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Polycaprolactone/nano-hydroxyapatite composite material and method for preparing same

A nano-hydroxyapatite and composite material technology, which is applied in the field of medical nano-composite materials, can solve the problems of polymer molecular weight drop, difficulty in compatibility, and reduced material performance, and achieve the goal of enhancing dispersion and interfacial compatibility Effect

Active Publication Date: 2019-04-05
DALIAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The blending method usually adopts solution blending and melt blending. Although this method is simple, it is difficult to disperse nano-hydroxyapatite uniformly. The inorganic phase and organic phase in the composite material are only purely physically mixed, and the phase separation is obvious. This relatively weak combination will make the material easy to break under the action of external tensile stress, reducing the performance of the material
The copolymerization method is mainly realized by using hydroxyapatite as an initiator to initiate the ring-opening polymerization of caprolactone. The steric hindrance is increased by grafting polycaprolactone segments on the nanoparticles. Although it can be dispersed uniformly, due to the hydroxyapatite Stone nanoparticles are initiators, and its addition amount will affect the molecular weight of the polymer. Too much addition will lead to a decrease in the molecular weight of the polymer, resulting in a decrease in toughness and greater brittleness of the material.
At the same time, this method needs to add toxic solvents and metals or their compounds as catalysts, and the preparation process is complicated, which limits its application in the field of biomedical materials

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Prepare polycaprolactone / nano-hydroxyapatite composites by bulk in-situ polymerization according to the following formula: Weigh the initiator and monomer respectively according to the molar ratio of anhydrous citric acid:ε-caprolactone of 1:15, and weigh Take dry nano-hydroxyapatite, its mass is 5% of monomer mass.

[0024] First, mix nano-hydroxyapatite and ε-caprolactone uniformly in ultrasonic to form a white suspension; put anhydrous citric acid in a dry flask, perform vacuum pumping and nitrogen gas repeatedly for three times, and finally heat up under nitrogen protection to 110°C; add the suspension liquid dropwise to the reaction system, complete the dropwise addition, and react for 24 hours under magnetic stirring; after the reaction is completed, the product is repeatedly washed and precipitated in deionized water, vacuum filtered and dried to obtain polycaprolactone / Nano-hydroxyapatite composites.

Embodiment 2

[0026] Prepare polycaprolactone / nano-hydroxyapatite composites by bulk in-situ polymerization according to the following formula: Weigh the initiator and monomer respectively according to the molar ratio of malic acid:ε-caprolactone of 1:12, and weigh and dry The nano-hydroxyapatite whose mass is 1% of the monomer mass.

[0027] First, mix the nano-hydroxyapatite and the monomer evenly in an ultrasonic wave to form a white suspension; put the malic acid in a dry flask, perform vacuum pumping and nitrogen gas repeatedly for three times, and finally raise the temperature to 130°C under the protection of nitrogen gas; The suspension was added dropwise to the reaction system, all the addition was completed, and reacted for 10 hours under magnetic stirring; after the reaction, the product was repeatedly washed and precipitated in deionized water, vacuum filtered and dried to obtain polycaprolactone / nano-hydroxyapatite composite material.

Embodiment 3

[0029] Carry out bulk in-situ polymerization according to the following formula to prepare polycaprolactone / nanometer hydroxyapatite composite material: according to tartaric acid: ε-caprolactone molar ratio is 1:6 to weigh initiator and monomer respectively, and weigh dry Nano-hydroxyapatite, its mass is 0.1% of monomer mass.

[0030] First, mix the nano-hydroxyapatite and the monomer uniformly in the ultrasonic wave to form a white suspension; put the tartaric acid in a dry flask, perform vacuum pumping and nitrogen gas repeatedly for three times, and finally raise the temperature to 90°C under the protection of nitrogen gas; Add the mixed solution dropwise to the reaction system, complete the dropwise addition, and react under magnetic stirring for 48 hours; after the reaction, the product is washed and precipitated repeatedly in deionized water, filtered and dried under vacuum to obtain a polycaprolactone / nano-hydroxyapatite composite Material.

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Abstract

The invention relates to a polycaprolactone / nano-hydroxyapatite composite material and a method for preparing the same. The method includes steps of (1), weighing dried nano-hydroxyapatite and monomers epsilon-caprolactone according to certain mass ratios, and uniformly dispersing and mixing the nano-hydroxyapatite and the monomers epsilon-caprolactone with one another in ultrasound to form mixedsuspension; (2), carrying out ring-opening polymerization reaction on the mixed suspension and initiators according to certain ratios; (3), repeatedly washing and precipitating products by deionized water, carrying out vacuum filter on the products and drying the products to obtain the polycaprolactone / nano-hydroxyapatite composite material. The polycaprolactone / nano-hydroxyapatite composite material and the method have the advantages that in-situ bulk polymerization is adopted, the nano-hydroxyapatite is uniformly dispersed in polycaprolactone materials, accordingly, the products are high inpurity, and toxic solvents are omitted in polymerization and after-treatment procedures; hydroxy acid is used as an initiator and a catalyst, accordingly, the method includes simple processes, and thepolycaprolactone / nano-hydroxyapatite composite material prepared by the aid of the method can be applied to bone repair materials.

Description

technical field [0001] The invention relates to a polycaprolactone / nanometer hydroxyapatite composite material and a preparation method thereof, belonging to the field of medical nanometer composite materials. Background technique [0002] Polycaprolactone (PCL) has excellent biodegradability, good biocompatibility and mechanical properties, and is a class of biomedical materials approved by the US Food and Drug Administration (FDA). Polycaprolactone is a crystalline polymer with a melting point of 59-64°C and a glass transition temperature of around -60°C. It has good flexibility and processability; it also has excellent drug permeability and can be used As drug controlled release carrier. [0003] Hydroxyapatite (HA) is the main inorganic component in human and animal bones. Hydroxyapatite has excellent biocompatibility and bioactivity, nano-scale hydroxyapatite can be used as a bone or tooth inducing factor, and can be applied to bone tissue regeneration engineering. I...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G63/08C08G63/78C08K3/32
CPCC08G63/08C08G63/78C08K3/32C08K2201/011
Inventor 侯维敏詹世平高逸飞
Owner DALIAN UNIV
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