Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned the deficiencies in the prior art, a kind of intensity height, good, the retention fracture strength height of pliability are provided, have the suture tissue response light, the wound healing cicatrix is little, has tangible body temperature memory effect, may command degraded, and the preparation method of the absorbable medical suture that can absorb fully.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of preparation method of medical absorbable suture:
(1) it is raw material with the carbon dioxide copolymer, and the carbon dioxide copolymer structural formula is:
x=0.5-1.0
N is an integer, between 200 to 5000, is equivalent to number-average molecular weight between 20000 to 500000;
(2) carbon dioxide copolymer of described structure adds maleic anhydride or the acetic anhydride of the 0.1-4wt% of copolymer weight, the blend pelletize 120-160 ℃ of following fusion; With the copolymer after the pelletize 120-180 ℃ of down fusing, remove bubble after, be the spinneret of 1-20 millimeter by the aperture, form the primary filament of 0.8-10 millimeter; Primary filament carries out succeeding stretch again under 20-40 ℃ of water-bath, make the pure carbon dioxide copolymer stitching thread of different model.
The present invention is based on the preparation method of the medical absorbable suture of carbon dioxide copolymer, and the carbon dioxide copolymer of said structure adds maleic anhydride or the acetic anhydride of the 0.1-4wt% of copolymer weight, the blend pelletize 120-160 ℃ of following fusion; Carbon dioxide copolymer after the pelletize 150-180 ℃ of fusing down, is added polylactic acid or poly butyric ester, and content is the 10-40wt% of blend, melt blended back extruding pelletization; Adopt the melt spinning method 160-180 ℃ of fusing down the blend pellet after the pelletize, remove bubble after, be the spinneret of 1-20 millimeter by the aperture, form the primary filament of 0.8-10 millimeter; Primary filament carries out succeeding stretch again under 30-50 ℃ of water-bath, make the stitching thread of different model.
The present invention is owing to adopt complete biolytic carbon dioxide copolymer to prepare absorbable stitching thread, the stitching thread that carbon dioxide copolymer is made is through biological test, not only have advantages such as tissue reaction is light, the wound healing cicatrix is little, simultaneously since the vitrification point of selected carbon dioxide copolymer at 35-38 ℃, suitable with human body temperature, also have tangible body temperature memory effect.This moment, sutural extensibility can be controlled between the 50-500%, and good springiness can firmly be sewed up wound surface and not become flexible, knot knotting strength height.In addition and since the degraded of carbon dioxide copolymer be from skin gradually to internal layer, degraded mode is layer by layer carried out, so problem such as stitching thread can not expand, the difficulty of tiing a knot and knot are not firm, have intensity height, pliability good, retain many advantages such as fracture strength height.Introducing by comonomer is the may command degradation time also, makes degradation time controlled at 5-60 days, absorbs fully in 6 months.
The specific embodiment
The present invention is further described below in conjunction with embodiment:
A kind of preparation method of medical absorbable suture:
(1) it is raw material with the carbon dioxide copolymer, and the carbon dioxide copolymer structural formula is:
x=0.5-1.0
N is an integer, between 200 to 5000, is equivalent to number-average molecular weight between 20000 to 500000.
The above-mentioned carbon dioxide copolymer of the present invention can be carbon dioxide-ethylene oxide copolymer, or carbon dioxide-epoxy propane copolymer, or carbon dioxide-oxidizing ethyle alkyl copolymer, or carbon dioxide-styrene oxide copolymer, or carbon dioxide-epoxy propane-7-oxa-bicyclo[4.1.0 terpolymer, or one or both of carbon dioxide-epoxy propane-oxirane terpolymer.
The preparation method of the above-mentioned carbon dioxide copolymer of the present invention is not done detailed description here as 98125655.4 and 00136189.9 method of announcing.
The carbon dioxide copolymer of said structure adds maleic anhydride or the acetic anhydride of the 0.1-4wt% of copolymer weight, the blend pelletize 120-160 ℃ of following fusion.Maleic anhydride or acetic anhydride play the end capped effect of melt.With the copolymer after the pelletize 120-180 ℃ of down fusing, remove bubble after, be the spinneret of 1-20 millimeter by the aperture, form the primary filament of 0.8-10 millimeter; Primary filament carries out succeeding stretch again under 20-40 ℃ of water-bath, make the pure carbon dioxide copolymer stitching thread of different model.
