CN101045032A - Novel stop blooding and anti water seeping gel - Google Patents
Novel stop blooding and anti water seeping gel Download PDFInfo
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- CN101045032A CN101045032A CNA200610020569XA CN200610020569A CN101045032A CN 101045032 A CN101045032 A CN 101045032A CN A200610020569X A CNA200610020569X A CN A200610020569XA CN 200610020569 A CN200610020569 A CN 200610020569A CN 101045032 A CN101045032 A CN 101045032A
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Abstract
A staltic impervious hydrogel with high biodegradability, biocompatibility and safety and used after operation is prepared from solvent water and one or move of ethylenic bond terminated polyethanediol (PEG), polylactic acid (PLA), polytrimethylene dimethyl carbonate (PTMC), poly-p-dioxycyclohexone (PDO) and epsilon-caprolactone.
Description
The present invention relates to a kind of novel medical bio degradable anti-seeping gel for stanching, particularly the anti-seeping gel for stanching that is composited by the homopolymer of the Polyethylene Glycol (PEG) of end-functionalization (ethylene linkage end-blocking), polylactic acid (PLA), PTMC (PTMC), PPDO (PDO), poly-epsilon-caprolactone (PCL) etc. or copolymer and solvent.
Gained copolymer and acryloyl chloride reaction obtain end and contain two acrylate-based macromonomers (Macromonomer).This macromonomer is mixed with certain density solution, is applied in specific operative site with conduit or other means with normal saline, can form the hydrogel with hemostasis and antiseep function through the long wave ultraviolet light irradiation under the poly-action of evocating of light.This macromonomer prepares easily, cost is lower, and the hydrogel of its formation has favorable biological degradability, Bioabsorbable and safety, can be used for treating postoperative hemorrhage, oozing of blood and prevents leakage of body fluids and aspect such as tissue adhesion.
Hemorrhage and oozing of blood in surgical operation and the trauma operation is a difficult problem of medical circle always.For general common operation, perform the operation as trunks such as operation on vessels of heart, liver operation on spleen, abdominal operations, usually can adopt and connect the way of pricking and sewing up: and for blood capillary and blood capillary, depend merely on to connect and prick and sew up and do not deal with problems, usually adopt direct compression method, the hemostasis of fulgerizing, prepare the defective time-consuming, that grumeleuse comes off too early yet these methods exist.In addition, for multivessel internal organs, hemorrhage as liver trauma, the coagulation disorders that often causes during wound with bleeding profusely, in this case, classical hemostasis method just is difficult to prove effective, and just needs this moment to use effective hemostatic material to realize satisfactory results.Therefore, constantly seek the vital task that hemostatic material and method have safely and effectively become medical circle.
For a long time, clinically expectation always can develop a kind ofly have no side effect, safe and reliable, haemostatic effect good, degradable absorbs hemostatic material.Along with the continuous research of people to hemostatic material, having occurred gelatin fiber, oxidized cellulose, chitosan film, gelfoam etc. successively a series of is the hemostatic material of carrier with the natural material, though these materials have been obtained certain haemostatic effect, but limitation is separately arranged all, the prerequisite that they play a role is that coagulation function is wanted normally, and generally speaking haemostatic effect is undesirable.In recent years, biological fibrin glue of newly developing such as collagen protein etc., better through clinical proving effect, be the best product of present known haemostatic effect.Whether but this product comes from the blood of people or animal, can stop the various infectious disease of autoblood to remain to be investigated fully, and the cost of Fibrin Glue is higher simultaneously, the medical expense costliness.
The generation of seepage simultaneously also is a problem that can not be ignored after the operation, because the generation of seepage can cause gathering of tissue fluid, thereby causes various diseases, health risk.Many hemostatic materials are because can't form one firmly and the organic whole of density with tissue surface, promptly lack certain adhesive force, make material system to form stronger active force, finally influenced therapeutic effect with tissue system (such as protein and the formed system of glycosaminoglycan).
The object of the present invention is to provide a kind of have favorable biological degradability, biocompatibility, the safe and reliable hemostasis that is used for postoperative, prevent the biodegradable anti-seeping gel for stanching that oozing of blood reduces simultaneously or avoids seepage to take place.This biodegradable anti-seeping gel for stanching is by the Biodegradable material and the solvent composition of end-functionalization (ethylene linkage end-blocking), only need during use product is spread upon the position that needs the hemostasis antiseepage, cause the terminal double bond of above-mentioned material by radical initiator, thereby form crosslinked, seal the tissue site of oozing of blood sepage, thereby reach the purpose of hemostasis antiseepage.
