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Preparation and application of linear biodegradable polyester elastomer with controllable elasticity and shape memory effect

A technology of memory effect and degradation of polyester, used in prosthesis, medical science, pharmaceutical formulation, etc., can solve the problems of low shape recovery rate, gap in elasticity, too hard, etc., and achieve the effect of improving viscoelasticity

Inactive Publication Date: 2016-04-20
JINAN UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the mechanical properties of such materials are single and too hard. In order to improve their mechanical properties, researchers from various countries have done a lot of research work, and obtained a series of copolyester materials with improved mechanical properties through copolymerization, such as: P(LLA- CL), P(TMC / CL), P(TMC / DLLA), and studied the structure-activity relationship between the structure and performance of this type of material. Existing studies have shown that by combining lactide (LA) with caprolactone (CL) copolymerization can obtain a degradable polyester material with reduced modulus and improved elasticity, but there is still a gap between its elasticity and the elasticity of natural tissues of the human body; copolymerization of carbonate with lactide or caprolactone can obtain a more Highly elastic linear polyester, but due to the large difference in the reactivity rate of the ring-opening polymerization of carbonate monomers and cyclic ester monomers, the molecular weight of the resulting product is not high, and the strength of the material is lost while obtaining elasticity. Further cross-linking to achieve the strength requirements of the scaffold material
[0005] After searching the literature of the prior art, it was found that ChenQZ et al. (Elastomericbiomaterialsfortissueengineering.ProgPolymSci.2013; 38:584-671) and SerranoMC et al. (Advances and Applications of Biodegradable Elastomers in Regenerative Medicine. AdvFunctMater.2010; The significance of the development of medical polymer materials and the progress they have made so far, but the shortcomings of the currently obtained degradable elastomeric scaffolds are: 1. The strength of the existing linear degradable elastic scaffold materials is not enough, and it needs to be exchanged. 2. The currently existing network-type degradable elastic scaffold materials have the disadvantage of excessive strength loss during use; 3. Elastic scaffold materials obtained from living organisms, such as acellular matrix materials, elastin, etc., also exist Poor preparation reproducibility, expensive, immune rejection, disease contamination and other issues
PCL is a kind of shape memory polymer with good mechanical properties. It has been widely used as a medical shape memory material. The effect of shape memory comes from the entanglement points between the crystalline part and the macromolecular chain as the stationary phase. The amorphous part is used as a reversible phase; however, due to the high crystallinity of PCL materials, the reversible phase content is low, and the shape recovery rate is low. At the same time, its melting point is about 60-63 ° C, resulting in a high temperature range for shape deformation, which is not suitable for It is applied to the human body, so caprolactone is copolymerized with other monomers to reduce the melting point of the material to realize the adjustable melting point of the material, which directly affects the adjustable temperature range of the shape deformation; at the same time, the crystallinity of the material is reduced and the content of the amorphous reversible phase is increased. , to achieve a higher shape recovery rate, is the current research direction of shape memory polycaprolactone materials

Method used

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  • Preparation and application of linear biodegradable polyester elastomer with controllable elasticity and shape memory effect
  • Preparation and application of linear biodegradable polyester elastomer with controllable elasticity and shape memory effect
  • Preparation and application of linear biodegradable polyester elastomer with controllable elasticity and shape memory effect

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] Example 1: Preparation of linear degradable polyester elastomer with adjustable elasticity and shape memory effect

[0045] Take 9.0 g of ε-caprolactone and 1.0 g of 4-(ethylene glycol ketal)-ε-caprolactone, mix the above-mentioned raw materials evenly, and add 2 mg of stannous isooctanoate under the protection of an inert atmosphere, and then Under low temperature (less than 50Pa) at 115°C for 24 hours. After the reaction is completed, use dichloromethane / ethanol system (volume ratio 1:2) to carry out sedimentation purification to obtain a copolymer, which is marked as PCT9-1. The number average molecular weight measured by GPC is 104,000, and the weight average molecular weight is 19.3 Wan, the Young's modulus of the film cast from dichloromethane is 146.2MPa, the elongation at break is 676.8%, and the tensile strength is 9.79MPa.

