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Multi-block biodegradable shape memory polymeric compound with regular structure and preparation thereof

A memory polymer, biodegradable technology, applied in the field of multi-block biodegradable shape memory polymer and its preparation, can solve the problems of high content of non-degradable chain segments, random arrangement, narrow adjustment range, etc., to achieve deformation fixation High recovery rate and recovery rate, controllable deformation recovery rate, and excellent biocompatibility

Inactive Publication Date: 2009-07-08
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0014] In 2001, Japan’s Takiron Company applied for a patent (US6281262)9 on the use of polylactic acid and its copolymers, blends and fillers as thermogenic BSMP, but there is a problem that the deformation recovery temperature is too high (65-85°C) and difficult to control. Insufficient, inconvenient to apply
[0016] The polyurethane disclosed in Chinese patent 200410010734.4 is prepared by the prepolymer method. Its structure is similar to that of traditional polyurethane, and it is also a multi-block structure. The soft and hard segments are arranged alternately. The hard segment cannot be degraded, therefore, it is actually difficult to apply in the human body
[0017] Chinese patent CN200410043386.0 discloses that the soft and hard segments of multi-block copolymers can be degraded, but the hard segments and soft segments are arranged randomly; moreover, the hard segments are made of polylactide homopolymer, and the mechanical properties and degradation rate are inconvenient adjust
However, summarizing the existing disclosed multi-block thermotropic BSMP materials, there are still defects in the structure such as random arrangement of hard segments and soft segments, single structure of hard segments or soft segments, and high content of non-degradable segments, resulting in unadjustable properties. Or defects and deficiencies such as narrow adjustment range, high or low transition temperature, poor biodegradability, mechanical properties and degradation properties cannot be independently adjusted, so the above requirements cannot or cannot be fully met

Method used

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  • Multi-block biodegradable shape memory polymeric compound with regular structure and preparation thereof
  • Multi-block biodegradable shape memory polymeric compound with regular structure and preparation thereof
  • Multi-block biodegradable shape memory polymeric compound with regular structure and preparation thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0055] Example 1 Synthesis of ε-caprolactone / glycolide copolymer macromolecular diol (PCG-diol)

[0056] Add ε-caprolactone (CL, 51.3g, 0.45mol), glycolide (5.8g, 0.05mol), 1,4-butanediol (0.52g, 5.8 mmol), stir evenly, then add the catalyst stannous octoate (28.6mg, 0.05wt%), mix well, seal the tube after vacuumizing, and react at 120°C for 8h; the product is dissolved in chloroform, precipitated with excess methanol, and precipitated After repeated washing, the product was dried under vacuum at 50°C for 48 hours, and the obtained sample was recorded as PCG-diol (90 / 10, 10000), where 90 / 10 represents the molar ratio of ε-caprolactone to glycolide, and 10000 represents the designed number average molecular weight. The number average molecular weight of PCG-diol (90 / 10, 10000) is 10000, the polydispersity index is 1.49, and the melting point is 49.5°C.

[0057] Change the ratio of ε-caprolactone and glycolide or the ratio of monomer (the sum of ε-caprolactone and glycolide) a...

Embodiment 2

[0060] Example 2 Synthesis of L-lactide / glycolide copolymer macromolecular diol (PLLG-diol)

[0061] Add LLA (64.8g, 0.45mol), GA (5.8g, 0.05mol), BDO (0.52g, 5.8mmol) in the reaction flask that has been fully pumped / roasted, stir evenly, then add catalyst stannous octoate (35.3 mg, 0.05wt%), mix well, seal the tube after vacuuming, and react at 160°C for 8h; the product is dissolved in chloroform, precipitated with excess methanol, and the precipitate is dried under vacuum at 75°C for 48h after repeated washing. The obtained sample is recorded as PLLG-diol (90 / 10, 10000), with a number average molecular weight of 10500, a polydispersity index of 1.10, a glass transition temperature of 44.3 and a melting point of 136°C.

[0062] Table 2 Synthesis conditions and results of PLLG-diol macromolecular diol

[0063]

Embodiment 3

[0065] Add PCG-diol (90 / 10, 6000, 5.1 g, 0.81 mmol) into a three-necked flask equipped with a constant pressure dropping funnel, a thermometer and a nitrogen tube. TDI (1.7mmol, molar ratio to PCG-diol is 2.1:1), pre-polymerized at 80°C for 4 hours after the dropwise addition; then, add PLLG-diol (90 / 10, 6000, 5 grams, 0.81mmol) , chain extension reaction was carried out at 110°C for 8 hours; the temperature was lowered to 110°C, and 1 g of n-butanol was added for post-treatment, and the reaction was carried out for 1 hour; vacuum was applied to remove excess n-butanol to obtain P(LLG- mb-CG) multi-block copolymer with a molecular weight of 53000 and a soft segment / hard segment molar ratio of 50 / 50.

[0066] After the reaction is over, the polymer melt is added into the mold while it is hot, and a flake-like sample is obtained after cooling. A dumbbell-shaped sample is pressed with a dumbbell-shaped mold, and its effective size is 20×4×0.2~0.3 (mm). On a universal material t...

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Abstract

The invention discloses a regular structure multi-block biodegradable thermic shape memory polymer and a preparation method thereof. The shape memory polymer consists of a plurality of soft blocks and hard blocks which are alternately arranged. The soft blocks and the hard blocks are both copolymers and both have even chain length; the content of the hard blocks is between 50 and 90 weight percent; and the content of the soft blocks is between 10 and 50 weight percent. Each soft block is a crystalline poly(epsilon-caprolactone-glycolide)chain segment which has the fusion point 3 DEG C above a body temperature; and each hard block is a crystalline poly(L-lactide-glycolide)chain segment which has the fusion point 50 DEG C above the body temperature and a controllable deformation recovery rate. The shape memory polymer can relatively independently control the mechanical properties and the degradation rate, thereby having the mechanical properties and the controllable degradation rate matched with the implanted tissue in vivo. With good forming machining performance and excellent biocompatibility, the shape memory polymer can be used as a new functional biological medical material. The preparation method is characterized by simplicity, short reaction time, no residual harmful reagent content, and the like, thereby facilitating the commercialization.

Description

technical field [0001] The invention relates to a biodegradable polymer material and a preparation method thereof, in particular to a multi-block biodegradable shape memory polymer with regular structure and a preparation method thereof. Background technique [0002] Shape memory materials are a typical class of smart materials, including shape memory alloys (SMA), shape memory ceramics (SMC) and shape memory polymers (SMP). When the original shape obtained by the first molding is processed into a temporary shape, it can "remember" the original shape and restore the original shape under the action of external stimuli. Its shape recovery function can be triggered by external heat, light, electricity, magnetic and other stimuli. From the perspective of material application, thermal triggering is the most direct and effective way. Therefore, thermotropic shape memory polymers have the most practical value and are also the focus of current research and development. In 2002, pr...

Claims

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Application Information

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IPC IPC(8): C08G18/42C08G18/83C08G63/60C08G63/91
Inventor 吴林波姬斌袁征
Owner ZHEJIANG UNIV
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