CN116375996A - Preparation method of medical polycaprolactone - Google Patents

Preparation method of medical polycaprolactone Download PDF

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CN116375996A
CN116375996A CN202310422122.9A CN202310422122A CN116375996A CN 116375996 A CN116375996 A CN 116375996A CN 202310422122 A CN202310422122 A CN 202310422122A CN 116375996 A CN116375996 A CN 116375996A
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polycaprolactone
derivatives
molecular weight
solvent
reaction
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何媛
戴汝熙
林雅滢
徐人威
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Sinochem Quanzhou Energy Technology Co Ltd
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Sinochem Quanzhou Energy Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/88—Post-polymerisation treatment
    • C08G63/90—Purification; Drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses a preparation method of medical grade polycaprolactone and derivatives thereof, belonging to the field of high polymer materials. The method adopts a solution polymerization method, uses lactide and epsilon-caprolactone as monomers to prepare Polycaprolactone (PCL) and derivatives (PLLCL and PDLCL) thereof, has simple production process and milder reaction conditions; compared with the melt catalytic polymerization method, the high-efficiency catalytic system adopting the organometallic compound as a main catalyst and the active hydrogen-containing substance as an initiator has the advantages of high reaction speed, short reaction time, adjustable weight average molecular weight of the product, minimum molecular weight distribution index of 1.2, and capability of better adapting to the application requirements of medical polymer materials, and solves the problem of difficult post-treatment of the reaction product with high molecular weight and high viscosity.

Description

Preparation method of medical polycaprolactone
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of medical grade Polycaprolactone (PCL) and derivatives (PLLCL and PDLCL) thereof.
Background
Polycaprolactone (PCL) and derivatives thereof, namely poly L-lactide-caprolactone (PLLCL) and poly D-lactide-caprolactone (PDLCL), are common degradable high molecular materials, are white solid powder in appearance, are nontoxic and insoluble in water, are easily dissolved in various polar organic solvents, have good biocompatibility and good organic high polymer compatibility, and good biodegradability, can be used as cell growth support materials, are compatible with various conventional plastics, and can be completely degraded in natural environment for 6-12 months. In addition, polycaprolactone and derivatives thereof have good shape memory temperature control property, and are widely applied to the fields of production and processing of drug carriers, plasticizers, degradable plastics, nanofiber spinning and molding materials.
The polymerization methods of polycaprolactone and its derivatives are mainly two: solution polymerization and bulk polymerization, the bulk polymerization method is a polymerization method widely used at present. For example, patent CN 1810848A discloses a method for producing thermoplastic PCL by vacuum distillation, normal pressure microwave pretreatment, normal pressure prepolymerization, high temperature high vacuum polymerization and other processes by using tin catalyst and organic acid as catalyst, patent CN 1341674 discloses a method for performing bulk ring-opening polymerization of epsilon-CL under the catalysis of tetrabutyl titanate, patent CN 103539925B discloses a PCL synthesis method by using organic metal salt as catalyst and aromatic alcohol of C7-C11 as molecular weight regulator, and patent CN 111004373a discloses a method for preparing multi-arm polycaprolactone by bulk melt polymerization. The polymer produced by the above synthetic method has large molecular weight and viscosity, and the post-treatment is difficult. Therefore, it is necessary to develop a novel polymerization process which is more efficient, simple and gives polymers having better properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of medical grade polycaprolactone and derivatives thereof, which aims to solve the problem of higher viscosity in the post-treatment process of the polycaprolactone and derivatives thereof in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing medical grade polycaprolactone and derivatives thereof, comprising the following steps:
1) Mixing monomer lactide and epsilon-caprolactone in proportion under the protection of inert atmosphere, and adding a catalyst, an initiator and a solvent;
2) Stirring the mixture obtained in the step 1) for a period of time under heating, and cooling to room temperature;
3) Adding a proper amount of benign solvent into the reaction mixture obtained in the step 2) for dilution, then dripping the mixture into a non-benign solvent to separate out the polymer in a precipitation form, and then centrifuging, filtering and vacuum drying;
4) Heating the dried polymer to a molten state, adding a proper amount of chain extender, reacting for a period of time, and cooling to obtain polycaprolactone or derivatives thereof.
