CN103374208B - A kind of can the polymer materials and preparation method thereof of gradient degradation - Google Patents
A kind of can the polymer materials and preparation method thereof of gradient degradation Download PDFInfo
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- CN103374208B CN103374208B CN201210120920.8A CN201210120920A CN103374208B CN 103374208 B CN103374208 B CN 103374208B CN 201210120920 A CN201210120920 A CN 201210120920A CN 103374208 B CN103374208 B CN 103374208B
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- 238000006731 degradation reaction Methods 0.000 title claims abstract description 112
- 230000015556 catabolic process Effects 0.000 title claims abstract description 102
- 239000002861 polymer material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title description 20
- 210000000626 ureter Anatomy 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 32
- 229920003232 aliphatic polyester Polymers 0.000 claims abstract description 18
- 238000002844 melting Methods 0.000 claims abstract description 8
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- 239000000126 substance Substances 0.000 description 68
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- 238000000338 in vitro Methods 0.000 description 49
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- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 48
- 241000973497 Siphonognathus argyrophanes Species 0.000 description 47
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical group [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 description 47
- 229910052757 nitrogen Inorganic materials 0.000 description 47
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- 239000012634 fragment Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 10
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- 229940059574 pentaerithrityl Drugs 0.000 description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- VPVXHAANQNHFSF-UHFFFAOYSA-N 1,4-dioxan-2-one Chemical compound O=C1COCCO1 VPVXHAANQNHFSF-UHFFFAOYSA-N 0.000 description 4
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 4
- 229930012538 Paclitaxel Natural products 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
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- SORGMJIXNUWMMR-UHFFFAOYSA-N lanthanum(3+);propan-2-olate Chemical compound [La+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SORGMJIXNUWMMR-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
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- RCINICONZNJXQF-MZXODVADSA-N taxol Chemical compound O([C@@H]1[C@@]2(C[C@@H](C(C)=C(C2(C)C)[C@H](C([C@]2(C)[C@@H](O)C[C@H]3OC[C@]3([C@H]21)OC(C)=O)=O)OC(=O)C)OC(=O)[C@H](O)[C@@H](NC(=O)C=1C=CC=CC=1)C=1C=CC=CC=1)O)C(=O)C1=CC=CC=C1 RCINICONZNJXQF-MZXODVADSA-N 0.000 description 4
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- XUBKPYAWPSXPDZ-UHFFFAOYSA-N [Ba].OS(O)(=O)=O Chemical compound [Ba].OS(O)(=O)=O XUBKPYAWPSXPDZ-UHFFFAOYSA-N 0.000 description 3
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- AOJJSUZBOXZQNB-VTZDEGQISA-N 4'-epidoxorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-VTZDEGQISA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 2
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 2
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000001356 surgical procedure Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 230000002485 urinary effect Effects 0.000 description 2
- 210000001635 urinary tract Anatomy 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 208000032843 Hemorrhage Diseases 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 239000008118 PEG 6000 Substances 0.000 description 1
- -1 PEG10000 Polymers 0.000 description 1
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 description 1
- 229920002560 Polyethylene Glycol 3000 Polymers 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 1
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 1
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 description 1
- 208000004608 Ureteral Obstruction Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
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- 230000000975 bioactive effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000007906 compression Methods 0.000 description 1
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- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 210000004379 membrane Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000009521 phase II clinical trial Methods 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 230000002980 postoperative effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 208000037816 tissue injury Diseases 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- 230000003202 urodynamic effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- FBTUMDXHSRTGRV-ALTNURHMSA-N zorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(\C)=N\NC(=O)C=1C=CC=CC=1)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 FBTUMDXHSRTGRV-ALTNURHMSA-N 0.000 description 1
- 229960000641 zorubicin Drugs 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
- A61L17/06—At least partially resorbable materials
- A61L17/10—At least partially resorbable materials containing macromolecular materials
- A61L17/12—Homopolymers or copolymers of glycolic acid or lactic acid
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
Abstract
The invention discloses a kind of can the polymer materials of gradient degradation, described polymer materials is arranged by the aliphatic polyester of at least two kinds of different degradation speeds according to degradation speed order from low to high or from high to low and is formed by connecting by the mode of melting, described polymer materials can be made into can the wire rod of gradient degradation, sheet material, tubing and medicine controlled release carrier, specifically comprise suture line, medical dressing, adherence preventing material, hemostatic material, periodontal regenerative sheet, tissue renovation material is (as artificial dermis, joint prosthesis, nail, bone clamping plate), enhancement reticulated, pharmaceutical carrier, cartilaginous tissue cultivates support, support tube (comprises intravascular stent pipe, trachea bracket pipe, Esophageal Stent pipe and ureter rack tube), especially ureter rack tube, have a wide range of applications in absorbable material field, good economic worth and social effect can be produced.
Description
Technical field
The present invention relates to biomaterial for medical purpose and technical field, be specifically related to a kind of can the polymer materials and preparation method thereof of gradient degradation.
Background technology
The nonuniformity of polymkeric substance of gradient degradation can just require that the polymer degradation speed forming product different sites is different.The degradation speed of polymkeric substance is subject to the impact of multiple factor, as structure, molecular weight, composition etc.
