CN102295736A - Preparation method of polylactic acid material with X-ray developing functions - Google Patents
Preparation method of polylactic acid material with X-ray developing functions Download PDFInfo
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- CN102295736A CN102295736A CN 201110149679 CN201110149679A CN102295736A CN 102295736 A CN102295736 A CN 102295736A CN 201110149679 CN201110149679 CN 201110149679 CN 201110149679 A CN201110149679 A CN 201110149679A CN 102295736 A CN102295736 A CN 102295736A
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Abstract
The invention discloses a preparation method of a polylactic acid material with X-ray developing functions. The preparation method comprises the following steps that polylactic acid with two terminal hydroxyl groups and a diisocyanate are dissolved in an organic solvent according to a certain proportion; the mixture is heated to a temperature of 50 to 100 DEG C with stirring and then undergoes a reaction for 1 to 4 hours to produce a prepolymer; and the prepolymer is added with a chain extender according to a certain proportion and then undergoes a reaction with stirring for 0.5 to 2 hours to produce a desired product. The preparation method adopts a polylactic acid with good biodegradability as a raw material and thus the polylactic acid material prepared by the preparation method also has biodegradability and is suitable for a case that implanted materials only have temporary effects and can be degraded by themselves after action, wherein implanted materials comprise vessel support materials, tissue engineering support implanted materials and other materials implanted into human bodies. The polylactic acid material prepared by the preparation method does not need curing and can coagulate naturally for forming to be utilized as an X-ray developing material.
Description
Technical field
The invention belongs to the preparation and the modification technology field of biological medical degradable material, be specifically related to the preparation method of the poly-lactic acid material of development under a kind of X-ray.
Background technology
In recent years, macromolecular material is being played the part of more and more important role because of its excellent biological compatibility, physical and mechanical properties, processing characteristics and biodegradable performance etc. in modern medicine.When its during as medical embedded material, if the situation after can't implanting to implant with observation of use instrument will be brought many difficulties to anaphase, this just requires embedded material to have development.X-ray fluoroscopy is the most commonly used clinically and most economical detection means.Yet macromolecular material self only contains low electron densities such as C, H, O and low-gravity element mostly and can not be by X-ray check.Mainly be under X-ray, to develop at present by adding heavy metal contrast medium such as barium sulfate, disclose a kind of developing polylactic acid microsphere blood vessel suppository that contains antitumor drug as Chinese patent 200720047301.5, reached development by wrapping up roentgenopaque developing material.Chinese patent 200910197950.7 discloses a kind of developed degradable lactic acid composite material and preparation method thereof, processes composite powder/solvent-borne type photographic developer to reach development by coating or blend; But the method contrast medium consumption of this physical blending is big, is about 20～30wt%, and it is rotten to be easy to cause material property to worsen simultaneously, and the plurality of heavy metal ionic is separated out and will be produced harm to human body.
Thereby people attempt introducing the development group by the mode of chemical bonding on polymer chain makes macromolecular material itself have the radiation impermeability.Halogen atom such as iodine, bromine relative atomic mass higher density is big, can absorb X-ray, have good effect, therefore halogen atoms such as iodine, bromine are introduced the macromolecular material that obtains stable development in the polymer chain by the mode of covalent linkage, just more and more paid close attention to and study.Contain the existing report of X-ray development modified polymer materials such as iodopropylene acid resin, polycarbonate, urethane, have stable developing performance.Chinese patent 200810223421.5 discloses a kind of developing polyurethane recently, it is characterized in that with PTMG and polycarbonate diol be soft section, terminal hydroxy group or end aminocompound at halogen atom-containing development group are made chainextender, have satisfactory stability and long lasting development effect.Yet selected flexible polyurethane section is PTMG and polycarbonate non-degradable polymkeric substance, and therefore the disappearance of can not degrading voluntarily of prepared urethane, is restricted in the use occasion of having degraded voluntarily after much having needed temporary effect.
