CN104559094A - High-strength completely biodegradable medical resin composition and preparation method thereof - Google Patents
High-strength completely biodegradable medical resin composition and preparation method thereof Download PDFInfo
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- CN104559094A CN104559094A CN201310516693.5A CN201310516693A CN104559094A CN 104559094 A CN104559094 A CN 104559094A CN 201310516693 A CN201310516693 A CN 201310516693A CN 104559094 A CN104559094 A CN 104559094A
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Abstract
The present invention discloses a high-strength completely biodegradable medical resin composition and a preparation method thereof. The raw materials of the composition comprise the following components in parts by weight: 10-90 parts of polyglycolic acid, 10-90 parts of polylactic acid, 0-10 parts of polyethylene glycol and 0.1-0.8 part of antioxidant. The preparation method comprises the following steps: drying the raw materials in an oven for 5-8 hours at 60 DEG C, pre-mixing the raw materials in a high speed mixer, carrying out melt extrusion by using a twin-screw extruder, cooling and granulating to obtain the product. The obtained product has such excellent mechanical properties as high tensile strength, high flexural modulus and the like and has the characteristics of easy processing and forming, and can be completely degraded into such matters harmless to a human body in vivo as H2O and CO2 and the like. So that the product can be used in such medical fields as internal fracture fixation materials, tissue repair materials and surgical sutures and the like, and the product is a medical polymer material having a wide application prospect.
Description
Technical field
The present invention relates to a kind of resin combination and preparation method thereof, especially relate to a kind of high strength complete biodegradable medical resin composition and method of making the same.
Background technology
The main chain of biodegradable polyesters is formed by connecting by the ester bond of aliphatic structure unit by facile hydrolysis, is hydrolyzed, finally forms H under the promotion of microorganism or organism endoenzyme or acid, alkali
2o and CO
2, have good histocompatibility simultaneously, be widely used in medical surgery sutures, Fracture internal fixaiion, organizational project repair materials and controlled drug delivery system etc.
Polyglycolic acid is structure the simplest linear aliphatic adoption ester, and it has higher tensile strength and modulus, excellent in mechanical performance, is a commercial kind the earliest in resorbable polymeric materials in body.Just PGA was synthesized when Garothers is at research synthon as far back as the thirties.Before more than 40 year, the high molecular polyglycolic acid obtained by glycollide (dimer of oxyacetic acid) ring-opening polymerization, because it is easily hydrolyzed, and the product hydroxy acetic acid of degraded is the intermediate product of organism metabolism, makes this kind polyester be paid the utmost attention to as degradable sutures and replace collagen.But, because polyglycolic acid has very submissive molecular chain structure, thus there is higher degree of crystallinity, generally can reach 40-80%, and fusing point up to more than 210 DEG C, can mean that polyglycolic acid needs at a higher temperature could machine-shaping.And higher temperature very easily causes its molecule chain break, thus its mechanical property is declined to a great extent.Meanwhile, polyglycolic acid has degradation rate faster, and generally within 3-6 month, can degrade completely in vivo, too fast degradation rate makes it in most of the cases can not play its mechanical property advantage completely, thus also inhibits its application to a certain extent.
The feature that its processing temperature is high in order to solve, degradation cycle is short, Many researchers is taked the method for oxyacetic acid and other degradation material copolymerization to improve.Such as, people is had to introduce polylactic acid chain segment in polyglycolic acid segment.Poly(lactic acid) has the tensile strength higher compared with polyglycolic acid and modulus, can maintain the mechanical property of its excellence, and poly(lactic acid) has the vivo degradation cycle of 6-24 month, effectively can improve the shorter deficiency of polyglycolic acid degradation cycle.But, because the method adopts the chemical synthesis route of copolyreaction, thus, need higher production cost: simultaneously, the introducing of polylactic acid chain segment, though can reduce its processing temperature to a certain extent, the insufficient amplitude reduced, molecule chain break also can reduce the mechanical property of multipolymer to a certain extent.
Therefore, from the thinking improving above-mentioned technological deficiency, we take the method for polyglycolic acid and poly(lactic acid) copolymerization, while keeping the same excellent mechanical performance of same PLGA multipolymer, can effectively reduce costs.Special needs to be pointed out is, have chosen in the present invention and add a small amount of low molecular poly as three components.Polyoxyethylene glycol is also a kind of complete biodegradable macromolecular material, and has good biocompatibility.The polyoxyethylene glycol that molecular weight is lower is a kind of well molecular chain lubricant, particularly for the intermingling material of polyglycolic acid and poly(lactic acid), low-molecular-weight peg molecule chain can enter in its structural network, polyglycolic acid and polylactic acid molecule chain are more easily moved, thus can effectively reduce its processing temperature.Meanwhile, polyoxyethylene glycol also can play the effect of softening agent, makes up the feature that PLGA intermingling material is partially crisp to a certain extent.