The polymkeric substance of same composition, its degradation speed reduces along with the increase of molecular weight; Can by the aliphatic polyester regulating the kind of the ratio of different monomers and change initiator, consumption preparation has different composition; The degradation speed of polymkeric substance can increase along with the increase of polyglycolic acid content, increases along with the increase of hydrophilic segment content, thus reaches the object regulating degradation speed.
The degraded of aliphatic polyester is the hydrolysis of ester bond in essence, the product made by homogeneous material easily produces larger degraded fragment in degradation process, even degraded later stage material disintegration, capital makes troubles to the application in biomedicine, in order to address this problem, the present invention is made by degraded order " melting " by the aliphatic poly ester material of two or more different degradation speeds can the polymer materials of gradient degradation.
Can the polymer materials of gradient degradation can make can the wire rod of gradient degradation, sheet material, tubing and medicine controlled release carrier, specifically comprise suture line, medical dressing, adherence preventing material, hemostatic material, periodontal regenerative sheet, tissue renovation material is (as artificial dermis, joint prosthesis, nail, bone clamping plate), enhancement reticulated, pharmaceutical carrier, cartilaginous tissue cultivates support, support tube (comprises intravascular stent pipe, trachea bracket pipe, Esophageal Stent pipe and ureter rack tube), especially ureter rack tube, contrast medium can also be added as the one in barium sulfate and Operand.
Ureter rack tube is widely used in upper urinary venereal disease and becomes, in the urological surgeries such as kidney or ureter stone disease, Urinary injury, upper urinary tract reconstruction.Since double J pipe in 1978 comes out, substantially increased the success ratio of Upper urinary tract operation, the major function of ureter rack tube keeps ureteral unobstructed, and drainage of urine enters bladder.
The main component of the ureter rack tube of current application is the poly-aethylis carbamas of nonabsorable, silicon rubber and metallic substance, histocompatibility is poor, easy formation calculus, infection, hemorrhage and tissue injury, need second operation to remove the support tube of indwelling, cause health, spirit, multiple infringement economically to patient.
Ureter rack tube design emphasis be the aspects such as starting material, surface property, configuration design, desirable ureter rack tube should meet following some: biocompatibility is good; There is certain resistance to compression and stretch-proof characteristic, ureteral pressure and wriggling can be resisted, keep ureter unobstructed; Quality is soft, and smooth surface is calculus deposition not easily; Can absorbed themselves or discharge, do not need second operation tube drawing.Therefore, develop and a kind ofly do not need tube drawing and the support tube that can degrade voluntarily has important clinical value.The development of degradable ureter rack tube becomes the focus of researchist's concern gradually.
The domestic Hou Yu river seminar early stage work study inside and outside degradation characteristic of biodegradable material PLGA (80:20), result shows about 6 weeks this material degradation time.And inquired into the feasibility of PLGA (80:20) endoureteral stent in domesticated dog body, result shows that PLGA support tube biocompatibility is good, degradation time is suitable for, in urine, drainage effect still can, but support tube is comparatively hard and become fragile in degradation process, its exterior design, fixed form etc. are still needed research further and improving.
The ureter bracket PCLGA (20:60:20) studied afterwards is tested by animal muscle heeling-in, show to implant rear animal survival in good condition, local organization reaction is non-bacteria inflammation reaction, the requirement that the membrane wrapping thickness that when 12 weeks, surrounding materials fibers encapsulation layer thickness is starkly lower than U.S. material test proposition is less than 30 μm.Ureter rack tube is implanted in experiment, degradable in 12 weeks, and ureteral lumen is interior to be remained without material fragment, and the postoperative ureter inflammatory reaction of stenter to implant is disappeared gradually with material degradation.
In external form, this seminar once designed funnel shaped PCLGA (20:60:20) support tube, and result shows that this support tube biocompatibility is good, and degradation time is suitable for, have in epimere operation on ureter good in drainage effect.
Electrospinning is adopted again the PLGA of different ratios to be prepared into the ureter rack tube with nanofibrous structures recently, external degradation test in urine shows PLGA (50:50) disintegration in about 6 weeks, PLGA (70:30) disintegration in about 10 weeks, and PLGA (80:20) degradation time about 8 weeks.PLGA (80:20) and PLGA (50:50) meets the requirement of ureter rack tube to degradation time, but still there is the not change of support tube material entirety, and the probability of degrading everywhere is identical, the uncontrollable problem of degraded order.
External OlwenyEO etc. have studied the degradation time of PLGA (SR-PLGA80:20), and find the degradable need of this material about 3 months, degradation time is partially long, and biocompatibility is not so good.
The research such as LumiahoJ finds that SR-PLA96 ureter bracket can guarantee urine drainage, does not affect urodynamics; Nearly 3 months of its degradation time, before support tube is not degradable 12 weeks, ureter topical manifestations is epithelial proliferation, lamina propria oedema and a small amount of inflammatory cell infiltration, and ureteral inflammatory reaction is normal in the degradable rear recovery of support tube, shows that support tube Biocompatibility is good.
The ureter bracket of the development such as BenH.Chew is a kind of fibre reinforced composites, is made up of: 1) soft segment base body is made up of poly (l-lactic acid) and PEG two portions; 2) fibrous texture is made up of polyglycolic acid.Containing radial radiotransparen barium sulfate coil and knitted mesh, when Inside coil is degraded, knitted mesh and matrix also can be absorbed.Their research and development second and third in generation ureter rack tube owing to adding a large amount of coil in every one-inch flexible substrate, make its axially and radial strength be largely increased.The coat-thickness of s-generation support tube proximal part is larger, degraded can be made distally to start, avoid near-end to block.Degradation time is 4-7 week, and third generation ureter bracket degradation time is faster, is 2-4 week.
