CN113234209A - Method for initiating lactide ring-opening dispersion polymerization by luteolin in supercritical carbon dioxide - Google Patents
Method for initiating lactide ring-opening dispersion polymerization by luteolin in supercritical carbon dioxide Download PDFInfo
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- IQPNAANSBPBGFQ-UHFFFAOYSA-N luteolin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(O)C(O)=C1 IQPNAANSBPBGFQ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- LRDGATPGVJTWLJ-UHFFFAOYSA-N luteolin Natural products OC1=CC(O)=CC(C=2OC3=CC(O)=CC(O)=C3C(=O)C=2)=C1 LRDGATPGVJTWLJ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 235000009498 luteolin Nutrition 0.000 title claims abstract description 50
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical group CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 title claims abstract description 43
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 24
- 238000012674 dispersion polymerization Methods 0.000 title claims abstract description 18
- 238000007142 ring opening reaction Methods 0.000 title claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 16
- 230000000977 initiatory effect Effects 0.000 title claims abstract description 6
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000007664 blowing Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 239000003519 biomedical and dental material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 7
- 229920001610 polycaprolactone Polymers 0.000 description 7
- 239000004626 polylactic acid Substances 0.000 description 7
- 235000013824 polyphenols Nutrition 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000021615 conjugation Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- -1 flavonoid compound Chemical class 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920001432 poly(L-lactide) Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C08G63/81—Preparation processes using solvents
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A method for initiating lactide ring-opening dispersion polymerization by luteolin in supercritical carbon dioxide belongs to the field of medical high polymer materials. According to the invention, lactide is used as a raw material, luteolin is used as an initiator, stannous octoate is used as a catalyst, a triblock polymer PCL-PDMS-PCL is used as a stabilizer, and the polylactide is synthesized by adopting a ring-opening dispersion polymerization method. The invention adopts luteolin as an initiator to synthesize the biomedical material polylactide in supercritical CO2, the obtained polymer product is granular powder, the product yield reaches 93 percent, the number average molecular weight of the polymer is 13799, and the molecular weight distribution is 1.98. The initiator and the solvent are green reagents, the preparation method is simple and efficient, and the method is a preparation method of the biomedical polymer material with wide application prospect.
Description
Technical Field
The invention belongs to the field of medical high polymer materials, and particularly relates to a method for ring-opening dispersion polymerization of lactide initiated by luteolin in supercritical carbon dioxide.
Background
The polylactic acid in the aliphatic polyester is called as bioplastic, is a thermoplastic polymer with high strength and high modulus, and has the advantages of good biocompatibility, biodegradability, melt processability and the like. Supercritical carbon dioxide(ScCO2) The technology has become a popular subject for many scholars to study, and due to the advantages of wide sources, gas-like diffusibility, liquid density, no toxicity, inertness, easy separation and purification of reaction products and the like, the organic solvent is widely studied and applied as a green solvent to replace a plurality of toxic and harmful organic solvents, and is particularly popularized and used in the field of dispersion polymerization.
The current methods for synthesizing polylactic acid mainly comprise two methods: the direct polycondensation of lactic Acid (ATRP) and the ring-opening polymerization of lactide (ROP). However, the production conditions of the direct polycondensation method of lactic acid are difficult, and the by-product water is difficult to remove, resulting in a low yield. Therefore, the lactide ring-opening polymerization method is a main method for preparing the polylactic acid with high molecular weight, and has the characteristics of low heat effect, high polymerization rate, high yield, high stereoregularity and the like. The initiator for lactide ring-opening polymerization generally adopts alcohol compounds, and the use of phenol compounds as the initiator has not been reported. Luteolin is a natural flavonoid compound with chemical name of 3 ', 4', 5, 7-tetrahydroxy flavone, widely distributed in nature, and extracted and separated from various plants. Luteolin has various physiological activities such as antioxidant effect, antibacterial effect, antiviral effect, antiinflammatory effect, and antitumor effect. Luteolin has good super-delocalization degree and a larger pi-bond conjugated system, and a molecular structure of luteolin has a plurality of phenolic hydroxyl groups, so that luteolin can easily react with lactide. The luteolin is used as a medicine, the graft copolymerization of the luteolin and polylactic acid greatly increases the effect of the polylactic acid in organisms, and the luteolin-containing polylactic acid bone fixing material, the heart stent and the like can directly achieve the treatment effect.
Disclosure of Invention
Aiming at the defects, the invention provides a method for initiating lactide ring-opening dispersion polymerization by luteolin in supercritical carbon dioxide, an initiator and a solvent used in the method are green reagents, and the preparation method is simple and efficient.