Further, the inert gas used in step 1) is nitrogen.
Further, the mass ratio of lactide to epsilon-caprolactone used in step 1) is (0 to 10): 1, preferably (1 to 2): 1, more preferably 1:1.
Further, the catalyst in step 1) is used in an amount of 0.01% to 10% by weight based on the total weight of the monomers used. The catalyst is any one of stannous octoate, stannous chloride, tributyl (methoxy) stannane, dibutyl tin dioctoate, dibutyl diisooctoate tin, tetraphenyl tin, dibutyl zinc, triethyl cadmium acetate and zirconium acetylacetonate.
Further, the initiator is used in step 1) in an amount of 0.01% to 10% by weight based on the total weight of the monomers used. The initiator is any one of n-butanol, 1, 4-butanediol, benzyl alcohol, phenethyl alcohol, n-dodecanol, n-tetradecanol, glycolic acid, propionic acid, 3-phenylpropanol and 3-fluoroacetic acid.
Further, the solvent in the step 1) is any one or more of benzene, toluene, benzotrifluoride, xylene, benzyl chloride and trimethylbenzene.
Further, in the step 2), the temperature of heating and stirring is 100-300 ℃ and the time is 0.5-48h.
Further, the benign solvent in the step 3) is any one or more of benzene, toluene, benzotrifluoride, xylene, benzyl chloride, trimethylbenzene, tetrahydrofuran, dichloromethane, dichloroethane, chloroform and ethyl acetate.
Further, the total amount of the solvent used in step 1) and the benign solvent used in step 3) is 0.1 to 10 times the total weight of the monomers used.
Further, the non-benign solvent in the step 3) is any one or more of methanol, ethanol, diethyl ether, petroleum ether and n-hexane.
Further, the temperature of the vacuum drying in the step 3) is 20-50 ℃ and the time is 5-14 h.
Further, the chain extender in step 4) is added in an amount of 0.1% -10% of the total weight of the monomers used.
Further, the chain extender in the step 4) is any one of TDI, HDI, MDI and basf ADR chain extender.
Further, the temperature of the reaction in the step 4) is 170-300 ℃ and the time is 1-60min.
The polycaprolactone and the derivatives thereof prepared by the method can be applied to medical materials.
The invention has the beneficial effects that:
(1) The method adopts a solution polymerization method to directly obtain the diluted polymer, has simple production process, simpler reaction conditions, high reaction speed and short reaction time, can greatly shorten the time and reduce the solvent consumption in the process of precipitation washing post-treatment, is convenient for post-treatment, and has good product performance and adjustable molecular weight as required.
(2) The invention adopts a high-efficiency catalytic initiation system which takes an organic metal compound as a main catalyst and takes a substance containing active hydrogen as an initiator, overcomes the defects of high reaction temperature, high side reaction degree, poor reaction controllability and the like in the reaction process of a single catalyst, has short reaction time, and can adjust the weight average molecular weight of the obtained product, wherein the maximum molecular weight can reach 32 ten thousand, and the lowest molecular weight distribution index can reach 1.2.
(3) The invention can remove unreacted monomers and side reaction products by precipitating the polymerized crude product, improve the purity of the product and reduce the molecular weight distribution index.
(4) The invention carries out chain extension and crosslinking on the polymer, so that the molecular weight of the product is further increased, the complex viscosity of the polymer is increased, and the crosslinking process can generate a net structure, so that the product has more excellent performance and can meet the requirements of medical materials.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of polycaprolactone oligomer prepared in example 1.
FIG. 2 is a gel permeation chromatogram of the polycaprolactone homopolymer prepared in example 1.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of PLLCL-2 prepared in example 3.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of PDLCL-1 prepared in example 4.
FIG. 5 is a gel permeation chromatogram of PDLCL-1 prepared in example 4.
Detailed Description
The technical solutions of the present invention are further stated below by examples.
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art unless otherwise indicated.
In the following examples, various processes and methods, which are not described in detail, are conventional methods well known in the art. Meanwhile, since the catalyst has a plurality of types and the polymer structure proportion is various, all preparation methods are not described in detail, and the specific process steps of the invention are illustrated by taking typical examples.
