CN103739810A - Degradable pipeline material and preparation method thereof - Google Patents
Degradable pipeline material and preparation method thereof Download PDFInfo
- Publication number
- CN103739810A CN103739810A CN201310720856.1A CN201310720856A CN103739810A CN 103739810 A CN103739810 A CN 103739810A CN 201310720856 A CN201310720856 A CN 201310720856A CN 103739810 A CN103739810 A CN 103739810A
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- China
- Prior art keywords
- degradable
- polylactic acid
- pipeline
- preparation
- dimethylacetamide
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4283—Hydroxycarboxylic acid or ester
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a degradable pipeline material and a preparation method thereof. The degradable pipeline material is synthesized from 100 parts by weight of polyisocyanate and 60-100 parts by weight of polylactic acid-polyethylene glycol copolymer. The preparation method comprises the following steps of heating the polylactic acid-polyethylene glycol copolymer for water removal under reduced pressure, then adding the solvent N,N-dimethylacetamide and the polyisocyanate, stirring at 80 DEG C for ten hours under the protection of nitrogen, next, adding the catalyst stannous octoate and the chain extender 1,4-butanediol, continuing a chain-extending reaction for ten hours, precipitating the product with water to obtain white solid, carrying out suction filtration and drying, and then dissolving with N,N-dimethylacetamide to form a film, and drying in a vacuum oven for later use. The degradable pipeline material has the characteristics that polylactic acid is introduced into the polyurethane polymer in the form of the copolymer so that a polyurethane material good in degradability can be obtained.
Description
?
Technical field
The present invention relates to material and preparation method thereof for a kind of degradable pipeline.
Background technology
In recent years, along with the development of biomedical and polymer material science, Degradable Biomedical Materials is just causing people's interest more and more widely.At pharmaceutical sanitary field, Degradable Biomedical Materials has obtained Devoting Major Efforts To Developing, be widely used in suture line in body, " human tissue engineering " material, drug release carrier, surgery with fields such as bonesetting materials, especially aspect the form reparation of human tissue engineering and reconstruction, having a extensive future.
Poly(lactic acid) and tissue have good biocompatibility, can not cause tissue inflammation, without characteristics such as obvious rejections.Poly(lactic acid) is degraded and is very seriously existed the multiple DeRs such as Heat of Hydrolysis degraded of ester bond and the palliating degradation degree of the higher poly(lactic acid) of spinning temperature more macromolecule is lower in melt-spinning process.So too fast due to degraded of the poly(lactic acid) obtaining in human body, mechanical property reduces, and can not meet the requirement to poly(lactic acid) in modern medicine.
Summary of the invention
For existing technological deficiency, the invention provides material and preparation method thereof for a kind of degradable pipeline.
A degradable pipeline material, is synthesized by following material:
Polyisocyanates 100 weight parts
Polylactic acid poly glycol copolymer 60-100 weight part
Preferably, described polyisocyanates is selected from a kind of in TDI, MDI and PAPI.
The preparation method of aqueous polyurethane of the present invention, comprises the following steps:
After polylactic acid poly glycol copolymer heating decompression is dewatered, add solvent N,N-dimethylacetamide and polyisocyanates; under nitrogen protection, 80 ℃ are stirred ten hours; then add the sub-tin of octoate catalyst and chainextender l, 4-butyleneglycol, continues chain extending reaction 10 hours.Product water precipitation, obtains white solid, and suction filtration is dried, then film forming after dissolving by N,N-dimethylacetamide, dried for standby in vacuum drying oven.
The preparation method of polylactic acid poly glycol copolymer:
B1, by different proportionings, calculate required raw materials quality, then take the lactic acid of polyoxyethylene glycol and 10-30 times mole in reaction flask, then in flask, add toluene, concussion, then reaction flask is put on Rotary Evaporators and removes moisture and toluene, Temperature Setting is 60-80 ℃.
B2, until the toluene evaporates in flask is clean, takes off flask, puts into catalyzer, in the silicone oil bath of 100 ℃, vacuumizes two hours, and toluene and moisture remaining in reactant are removed;
B3, exhaust vacuum after, close vacuum valve, be warming up to 140 ℃, react and within 20 hours, obtain above polylactic acid poly glycol copolymer;
B4, by the reactant cool to room temperature in flask, add trichloromethane with lysate, with ether sedimentation, suction filtration obtains white thickness circle; Dry after 24 hours in the baking oven of 60 ℃, continue in 60 ℃ of vacuum drying ovens dry 24 hours, to go out wherein residual ether and trichloromethane; Obtain pure polylactic acid poly glycol copolymer.
The number-average molecular weight of described polyoxyethylene glycol is between 1000-3000.
Degradable pipeline of the present invention, is introduced poly(lactic acid) in polyether polyols with reduced unsaturation by the form of multipolymer with material, has obtained the polyurethane material with better degradation property.
Embodiment
Below in conjunction with specific embodiment, further describe the present invention, advantage and disadvantage of the present invention will be more clear along with description.But these embodiment are only exemplary, scope of the present invention are not formed to any restriction.It will be understood by those skilled in the art that lower without departing from the spirit and scope of the present invention and can the details of technical solution of the present invention and form be modified or be replaced, but these modifications and replacement all fall within the scope of protection of the present invention.