Poly(lactic acid) has good biodegradability and good biocompatibility concurrently, nontoxic, nonirritant, and the mechanical property excellence, advantages such as easy-formation processing are present ideal biodegradable tissue engineering bracket materials.Yet poly(lactic acid) can not be developed under X-ray, follows the tracks of as body implanting material to have obstacle.Therefore, in the polylactic acid molecule chain, introduce development groups such as iodine, bromine, it can be developed under X-ray by covalent linkage.Owing to do not have the group of reactive behavior on the polylactic acid molecule chain, be difficult to directly introduce the development atom.Therefore, the present invention will contain the chainextender of halogen development groups such as iodine, bromine by the mode of covalent bonds, be incorporated in the polylactic acid based urethane, make material itself have the radiation impermeability.
Summary of the invention
The present invention proposes a kind of preparation method of X-ray developing polylactic acid urethane, at the problems referred to above, with the degradation material poly(lactic acid) as soft section with the urethane hybrid reaction, the chainextender that mode by covalent bonds will contain halogen development groups such as iodine, bromine is incorporated in the polylactic acid based urethane, thereby material itself can be degraded, have the radiation impermeability simultaneously.
For achieving the above object, the present invention carries out as follows:
(1) with both-end hydroxyl poly(lactic acid) and vulcabond (0.2～0.8) in molar ratio: 1 is dissolved in the organic solvent, is heated with stirring to 50～100 ℃ of reactions 1～4 hour, obtains prepolymer;
(2) add chainextender in step (1) gained prepolymer, the add-on of chainextender is a chainextender in molar ratio: vulcabond=(0.2～0.8): 1, and stirring reaction 0.5～2 hour gets target product.
Among the present invention, described vulcabond is diphenylmethanediisocyanate, tolylene diisocyanate, 1, a kind of in 4-cyclohexyl diisocyanate, isophorone diisocyanate or the hexamethylene diisocyanate; The molecular weight of described both-end hydroxyl poly(lactic acid) is 500～5000.
Among the present invention, organic solvent is selected from tetrahydrofuran (THF), 1,4-dioxane, N, a kind of in dinethylformamide, the dimethyl sulfoxide (DMSO).
Described chainextender is that small molecules contains the terminal hydroxy group compound of halogen atom or the end aminocompound that small molecules contains halogen atom, and wherein halogen atom is bromine atoms or iodine atom; A kind of among the present invention in the preferred iodo dihydroxyphenyl propane of chainextender, bromo dihydroxyphenyl propane, phenyl-iodide dimethanol, bromobenzene dimethanol, phenyl-iodide dimethylamine, bromobenzene dimethylamine, phenyl-iodide diphenol, bromobenzene diphenol, phenyl-iodide diamines, bromobenzene diamines, iodo ethylene glycol, bromo ethylene glycol, iodo quadrol, bromo quadrol, iodo butyleneglycol, bromo butyleneglycol, iodo butanediamine, the bromo butanediamine.
Simple, the easy row of the method for the invention, controlled; The developing material of preparation has favorable tissue consistency and blood compatibility, good physicochemical performance, mechanical property, processing characteristics, and biodegradability is controlled, therefore the radiation impermeability progressively decays with the degraded of poly(lactic acid), and the application facet that plays temporary effect at vascular stent material, organization bracket embedded material and other body implanting material etc. has a extensive future.
The X-ray development poly-lactic acid material preparation method that the present invention proposes, have following advantage: it is raw material that the present invention adopts the poly(lactic acid) with good biological degradability, make prepared poly-lactic acid material also have degradation property, be particularly suitable for institute's embedded material and only need play the use occasion of degrading voluntarily after the temporary effect, such as vascular stent material, tissue engineering bracket embedded material and other body implanting material etc.Because poly(lactic acid) does not possess the X-ray development, the present invention selects the small molecule chain extender that contains iodine or bromine with development effect under the X-ray for use, mode by covalent bonds is incorporated into iodine or bromine atoms in the poly(lactic acid) polyurethane molecular chain, makes it have the X-ray development effect.And gained target product of the present invention need not slaking, and the natural coagulation moulding promptly can be used as the X-ray developing material and uses.
Description of drawings
Fig. 1 is the development effect of embodiment sample under roentgen machine; Among the figure, A1 represents the reference aluminium foil, and 1～5 is respectively embodiment 1～5;
Fig. 2 is the degradation property of embodiment sample; Degraded environment: simulated body fluid, 37 ℃, pH=7.4.