Therefore, the present invention is based on above-mentioned technical problem, propose a kind of high strength complete biodegradable medical resin composition and method of making the same.
Summary of the invention
The object of the invention is to solve above-mentioned deficiency of the prior art, a kind of high strength complete biodegradable medical resin composition and method of making the same is provided, it has the feature of the excellent mechanical property such as high tensile, high modulus in flexure and easily machine-shaping, and can degradable be in vivo H
2o and CO
2etc. harmless small-molecule substance.
Object of the present invention can be achieved through the following technical solutions:
The invention provides the complete biodegradable medical resin of a kind of high strength, the component that said composition comprises and parts by weight as follows:
The weight-average molecular weight of described polyglycolic acid is 20,000 ~ 800,000, preferably 100,000 ~ 200,000, and not containing any harmful additive in its composition.
Described poly(lactic acid) is L-isomer or D-isomer, and its weight-average molecular weight is 20,000 ~ 800,000, and preferred Poly-L-lactic acid, preferable weight-average molecular weight is 100,000 ~ 200,000, and not containing any harmful additive in its composition.
Described polyoxyethylene glycol is 2,000 ~ 20,000, preferably 2,000 ~ 5,000, and not containing any harmful additive in its composition.
Described oxidation inhibitor is phosphite ester kind antioxidant or Hinered phenols antioxidant, comprises one or more in commercially available irgasfos 168, antioxidant 1010, antioxidant 1076 or oxidation inhibitor 245.
The invention provides a kind of high strength complete biodegradable medical resin composition and method of making the same, the method comprises the following steps:
(1) raw material is prepared according to following component and parts by weight:
(2) above raw material dry 5 ~ 8h in 60 DEG C of baking ovens, is then placed in super mixer premix 3 ~ 10min, obtains Preblend;
(3) twin screw extruder is passed through in Preblend, control temperature is 130 ~ 230 DEG C, and screw speed is that 200 ~ 600rpm melt extrudes, and then through cooling granulation, namely obtains a kind of high strength complete biodegradable medical resin composition.
The present invention is on the existing basis studied polyglycolic acid mechanical property, degradation rate and machine-shaping property etc., by the formula of appropriate design composition, the product prepared has the feature of the excellent mechanical property such as high tensile, high modulus in flexure and easily machine-shaping, and can degradable be in vivo H
2o and CO
2etc. harmless material.To can be used for the medical field such as bone fracture internal fixation material, tissue renovation material and operating sutures, be the medical macromolecular materials that a class has wide application prospect.
Embodiment
Below in conjunction with embodiment, the technical solution of the present invention is further explained, but following content is not intended to limit the scope of the invention.
Comparative example 1
By 10kg polyglycolic acid, 0.02kg oxidation inhibitor 245,0.02kg irgasfos 168, dry 5 ~ 8h in 60 DEG C of baking ovens, then join in high-speed mixer and stir discharging after 3-10 minute, again length-to-diameter ratio be 36, diameter is extruding pelletization in the twin screw extruder of 35mm, the barrel zone temperature of forcing machine is 200 ~ 230 DEG C, and screw speed is 200-600rpm.
In order to embody the impact of poly(lactic acid) on polyglycolic acid mechanical property and processing characteristics, following example is implemented in special contrast.
Embodiment 1
By 9.0kg polyglycolic acid, 1.0kg poly(lactic acid), 0.02kg oxidation inhibitor 245,0.02kg irgasfos 168, dry 5 ~ 8h in 60 DEG C of baking ovens, then join in high-speed mixer and stir discharging after 3-10 minute, again length-to-diameter ratio be 36, diameter is extruding pelletization in the twin screw extruder of 35mm, the barrel zone temperature of forcing machine is 160-200 DEG C, and screw speed is 200-600rpm.
Embodiment 2
By 7.5kg polyglycolic acid, 2.5kg poly(lactic acid), 0.02kg oxidation inhibitor 245,0.02kg irgasfos 168, dry 5 ~ 8h in 60 DEG C of baking ovens, then join in high-speed mixer and stir discharging after 3-10 minute, again length-to-diameter ratio be 36, diameter is extruding pelletization in the twin screw extruder of 35mm, the barrel zone temperature of forcing machine is 160-200 DEG C, and screw speed is 200-600rpm.
Embodiment 3
By 6.0kg polyglycolic acid, 4.0kg poly(lactic acid), 0.02kg oxidation inhibitor 245,0.02kg irgasfos 168, dry 5 ~ 8h in 60 DEG C of baking ovens, then join in high-speed mixer and stir discharging after 3-10 minute, again length-to-diameter ratio be 36, diameter is extruding pelletization in the twin screw extruder of 35mm, the barrel zone temperature of forcing machine is 160-200 DEG C, and screw speed is 200-600rpm.
