CN101508772B - Polyester type biodegradable shape memory polymeric compounds and methods of formulating same - Google Patents
Polyester type biodegradable shape memory polymeric compounds and methods of formulating same Download PDFInfo
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- CN101508772B CN101508772B CN2009100715319A CN200910071531A CN101508772B CN 101508772 B CN101508772 B CN 101508772B CN 2009100715319 A CN2009100715319 A CN 2009100715319A CN 200910071531 A CN200910071531 A CN 200910071531A CN 101508772 B CN101508772 B CN 101508772B
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Abstract
The invention relates to a polyester type biodegradable shape memory polymer and a preparation method thereof. The product is essentially formed by the copolymerization and the cross linking of sebacic acid, propanetriol and diol. The method is as follows: a. the sebacic acid and the diol are copolymerized, and the propanetriol is added for copolymerizing; and b. the product is obtained by moulding, cross linking and solidifying. The product has the advantages of large deformation, the high restoration ratio of deformation and good biocompatibility. The shape restoration temperature is 0 DEG C to 45 DEG C; the tensile strength is 0.5-10MPa; and the degradation time is 30 to 300 days. The polyester type biodegradable shape memory polymer can be used as material for repairing human body soft tissue injury, such as cornea, retina, skin, blood vessel, connective tissue, islet tissue, musculature, nervous tissue, etc. The method has simple technology and convenient operation.
Description
Technical field
The present invention relates to biodegradable shape memory polymers and preparation method thereof.
Background technology
At present, the biodegradable shape memory polymers of having developed comprises: Langer study group is with poly-1,4-dioxane-2-ketone oligopolymer is a stationary phase, and polycaprolactone oligopolymer or polylactide glycolide copolymer are that reversible segmented copolymer that is combined to and polycaprolactone oligopolymer are the reversible methacrylic ester cross-linked polymer that is combined to (US Patent 6160084); Yasuo Shikinami study group synthetic has shape memory characteristic, biodegradable and biological absorbable poly(lactic acid) (US Patent 6281262) or the like simultaneously.But, but the mechanical property of these materials only is applicable to the performance requriements of sclerous tissues's (as bone) of human body, very big with the mechanical property difference of human body soft tissue, be very restricted in the use; Simultaneously, the mechanism of degradation of existing biodegradable shape memory polymeric all belongs to bulk degradation, after implanting, when quality and shape do not change as yet, mechanical property is decay rapidly, and total collapse takes place, and causes the initial purpose of implanting to satisfy.The shape recovery temperature of these materials is all distant with body temperature in addition, can't directly directly use in vivo.
Summary of the invention
The invention provides polyester type biodegradable shape memory polymkeric substance and preparation method thereof.Polyester type biodegradable shape memory polymkeric substance of the present invention has the mechanical property of human soft tissue injury's material for repairing (as cornea, retina, skin, blood vessel, reticular tissue, islet tissue, muscle tissue and nervous tissue); And shape recovery temperature is near body temperature, and shape can be recovered automatically after implanting; Its mechanism of degradation is surface corrosion, and mechanical property satisfies clinical medical application fully along with the minimizing of the quality of implant and volume and reduce.The present invention provides new approaches for the exploitation of biodegradable polymer, and the biodegradable shape memory polymers with clinical medicine value on probation is provided.
Among the present invention the polyester type biodegradable shape memory polymkeric substance mainly be by sebacic acid, glycerol and dibasic alcohol after copolymerization again crosslinking curing form, wherein dibasic alcohol is ethylene glycol, butyleneglycol or hexylene glycol, the mol ratio of glycerol and sebacic acid is 1: 1, and the mol ratio of dibasic alcohol and sebacic acid is 0.5～1.0: 1.
The polyester type biodegradable shape memory polymkeric substance also comprises bioactive particles among the present invention, and bioactive particles accounts for 5%～30% of polyester type biodegradable shape memory total polymer mass.
The polyester type biodegradable shape memory polymer surfaces also is impregnated with hemostatic agent, antiphlogistic or somatomedin among the present invention.