LingemanJE etc. are investigated a kind of biodegradable, maintain the interim ureter drainage stent (TUDS) of drainage 48h, gradually softening, Self-discharged, think that TUDS can effectively keep ureter drainage unobstructed in 48h after surgery by first phase and phase ii clinical trial; Major part patient tolerance is good, only has slight discomfort; Complication rate is low, and security is good.
Although the development of above-mentioned degradable ureter rack tube has achieved certain progress, but for some problems existed, as being all be prepared from by homogeneous material, the various piece degraded probability of support tube is consistent, degraded order is uncontrollable, may cause ureteral obstruction; Quality is comparatively hard, wetting ability and histocompatibility not good enough, easily cause inorganic salt at rack surface deposition, conjunctiva, bring larger hidden danger etc. to patient, illustrate also there is very large development space.
Preparation can the material of good biocompatibility of gradient degradation be that doctor and patient wish application always, in view of application disclosed technology cannot make meet Clinical practice requirement can the ureter rack tube of gradient degradation, until do not have related products to go on the market at present yet, the technology that the present invention adopts has filled up the blank in this field undoubtedly, has extraordinary market outlook.
Summary of the invention
The object of the present invention is to provide a kind of can the polymer materials of gradient degradation.
The invention discloses a kind of can the polymer materials of gradient degradation, described polymer materials is formed by connecting according to the degradation speed mode sequentially passing through melting from low to high or from high to low by the aliphatic polyester of at least two kinds of different degradation speeds.
In a preferred embodiment of the present invention, described polymer materials is formed by connecting according to the degradation speed mode sequentially passing through melting from low to high or from high to low by the aliphatic polyester of four kinds of different degradation speeds.
In a preferred embodiment of the present invention, described aliphatic polyester adopts aliphatic monomer to be polymerized under the effect of initiator and catalyzer, wherein said aliphatic monomer is D, L-rac-Lactide, L-rac-Lactide, glycollide, 6-caprolactone, valerolactone, hydroxyalkyl acid, Lanthanum Isopropoxide, to dioxanone, acid anhydrides, ortho acid, carbonic acid and sub-propyl alcohol, succsinic acid and butyleneglycol, the combination of one or more in hexanodioic acid and butyleneglycol, described initiator is selected from PEG200, PEG400, PEG600, PEG800, PEG1000, PEG1500, PEG2000, PEG3000, PEG4000, PEG6000, PEG8000, PEG10000, PEG20000, TriMethylolPropane(TMP), glycerol, tetramethylolmethane, the combination of one or more in eight hydroxyl cagelike silsesquioxanes, described catalyzer is zinc lactate, zinc acetate, zinc sulfate, Zinic stearass etc. contain salt and the vitriol oil of metallic zinc, tosic acid.
In a preferred embodiment of the present invention, the described preferred D of aliphatic monomer, L-rac-Lactide, L-rac-Lactide, glycollide, 6-caprolactone, the combination of one or more in the preferred PEG200 of described initiator, PEG4000, PEG10000, PEG20000, glycerol, tetramethylolmethane, the preferred zinc lactate of described catalyzer.
In a preferred embodiment of the present invention, the number-average molecular weight of polymkeric substance is 5,000-50 ten thousand, and degradation time was at 3 days-12 months.
In a preferred embodiment of the present invention, described polymer materials can be used for making can the wire rod of gradient degradation, sheet material, tubing and medicine controlled release carrier, is specially suture line, medical dressing, adherence preventing material, hemostatic material, periodontal regenerative sheet, tissue renovation material, enhancement reticulated, pharmaceutical carrier, cartilaginous tissue cultivate support, intravascular stent pipe, trachea bracket pipe, Esophageal Stent pipe and ureter rack tube.
Of the present invention can the preparation method of polymer materials of gradient degradation, comprise the following steps:
1) by the aliphatic polyester segment of described at least two kinds of different degradation speeds.
2) aliphatic polyester of described segment is arranged according to degradation speed order from low to high or from high to low.
3) aliphatic polyester arranged is connected by melting, with obtained described polymer materials.
Of the present invention can the preparation method of polymer materials of gradient degradation, following method can also be taked to process, and concrete steps are as follows:
1) by the aliphatic polyester heating materials melting of at least two or more different degradation speeds or melt with after dissolution with solvents.
2) require according to degradation rate the die cavity aliphatic polyester segmentation arranged being injected forcing machine, order is extruded and get final product.
If with being melted into machinable material after dissolution with solvents, need to increase the step vacuumizing and add heat extraction and dissolve.
Of the present invention can the polymer materials of gradient degradation, comprise and the aliphatic poly ester material of at least two or more different degradation speeds is made the consistent conduit of bore, the conduit section of shearing is become the run of 1-10cm, according to degradation speed order arrangement from low to high or from high to low, finally the mode of run by hot melt or electric smelting linked together, being formed can the ureter rack tube of gradient degradation.