Embodiment 4
By 4.5kg polyglycolic acid, 5.5kg poly(lactic acid), 0.02kg oxidation inhibitor 245,0.02kg irgasfos 168, dry 5 ~ 8h in 60 DEG C of baking ovens, then join in high-speed mixer and stir discharging after 3-10 minute, again length-to-diameter ratio be 36, diameter is extruding pelletization in the twin screw extruder of 35mm, the barrel zone temperature of forcing machine is 160-200 DEG C, and screw speed is 200-600rpm.
Embodiment 5
By 3.0kg polyglycolic acid, 7.0kg poly(lactic acid), 0.02kg oxidation inhibitor 245,0.02kg irgasfos 168, dry 5 ~ 8h in 60 DEG C of baking ovens, then join in high-speed mixer and stir discharging after 3-10 minute, again length-to-diameter ratio be 36, diameter is extruding pelletization in the twin screw extruder of 35mm, the barrel zone temperature of forcing machine is 160-200 DEG C, and screw speed is 200-600rpm.
Embodiment 6
By 1.0kg polyglycolic acid, 9.0kg poly(lactic acid), 0.02kg oxidation inhibitor 245,0.02kg irgasfos 168, dry 5 ~ 8h in 60 DEG C of baking ovens, then join in high-speed mixer and stir discharging after 3-10 minute, again length-to-diameter ratio be 36, diameter is extruding pelletization in the twin screw extruder of 35mm, the barrel zone temperature of forcing machine is 160-200 DEG C, and screw speed is 200-600rpm.
In order to embody the impact of polyethyleneglycol content on PLGA intermingling material mechanical property and processing characteristics, according in practical application to the requirement in material degradation cycle, choose PLGA ratio 75/25 for bench-marking sample (embodiment 2), the following example of special enforcement.
Embodiment 7
By 7.5kg polyglycolic acid, 2.5kg poly(lactic acid), 0.02kg oxidation inhibitor 245,0.02kg irgasfos 168,0.1kg polyoxyethylene glycol is added after dry 5 ~ 8h in 60 DEG C of baking ovens, then join in high-speed mixer and stir discharging after 3-10 minute, again length-to-diameter ratio be 36, diameter is extruding pelletization in the twin screw extruder of 35mm, the barrel zone temperature of forcing machine is 130-160 DEG C, and screw speed is 200-600rpm.
Embodiment 8
By 7.5kg polyglycolic acid, 2.5kg poly(lactic acid), 0.02kg oxidation inhibitor 245,0.02kg irgasfos 168,0.3kg polyoxyethylene glycol is added after dry 5 ~ 8h in 60 DEG C of baking ovens, then join in high-speed mixer and stir discharging after 3-10 minute, again length-to-diameter ratio be 36, diameter is extruding pelletization in the twin screw extruder of 35mm, the barrel zone temperature of forcing machine is 130-160 DEG C, and screw speed is 200-600rpm.
Embodiment 9
By 7.5kg polyglycolic acid, 2.5kg poly(lactic acid), 0.02kg oxidation inhibitor 245,0.02kg irgasfos 168,0.6kg polyoxyethylene glycol is added after dry 5 ~ 8h in 60 DEG C of baking ovens, then join in high-speed mixer and stir discharging after 3-10 minute, again length-to-diameter ratio be 36, diameter is extruding pelletization in the twin screw extruder of 35mm, the barrel zone temperature of forcing machine is 130-160 DEG C, and screw speed is 200-600rpm.
Embodiment 10
By 7.5kg polyglycolic acid, 2.5kg poly(lactic acid), 0.02kg oxidation inhibitor 245,0.02kg irgasfos 168,1.0kg polyoxyethylene glycol is added after dry 5 ~ 8h in 60 DEG C of baking ovens, then join in high-speed mixer and stir discharging after 3-10 minute, again length-to-diameter ratio be 36, diameter is extruding pelletization in the twin screw extruder of 35mm, the barrel zone temperature of forcing machine is 130-160 DEG C, and screw speed is 200-600rpm.
Above-described embodiment is carried out the simultaneous test of tensile strength, flexural strength, modulus in flexure, resistance to impact shock and actual processing temperature, specific practice is:
Carry out tensile strength test according to ASTMD638, draw speed is 50mm/min.
Carry out flexural strength according to ASTMD790 and modulus in flexure is tested, test speed is 3mm/min.
Carry out notched Izod impact strength test according to ASTMD256, batten thickness is 3.2mm, and probe temperature is 23 DEG C.
Record actual processing temperature.
