CN110885430A - Method for initiating lactide ring-opening dispersion polymerization by using arginine - Google Patents

Method for initiating lactide ring-opening dispersion polymerization by using arginine Download PDF

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CN110885430A
CN110885430A CN201911306640.4A CN201911306640A CN110885430A CN 110885430 A CN110885430 A CN 110885430A CN 201911306640 A CN201911306640 A CN 201911306640A CN 110885430 A CN110885430 A CN 110885430A
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arginine
lactide
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pcl
dispersion polymerization
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詹世平
万泽韬
王景昌
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Dalian University
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Health & Medical Sciences (AREA)
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Abstract

The invention relates to a method for initiating lactide ring-opening dispersion polymerization by using arginine. According to the invention, lactide is used as a raw material, L-arginine is used as an initiator and also used as a catalyst, a triblock polymer PCL-PDMS-PCL is used as a stabilizer, and the polylactide is synthesized by a ring-opening dispersion polymerization method. The structure and performance of the obtained polymer are characterized, and the result shows that when the reaction temperature is 130 ℃, the pressure is 12MPa, the molar ratio of the L-arginine to the lactide is 1:50, and the reaction time is 48 hours, the obtained polymer product is granular powder, the product yield reaches 85%, the number average molecular weight of the polymer is 11700, and the molecular weight distribution is 1.31. The invention adopts the amino acid L-arginine required by human body as an initiator and adopts supercritical CO2The initiator and the solvent used in the method are green reagents, and the preparation method is simple and efficient, thereby being a biological medical material polylactide with wide application prospectA preparation method of medical polymer material.

