CN101461966B - Method for preparing degradable flexible medical film material - Google Patents
Method for preparing degradable flexible medical film material Download PDFInfo
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- CN101461966B CN101461966B CN2007100509331A CN200710050933A CN101461966B CN 101461966 B CN101461966 B CN 101461966B CN 2007100509331 A CN2007100509331 A CN 2007100509331A CN 200710050933 A CN200710050933 A CN 200710050933A CN 101461966 B CN101461966 B CN 101461966B
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Abstract
The invention belongs to the preparation field of medical supplies, and in particular relates to a method for preparing a degradable flexible medical film material. The method is to prepare the degradable flexible medical film material through pre-polymerization, copolymerization and blending; in pre-polymerization, polyethylene glycol with molecular weight of between 500 and 12,000 is pre-polymerized with lactide at a temperature of between 100 and 200 DEG C for 1 to 6 hours to form a pre-polymerizing product, wherein the pre-polymerizing product comprises the compositions in percentage by weight : 5 to 90 percent of the polyethylene glycol, and 10 to 95 percent of the lactide; in copolymerization, the pre-polymerizing product is copolymerized with caprolactone at a temperature of between 100 and 200 DEG C for 4 to 8 hours to form a triblock copolymer, wherein the mixture comprises the compositions in percentage by weight: 40 to 99 percent of the pre-polymerizing product and 1 to 60 percent of the caprolactone; in blending, the triblock copolymer is blended with chitosan or/and hyaluronic acid at a temperature of 50 and 200 DEG C, wherein the mixture comprises the compositions in percentage by weight: 50 to 100 percent of the triblock copolymer, 0 to 50 percent of the chitosan, and 0 to 50 percent of the hyaluronic acid.
Description
Technical field: the invention belongs to the preparation field of medical supplies, especially relate to a kind of method for preparing of degradable flexible medical film material.
Background technology: in the orthopaedic surgical operations operation, often adopt Antiadhesive film to prevent tissue adhesion.Antiadhesive film is the medical film of biodegradable, and two kinds of polylactic acid membrane and hyaluronic acid membranes are arranged, and hyaluronic acid membrane still under study for action; Commercially available polylactic acid membrane is the copolymer of polylactic acid+glycolic or the homopolymer of polylactic acid now, and matter is crisp inhomogeneous, and pliability is poor; Non-stretchable, in technical specification, there is not the index of correlation of reflection hot strength; Properties of product are hard, crisp, and result of use is very poor.Chinese patent 03117128.1 provides a kind of polylactic acid/Polyethylene Glycol/caprolactone copolymer method for preparing, is used to prepare degradable flexible medical film material, but its pliability of copolymer of this method preparation and degradation time are difficult to control, and quality stability is poor.
Summary of the invention: the pliability and the unmanageable technical barrier of degradation time that the objective of the invention is to overcome existing degradable flexible medical film material; For people provide a kind of steady quality; Degradation time is adjustable, the method for preparing of pliability and the better degradable flexible medical film material of draftability, prepared medical film material can be used for producing that thickness is even, quality evenly, can stretch, flexible, the degradable flexible medical film that is fit to do Antiadhesive film.
The objective of the invention is to realize through following proposal:
The method for preparing of degradable flexible medical film material of the present invention is to make degradable flexible medical film material through pre-polymerization, copolymerization and blend operation; Wherein, during pre-polymerization, elder generation is with Polyethylene Glycol and the lactide pre-polymerization of molecular weight 500-12000; Form prepolymer product, the percentage by weight of each component is: Polyethylene Glycol 5%～90%, lactide 10%～95%; The prepolymerization reaction temperature: 100～200 ℃, the time: 1～6 hour; During copolymerization, with prepolymer product and caprolactone copolymerization, form triblock copolymer, the percentage by weight of each component is: prepolymer product 40～99%, caprolactone 1%～60%, 100～200 ℃ of copolyreaction temperature, time: 4～8 hours; During blend, triblock copolymer again with chitosan or/and the hyaluronic acid blend, the percentage by weight of each component is: triblock copolymer 50%～100%, chitosan 0～50%, hyaluronic acid 0～50%; 50～200 ℃ of blending temperatures.
In the such scheme, pre-polymerization and copolymerization operation are: during pre-polymerization, with Polyethylene Glycol and the caprolactone pre-polymerization of molecular weight 500-12000, form prepolymer product earlier, the percentage by weight of each component is: Polyethylene Glycol 40%～99%, caprolactone 1%～60%; During copolymerization, with prepolymer product and lactide copolymerization, form triblock copolymer, the percentage by weight of each component is: prepolymer product 10～60%, lactide 40%～90%.
Inventor of the present invention finds that after deliberation in Polyethylene Glycol/lactide (or polylactic acid)/caprolactone terpolymer, the block structure of copolymer has crucial influence to the degradability and the pliability of material; Wherein, the polylactic acid section is the major influence factors of material degradation characteristic, is hydrophobic; The Polyethylene Glycol section is hydrophilic; Adjustable material degradability and film forming characteristics, the flexibility of the molecular weight of caprolactone section and content influence membrane material, and to certain influence of having degraded.And prior art is to obtain random triblock copolymer, causes the pliability of material and degradation time to be difficult to control, and quality is unstable.