The present invention is based on the preparation method of the medical absorbable suture of carbon dioxide copolymer, and the carbon dioxide copolymer of said structure adds maleic anhydride or the acetic anhydride of the 0.1-4wt% of copolymer weight, the blend pelletize 120-160 ℃ of following fusion; Carbon dioxide copolymer after the pelletize 150-180 ℃ of fusing down, is added polylactic acid or poly butyric ester, and content is the 10-40wt% of blend, melt blended back extruding pelletization; Adopt the melt spinning method 160-180 ℃ of fusing down the blend pellet after the pelletize, remove bubble after, be the spinneret of 1-20 millimeter by the aperture, form the primary filament of 0.8-10 millimeter; Primary filament carries out succeeding stretch again under 30-50 ℃ of water-bath, make the stitching thread of different model.
The carbon dioxide copolymer stitching thread that the present invention makes can be monofilament, multifilament or twisted filament, specification between 12-0 to 5 line, monofilament lines footpath between 0.010~0.799mm, not the intensity in collinear footpath between 0.25~71.44N, specifically as shown in table 1.
The specification of the medical absorbable suture of table 1 carbon dioxide copolymer, line footpath and intensity
Specification |
Silk footpath (mm) |
Intensity (N), 〉= |
12-0 |
0.001~0.009 |
/ |
11-0 |
0.010~0.019 |
/ |
10-0 |
0.020~0.029 |
0.25 |
9-0 |
0.030~0.039 |
0.49 |
8-0 |
0.040~0.049 |
0.69 |
7-0 |
0.050~0.069 |
1.37 |
6-0 |
0.070~0.099 |
2.45 |
5-0 |
0.100~0.149 |
6.66 |
4-0 |
0.150~0.199 |
9.31 |
3-0 |
0.200~0.249 |
17.35 |
2-0 |
0.300~0.339 |
26.26 |
0 |
0.350~0.399 |
38.22 |
1 |
0.400~0.499 |
49.78 |
2 |
0.500~0.599 |
62.23 |
3 and 4 |
0.600~0.699 |
71.44 |
5 |
0.700~0.799 |
/ |
Compare with existing absorbable suture, the present invention has following advantage: (1) stitching thread has the advantage that tissue reaction is light, the wound healing cicatrix is little through biological test; (2) since the vitrification point of selected carbon dioxide copolymer at 35-38 ℃, suitable with human body temperature, have tangible body temperature memory effect.This moment, sutural extensibility can be controlled between the 50-500%, and good springiness can firmly be sewed up wound surface and not become flexible, knot knotting strength height.(3) since the degraded of carbon dioxide copolymer be from skin gradually to internal layer, degraded mode is layer by layer carried out, so problem such as stitching thread can not expand, the difficulty of tiing a knot and knot are not firm, have intensity height, pliability good, retain many advantages such as fracture strength height.(4) spinning process is a melt spinning, without any organic solvent, and the therefore side effect of having avoided organic solvent to bring.
Carbon dioxide copolymer of the present invention is carbon dioxide-epoxy propane-oxirane terpolymer, and wherein the content of carbon dioxide-epoxy propane unit in copolymer is between 50%-100%, and the copolymer number-average molecular weight is between 20000 to 500000.In addition, the content in copolymer by adjustable ring Ethylene Oxide and ethylene oxide unit, the may command degradation time makes degradation time controlled at 1-30 days, and soak time is in 6 months fully.
By introducing polylactic acid or the poly butyric ester of 20-40%, the sutural mechanical strength of scalable; Filament strength can improve.Maleic anhydride or acetic anhydride play the end capped effect of melt.
Embodiment 1
Carbon dioxide copolymer (carbon dioxide-epoxy propane unit content 58%, number-average molecular weight 21000, molecular weight distributing index 4.2) 120 ℃ of following fusions, is added blend pelletize behind the maleic anhydride of 4wt% of copolymer weight.Carbon dioxide copolymer after the pelletize is adopted the spinning mechanical spinning or fusing under 155 ℃, after removing bubble, it by the aperture 4 millimeters spinneret, form 2 millimeters fiber after the preliminary drawing-off, primary filament carries out succeeding stretch again under 25 ℃ of water-baths, prepare the 2-0 stitching thread, intensity 26.50N.