The object of the present invention is achieved like this: a kind of independent use in the Polyethylene Glycol (PEG) of end-functionalization (ethylene linkage end-blocking), polylactic acid (PLA), polytrimethylene DMC dimethyl carbonate (PTMC), PPDO (PDO), the poly-epsilon-caprolactone (PCL) etc. or more than one blend are used, or used two or more copolymer in the above-mentioned material.Above-mentioned substance and aqueous solvent form target product.Only need during use spread upon the position that needs anti to product, cause the terminal double bond of above-mentioned material by radical initiator, thus form crosslinked, the tissue site of sealing oozing of blood sepage, thus reach the purpose of hemostasis antiseepage.
The Polyethylene Glycol (PEG) of the end-functionalization of indication of the present invention (ethylene linkage end-blocking), polylactic acid (PLA), PTMC (PTMC), PPDO (PDO), a kind of independent use in the poly-epsilon-caprolactone (PCL) etc. or more than one blend are used, or use two or more the copolymer in the above-mentioned material to be meant a Polyethylene Glycol (PEG), polylactic acid (PLA), PTMC (PTMC), PPDO (PDO), the small molecule monomer of the two keys of the homopolymer of poly-epsilon-caprolactone (PCL) or copolymer and band such as propionyl chloride reaction generate the functionalization homopolymer of the two keys of terminal band, blend or copolymer.
Its intrinsic viscosity (dark type viscometer of homopolymer, blend or copolymer of the used biodegradable Polyethylene Glycol (PEG) of the present invention, polylactic acid (PLA), PTMC (PTMC), PPDO (PDO), poly-epsilon-caprolactone (PCL), chloroform solvent, 25 ℃) scope is 0.01-5dl/g, wherein the best is 0.05-0.2dl/l; Molecular weight ranges is 500-600000, and wherein the best is 500-100000.Solvent for use is a normal saline, is that hydrogel forms later degradable part; A represents PEG, is hydrophilic parts, and it plays biocompatibility and forms the effect of gel.Macromonomer can also can be solid for liquid.During use, earlier the poly-initiator eosin W or W S of light is introduced and treated the hemostatic tissue site, and the triethanolamine of interpolation minute quantity is as electron donor, then Macromonomer is mixed with the solution of 20-30% with normal saline, be applied in the position of hemostasis and antiseep, through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Because this gel has been penetrated in the tissue texture, crosslinked with protein and glycosaminoglycan system, so adhesive force is very strong, and can effectively prevent the generation of seepage.After after a while, gel degradation for have no side effect, absorbable monomer and oligomer, as PEG, acrylic acid oligomer (DP=2-3), lactic acid etc.Final these catabolites are absorbed fully, do not leave over any harmful substance.The PEG molecular weight is 400-20000 among the present invention, it and lactide (LA), trimethylene DMC dimethyl carbonate (TMC), is 19 to the ratios a kind of or two kinds of copolymerization in dioxy Ketohexamethylene (DO), the 6-caprolactone (CL): 1-1: 1,18: 1: 1-1: 1: 1.The polymer monomer concentration that used normal saline is prepared is 5%-40%, and optium concentration is 20%-30%.Can adopt the optical fiber conduit during irradiation under ultraviolet ray, illumination wavelength is 450-600nm, and the best is the 510-530nm ultraviolet lighting.The terminal groups functionalization of PEG copolymer can adopt acryloyl chloride, methacrylic chloride, cyano group acryloyl chloride, isocyano group acryloyl chloride etc., and wherein acryloyl chloride, methacrylic chloride effect are preferable.The preservation of this product should be preserved under lucifuge.
Embodiments of the invention are as follows:
The intrinsic viscosity of polymer is measured with dark type viscometer, is solvent with the chloroform, and temperature is 25 ℃.