Description

Method for initiating lactide ring-opening dispersion polymerization by using arginine
Technical Field
The invention relates to the technical field of preparation of biomedical high polymer materials, in particular to a method for initiating lactide ring-opening dispersion polymerization by arginine in supercritical carbon dioxide.
Background
Supercritical carbon dioxide (ScCO)2) The technology has become a popular subject for many scholars to study, because it has advantages of wide source, gas-like diffusivity, liquid density, innocuity, inertness, easy separation and purification of reaction products, etcTherefore, the organic solvent is widely researched and applied as a green solvent instead of a plurality of toxic and harmful organic solvents, and is particularly popularized and used in the field of dispersion polymerization.
The catalysts used for synthesizing the polylactide are mainly metal catalysts, and the problems of biosafety and difficult removal in products of the metal catalysts cause researchers to pay attention to the development of non-metal catalysts, which is very important for green preparation of materials. The development of non-metallic initiators/catalysts and enzymatic ring-opening polymerizations solved this problem to some extent. The main nonmetal initiators include alcohol, amine and the like; the catalyst comprises: protonic acids, phosphines, and the like, which may be used alone or in combination. The enzyme-catalyzed ring-opening polymerization is also widely concerned by researchers by virtue of the characteristics of lower reaction temperature, higher monomer utilization rate, more excellent safety and the like.
Disclosure of Invention
The invention aims to provide a method for initiating lactide ring-opening dispersion polymerization by arginine in supercritical carbon dioxide.
The invention has the following inventive concept:
the amino acid is a basic substance of protein required by a human body and plays an important role in human nutrition and physiology, wherein, the L-arginine is a non-essential amino acid which can be synthesized by the human body and meets the metabolic demand. The melting point of L-arginine is 228 ℃, the guanidyl of the side chain group of the L-arginine is a strong basic group, lactide can be initiated to form negative ions with a planar structure, and then polymerization reaction is initiated, and carboxyl can catalyze ring-opening polymerization reaction at high temperature.
The invention adopts arginine as initiator in supercritical CO2The obtained polymer product is granular powder, the used initiator and solvent are green reagents, the initiator has the function of a catalyst, and the preparation method is simple and efficient. The yield of the product reaches 85 percent, the number average molecular weight of the polymer is 11700, and the molecular weight distribution is 1.31.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for initiating lactide ring-opening dispersion polymerization by using arginine adopts lactide as a raw material, arginine as an initiator and a catalyst, and a triblock polymer PCL-PDMS-PCL as a stabilizer to synthesize polylactide by adopting a ring-opening dispersion polymerization method.
Amino acids act as initiators, which are essentially primary amino groups that attack the carbonyl group at high temperatures (greater than 130 ℃) to form hydroxyl end groups, which then initiate a chain extension reaction between the monomers, in which the amide groups enter the polymer chain. The synthesis principle is as follows:
Figure BDA0002323324530000021
the method comprises the following steps:
(1) adding lactide, a certain amount of arginine and stabilizer PCL-PDMS-PCL into a reaction kettle, installing the reaction kettle, introducing CO2And blowing the reaction kettle for 5min, and then stopping blowing. Adjusting the rotating speed of the stirrer to 400-600 rpm, starting heating, starting a plunger pump when the temperature reaches 130-160 ℃ to pressurize the system to the required pressure of 8-16 MPa, and reacting for 48-72 h;
(2) and (2) stopping heating after the reaction in the step (1) is finished, stopping stirring after the temperature of the system is cooled to room temperature, and slowly discharging gas to normal pressure. Collecting the crude product in a beaker, slowly adding dichloromethane dropwise until the product is completely dissolved, precipitating in 10 times volume of frozen methanol to obtain white powder, and drying the obtained polymer in a vacuum drying oven at 40 ℃ to constant weight to obtain the product polylactide.
The molar ratio of arginine to lactide in the step (1) is 1: 10-1: 300; the mass ratio of the stabilizer to the lactide was 5 wt%.
Preferably, in the step (1), the reaction temperature is 130 ℃, the reaction pressure is 12MPa, the molar ratio of arginine to lactide is 1:50, and the reaction time is 48 h.
Has the advantages that:
compared with the prior art, the invention has the advantages ofThe method comprises the following steps: the invention adopts arginine to initiate lactide ring-opening dispersion in supercritical carbon dioxide to synthesize polylactide, the product yield reaches 85%, the number average molecular weight of the polymer is 11700, and the molecular weight distribution is 1.31. The invention adopts arginine as an initiator, the initiator has the function of a catalyst, and the method is used for supercritical CO2The initiator and the solvent used in the synthesis of the biomedical material polylactide are green reagents, and the preparation method is simple and efficient, and is a preparation method of the biomedical polymer material with wide application prospect.
Drawings
FIG. 1 is an infrared spectrum of a polylactide as a synthetic product;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the synthesized polylactide.
Detailed Description
The present invention is further illustrated by the following specific examples. The stabilizer polycaprolactone polydimethylsiloxane PCL-PDMS-PCL, which is a dispersion of the polymer in the solvent in which it is suspended, so that it does not sink to the bottom of the tank, can be prepared as a triblock polymer by the method mentioned in the inventor's prior application CN 10319363A.
Example 1
