CN102675586A - Polycarbonate-polyether polyurethane and preparation method thereof - Google Patents
Polycarbonate-polyether polyurethane and preparation method thereof Download PDFInfo
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- CN102675586A CN102675586A CN2012101519454A CN201210151945A CN102675586A CN 102675586 A CN102675586 A CN 102675586A CN 2012101519454 A CN2012101519454 A CN 2012101519454A CN 201210151945 A CN201210151945 A CN 201210151945A CN 102675586 A CN102675586 A CN 102675586A
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Abstract
The invention discloses a polycarbonate-polyether polyurethane which is formed by carrying out alternating copolymerization on flexible chain segment formed by polycarbonate diol and polyether diol as well as rigid chain segment formed by diisocyanate and chain extender; in the flexible chain segment part of the polyether polyurethane, the molecular weight of the polycarbonate diol is 500-3000, and the molecular weight of the polyether diol is 500-2000. The invention also provides a method for preparing the polycarbonate-polyether polyurethane material. The polycarbonate-polyether polyurethane contains the polycarbonate diol, thus having good inoxidizability and water resistance, high mechanical strength and good mechanical performance; therefore, the polycarbonate-polyether polyurethane can be used for preparing products such as artificial blood vessel, an artificial pacemaker lead, heart valve prosthesis, and various medical intervention catheters which are implanted into the human body for a long time, and is also used for other industrial purposes.
Description
Technical field
The invention belongs to high-molecular biologic medical material and preparing technical field thereof, be specifically related to a kind of polycarbonate-Texin 5590 and preparation method thereof.
Background technology
Urethane is the abbreviation of polyurethane(s), is the general name that has the polymkeric substance of multiple carbamate structural unit (NHCOO-group) on the family macromolecule main chain.In polyurethane elastomer, because there is tangible micro phase separation structure in the uncompatibility of soft or hard section, wherein soft section provides elasticity, and hard section plays to strengthen and fills and crosslinked action.Just because of the special construction of urethane, it has good consistency, and the molecular designing degree of freedom is big, even do not use additives such as softening agent also to be easy to make it to have multiple different physical property, polyurethane elastomer is widely used aspect bio-medical.For polymeric biomaterial as implant into body, must satisfy complicated and strictly in the body require 1, good biocompatibility; 2, high chemical stability; 3, suitable physical and mechanical properties; 4, be prone to machine-shaping; 5, performance and shape do not receive the influence of sterilizing process; 6, physics, chemistry and mechanical property keep stable in physiological environment; 7, do not cause blood coagulation 8, activating complement system not; 9, do not cause serious inflammatory and foreign body reaction; 10, do not cause canceration, sudden change, teratogenesis, nontoxic not.
Implant with field of materials that blood contacts in; Urethane has HS, snappiness, good biocompatibility and processibility etc. with it and is used widely; Such as the insulated wire as cardiac pacemaker wire, artificial blood vessel and various medical catheters etc.The Texin 5590 material has excellent mechanical performances and biocompatibility; Since Boretos in 1967 and Pierce were used for polyether(poly)urethane left heart auxiliary circulation blood pump first, oneself became the preferred material of making the ventricle cavity in all kinds of artificial hearts and the ventricle auxiliary circulation system polyether(poly)urethane.But people find that gradually the polyether chain in the polyether(poly)urethane can receive the effect of the oxyradical that scavenger cell produced in the blood and degrades, and causes the stress cracking under the physiological environment.In addition, the polyether(poly)urethane material is also higher to the transmitance of water and steam, and in life-time service, water or water vapour can see through the ventricle wall of polyether(poly)urethane and pollute motor.PAUR produces catalyzed degradation effect effect with release fat acid owing to exist ester bond to be easy to hydrolysis after the hydrolysis.For these urethane; Recently the polycarbonate polyurethane of developing; Like Shan-hui Hsu, Chih-Wei Chou.Enhanced biostability of polyurethane containing gold nanoparticles.Polymer Degradation and Stability, 2004; 85 (1): the 675-680 report has better biologically stable and biocompatibility in the long-term transplanting of medical material.