The sign of product adopts high-resolution HNMR (CDCl3 makes solvent)
The mensuration of molecular weight chromatograph of gel permeation (GPC)
Mentioned molecular weight is viscosity-average molecular weight M in the implementation example
η
Embodiment one:
(molecular weight is 3500 to get the PEG-PLA copolymer of the terminal acryloyl group functionalization of 10g; PEG2000: LA=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment two:
(molecular weight is 5000 to get the PEG-PLA copolymer of the terminal acryloyl group functionalization of 10g; PEG4000: LA=1: 8 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment three:
(molecular weight is 9000 to get the PEG-PLA copolymer of the terminal acryloyl group functionalization of 10g; PEG8000: LA=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment four:
(molecular weight is 12000 to get the PEG-PLA copolymer of the terminal acryloyl group functionalization of 10g; PEG10000: LA=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment five:
(molecular weight is 21400 to get the PEG-PLA copolymer of the terminal acryloyl group functionalization of 10g; PEG20000: LA=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment six:
(molecular weight is 3000 to get the PEG-PTMC copolymer of the terminal acryloyl group functionalization of 10g; PEG2000: TMC=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment seven:
(molecular weight is 7000 to get the PEG-PTMC copolymer of the terminal acryloyl group functionalization of 10g; PEG6000: TMC=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment eight:
(molecular weight is 9000 to get the PEG-PTMC copolymer of the terminal acryloyl group functionalization of 10g; PEG8000: TMC=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment nine:
(molecular weight is 21000 to get the PEG-PTMC copolymer of the terminal acryloyl group functionalization of 10g; PEG20000: TMC=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment ten:
(molecular weight is 186000 to get the PEG-PTMC copolymer of the terminal acryloyl group functionalization of 10g; PEG185000: TMC=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment 11:
(molecular weight is 5200 to get the PEG-PTMC-PLA copolymer of the terminal acryloyl group functionalization of 10g; PEG4000: TMC: LA=1: 5: 5 (mol/mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment 12:
(molecular weight is 9200 to get the PEG-PTMC-PLA copolymer of the terminal acryloyl group functionalization of 10g; PEG8000: TMC: LA=1: 5: 5 (mol/mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment 13:
(molecular weight is 21000 to get the PEG-PTMC-PLA copolymer of the terminal acryloyl group functionalization of 10g; PEG20000: TMC: LA=1: 5: 5 (mol/mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment 14:
(molecular weight is 5000 to get the PEG-PDO copolymer of the terminal acryloyl group functionalization of 10g; PEG4000: DO=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment 15:
(molecular weight is 9000 to get the PEG-PDO copolymer of the terminal acryloyl group functionalization of 10g; PEG8000: DO=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment 16:
(molecular weight is 21000 to get the PEG-PDO copolymer of the terminal acryloyl group functionalization of 10g; PEG20000: DO=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment 17:
(molecular weight is 7100 to get the PEG-PCL copolymer of the terminal acryloyl group functionalization of 10g; PEG6000: CL=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment 18:
(molecular weight is 11400 to get the PEG-PCL copolymer of the terminal acryloyl group functionalization of 10g; PEG10000: CL=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment 19:
(molecular weight is 21400 to get the PEG-PCL copolymer of the terminal acryloyl group functionalization of 10g; PEG20000: CL=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Embodiment 20:
(molecular weight is 186100 to get the PEG-PCL copolymer of the terminal acryloyl group functionalization of 10g; PEG185000: CL=1: 10 (mol/mol)); be mixed with 25% aqueous solution; be applied in the hemostasis position; add the eosin W or W S initiator; through the irradiation under ultraviolet ray of 510-530nm, in the time of 30-60s, can form gel.Can reach ideal hemostasis and anti-seepage effect.
Claims (7)
1, a kind of novel medical bio degradable hemostasis antiseepage glue, particularly the hemostasis antiseepage glue that is composited by the homopolymer of the Polyethylene Glycol (PEG) of end-functionalization (ethylene linkage end-blocking), polylactic acid (PLA), PTMC (PTMC), PPDO (PDO), poly-epsilon-caprolactone (PCL) etc. or copolymer and solvent.This macromonomer is mixed with certain density solution, is applied in specific operative site with conduit or other means with the solvent normal saline, can form the hydrogel with hemostasis and antiseep function through the long wave ultraviolet light irradiation under the poly-action of evocating of light.
2, biodegradable anti-seeping gel for stanching according to claim 1, the Polyethylene Glycol (PEG) that it is characterized in that end-functionalization (ethylene linkage end-blocking), polylactic acid (PLA), PTMC (PTMC), PPDO (PDO), a kind of independent use in the poly-epsilon-caprolactone (PCL) etc. or more than one blend are used, or use two or more the copolymer in the above-mentioned material to be meant a Polyethylene Glycol (PEG), polylactic acid (PLA), PTMC (PTMC), PPDO (PDO), the small molecule monomer of the two keys of the homopolymer of poly-epsilon-caprolactone (PCL) or copolymer and band such as interior acyl chloride reaction generate the functionalization homopolymer of the two keys of terminal band, blend or copolymer.
3, biodegradable anti-seeping gel for stanching according to claim 1, its intrinsic viscosity (dark type viscometer of homopolymer, blend or copolymer that it is characterized in that biodegradable Polyethylene Glycol (PEG), polylactic acid (PLA), PTMC (PTMC), PPDO (PDO), poly-epsilon-caprolactone (PCL), chloroform solvent, 25 ℃) scope is 0.01-5dl/g, wherein the best is 0.05-0.2dl/l; Molecular weight ranges is 500-600000, and wherein the best is 500-100000.Solvent for use is a normal saline.
