CN101081310A - Adsorbable hemostatic ligation clip - Google Patents

Adsorbable hemostatic ligation clip Download PDF

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Publication number
CN101081310A
CN101081310A CN 200610051687 CN200610051687A CN101081310A CN 101081310 A CN101081310 A CN 101081310A CN 200610051687 CN200610051687 CN 200610051687 CN 200610051687 A CN200610051687 A CN 200610051687A CN 101081310 A CN101081310 A CN 101081310A
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Prior art keywords
ppdo
lactide
dioxy ketohexamethylene
internal layer
ligation clip
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CN 200610051687
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CN101081310B (en
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熊成东
石磊
张胜蓝
李庆
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Hangzhou Shengshi Technology Co.,Ltd.
Chengdu Organic Chemicals Co Ltd of CAS
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HANGZHOU SHENGSHI TECHNOLOGY Co Ltd
Chengdu Organic Chemicals Co Ltd of CAS
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Abstract

The present invention discloses one kind of hemostatic ligating clip of absorbable material for surgical abdominoscope operation. The hemostatic ligating clip includes one outer layer of polyglycolide and one inner layer of poly-p-dioxanone or p-dioxanone-lactide copolymer. The hemostatic ligating clip made of materials with high hydrophilicity and flexibility has high compatibility to skin and tissue, no injury to the tissue of human body and the degradation speed determined by the outer layer.