Therefore; Inventor of the present invention has adopted polymeric method (the first pre-polymerization of two stages; Copolymerization again), to regulate the block structure of terpolymer, reaction is divided into two stages: one, the pre-polymerization of lactide and Polyethylene Glycol; Synthetic " polylactic acid-polyglycol-polylactic acid " type polymer (polylactic acid content much larger than Polyethylene Glycol time), perhaps " polyethylene glycol-lactic acid-Polyethylene Glycol " type polymer.(polylactic acid content much smaller than Polyethylene Glycol time); Two, the copolymerization of prepolymer product and caprolactone, synthetic " polylactic acid-polyglycol-polylactic acid-polycaprolactone " type or " polyethylene glycol-lactic acid-polyethylene glycol-caprolactone " type triblock polymer.
Lactide is as a kind of raw material (ring-opening polymerisation) of synthesizing polylactic acid; With it and Polyethylene Glycol pre-polymerization; Compare with polyethylene glycol polymeric with polylactic acid with direct, conditioned reaction condition (temperature, vacuum, response time, initiator, terminator etc.) easily, " polylactic acid-polyglycol-polylactic acid " type that obtains suitable polymeric degree and ratio is " polyethylene glycol-lactic acid-Polyethylene Glycol " type prepolymer product perhaps; And can reduce cost, improve the degree of polymerization.
The copolymerization of second stage through conditioned reaction condition (temperature, vacuum, response time, initiator, terminator etc.), can be regulated the content and the molecular weight of caprolactone, thereby regulates the pliability and the degradability of membrane material.
The present invention adopts polymeric method (the first pre-polymerization of two stages; Copolymerization again); Type that the polymerizate that obtains is controlled to be made as " polylactic acid-polyglycol-polylactic acid-polycaprolactone "; Or " polyethylene glycol-lactic acid-polyethylene glycol-caprolactone " type; The random triblock copolymer that is different from the direct copolymerization of monomer and forms; Be convenient to the degradability (phase I pre-polymerization) of telomerized polymer and the pliability (second stage copolymerization) of polymer, can conveniently regulate degradable flexible medical film material degradability and pliability, stay-in-grade method for preparing thereby provide a kind of, prepared medical film material can be used for producing that thickness is even, quality evenly, can stretch, flexible, the degradable flexible medical film that is fit to do Antiadhesive film.
The major parameter that uses method of the present invention to take out the medical film material of preparation is:
Molecular weight: 5～250,000 Da;
Hot strength: 1.0 ± 2P (Young's modulus);
Degradation time: 15 days～March;
Content of beary metal: less than 10ug/g;
Ignition residue: less than 0.2%;
Aseptic, no pyrogen;
Hemolysis rate is less than 5%;
Cytotoxicity 0-1 level;
There is not irritated reaction:
Hereditary-less toxicity.
The specific embodiment:
The invention is further illustrated by the following examples, and the present invention is not limited only to said embodiment.
Embodiment one
With lactide 95g, Polyethylene Glycol 5g (molecular weight 12000) pre-polymerization, 100 ℃ of reaction temperatures, 6 hours time, obtain prepolymer product, with prepolymer product 40g, caprolactone 60g copolymerization, 200 ℃ of reaction temperatures, 4 hours time, thus make degradable flexible medical film material.
Embodiment two
With caprolactone 60g, Polyethylene Glycol 40g (molecular weight 1000) pre-polymerization, 200 ℃ of reaction temperatures, 1 hour time, obtain prepolymer product, with prepolymer product 10g, lactide 90g copolymerization, 100 ℃ of reaction temperatures, 8 hours time, thus make degradable flexible medical film material.
Embodiment three
With lactide 40g, Polyethylene Glycol 60g (molecular weight 1500) pre-polymerization, 200 ℃ of reaction temperatures; 1 hour time obtained prepolymer product, with prepolymer product 99g; Caprolactone 1g copolymerization, 100 ℃ of reaction temperatures, 8 hours time; Copolymerization product 80g adds chitosan 20g blend again, and 120 ℃ of temperature make degradable flexible medical film material from face.
Embodiment four
With lactide 40g, Polyethylene Glycol 60g (molecular weight 1500) pre-polymerization, 200 ℃ of reaction temperatures; 1 hour time obtained prepolymer product, with prepolymer product 99g; Caprolactone 1g copolymerization, 100 ℃ of reaction temperatures, 8 hours time; Copolymerization product 80g adds hyaluronic acid 20g blend again, 50 ℃ of temperature, thus make degradable flexible medical film material.