Adding 2g lactide, arginine and lactide at a molar ratio of 1:50, and 0.1g stabilizer PCL-PDMS-PCL into a reaction kettle, installing the reaction kettle, introducing CO2And blowing the reaction kettle for 5min, and then stopping blowing. Adjusting the rotating speed of the stirrer to 400rpm, starting heating, starting a plunger pump to pressurize the system to the required 12MPa after the temperature reaches 130 ℃, and reacting for 48 hours; and stopping heating after the reaction is finished, stopping stirring after the temperature of the system is cooled to room temperature, and slowly discharging gas to normal pressure. Collecting the crude product in a beaker, slowly dropwise adding dichloromethane until the product is completely dissolved, precipitating in 10 times volume of frozen methanol to obtain white powder, and then putting the obtained polymer in a vacuum drying oven at 40 ℃ to dry to constant weight to obtain the product polycaprolactone, wherein the yield of the product is 85%, the number average molecular weight is 11700, and the molecular weight distribution is 1.31.
Example 2
Adding 2g lactide, arginine and lactide at a molar ratio of 1:100, 0.1g stabilizer PCL-PDMS-PCL into a reaction kettle, installing the reaction kettle, introducing CO2And blowing the reaction kettle for 5min, and then stopping blowing. Adjusting the rotating speed of the stirrer to 400rpm, starting heating, starting a plunger pump to pressurize the system to the required 16MPa after the temperature reaches 150 ℃, and reacting for 48 hours; and stopping heating after the reaction is finished, stopping stirring after the temperature of the system is cooled to room temperature, and slowly discharging gas to normal pressure. Collecting the crude product in a beaker, slowly dropwise adding dichloromethane until the product is completely dissolved, precipitating in 10 times volume of frozen methanol to obtain white powder, and then putting the obtained polymer in a vacuum drying oven at 40 ℃ for drying to constant weight to obtain the product polycaprolactone, wherein the yield of the product is 32%, the number average molecular weight is 13400, and the molecular weight distribution is 1.32.
Example 3
Adding 2g of lactide, the molar ratio of arginine to lactide of 1:300 and 0.1g of stabilizer PCL-PDMS-PCL into a reaction kettle, installing the reaction kettle, introducing CO2And blowing the reaction kettle for 5min, and then stopping blowing. Adjusting the rotating speed of the stirrer to 400rpm, starting heating, starting a plunger pump to pressurize the system to 12MPa when the temperature reaches 130 ℃, and reacting for 72 hours; and stopping heating after the reaction is finished, stopping stirring after the temperature of the system is cooled to room temperature, and slowly discharging gas to normal pressure. Collecting the crude product in a beaker, slowly dropwise adding dichloromethane until the product is completely dissolved, precipitating in 10 times volume of frozen methanol to obtain white powder, and then putting the obtained polymer in a vacuum drying oven at 40 ℃ for drying to constant weight to obtain the product polycaprolactone, wherein the yield of the product is 59%, the number average molecular weight is 18200, and the molecular weight distribution is 1.05.
Example 4
Adding 2g lactide, arginine and lactide at a molar ratio of 1:50, and 0.1g stabilizer PCL-PDMS-PCL into a reaction kettle, installing the reaction kettle, introducing CO2And blowing the reaction kettle for 5min, and then stopping blowing. Adjusting the rotating speed of the stirrer to 400rpm, starting heating, starting a plunger pump to pressurize the system to 8MPa when the temperature reaches 130 ℃, and reactingThe time is 48 h; and stopping heating after the reaction is finished, stopping stirring after the temperature of the system is cooled to room temperature, and slowly discharging gas to normal pressure. Collecting the crude product in a beaker, slowly dropwise adding dichloromethane until the product is completely dissolved, precipitating in 10 times volume of frozen methanol to obtain white powder, and then putting the obtained polymer in a vacuum drying oven at 40 ℃ for drying to constant weight to obtain the product polycaprolactone, wherein the product yield is 58%, the number average molecular weight is 5600, and the molecular weight distribution is 1.38.
FIG. 1 is an infrared spectrum of polylactide which is a synthesized product in example 1. The product has ester carbonyl C ═ O stretching vibration peak (1758 cm)-1) C-H stretching vibration peak of methine and methyl (2997 cm)-1、2947cm-1And 2871cm-1) C-O stretching vibration peak of ester group (1186 cm)-1) This may initially indicate that the polymer is polylactide; and a characteristic absorption peak (1146 cm) of the polylactide acyclic ester compound compared with lactide-1Nearby) and typical band (933 cm) of cyclic compound structure-1Nearby), indicating that there is no lactide monomer in the product; in addition, primary amine is used as an initiator and enters into the polymer chain when the reaction temperature is higher than 130 ℃, which can be represented by 1680--1Characteristic absorption peaks of amide bonds were observed.
FIG. 2 is a diagram of the polylactide synthesized in example 11H-NMR spectrum. In the figure, a characteristic peak of-HNCO was observed at 6.47ppm, which indicates that arginine is used as an initiator, and a primary amino group therein plays a decisive role, and which also indicates that arginine enters a polymer molecular chain, and in combination with FT-IR spectrum analysis, it can be seen that PCL-PDMS-PCL stabilizer is used in ScCO2In the method, arginine is used for triggering lactide ring-opening polymerization to obtain the product polylactide.
The invention adopts arginine to initiate lactide ring-opening dispersion in supercritical carbon dioxide to synthesize polylactide, uses arginine as an initiator and has the function of a catalyst, the product yield reaches 85%, the number average molecular weight of a polymer is 11700, and the molecular weight distribution is 1.31. The invention adopts arginine as an initiator, the initiator has the function of a catalyst, and the method is used for supercritical CO2The initiator and the solvent used in the synthesis of the biomedical material polylactide are green reagents, and the preparation method is simple and efficient, and is a preparation method of the biomedical polymer material with wide application prospect.
The above description is only for the purpose of creating a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.