(Oxidative mechanisms of poly (carbonate urethane) and poly (ether urethane) biodegradation:In vivo and in vitro correlations Elizabeth M.Christenson; James M.Anderson; Anne Hiltner 2004.Wiley Periodicals; Inc.J Biomed Mater Res 69A:407 – 416) prove polycarbonate polyurethane than polyether(poly)urethane oxidation-resistance, more stable.In addition; Because soft section polycarbonate structure has been compared in limit more the segmental motion with polyether structure; Therefore the transmitance of the pure water transmitance of polycarbonate polyurethane and Physiological Medium is all well below polyether(poly)urethane; Under the condition of same film thickness, the WVTR water vapor trausmission rate of polycarbonate polyurethane than the low 2-4 of polyether(poly)urethane doubly.Result (the Yue Xuehai that adopts the visual microtechnique of fluorescent mark the blood compatibility of polycarbonate polyurethane and polyether-type ammonia ester material to be carried out evaluation analysis; M R Najarajan; T G Grasel; Etal.Polydimethylsiloxane-polyurethane Elastomers:Synthesis and Properties of Segmented Copolymers and Related Zwitterionomers.Journal of Polymer Science:Polymer physics Edition; 1985, show that 23:2319-2338) the platelet adhesion quantity on polycarbonate polyurethane surface is compared with polyether(poly)urethane and significantly reduced; Simultaneously, the activation degree to complement also obviously reduces (C3a mensuration).Simultaneously; Compare with Texin 5590, PCU has demonstrated better inwardly energy for growth in small-diameter intravascular and internal blood vessel treatment; PCU also has the phase degree of mixing better than Texin 5590; This has improved mechanical property (Y W Tang, R S Labowb, the J P Santerrea.Isolation of methylene dianiline and aqueous-soluble biodegradation products from polycarbonate-polyurethanes.Biomaterials of Texin 5590; 2003,24:2805-2819).But a large amount of research work have proved that PCU is easy to hydrolysis, and the degree of degraded mainly depends on hard section interactional essence, like hydrogen bond, the crystallization degree between hard section, between hard section and the carbonic ether.
Hard section district hydrogen bond action is strong more, and percent crystallinity is big more, and stability to hydrolysis is good more.The hydrolysis-stable degree of whole polycarbonate polyurethane chain is in proper order: the carbonic acid ester bond of no hydrogen bond action>amino-formate bond of no hydrogen bond action>carbonic acid ester bond of hydrogen bond action>amino-formate bond (the Y W Tang of hydrogen bond action; R S Labowb; J P Santerrea.Enzyme induced biodegradation ofpolycarbonate-polyurethanes:dose dependence effect of cholesterol esterase.Biomaterials; 2003,24:2003-2011; Alexander Welle; Siegfried Horn; Jutta Schimmelpfeng.Photo-chemically patterned polymer surfaces for controlled PC-12adhesion and neurite guidance.Journal of Neuroscience Methods; 2005,142:243-250).
Summary of the invention
The present invention seeks to: some problems that the present invention is directed to present Texin 5590; Such as can receiving the effect of the oxyradical that scavenger cell produced in the blood, the polyether chain in the polyether(poly)urethane degrades; Cause the stress cracking under the physiological environment, the polyether(poly)urethane material is also higher to the transmitance of water and steam, and a kind of good in oxidation resistance is provided; Water-intake rate is low; Mechanical strength is high, makes material that excellent biocompatibility arranged, the polycarbonate of biologically stable-Texin 5590 material; This preparation methods also is provided.
Technical scheme of the present invention is:
A kind of polycarbonate-Texin 5590 is characterized in that, by mole per-cent, starting monomer is formed as follows:
Wherein, the total amount of said PCDL, polyether Glycols, vulcabond and chainextender is 100%;
Wherein, said PCDL and polyether Glycols constitute soft segment, and said vulcabond and chainextender constitute rigid chain segment, and said soft segment and rigid chain segment alternating copolymerization form said polycarbonate-Texin 5590, and structural formula is following:
Wherein, R1 is the alkyl of phenyl ring or vulcabond, and mixing soft section is PCDL and polyether Glycols, and R2 is the methylene radical of 2-10, if diamine, the oxygen on R2 both sides changes nitrogen into, and n is the polymerization degree.
