CN114479027A - Polyester catalyst with antibacterial and osteogenic activity and preparation method thereof - Google Patents

Polyester catalyst with antibacterial and osteogenic activity and preparation method thereof Download PDF

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Publication number
CN114479027A
CN114479027A CN202210167051.8A CN202210167051A CN114479027A CN 114479027 A CN114479027 A CN 114479027A CN 202210167051 A CN202210167051 A CN 202210167051A CN 114479027 A CN114479027 A CN 114479027A
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China
Prior art keywords
zinc
catalyst
acid
diethyl
dimethyl
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CN202210167051.8A
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Chinese (zh)
Inventor
李晓军
张巧
张洪杰
罗巧洁
朱蔚璞
李晓东
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Zhejiang University ZJU
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Zhejiang University ZJU
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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
    • C08G63/12—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
    • 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

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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

The invention provides a polyester catalyst with antibacterial and osteogenic activity, which uses dicarboxylic acid or dibasic ester and excessive dihydric alcohol to carry out pre-polycondensation so as to fully react to form a prepolymer; and (3) carrying out ester exchange reaction on the prepolymer by using a zinc catalyst, and continuously removing micromolecular byproducts under reduced pressure to obtain the prepolymer. Compared with the prior art, the invention has the following outstanding advantages: (1) the invention provides a novel ester exchange catalyst, zinc is an important metal element in a living body, has the characteristics of no toxicity and absorbability, has bioactivity, has the effect of promoting the proliferation of skeletal osteoblasts of a human body, has a bactericidal effect on zinc ions, is low in cost, can be used in a large amount, and can be used in the field of biomedicine. (2) The aliphatic polyester prepared by the invention has the characteristics of degradability and strong safety, and has good market space and value.