Example 1
Mixing 3.0 g epsilon-caprolactone, 0.03 g stannous octoate serving as a catalyst, 0.005 g n-butyl alcohol serving as an initiator and 9 mL solvent toluene in nitrogen atmosphere, adding the mixture into a 50 mL reaction bottle, starting magnetic stirring at 300 rpm, and then reacting the mixture in an oil bath at 150 ℃ for 8 hours, and closing the oil bath and the magnetic stirring; after the reaction mixture was cooled to room temperature, 9 mL methylene chloride was added to the reaction mixture to dissolve the reaction mixture completely, the resulting mixture solution was dropped into 30 mL absolute ethanol, and the resulting white precipitate was centrifuged and filtered, and the resulting solid was dried at 30 ℃ in a vacuum oven for 12 h. Taking dried polymer 1 g, adding a chain extender ADR 4400.0 mg in a molten state at 200 ℃, reacting for 10 min, and cooling to room temperature to obtain white powder of a final product, namely PCL-1.
The molecular weight and the molecular weight distribution index were measured by gel permeation chromatography. The result showed that the weight average molecular weight of the obtained polymer was 323 kg/mol and the molecular weight distribution index was 1.9.
Example 2
Mixing 1.5g L-lactide and 1.5g epsilon-caprolactone, 0.03 g catalyst stannous octoate, 0.005 g initiator n-butanol and 9 mL solvent toluene in nitrogen atmosphere, adding the mixture into a 50 mL reaction bottle, starting magnetic stirring at 300 rpm, and then reacting the mixture in an oil bath at 150 ℃ for 8 hours, and then closing the oil bath and the magnetic stirring; after the reaction mixture was cooled to room temperature, 9 mL methylene chloride was added to the reaction mixture to dissolve the reaction mixture completely, the resulting mixture solution was dropped into 30 mL absolute ethanol, and the resulting white precipitate was centrifuged and filtered, and the resulting solid was dried at 30 ℃ in a vacuum oven for 12 h. Taking dried polymer 1 g, adding a chain extender ADR 4400.0 mg in a molten state at 200 ℃, reacting for 10 min, and cooling to room temperature to obtain white powder of a final product, which is denoted as PLLCL-1.
The molecular weight and the molecular weight distribution index were measured by gel permeation chromatography. The result showed that the weight average molecular weight of the obtained polymer was 184 kg/mol and the molecular weight distribution index was 1.7.
Example 3
Mixing 0.9 g of L-lactide and 2.1 g epsilon-caprolactone, 0.03 g catalyst stannous octoate, 0.005 g initiator n-butyl alcohol and 9 mL solvent toluene in nitrogen atmosphere, adding the mixture into a 50 mL reaction bottle, starting magnetic stirring at 300 rpm, and then reacting the mixture in an oil bath at 150 ℃ for 8 hours, and then closing the oil bath and the magnetic stirring; after the reaction mixture was cooled to room temperature, 9 mL methylene chloride was added to the reaction mixture to dissolve the reaction mixture completely, the resulting mixture solution was dropped into 30 mL absolute ethanol, and the resulting white precipitate was centrifuged and filtered, and the resulting solid was dried at 30 ℃ in a vacuum oven for 12 h. Taking dried polymer 1 g, adding a chain extender ADR 4400.0 mg in a molten state at 200 ℃, reacting for 10 min, and cooling to room temperature to obtain white powder of a final product, which is denoted as PLLCL-2.
The molecular weight and the molecular weight distribution index were measured by gel permeation chromatography. The result showed that the weight average molecular weight of the obtained polymer was 163 kg/mol and the molecular weight distribution index was 1.6.
Example 4
Mixing 1.0 g of D-lactide and 2.0 g epsilon-caprolactone, 0.03 g catalyst stannous octoate, 0.005 g initiator n-butyl alcohol and 9 mL solvent toluene in nitrogen atmosphere, adding the mixture into a 50 mL reaction bottle, starting magnetic stirring at 300 rpm, and then reacting the mixture in an oil bath at 150 ℃ for 8 hours, and then closing the oil bath and the magnetic stirring; after the reaction mixture was cooled to room temperature, 9 mL methylene chloride was added to the reaction mixture to dissolve the reaction mixture completely, the resulting mixture solution was dropped into 30 mL absolute ethanol, and the resulting white precipitate was centrifuged and filtered, and the resulting solid was dried at 30 ℃ in a vacuum oven for 12 h. Taking dried polymer 1 g, adding a chain extender ADR 4400.0 mg in a molten state at 200 ℃, reacting for 10 min, and cooling to room temperature to obtain white powder of a final product, namely PDLCL-1.
