CN110938200B - Preparation method of amine polyester containing dimethyl pyridine on side chain - Google Patents
Preparation method of amine polyester containing dimethyl pyridine on side chain Download PDFInfo
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- CN110938200B CN110938200B CN201911234554.7A CN201911234554A CN110938200B CN 110938200 B CN110938200 B CN 110938200B CN 201911234554 A CN201911234554 A CN 201911234554A CN 110938200 B CN110938200 B CN 110938200B
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
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- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/51—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent
- A61K47/56—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic macromolecular compound, e.g. an oligomeric, polymeric or dendrimeric molecule
- A61K47/59—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic macromolecular compound, e.g. an oligomeric, polymeric or dendrimeric molecule obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyureas or polyurethanes
- A61K47/593—Polyesters, e.g. PLGA or polylactide-co-glycolide
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- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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Abstract
The invention belongs to the technical field of polymer science, and provides a preparation method of a side chain containing dimethyl pyridine amine polyester, which is obtained by one-step bulk polymerization of 1, 3-acetone dicarboxylic acid monomer and dihydric alcohol monomer under the action of a catalyst tetrabutyl titanate, grafting reaction of the polymerized product and DPA under the catalysis of p-toluenesulfonic acid, and finally coordination of the polymerized product and zinc nitrate to obtain the side chain containing DPA-Zn polyester material. The preparation method of the invention provides technical reference for synthesizing novel polyester materials and widens the biological application of the polyester materials. The polyester prepared by polymerizing the dicarboxylic acid dimethyl ester containing post-modifiable sites as a raw material and various types of diols has good gene recombination capability after being coordinated with zinc ions by using DPA, is expected to be applied to the entrapment of hydrophobic drugs and the co-delivery of genes, and overcomes the defect that the traditional polyester can only deliver the hydrophobic drugs and can not deliver the genes together.
Description
Technical Field
The invention belongs to the technical field of polymer science, and relates to a preparation method of a polyester containing dimethyl pyridine amine on a side chain.
Background
At present, the polymer materials have various varieties and different properties, so the polymer materials can be widely used for repairing and replacing various tissues of human bodies, such as ligaments, tendons, skins, blood vessels and other soft and hard tissues of human bodies, and the biodegradable polymer materials are used as carrier materials of drug control systems and short-term implants in vivo in the most extensive medical application. When the long-acting drug taking the biodegradable high molecular material as the carrier is implanted into a body, the carrier does not need to be taken out through an operation after the drug is released, so that the curative effect of the drug is improved, and the pain and trouble of a user can be greatly reduced. Under the action of biological environment, these carrier materials are subject to structural destruction and property disintegration, and the degraded products can be absorbed by the body or be discharged from the body through normal metabolism. Currently, biodegradable polymer materials widely studied as drug carriers include aliphatic polyester polymer materials such as polylactic acid, lactic acid-caprolactone copolymer, glycolide-lactide copolymer, and caprolactone-polyether copolymer, and natural polymer materials such as collagen, alginate, chitin, and cellulose derivatives. The biodegradable high molecular materials are ideal carriers for long-term administration of anti-cancer drugs, glaucoma drugs, heart diseases drugs, hypertension drugs, pain relievers, contraception drugs and the like.
However, with the wide application of drugs, multidrug resistance has become an urgent problem to be solved, and meanwhile, the extremely low water solubility is also a great obstacle to the clinical application of anticancer drugs. The appearance of new preparation technology and the continuous development of biodegradable materials provide possibility for solving the problems. The prior aliphatic polyester has high biocompatibility, no physiological toxicity and biodegradability, but is easy to be recognized and captured by protein adsorption and reticuloendothelial cells due to strong hydrophobicity, the circulation time in vivo is short, the monomer has no post-modification site, and the hydrophilicity of the monomer can be increased and the degradation rate of the monomer can be improved only by blending copolymerization and block copolymer, aiming at the background, the invention uses dicarboxylic acid dimethyl ester containing post-modification sites as raw materials and polyester formed by polymerizing with various types of dihydric alcohol, uses a side chain grafted Dimethyl Pyridylamine (DPA) compound in a post-polymerization modification mode, and utilizes the strong combination effect of the side chain grafted Dimethyl Pyridylamine (DPA) compound and a phosphorus ester structure in a gene after the side chain is coordinated with zinc ions, so that the hydrophobicity of the side chain grafted dimethyl pyridylamine compound is improved, the side chain grafted dimethyl pyridylamine compound is more expected to be applied to the entrapment of hydrophobic drugs and the co-delivery of genes, technical reference is provided for synthesizing novel polyester materials, and the biological application of the polyester materials is widened.
Disclosure of Invention
The invention aims to solve the problems that aliphatic polyester has insufficient hydrophilicity and can not jointly deliver hydrophobic drugs and hydrophilic genes, and discloses a preparation method of polyester with a side chain containing DPA.