Description

Polyester catalyst with antibacterial and osteogenic activity and preparation method thereof
Technical Field
The invention belongs to the technical field of synthesis of degradable polyester, and particularly relates to a polyester catalyst with antibacterial and osteogenic activities and a preparation method thereof, which are a novel ester exchange catalyst of degradable polyester and a polyester synthesis method.
Background
The degradable material is a product which can be degraded into small molecules harmless to the environment under the action of factors such as light, heat, oxygen, water, microorganisms and the like in the natural environment. At present, various countries in the world vigorously develop researches on the products. In the current research on degradable materials, polyester-based degradable materials play an important role. Aliphatic polyester polymers contain ester bonds in their molecular chains, and are therefore easily hydrolyzed or degraded by microorganisms into small molecules such as water and carbon dioxide. For example, the surgical suture used in the biomaterial, the conventional surgical suture needs a secondary suture removal treatment after the wound is sutured, and is easy to generate inflammatory reaction and other problems. Based on the concept of degradable materials, the degradable polylactic acid surgical suture is invented, and because polylactic acid can be digested by a human body, and the final products obtained by digestion are carbon dioxide and water which are harmless to the human body, secondary suture removing treatment is not needed, and the pain of the operation is reduced. The problem of white pollution can be easily solved if the degradable polyester material is used for replacing the traditional non-degradable material.
At present, a plurality of catalyst systems are used for preparing polyester by condensation polymerization, and the catalysts with the best reported effect can be divided into three types: titanium, antimony, and germanium. When the titanium element is used as a catalyst, the catalytic activity is high, but the titanium catalyst can accelerate the aging of polyester materials, and yellow the product, which affects the use, and a stabilizer is generally required to be added for stabilizing the polyester materials. Antimony is toxic, not beneficial to environmental protection, and can not be applied to biological materials. Germanium is expensive and not suitable for a wide range of applications. It has also been reported that organic solvents are used as catalysts, and because organic solvents are toxic and difficult to remove from the product, their use in biomedical applications is limited. Therefore, the search for a catalyst which is nontoxic, low in price and high in catalytic activity becomes an urgent problem to be solved.
The zinc and the compound thereof not only have good antibacterial activity, but also have remarkable osteogenic activity, can stimulate the differentiation of stem cells to osteoblasts, promote the growth and proliferation of the osteoblasts, help the generation of new bone and play an important role in the repair of bones and teeth. Biomedical materials based on zinc and its compounds, such as bioactive glass, bioceramic scaffolds, metal alloys, etc., have been developed and have been partially used in clinical diagnosis and treatment in orthopedics and stomatology. If the synthesis of the degradable polyester can be catalyzed by zinc and compounds thereof, the obtained polyester material is nontoxic and can be used for human bodies, and metal ions contained in the product can be used as functional components to endow the material with biological activity and promote the proliferation and growth of repaired tissues and cells; and endowing the antibacterial activity to the antibacterial fiber to obtain antibacterial ability; meanwhile, the catalyst is not required to be removed, so that the method completely accords with the principle of green synthesis, and the application cost is reduced.
Disclosure of Invention
The invention overcomes the defects of the traditional ester exchange catalyst, provides a polyester catalyst with antibacterial and osteogenic activity, is a novel zinc catalyst, and uses dicarboxylic acid or dibasic ester and excessive dihydric alcohol to carry out pre-polycondensation so as to fully react to form a prepolymer; and (3) carrying out ester exchange reaction on the prepolymer by using a corresponding zinc catalyst, and continuously removing small molecular byproducts under reduced pressure to obtain the polyester catalyst with high molecular weight and bioactivity. The catalyst has the advantages of no toxicity, low cost, biological activity, no introduction of negative anion impurities, no need of removal, and applicability to human body.
The polyester catalyst with antibacterial and osteogenic activities is realized by the following preparation steps:
(1) pre-polycondensation: carrying out pre-polycondensation reaction on dicarboxylic acid or dibasic ester and dihydric alcohol at 140-200 ℃, wherein the reaction time is 6-24 hours, removing generated micromolecular byproducts under the protection of nitrogen, argon or carbon dioxide inert atmosphere, and carrying out ester exchange reaction when no micromolecular byproducts are generated;