Test result sees the following form:
Contrast comparative example 1 and embodiment 1-6, as can be seen from experimental data, adding of poly(lactic acid), can keep the mechanical property of polyglycolic acid preferably, but processing temperature can be made to a certain degree to decline; Comparative example 2,7-10, can find that polyoxyethylene glycol obviously can reduce the processing temperature of blend, and shock strength promotes obviously, but tensile strength, flexural strength and modulus in flexure to a certain degree decline.Comprehensive analysis, when adding 3% polyoxyethylene glycol, mechanical property and processing characteristics reach comparatively ideal equilibrium state.
For those skilled in the art, after knowing the instruction that aforementioned description provides, many amendments of the present invention and other embodiments can be expected.Therefore, be to be understood that the present invention should not be limited to the specific embodiment of disclosure, in the appended right that these amendments and other embodiments comprise.Although employ specific term in the text, they are only used without the object for limiting with general and descriptive meaning, scope of the present invention have the right claim limit.
Claims (6)
1. a high strength complete biodegradable medical resin composition, is characterized in that the component that comprises and parts by weight are:
2. a kind of high strength according to claim 1 complete biodegradable medical resin composition, is characterized in that: the weight-average molecular weight of described polyglycolic acid is 20,000 ~ 800,000, and not containing any harmful additive in its composition.
3. a kind of high strength according to claim 1 complete biodegradable medical resin composition, it is characterized in that: described polylactic resin is L-isomer or D-isomer, and its weight-average molecular weight is 20,000 ~ 800,000, and not containing any harmful additive in its composition.
4. a kind of high strength according to claim 1 complete biodegradable medical resin composition, is characterized in that: described polyoxyethylene glycol is 2,000 ~ 20,000, and not containing any harmful additive in its composition.
5. a kind of high strength according to claim 1 complete biodegradable medical resin composition, it is characterized in that: described oxidation inhibitor is phosphite ester kind antioxidant or Hinered phenols antioxidant, comprise one or more in commercially available irgasfos 168, antioxidant 1010, antioxidant 1076 or oxidation inhibitor 245.
6. a high strength complete biodegradable medical resin composition and method of making the same, is characterized in that: the method comprises the following steps:
(1) raw material is prepared according to following component and parts by weight:
(2) above raw material dry 5 ~ 8h in 60 DEG C of baking ovens, is then placed in super mixer premix 3 ~ 10min, obtains Preblend;
(3) twin screw extruder is passed through in Preblend, control temperature is 130 ~ 230 DEG C, and screw speed is that 200 ~ 600rpm melt extrudes, and then through cooling granulation, namely obtains a kind of high strength complete biodegradable medical resin composition.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927034A (en) * | 2015-06-01 | 2015-09-23 | 江苏金聚合金材料有限公司 | Preparation method of absorbable poly-methoxycarbonyl glycolate surgical suture |
| CN105088465A (en) * | 2015-08-11 | 2015-11-25 | 安徽省康宁医疗用品有限公司 | Absorbable surgical suture line resistant to degradation and good in compatibility and preparing method of absorbable surgical suture line resistant to degradation and good in compatibility |
| CN107083032A (en) * | 2017-04-10 | 2017-08-22 | 同济大学 | Cross-linking reaction prepares high intensity and the method for high tenacious biodegradable polylactic acid-base composite material in a kind of processing extrusion |
| CN112336395A (en) * | 2020-11-07 | 2021-02-09 | 单县华宇缝合制品有限公司 | High-strength biological suture and preparation method thereof |
-
2013
- 2013-10-28 CN CN201310516693.5A patent/CN104559094A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927034A (en) * | 2015-06-01 | 2015-09-23 | 江苏金聚合金材料有限公司 | Preparation method of absorbable poly-methoxycarbonyl glycolate surgical suture |
| CN104927034B (en) * | 2015-06-01 | 2018-10-02 | 江苏金聚合金材料有限公司 | The preparation method of polyglycolic acid carbomethoxy medical absorbable suture |
| CN105088465A (en) * | 2015-08-11 | 2015-11-25 | 安徽省康宁医疗用品有限公司 | Absorbable surgical suture line resistant to degradation and good in compatibility and preparing method of absorbable surgical suture line resistant to degradation and good in compatibility |
| CN107083032A (en) * | 2017-04-10 | 2017-08-22 | 同济大学 | Cross-linking reaction prepares high intensity and the method for high tenacious biodegradable polylactic acid-base composite material in a kind of processing extrusion |
| CN112336395A (en) * | 2020-11-07 | 2021-02-09 | 单县华宇缝合制品有限公司 | High-strength biological suture and preparation method thereof |
| CN112336395B (en) * | 2020-11-07 | 2023-01-24 | 单县华宇缝合制品有限公司 | High-strength biological suture and preparation method thereof |
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Application publication date: 20150429 |