CN1857235A - Absorbable medical film - Google Patents
Absorbable medical film Download PDFInfo
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- CN1857235A CN1857235A CNA2006100204998A CN200610020499A CN1857235A CN 1857235 A CN1857235 A CN 1857235A CN A2006100204998 A CNA2006100204998 A CN A2006100204998A CN 200610020499 A CN200610020499 A CN 200610020499A CN 1857235 A CN1857235 A CN 1857235A
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Abstract
The present invention relates to a kind of absorbable medical film used for coating tendon, repairing hard old film and nerve duct, and post-operation antiblocking in medical operation. The absorbable medical film consists of polylactic acid 50-100 wt%, medical plasticizer 0-50 wt% and lactic acid-glycolic acid copolymer 50-100 wt%. Changing the composition can obtain different absorbable medical film products of different degrading rate and different flexibility for different surgical operation requirements.
Description
Technical field
The present invention relates to a kind of absorbable medical film, be used for the parcel of medical surgery tendon, reparation, nerve trachea and the post-operation adhesion preventing of hard old film, belong to the biomaterial for medical purpose technical field.
Background technology
Absorbable medical film is used quite extensive in surgical operation, especially in the reparation of the parcel of tendon, hard old film, to be used as operation application such as nerve trachea and post-operation adhesion preventing wider.That uses clinically at present has hyaluronate sodium, chitosan, chitosan film, polylactic acid membrane and a polylactic acid-polyglycolic acid film.Because the operation kind difference of using, the requirement of material also there is difference.Pure polylactic acid membrane and pure polylactic acid-polyglycolic acid film but to having used, though its intensity meets instructions for use, but its pliability and degradation time then are difficult to control, in the process of degraded, be easy to generate the fragment of some films simultaneously, these fragments are transformed into the meat tooth easily, are unfavorable for healthy.Owing to these unfavorable factors have been arranged, just can't reach requirement in the use, thereby limit its extensive use in surgical operation.At this situation; some solves the pliability of film and the way of degraded is to add plasticizer and regulator; yet these plasticizers and regulator mainly are some micromolecular materials, and more common is adds tributyl citrate that some can be medical, triethyl citrate, citroflex A-4, ethyl oleate, Polyethylene Glycol, oleic acid, stearic acid, capric acid etc.Though the adding of these materials can play a role, can solve the pliability of film and the vivo degradation time of adjusting film to a certain extent.But add these micromolecular films, small-molecule substance is very fast in human body is dissolved out easily, makes film hardening after heeling-in a period of time in vivo, can not keep long-term plastifying effect; Because these small-molecule substances are dissolved out from film fast, make film in the intravital degradation process of people, be easy to produce fragment simultaneously, thereby form the granulation kind.Film is if adopt the oxirane disinfection sterilization, then cause these micromolecule that are added in the film to act on mutually easily and ooze out surface in film with oxirane, thereby part has lost these micromolecular effects of adding, and the surface of film also changes simultaneously, and its mechanical strength also is affected.If adopt the mode of irradiation sterilization, cause that easily the matrix material of these micromolecule and film reacts, impel the matrix material accelerated degradation, thereby influence the quality and the use of film.
Summary of the invention
According to above-mentioned these drawbacks, we design the molecular weight ratio matrix material and hang down the macromolecule polyester of some, and this is a kind of Reoplex, are the absorbable medical materials of FDA permission.These macromolecule polyesters have similar structure to matrix material, can reach the purpose of " similar mixing " blended the time, and company's section that will play plasticization simultaneously again is incorporated in the molecule of this polyphosphazene polymer ester structure, thereby plays plastifying effect.Because the molecular weight ratio matrix material of these Reoplexs is little, thereby than the easier degraded of matrix material, the degraded of Reoplex also just drives and promoted the degraded of matrix material like this, thereby play the effect of regulating the matrix material degradation time.In addition, because Reoplex and matrix material energy mix homogeneously, the process of film degradation in vivo is even, is not easy to produce fragment, nearly all is at last to change with slimy form.The adding of these auxiliary agents can be very not big to the film strength influence yet; In the effect product sterilization sterilization, also overcome plasticizer exudation and crosslinked.Simultaneously according to the requirement of operative site to film strength, pliability, degradation time and film thickness, can choose the polylactic acid of different molecular weight ranges and polylactic acid-polyglycolic acid as matrix material, adding the Reoplex allotment of a certain amount of particular requirement, make it to reach application requirements.