(2) ester exchange: in the presence of a zinc catalyst, the prepolymer is subjected to ester exchange reaction at the reaction temperature of 200-260 ℃ for 6-24 hours, and meanwhile, the pressure is reduced to remove small molecular byproducts (alcohol), and the vacuum pressure is 0.1-200 Pa.
The catalyst is selected from any one of zinc, zinc oxide, zinc hydroxide and zinc carbonate.
The dihydric alcohol is at least one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol and decanediol.
The dibasic ester is at least one selected from dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, diethyl oxalate, diethyl malonate, diethyl succinate, diethyl glutarate, diethyl adipate, diethyl pimelate, diethyl suberate, diethyl azelate and diethyl sebacate.
The dicarboxylic acid is at least one selected from oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
The molar ratio of the dicarboxylic acid or the diester to the dihydric alcohol is 1: 1.1-1: 5.
Preferably, the temperature of the transesterification reaction is 200-260 ℃.
The amount of zinc or its oxide in the zinc catalyst is 0.05-5 wt% relative to the total mass of the dicarboxylic acid or diester and diol.
Compared with the prior art, the invention has the following outstanding advantages: (1) the invention creates a novel ester exchange catalyst, zinc is an important metal element in a living body, has the characteristics of no toxicity and absorbability, has bioactivity, has the effect of promoting the proliferation of skeletal osteoblasts of the human body, has the bactericidal effect on zinc ions, has low cost, can be used in a large amount, and can be used in the field of biomedicine. (2) The aliphatic polyester synthesized by the invention has the characteristics of degradability and strong safety, and has good market space and value. (3) The antibacterial polyester is prepared by a one-pot method for the first time, and the catalyst is also a functional antibacterial agent. No chemical post-modification and physical blending steps with other antimicrobial agents are required.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples. Its purpose is merely to better understand the invention and not to limit its scope.
Example 1
(1) 0.35 g of zinc powder was added to a 250mL three-necked flask equipped with a mechanical stirrer, a thermometer, a nitrogen introduction tube, a condenser, a water separator and the like, 20 g of succinic acid and 15 g of 1, 4-butanediol were added to the three-necked flask, argon gas was introduced, the mixture was gradually heated to 180 ℃ and reacted with stirring at 100r.p.m, the produced water was removed by the water separator, and the reaction was stopped when no water was produced.
(2) Heating to 230 ℃, simultaneously connecting an oil pump for vacuum pumping, performing polycondensation reaction for 12 hours under the stirring of the pressure of 0.1-200 Pa and the pressure of 100r.p.m, and obtaining the non-optically active fully biodegradable poly (butylene succinate) with the intrinsic viscosity of 0.91dL/g (chloroform as a solvent) and the molecular weight of 50 kDa.
Examples 2 to 5
The synthesis process is the same as that of example 1, except that succinic acid in the polyester synthesis process is replaced by glutaric acid, adipic acid, pimelic acid, suberic acid. The resulting polyester has a molecular weight of between 20kDa and 60 kDa.
Examples 6 to 9
The synthesis process is the same as that of example 1, except that butanediol in the polyester synthesis process is replaced by pentanediol, hexanediol, heptanediol, octanediol, and the obtained polyester has a molecular weight of 15kDa to 50 kDa.
Examples 10 to 13
The synthesis process is the same as that of example 1, except that succinic acid in the polyester synthesis process is replaced by dimethyl succinate, dimethyl suberate, diethyl pimelate and diethyl sebacate, and the obtained polyester has a molecular weight of 22kDa to 55 kDa.
Examples 14 to 16
The synthesis process was the same as in example 1 except that the amount of the catalyst used in the synthesis of polyester was replaced with 0.05 wt%, 1 wt% and 5 wt%, respectively, based on the total weight of the raw materials. The molecular weights of the obtained polyesters are 31kDa, 55kDa and 32kDa respectively.
Example 17
(1) 0.35 g of zinc oxide is added into a 250mL three-neck flask which is provided with a mechanical stirrer, a thermometer, a nitrogen inlet pipe, a condenser, a water separator and the like, 20 g of succinic acid and 15 g of 1, 4-butanediol are added into the three-neck flask, argon is introduced, the three-neck flask is gradually heated to 180 ℃, the three-neck flask is reacted under stirring at 100 r.p.m., generated water is removed through the water separator, and the reaction is stopped when no water is generated.
(2) Heating to 230 ℃, simultaneously connecting an oil pump for vacuum pumping, performing polycondensation reaction for 12 hours under the conditions that the pressure is 0.1-200 Pa and the stirring is carried out at 100r.p.m, and obtaining the non-optically active fully biodegradable poly (butylene succinate) with the intrinsic viscosity of 0.72dL/g (chloroform is used as a solvent) and the molecular weight of 35 kDa.
Example 18