The preparation method of polyester type biodegradable shape memory polymkeric substance is realized by following step among the present invention: a, with dibasic alcohol and sebacic acid by mol ratio melting mixing under 110 ℃ of conditions of 0.5～1.0: 1, restir reaction 2h, temperature rise rate with 10 ℃/h is warming up to 160 ℃ then, at the uniform velocity be decompressed to simultaneously pressure 0.1MPa (purpose is to slough the moisture that esterification generates), restir reaction 24h, boost to normal pressure then and be cooled to 110 ℃ simultaneously, add glycerol again, the mol ratio of glycerol and sebacic acid is 1: 1, temperature rise rate with 10 ℃/h is warming up to 140 ℃, at the uniform velocity being decompressed to pressure is 0.1MPa, restir reaction 48h; B, the product of step a watered cast from the mould, under 110 ℃～135 ℃ conditions, carry out crosslinking curing 24h～72h then; Promptly obtain the polyester type biodegradable shape memory polymkeric substance; Wherein the dibasic alcohol of step a is ethylene glycol, butyleneglycol or hexylene glycol.
Before method of the present invention can also be cast, the product of step a is dissolved in to be made into concentration in the dehydrated alcohol be 0.1mol/L～0.4mol/L solution in step b.
Before method of the present invention can also be cast in step b, the product of step a is dissolved in to be made into concentration in the dehydrated alcohol be 0.1mol/L～0.4mol/L solution, add bioactive particles again, bioactive particles accounts for 5%～30% of polyester type biodegradable shape memory total polymer mass, and ultrasonic vibration is to even.
Method of the present invention can also be carried out in step b after the crosslinking curing, and will be immersed in mass concentration through the product of crosslinking curing and be 1%～20% contain hemostatic agent solution, mass concentration is that 3%～15% contain antiphlogistic solution or mass concentration are 3%～10% the 0.5h～10h in the growth factor solution that contains.
Described bioactive particles is that the described hemostatic agent of hydroxyapatite particle, Lin Suanergai, tricalcium phosphate or bio-vitric is calcium ion, batroxobin and zymoplasm; Described antiphlogistic is a silver ions; Described somatomedin is Urogastron, insulin-like growth factor or nerve growth factor.
In the product of the present invention, multipolymer (being formed by sebacic acid, glycerol and dibasic alcohol copolymerization) has the three-dimensional crosslinked network structure and serves as the fixedly stationary phase of original shape, and it can vary with temperature and (is below or above fusing point T
m) but crystallization and fused crystallization phases served as anti-phase.When the multipolymer of curing molding is heated to texturing temperature T
f(T
fBe higher than Tc) time, watery fusion, material is easy to be deformed into second kind of shape under the effect of external force, under the effect that keeps stress, multipolymer is cooled to below the fusing point, but anti-phase enters crystal form, molecular chain is frozen, and multipolymer hardens into the stable solid shaped bodies with distortion back shape.When the multipolymer with second kind of shape is heated to shape recovery temperature (at T
fMore than the temperature) time, but anti-phase is softening again, and multipolymer returns to the original shape by the stationary phase memory.By regulating two kinds of monomeric ratios and crosslinked degree, we can obtain the deformation temperature difference, are fit to the copolymer shape memory polymkeric substance of various needs.
The present invention has following advantage:
1, product of the present invention has big, the deformation recovery rate height of deformation quantity, and its deformation quantity reaches 300%～400%, and the deformation recovery rate surpasses 99%.
2, the shape recovery temperature of product of the present invention is 0～45 ℃, and shape recovery temperature after implanting, need not further means near body temperature, and shape can be recovered automatically; The tensile strength of product of the present invention is 0.5～10MPa, and its degradation time is 30～300 days.
3, product of the present invention mechanism of degradation in human body is a superficial degradation, its in vivo hold-time of shape and mechanical property longer, along with the minimizing of the quality of implant and volume and reduce.
4, have on the main chain of product of the present invention-OH, have good biocompatibility, so meet the requirement of body implanting material; Also can carry out graft modification, further improve its biocompatibility, make it be more suitable for the requirement of body implanting material it.