The Main Ingredients and Appearance that absorbable medical film of the present invention contains is polylactic acid and medical Reoplex or polylactic acid-polyglycolic acid copolymer and medical Reoplex, and shared weight ratio is:
Polylactic acid 50%～100%, medical Reoplex 0～50%.
Polylactic acid-polyglycolic acid copolymer 50%～100%, polylactic acid 50%～100 (molar percentage) % wherein, polyglycolic acid 0～50% (molar percentage); Medical Reoplex 0～50%.The medical Reoplex that is wherein added is a macromolecule polyester.Molecular weight is 500～100000, and these polyester are the homopolymer of glycolic or Acetic acid, hydroxy-, bimol. cyclic ester, lactic acid or lactide, caprolactone, diethyleno dioxide ketone (1.3-diethyleno dioxide ketone or 1.4-diethyleno dioxide ketone), 3-methyl Acetic acid, hydroxy-, bimol. cyclic ester or the wherein copolymerization more than two and two and the macromolecule polyester that generates and one or more the copolymer polyester in Polyethylene Glycol and these monomers.Employed matrix material is polylactic acid or is the polylactic acid-polyglycolic acid copolymer that its molecular weight is 5～1,000,000.When matrix material was the polylactic acid-polyglycolic acid copolymer, its constituent content was: polylactic acid 50%～100%, polyglycolic acid account for 0～50% (by mole percentage ratio).
The present invention adopts the method in common film forming, as curtain coating, calendering, blowing etc.When with methods such as calendering, blowings, matrix material and Reoplex adopt dissolution with solvents mixing after drying and get membrane material.Solvent can be used acetone, ethyl acetate, chloroform, dichloromethane etc.
The molecular weight of polylactic acid and polylactic acid-polyglycolic acid copolymer is viscosity-average molecular weight (Mn), and with Ubbelohde viscometer 30 ℃ of intrinsic viscositys ([η]) that record polymer in oxolane, the following formula of reuse calculates viscosity-average molecular weight earlier:
[η]＝1.04×10
-4Mn
0.75
The molecular weight of Reoplex adopts gel chromatography (GPC) to measure.
Below in conjunction with the more detailed understanding the present invention of embodiment.
The specific embodiment:
Embodiment 1.
Matrix material: polylactic acid preparation
In the four-hole boiling flask of 2L, add 300 gram lactides; With the high pure nitrogen displacement, 60 ℃ of vacuum dryings added 300 milliliters of dimethylbenzene through the sodium metal dehydration after 2 hours under the protection of high pure nitrogen; Heated and stirred dissolving, solution is constant during to 115 ℃, adds 2.5 milliliters of 1M triisobutyl aluminium xylene solutions, and isothermal reaction obtained polylactic acid polymer in 4 hours; This polymer dissolution in acetone, is precipitated precipitate 40 ℃ of dryings 48 hours in vacuum desiccator in ethanol.The molecular weight of product is 300,000.
Embodiment 2.