Preferably, said PCDL structural formula is:
N is 4,5 or 6 in
formula; M is 1,2 or 6; A is 2-12, and b is 2-11.
Preferably; Said PCDL is for gathering (1,4-butyleneglycol carbonic ether) glycol, gather (1,6-pinakon carbonic ether) glycol, gathering (1; 6-pinakon-1; The 2-ethylene carbonate) glycol, gather at least a or several kinds of compsns in (1,5-pentanediol-1,6 pinakon carbonic ether) glycol.
Preferably, said polyether Glycols is W 166, polyoxyethylene glycol, PTMG, gathers at least a or several kinds of compsns in (1, the 2-Ucar 35) glycol.
Preferably, be low-molecular-weight diol or low molecule diamine at said chainextender; Said low-molecular-weight diol is at least a or several kinds of compsns that contain the aliphatic dihydroxy alcohol of 2-10 carbon atom; Said low molecule diamine is at least a or several kinds of compsns that contain the aliphatic diamine of 2-10 carbon atom.
Preferably, the molecular weight of said PCDL is 500 ~ 3000; The molecular weight of said polyether Glycols is 500 ~ 2000.
Preferably, the blend of selecting PCDL and polyether Glycols simultaneously for use is during as soft segment, and the molar weight of said PCDL is 20 ~ 80% of a said soft segment integral molar quantity; The molar weight of said polyether Glycols is 20 ~ 80% of a said soft segment integral molar quantity.
The preparation method of above-mentioned polycarbonate-Texin 5590 is that said PCDL, polyether Glycols, vulcabond and chainextender are processed said polycarbonate-Texin 5590 by the proportioning of above-mentioned molar percentage with the mass polymerization and the solvent polymeric of single stage method or two step method or semi-prepolymer.
The preparation method of above-mentioned polycarbonate-Texin 5590 also can distinguish polycarbonate synthesis urethane and Texin 5590 earlier, then its melt blending and solvent blend is processed said polycarbonate-Texin 5590.
Advantage of the present invention is:
1. what the present invention adopted is PCDL; Polyether Glycols mixes soft section; Polycarbonate has better oxidation-resistance, stability, and this material has excellent water tolerance, oxidation-resistance, mechanical strength height, good mechanical properties, excellent biological compatibility.
2. the used polycarbonate polyurethane that contains of the present invention; Because soft section polycarbonate structure has been compared in limit more the segmental motion with polyether structure; Therefore the transmitance of the pure water transmitance of polycarbonate polyurethane and Physiological Medium is all well below polyether(poly)urethane; Under the condition of same film thickness, the WVTR water vapor trausmission rate of polycarbonate polyurethane is than the low 2-4 of polyether(poly)urethane times, and the platelet adhesion quantity on polycarbonate polyurethane surface is compared with polyether(poly)urethane and significantly reduced; Simultaneously, the activation degree to complement also obviously reduces (C3a mensuration).
3. the present invention is widely used, and can be used for making the artificial blood vessel, artificial cardiac pacemaker lead, prosthetic valves, interposing catheter etc.
4. synthetic process of the present invention is existing ordinary method, and is simple, and maturation is easy to control, implements easily.
Description of drawings
The mould material of Fig. 1: embodiment and comparative example in degradation process rate of weight loss with the change curve of hydrolysis time;
The mould material of Fig. 2: embodiment and comparative example in degradation process rate of weight loss with the change curve of enzymolysis time.
Wherein, PEU is a Texin 5590, and PCPEU is polycarbonate-Texin 5590 according to the invention.
Embodiment
Present invention is described through specific embodiment below; Be necessary to be pointed out that at this following examples only are used for the present invention is described further; Can not be interpreted as restriction to protection domain of the present invention; The person skilled in the art in this field, still belongs within the protection domain of the present invention improvement and adjustment that the present invention makes unsubstantiality according to the content of the invention described above.