The invention has the beneficial effects as follows:, this polymer materials can be made can the wire rod of gradient degradation, sheet material, tubing and medicine controlled release carrier, specifically comprise suture line, medical dressing, adherence preventing material, hemostatic material, periodontal regenerative sheet, tissue renovation material is (as artificial dermis, joint prosthesis, nail, bone clamping plate), enhancement reticulated, pharmaceutical carrier, cartilaginous tissue cultivates support, support tube (comprises intravascular stent pipe, trachea bracket pipe, Esophageal Stent pipe and ureter rack tube), especially ureter rack tube, degradation time is desirable, good biocompatibility, conform to user demand, there is larger economic worth and social value.
Accompanying drawing explanation
Fig. 1 is that a preferred embodiment of the present invention can remaining useful length graphic representation in the ureter rack tube degradation time of the gradient degradation ureter rack tube degradation process of gradient degradation of having degraded in 4 weeks from 1 week;
Fig. 2 be the another preferred embodiment of the present invention can the ureter rack tube degradation time of gradient degradation from 2 weeks, remaining useful length graphic representation in the ureter rack tube degradation process of the gradient degradation of having degraded in 5 weeks;
Fig. 3 be the another preferred embodiment of the present invention can the ureter rack tube degradation time of gradient degradation from 3 weeks, remaining useful length graphic representation in the ureter rack tube degradation process of the gradient degradation of having degraded in 5 weeks;
Fig. 4 be the another preferred embodiment of the present invention can the ureter rack tube degradation time of gradient degradation from 4 weeks, remaining useful length graphic representation in the ureter rack tube degradation process of the gradient degradation of having degraded in 6 weeks.
Embodiment
one, there is the synthetic example of the polymer materials of different degradation speed
Embodiment 1
Take 0.833gD respectively, L-rac-Lactide, 0.167g glycollide, 0.08gPEG200,0.001g zinc acetate, adds in vitro, add a magnetic stir bar again, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts the polymkeric substance that 24h obtains line style.
Embodiment 2
Take 0.555gL-rac-Lactide respectively, 0.176g 6-caprolactone, 0.08gPEG200,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts the polymkeric substance that 24h obtains line style.
Embodiment 3
Take 0.833gD respectively, L-rac-Lactide, 0.126g glycollide, 0.041g 6-caprolactone, 0.08gPEG4000,0.001g zinc sulfate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts the polymkeric substance that 24h obtains line style.
Embodiment 4
Take 0.745gD respectively, L-rac-Lactide, 0.171g glycollide, 0.084g 6-caprolactone, 0.08gPEG10000,0.001g Zinic stearas, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts the polymkeric substance that 24h obtains line style.
Embodiment 5
Take 0.833gD respectively, L-rac-Lactide, 0.126g glycollide, 0.041g 6-caprolactone, 0.05g glycerol, 0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts 24h and obtains star-like polymkeric substance.
Embodiment 6
Take 0.745gD respectively, L-rac-Lactide, 0.171g glycollide, 0.084g 6-caprolactone, 0.03g tetramethylolmethane, 0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts 24h and obtains star-like polymkeric substance.
Embodiment 7
Take 0.833gD respectively, L-rac-Lactide, 0.126g glycollide, 0.041g valerolactone, 0.08gPEG400,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts the polymkeric substance that 36h obtains line style.
Embodiment 8
Take 0.833gD respectively, L-rac-Lactide, 0.126g glycollide, 0.041g Lanthanum Isopropoxide, 0.08gPEG4000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts the polymkeric substance that 36h obtains line style.
Embodiment 9
Take 0.833gD respectively, L-rac-Lactide, 0.126g glycollide, 0.041g to dioxanone, 0.08gPEG10000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts the polymkeric substance that 36h obtains line style.
Embodiment 10
Take 0.8g hydroxybutyric acid respectively, 0.1g succsinic acid, 0.1g butyleneglycol, 0.001g tosic acid, add in single port flask, then add a magnetic stir bar, under decompression state, in the oil bath pan of 140 DEG C, react the polymkeric substance that 36h obtains line style.
Embodiment 11
Take 0.8g hydroxypentanoic acid respectively, 0.1g hexanodioic acid, 0.1g butyleneglycol, the 0.001g vitriol oil, add in single port flask, then add a magnetic stir bar, under decompression state, in the oil bath pan of 140 DEG C, react the polymkeric substance that 36h obtains line style.
Embodiment 12
Take 0.7g ortho acid respectively, 0.15g carbonic acid, the sub-propyl alcohol of 0.15g, 0.001gDCC/DMAP, adds in vitro, then adds a magnetic stir bar, reacts the polymkeric substance that 36h obtains line style under decompression state in the oil bath pan of 150 DEG C.
Embodiment 13
Take 0.745gD respectively, L-rac-Lactide, 0.171g glycollide, 0.084g 6-caprolactone, 0.08gPEG4000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 150 DEG C reacts the polymkeric substance that 36h obtains line style.
Embodiment 14
Take 0.652gD respectively, L-rac-Lactide, 0.262g glycollide, 0.086g 6-caprolactone, 0.08gPEG4000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 150 DEG C reacts the polymkeric substance that 36h obtains line style.
Embodiment 15
Take 0.555gD respectively, L-rac-Lactide, 0.269g glycollide, 0.176g 6-caprolactone, 0.08gPEG4000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 150 DEG C reacts the polymkeric substance that 36h obtains line style.