The method for solving the technical problems adopts lactide as a raw material, luteolin as an initiator, stannous octoate as a catalyst and a triblock polymer PCL-PDMS-PCL as a stabilizer, and adopts a ring-opening dispersion polymerization method to synthesize the polylactide.
Further, the method comprises the following steps:
(1) adding lactide, luteolin, stabilizer and catalyst into a reaction kettle, installing the reaction kettle, introducing CO2Blowing the reaction kettle for 5min, stopping blowing, adjusting the rotating speed of a stirrer to 400rpm, starting heating, and starting a plunger pump to pressurize the system when the temperature reaches a certain temperature to react;
(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 white powder in frozen methanol, and drying the obtained polymer in a vacuum drying oven to constant weight to obtain the product polylactide.
Furthermore, the addition amount of luteolin is 1mol of luteolin per 100mol of lactide based on the amount of lactide.
Further, the stabilizer was added in an amount of 1g per 20g of lactide based on the amount of lactide.
Further, the catalyst was added in an amount of 0.4g per 20g of lactide based on the amount of lactide.
Further, in the step (1), when the temperature reaches 110-130 ℃, a plunger pump is started to pressurize the system to 16-20 MPa, and the reaction time is 24 hours.
Further, the amount of the frozen methanol in the step (2) is 10 times of the volume of the dichloromethane.
Further, the temperature of the vacuum drying oven was 40 ℃.
Further, in the step (1), when the temperature reaches 130 ℃, a plunger pump is turned on to pressurize the system to 16 MPa.
The principle is as follows: luteolin is used as an initiator and follows a coordination-insertion mechanism, the essence is that phenolic hydroxyl on luteolin is coordinated with a stannous octoate metal center, then O atoms with negative charges on stannate attack acyl carbon of lactide and form bonds with the acyl carbon, and pi bonds are broken to promote the ring opening of the lactide, and an amide group enters a polymer chain in the mechanism. The synthesis principle is as follows:
has the advantages that: the invention adopts luteolin as an initiator to synthesize the biomedical material polylactide in supercritical CO2, the obtained polymer product is granular powder, the product yield reaches 93 percent, the number average molecular weight of the polymer is 13799, and the molecular weight distribution is 1.98. The initiator and the solvent are green reagents, the preparation method is simple and efficient, and the method 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 NMR spectrum of the synthesized polylactide.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Adding 1.5g lactide, 1:100 molar ratio of luteolin to lactide, 0.03g stannous octoate catalyst 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 16MPa after the temperature reaches 130 ℃, and reacting for 24 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 93%, the number average molecular weight is 13799, and the molecular weight distribution is 1.98.
Example 2
Mixing 1.5g lactide, luteolin and lactideAdding 0.03g of stannous octoate catalyst and 0.1g of stabilizer PCL-PDMS-PCL into a reaction kettle in a ratio of 1:100, 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 18MPa after the temperature reaches 120 ℃, and reacting for 24 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 95%, the number average molecular weight is 12824, and the molecular weight distribution is 1.74.
Example 3
Adding 1.5g lactide, 1:100 molar ratio of luteolin to lactide, 0.03g stannous octoate catalyst 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 18MPa after the temperature reaches 110 ℃, and reacting for 20 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 78%, the number average molecular weight is 12992, and the molecular weight distribution is 1.87.
FIG. 1 is an infrared spectrum of polylactide which is a synthesized product in example 1. The synthesized product is at 3440cm-1Is at the peak of stretching vibration of the terminal hydroxyl group, 3417cm-1The absorption peak is wide due to the stretching vibration peak of luteolin phenolic hydroxyl, and the product is 3417cm in the comparison graph-1The absorption peak and the spectrogram of the luteolin molecule can indicate that the phenolic hydroxyl group of the luteolin still exists in the product, which indicates that the luteolin is successfully initiated and grafted to the polylactic acid and the luteolinWith 4 phenolic hydroxy groups not fully reacted, with the product1H NMR spectrum of the product was confirmed by1The H NMR spectrum shows that luteolin 5-OH and 7-OH phenolic hydroxyl exist in the product. 2955cm-1，2864cm-13005cm of CH stretching vibration peak at PLLA methine-1Is methyl CH3Peak of stretching vibration 1658cm-1The site is a C ═ O stretching vibration peak on the luteolin ring, the product is the same as the luteolin molecule, and the change is not changed, and meanwhile, the successful initiation and grafting of the luteolin on the product PLLA can be proved.