Description

Adsorbable hemostatic ligation clip
Technical field
Special-purpose consumptive material when the present invention relates to a kind of surgery and implementing laparoscopic surgery more particularly, the present invention relates to the hemostatic ligation clip that a kind of absorbable material is made.
Background technology
Surgery is implemented often to adopt the clip of metal material in the laparoscopic surgery, is used for pressing from both sides and pricks intraluminal tissue, and envelope is pricked tubular tissue in the human body, prevents the liquid leakage, plays the effect of hemostasis or ligation.The clip of metal material such as rustless steel folder, titanium folder because can not degraded and absorbed, may produce foreign body reaction for a long time in vivo or the stimulation of tissue is produced complications such as inflammation, pain; Simultaneously because opacity often influences the inspection of X ray.Hemostatic ligation clip (the Surgical fastenermade from glycolide-rich polymer blends that makes with absorbable material the eighties appearred in twentieth century, Ethicon, Appl.No.:146014, Filed:January 20,1988), material therefor mainly is poly-Acetic acid, hydroxy-, bimol. cyclic ester and blend thereof.Can absorb folder and compare, have the energy degraded and absorbed, not produce foreign body reaction, not influence the advantages such as inspection of X ray with metal clip.
The absorbed folder of the safe section of U.S. medical device company limited production is divided into internal layer and skin, and internal layer adopts Acetic acid, hydroxy-, bimol. cyclic ester-propanoic acid trimethyl copolymer, outer strata Acetic acid, hydroxy-, bimol. cyclic ester.This can absorb folder and operate by means of applicator.But because internal layer adopts Acetic acid, hydroxy-, bimol. cyclic ester-propanoic acid trimethyl copolymer, hydrophilic is poor, and softish inadequately shortcoming is damaged tubular tissue or other intraluminal tissue in the human body sometimes.
Summary of the invention
At above-mentioned shortcoming, the objective of the invention is to adopt the material of good hydrophilic property to replace Acetic acid, hydroxy-, bimol. cyclic ester-propanoic acid trimethyl copolymer as internal layer, it has suitable flexibility, and degradation speed is with outer consistent.
The folder that absorbs of the present invention divides internal layer and skin (internal layer card and outer card), and outer for gathering Acetic acid, hydroxy-, bimol. cyclic ester, internal layer is made by the PPDO material or to dioxy Ketohexamethylene-lactide copolymer.
The folder that absorbs of the present invention, internal layer has the hole, and being shaped as of hole is square or circular.
The folder that absorbs of the present invention, internal layer also can have alternative dentation.
The folder that absorbs of the present invention, internal layer are by dioxy Ketohexamethylene-lactide copolymer is made, and in dioxy Ketohexamethylene-lactide copolymer, to the unit mol ratio 95%-5% of dioxy Ketohexamethylene and lactide, molecular weight is 20-90 ten thousand.
Wherein, preferred range is the unit mol ratio 80%-20% to dioxy Ketohexamethylene and lactide, and molecular weight is 50-80 ten thousand.Preferred scheme is in dioxy Ketohexamethylene-lactide copolymer, and to the unit mol ratio 70% of dioxy Ketohexamethylene and lactide, molecular weight is 650,000.
PPDO among the present invention (poly (p-dioxanone)) adopts following method preparation;
Polymer grade is placed reactor to the dioxy Ketohexamethylene, add stannous octoate catalyst, at vacuum condition, 140 ℃ of following reaction appropriate times, under 140 ℃, reactant is added extruding machine and obtain diameter 1-2 millimeter, the granule PPDO of long 5-10 millimeter, with above pellet 50 ℃ of following vacuum dryings 24 hours.Its molecular weight is according to Mark-Houwink equation [η]=KM w a(a=0.63, K=79x10 -3Cm 3g -1) can calculate.With phenol/1,1, (2: 3/W: W) mixed solution is made solvent to 2,2 one sym-tetrachloroethanes, uses Ubbelohde viscometer in 25 ℃ of waters bath with thermostatic control, the intrinsic viscosity that records PPDO.Choose the Polymer Processing of molecular weight 20-90 ten thousand.
To dioxy Ketohexamethylene-lactide copolymer, adopt following method preparation among the present invention;
Polymer grade is placed reactor to dioxy Ketohexamethylene and lactide, add stannous octoate catalyst, at vacuum condition, 140 ℃ of following reaction appropriate times, under 140 ℃, reactant is added extruding machine and obtain diameter 1-2 millimeter, the granule of long 5-10 millimeter, with above pellet 50 ℃ of following vacuum dryings 24 hours.Its molecular weight is according to Mark-Houwink equation [η]=KM w a(a=0.63, K=79 * 10 -3Cm 3g -1) can calculate.With phenol/1,1, (2: 3/W: W) mixed solution is made solvent to 2,2 one sym-tetrachloroethanes, uses Ubbelohde viscometer in 25 ℃ of waters bath with thermostatic control, the intrinsic viscosity that records PPDO.Choose the Polymer Processing of molecular weight 20-90 ten thousand.Dioxy Ketohexamethylene unit accounts for 5%-95% in the copolymer.
Utilize above-mentioned material processing adsorbable hemostatic ligation clip, can adopt conventional forming method as extrude, injection etc.
The anchor clamps that absorb of the present invention have following advantage:
1) the PPDO class material of good hydrophilic property replaces internal layer to adopt Acetic acid, hydroxy-, bimol. cyclic ester-propanoic acid trimethyl copolymer, has increased hydrophilic, and is better with skin or histocompatibility.
2) include the ehter bond that can rotate freely owing in the PPDO molecule segment, so material is more soft, can damage tubular tissue or other intraluminal tissue in the human body.
3) utilize PPDO class copolymeric material, degradation speed can be regulated by the adjusting of molecular weight or with the copolymerization ratio of lactide, and degradation speed can be with outer consistent.
In addition, internal layer is provided with some and replaces dentation, helps the clamping to tubular tissue in the human body or other intraluminal tissue.
Description of drawings
Fig. 1 is a sketch map of the present invention.
Among Fig. 1,1 is internal layer, and 2 is outer.Have dentation on the internal layer inner side plane, its objective is to clamp tubular tissue or other intraluminal tissue in the human body, anti-sliding stop.
The specific embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
The PPDO material preparation:
Polymer grade is placed reactor to dioxy Ketohexamethylene 200 grams, the stannous octoate catalyst of adding 0.01%, vacuum condition, 140 ℃ of following reactions 6 hours, under 140 ℃, reactant is added extruding machine and obtain diameter 1-2 millimeter, the granule PPDO of long 5-10 millimeter, with above pellet 50 ℃ of following vacuum dryings weighed in 24 hours 187 the gram, yield 93.5%.With phenol/1,1, (2: 3/W: W) mixed solution is made solvent to 2,2 one sym-tetrachloroethanes, and in 25 ℃ of waters bath with thermostatic control, the intrinsic viscosity that records PPDO is 2.78dl/g with Ubbelohde viscometer.
The preparation of poly-Acetic acid, hydroxy-, bimol. cyclic ester:
The polymer grade Acetic acid, hydroxy-, bimol. cyclic ester is placed reactor, add stannous octoate catalyst, at vacuum condition, 240 ℃ of following reaction appropriate times, under 240 ℃, reactant is added extruding machine and obtain diameter 1-2 millimeter, the granule of long 5-10 millimeter gathers Acetic acid, hydroxy-, bimol. cyclic ester, with above pellet 50 ℃ of following vacuum dryings 24 hours.Using fusion index instrument, is 8g/10s 230 ℃ of melt index of measuring poly-Acetic acid, hydroxy-, bimol. cyclic ester.
The processing of adsorbable hemostatic ligation clip: the poly-Acetic acid, hydroxy-, bimol. cyclic ester of method for preparing is processed into outer card by injection molding forming method, and temperature 220-230 ℃, it is 98MPa that outer after tested OK a karaoke club is stretched intensity.Above-mentioned synthetic PPDO is processed into the internal layer card by injection molding forming method, and temperature 170-175 ℃, the internal layer hot strength is 62MPa after tested.
Embodiment 2
The PPDO material preparation:
Polymer grade is placed reactor to dioxy Ketohexamethylene 200 grams, the stannous octoate catalyst of adding 0.02%, vacuum condition, 140 ℃ of following reactions 10 hours, under 140 ℃, reactant is added extruding machine and obtain diameter 1-2 millimeter, the granule PPDO of long 5-10 millimeter, with above pellet 50 ℃ of following vacuum dryings weighed in 24 hours 196 the gram, yield 98%.With phenol/1,1, (2: 3/W: W) mixed solution is made solvent to 2,2 one sym-tetrachloroethanes, and in 25 ℃ of waters bath with thermostatic control, the intrinsic viscosity that records PPDO is 4.78dl/g with Ubbelohde viscometer.
The processing of adsorbable hemostatic ligation clip: above-mentioned synthetic PPDO is processed into the internal layer card by injection molding forming method, and temperature 175-180 ℃, the internal layer hot strength is 78Mpa after tested.
Embodiment 3
The PPDO material preparation:
Polymer grade is placed reactor to dioxy Ketohexamethylene 200 grams, the stannous octoate catalyst of adding 0.01%, vacuum condition, 140 ℃ of following reactions 10 hours, under 140 ℃, reactant is added extruding machine and obtain diameter 1-2 millimeter, the granule PPDO of long 5-10 millimeter, with above pellet 50 ℃ of following vacuum dryings weighed in 24 hours 190 the gram, yield 95%.With phenol/1,1, (2: 3/W: W) mixed solution is made solvent to 2,2 one sym-tetrachloroethanes, and in 25 ℃ of waters bath with thermostatic control, the intrinsic viscosity that records PPDO is 3.29dl/g with Ubbelohde viscometer.
The processing of adsorbable hemostatic ligation clip: above-mentioned synthetic PPDO is processed into the internal layer card by injection molding forming method, and temperature 170-175 ℃, the internal layer hot strength is 70MPa after tested.
Embodiment 4
The preparation of PPDO-lactide copolymer material:
Polymer grade is placed reactor to dioxy Ketohexamethylene 190, lactide 10 grams, the stannous octoate catalyst of adding 0.02%, vacuum condition, 140 ℃ of following reactions 10 hours, under 140 ℃, reactant is added extruding machine and obtain diameter 1-2 millimeter, the granule of long 5-10 millimeter, with above pellet 50 ℃ of following vacuum dryings weighed in 24 hours 170 the gram, yield 85%.With phenol/1,1, (2: 3/W: W) mixed solution is made solvent to 2,2 one sym-tetrachloroethanes, and in 25 ℃ of waters bath with thermostatic control, the intrinsic viscosity that records the PPDO copolymer is 3.928dl/g with Ubbelohde viscometer.
The processing adsorbable hemostatic ligation clip: above-mentioned synthetic PPDO-lactide copolymer is processed into the internal layer card by injection molding forming method, and temperature 170-175 ℃, the internal layer hot strength is 72MPa after tested.
Embodiment 5
The preparation of PPDO-lactide copolymer material:
Polymer grade is placed reactor to dioxy Ketohexamethylene 190 grams, lactide 10 grams, the stannous octoate catalyst of adding 0.02%, vacuum condition, 140 ℃ of following reactions 20 hours, under 140 ℃, reactant is added extruding machine and obtain diameter 1-2 millimeter, the granule of long 5-10 millimeter, with above pellet 50 ℃ of following vacuum dryings weigh after 24 hours 180 the gram, yield 90%.With phenol/1,1, (2: 3/W: W) mixed solution is made solvent to 2,2 one sym-tetrachloroethanes, and in 25 ℃ of waters bath with thermostatic control, the intrinsic viscosity that records the PPDO copolymer is 4.928dl/g with Ubbelohde viscometer.
PPDO-lactide copolymer after measured, dioxy Ketohexamethylene unit accounts for 94.6%.
The processing adsorbable hemostatic ligation clip: above-mentioned synthetic PPDO-lactide is processed into the internal layer card by injection molding forming method, and temperature 180-185 ℃, the internal layer hot strength is 77MPa after tested.
Embodiment 6
The preparation of PPDO-lactide copolymer material;
Polymer grade is placed reactor to dioxy Ketohexamethylene 100 grams, lactide 100 grams, the stannous octoate catalyst of adding 0.02%, vacuum condition, 140 ℃ of following reactions 12 hours, under 140 ℃, reactant is added extruding machine and obtain diameter 1-2 millimeter, the granule of long 5-10 millimeter, with above pellet 50 ℃ of following vacuum dryings 24 hours.With phenol/1,1, (2: 3/W: W) mixed solution is made solvent to 2,2 one sym-tetrachloroethanes, and in 25 ℃ of waters bath with thermostatic control, the intrinsic viscosity that records the PPDO copolymer is 3.526dl/g with Ubbelohde viscometer.
PPDO-lactide copolymer after measured, dioxy Ketohexamethylene unit accounts for 46.6%.
Embodiment 7
The preparation of PPDO-lactide copolymer material;
Polymer grade is placed reactor to dioxy Ketohexamethylene 160 grams, lactide 40 grams, the stannous octoate catalyst of adding 0.02%, vacuum condition, 140 ℃ of following reactions 18 hours, under 140 ℃, reactant is added extruding machine and obtain diameter 1-2 millimeter, the granule of long 5-10 millimeter, with above pellet at 50 ℃ of following vacuum dryings after 24 hours, with phenol/1,1,2, (2: 3/W: W) mixed solution is made solvent to 2 one sym-tetrachloroethanes, and in 25 ℃ of waters bath with thermostatic control, the intrinsic viscosity that records the PPDO copolymer is 3.826dl/g with Ubbelohde viscometer.
PPDO-lactide copolymer after measured, dioxy Ketohexamethylene unit accounts for 76.2%.
Embodiment 8
The preparation of PPDO-lactide copolymer material;
Polymer grade is placed reactor to dioxy Ketohexamethylene 140 grams, lactide 60 grams, the stannous octoate catalyst of adding 0.02%, vacuum condition, 140 ℃ of following reactions 12 hours, under 140 ℃, reactant is added extruding machine and obtain diameter 1-2 millimeter, the granule of long 5-10 millimeter, with above pellet 50 ℃ of following vacuum dryings 24 hours.With phenol/1,1, (2: 3/W: W) mixed solution is made solvent to 2,2 one sym-tetrachloroethanes, and in 25 ℃ of waters bath with thermostatic control, the intrinsic viscosity that records the PPDO copolymer is 4.126dl/g with Ubbelohde viscometer.
PPDO-lactide copolymer after measured, dioxy Ketohexamethylene unit accounts for 68.6%.
Above-mentioned copolymer can be processed adsorbable hemostatic ligation clip.