Embodiment 16
Take 0.833gD respectively, L-rac-Lactide, 0.126g glycollide, 0.041g 6-caprolactone, 0.08gPEG10000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 150 DEG C reacts the polymkeric substance that 36h obtains line style.
Embodiment 17
Take 0.745gD respectively, L-rac-Lactide, 0.171g glycollide, 0.084g 6-caprolactone, 0.08gPEG10000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 150 DEG C reacts the polymkeric substance that 36h obtains line style.
Embodiment 18
Take 0.5g succinic acid respectively, 0.5g toxilic acid, 0.05g glycerol, 0.001g zinc lactate, adds in vitro, then adds a magnetic stir bar, reacts 36h and obtain star-like polymkeric substance under reduced pressure in the oil bath pan of 150 DEG C.
Embodiment 19
Take 0.745gD respectively, L-rac-Lactide, 0.171g glycollide, 0.084g 6-caprolactone, 0.03g tetramethylolmethane, 0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 150 DEG C reacts 36h and obtains star-like polymkeric substance.
Embodiment 20
Take 0.745gD respectively, L-rac-Lactide, 0.171g glycollide, 0.084g 6-caprolactone, 0.08gPEG800,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts the polymkeric substance that 36h obtains line style.
Embodiment 21
Take 0.652gD respectively, L-rac-Lactide, 0.262g glycollide, 0.086g 6-caprolactone, 0.08gPEG200,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts the polymkeric substance that 36h obtains line style.
Embodiment 22
Take 0.745gD respectively, L-rac-Lactide, 0.171g glycollide, 0.084g 6-caprolactone, 0.08gPEG1000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts the polymkeric substance that 36h obtains line style.
Embodiment 23
Take 0.833gD respectively, L-rac-Lactide, 0.126g glycollide, 0.041g Lanthanum Isopropoxide, 0.08gPEG10000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts the polymkeric substance that 36h obtains line style.
Embodiment 24
Take 0.745gD respectively, L-rac-Lactide, 0.171g glycollide, 0.084g to dioxanone, 0.08gPEG10000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts the polymkeric substance that 36h obtains line style.
Embodiment 25
Take 0.745gD respectively, L-rac-Lactide, 0.171g glycollide, 0.084g 6-caprolactone, 0.03g tetramethylolmethane, 0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts 36h and obtains star-like polymkeric substance.
Embodiment 26
Take 0.745gD respectively, L-rac-Lactide, 0.171g glycollide, 0.084g 6-caprolactone, 0.02g eight hydroxyl cagelike silsesquioxane, 0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts 36h and obtains star-like polymkeric substance.
Embodiment 27
Take 0.652gD respectively, L-rac-Lactide, 0.262g glycollide, 0.086g 6-caprolactone, 0.08gPEG1500,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 28
Take 0.555gD respectively, L-rac-Lactide, 0.269g glycollide, 0.176g 6-caprolactone, 0.08gPEG200,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 29
Take 0.745gD respectively, L-rac-Lactide, 0.171g glycollide, 0.084g 6-caprolactone, 0.08gPEG4000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 30
Take 0.652gD respectively, L-rac-Lactide, 0.262g glycollide, 0.086g 6-caprolactone, 0.08gPEG4000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 31
Take 0.555gD respectively, L-rac-Lactide, 0.269g glycollide, 0.176g 6-caprolactone, 0.08gPEG4000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 32
Take 0.652gD respectively, L-rac-Lactide, 0.262g glycollide, 0.086g 6-caprolactone, 0.08gPEG10000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 33
Take 0.652gD respectively, L-rac-Lactide, 0.262g glycollide, 0.086g 6-caprolactone, 0.05g glycerol, 0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts 48h and obtains star-like polymkeric substance.
Embodiment 34
Take 0.555gD respectively, L-rac-Lactide, 0.269g glycollide, 0.176g 6-caprolactone, 0.05g glycerol, 0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts 48h and obtains star-like polymkeric substance.
Embodiment 35
Take 0.652gD respectively, L-rac-Lactide, 0.262g glycollide, 0.086g 6-caprolactone, 0.03g tetramethylolmethane, 0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 140 DEG C reacts 48h and obtains star-like polymkeric substance.
Embodiment 36
Take 0.555gD respectively, L-rac-Lactide, 0.269g glycollide, 0.176g 6-caprolactone, 0.08gPEG200,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 150 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 37
Take 0.745gD respectively, L-rac-Lactide, 0.171g glycollide, 0.084g 6-caprolactone, 0.08gPEG4000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 150 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 38
Take 0.652gD respectively, L-rac-Lactide, 0.262g glycollide, 0.086g 6-caprolactone, 0.08gPEG3000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 150 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 39
Take 0.555gD respectively, L-rac-Lactide, 0.269g glycollide, 0.176g to dioxanone, 0.08gPEG2000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 150 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 40
Take 0.833gD respectively, L-rac-Lactide, 0.126g glycollide, 0.041g 6-caprolactone, 0.08gPEG10000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 150 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 41
Take 0.745gD respectively, L-rac-Lactide, 0.171g glycollide, 0.084g 6-caprolactone, 0.08gPEG10000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 150 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 42
Take 0.555gD respectively, L-rac-Lactide, 0.269g glycollide, 0.176g 6-caprolactone, 0.05g TriMethylolPropane(TMP), 0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 150 DEG C reacts 48h and obtains star-like polymkeric substance.