The molecular weight and the molecular weight distribution index were measured by gel permeation chromatography. The result showed that the weight average molecular weight of the obtained polymer was 94 k g/mol and the molecular weight distribution index was 1.7.
Example 5
Mixing 1.5g of D-lactide and 1.5g epsilon-caprolactone, 0.03 g catalyst stannous octoate, 0.005 g initiator n-butyl alcohol and 9 mL solvent toluene in nitrogen atmosphere, adding the mixture into a 50 mL reaction bottle, starting magnetic stirring at 300 rpm, and then reacting the mixture in an oil bath at 150 ℃ for 8 hours, and then closing the oil bath and the magnetic stirring; after the reaction mixture was cooled to room temperature, 9 mL methylene chloride was added to the reaction mixture to dissolve the reaction mixture completely, the resulting mixture solution was dropped into 30 mL absolute ethanol, and the resulting white precipitate was centrifuged and filtered, and the resulting solid was dried at 30 ℃ in a vacuum oven for 12 h. Taking dried polymer 1 g, adding a chain extender ADR 4400.0 mg in a molten state at 200 ℃, reacting for 10 min, and cooling to room temperature to obtain white powder of a final product, namely PDLCL-2.
The molecular weight and the molecular weight distribution index were measured by gel permeation chromatography. The result showed that the weight average molecular weight of the obtained polymer was 103. 103 kg/mol and the molecular weight distribution index was 1.5.
Example 6
Preparation was carried out by weighing stannous octoate 0.09 g as catalyst, and the final product obtained in the same manner as in example 2 was designated PLLCL-3.
The molecular weight and the molecular weight distribution index were measured by gel permeation chromatography. The result showed that the weight average molecular weight of the obtained polymer was 224. 224 kg/mol and the molecular weight distribution index was 1.3.
Example 7
Preparation was carried out by weighing 0.03. 0.03 g of dibutylzinc as catalyst, and the final product obtained in the same manner as in example 2 was designated PLLCL-4.
The molecular weight and the molecular weight distribution index were measured by gel permeation chromatography. The result showed that the weight average molecular weight of the obtained polymer was 116. 116 kg/mol and the molecular weight distribution index was 1.4.
Example 8
Prepared using 3 mL toluene as a solvent, the end product obtained in the same manner as in example 2 was designated PLLCL-5.
The molecular weight and the molecular weight distribution index were measured by gel permeation chromatography. The result showed that the weight average molecular weight of the obtained polymer was 206. 206 kg/mol and the molecular weight distribution index was 1.7.
Example 9
The reaction was carried out as in example 2, with the solvent used being changed to 6 mL toluene and 3 mL benzotrifluoride, and after the reaction was completed, without using dichloromethane as a benign solvent for dissolution, the resulting reaction mixture was directly added dropwise to 30 mL absolute ethanol to precipitate the product, and the obtained final product was designated PLLCL-6.
The molecular weight and the molecular weight distribution index were measured by gel permeation chromatography. The result showed that the weight average molecular weight of the obtained polymer was 89 kg/mol and the molecular weight distribution index was 1.2.
Example 10
The temperature of the reaction in the oil bath was 180℃and the final product obtained in the same manner as in example 2 was designated PLLCL-7.
The molecular weight and the molecular weight distribution index were measured by gel permeation chromatography. The result showed that the weight average molecular weight of the obtained polymer was 174 kg/mol and the molecular weight distribution index was 1.8.
Example 11
The reaction time in the oil bath was set to 16 h, and the final product obtained in the same manner as in example 2 was designated PLLCL-8.
The molecular weight and the molecular weight distribution index were measured by gel permeation chromatography. The result showed that the weight average molecular weight of the obtained polymer was 205. 205 kg/mol and the molecular weight distribution index was 1.7.
Example 12
The procedure of example 2 was repeated except for using 0.005 g of 1, 4-butanediol as an initiator to give a final product designated PLLCL-9.