Matrix material: polylactic acid-polyglycolic acid copolymer
In the four-hole boiling flask of 2L, add 288 gram lactides and 4.73 gram Acetic acid, hydroxy-, bimol. cyclic esters; With the high pure nitrogen displacement, 60 ℃ of vacuum dryings added 300 milliliters of dimethylbenzene through the sodium metal dehydration after 2 hours under the protection of high pure nitrogen; Heated and stirred dissolving, solution is constant during to 115 ℃, adds 2.3 milliliters of 1M triisobutyl aluminium xylene solutions, and isothermal reaction obtained polylactic acid polymer in 4 hours; This polymer dissolution in acetone, is precipitated precipitate 40 ℃ of dryings 48 hours in vacuum desiccator in ethanol.The molecular weight of product is 250,000.
Embodiment 3.
Reoplex: lactide and 1.4-diethyleno dioxide ketone copolymer
1.4-diethyleno dioxide ketone 40 grams and lactide 60 that dehydration and purification is handled restrain the reaction bulb that places 500ml, add 0.01% stannous octoate catalyst again, reaction is 6 hours under vacuum condition and under 150 ℃, obtain elastic polymer, with this polymer dissolution in acetone, precipitate in ethanol, precipitate drying in vacuum desiccator promptly obtained elastomeric material in 48 hours.The molecular weight of product is 50,000.
Embodiment 4.
Reoplex: PLCL preparation
Caprolactone 60 grams and lactide 40 that dehydration and purification is handled restrain the reaction bulb that places 500ml, add 0.01% stannous octoate catalyst again, reaction is 6 hours under vacuum condition and under 150 ℃, obtain elastic polymer, with this polymer dissolution in acetone, precipitate in ethanol, precipitate drying in vacuum desiccator promptly obtained elastomeric material in 48 hours.The molecular weight of product is 30,000.
Embodiment 5～12.
The Reoplex copolymer
Experimental implementation is with embodiment 3., and raw material components and ingredient proportion and the Reoplex molecular weight of copolymer that generates see the following form 1.
Table 1:
| The embodiment sequence number | Raw material components and ingredient proportion (mass percent) | Molecular weight of copolymer |
| 5 | 3-methyl Acetic acid, hydroxy-, bimol. cyclic ester 60%, 1.4-diethyleno dioxide ketone 40% | 60,000 |
| 6 | Acetic acid, hydroxy-, bimol. cyclic ester 5%, caprolactone 10%, 1.4-diethyleno dioxide ketone 85% | 5.5 ten thousand |
| 7 | 3-methyl Acetic acid, hydroxy-, bimol. cyclic ester 80%, caprolactone 10%, 1.4-diethyleno dioxide ketone 10% | 7.5 ten thousand |
| 8 | 3-methyl Acetic acid, hydroxy-, bimol. cyclic ester 85%, caprolactone 5%, 1.3-diethyleno dioxide ketone 10% | 4.5 ten thousand |
| 9 | 3-methyl Acetic acid, hydroxy-, bimol. cyclic ester 85%, caprolactone 5%, 1.3-diethyleno dioxide ketone 10% | 4.5 ten thousand |
| 10 | Polyethylene Glycol (molecular weight is 1500) 30%, lactide 70% | 7.5 ten thousand |
| 11 | Polyethylene Glycol (molecular weight is 2000) 30%, 3-methyl Acetic acid, hydroxy-, bimol. cyclic ester 50%, 1.4-diethyleno dioxide ketone 20%, | 30,000 |
| 12 | Polyethylene Glycol (molecular weight is 2000) 40%, caprolactone 15%, 1.3-diethyleno dioxide ketone 45% | 50,000 |
Embodiment 13
Matrix material: polylactic acid-polyglycolic acid (wherein polyglycolic acid accounts for 2% in molar percentage)
Molecular weight is 250,000 7 grams
Reoplex copolymer: lactide and 1.4-diethyleno dioxide ketone copolymer (wherein the 1.4-diethyleno dioxide ketone accounts for 40% by weight)
Molecular weight is 50,000 3 grams
Be dissolved in 200 milliliters of ethyl acetate, pour film forming on the plate glass into, behind the vacuum drying, film thickness is 0.02mm, and its elongation at break is 120%.