Embodiment 43
Take 0.555gD respectively, L-rac-Lactide, 0.269g glycollide, 0.176g Lanthanum Isopropoxide, 0.03g tetramethylolmethane, 0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 150 DEG C reacts 48h and obtains star-like polymkeric substance.
Embodiment 44
Take 0.652gD respectively, L-rac-Lactide, 0.262g glycollide, 0.086g 6-caprolactone, 0.08gPEG200,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 45
Take 0.555gD respectively, L-rac-Lactide, 0.269g glycollide, 0.176g 6-caprolactone, 0.08gPEG6000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 46
Take 0.555gD respectively, L-rac-Lactide, 0.269g glycollide, 0.176g 6-caprolactone, 0.08gPEG8000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 47
Take 0.833gL-rac-Lactide respectively, 0.126g glycollide, 0.041g 6-caprolactone, 0.08gPEG10000,0.001g zinc lactate, adds in vitro, add a magnetic stir bar again, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 48
Take 0.555gD respectively, L-rac-Lactide, 0.269g glycollide, 0.176g 6-caprolactone, 0.08gPEG10000,0.001g zinc lactate, add in vitro, then add a magnetic stir bar, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 49
Take 0.833gL-rac-Lactide respectively, 0.126g glycollide, 0.041g 6-caprolactone, 0.08gPEG20000,0.001g zinc lactate, adds in vitro, add a magnetic stir bar again, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 50
Take 0.745gL-rac-Lactide respectively, 0.171g glycollide, 0.084g 6-caprolactone, 0.08gPEG20000,0.001g zinc lactate, adds in vitro, add a magnetic stir bar again, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts the polymkeric substance that 48h obtains line style.
Embodiment 51
Take 0.652gL-rac-Lactide respectively, 0.262g glycollide, 0.086g 6-caprolactone, 0.08gPEG20000,0.001g zinc lactate, adds in vitro, add a magnetic stir bar again, vacuumize/inflated with nitrogen circulates 3 times, and under vacuumized conditions sealing by fusing test tube mouth, the oil bath pan putting into 160 DEG C reacts the polymkeric substance that 48h obtains line style.
two, the preparation of the tubing ureter rack tube of gradient degradation and degradation experiment embodiment
Embodiment 52
Degradation time from 1 week, the preparation of the ureter rack tube of the gradient degradation of having degraded in 4 weeks:
Polymkeric substance is synthesized according to the method in embodiment 35,28,30,41, the conduit that size is 5F is extruded into respectively with tight conduit forcing machine, cut into the long pipe for 5cm of each conduit, adopt plastic welding machine by every section successively heat melt and be connected to become the long pipe of 20cm, after polishing grinding, be defined as support tube by the sequence of one end to the other end according to the sequence from front to back of sample in embodiment.
Gradient degradation experiment is as follows:
A complete ureter rack tube is placed in the glass reagent bottle of 125mL, add the urine of 30mL, be placed in the constant temperature low rate mixing water-bath of 37 DEG C, six sampling time points (the 1st, 2,3,4,5,6 week) established by sample, each time point establishes three parallel group, each sample all adopts independent container, and the degraded medium in container is changed once every day.
In the time point observed and recorded sample topography of setting and the change of degraded fragment, in result display degradation process, sample becomes white from transparent, and degrade from the far-end of sample, extend to near-end gradually, degraded fragment is 0.5-2mm, differs in size.PH meter measures the pH value of degraded medium between 7.0-7.4.In the point in time sampling of setting, length measurment is carried out to the sample not containing collapsed portion taken out and remaining support tube, regulation useful length is proximally arrive far-end to have degraded out the length of intact stent pipe at fragment position, and three samples of each time point are averaged.The degradation time of result display ureter rack tube is from the 1st weekend, and the 4th week terminates (experimental result is shown in Fig. 1).
Embodiment 53
Degradation time from 2 weeks, the preparation of the ureter rack tube of the gradient degradation of having degraded in 5 weeks:
Polymkeric substance is synthesized according to the method in embodiment 34,28,30,14,17,24, the conduit that size is 4F is extruded into respectively with tight conduit forcing machine, cut into the long pipe for 5cm of each conduit, adopt plastic welding machine by every section successively heat melt and be connected to become the long pipe of 30cm, after polishing grinding, be defined as support tube by the sequence of one end to the other end according to the sequence from front to back of sample in embodiment.
Gradient degradation experiment is as follows:
A complete ureter rack tube is placed in the glass reagent bottle of 125mL, add the urine of 30mL, be placed in the constant temperature low rate mixing water-bath of 37 DEG C, six sampling time points (the 1st, 2,3,4,5,6 week) established by sample, each time point establishes three parallel group, each sample all adopts independent container, and the degraded medium in container is changed once every day.
In the time point observed and recorded sample topography of setting and the change of degraded fragment, in result display degradation process, sample becomes white from transparent, and degrade from the far-end of sample, extend to near-end gradually, degraded fragment is 0.5-2mm, differs in size.PH meter measures the pH value of degraded medium between 7.0-7.4.In the point in time sampling of setting, length measurment is carried out to the sample not containing collapsed portion taken out and remaining support tube, regulation useful length is proximally arrive far-end to have degraded out the length of intact stent pipe at fragment position, and three samples of each time point are averaged.The degradation time of result display ureter rack tube was from the 2nd week, and the 5th week terminates (experimental result is shown in Fig. 2).