Embodiment five
With caprolactone 10g, Polyethylene Glycol 90g (molecular weight 500) pre-polymerization, 100 ℃ of reaction temperatures; 4 hours time obtained prepolymer product, with prepolymer product 60g; Lactide 40g copolymerization, 150 ℃ of reaction temperatures, 6 hours time; Copolymerization product 95g adds chitosan 5g blend again, 200 ℃ of temperature, thus make degradable flexible medical film material.
Embodiment six
With caprolactone 10g, Polyethylene Glycol 90g (molecular weight 500) pre-polymerization, 100 ℃ of reaction temperatures; 4 hours time obtained prepolymer product, with prepolymer product 60g; Lactide 40g copolymerization, 150 ℃ of reaction temperatures, 6 hours time; Copolymerization product 95g adds hyaluronic acid 5g blend again, 180 ℃ of temperature, thus make degradable flexible medical film material.
Embodiment seven
With lactide 40g, Polyethylene Glycol 60g (molecular weight 1500) pre-polymerization, 200 ℃ of reaction temperatures; 1 hour time obtained prepolymer product, with prepolymer product 99g; Caprolactone 1g copolymerization, 100 ℃ of reaction temperatures, 8 hours time; Copolymerization product 80g adds chitosan 10g, hyaluronic acid 10g blend again, 150 ℃ of temperature, thus make degradable flexible medical film material.
Embodiment eight
With caprolactone 1g, Polyethylene Glycol 99g (molecular weight 500) pre-polymerization, 100 ℃ of reaction temperatures; 4 hours time obtained prepolymer product, with prepolymer product 60g; Lactide 40g copolymerization, 150 ℃ of reaction temperatures, 6 hours time; Copolymerization product 80g adds chitosan 10g, hyaluronic acid 10g blend again, 150 ℃ of temperature, thus make degradable flexible medical film material.
Embodiment nine
With lactide 10g, Polyethylene Glycol 90g (molecular weight 1500) pre-polymerization, 150 ℃ of reaction temperatures; 4 hours time obtained prepolymer product, with prepolymer product 90g; Caprolactone 10g copolymerization, 100 ℃ of reaction temperatures, 8 hours time; Copolymerization product 50g adds chitosan 50g blend again, 120 ℃ of temperature, thus make degradable flexible medical film material.
Embodiment nine
With lactide 10g, Polyethylene Glycol 90g (molecular weight 1500) pre-polymerization, 150 ℃ of reaction temperatures; 4 hours time obtained prepolymer product, with prepolymer product 90g; Caprolactone 10g copolymerization, 100 ℃ of reaction temperatures, 8 hours time; Copolymerization product 50g adds hyaluronic acid 50g blend again, 120 ℃ of temperature, thus make degradable flexible medical film material.
Claims (1)
1. the method for preparing of a degradable flexible medical film material is characterized in that making degradable flexible medical film material through pre-polymerization, copolymerization and blend operation; Wherein, during pre-polymerization, elder generation is with Polyethylene Glycol and the lactide pre-polymerization of molecular weight 500-12000; Form prepolymer product, the percentage by weight of each component is: Polyethylene Glycol 5%～90%, lactide 10%～95%; The prepolymerization reaction temperature: 100～200 ℃, the time: 1～6 hour; During copolymerization, with prepolymer product and caprolactone copolymerization, form triblock copolymer, the percentage by weight of each component is: prepolymer product 40～99%, caprolactone 1%～60%, 100～200 ℃ of copolyreaction temperature, time: 4～8 hours; Or during pre-polymerization, earlier with Polyethylene Glycol and the caprolactone pre-polymerization of molecular weight 500-12000, the formation prepolymer product, the percentage by weight of each component is: Polyethylene Glycol 40%～99%, caprolactone 1%～60%; During copolymerization, with prepolymer product and lactide copolymerization, form triblock copolymer, the percentage by weight of each component is: prepolymer product 10～60%, lactide 40%～90%; During blend, triblock copolymer again with chitosan or/and the hyaluronic acid blend, the percentage by weight of each component is: triblock copolymer 50%～100%, chitosan 0～50%, hyaluronic acid 0～50%; 50～200 ℃ of blending temperatures.
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| CN2007100509331A CN101461966B (en) | 2007-12-21 | 2007-12-21 | Method for preparing degradable flexible medical film material |
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| CN2007100509331A CN101461966B (en) | 2007-12-21 | 2007-12-21 | Method for preparing degradable flexible medical film material |
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| CN101461966B true CN101461966B (en) | 2012-08-08 |
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| CN102344558A (en) * | 2011-07-05 | 2012-02-08 | 电子科技大学 | Polyester-polyether copolymer and its synthesis method and use |
| CN104592523B (en) * | 2014-12-24 | 2017-06-30 | 天津大学 | A kind of peptide modified polycation gene carrier and preparation method and application |
| CN108697829B (en) * | 2015-10-19 | 2021-06-11 | 西兰丁姆医疗公司 | Improved fibrinogen-based tissue adhesive patch |
| US11471556B2 (en) | 2015-10-19 | 2022-10-18 | Sealantium Medical Ltd. | Fibrinogen-based tissue adhesive patch |
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