In order to express easily, adopt following code name at the instance that provides:
PHC=gathers (1,6-pinakon carbonic ether) glycol
PBC=gathers (1,4-butyleneglycol carbonic ether) glycol
The PTMG=PTMG
PPG=gathers (1, the 2-Ucar 35) glycol
MDI=4,4 '-diphenylmethanediisocyanate
TDI=2,4-or 2,6-tolylene diisocyanate
HDI=1, hexamethylene-diisocyanate
The THF=THF
DMAc=N, the N-N,N-DIMETHYLACETAMIDE
DMF=N, dinethylformamide
Embodiment 1 and 3:
Adopt single stage method solvent polymeric technology
THF/DMAc (the perhaps difluoro tetrachloroethane/DMF volume ratio: 1:3) mixed solvent that at first in a reaction kettle that whisking appliance, TM, reflux be housed, adds volume ratio 1:5; The weight ratio of the amount of its adding and the reactant of adding is 4:1, presses formula table 1 listed prescription, and the PCDL, the polyether Glycols that add different molecular weight stir (under condition of nitrogen gas); And be warming up to 50 ℃-80 ℃; Press formula ratio again and add chainextender 1,4-butyleneglycol or quadrol fully stir and make reactants dissolved; Press formula ratio at last and add vulcabond; Be warming up to 80 ℃-100 ℃, reacted 4-6 hour, stop to stir, cooling promptly gets polycarbonate-Texin 5590 solution.
Embodiment 4
Adopt the two-step approach solvent polymeric
At first in a reaction kettle that whisking appliance, TM, reflux be housed, add volume ratio 1:5 THF/DMAc (perhaps difluoro tetrachloroethane/DMF volume ratio: 1:3) mixed solvent, the weight ratio of the amount of its adding and the reactant of adding is 4:1, presses formula table 1 listed prescription; Add molecular weight PCDL, polyether Glycols, stir (under condition of nitrogen gas), and be warming up to 50 ℃-80 ℃, fully dissolving; Secondly there is catalyzer just to add catalyzer like prescription; Be stirred well to dissolving fully, add vulcabond HDI reaction 30-60 minute then, measure the free isocyano-content in the reaction;, isocyano-content adds the chainextender quadrol when reducing to theoretical amount; Reacted 3-6 hour again, and stopped to stir, cooling promptly gets polycarbonate-Texin 5590 material solution.
Adopt the single stage method mass polymerization
The PCDL, the polyether Glycols that at first in a reaction kettle that whisking appliance, TM, reflux be housed, add the prescription molecular weight; Stirring is warming up to 80 ℃-100 ℃, and under agitation condition, after vacuum outgas 30-60 minute, is cooled to 50 ℃-60 ℃; Secondly there is catalyzer to add catalyzer like prescription; And add chainextender and vulcabond successively, and stir and be warming up to 100 ℃ of reactions 10-20 minute, then reaction mixture is transferred in the polytetrafluoroethyldisk disk of 100 ℃ of preheatings; In 100 ℃ of-120 ℃ of baking ovens post curing 3-6 hour, cooling promptly got product.
Adopt the two-step approach mass polymerization
The PCDL, the polyether Glycols that at first in a reaction kettle that whisking appliance, TM, reflux be housed, add different molecular weight in the formula table stir and are warming up to 80 ℃-100 ℃; And under agitation condition, after vacuum outgas 30-60 minute, be cooled to 50 ℃-60 ℃, secondly there is catalyzer to add catalyzer like prescription; Press formula ratio again and added di-isocyanate reaction 20-30 minute; Measure the free isocyano-content, when isocyano-content is reduced to theoretical amount, add chainextender 1,4-butyleneglycol or quadrol; Restir is warming up to 100 ℃ of reactions 10-20 minute; Then reaction mixture is transferred in the polytetrafluoroethyldisk disk of 100 ℃ of preheatings, in 100 ℃ of-120 ℃ of baking ovens post curing 3-6 hour, cooling promptly got product.
Comparative example 1
This comparative example synthesis technique is with embodiment 1, and composition of raw materials is different.Get polyether(poly)urethane at last.