Embodiment 54
Degradation time from 3 weeks, the preparation of the ureter rack tube of the gradient degradation of having degraded in 5 weeks:
Polymkeric substance is synthesized according to the method in embodiment 31,15,38,32,17,16,24,23, add moderate amount of sulfuric acid barium, the conduit that size is 6F is extruded into respectively with tight conduit forcing machine, cut into the long pipe for 5cm of each conduit, adopt plastic welding machine by every section successively heat melt and be connected to become the long pipe of 40cm, after polishing grinding, be defined as support tube by the sequence of one end to the other end according to the sequence from front to back of sample in embodiment.
Gradient degradation experiment is as follows:
A complete ureter rack tube is placed in the glass reagent bottle of 125mL, add the urine of 30mL, be placed in the constant temperature low rate mixing water-bath of 37 DEG C, six sampling time points (the 1st, 2,3,4,5,6 week) established by sample, each time point establishes three parallel group, each sample all adopts independent container, and the degraded medium in container is changed once every day.
In the time point observed and recorded sample topography of setting and the change of degraded fragment, in result display degradation process, sample becomes white from transparent, and degrade from the far-end of sample, extend to near-end gradually, degraded fragment is 0.5-2mm, differs in size.PH meter measures the pH value of degraded medium between 7.0-7.4.In the point in time sampling of setting, length measurment is carried out to the sample not containing collapsed portion taken out and remaining support tube, regulation useful length is proximally arrive far-end to have degraded out the length of intact stent pipe at fragment position, and three samples of each time point are averaged.The degradation time of result display ureter rack tube was from the 3rd week, and the 5th week terminates (experimental result is shown in Fig. 3).
Embodiment 55
Degradation time from 4 weeks, the preparation of the ureter rack tube of the gradient degradation of having degraded in 6 weeks:
Polymkeric substance is synthesized according to the method in embodiment 36,21,44,29,13,37,16,40,23,47, add moderate amount of sulfuric acid barium, the conduit that size is 8F is extruded into respectively with tight conduit forcing machine, cut into the long pipe for 5cm of each conduit, adopt plastic welding machine by every section successively heat melt and be connected to become the long pipe of 50cm, after polishing grinding, be defined as support tube by the sequence of one end to the other end according to the sequence from front to back of sample in embodiment.
Gradient degradation experiment is as follows:
A complete ureter rack tube is placed in the glass reagent bottle of 125mL, add the urine of 30mL, be placed in the constant temperature low rate mixing water-bath of 37 DEG C, six sampling time points (the 1st, 2,3,4,5,6 week) established by sample, each time point establishes three parallel group, each sample all adopts independent container, and the degraded medium in container is changed once every day.
In the time point observed and recorded sample topography of setting and the change of degraded fragment, in result display degradation process, sample becomes white from transparent, and degrade from one end of sample, extend to the other end gradually, degraded fragment is 0.5-2mm, differs in size.PH meter measures the pH value of degraded medium between 7.0-7.4.In the point in time sampling of setting, length measurment is carried out to the sample not containing collapsed portion taken out and remaining support tube, regulation useful length is proximally arrive far-end to have degraded out the length of intact stent pipe at fragment position, and three samples of each time point are averaged.The degradation time of result display ureter rack tube was from the 4th week, and the 6th week terminates (experimental result is shown in Fig. 4).
Three
, gradient degradation the preparation of microballoon of controlled bioactive molecule release
Embodiment 56
The preparation of the gradient degradation microballoon of the loading liquifier Zorubicin that degradation time has been degraded in 3 months:
Synthesizing polymkeric substance according to the method in embodiment 40,47,51, is 1g according to total polymer mass, and the mass ratio of three kinds of polymkeric substance is 1:1:1, is dissolved in 20mL methylene dichloride, adds the pidorubicin of recipe quantity, ultrasonic dissolution, is organic phase; 100mL aqueous phase is certain density polyvinyl alcohol water solution, and ice-water bath keeps 0 DEG C.At (800 ± 10) rmin
-1under agitation condition, organic phase is slowly injected aqueous phase, continue to be stirred to after organic phase volatilizees completely, with 0.45 μm of millipore filtration collected by suction microballoon, distilled water wash, is dried to constant weight.
Drug release result shows: in initial 24h, drug release rate is 6.06%, a month pidorubicin is afterwards slow sustained release from microballoon, 30d adds up release and reaches 36.19%, and can discharge further, 3 month to date releases reach 91.36%, and the microballoon of visible gained meets the requirement of slow release long-acting.
Embodiment 57
The preparation of the paclitaxel loaded gradient degradation microballoon that degradation time has been degraded in 6 months:
Synthesizing polymkeric substance according to the method in embodiment 48,50,49, is 1g according to total polymer mass, and the mass ratio of three kinds of polymkeric substance is 1:1:1, is dissolved in 20mL methylene dichloride, adds the taxol of recipe quantity, ultrasonic dissolution, is organic phase; 100mL aqueous phase is certain density polyvinyl alcohol water solution, and ice-water bath keeps 0 DEG C.At (800 ± 10) rmin
-1under agitation condition, organic phase is slowly injected aqueous phase, continue to be stirred to after organic phase volatilizees completely, with 0.45 μm of millipore filtration collected by suction microballoon, distilled water wash, is drying to obtain.