Claims (3)

1. A method for initiating lactide ring-opening dispersion polymerization by using arginine is characterized in that lactide is used as a raw material, arginine is used as an initiator and a catalyst, a triblock polymer PCL-PDMS-PCL is used as a stabilizer, and a ring-opening dispersion polymerization method is used for synthesizing polylactide; wherein the molar ratio of arginine to lactide is 1: 10-1: 300, and the mass ratio of the stabilizer to the lactide is 5 wt%.
2. The method for initiating lactide ring-opening dispersion polymerization by using arginine as claimed in claim 1, which comprises the following steps:
(1) adding L-arginine, lactide and stabilizer PCL-PDMS-PCL into a reaction kettle according to the molar ratio of 1: 10-1: 300, installing the reaction kettle, introducing CO2Purging the reaction kettle for 5min, stopping purging, adjusting the rotating speed of a stirrer to be 400-600 rpm, starting heating, starting a plunger pump when the temperature reaches 130-160 ℃ to pressurize the system to 8-16 MPa, and reacting for 48-72 h;
(2) and (2) stopping heating after the reaction in the step (1) is finished, stopping stirring after the temperature of the system is cooled to room temperature, slowly discharging gas to normal pressure, collecting a crude product in a beaker, slowly dropwise adding dichloromethane until the product is completely dissolved, precipitating the product in frozen methanol with the volume of 10 times of that of the product to obtain white powder, and then putting the obtained polymer in a vacuum drying oven at 40 ℃ to dry the product to constant weight to obtain the product polylactide.
3. The method for initiating the ring-opening dispersion polymerization of lactide by using arginine according to claim 2, wherein the reaction temperature in the step (1) is 130 ℃, the reaction pressure is 12MPa, the molar ratio of L-arginine to lactide is 1:50, the mass ratio of the stabilizer to the lactide is 5 wt%, and the reaction time is 48 h.
CN201911306640.4A 2019-12-18 2019-12-18 Method for initiating lactide ring-opening dispersion polymerization by using arginine Pending CN110885430A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101367921A (en) * 2008-10-06 2009-02-18 中国人民解放军第二军医大学 Method for synthesis of polylactic acid with lactide opened loop
CN105601891A (en) * 2016-03-16 2016-05-25 大连大学 Method for preparing poly-L-lactide (PLLA) by dispersion polymerization in supercritical carbon dioxide
US20170042827A1 (en) * 2015-08-10 2017-02-16 Bar-Ilan University Proteinoid compounds, process of preparing same and uses thereof
CN109912785A (en) * 2019-03-19 2019-06-21 大连大学 A kind of research method of the immobilized enzyme catalysis efficiency in supercritical carbon dioxide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101367921A (en) * 2008-10-06 2009-02-18 中国人民解放军第二军医大学 Method for synthesis of polylactic acid with lactide opened loop
US20170042827A1 (en) * 2015-08-10 2017-02-16 Bar-Ilan University Proteinoid compounds, process of preparing same and uses thereof
CN105601891A (en) * 2016-03-16 2016-05-25 大连大学 Method for preparing poly-L-lactide (PLLA) by dispersion polymerization in supercritical carbon dioxide
CN109912785A (en) * 2019-03-19 2019-06-21 大连大学 A kind of research method of the immobilized enzyme catalysis efficiency in supercritical carbon dioxide

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Application publication date: 20200317