CN104292477A - Preparation method, product and application of polyurethane material capable of being self-assembled into nano tube - Google Patents
Preparation method, product and application of polyurethane material capable of being self-assembled into nano tube Download PDFInfo
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- CN104292477A CN104292477A CN201410551610.0A CN201410551610A CN104292477A CN 104292477 A CN104292477 A CN 104292477A CN 201410551610 A CN201410551610 A CN 201410551610A CN 104292477 A CN104292477 A CN 104292477A
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Abstract
The invention discloses a preparation method, a product and application of polyurethane material capable of being self-assembled into a nano tube, aiming at solving the problem that no polyurethane material capable of being self-assembled into the nano tube is applied to the aspect of biological medicines at present. According to the preparation method of the polyurethane material capable of being self-assembled into the nano tube, esterification reaction is carried out on ethylenediamine tetraacetic acid disodium salt and polyethylene glycol to obtain ethylenediamine tetraacetic acid-diol, ethylenediamine tetraacetic acid-diol and polyadipic acid-1,4-butanediol ester diol are taken as soft segments, and micromolecule polyol and diisocyanate are taken as hard segments, so that anticoagulant and biodegradable multiblock polyurethane is prepared; and the polyurethane has amphiphilic property and good biocompatibility, can be self-assembled into a nanoparticle and a nano tube and can be applied to the fields of tissue engineering, drug carrier and controlled release, nano reactors, nano catalysts and the like.
Description
Technical field
The present invention is specifically related to a kind of preparation method being self-assembled into the polyurethane material of nanotube, belongs to the preparation field of bio-medical functional high molecule material.
Background technology
In the past between decades, because Biodegradable material Relative biological stable material has excellent biocompatibility, it is caused to be used widely at pharmaceutical sanitary field (as suture line, human tissue engineering, gene therapy, regenerative medicine, drug controlled release etc. in body).In the last few years, the research and development focus of biomaterial concentrated on and opened sending out of novel biodegradable polymkeric substance and derivative thereof (as polyester, polyurethanes, polycaprolactone class, polyamide-based etc.).Wherein, biodegradable urethane causes great concern because the mechanical property of its excellence, processing characteristics, blood compatibility and be easy to synthesize characteristic.Urethane is made up of soft section and hard section, soft section is made up of oligomer polyol usually, hard section is made up of vulcabond and small molecule chain extender (as diamines and glycol), the polyurethane material of different structure and performance can be synthesized, to meet different ranges of application by regulating the ratio of soft or hard section.Especially have broad application prospects to have good biocompatibility, nontoxic and biodegradable low molecular poly or polycaprolactone as the polyurethane material that soft section is prepared.
Meanwhile, polymer nanostructures (as nanometer ball, nanofiber, nano wire, nanotube etc.) causes people's great interest, because their functional and physicochemical characteristics of uniqueness of having at Nano grade.Wherein, hollow polymer nanostructure comprises hollow nano-sphere and nanotube becomes study hotspot.Usually, two kinds are had to prepare hollow nanostructured method---template and non-template method.In template, synthesis mainly occurs in micropore metal oxide compound (as Al
2o
3, MoO
3, VO
2deng) in template, the advantage of this method is can preparation size is controlled under comparatively gentle reaction conditions dispersed nano material.In non-template method, can prepare hollow nanostructured by the self-assembly of amphiphilic multi-block polymer.In self assembling process, the length, proportion, structure etc. of the size of the nanostructure formed and number and hydrophilic segment are closely related.
Nontoxic, nonirritant must be met as medical material, without mutagenicity, antigenicity, do not cause the condition such as haemolysis and blood coagulation, pathology could do not caused with tissue compatible.And have anticoagulant effect concurrently with the urethane that ethylenediamine tetraacetic acid (EDTA)-glycol is the preparation of one of soft section of composition.At present, also not about the polyurethane material of superfine nano pipe can be self-assembled into for the research report in biological medicine, prepare ultra-fine monodisperse polymer nanotube and be still a huge challenge.Therefore, it is very necessary for developing a kind of novel, biodegradable polyurethane nano pipe.
Summary of the invention
The object of the invention is a kind of preparation method being self-assembled into the polyurethane material of nanotube proposed for prior art deficiency, be characterized in that self-assembly obtains a series of polyurethane material with different nanostructure (as Nano microsphere, nanotube, concentric circles Nanotube Aggregates) by regulating the content of EDTA-diol in hard section and soft section, achieves microtexture controlled.