(1) 0.35 g of zinc carbonate is added into a 250mL three-neck flask which is provided with a mechanical stirrer, a thermometer, a nitrogen inlet pipe, a condenser, a water separator and the like, 20 g of succinic acid and 15 g of 1, 4-butanediol are added into the three-neck flask, argon is introduced, the three-neck flask is gradually heated to 180 ℃, the three-neck flask is stirred and reacts, the generated water is removed through the water separator, and the reaction is stopped when no water is generated.
(2) Heating to 230 ℃, simultaneously connecting an oil pump for vacuum pumping, performing polycondensation reaction for 12 hours under the conditions that the pressure is 0.1-200 Pa and the stirring is carried out at 100r.p.m, and obtaining the non-optically active fully biodegradable poly (butylene succinate) with the intrinsic viscosity of 0.70dL/g (chloroform is used as a solvent) and the molecular weight of 33 kDa.
Example 19
(1) 0.35 g of zinc hydroxide was added to a 250mL three-necked flask equipped with a mechanical stirrer, a thermometer, a nitrogen introduction tube, a condenser, a water separator and the like, 20 g of succinic acid and 15 g of 1, 4-butanediol were added to the three-necked flask, argon gas was introduced, the mixture was gradually heated to 180 ℃ and reacted under stirring at 100r.p.m, the produced water was removed by the water separator, and the reaction was stopped when no water was produced.
(2) Heating to 230 ℃, simultaneously connecting an oil pump for vacuum pumping, performing polycondensation reaction for 12 hours under the conditions that the pressure is 0.1-200 Pa and the stirring is carried out at 100r.p.m, and obtaining the non-optically active fully biodegradable poly (butylene succinate) with the intrinsic viscosity of 0.75dL/g (chloroform is used as a solvent) and the molecular weight of 38 kDa.
Example 20
(1) 0.35 g of zinc powder was added to a 250mL three-necked flask equipped with a mechanical stirrer, a thermometer, a nitrogen introduction tube, a condenser, a water separator and the like, 20 g of succinic acid and 15 g of 1, 4-butanediol were added to the three-necked flask, argon gas was introduced, the mixture was gradually heated to 180 ℃ and reacted with stirring at 100r.p.m, the produced water was removed by the water separator, and the reaction was stopped when no water was produced.
(2) Heating to 260 ℃, simultaneously connecting an oil pump for vacuum pumping, performing polycondensation reaction for 12 hours under the conditions that the pressure is 0.1-200 Pa and the stirring is carried out at 100r.p.m, and obtaining the non-optically active fully biodegradable poly (butylene succinate) with the intrinsic viscosity of 0.89dL/g (chloroform is used as a solvent) and the molecular weight of 49 kDa.
Example 21
(1) 0.35 g of zinc powder was added to a 250mL three-necked flask equipped with a mechanical stirrer, a thermometer, a nitrogen introduction tube, a condenser, a water separator and the like, 20 g of succinic acid and 15 g of 1, 4-butanediol were added to the three-necked flask, argon gas was introduced, the mixture was gradually heated to 180 ℃ and reacted with stirring at 100r.p.m, the produced water was removed by the water separator, and the reaction was stopped when no water was produced.
(2) Heating to 200 ℃, simultaneously connecting an oil pump for vacuum pumping, performing polycondensation reaction for 12 hours under the stirring of the pressure of 0.1-200 Pa and the pressure of 100r.p.m, and obtaining the non-optically active fully biodegradable poly (butylene succinate) with the intrinsic viscosity of 0.63dL/g (chloroform as a solvent) and the molecular weight of 30 kDa.
Example 22
(1) 0.35 g of zinc powder was added to a 250mL three-necked flask equipped with a mechanical stirrer, a thermometer, a nitrogen introduction tube, a condenser, a water separator and the like, 20 g of succinic acid and 15 g of 1, 4-butanediol were added to the three-necked flask, argon gas was introduced, the mixture was gradually heated to 140 ℃ and reacted under stirring at 100 r.p.m., the produced water was removed by the water separator, and the reaction was stopped when no water was produced.
(2) Heating to 230 ℃, simultaneously connecting an oil pump for vacuum pumping, performing polycondensation reaction for 12 hours under the stirring of the pressure of 0.1-200 Pa and the pressure of 100r.p.m, and obtaining the non-optically active fully biodegradable poly (butylene succinate) with the intrinsic viscosity of 0.61dL/g (chloroform as a solvent) and the molecular weight of 29 kDa.
Example 23
(1) 0.35 g of zinc powder was added to a 250mL three-necked flask equipped with a mechanical stirrer, a thermometer, a nitrogen introduction tube, a condenser, a water separator and the like, 20 g of succinic acid and 15 g of 1, 4-butanediol were added to the three-necked flask, argon gas was introduced, the mixture was gradually heated to 200 ℃ and reacted with stirring at 100r.p.m, the produced water was removed by the water separator, and the reaction was stopped when no water was produced.
(2) Heating to 230 ℃, simultaneously connecting an oil pump for vacuum pumping, performing polycondensation reaction for 12 hours under the conditions that the pressure is 0.1-200 Pa and the stirring is carried out at 100r.p.m, and obtaining the non-optically active fully biodegradable poly (butylene succinate) with the intrinsic viscosity of 0.88dL/g (chloroform is used as a solvent) and the molecular weight of 48 kDa.