5, product of the present invention possesses performances such as shape memory function, biodegradable performance and good biocompatibility simultaneously, and can adjust within a large range by modified methods such as copolymerizing and blendings, be the high molecular polymer that substitutes existing medical embedded material of tool potentiality; It can be used as human soft tissue injury's material for repairing (as cornea, retina, skin, blood vessel, reticular tissue, islet tissue, muscle tissue and nervous tissue etc.), has filled up the blank of the degradable shape-memory material that is applicable to human body soft tissue; Its performance perameter can design according to the performance of human body soft tissue, satisfies clinical medical application.
6, the inventive method technology is simple, is convenient to operation, and its moulding and processing are easier than TiNi shape memory alloy.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment polyester type biodegradable shape memory polymkeric substance be by sebacic acid, glycerol and dibasic alcohol after copolymerization again crosslinking curing form, wherein dibasic alcohol is ethylene glycol, butyleneglycol or hexylene glycol, the mol ratio of glycerol and sebacic acid is 1: 1, and the mol ratio of dibasic alcohol and sebacic acid is 0.5～1.0: 1.
The deformation quantity of present embodiment product reaches 300%～400%, and the deformation recovery rate surpasses 99%, and shape recovery temperature is 0～45 ℃, and tensile strength is 0.5～10MPa, and degradation time is 30～300 days.Have-OH on the present embodiment product main chain, have good biocompatibility.
Embodiment two: what present embodiment and embodiment one were different is: the mol ratio of dibasic alcohol and sebacic acid is 0.6～0.9: 1.Other is identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is: the mol ratio of dibasic alcohol and sebacic acid is 0.7～0.8: 1.Other is identical with embodiment one.
Embodiment four: what present embodiment and embodiment one were different is: the mol ratio of dibasic alcohol and sebacic acid is 0.75: 1.Other is identical with embodiment one.
Embodiment five: the difference of present embodiment and embodiment one to four is: the polyester type biodegradable shape memory polymkeric substance also comprises bioactive particles, and bioactive particles accounts for 5%～30% of polyester type biodegradable shape memory total polymer mass.Other is identical with embodiment one to four.
Embodiment six: the difference of present embodiment and embodiment five is: bioactive particles is hydroxyapatite particle, Lin Suanergai, tricalcium phosphate or bio-vitric.Other is identical with embodiment five.
Embodiment seven: present embodiment is implemented one to six and different is with concrete: the polyester type biodegradable shape memory polymer surfaces also is impregnated with hemostatic agent, antiphlogistic or somatomedin.Other is identical with embodiment one to five.
Embodiment eight: what present embodiment and embodiment seven were different is: hemostatic agent is calcium ion, batroxobin and zymoplasm.Other is identical with embodiment seven.
Embodiment nine: what present embodiment and embodiment seven were different is: antiphlogistic is a silver ions.Other is identical with embodiment seven.
Embodiment ten: what present embodiment and embodiment seven were different is: somatomedin is Urogastron, insulin-like growth factor or nerve growth factor.Other is identical with embodiment seven.
Embodiment 11: the preparation method of present embodiment polyester type biodegradable shape memory polymkeric substance is realized by following step: a, with dibasic alcohol and sebacic acid by mol ratio melting mixing under 110 ℃ of conditions of 0.5～1.0: 1, restir reaction 2h, temperature rise rate with 10 ℃/h is warming up to 160 ℃ then, at the uniform velocity be decompressed to simultaneously pressure 0.1MPa (purpose is to slough the moisture that esterification generates), restir reaction 24h, boost to normal pressure then and be cooled to 110 ℃ simultaneously, add glycerol again, the mol ratio of glycerol and sebacic acid is 1: 1, temperature rise rate with 10 ℃/h is warming up to 140 ℃, at the uniform velocity being decompressed to pressure is 0.1MPa, restir reaction 48h; B, the product of step a watered cast from the mould, under 110 ℃～135 ℃ conditions, carry out crosslinking curing 24h～72h then; Promptly obtain the polyester type biodegradable shape memory polymkeric substance; Wherein the dibasic alcohol of step a is ethylene glycol, butyleneglycol or hexylene glycol.