FIG. 2 is the NMR spectrum of the synthesized polylactide. The product contained H atoms (7.31ppm, 6.42ppm, 6.12ppm) on the benzene ring of luteolin, H atoms (6.63ppm) on the carbon of the 3-double bond and phenolic hydroxyl groups 5-OH, 7-OH (13.05ppm, 10.72ppm) on the benzene ring (A) which has a conjugation effect with the six-membered ring (C). The ketocarbonyl on the luteolin six-membered ring (C) and a carbon-carbon double bond generate pi and pi-conjugation, lone pair electrons on an ether bond O atom and a connected benzene ring as well as the carbon-carbon double bond generate p and pi-conjugation, so that the benzene ring (A) and the six-membered ring (C) have extremely strong pi-bond conjugation effect, ring current is generated under the action of an external magnetic field, the shielding effect exists, the system is very stable, but the conjugation effect of phenolic hydroxyl on the benzene ring (B) and the benzene ring is weak, and the reaction is easy to occur.
The invention adopts luteolin to initiate lactide to open ring and disperse in supercritical carbon dioxide to synthesize polylactide, luteolin is used as an initiator, stannous octoate is used as a catalyst, the product yield reaches 93%, the number average molecular weight of the polymer is 14799, and the molecular weight distribution is 1.98. The invention adopts luteolin as an initiator and adopts 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 foregoing examples are provided for illustration and description of the invention only and are not intended to limit the invention to the scope of the described examples. Furthermore, it will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that many variations and modifications may be made in accordance with the teachings of the present invention, which variations and modifications are within the scope of the present invention as claimed.
Claims (9)
1. A method for initiating lactide ring-opening dispersion polymerization by luteolin in supercritical carbon dioxide is characterized in that the method adopts lactide as a raw material, luteolin as an initiator, stannous octoate as a catalyst and a triblock polymer PCL-PDMS-PCL as a stabilizer, and adopts a ring-opening dispersion polymerization method to synthesize the polylactide.
2. The method for the ring-opening dispersion polymerization of lactide initiated by luteolin in supercritical carbon dioxide as claimed in claim 1, wherein the steps of the method are as follows:
s1, adding lactide, luteolin, a stabilizer and a catalyst into a reaction kettle, installing the reaction kettle, and introducing CO2Blowing the reaction kettle for 5min, stopping blowing, adjusting the rotating speed of a stirrer to 400rpm, starting heating, and starting a plunger pump to pressurize the system when the temperature reaches a certain temperature to react;
s2, stopping heating after the reaction in the step S1 is finished, stopping stirring after the temperature of the system is cooled to room temperature, simultaneously slowly discharging gas to normal pressure, collecting a crude product in a beaker, slowly dropwise adding dichloromethane until the product is completely dissolved, precipitating in frozen methanol to obtain white powder, and then putting the obtained polymer in a vacuum drying oven to dry to constant weight to obtain the product polylactide.
3. The method for the ring-opening dispersion polymerization of lactide initiated by luteolin in supercritical carbon dioxide as claimed in claim 1, wherein luteolin is added in an amount of 1mol of luteolin per 100mol of lactide based on the amount of lactide.
4. The method for the ring-opening dispersion polymerization of lactide initiated by luteolin in supercritical carbon dioxide as claimed in claim 1, wherein the stabilizer is added in an amount of 1g per 20g lactide based on the amount of lactide.
5. The method for the ring-opening dispersion polymerization of lactide initiated by luteolin in supercritical carbon dioxide as claimed in claim 1, wherein the amount of the catalyst added is 0.4g per 20g of lactide based on the amount of lactide.
6. The method for the ring-opening dispersion polymerization of lactide initiated by luteolin in supercritical carbon dioxide as claimed in claim 1, wherein in step S1, when the temperature reaches 110-130 ℃, a plunger pump is turned on to pressurize the system to 16-20 MPa, and the reaction time is 24 h.
7. The method for the ring-opening dispersion polymerization of lactide initiated by luteolin in supercritical carbon dioxide as claimed in claim 1, wherein the amount of the frozen methanol in the step S2 is 10 times the volume of the dichloromethane.
8. The method for the ring-opening dispersion polymerization of lactide initiated by luteolin in supercritical carbon dioxide as claimed in claim 1, wherein the temperature of the vacuum drying oven is 40 ℃.
9. The method for the ring-opening dispersion polymerization of lactide initiated by luteolin in supercritical carbon dioxide as claimed in claim 1 or 6, wherein in step S1, when the temperature reaches 130 ℃, the plunger pump is turned on to pressurize the system to 16 MPa.
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| CN114807252A (en) * | 2022-04-25 | 2022-07-29 | 大连大学 | Method for synthesizing four-arm star polylactic acid in supercritical carbon dioxide |
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| CN114807252B (en) * | 2022-04-25 | 2024-04-12 | 大连大学 | Synthesis method of four-arm star polylactic acid in supercritical carbon dioxide |
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