4, biodegradable anti-seeping gel for stanching according to claim 1 is characterized in that the macromonomer solution concentration of preparing with normal saline is 5%-40%, and optium concentration is 20%-30%.
5, biodegradable anti-seeping gel for stanching according to claim 1 can adopt the optical fiber conduit when it is characterized in that penetrating, and illumination wavelength is 450-600nm, and the best is the 510-530nm ultraviolet lighting.Irradiation time is less than 60s.
6, biodegradable anti-seeping gel for stanching according to claim 1 is characterized in that the poly-initiator of light is an eosin W or W S, and electron donor is a triethanolamine.
7, biodegradable anti-seeping gel for stanching according to claim 1, the terminal groups functionalization that it is characterized in that the PEG copolymer can adopt acryloyl chloride, methacrylic chloride, cyano group acryloyl chloride, isocyano group acryloyl chloride etc., and wherein acryloyl chloride, methacrylic chloride effect are preferable.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200610020569XA CN101045032A (en) | 2006-03-28 | 2006-03-28 | Novel stop blooding and anti water seeping gel |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA200610020569XA CN101045032A (en) | 2006-03-28 | 2006-03-28 | Novel stop blooding and anti water seeping gel |
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| CN101045032A true CN101045032A (en) | 2007-10-03 |
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| CNA200610020569XA Pending CN101045032A (en) | 2006-03-28 | 2006-03-28 | Novel stop blooding and anti water seeping gel |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012521439A (en) * | 2009-03-26 | 2012-09-13 | ウォーソー・オーソペディック・インコーポレーテッド | Site localization and method for monitoring treatment of impaired blood vessels |
| JP2012521438A (en) * | 2009-03-26 | 2012-09-13 | ウォーソー・オーソペディック・インコーポレーテッド | Compositions and methods for the treatment of bleeding |
| CN104606725A (en) * | 2015-01-19 | 2015-05-13 | 哈尔滨医科大学 | Postoperative anti-adhesion product as well as preparation method and application thereof |
| CN106867020A (en) * | 2017-01-24 | 2017-06-20 | 浙江大学 | A kind of temperature-induced self-healing porous material and its preparation method and application |
| CN108633253A (en) * | 2017-01-19 | 2018-10-09 | 崔性铉 | The alleviation and treatment of the exudative skin disease of plasma proteins including atopic diseases pad |
| WO2019057035A1 (en) * | 2017-09-19 | 2019-03-28 | The Hong Kong University Of Science And Technology | Biocompatible material and methods for making and using thereof |
| WO2021034899A1 (en) * | 2019-08-20 | 2021-02-25 | Xerox Corporation | Biodegradable electrochemical device |
-
2006
- 2006-03-28 CN CNA200610020569XA patent/CN101045032A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012521439A (en) * | 2009-03-26 | 2012-09-13 | ウォーソー・オーソペディック・インコーポレーテッド | Site localization and method for monitoring treatment of impaired blood vessels |
| JP2012521438A (en) * | 2009-03-26 | 2012-09-13 | ウォーソー・オーソペディック・インコーポレーテッド | Compositions and methods for the treatment of bleeding |
| CN104606725A (en) * | 2015-01-19 | 2015-05-13 | 哈尔滨医科大学 | Postoperative anti-adhesion product as well as preparation method and application thereof |
| CN108633253A (en) * | 2017-01-19 | 2018-10-09 | 崔性铉 | The alleviation and treatment of the exudative skin disease of plasma proteins including atopic diseases pad |
| CN106867020A (en) * | 2017-01-24 | 2017-06-20 | 浙江大学 | A kind of temperature-induced self-healing porous material and its preparation method and application |
| CN106867020B (en) * | 2017-01-24 | 2019-05-28 | 浙江大学 | A kind of temperature-induced self-healing porous material and its preparation method and application |
| WO2019057035A1 (en) * | 2017-09-19 | 2019-03-28 | The Hong Kong University Of Science And Technology | Biocompatible material and methods for making and using thereof |
| CN111194218A (en) * | 2017-09-19 | 2020-05-22 | 香港科技大学 | Biocompatible materials and methods for making and using the same |
| CN111194218B (en) * | 2017-09-19 | 2024-02-20 | 香港科技大学 | Biocompatible materials and methods for making and using the same |
| WO2021034899A1 (en) * | 2019-08-20 | 2021-02-25 | Xerox Corporation | Biodegradable electrochemical device |
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