the temperature of the reaction mixture reaches 90-120 ℃, putting the mixture into a 110 ℃ oven, drying for 24 hours, and completely removing residual moisture from the mixture and the ethyl acetate and the dichloroethane in the mixed reactant.
The polymerization inhibitor is one or a mixture of more of phosphorus pentoxide, hydroquinone and thiodiphenylamine.
The dosage proportion of the paraformaldehyde, the phosphorus pentoxide, the hydroquinone and the thiodiphenylamine is 1g:0.2-0.3g:0.1-0.2g:0.03-0.04g.
Taking paraformaldehyde and n-octyl cyanoacetate as raw materials, taking dichloroethane, ethyl acetate and other composite solvents as reaction media, and carrying out polycondensation reaction for 5-6 hours at 50-90 ℃ under the catalytic action of an alkaline catalyst to obtain a prepolymerization reactant of the alpha-n-octyl cyanoacrylate; the dosage ratio of the paraformaldehyde, the n-octyl cyanoacetate, the dichloroethane and the ethyl acetate is 1g:1-1.5g:3-4g:5-6g;
after the reaction is finished, heating the dichloroethane and the ethyl acetate to 90-120 ℃ by using a distillation condensation method, collecting the finished reaction prepolymer, drying the reaction prepolymer for 24 hours by using a dryer until the moisture in the prepolymer is completely dried out, adding a polymerization inhibitor phosphorus pentoxide, hydroquinone and thiodiphenylamine, and carrying out reduced pressure distillation to obtain an alpha-n-octyl cyanoacrylate crude monomer;
when the reduced pressure distillation is carried out, a receiving device filled with polymerization inhibitor is used for collecting the alpha-cyanoacrylate crude monomer cracked at the temperature of 130-235 ℃ and the vacuum degree of 0-300P alpha.
The step of purifying the crude monomer of the n-octyl alpha-cyanoacrylate comprises the following steps: rectifying the alpha-n-octyl cyanoacrylate crude monomer, and collecting fractions with the vacuum degree of 0-300 Pa and the distilled steam temperature of 60-150 ℃.
The method takes paraformaldehyde and n-octyl cyanoacetate as raw materials and a composite solvent of dichloroethane and ethyl acetate as a reaction medium, so that the reaction rate of the raw materials is up to more than 97%, the product yield is up to 70%, and the product purity is up to 99.5%. The used raw material paraformaldehyde is solid, is cheap and easy to obtain, and does not need to use (prepare) a methanol solution, so that the process is greatly simplified; the high-purity alpha-n-octyl cyanoacrylate monomer prepared by the scheme has the advantages of good adhesive strength, moderate curing speed, reduced whitening and reduced intradermal tissue reaction, and is particularly suitable for preparing medical glue.
Detailed Description
The following further describes the present invention, and the preferred embodiments of the present invention are:
example 1, the method for synthesizing n-octyl α -cyanoacrylate of this example includes the following steps:
the first step is as follows: taking paraformaldehyde and n-octyl cyanoacetate as raw materials, taking a composite solvent of dichloroethane and ethyl acetate as a reaction medium, and carrying out polycondensation reaction at 50-90 ℃ under the action of an alkaline catalyst to obtain a prepolymerization reactant of the alpha-n-octyl cyanoacrylate;
among them, preferable one is:
the dosage ratio of the paraformaldehyde to the n-octyl cyanoacetate is 1g:1-1.5g;
the dosage ratio of the paraformaldehyde and the dichloroethane is 1g:3-4g;
the dosage proportion of paraformaldehyde and ethyl acetate is 1g:5-6g;
the second step is as follows: after the reaction is finished, the dichloroethane, ethyl acetate and other composite solvents are recycled by a distillation condensation method, and then dried by a dryer for 24 hours until the moisture in the prepolymer is completely dried out, and then added with a polymerization inhibitor for reduced pressure distillation to obtain the alpha-n-octyl cyanoacrylate crude monomer; when the reduced pressure distillation is carried out, a receiving device filled with a polymerization inhibitor is used for collecting a coarse monomer of the alpha-n-octyl cyanoacrylate which is cracked when the vacuum degree is 0-300P alpha and the temperature is 130-235 ℃;
the distillation condensation method is that when the ethyl acetate and the dichloroethane in the reaction mixture are recovered and the temperature of the reaction mixture is between 90 and 120 ℃, the mixture is put into a 110 ℃ oven and dried, and after 24 hours, the residual moisture and the ethyl acetate and the dichloroethane in the mixed reactant are completely removed;
the third step: adding polymerization inhibitor into the dried mixed reactant, and heating and cracking to obtain a coarse alpha-n-octyl cyanoacrylate monomer; the polymerization inhibitor is phosphorus pentoxide, hydroquinone and thiodiphenylamine;
the fourth step: purifying the coarse alpha-octyl cyanoacrylate monomer to obtain a high-purity alpha-octyl cyanoacrylate monomer, wherein the step of purifying the coarse alpha-octyl cyanoacrylate monomer comprises the following steps: rectifying the crude alpha-octyl cyanoacrylate monomer, and collecting the fraction at vacuum degree of 0-300 Pa and distilled steam temperature of 60-150 deg.c.