Embodiment 14.
Matrix material: the polylactic acid molecule amount is 300,000 6 grams
Reoplex copolymer: lactide and 1.4-diethyleno dioxide ketone copolymer (wherein the 1.4-diethyleno dioxide ketone accounts for 40% by weight)
Molecular weight is 50,000 4 grams
Be dissolved in 200 milliliters of ethyl acetate, pour film forming on the plate glass into, behind the vacuum drying, film thickness is 0.02mm, and its elongation at break is 128%.
Embodiment 15～18
Experimental implementation is with embodiment 13., and matrix material and Reoplex kind and film forming the results are shown in following table 2.
Table 2
| The embodiment sequence number | Matrix material and content | Reoplex and content (percentage by weight) | Film thickness (mm) | The film elongation at break |
| 15 | Polylactic acid-polyglycolic acid (polyglycolic acid mol ratio 2%) molecular weight: 250,000, weight 8 grams | Caprolactone 60% and lactide 40% molecular weight of copolymer: 30,000, weight: 2 grams | 0.02 | 140％ |
| 16 | Polylactic acid molecule amount: 300,000 weight: 7 grams | 3-methyl Acetic acid, hydroxy-, bimol. cyclic ester 60% and 1.4-diethyleno dioxide ketone 40% molecular weight of copolymer: 60,000, weight: 3 grams | 0.02 | 132％ |
| 17 | Polylactic acid molecule amount: 300,000 weight: 7 grams | 1.4-diethyleno dioxide ketone 85%, Acetic acid, hydroxy-, bimol. cyclic ester 5% and caprolactone 10% molecular weight of copolymer: 5.5 ten thousand, weight: 3 grams | 0.02 | 112％ |
| 18 | Polylactic acid molecule amount: 300,000 weight: 7 grams | Polyethylene Glycol (molecular weight is 1500) 30%, lactide 70% molecular weight of copolymer: 7.5 ten thousand, weight: 3 grams | 0.02 | 92％ |
| 19 | Polylactic acid-polyglycolic acid (polyglycolic acid mol ratio 2%) molecular weight: 250,000, weight 8 grams | Polyethylene Glycol (molecular weight is 2000) 40%, caprolactone 15%, 1.3-diethyleno dioxide ketone 45% molecular weight of copolymer: 50,000, weight: 2 grams | 0.02 | 70％ |
Embodiment 20.
Matrix material: the polylactic acid molecule amount is 300,000 7 grams
Reoplex copolymer: 3-methyl Acetic acid, hydroxy-, bimol. cyclic ester, 1.4-diethyleno dioxide ketone and caprolactone copolymer (wherein by weight: 3-methyl Acetic acid, hydroxy-, bimol. cyclic ester 80%, caprolactone 10%, 1.4-diethyleno dioxide ketone 10%)
Molecular weight is 7.5 ten thousand 3 grams
With above material usefulness solwution method mix homogeneously after drying, after cylinder is hot-forming, film thickness is 0.08mm to the usefulness screw extruder at 150 ℃ of extruded materials, and its elongation at break is 108%.
Embodiment 21.
Matrix material: polylactic acid-polyglycolic acid (wherein polyglycolic acid accounts for 2% by weight)
Molecular weight is 250,000 7 grams
Reoplex copolymer: 3-methyl Acetic acid, hydroxy-, bimol. cyclic ester, 1.3-diethyleno dioxide ketone and caprolactone copolymer (wherein by weight: 3-methyl Acetic acid, hydroxy-, bimol. cyclic ester 85%, caprolactone 5%, 1.3-diethyleno dioxide ketone 10%)
Molecular weight is 4.5 ten thousand 3 grams
Operation is with embodiment 20, and film thickness is 0.08mm, and its elongation at break is 160%.
Implement sharp 22.