Comparative example 2
This comparative example synthesis technique is with embodiment 4, and composition of raw materials is different.Last polyether(poly)urethane.
Embodiment and comparative example formula table
In order to investigate the anti-hydrolysis ability and the resistance of oxidation of polycarbonate provided by the invention-Texin 5590 material, the material that obtains in embodiment and the comparative example extracorporeal hydrolysis experiment and external degradation experiment have been carried out.And following respectively explanation (comparing with embodiment 1) with comparative example 1:
The material of gained is made into casting film behind the solution of 10% (w/v) with DMAc, the about 1mm of thickness adopts dumbbell shape standard cut-off knife to process print, each 5 of every kind of materials.
Extracorporeal hydrolysis experiment with the sample diaphragm of accurate weighing be embedded in 2.0-3.0mm thick in the glass wool; Whole system is placed in the petridish that diameter is 120mm, adds the PBS damping fluid (7.4) that 60ml configures, and diaphragm is immersed in the PBS damping fluid fully; The petridish that sample will be housed is then put into 37 ℃ of constant temperature ovens; Constant temperature is placed, and damping fluid does not have 7d to change once, and glass wool changed once in one month.Degradation time is respectively 7d, 21d, 42d, 51d, 70d, 112d.
External H2O2/CoCl2 preoxidation experiment: same hydrolysising experiment, get the mixing solutions of 30mL 1.63mol/L H2O2 and 30mL 0.05mol/L CoCl2 and pour in the above-mentioned petridish.Preoxidation liquid changed 1 time in per three or four days.Degradation time is 7d, proceeds the enzyme liberating experiment then.
External Lipase AK enzyme liberating experiment: the sample diaphragm of oxidation pre-treatment is immersed in the Lipase AK enzyme liberating liquid for preparing.The petridish that sample is housed is placed in 37 ℃ of constant temperature ovens.The every 7d of enzyme liberating liquid changes 1 time.Preoxidation begins then that enzymolysis time is respectively 7d, 21d, 42d, 51d, 70d, 112d.
Can know that with hydrolysis (like Fig. 1) and enzymolysis (like Fig. 2) change of time curve synthetic polycarbonate-Texin 5590 anti-hydrolytic performance and anti-enzymolysis performance all are superior to Texin 5590 from mould material rate of weight loss degradation process.
Claims (9)
1. a polycarbonate-Texin 5590 is characterized in that, by mole per-cent, starting monomer is formed as follows:
Wherein, the total amount of said PCDL, polyether Glycols, vulcabond and chainextender is 100%;
Wherein, said PCDL and polyether Glycols constitute soft segment, are called for short soft section; Said vulcabond and chainextender constitute rigid chain segment, are called for short hard section; Said soft segment and rigid chain segment alternating copolymerization form said polycarbonate-Texin 5590, and structural formula is following:
Wherein, R1 is the alkyl of phenyl ring or vulcabond, and R2 is the methylene radical of 2-10, if diamine, the oxygen on R2 both sides changes nitrogen into, and n is the polymerization degree.
2. polycarbonate-Texin 5590 according to claim 1 is characterized in that, said PCDL structural formula is:
N is 4,5 or 6 in
formula; M is 1,2 or 6; A is 2-12, and b is 2-11
3. polycarbonate-Texin 5590 according to claim 1 is characterized in that said PCDL is for gathering (1; 4-butyleneglycol carbonic ether) glycol, gather (1; 6-pinakon carbonic ether) glycol, gather (1,6-pinakon-1 carbonic ether) glycol, gather (1; 5-pentanediol-1,6 pinakon carbonic ether) at least a or several kinds of compsns in the glycol.
4. polycarbonate-Texin 5590 according to claim 1 is characterized in that, said polyether Glycols is W 166, polyoxyethylene glycol, PTMG, gather at least a or several kinds of compsns in (1, the 2-Ucar 35) glycol.
5. polycarbonate-Texin 5590 according to claim 1 is characterized in that, is low-molecular-weight diol or low molecule diamine at said chainextender; Said low-molecular-weight diol is at least a or several kinds of compsns that contain the aliphatic dihydroxy alcohol of 2-10 carbon atom; Said low molecule diamine is at least a or several kinds of compsns that contain the aliphatic diamine of 2-10 carbon atom.