Embodiment
The X-ray development poly-lactic acid material of the present invention preparation is as chainextender the prepolymer chain of both-end hydroxyl poly(lactic acid) and vulcabond to be connected into segmented copolymer by the small molecules that contains halogens such as iodine or bromine, and its general structure is as follows:
Wherein, R1 is aryl or alkyl, and R2 is iodo or bromo aryl, alkyl.
The structural formula of the used chainextender that contains iodine or bromine is as follows in the embodiments of the invention:
Embodiment 1:
It with the molecular weight of vacuum hydro-extraction in advance 650 both-end hydroxyl poly(lactic acid) and 4,4 '-diphenylmethanediisocyanate is at N, mixes in the dinethylformamide, and mixing mol ratio is 0.75: 1, under the nitrogen protection in 80 ℃ mix the reaction 2 hours, obtain prepolymer; Add again and be dissolved in N in advance, the phenyl-iodide diamines in the dinethylformamide (seeing structural formula I), itself and 4,4 '-diphenylmethanediisocyanate mole proportioning is 0.25: 1, stirring reaction discharging in about 2 hours.
Embodiment 2:
With the molecular weight of vacuum hydro-extraction in advance is that 1000 both-end hydroxyl poly(lactic acid) and tolylene diisocyanate mix in dimethyl sulfoxide (DMSO), and mixing mol ratio is 0.50: 1, mixes reaction 4 hours in 100 ℃ under the nitrogen protection, obtains prepolymer; Add iodo dihydroxyphenyl propane (seeing structural formula II) again, itself and tolylene diisocyanate mole proportioning are 0.50: 1, stirring reaction discharging in about 4 hours.
Embodiment 3:
With the molecular weight of vacuum hydro-extraction in advance be 2000 both-end hydroxyl poly(lactic acid) and isophorone diisocyanate at N, mix in the dinethylformamide, mixing mol ratio is 0.40: 1, mixes reaction 2 hours in 80 ℃ under the nitrogen protection, obtains prepolymer; Add bromo butanediamine (seeing structural formula II I) again, itself and isophorone diisocyanate mole proportioning are 0.55: 1, stirring reaction discharging in about 1 hour.
Embodiment 4:
With the molecular weight of vacuum hydro-extraction in advance be 4000 both-end hydroxyl poly(lactic acid) and hexamethylene diisocyanate 1, mix in the 4-dioxane, mixing mol ratio is 0.60: 1, mixes reaction 2 hours in 80 ℃ under the nitrogen protection, obtains prepolymer; Add bromobenzene diphenol (seeing structural formula IV) again, itself and hexamethylene diisocyanate mole proportioning are 0.40: 1, stirring reaction discharging in about 2 hours.
Embodiment 5:
With the molecular weight of vacuum hydro-extraction in advance is 800 both-end hydroxyl poly(lactic acid) and 1, and the 4-cyclohexyl diisocyanate is mixed in dimethyl sulfoxide (DMSO), and mixing mol ratio is 0.65: 1, mixes reaction 3 hours in 50 ℃ under the nitrogen protection, obtains prepolymer; Add the phenyl-iodide dimethanol (seeing structural formula V) be dissolved in advance in the dimethyl sulfoxide (DMSO) again, itself and 1,4-cyclohexyl diisocyanate mole proportioning is 0.40: 1, stirring reaction discharging in about 2 hours.
Claims (7)
1. the preparation method with poly-lactic acid material of X-ray developing function is characterized in that this preparation method comprises the steps:
(1) with both-end hydroxyl poly(lactic acid) and vulcabond (0.2～0.8) in molar ratio: 1 is dissolved in the organic solvent, is heated with stirring to 50～100 ℃ of reactions 1～4 hour, obtains prepolymer;
(2) add chainextender in step (1) gained prepolymer, the add-on of chainextender is a chainextender in molar ratio: vulcabond=(0.2～0.8): 1, and stirring reaction 0.5～2 hour gets target product.
2. the preparation method with poly-lactic acid material of X-ray developing function according to claim 1 is characterized in that: the molecular weight of described both-end hydroxyl poly(lactic acid) is 500～5000.
3. the preparation method with poly-lactic acid material of X-ray developing function according to claim 1, it is characterized in that: described vulcabond is diphenylmethanediisocyanate, tolylene diisocyanate, 1, a kind of in 4-cyclohexyl diisocyanate, isophorone diisocyanate or the hexamethylene diisocyanate.