In the present embodiment among the step a stirring velocity be 200～500r/min.
Present embodiment adopts bending method to measure its shape memory effect, and concrete operations are as follows: make the sample of length * wide * thick=5cm * 0.8cm * 0.1cm by the present embodiment method, sample is bent to certain angle θ more than fusing point
i, keeping being cooled under the strained situation below the fusing point to remove stress, sample springs back to certain angle θ
d, sample is heated to more than the fusing point once more then, and obtaining the final angle of sample is θ
f, its deformation recovery rate can be calculated by following formula:
Deformation recovery rate=(θ
i-θ
f)/θ
i
Shape conservation rate=θ
d/ θ
i
After tested, the present embodiment deformation fixed rate and the deformation recovery rate that make the polyester type biodegradable shape memory polymkeric substance is 100%.
Embodiment 12: what present embodiment and embodiment 11 were different is: the mol ratio of dibasic alcohol and sebacic acid is 0.6～0.9: 1 among the step a.Other is identical with embodiment 11.
Embodiment 13: what present embodiment and embodiment 11 were different is: the mol ratio of dibasic alcohol and sebacic acid is 0.7～0.8: 1 among the step a.Other is identical with embodiment 11.
Embodiment 14: what present embodiment and embodiment 11 were different is: the mol ratio of dibasic alcohol and sebacic acid is 0.75: 1 among the step a.Other is identical with embodiment 11.
Embodiment 15: what present embodiment and embodiment 11 to 14 were different is: before casting in step b, the product of step a is dissolved in to be made into concentration in the dehydrated alcohol be 0.1mol/L～0.4mol/L solution.Other step and parameter are identical with embodiment 11 to 14.
Present embodiment adopts the method for embodiment 11 to shape memory effect test, makes the deformation fixed rate of polyester type biodegradable shape memory polymkeric substance and deformation recovery rate after tested for being 100%.
Embodiment 16: what present embodiment and embodiment 11 to 14 were different is: before casting in step b, the product of step a is dissolved in to be made into concentration in the dehydrated alcohol be 0.1mol/L～0.4mol/L solution, add bioactive particles again, bioactive particles accounts for 5%～30% of polyester type biodegradable shape memory total polymer mass, and ultrasonic vibration is to even.Other step and parameter are identical with embodiment 11 to 14.
Present embodiment is to the method for shape memory effect test employing embodiment 11, and the deformation fixed rate and the deformation recovery rate that make the polyester type biodegradable shape memory polymkeric substance after tested all surpass 99%.
Embodiment 17: what present embodiment and embodiment 16 were different is: bioactive particles is hydroxyapatite particle, Lin Suanergai, tricalcium phosphate or bio-vitric.Other step and parameter are identical with embodiment 16.
Embodiment 18: what present embodiment present embodiment and embodiment 11 to 17 were different is: carry out in step b after the crosslinking curing, will be immersed in mass concentration through the product of crosslinking curing and be 1%～20% contain hemostatic agent solution, mass concentration is that 3%～15% contain antiphlogistic solution or mass concentration are 3%～10% the 0.5h～10h in the growth factor solution that contains.Other step and parameter are identical with embodiment 11 to 17.
Present embodiment adopts the method for embodiment 11 to shape memory effect test, makes the deformation fixed rate of polyester type biodegradable shape memory polymkeric substance and deformation recovery rate after tested for all surpassing 99%.
Embodiment 19: what present embodiment and embodiment 18 were different is: hemostatic agent is calcium ion, batroxobin and zymoplasm.Other step and parameter are identical with embodiment 18.
Calcium ion is by CaCl in the present embodiment
2Solution provides.
Embodiment 20: what present embodiment and embodiment 18 were different is: antiphlogistic is a silver ions.Other step and parameter are identical with embodiment 18.