Claims (7)

1. an adsorbable hemostatic ligation clip divides internal layer and skin, and is outer for poly-Acetic acid, hydroxy-, bimol. cyclic ester, it is characterized in that internal layer is made by PPDO or to dioxy Ketohexamethylene-lactide copolymer.
2. according to the described adsorbable hemostatic ligation clip of claim 1, it is characterized in that internal layer has the hole, being shaped as of hole is square or circular.
3. according to the described adsorbable hemostatic ligation clip of claim 1, it is characterized in that there is alternative dentation at the internal layer edge.
4. according to the described adsorbable hemostatic ligation clip of claim 1, it is characterized in that wherein, the intrinsic viscosity of described PPDO is 1.0-7.0dl/g.
5. according to the described adsorbable hemostatic ligation clip of claim 1, it is characterized in that, wherein, described in dioxy Ketohexamethylene-lactide copolymer, the unit mol ratio 95%-5% of dioxy Ketohexamethylene and lactide is 1.0-6.0dl/g to the intrinsic viscosity of dioxy Ketohexamethylene-lactide copolymer.
6. according to the described adsorbable hemostatic ligation clip of claim 5, it is characterized in that, wherein, described in dioxy Ketohexamethylene-lactide copolymer, to the unit mol ratio 80%-20% of dioxy Ketohexamethylene and lactide, be 2.0-4.0dl/g to the intrinsic viscosity of dioxy Ketohexamethylene-lactide copolymer.
7. according to the described adsorbable hemostatic ligation clip of claim 5, it is characterized in that, wherein, described PPDO or in dioxy Ketohexamethylene-lactide copolymer, to the unit mol ratio 70% of dioxy Ketohexamethylene and lactide, be 3.2dl/g to the intrinsic viscosity of dioxy Ketohexamethylene-lactide copolymer.
CN2006100516877A 2006-05-29 2006-05-29 Adsorbable hemostatic ligation clip Active CN101081310B (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102973988A (en) * 2012-12-19 2013-03-20 杭州铭众生物科技有限公司 Absorbable vessel ligature clamp and preparation method thereof
CN103006288A (en) * 2012-12-19 2013-04-03 杭州铭众生物科技有限公司 V-shaped vessel ligature clamp with single-layer structure and method for preparing V-shaped vessel ligature clamp
CN103462654A (en) * 2013-10-08 2013-12-25 王学建 Retaining clip for reconstructing skull base
CN103848979A (en) * 2011-07-04 2014-06-11 电子科技大学 P-dioxanone polymer as well as synthetic method and application thereof
CN106075543A (en) * 2016-06-24 2016-11-09 山东省药学科学院 A kind of adsorbable hemostatic ligation clip and preparation method thereof
CN107137755A (en) * 2017-06-07 2017-09-08 浙江微度医疗器械有限公司 A kind of hemostatic ligation clip that can quickly absorb
CN107981909A (en) * 2017-12-22 2018-05-04 山东赛克赛斯生物科技有限公司 Running fire Clip Applier and running fire clamp device
CN111084646A (en) * 2019-12-05 2020-05-01 北京天助畅运医疗技术股份有限公司 Absorbable hemostatic ligation clamp
CN114699566A (en) * 2022-04-08 2022-07-05 刘家起 Preparation method of absorbable ligation clip