Embodiment 2
Carbon dioxide copolymer (carbon dioxide-epoxy propane unit content 100%, number-average molecular weight 198000, molecular weight distributing index 5.3) 150 ℃ of following fusions, is added blend pelletize behind the maleic anhydride of 1.2wt% of copolymer weight.Carbon dioxide copolymer after the pelletize is adopted the spinning mechanical spinning or fusing under 160 ℃, after removing bubble, it by the aperture 6 millimeters spinneret, form 4 millimeters primary filament after the preliminary drawing-off, primary filament carries out succeeding stretch again under 25 ℃ of water-baths, prepare the 6-0 stitching thread, intensity 2.50N.
Embodiment 3
Carbon dioxide copolymer (carbon dioxide-epoxy propane unit content 92%, number-average molecular weight 423000, molecular weight distributing index 5.7) 160 ℃ of following fusions, is added blend pelletize behind the maleic anhydride of 0.6wt% of copolymer weight.Carbon dioxide copolymer after the pelletize is adopted the spinning mechanical spinning or fusing under 165 ℃, after removing bubble, it by the aperture 8 millimeters spinneret, form 6 millimeters primary filament after the preliminary drawing-off, primary filament carries out succeeding stretch again under 38 ℃ of water-baths, prepare the 8-0 stitching thread, intensity 0.70N.
Embodiment 4
Carbon dioxide copolymer (expoxy propane-carbon dioxide unit content 82%, number-average molecular weight 89000, molecular weight distributing index 3.6) 140 ℃ of following fusions, is added blend pelletize behind the acetic anhydride of 1wt% of copolymer weight.Carbon dioxide copolymer after the pelletize is adopted the spinning mechanical spinning or fusing under 155 ℃, after removing bubble, it by the aperture 5 millimeters spinneret, form 2 millimeters fiber after the preliminary drawing-off, primary filament carries out succeeding stretch again under 28 ℃ of water-baths, prepare the 3-0 stitching thread, intensity 17.53N.
Embodiment 5
To melt down at 170 ℃ after the carbon dioxide copolymer pelletize among the embodiment 4, add the polylactic acid (number-average molecular weight 320000, molecular weight distributing index 2.4) of 38wt%, melt blended back extruding pelletization.Blend pellet after the pelletize adopted the spinning mechanical spinning or 170 ℃ of fusings down, remove bubble after, be 8 millimeters spinneret by the aperture, form 4 millimeters fiber; Primary filament carries out succeeding stretch again under 40 ℃ of water-baths, prepare the 6-0 stitching thread, intensity 3.00N.
Embodiment 6
To melt down at 170 ℃ after the carbon dioxide copolymer pelletize among the embodiment 3, add the polylactic acid (number-average molecular weight 440000, molecular weight distributing index 2.6) of 18wt%, melt blended back extruding pelletization.Blend pellet after the pelletize adopted the spinning mechanical spinning or 170 ℃ of fusings down, remove bubble after, be 10 millimeters spinneret by the aperture, form 5 millimeters fiber; Primary filament carries out succeeding stretch again under 45 ℃ of water-baths, prepare stitching thread No. 8, fibre strength 0.74N.
Embodiment 7
To melt down at 170 ℃ after the carbon dioxide copolymer pelletize among the embodiment 4, add the poly butyric ester (number-average molecular weight 230000, molecular weight distributing index 4.9) of 28wt%, melt blended back extruding pelletization.Blend pellet after the pelletize adopted the spinning mechanical spinning or 175 ℃ of fusings down, remove bubble after, be 10 millimeters spinneret by the aperture, form 4 millimeters primary filament; Primary filament carries out succeeding stretch again under 40 ℃ of water-baths, prepare the 5-0 stitching thread, intensity 6.85N.
Embodiment 8
To melt down at 170 ℃ after the carbon dioxide copolymer pelletize among the embodiment 1, add the poly butyric ester (number-average molecular weight 281000, molecular weight distributing index 5.4) of 35wt%, melt blended back extruding pelletization.Blend pellet after the pelletize adopted the spinning mechanical spinning or 175 ℃ of fusings down, remove bubble after, be 8 millimeters spinneret by the aperture, form 4 millimeters primary filament, primary filament carries out succeeding stretch again under 35 ℃ of water-baths, prepare the 4-0 stitching thread, intensity 10.05N.