Silver ions is by silver chloride solution, silver nitrate solution or silver lactate solution in the present embodiment
Embodiment 21: what present embodiment and embodiment 18 were different is: somatomedin is Urogastron, insulin-like growth factor or nerve growth factor.Other step and parameter are identical with embodiment 18.
Embodiment 22: the preparation method of polyester type biodegradable shape memory polymkeric substance is realized by following step in the present embodiment: a, with ethylene glycol and sebacic acid mol ratio melting mixing under 110 ℃ of conditions by 1: 1, restir reaction 2h, temperature rise rate with 10 ℃/h is warming up to 160 ℃ then, simultaneously at the uniform velocity being decompressed to pressure is 0.1MPa, restir reaction 24h, boost to normal pressure then and be cooled to 110 ℃ simultaneously, add glycerol again, the mol ratio of glycerol and sebacic acid is 1: 1, temperature rise rate with 10 ℃/h is warming up to 140 ℃, progressively at the uniform velocity being decompressed to pressure is 0.1MPa, restir reaction 48h; B, the product of step a watered cast from the mould, under 120 ℃ of conditions, carry out crosslinking curing 36h then; Promptly obtain the polyester type biodegradable shape memory polymkeric substance.
Present embodiment adopts the method for embodiment 11 to shape memory effect test, makes the deformation fixed rate of polyester type biodegradable shape memory polymkeric substance and deformation recovery rate after tested and is all 100%.
Embodiment 23: what present embodiment and embodiment 22 were different is: adopt butyleneglycol to substitute ethylene glycol among the step a; The crosslinking curing time is 36h among the step b.Other step and parameter are identical with embodiment 22.
Present embodiment adopts the method for embodiment 11 to shape memory effect test, makes the deformation fixed rate of polyester type biodegradable shape memory polymkeric substance and deformation recovery rate after tested and is all 100%.
Embodiment 24: what present embodiment and embodiment 22 were different is: adopt hexylene glycol to substitute ethylene glycol among the step a; The crosslinking curing time is 36h among the step b.Other step and parameter are identical with embodiment 22.
Present embodiment adopts the method for embodiment 11 to shape memory effect test, makes the deformation fixed rate of polyester type biodegradable shape memory polymkeric substance and deformation recovery rate after tested and is all 100%.
Embodiment 25: differently with 22 in the present embodiment be: before casting in step b, the sebacic acid and propyl tri-alcohol ester that step a is obtained is dissolved in that to be made into concentration in the dehydrated alcohol be 0.3mol/L solution.Other step and parameter are identical with embodiment 22.
Present embodiment adopts the method for embodiment 11 to shape memory effect test, makes the deformation fixed rate of polyester type biodegradable shape memory polymkeric substance and deformation recovery rate through test and is all 100%.
Embodiment 26: what present embodiment and embodiment 22 were different is: before casting in step b, the sebacic acid and propyl tri-alcohol ester that step a is obtained is dissolved in that to be made into concentration in the dehydrated alcohol be 0.3mol/L solution, add the hydroxyapatite particle again, hydroxyapatite particle bioactive particles accounts for 15% of polyester type biodegradable shape memory total polymer mass, and ultrasonic vibration is to even.Other step and parameter are identical with embodiment 22.
Present embodiment adopts the method for embodiment 11 to shape memory effect test, makes the deformation fixed rate of polyester type biodegradable shape memory polymkeric substance and deformation recovery rate through test and is all 100%.
Embodiment 27: what present embodiment and embodiment 22 were different is: carry out in step b after the crosslinking curing, will be immersed in mass concentration through the product of crosslinking curing and be 1%～20% CaCl
23h in the solution.Other step and parameter are identical with embodiment 22.
Present embodiment adopts the method for embodiment 11 to shape memory effect test, makes the deformation fixed rate of polyester type biodegradable shape memory polymkeric substance and deformation recovery rate through test and is all 100%.
Embodiment 28: what present embodiment and embodiment 22 were different is: carry out in step b after the crosslinking curing, will be immersed in mass concentration through the product of crosslinking curing and be 5h in 3%～15% the AgCl solution.Other step and parameter are identical with embodiment 22.