Claims (7)

1. The preparation method of the polyester catalyst with antibacterial and osteogenic activities is characterized in that the polyester catalyst is subjected to pre-polycondensation by using dicarboxylic acid or diester and excessive diol, so that the dicarboxylic acid or diester and the excess diol are fully reacted to form prepolymer; and (3) carrying out ester exchange reaction on the prepolymer by using a zinc catalyst, and continuously removing micromolecular byproducts by reducing pressure to obtain the target polyester catalyst.
2. The method for preparing the polyester catalyst according to claim 1, comprising the steps of:
(1) pre-polycondensation: carrying out pre-polycondensation reaction on dicarboxylic acid or diester and dihydric alcohol at 140-200 ℃, wherein the reaction time is 6-24 hours, removing generated micromolecular byproducts under the protection of nitrogen, argon or carbon dioxide inert atmosphere, and carrying out ester exchange reaction when no micromolecular byproducts are generated;
(2) ester exchange: in the presence of a zinc catalyst, the prepolymer is subjected to ester exchange reaction at the reaction temperature of 200-260 ℃ for 6-24 hours, and meanwhile, a small molecular byproduct (alcohol) is removed under reduced pressure, and the vacuum degree is 0.1-200 Pa.
3. The method according to claim 2, wherein the zinc catalyst is selected from any one of zinc, zinc oxide, zinc hydroxide, and zinc carbonate.
4. The method according to claim 2, wherein the diol is at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, and decylene glycol.
5. The method according to claim 2, wherein said dibasic ester is at least one selected from the group consisting of dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, diethyl oxalate, diethyl malonate, diethyl succinate, diethyl glutarate, diethyl adipate, diethyl pimelate, diethyl suberate, diethyl azelate and diethyl sebacate. The dicarboxylic acid is at least one selected from oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
6. The preparation method according to claim 2, wherein the molar ratio of the dicarboxylic acid or diester to the diol is 1:1.1 to 1: 5.
7. The production method according to claim 2, wherein the amount of zinc or an oxide thereof in the zinc-zinc catalyst is 0.05 to 5 wt% based on the total mass of the starting materials, relative to the total mass of the dicarboxylic acid or diester and the diol.
CN202210167051.8A 2022-02-23 2022-02-23 Polyester catalyst with antibacterial and osteogenic activity and preparation method thereof Pending CN114479027A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1961022A (en) * 2004-05-05 2007-05-09 沙特基础工业公司 Process for the production of polyethylene terephthalate copolyester, copolyester obtained thereby and its use and catalyst useful in the process
CN113292712A (en) * 2021-05-25 2021-08-24 吉林建筑大学 1, 4-succinic acid-based copolyester material and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1961022A (en) * 2004-05-05 2007-05-09 沙特基础工业公司 Process for the production of polyethylene terephthalate copolyester, copolyester obtained thereby and its use and catalyst useful in the process
CN113292712A (en) * 2021-05-25 2021-08-24 吉林建筑大学 1, 4-succinic acid-based copolyester material and preparation method and application thereof

Non-Patent Citations (3)

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Title
任杰等: "生物可降解聚乳酸及其共聚物的制备", 《建筑材料学报》 *
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Application publication date: 20220513