The technical scheme of the invention is as follows:
a preparation method of a side chain containing dimethyl pyridine amine polyester comprises the following steps:
(1) adding 0.5-1.5 molar equivalents of diol monomer B (preferably the molar ratio A/B is 1/1) to 1, 3-acetone dicarboxylic acid monomer A, and adding 0.5-2 mol% equivalent of catalyst tetrabutyl titanate (TBT) (preferably 1.5 mol% equivalent); heating the mixed system to 100-150 ℃, continuously stirring for 12-24h, stopping reaction, adding chloroform for dissolving, centrifugally separating in methanol, normal hexane or diethyl ether, collecting precipitate, and drying for 12-48h to obtain a polyester material;
(2) adding 0.5-1.5 molar equivalent of Dimethyl Pyridylamine (DPA) (the amount of the monomer A in the polymer is 1 equivalent) into a polyester material, adding 0.05-0.1 molar equivalent of p-toluenesulfonic acid (PTSA), adding dimethyl sulfoxide (DMSO) as a reaction solvent, placing the mixture on a hot table at 50-120 ℃ for stirring and heating to react for 12-24 hours, wherein the concentration of reactants in a reaction system is in a range of 0.1-1M; stopping the reaction, settling in ether for 3-5 times, removing reaction raw materials and solvent, and pumping the product obtained by settling in a vacuum oven for 12-48h to obtain the polyester material containing DPA on the side chain;
(3) adding 1-5 molar equivalent zinc nitrate into the post-modified polyester material, adding DMSO (dimethyl sulfoxide) as a reaction solvent, wherein the concentration of reactants in a reaction system is within the range of 0.1-1M, and stirring at room temperature for reaction for 12-24 h; stopping the reaction, settling for 3-5 times in diethyl ether, n-hexane or water, removing reaction raw materials and solvent, and pumping the product obtained by settling in a vacuum oven for 12-48h to obtain the polyester material containing DPA-Zn on the side chain.
The 1, 3-acetone dicarboxylic acid monomer A is as follows:
the dihydric alcohol monomer B is as follows:
the invention has the beneficial effects that:
(1) the invention provides a method for synthesizing a biodegradable polyester material with post-modification sites, provides technical reference for synthesizing a novel polyester material and widens the biological application of the polyester material.
(2) The polyester prepared by polymerizing the dicarboxylic acid dimethyl ester containing post-modifiable sites as a raw material and various types of diols has good gene recombination capability after being coordinated with zinc ions by using DPA, is expected to be applied to the entrapment of hydrophobic drugs and the co-delivery of genes, and overcomes the defect that the traditional polyester can only deliver the hydrophobic drugs and can not deliver the genes together.
Drawings
FIG. 1 is a nuclear magnetic diagram of a polyester material containing post-modifiable functional groups prepared in example 1 of the present invention.
FIG. 2 is a nuclear magnetic diagram of a polyester material modified after DPA is prepared in example 2 of the present invention.
FIG. 3 is a nuclear magnetic diagram of a zinc-coordinated polyester material prepared in example 3 of the present invention.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
Taking the monomer B as 1,6 hexanediol for example: 3.588g (0.02mol, 1eq) of 1, 3-acetone dicarboxylic acid dimethyl ester is accurately weighed by a precision balance, 2.363g (0.02mol, 1eq) of 1, 6-hexanediol is accurately weighed in a 20mL reaction bottle, and finally 102mg (3 x 10) of 1, 6-hexanediol is weighed-4And (3) 0.015eq) of TBT, adding magnetons, placing in a 100 ℃ round table, heating to 10 ℃ every 20min until the temperature is raised to 150 ℃, and keeping the temperature at 150 ℃ for reaction for 4 hours. The reaction was stopped, cooled to room temperature, heated with 4-5ml chloroform and sonicated to dissolve. 15mL of methanol was added into a 20mL centrifuge tube, 2mL of the product was added each time, the mixture was centrifuged at 6000r/min for 5min to remove the remaining starting materials and oligomers, the product obtained by centrifugation was dried in a vacuum oven for 24h, and the nuclear magnetic characterization of the obtained polymer is shown in FIG. 1. Similar polymers can be obtained by expanding the diol monomers into a series of aliphatic diols with different lengths, and the molecular weight and distribution characteristics of the similar polymers are shown in table 1.
TABLE 1 characterization of the molecular weights and distributions of the polymers obtained by polymerization of different diols with dimethyl 1, 3-acetonedicarboxylate
Note: a) represents data measured by hydroxyl titration; b) represents data measured by nuclear magnetism; c) represents data measured by GPC
Example 2
Taking the monomer B as 1,6 hexanediol for example: accurately weighing 54mg of polymer (0.008mmol, 1eq of carbonyl content) in a 20mL reaction flask by using a precision balance, accurately weighing 36.6mg (0.184mmol, 1eq) of DPA in the reaction flask, finally weighing 0.076mg (0.09mmol, 0.05eq) of PTSA, adding 2mL of DMSO as a reaction solvent, adding a magneton, stirring and heating to 100 ℃, and reacting for 24 hours. Stopping the reaction, settling in ether for 5 times, removing the reaction raw materials and the solvent, drying the product obtained by settling in a vacuum oven for 24 hours, and carrying out nuclear magnetic characterization on the obtained polymer with the side chain containing DPA as shown in figure 2.