Embodiment 2

[0046] Example 2: Preparation of linear degradable polyester elastomer with adjustable elasticity and shape memory effect

[0047] Take 8.0 g of ε-caprolactone and 2.0 g of 4-(ethylene glycol ketal)-ε-caprolactone, mix the above raw materials evenly, and add 2 mg of stannous isooctanoate under the protection of an inert atmosphere, and then Under low temperature (less than 50Pa) at 115°C for 24 hours. After the reaction was completed, the dichloromethane / ethanol system (volume ratio 1:2) was used for sedimentation and purification to obtain a copolymer marked as PCT8-2. The number average molecular weight measured by GPC was 139,000, and the weight average molecular weight was 26.9 Wan, the Young's modulus of the film cast from dichloromethane is 18.3MPa, the elongation at break is 1663.3%, and the tensile strength is 11.5MPa.

Embodiment 3

[0048] Example 3: Preparation of linear degradable polyester elastomer with adjustable elasticity and shape memory effect

[0049] Take 7.0 g of ε-caprolactone and 3.0 g of 4-(ethylene glycol ketal)-ε-caprolactone, mix the above-mentioned raw materials evenly, and add 2 mg of stannous isooctanoate under the protection of an inert atmosphere, and then Under low temperature (less than 50Pa) at 115°C for 24 hours. After the reaction is completed, use dichloromethane / ethanol system (volume ratio 1:2) to carry out sedimentation purification to obtain a copolymer, which is marked as PCT7-3. The number average molecular weight measured by GPC is 130,000, and the weight average molecular weight is 22.4 Wan, the Young's modulus of the film cast from dichloromethane is 1.2MPa, the elongation at break is 244.7%, and the tensile strength is 0.05MPa.

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Abstract

The invention discloses preparation and application of a linear biodegradable polyester elastomer with a controllable elasticity and shape memory effect. The linear biodegradable polyester elastomer with the controllable elasticity and shape memory effect is formed by conducting copolymerization on a caprolactone monomer containing a lateral cyclic ether structural unit and caprolactone, wherein the molar ratio of the caprolactone monomer containing the lateral cyclic ether structural unit to the caprolactone is 5:95-25:75, and the structural formula can be found in description. The viscoelasticity of the linear biodegradable polyester elastomer with the controllable elasticity and shape memory effect is remarkably improved, the elongation at break can reach 1600% and above, the elastomer can be dissolved in a conventional organic solvent, a three-dimensional porous support can be constructed conveniently through a construction technology of the porous support such as, electrostatic spinning, three-dimensional printing and phase separation, tissue engineering blood vessel scaffold materials, myocardial patches, nervous tissue engineering scaffold materials and the like are prepared, and the preparation and application of the linear biodegradable polyester elastomer can be widely applied to the fields of soft tissue engineering scaffolds, tissue repair and regenerative medicine.

Description

technical field [0001] The invention belongs to the technical field of biodegradable elastic polyester preparation, in particular to the preparation and application of a linear degradable polyester elastomer capable of regulating elasticity and shape memory effect. This type of linear elastic polyester has good elastic characteristics, shape memory properties and good biodegradability. By adjusting the components and molecular weight of the elastic polyester, the mechanical properties, shape memory behavior and biodegradation behavior of the obtained material can be easily adjusted. , has important application prospects in minimally invasive surgery and medical device implants, and can be widely used in surgical sutures, bone fixation materials, tissue engineering and drug controlled release systems. Background technique [0002] Biomedical polymer materials play an extremely important role in the improvement of clinical medical technology, and biodegradable implant material...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G63/664C08G63/08A61L17/10A61L27/18A61L27/50A61L27/54A61L27/58
CPCA61L17/105A61L27/18A61L27/507A61L27/54A61L27/58A61L2300/414A61L2400/16A61L2430/06A61L2430/30C08G63/08C08G63/664C08G2230/00C08G2280/00C08L67/04
Inventor 王小莺汤顺清邓海钦林卉恒武征何留民罗丙红
Owner JINAN UNIVERSITY
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