The present invention is achieved through the following technical solutions:
Be self-assembled into a preparation method for the polyurethane material of nanotube, comprise the following steps:
(1) ethylenediamine tetraacetic acid (EDTA)-2 sodium, PEG-4000 are carried out esterification in 1:1 ~ 2 in molar ratio under sulfuric acid catalysis; Its temperature of reaction is 120 ~ 200 DEG C, and the reaction times is 4 ~ 8h.Then underpressure distillation removing moisture, crosses and filters unreacted ethylenediamine tetraacetic acid (EDTA)-2 sodium, then filtration product poured in a large amount of solvent orange 2 A and wash away unreacted PEG-4000 and oligopolymer thereof, finally centrifugal, dry, obtains ethylenediamine tetraacetic acid (EDTA)-glycol;
(2) under organotin catalyzed, by ethylenediamine tetraacetic acid (EDTA)-glycol, poly-hexanodioic acid-1,4 butanediol ester glycol, and vulcabond 3 ~ 42:3 in mass ratio ~ 42:15 ~ 26 join in solvent B and are polymerized, its temperature of reaction is 50 ~ 80 DEG C, reaction times is 1 ~ 4h, then the chainextender desolventizing the outer quality 0.5 ~ 2% of B is added, continue reaction 1 ~ 2h, then reaction product is poured in Teflon mould, and be placed on slaking 8 ~ 10h in 60 ~ 80 DEG C of baking ovens, obtain anticoagulant biodegradable polyurethane material;
(3) under agitation, the polyurethane material of step (2) gained is dissolved in solvent B, the solution that massfraction is 3 ~ 7% can be obtained, a large amount of deionized water is dropwise added again in this solution under ultrasound condition, obtain the polyurethane suspension that concentration is 1 ~ 3mg/mL, finally move in dialysis tubing by described polyurethane suspension, carry out dialysis in deionized water 2 days, namely obtaining concentration after dilution is 10
-4the be self-assembled into different size Nano microsphere of ~ 1mg/mL and the aqueous polyurethane of nanotube.
Further, described solvent orange 2 A is at least one in methyl acetate, ethyl acetate, butylacetate, acetone, toluene, dimethylbenzene.
Again further, described vulcabond is at least one in PPDI, tolylene diisocyanate, diphenylmethanediisocyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate, lazy propylhomoserin vulcabond.
Further, described chainextender is at least one in ethylene glycol, butyleneglycol, hexylene glycol, glycerol, 1,3-dihydroxypropionic acid, quadrol, hexanediamine.
In addition, described solvent B is at least one in DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene.
Preferred as one, the molecular weight of described poly-hexanodioic acid-Isosorbide-5-Nitrae butanediol ester glycol is 1000 ~ 5000g/mol.
Preferred as one, the mol ratio 1:1.35 of described ethylenediamine tetraacetic acid (EDTA)-2 sodium, PEG-4000.
The polyurethane material of the be self-assembled into nanotube that preparation method of the present invention obtains.
The application of polyurethane material on organizational project, pharmaceutical carrier and Co ntrolled release, nano-reactor, nanocatalyst field being self-assembled into nanotube of the present invention.
The present invention has the following advantages and beneficial effect:
(1) polyurethane material prepared by the present invention not only self-servicely can dress up nano tube structure, also has excellent biodegradable and biocompatibility.
(2) polyurethane material prepared by the present invention is soft section with ethylenediamine tetraacetic acid (EDTA)-glycol, nontoxic, has anticoagulant effect concurrently.
(3) polyurethane material prepared by the present invention realizes microtexture from Nano microsphere to the conversion of hollow Nano pipe polyurethane material by regulating soft, hard segment content.
(4) polyurethane material prepared by the present invention has lower micelle-forming concentration in water medium, has larger using value in drug controlled release field.
Accompanying drawing explanation
Fig. 1 be polyurethane nano pipe from loader aid reason schematic diagram.
Fig. 2 is that ethylenediamine tetraacetic acid (EDTA)-glycol content forms the impact of concentration (CMC) to polyurethane nano pipe.
Fig. 3 is the transmission electron microscope shape appearance figure of concentric circles polyurethane nano pipe.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described, and embodiments of the present invention include but not limited to the following example.
Embodiment 1
As shown in Figures 1 to 3, a kind of preparation method being self-assembled into the polyurethane material of nanotube, comprises the following steps:
(1) in the four-hole boiling flask carrying heating and whipping appts, 33.6g ethylenediamine tetraacetic acid (EDTA)-2 sodium, 54g PEG-4000,0.85g sulfuric acid is added successively.At 140 DEG C of reaction 8h, and underpressure distillation removes moisture under equal temperature, gained mixture removes unreacted ethylenediamine tetraacetic acid (EDTA)-2 sodium after filtration, products therefrom is poured into wash away unreacted PEG-4000 and oligopolymer thereof in a large amount of acetone, finally namely obtain ethylenediamine tetraacetic acid (EDTA)-glycol after centrifugal, drying.