Present embodiment adopts the method for embodiment 11 to shape memory effect test, makes the deformation fixed rate of polyester type biodegradable shape memory polymkeric substance and deformation recovery rate through test and is all 100%.
Claims (4)
1. polyester type biodegradable shape memory polymkeric substance, it is characterized in that the polyester type biodegradable shape memory polymkeric substance mainly be by sebacic acid, glycerol and dibasic alcohol after copolymerization again crosslinking curing form, the degradable shape-memory polymer also comprises bioactive particles, and bioactive particles accounts for 5%～30% of polyester type biodegradable shape memory total polymer mass; Wherein said bioactive particles is hydroxyapatite particle, Lin Suanergai, tricalcium phosphate or bio-vitric; The polyester type biodegradable shape memory polymer surfaces also is impregnated with hemostatic agent, antiphlogistic or somatomedin; Described hemostatic agent is a calcium ion; Described antiphlogistic is a silver ions; Described somatomedin is Urogastron, insulin-like growth factor or nerve growth factor; Wherein dibasic alcohol is ethylene glycol, butyleneglycol or hexylene glycol, and the mol ratio of glycerol and sebacic acid is 1: 1, and the mol ratio of dibasic alcohol and sebacic acid is 0.5～1.0: 1; It is that 1%～20% contain hemostatic agent solution, mass concentration are that 3%～15% contain antiphlogistic solution or mass concentration are 3%～10% the 0.5h～10h in the growth factor solution that contains that the product of crosslinking curing is immersed in mass concentration.
2. polyester type biodegradable shape memory polymkeric substance according to claim 1, the mol ratio that it is characterized in that dibasic alcohol and sebacic acid is 0.6～0.9: 1.
3. the preparation method of polyester type biodegradable shape memory polymkeric substance according to claim 1, the preparation method who it is characterized in that the polyester type biodegradable shape memory polymkeric substance is realized by following step: a, with dibasic alcohol and sebacic acid by mol ratio melting mixing under 110 ℃ of conditions of 0.5～1.0: 1, restir reaction 2h, temperature rise rate with 10 ℃/h is warming up to 160 ℃ then, at the uniform velocity be decompressed to simultaneously pressure 0.1MPa, restir reaction 24h, boost to normal pressure then and be cooled to 110 ℃ simultaneously, add glycerol again, the mol ratio of glycerol and sebacic acid is 1: 1, temperature rise rate with 10 ℃/h is warming up to 140 ℃, at the uniform velocity being decompressed to pressure is 0.1MPa, restir reaction 48h; B, the product of step a watered cast from the mould, under 110 ℃～135 ℃ conditions, carry out crosslinking curing 24h～72h then; Promptly obtain the polyester type biodegradable shape memory polymkeric substance; Wherein the dibasic alcohol of step a is ethylene glycol, butyleneglycol or hexylene glycol; Before in step b, casting, the product of step a is dissolved in to be made into concentration in the dehydrated alcohol be 0.1mol/L～0.4mol/L solution, add bioactive particles again, bioactive particles accounts for 5%～30% of polyester type biodegradable shape memory total polymer mass, and ultrasonic vibration is to even; Wherein said bioactive particles is hydroxyapatite particle, Lin Suanergai, tricalcium phosphate or bio-vitric; Carry out in step b after the crosslinking curing, will be immersed in mass concentration through the product of crosslinking curing and be 1%～20% contain hemostatic agent solution, mass concentration is that 3%～15% contain antiphlogistic solution or mass concentration are 3%～10% the 0.5h～10h in the growth factor solution that contains; Described hemostatic agent is a calcium ion; Described antiphlogistic is a silver ions; Described somatomedin is Urogastron, insulin-like growth factor or nerve growth factor.
4. the preparation method of polyester type biodegradable shape memory polymkeric substance according to claim 3 before it is characterized in that casting, is dissolved in the product of step a that to be made into concentration in the dehydrated alcohol be 0.1mol/L～0.4mol/L solution in step b.
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