Polyoxyethylene glycol A, number-average molecular weight 1500, Xi Bao biomaterial company limited;
Polyoxyethylene glycol B, number-average molecular weight 2000, Xi Bao biomaterial company limited;
Polyoxyethylene glycol C, number-average molecular weight 3000, Xi Bao biomaterial company limited;
Lactic acid, Liaoning Tianyuan biomaterial company limited.
Degradation experiment:
Sample is made to film, make 1 * 1cm
2the sample of size, dry 24h in the vacuum drying oven of 80 ℃, takes out and claims its quality for shouting, then sample is placed in to the water of 100 ℃, every same time, changes a water, and take out a slice sample, with thieving paper, blot surface-moisture, in the vacuum drying oven of 80 ℃, dry 24h, claims its residual mass.
Sample is placed in to the 10ml test tube of the phosphate buffer soln that pH=7.4 is housed, and test tube is placed in to the water bath with thermostatic control of 37 ℃, every 96h, change a water, and take out a slice sample, dry 24h in the vacuum drying oven of 80 ℃, taking-up is weighed, and calculates rate of weight loss.
Embodiment 1
Polyoxyethylene glycol A and lactic acid mol ratio: 1:30, according to the aforesaid preparation method of the present invention, obtain polylactic acid poly glycol copolymer A.
Embodiment 2
Polyoxyethylene glycol B and lactic acid mol ratio: 1:20, according to the aforesaid preparation method of the present invention, obtain polylactic acid poly glycol copolymer B.
Embodiment 3
Polyoxyethylene glycol C and lactic acid mol ratio: 1:10, according to the aforesaid preparation method of the present invention, obtain polylactic acid poly glycol copolymer C.
Embodiment 4-7
After polylactic acid poly glycol copolymer heating decompression is dewatered, add solvent N,N-dimethylacetamide and polyisocyanates; under nitrogen protection, 80 ℃ are stirred ten hours; then add the sub-tin of octoate catalyst and chainextender l, 4-butyleneglycol, continues chain extending reaction 10 hours.Product water precipitation, obtains white solid, and suction filtration is dried, then film forming after dissolving by N,N-dimethylacetamide, dry in vacuum drying oven, obtains degradable pipeline material.
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| TDI | 100 | 100 | ||
| MDI | 100 | 100 | ||
| Polylactic acid poly polyol copolymer A | 56.2 | |||
| Polylactic acid poly polyol copolymer B | 82.3 | 95.2 | ||
| Polylactic acid poly polyol copolymer C | 89.4 | |||
| Rate of weight loss (12h) | 12.45% | 15.59% | 13.89% | 18.52% |
| Rate of weight loss (24h) | 25.61% | 28.36% | 24.11% | 33.31% |
| Rate of weight loss (36h) | 32.56% | 37.12% | 31.02% | 41.02% |
Claims (3)
1. a degradable pipeline material, is characterized in that, described degradable pipeline is synthesized by following material with material:
Polyisocyanates 100 weight parts
Polylactic acid poly glycol copolymer 60-100 weight part.
2. a kind of degradable pipeline material according to claim 1, is characterized in that, described polyisocyanates is selected from a kind of in TDI, MDI and PAPI.
3. the preparation method of material for degradable pipeline, comprises the following steps:
After polylactic acid poly glycol copolymer heating decompression is dewatered, add solvent N,N-dimethylacetamide and polyisocyanates, under nitrogen protection, 80 ℃ are stirred ten hours, then add the sub-tin of octoate catalyst and chainextender l, 4-butyleneglycol, continues chain extending reaction 10 hours; Product water precipitation, obtains white solid, and suction filtration is dried, then film forming after dissolving by N,N-dimethylacetamide, dried for standby in vacuum drying oven.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310720856.1A CN103739810A (en) | 2013-12-24 | 2013-12-24 | Degradable pipeline material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310720856.1A CN103739810A (en) | 2013-12-24 | 2013-12-24 | Degradable pipeline material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103739810A true CN103739810A (en) | 2014-04-23 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310720856.1A Pending CN103739810A (en) | 2013-12-24 | 2013-12-24 | Degradable pipeline material and preparation method thereof |
Country Status (1)
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| CN (1) | CN103739810A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457092A (en) * | 2015-10-12 | 2016-04-06 | 圆容生物医药无锡有限公司 | Polyurethane (PU) composition with adjustable elasticity modulus and application of PU composition in medical implant materials |
-
2013
- 2013-12-24 CN CN201310720856.1A patent/CN103739810A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 李洁华等: "含PLA- PEG- PLA三嵌段共聚物的可降解聚氨酯的合成及表征", 《四川大学学报(工程科学版）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457092A (en) * | 2015-10-12 | 2016-04-06 | 圆容生物医药无锡有限公司 | Polyurethane (PU) composition with adjustable elasticity modulus and application of PU composition in medical implant materials |
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Application publication date: 20140423 |