(2) 3g ethylenediamine tetraacetic acid (EDTA)-glycol, 7g are gathered hexanodioic acid-1,4 butanediol ester glycol, 2.8g lysinediisocyanate, appropriate organotin catalysts add N successively, be polymerized in N-N,N-DIMETHYLACETAMIDE, temperature of reaction is 50 DEG C, and then reaction times 2h adds 0.15g ethylene glycol in system, continue reaction 1h, product is poured in Teflon mould, and is placed on slaking 10h in 60 DEG C of baking ovens, obtain anticoagulant biodegradable polyurethane material.
(3) under agitation, above-mentioned polyurethane material is dissolved in N, in N-N,N-DIMETHYLACETAMIDE, obtain the solution that massfraction is 5%, under ultrasound condition, dropwise add a large amount of deionized waters in this solution, obtain the polyurethane suspension that concentration is 2mg/mL, this suspension is transferred in dialysis tubing, dialyse 2 days in deionized water, and to be diluted to concentration with deionized water be 10
-4the aqueous polyurethane self-servicely can dressing up different size Nano microsphere and nanotube of mg/mL.
Wherein, the molecular weight of described poly-hexanodioic acid-Isosorbide-5-Nitrae butanediol ester glycol is 2000g/mol.
Embodiment 2
Be self-assembled into a preparation method for the polyurethane material of nanotube, comprise the following steps:
(1) in the four-hole boiling flask carrying heating and whipping appts, 33.6g ethylenediamine tetraacetic acid (EDTA)-2 sodium, 54g PEG-4000,0.85g sulfuric acid is added successively.At 180 DEG C of reaction 4h, and underpressure distillation removes moisture under equal temperature, gained mixture removes unreacted ethylenediamine tetraacetic acid (EDTA)-2 sodium after filtration, products therefrom is poured into wash away unreacted PEG-4000 and oligopolymer thereof in a large amount of butylacetate, finally namely obtain ethylenediamine tetraacetic acid (EDTA)-glycol after centrifugal, drying.
(2) 5g ethylenediamine tetraacetic acid (EDTA)-glycol, 5g are gathered hexanodioic acid-1,4 butanediol ester glycol, 2.72g tolylene diisocyanate, appropriate organotin catalysts add in dimethyl sulfoxide (DMSO) successively and are polymerized, temperature of reaction is 80 DEG C, reaction times 1h, then in system, add 0.58g quadrol, after continuing reaction 1h, product is poured in Teflon mould, and be placed on slaking 9h in 70 DEG C of baking ovens, obtain anticoagulant biodegradable polyurethane material.
(3) under agitation, above-mentioned polyurethane material is dissolved in dimethyl sulfoxide (DMSO), obtain the solution that massfraction is 5%, a large amount of deionized waters is dropwise added in this solution under ultrasound condition, obtain the polyurethane suspension that concentration is 2mg/mL, this suspension is transferred in dialysis tubing, dialyse 2 days in deionized water, and to be diluted to concentration with deionized water is 10
-2the aqueous polyurethane self-servicely can dressing up different size Nano microsphere and nanotube of mg/mL.
Wherein, the molecular weight of described poly-hexanodioic acid-Isosorbide-5-Nitrae butanediol ester glycol is 5000g/mol.
Embodiment 3
Be self-assembled into a preparation method for the polyurethane material of nanotube, comprise the following steps:
(1) in the four-hole boiling flask carrying heating and whipping appts, 33.6g ethylenediamine tetraacetic acid (EDTA)-2 sodium, 54g PEG-4000,0.85g sulfuric acid is added successively.At 160 DEG C of reaction 6h, and underpressure distillation removes moisture under equal temperature, gained mixture removes unreacted ethylenediamine tetraacetic acid (EDTA)-2 sodium after filtration, products therefrom is poured into wash away unreacted PEG-4000 and oligopolymer thereof in a large amount of ethyl acetate, finally namely obtain ethylenediamine tetraacetic acid (EDTA)-glycol after centrifugal, drying.
(2) 0.5g ethylenediamine tetraacetic acid (EDTA)-glycol, 4.5g are gathered hexanodioic acid-1,4 butanediol ester glycol, 2g tolylene diisocyanate, appropriate organotin catalysts add N successively, be polymerized in dinethylformamide, temperature of reaction is 60 DEG C, reaction times 2h, then in system, 0.42g1 is added, 4-butyleneglycol, after continuing reaction 1h, pours into product in Teflon mould, and be placed on slaking 8h in 80 DEG C of baking ovens, obtain anticoagulant biodegradable polyurethane material.