Example 3
Taking the monomer B as 1,6 hexanediol for example: 54mg of a polymer with a side chain containing DPA is accurately weighed by a precision balance, 17mg (0.184mmol) of zinc nitrate is accurately weighed in a 20ml reaction bottle, 1ml of DMSO is added as a reaction solvent, and the mixture is stirred and reacted for 24 hours at room temperature. Stopping the reaction, settling in ether for 5 times, removing the reaction raw materials and the solvent, drying the product obtained by settling in a vacuum oven for 24 hours, and carrying out nuclear magnetic characterization on the obtained polymer with the side chain containing DPA-Zn as shown in figure 3.
Claims (5)
1. A preparation method of polyester with side chains containing DPA-Zn is characterized by comprising the following steps:
(1) adding 0.5-1.5 molar equivalent of dihydric alcohol monomer B into 1, 3-acetone dicarboxylic acid monomer A, and then adding 0.5-2% molar equivalent of catalyst tetrabutyl titanate TBT, wherein the amount of the 1, 3-acetone dicarboxylic acid monomer A is 1 equivalent; heating the mixed system to 100-150 ℃, continuously stirring for 12-24h, stopping reaction, adding chloroform for dissolving, centrifugally separating in methanol, normal hexane or diethyl ether, collecting precipitate, and drying for 12-48h to obtain a polyester material;
(2) adding 0.5-1.5 mol equivalent of dimethyl pyridylamine DPA into the polyester material, and then adding 0.05-0.1 mol equivalent of p-toluenesulfonic acid PTSA, wherein the amount of the 1, 3-acetone dicarboxylic acid monomer A is 1 equivalent; adding dimethyl sulfoxide (DMSO) as a reaction solvent, placing the reaction system with the reactant concentration in the range of 0.1-1M on a hot platform at 50-120 ℃, stirring and heating, and reacting for 12-24 h; stopping the reaction, settling in ether for 3-5 times, removing reaction raw materials and solvent, and pumping the product obtained by settling in a vacuum oven for 12-48h to obtain the polyester material containing DPA on the side chain;
(3) adding 1-5 molar equivalents of zinc nitrate into a polyester material containing DPA in a side chain, wherein the amount of the 1, 3-acetone dicarboxylic acid monomer A is 1 equivalent; adding DMSO as a reaction solvent, wherein the concentration of reactants in a reaction system is within the range of 0.1M-1M, and stirring and reacting for 12-24h at room temperature; stopping the reaction, settling for 3-5 times in diethyl ether, n-hexane or water, removing reaction raw materials and solvent, and pumping the product obtained by settling in a vacuum oven for 12-48h to obtain the polyester material containing DPA-Zn on the side chain.
2. The process for producing a polyester having a side chain containing DPA-Zn according to claim 1, wherein the 1, 3-acetone dicarboxylic acid monomer A is:
3. the process for preparing polyesters having in the side chain thereof DPA-Zn group according to claim 1 or 2, characterized in that the diol monomer B is:
4. the process for producing a polyester having a DPA-Zn group in a side chain according to claim 1 or 2, wherein the molar ratio of the 1, 3-acetone dicarboxylic acid monomer A to the diol monomer B is 1/1, and the molar ratio of the 1, 3-acetone dicarboxylic acid monomer A to tetrabutyl titanate is 1/0.015.
5. The process for producing a polyester having a DPA-Zn group in a side chain according to claim 3, wherein the molar ratio of the 1, 3-acetone dicarboxylic acid monomer A to the diol monomer B is 1/1, and the molar ratio of the 1, 3-acetone dicarboxylic acid monomer A to tetrabutyl titanate is 1/0.015.
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| CN112725922B (en) * | 2020-12-29 | 2022-01-28 | 江苏恒力化纤股份有限公司 | Low-thermal-shrinkage polyester industrial yarn and preparation method thereof |
| CN113956456B (en) * | 2021-10-18 | 2023-09-05 | 大连理工常熟研究院有限公司 | Preparation method of reversible cross-linking water-soluble polyester with side chain containing sulfhydryl group |
| CN115068701B (en) * | 2022-06-28 | 2023-10-24 | 瑞聚再生(厦门)医学科技有限公司 | Degradable ureteral stent and preparation method thereof |
| CN115286764B (en) * | 2022-08-31 | 2024-01-05 | 江苏富琪森新材料有限公司 | Nonionic waterborne polyurethane and preparation method and application thereof |
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| CN103975031A (en) * | 2011-12-06 | 2014-08-06 | 帝斯曼知识产权资产管理有限公司 | Resin composition |
| CN109172819A (en) * | 2011-07-29 | 2019-01-11 | 西莱克塔生物科技公司 | Generate the synthesis nano-carrier of body fluid and cytotoxic T lymphocyte (CTL) immune response |
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| CN109172819A (en) * | 2011-07-29 | 2019-01-11 | 西莱克塔生物科技公司 | Generate the synthesis nano-carrier of body fluid and cytotoxic T lymphocyte (CTL) immune response |
| CN103975031A (en) * | 2011-12-06 | 2014-08-06 | 帝斯曼知识产权资产管理有限公司 | Resin composition |
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