6. according to the described polycarbonate-Texin 5590 of claim 1 ~ 4, it is characterized in that the molecular weight of said PCDL is 500 ~ 3000; The molecular weight of said polyether Glycols is 500 ~ 2000.
7. according to the described polycarbonate-Texin 5590 of claim 1 ~ 4; It is characterized in that; The blend of selecting PCDL and polyether Glycols simultaneously for use is during as soft segment, and the molar weight of said PCDL is 20 ~ 80% of a said soft segment integral molar quantity; The molar weight of said polyether Glycols is 20 ~ 80% of a said soft segment integral molar quantity.
8. the preparation method of right 1 ~ 7 described polycarbonate-Texin 5590; It is characterized in that, said PCDL, polyether Glycols, vulcabond and chainextender are processed said polycarbonate-Texin 5590 by the proportioning of above-mentioned molar percentage with the mass polymerization and the solvent polymeric of single stage method or two step method or semi-prepolymer.
9. the preparation method of polycarbonate-Texin 5590 according to claim 8 is characterized in that, can distinguish polycarbonate synthesis urethane and Texin 5590 earlier, then its melt blending and solvent blend is processed said polycarbonate-Texin 5590.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104208748A (en) * | 2014-07-24 | 2014-12-17 | 苏州大学 | Biodegradable polyurethane having gradient elasticity modulus and tissue engineering fibrous scaffold prepared through same |
| CN110885422A (en) * | 2019-11-19 | 2020-03-17 | 西南交通大学 | Ditellurium-containing degradable polycarbonate polyurethane and preparation method thereof |
| CN113490126A (en) * | 2021-05-26 | 2021-10-08 | 歌尔股份有限公司 | Vibrating diaphragm for sound production device, preparation method of vibrating diaphragm and sound production device |
| CN113490124A (en) * | 2021-05-26 | 2021-10-08 | 歌尔股份有限公司 | Vibrating diaphragm for sound production device, preparation method of vibrating diaphragm and sound production device |
| US20230302194A1 (en) * | 2016-03-31 | 2023-09-28 | Polyganics Ip B.V. | Biomedical Polyurethanes |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104208748A (en) * | 2014-07-24 | 2014-12-17 | 苏州大学 | Biodegradable polyurethane having gradient elasticity modulus and tissue engineering fibrous scaffold prepared through same |
| CN104208748B (en) * | 2014-07-24 | 2016-09-21 | 苏州大学 | There is the Biodegradable polyurethane of gradient elastic modelling quantity and the tissue-engineering fiber support of preparation thereof |
| US20230302194A1 (en) * | 2016-03-31 | 2023-09-28 | Polyganics Ip B.V. | Biomedical Polyurethanes |
| CN110885422A (en) * | 2019-11-19 | 2020-03-17 | 西南交通大学 | Ditellurium-containing degradable polycarbonate polyurethane and preparation method thereof |
| CN110885422B (en) * | 2019-11-19 | 2022-02-01 | 西南交通大学 | Ditellurium-containing degradable polycarbonate polyurethane and preparation method thereof |
| CN113490126A (en) * | 2021-05-26 | 2021-10-08 | 歌尔股份有限公司 | Vibrating diaphragm for sound production device, preparation method of vibrating diaphragm and sound production device |
| CN113490124A (en) * | 2021-05-26 | 2021-10-08 | 歌尔股份有限公司 | Vibrating diaphragm for sound production device, preparation method of vibrating diaphragm and sound production device |
| CN113490124B (en) * | 2021-05-26 | 2023-06-27 | 歌尔股份有限公司 | Vibrating diaphragm capable of being used for sound production device, preparation method of vibrating diaphragm and sound production device |
| CN113490126B (en) * | 2021-05-26 | 2023-06-27 | 歌尔股份有限公司 | Vibrating diaphragm capable of being used for sound production device, preparation method of vibrating diaphragm and sound production device |
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Application publication date: 20120919 |