The molecular weight and the molecular weight distribution index were measured by gel permeation chromatography. The result showed that the weight average molecular weight of the obtained polymer was 228. 228 kg/mol and the molecular weight distribution index was 1.5.
Example 13
The procedure of example 2 was followed using 0.005. 0.005 g n-dodecanol as the initiator to give the final product designated PLLCL-10.
The molecular weight and the molecular weight distribution index were measured by gel permeation chromatography. The result showed that the weight average molecular weight of the obtained polymer was 153. 153 kg/mol and the molecular weight distribution index was 1.6.
Example 14
The procedure of example 2 was otherwise followed using 1.0 mg ADR4468 as a chain extender to give the final product designated PLLCL-11.
The molecular weight and the molecular weight distribution index were measured by gel permeation chromatography. The result showed that the weight average molecular weight of the obtained polymer was 258 kg/mol and the molecular weight distribution index was 2.0.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (10)

1. A method for preparing medical grade polycaprolactone and derivatives thereof, which is characterized by comprising the following steps:
1) Mixing monomer lactide and epsilon-caprolactone in proportion under the protection of inert atmosphere, and adding a catalyst, an initiator and a solvent;
2) Stirring the mixture obtained in the step 1) for a period of time under heating, and cooling to room temperature;
3) Adding a proper amount of benign solvent into the reaction mixture obtained in the step 2) for dilution, then dripping the mixture into a non-benign solvent to separate out the polymer in a precipitation form, and then centrifuging, filtering and vacuum drying;
4) Heating the dried polymer to a molten state, adding a proper amount of chain extender, reacting for a period of time, and cooling to obtain polycaprolactone or derivatives thereof.
2. The method for producing polycaprolactone and derivatives thereof according to claim 1, wherein the mass ratio of lactide to epsilon-caprolactone used in step 1) is (0 to 10): 1;
the catalyst is used in an amount of 0.01-10% of the total weight of the monomers used, and the initiator is used in an amount of 0.01-10% of the total weight of the monomers used.
3. The method for preparing polycaprolactone and derivatives thereof according to claim 1 or 2, wherein the catalyst is any one of stannous octoate, stannous chloride, tributyl (methoxy) stannane, dibutyl tin dioctoate, dibutyl tin diisooctoate, tetraphenyl tin, dibutyl zinc, triethyl cadmium acetate, and zirconium acetylacetonate.
4. The method for producing polycaprolactone and derivatives thereof according to claim 1 or 2, wherein the initiator is any one of n-butanol, 1, 4-butanediol, benzyl alcohol, phenethyl alcohol, n-dodecanol, n-tetradecanol, glycolic acid, propionic acid, 3-phenylpropanol, 3-fluoroacetic acid.
5. The method for producing polycaprolactone and derivatives thereof according to claim 1, wherein the solvent in step 1) is any one or more of benzene, toluene, benzotrifluoride, xylene, benzyl chloride, and trimethylbenzene.
6. The process for producing polycaprolactone and derivatives thereof according to claim 1, wherein the temperature of heating and stirring in step 2) is 100-300 ℃ for 0.5-48h.
7. The method for preparing polycaprolactone and derivatives thereof according to claim 1, wherein the benign solvent in step 3) is any one or more of benzene, toluene, benzotrifluoride, xylene, benzyl chloride, trimethylbenzene, tetrahydrofuran, dichloromethane, dichloroethane, chloroform, ethyl acetate;
the non-benign solvent is one or more of methanol, ethanol, diethyl ether, petroleum ether and n-hexane.
8. The process for the preparation of polycaprolactone and derivatives thereof according to claim 1, wherein the amount of chain extender added in step 4) is between 0.1% and 10% of the total weight of monomers used;
the chain extender is any one of TDI, HDI, MDI and Pasteur ADR chain extender.
9. The process for the preparation of polycaprolactone and derivatives thereof according to claim 1, wherein the temperature of the reaction in step 4) is 170-300 ℃ for a period of time ranging from 1-60min.
10. Use of polycaprolactone and derivatives thereof prepared according to the method of claim 1 in medical materials.
CN202310422122.9A 2023-04-19 2023-04-19 Preparation method of medical polycaprolactone Pending CN116375996A (en)

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