Matrix material: the polylactic acid molecule amount is 300,000 8 grams
Reoplex copolymer: Polyethylene Glycol (molecular weight is 2000), 3-methyl Acetic acid, hydroxy-, bimol. cyclic ester, 1.4-diethyleno dioxide ketone copolymer (wherein by weight: Polyethylene Glycol 30%, 3-methyl Acetic acid, hydroxy-, bimol. cyclic ester 50%, 1.4-diethyleno dioxide ketone 20%)
Molecular weight is 30,000 2 grams
Operation is with embodiment 20, and film thickness is 0.08mm, and its elongation at break is 0.08mm, and its elongation at break is 58%.
Claims (7)
1. absorbable medical film, be used for the parcel of medical surgery tendon, reparation, nerve trachea and the post-operation adhesion preventing of hard old film, it is characterized in that: this medical film contains following Main Ingredients and Appearance, shared share is by weight percentage: polylactic acid 50%～100%, medical Reoplex 0～50%; Polylactic acid-polyglycolic acid copolymer 50%～100%, medical Reoplex 0～50%.
2. according to the described absorbable medical film of claim 1, it is characterized in that: wherein said medical Reoplex is a polyphosphazene polymer esters plasticizer.
3. according to the described absorbable medical film of claim 2, it is characterized in that: wherein said polyphosphazene polymer esters plasticizer is that molecular weight is 500～100000 polyester.
4. according to the described absorbable medical film of claim 3, it is characterized in that: the wherein said polyester that is used as Reoplex is the homopolymerization of Acetic acid, hydroxy-, bimol. cyclic ester or glycolic, lactide or lactic acid, caprolactone, diethyleno dioxide ketone (1.3-diethyleno dioxide ketone or 1.4-diethyleno dioxide ketone), 3-methyl Acetic acid, hydroxy-, bimol. cyclic ester or wherein two and two above copolymerization and the macromolecule polyester that generates, and the polyester of one or more copolymerization in Polyethylene Glycol and these monomers, wherein the molecular weight of Polyethylene Glycol is 200～20000.
5. according to the described absorbable medical film of claim 1, it is characterized in that: wherein said polylactic acid is that molecular weight is 5～1,000,000 poly-DL lactic acid or poly-L-lactic acid.
6. according to the described absorbable medical film of claim 1, it is characterized in that: wherein said polylactic acid-polyglycolic acid is that molecular weight is 5～1,000,000 the lactic acid and the copolymer of glycolic or lactide and Acetic acid, hydroxy-, bimol. cyclic ester.
7. according to the described absorbable medical film of claim 6, it is characterized in that: in the wherein said polylactic acid-polyglycolic acid copolymer (by mole percentage ratio): polylactic acid 50%～100%, polyglycolic acid 0～50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100204998A CN1857235A (en) | 2006-03-17 | 2006-03-17 | Absorbable medical film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100204998A CN1857235A (en) | 2006-03-17 | 2006-03-17 | Absorbable medical film |
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| CN1857235A true CN1857235A (en) | 2006-11-08 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105999431A (en) * | 2016-07-06 | 2016-10-12 | 张波 | Neurosurgical postoperative anti-adhesion membrane and preparation method thereof |
| CN106668938A (en) * | 2017-03-06 | 2017-05-17 | 山东赛克赛斯生物科技有限公司 | Nerve conduit and preparation method thereof |
-
2006
- 2006-03-17 CN CNA2006100204998A patent/CN1857235A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105999431A (en) * | 2016-07-06 | 2016-10-12 | 张波 | Neurosurgical postoperative anti-adhesion membrane and preparation method thereof |
| CN106668938A (en) * | 2017-03-06 | 2017-05-17 | 山东赛克赛斯生物科技有限公司 | Nerve conduit and preparation method thereof |
| CN106668938B (en) * | 2017-03-06 | 2019-12-06 | 赛克赛斯生物科技股份有限公司 | Nerve conduit and preparation method thereof |
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Open date: 20061108 |