Example 2, the method for synthesizing n-octyl α -cyanoacrylate of this example includes the following steps:
taking paraformaldehyde and n-octyl cyanoacetate as raw materials, taking a composite solvent of dichloroethane and ethyl acetate as a reaction medium, and carrying out polycondensation reaction for 5-6 hours at 50-90 ℃ under the catalytic action of an alkaline catalyst to obtain a prepolymerization reactant of the alpha-n-octyl cyanoacrylate; the dosage ratio of the paraformaldehyde, the n-octyl cyanoacetate, the dichloroethane and the ethyl acetate is 1g:1-1.5g:3-4g:5-6g;
after the reaction is finished, heating the dichloroethane and the ethyl acetate to 90-120 ℃ by using a distillation condensation method, collecting the finished reaction prepolymer, drying the reaction prepolymer for 24 hours by using a dryer until the moisture in the prepolymer is completely dried out, adding a polymerization inhibitor phosphorus pentoxide, hydroquinone and thiodiphenylamine, and carrying out reduced pressure distillation to obtain a crude monomer of the n-octyl alpha-cyanoacrylate;
during the reduced pressure distillation, a receiving device filled with a polymerization inhibitor is used for collecting a coarse monomer of the alpha-n-octyl cyanoacrylate which is cracked when the vacuum degree is 0-300P alpha and the temperature is 130-235 ℃. The step of purifying the crude monomer of the n-octyl alpha-cyanoacrylate comprises the following steps: rectifying the alpha-n-octyl cyanoacrylate crude monomer, and collecting fractions with the vacuum degree of 0-300 Pa and the distilled steam temperature of 60-150 ℃.
The above-mentioned embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereby, and all changes made according to the principle of the present invention should be covered within the scope of the present invention.
Claims (7)
1. A method for synthesizing alpha-n-octyl cyanoacrylate is characterized in that: the synthesis method comprises the following steps:
1) Performing polycondensation reaction at 50-90 ℃ under the action of an alkaline catalyst by taking paraformaldehyde and n-octyl cyanoacetate as raw materials and a composite solvent of dichloroethane and ethyl acetate as a reaction medium to obtain a prepolymerization reactant of the alpha-n-octyl cyanoacrylate;
2) After the reaction is finished, the compound solvent of dichloroethane and ethyl acetate is recycled by a distillation condensation method, and is dried for 24 hours by a dryer until the moisture in the prepolymer is completely dried out, and then a polymerization inhibitor is added for reduced pressure distillation to obtain the coarse monomer of the alpha-n-octyl cyanoacrylate;
3) And purifying the coarse alpha-n-octyl cyanoacrylate monomer to obtain the high-purity alpha-n-octyl cyanoacrylate monomer.
2. The method for synthesizing n-octyl alpha-cyanoacrylate according to claim 1, wherein: the dosage ratio of the paraformaldehyde to the n-octyl cyanoacetate is 1g:1-1.5g.
The dosage ratio of the paraformaldehyde to the dichloroethane is 1g:3-4g.
The dosage ratio of the paraformaldehyde to the ethyl acetate is 1g:5-6g.
3. The method for synthesizing n-octyl alpha-cyanoacrylate according to claim 1, wherein: and 2) recovering ethyl acetate and dichloroethane in the reaction mixture in the step 2) until the temperature of the reaction mixture reaches 90-120 ℃, putting the mixture into a 110 ℃ oven, drying for 24 hours, and completely removing residual moisture from the mixture and the ethyl acetate and the dichloroethane in the mixed reactant.
4. The method for synthesizing n-octyl alpha-cyanoacrylate according to claim 1, wherein: the polymerization inhibitor is one or a mixture of more of phosphorus pentoxide, hydroquinone and thiodiphenylamine.
5. The method for synthesizing n-octyl alpha-cyanoacrylate according to claim 1, wherein: the dosage ratio of the paraformaldehyde, the phosphorus pentoxide, the hydroquinone and the thiodiphenylamine is 1g:0.2-0.3g:0.1-0.2g:0.03-0.04g.
6. The method for synthesizing n-octyl alpha-cyanoacrylate according to claim 1, wherein: taking paraformaldehyde and n-octyl cyanoacetate as raw materials, taking dichloroethane, ethyl acetate and other composite solvents as reaction media, and carrying out polycondensation reaction for 5-6 hours at 50-90 ℃ under the catalytic action of an alkaline catalyst to obtain a prepolymerization reactant of the alpha-n-octyl cyanoacrylate; the dosage ratio of the paraformaldehyde, the n-octyl cyanoacetate, the dichloroethane and the ethyl acetate is 1g:1-1.5g:3-4g:5-6g;
after the reaction is finished, heating the dichloroethane and the ethyl acetate to 90-120 ℃ by using a distillation condensation method, collecting the finished reaction prepolymer, drying the reaction prepolymer for 24 hours by using a dryer until the moisture in the prepolymer is completely dried out, adding a polymerization inhibitor phosphorus pentoxide, hydroquinone and thiodiphenylamine, and carrying out reduced pressure distillation to obtain an alpha-n-octyl cyanoacrylate crude monomer;
when the reduced pressure distillation is carried out, a receiving device filled with polymerization inhibitor is used for collecting the alpha-cyanoacrylate crude monomer cracked at the temperature of 130-235 ℃ and the vacuum degree of 0-300P alpha.
7. The method for synthesizing n-octyl alpha-cyanoacrylate according to claim 1, wherein: the step of purifying the crude monomer of the n-octyl alpha-cyanoacrylate comprises the following steps: rectifying the alpha-n-octyl cyanoacrylate crude monomer, and collecting fractions with the vacuum degree of 0-300 Pa and the distilled steam temperature of 60-150 ℃.
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| CN202211384410.1A CN115611772A (en) | 2022-11-07 | 2022-11-07 | Synthesis method of alpha-n-octyl cyanoacrylate |
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| CN202211384410.1A CN115611772A (en) | 2022-11-07 | 2022-11-07 | Synthesis method of alpha-n-octyl cyanoacrylate |
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Citations (13)
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2022
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