(3) under agitation, above-mentioned polyurethane material is dissolved in N, in dinethylformamide, obtain the solution that massfraction is 5%, under ultrasound condition, dropwise add a large amount of deionized waters in this solution, obtain the polyurethane suspension that concentration is 2mg/mL, this suspension is transferred in dialysis tubing, dialyse 2 days in deionized water, and be diluted to deionized water the aqueous polyurethane self-servicely can dressing up different size Nano microsphere and nanotube that concentration is 1mg/mL.
Wherein, the molecular weight of described poly-hexanodioic acid-Isosorbide-5-Nitrae butanediol ester glycol is 1000g/mol.
Embodiment 4
Be self-assembled into a preparation method for the polyurethane material of nanotube, comprise the following steps:
(1) in the four-hole boiling flask carrying heating and whipping appts, 33.6g ethylenediamine tetraacetic acid (EDTA)-2 sodium, 54g PEG-4000,0.85g sulfuric acid is added successively.At 130 DEG C of reaction 7h, and underpressure distillation removes moisture under equal temperature, gained mixture removes unreacted ethylenediamine tetraacetic acid (EDTA)-2 sodium after filtration, products therefrom is poured into wash away unreacted PEG-4000 and oligopolymer thereof in a large amount of methyl acetate, finally namely obtain ethylenediamine tetraacetic acid (EDTA)-glycol after centrifugal, drying.
(2) 4g ethylenediamine tetraacetic acid (EDTA)-glycol, 10g are gathered hexanodioic acid-1,4 butanediol ester glycol, 4.1g tolylene diisocyanate, appropriate organotin catalysts add N successively, be polymerized in dinethylformamide, temperature of reaction is 50 DEG C, and then reaction times 4h adds 0.42g dimethylbenzene in system, after continuing reaction 1h, product is poured in Teflon mould, and is placed on slaking 9h in 75 DEG C of baking ovens, obtain anticoagulant biodegradable polyurethane material.
(3) under agitation, above-mentioned polyurethane material is dissolved in dimethylbenzene, obtain the solution that massfraction is 5%, a large amount of deionized waters is dropwise added in this solution under ultrasound condition, obtain the polyurethane suspension that concentration is 2mg/mL, this suspension is transferred in dialysis tubing, dialyses 2 days in deionized water, and be diluted to deionized water the aqueous polyurethane self-servicely can dressing up different size Nano microsphere and nanotube that concentration is 1mg/mL.
Wherein, the molecular weight of described poly-hexanodioic acid-Isosorbide-5-Nitrae butanediol ester glycol is 4000g/mol.
What deserves to be explained is that product of the present invention can be applicable to the field such as organizational project, pharmaceutical carrier and Co ntrolled release, nano-reactor, nanocatalyst, and excellent.
Should be noted that, above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although with reference to above-described embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: still can modify to the present invention or equivalent replacement, and not departing from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in right of the present invention.
Claims (10)
1. can be self-assembled into a preparation method for the polyurethane material of nanotube, it is characterized in that, comprise the following steps:
(1) ethylenediamine tetraacetic acid (EDTA)-2 sodium, PEG-4000 are carried out esterification under sulfuric acid catalysis; Then underpressure distillation removing moisture, crosses and filters unreacted ethylenediamine tetraacetic acid (EDTA)-2 sodium, then filtration product poured in solvent orange 2 A and wash away unreacted PEG-4000 and oligopolymer thereof, finally centrifugal, dry, obtains ethylenediamine tetraacetic acid (EDTA)-glycol;
(2) under organotin catalyzed, by ethylenediamine tetraacetic acid (EDTA)-glycol, poly-hexanodioic acid-1,4 butanediol ester glycol, and vulcabond joins in solvent B and is polymerized, add chainextender again, continue reaction, then reaction product is poured in mould, and be placed on slaking in baking oven, obtain biodegradable polyurethane material;
(3) under agitation, the polyurethane material of step (2) gained is dissolved in solvent B, then adds deionized water under ultrasound condition, obtain polyurethane suspension, finally described polyurethane suspension is moved in dialysis tubing, dialyse in deionized water, after dilution, namely obtain aqueous polyurethane.
2. a kind of preparation method being self-assembled into the polyurethane material of nanotube according to claim 1, is characterized in that, described solvent orange 2 A is at least one in methyl acetate, ethyl acetate, butylacetate, acetone, toluene, dimethylbenzene.