Drug release result shows: in initial 24h, drug release rate is 4.17%, a month taxol is afterwards slow sustained release from microballoon, 30d adds up release and reaches 23.49%, 3 month to date releases reach 51.86%, and can discharge further, until 6 months time, taxol release is complete.
By known with the contrast of embodiment 56, by the combination of the polymkeric substance of different degradation speed, obtain desirable sustained-release micro-spheres.
four, the preparation of the sheet material-hemostasis cloth of gradient degradation
Embodiment 58
Degradation time from the 3rd day, the preparation of the hemostasis cloth of the gradient degradation of having degraded in 15 days:
Synthesize polymkeric substance according to the method in embodiment 2,7,28, add moderate amount of sulfuric acid barium, add organic solvent (methylene dichloride or trichloromethane) and dissolve, put into plastics suction mould, vacuumize and add heat extraction organic solvent, matched moulds hot pressing and get final product.
Embodiment 59
Degradation time from the 10th day, the preparation of the hemostasis cloth of the gradient degradation of having degraded in 30 days:
Synthesize polymkeric substance according to the method in embodiment 27,14,23, add organic solvent (methylene dichloride or trichloromethane) and dissolve, put into plastics suction mould, vacuumize and add heat extraction organic solvent, matched moulds hot pressing and get final product.
five, the wire rod-sutural preparation of gradient degradation
Embodiment 60
Degradation time from the 10th day, the sutural preparation of the gradient degradation of having degraded in 30 days:
Synthesize polymkeric substance according to the method in embodiment 27,14,23, add organic solvent (methylene dichloride or trichloromethane) and dissolve, click and enter in die cavity by accurate adhesive supplier order, reeling off raw silk from cocoons while heating under vacuum removing organic solvent cools and get final product.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize specification sheets of the present invention and accompanying drawing content to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (2)
1. one kind can the polymer materials of gradient degradation, it is characterized in that, described polymer materials is arranged by the aliphatic polyester of at least two kinds of different degradation speeds according to degradation speed order from low to high or from high to low and is formed by connecting by the mode of melting, specifically comprises the following steps:
1) by the aliphatic polyester segment of described at least two kinds of different degradation speeds;
2) aliphatic polyester of described segment is arranged according to degradation speed order from low to high or from high to low;
3) aliphatic polyester arranged is connected by melting, with obtained described polymer materials.
2. polymer materials according to claim 1, it is characterized in that, comprise and the aliphatic poly ester material of at least two kinds of different degradation speeds is made the consistent conduit of bore, the conduit section of shearing is become the run of 1-10cm, according to degradation speed order arrangement from low to high or from high to low, finally the mode of run by hot melt or electric smelting linked together, being formed can the ureter rack tube of gradient degradation.
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| CN201210120920.8A CN103374208B (en) | 2012-04-24 | 2012-04-24 | A kind of can the polymer materials and preparation method thereof of gradient degradation |
| PCT/CN2012/000560 WO2013159244A1 (en) | 2012-04-24 | 2012-04-26 | Polymer material capable of gradient degradation and preparation method therefor |
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| CN104689367B (en) * | 2015-03-17 | 2017-01-11 | 浙江奥可生医疗器械有限公司 | Absorbable skin suturing nail and preparation method thereof |
| CN105903090B (en) * | 2016-05-11 | 2019-03-19 | 山东省药学科学院 | A kind of polyglycolic acid-polycaprolactone membrane and its preparation method and application |
| CN106565942A (en) * | 2016-10-21 | 2017-04-19 | 上海航天设备制造总厂 | Preparing method of POSS modified poly-butylene succinate |
| CN112386747B (en) * | 2017-06-02 | 2022-04-12 | 天津工业大学 | Ureteral stent tube with shape memory function and preparation method and application thereof |
| EP3670567A4 (en) * | 2017-08-17 | 2021-06-02 | Toray Industries, Inc. | Polyester copolymer and method for producing same |
| EP3727194A4 (en) * | 2017-12-22 | 2021-09-29 | Poly-Med, Inc. | Tubular implants with controlled biodegradation |
| CN112472873A (en) * | 2018-09-23 | 2021-03-12 | 湖南博隽生物医药有限公司 | Preparation method of artificial skin material |
| CN110698656A (en) * | 2019-10-12 | 2020-01-17 | 西安交通大学 | Synthesis method and application of low-temperature melting drug sustained-release medical polymer material |
| CN116212124B (en) * | 2023-05-09 | 2023-08-18 | 杭州糖吉医疗科技有限公司 | Intragastric balloon degradable self-closing valve and preparation method and application thereof |
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| US6319264B1 (en) * | 1998-04-03 | 2001-11-20 | Bionx Implants Oy | Hernia mesh |
| EP1493436A1 (en) * | 2003-06-27 | 2005-01-05 | Ethicon, Inc. | Compositions for parenteral administration and sustained-release of therapeutic agents |
| WO2008035088A2 (en) * | 2006-09-23 | 2008-03-27 | The University Of Nottingham | Degradable composite |
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