4. the preparation method with poly-lactic acid material of X-ray developing function according to claim 1 is characterized in that: described organic solvent is a tetrahydrofuran (THF), 1,4-dioxane, N, a kind of in dinethylformamide, the dimethyl sulfoxide (DMSO).
5. the preparation method with poly-lactic acid material of X-ray developing function according to claim 1 is characterized in that: described chainextender is that small molecules contains the terminal hydroxy group compound of halogen atom or the end aminocompound that small molecules contains halogen atom.
6. the preparation method with poly-lactic acid material of X-ray developing function according to claim 5 is characterized in that: described halogen atom is a kind of in iodine atom, the bromine atoms.
7. the preparation method with poly-lactic acid material of X-ray developing function according to claim 6 is characterized in that: the chainextender that described low molecule contains halogen is a kind of in iodo dihydroxyphenyl propane, bromo dihydroxyphenyl propane, phenyl-iodide dimethanol, bromobenzene dimethanol, phenyl-iodide dimethylamine, bromobenzene dimethylamine, phenyl-iodide diphenol, bromobenzene diphenol, phenyl-iodide diamines, bromobenzene diamines, iodo ethylene glycol, bromo ethylene glycol, iodo quadrol, bromo quadrol, iodo butyleneglycol, bromo butyleneglycol, iodo butanediamine, the bromo butanediamine.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108148173A (en) * | 2017-12-18 | 2018-06-12 | 苏州浩洋聚氨酯科技有限公司 | Biodegradable medical polyurethane and preparation method thereof |
| CN109535470A (en) * | 2018-11-21 | 2019-03-29 | 朱志荣 | A kind of high efficiency preparation method of high-intensity and high-tenacity degradable poly esters polymer |
| CN113017717A (en) * | 2019-12-25 | 2021-06-25 | 先健科技(深圳)有限公司 | Occlusion device |
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| US20070128120A1 (en) * | 2005-12-07 | 2007-06-07 | Zhao Jonathon Z | Organic radiographic contrasting agents for medical devices |
| CN101392048A (en) * | 2008-09-27 | 2009-03-25 | 清华大学 | Method for preparing developing polyurethane |
| US20090259297A1 (en) * | 2008-04-10 | 2009-10-15 | Yunbing Wang | Implantable Medical Devices Fabricated From Polyurethanes With Grafted Radiopaque Groups |
| CN102000366A (en) * | 2010-12-08 | 2011-04-06 | 苏州同科生物材料有限公司 | Degradable self-expandable esophageal stent and preparation method thereof |
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2011
- 2011-06-03 CN CN 201110149679 patent/CN102295736A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20070128120A1 (en) * | 2005-12-07 | 2007-06-07 | Zhao Jonathon Z | Organic radiographic contrasting agents for medical devices |
| US20090259297A1 (en) * | 2008-04-10 | 2009-10-15 | Yunbing Wang | Implantable Medical Devices Fabricated From Polyurethanes With Grafted Radiopaque Groups |
| CN101392048A (en) * | 2008-09-27 | 2009-03-25 | 清华大学 | Method for preparing developing polyurethane |
| CN102000366A (en) * | 2010-12-08 | 2011-04-06 | 苏州同科生物材料有限公司 | Degradable self-expandable esophageal stent and preparation method thereof |
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| 《中国医学影像技术》 20071231 孟波,王存龙,朱宁,等 X线下可显影的高分子材料尿道支架 第23卷, 第1期 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108148173A (en) * | 2017-12-18 | 2018-06-12 | 苏州浩洋聚氨酯科技有限公司 | Biodegradable medical polyurethane and preparation method thereof |
| CN109535470A (en) * | 2018-11-21 | 2019-03-29 | 朱志荣 | A kind of high efficiency preparation method of high-intensity and high-tenacity degradable poly esters polymer |
| CN109535470B (en) * | 2018-11-21 | 2021-04-13 | 朱志荣 | High-efficiency preparation method of high-strength high-toughness degradable polyester polymer |
| CN113017717A (en) * | 2019-12-25 | 2021-06-25 | 先健科技(深圳)有限公司 | Occlusion device |
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Application publication date: 20111228 |