3. a kind of preparation method being self-assembled into the polyurethane material of nanotube according to claim 1, it is characterized in that, described vulcabond is at least one in PPDI, tolylene diisocyanate, diphenylmethanediisocyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate, lazy propylhomoserin vulcabond.
4. a kind of preparation method being self-assembled into the polyurethane material of nanotube according to claim 1, it is characterized in that, described chainextender is at least one in ethylene glycol, butyleneglycol, hexylene glycol, glycerol, 1,3-dihydroxypropionic acid, quadrol, hexanediamine.
5. a kind of preparation method being self-assembled into the polyurethane material of nanotube according to claim 1, it is characterized in that, described solvent B is at least one in DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene.
6. a kind of preparation method being self-assembled into the polyurethane material of nanotube according to claim 1, is characterized in that, the molecular weight of described poly-hexanodioic acid-Isosorbide-5-Nitrae butanediol ester glycol is 1000 ~ 5000g/mol.
7. a kind of preparation method being self-assembled into the polyurethane material of nanotube according to claim 1, is characterized in that, in described step (1), the mol ratio of ethylenediamine tetraacetic acid (EDTA)-2 sodium and PEG-4000 is 1:1 ~ 2.
8. a kind of preparation method being self-assembled into the polyurethane material of nanotube according to claim 1, it is characterized in that, in described step (2), the mass ratio of ethylenediamine tetraacetic acid (EDTA)-glycol, poly-hexanodioic acid-Isosorbide-5-Nitrae butanediol ester glycol, vulcabond is 3 ~ 42:3 ~ 42:15 ~ 26; Described chainextender add-on is desolventize the outer total mass of B in polyreaction products therefrom 0.5 ~ 2%.
9. a polyurethane material, its polyurethane material of be self-assembled into nanotube for being obtained by the preparation method described in any one of claim 1 ~ 8.
10. the application of polyurethane material on organizational project, pharmaceutical carrier and Co ntrolled release, nano-reactor, nanocatalyst field being self-assembled into nanotube according to claim 9.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180902A (en) * | 2018-09-03 | 2019-01-11 | 四川大学 | The preparation method of polyurethane and polyurethane, ROS response polyurethane carrier micelle |
| CN114025959A (en) * | 2019-07-12 | 2022-02-08 | 陶氏环球技术有限责任公司 | Water-based composition |
| CN114072443A (en) * | 2019-07-12 | 2022-02-18 | 陶氏环球技术有限责任公司 | Solvent-based compositions |
| US20220275145A1 (en) * | 2019-07-12 | 2022-09-01 | Dow Global Technologies Llc | Solventless compositions |
| CN114025959B (en) * | 2019-07-12 | 2024-05-14 | 陶氏环球技术有限责任公司 | Water-based composition |
-
2014
- 2014-10-17 CN CN201410551610.0A patent/CN104292477A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| LIXIA BAO ET AL.: ""Synthesis, characterization, and self-assembly behaviors of a biodegradable and anti-clotting poly(EDTA-diol-co-butylene adipate glycol urethanes"", 《JOURNAL OF MATERIALS CHEMISTRY B》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180902A (en) * | 2018-09-03 | 2019-01-11 | 四川大学 | The preparation method of polyurethane and polyurethane, ROS response polyurethane carrier micelle |
| CN109180902B (en) * | 2018-09-03 | 2020-01-14 | 四川大学 | Polyurethane and preparation method of polyurethane and ROS (reactive oxygen species) -responsive polyurethane drug-loaded micelle |
| CN114025959A (en) * | 2019-07-12 | 2022-02-08 | 陶氏环球技术有限责任公司 | Water-based composition |
| CN114072443A (en) * | 2019-07-12 | 2022-02-18 | 陶氏环球技术有限责任公司 | Solvent-based compositions |
| US20220259364A1 (en) * | 2019-07-12 | 2022-08-18 | Dow Global Technologies Llc | Solvent-based compositions |
| US20220275145A1 (en) * | 2019-07-12 | 2022-09-01 | Dow Global Technologies Llc | Solventless compositions |
| US11807705B2 (en) * | 2019-07-12 | 2023-11-07 | Dow Global Technologies Llc | Solvent-based compositions |
| US11945903B2 (en) * | 2019-07-12 | 2024-04-02 | Dow Global Technologies Llc | Solventless compositions |
| CN114025959B (en) * | 2019-07-12 | 2024-05-14 | 陶氏环球技术有限责任公司 | Water-based composition |
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Application publication date: 20150121 |