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4744788A (en) * 1986-01-13 1988-05-17 Mercer Jr Leo C Method of using a surgical clip for cholangiography
GB0302098D0 (en) * 2003-01-29 2003-02-26 Univ London Improvements in and relating to surgical clips
CN1748802A (en) * 2005-08-04 2006-03-22 孙文善 Use of degradable material suture in acupoint burying

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103848979A (en) * 2011-07-04 2014-06-11 电子科技大学 P-dioxanone polymer as well as synthetic method and application thereof
CN103848979B (en) * 2011-07-04 2016-01-20 电子科技大学 P-Dioxane ketone polymer and synthetic method thereof and application
CN102973988B (en) * 2012-12-19 2014-05-07 杭州铭众生物科技有限公司 Absorbable vessel ligature clamp and preparation method thereof
CN102973988A (en) * 2012-12-19 2013-03-20 杭州铭众生物科技有限公司 Absorbable vessel ligature clamp and preparation method thereof
CN103006288B (en) * 2012-12-19 2014-06-18 杭州铭众生物科技有限公司 V-shaped vessel ligature clamp with single-layer structure and method for preparing V-shaped vessel ligature clamp
CN103006288A (en) * 2012-12-19 2013-04-03 杭州铭众生物科技有限公司 V-shaped vessel ligature clamp with single-layer structure and method for preparing V-shaped vessel ligature clamp
CN103462654A (en) * 2013-10-08 2013-12-25 王学建 Retaining clip for reconstructing skull base
CN106075543A (en) * 2016-06-24 2016-11-09 山东省药学科学院 A kind of adsorbable hemostatic ligation clip and preparation method thereof
CN106075543B (en) * 2016-06-24 2021-11-23 山东省药学科学院 Absorbable hemostatic ligation clamp and preparation method thereof
CN107137755A (en) * 2017-06-07 2017-09-08 浙江微度医疗器械有限公司 A kind of hemostatic ligation clip that can quickly absorb
CN107981909A (en) * 2017-12-22 2018-05-04 山东赛克赛斯生物科技有限公司 Running fire Clip Applier and running fire clamp device
CN107981909B (en) * 2017-12-22 2019-08-13 赛克赛斯生物科技股份有限公司 Running fire Clip Applier and running fire clamp device
CN111084646A (en) * 2019-12-05 2020-05-01 北京天助畅运医疗技术股份有限公司 Absorbable hemostatic ligation clamp
CN114699566A (en) * 2022-04-08 2022-07-05 刘家起 Preparation method of absorbable ligation clip
CN114699566B (en) * 2022-04-08 2022-12-20 海泽临床成果转化医学研究院(无锡)有限公司 Preparation method of absorbable ligation clip

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